U.S. patent application number 12/260512 was filed with the patent office on 2009-05-28 for methods of post chemical mechanical polishing and wafer cleaning using amidoxime compositions.
Invention is credited to Wai Mun Lee.
Application Number | 20090133716 12/260512 |
Document ID | / |
Family ID | 40276269 |
Filed Date | 2009-05-28 |
United States Patent
Application |
20090133716 |
Kind Code |
A1 |
Lee; Wai Mun |
May 28, 2009 |
METHODS OF POST CHEMICAL MECHANICAL POLISHING AND WAFER CLEANING
USING AMIDOXIME COMPOSITIONS
Abstract
The invention relates to a method for the removal of residues
and contaminants from metal or dielectric surfaces and to a method
for chemical mechanical polishing of a copper or aluminum surface.
The methods of the invention include using an aqueous amidoxime
complex agent. Optionally, the pH of the solution can be adjusted
with an acid or base. The method includes applying the above
composition to the copper or aluminum surface and polishing the
surface in the presence of the composition.
Inventors: |
Lee; Wai Mun; (Fremont,
CA) |
Correspondence
Address: |
MORGAN LEWIS & BOCKIUS LLP
1111 PENNSYLVANIA AVENUE NW
WASHINGTON
DC
20004
US
|
Family ID: |
40276269 |
Appl. No.: |
12/260512 |
Filed: |
October 29, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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61000727 |
Oct 29, 2007 |
|
|
|
61006225 |
Dec 31, 2007 |
|
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Current U.S.
Class: |
134/3 |
Current CPC
Class: |
H01L 21/02063 20130101;
H01L 21/02074 20130101; C11D 3/32 20130101; H01L 21/02071 20130101;
C09G 1/02 20130101; C11D 11/0047 20130101; C11D 7/3263
20130101 |
Class at
Publication: |
134/3 |
International
Class: |
C23G 1/02 20060101
C23G001/02 |
Claims
1. A method for removing residues and contaminants from a metal or
dielectric surface, said method comprising providing a
semiconductor surface, wherein said surface comprises at least one
metal or metal oxide and has undergone chemical mechanical
polishing by contacting the metal or dielectric surface with a
cleaning composition comprising: at least about 10% by weight of a
mixture of water; from about 0.1% to about 35% by weight of at
least one amidoxime compound; optionally an organic solvent; and
optionally one or more organic acid compounds.
2. The method of claim 1, wherein the cleaning composition
comprises between 0.1% to 45% by weight of one or more organic acid
compounds selected from the group consisting of monofunctional,
difunctional and trifunctional organic acids, and further comprises
between 0.5% and 30% by weight of an oxidizing agent.
3. The method of claim 1, further comprising a buffering amount of
at least one basic compounds selected from the group consisting of
an ammonium compound, hydroxylamine, a hydroxylamine derivative, an
alkanolamine and mixtures thereof.
4. The method of claim 3, wherein the at least one basic component
comprises hydroxylamine or a hydroxylamine derivative present in an
amount from about 0.3% to about 15% by weight.
5. The method of claim 3, wherein the ammonium compound comprises
tetraalkylammonium hydroxide, TMAH pentahydrate, BTMAH
(benzyltetramethylammonium hydroxide), TBAH, choline, or THEMAH
(Tris(2-hydroxyethyl)methylammonium hydroxide) present in an amount
from about 0.1% to about 50% by weight.
6. The method of claim 3, wherein the alkanolamine comprises
monoethanolamine, 2-(2-hydroxylethylamino)ethanol,
2-(2-aminoethoxy)ethanol, N,N,N-tris(2-hydroxyethyl)-ammonia,
isopropanolamine, 3-amino-1-propanol, 2-amino-1-propanol,
2-(N-methylamino)ethanol, 2-(2-aminoethylamino)ethanol,
tris(hydroxymethyl)aminoethane, or mixtures thereof.
7. The method of claim 2, where said one or more organic acid
compounds are selected from the group consisting of methanesulfonic
acid, oxalic acid, lactic acid, citric acid, xylenesulfonic acid,
dodecylbenzenesulfonic acid, toluenesulfonic acid, formic acid,
tartaric acid, propionic acid, benzoic acid, ascorbic acid,
gluconic acid, malic acid, malonic acid, succinic acid, gallic
acid, butyric acid, trifluoracetic acid, and mixtures thereof.
8. The method of claim 7, wherein the one or more organic acid
compounds are present in an amount from about 0.2% to about 45% by
weight.
9. The method of claim 2, where said one or more oxidizing agents
are selected from the group consisting of hydrogen peroxide,
ammonium peroxydisulfate, peracetic acid, urea hydroperoxide,
sodium percarbonate, sodium perboraten and mixtures thereof.
10. The method of claim 1, wherein the organic solvent is present
in an amount from about 5% to about 15% by weight.
11. The method of claim 1, further comprising a surface active
agent.
12. The method of claim 11, wherein the surface-active agent is
selected from the group consisting of: (a) non-ionic surfactants;
(b) anionic surfactants; (c) cationic surfactants; (d) zwitterionic
surfactants; (e) amphoteric surfactants; (f) and mixtures
thereof.
13. A method for cleaning a semiconductor work-piece after the
Chemical-Mechanical Planarization (CMP) of the wafer during the
manufacturing of semiconductor devices, the method comprising the
steps of. (a) providing a semiconductor work-piece, wherein said
semiconductor workpiece comprises: (i) a metal line, wherein said
metal line comprises copper or aluminum; (ii) a barrier material,
wherein said barrier material comprises one or more of materials
selected from the group consisting of: a). tantalum (Ta), b).
tantalum nitride (TaN), c). titanium (Ti), d). titanium nitride
(TiN), e). tungsten (W), and f). tungsten nitride (WN); and (iii) a
dielectric; (b) contacting said semiconductor work-piece with a
cleaning solution comprising a cleaning agent, wherein said
cleaning agent comprises: (i) water, and (ii) one or more amidoxime
compounds.
14. The method of claim 13, wherein said cleaning agent further
comprises a surface-active agent which is selected from the group
consisting of: (a) non-ionic; (b) anionic; (c) cationic; (d)
zwitterionic; (e) amphoteric surfactants; (f) and mixtures
thereof.
15. The method of claim 13, wherein the cleaning agent further
comprises at least one basic compound which includes one or more
alkanolamines selected from the group consisting of
monoethanolamine, 2-(2-hydroxylethylamino)ethanol,
2-(2-aminoethoxy)ethanol, N,N,N-tris(2-hydroxyethyl)-ammonia,
isopropanolamine, 3-amino-1-propanol, 2-amino-1-propanol,
2-(N-methylamino)ethanol, 2-(2-aminoethylamino)ethanol, and
mixtures thereof.
16. The method of claim 15, wherein the at least one basic compound
is present an amount from about 0.5% to about 50% by weight.
17. The method of claim 13, wherein the solution is substantially
free from fluoride-containing compounds, acid compounds, organic
solvents, alkanolamines, quaternary ammonium compounds,
hydroxylamine and hydroxylamine derivatives,
non-hydroxyl-containing amines, alkanolamines, non-amidoxime group
chelating agents, and surfactants.
18. The method of claim 13, wherein the amidoxime compound is
derived from a nitrile compound that is derived from the
cyanoethylation of a compound selected from the group consisting of
sugar alcohols, hydroxy acids, sugar acids, monomeric polyols,
polyhydric alcohols, glycol ethers, polymeric polyols, polyethylene
glycols, polypropylene glycols, amines, amides, imides, amino
alcohols, and synthetic polymers.
19. The method of claim 13, wherein the cleaning agent is further
diluted with water prior to contacting with the semiconductor
work-piece.
20. The method of claim 19, wherein the dilution factor is from
about 10 to about 500.
21. The method of claim 1, wherein the cleaning composition further
comprises at least one chelating agent which does not contain an
amidoxime functional group.
22. The method of claim 21, wherein at least one chelating agent is
selected from the group consisting of: ethylene diamine tetraacetic
acid, hydroxamic acid, an oxime, 8-hydroxy quinoline, a
polyalkylenepolyamine, triazole, a crown ether, and mixtures
thereof.
23. The method of claim 13, wherein the cleaning composition
further comprises an oxidizing agent.
24. The method of claim 23, wherein the oxidizing agent is selected
from the group consisting of ammonium peroxydisulfate, peracetic
acid, urea hydroperoxide, sodium percarbonate, organic peroxide,
sodium perborate and mixtures thereof.
25. A method for the removal of residues and contaminants from a
metal or dielectric surface, the method comprising: (1) providing a
semiconductor surface, wherein said surface comprises at least one
metal or metal oxide and has thereon a cleaning formulation
comprising amines, hydroxylamines, or mixtures thereof; and (2)
contacting the metal or dielectric surface with a post-cleaning
composition comprising: one or more amidoxime compounds, water,
between 1% to 25% by weight of one or more organic acids selected
from the group consisting of monofunctional, difunctional and
trifunctional organic acids, and between 0.5% and 30% by weight of
an oxidizing agent, for a time sufficient to remove the residual
cleaning formulation, wherein the post clean composition has a pH
between about 3.5 and about 7.
26. The method of claim 25, wherein the semiconductor surface
comprises a metal comprising Al, an Al/(0.5%)Cu alloy, Ti, W, Ta,
or alloys thereof.
27. The method of claim 25, wherein said contacting removes less
than about 17 Angstroms/min of Cu metal or Cu oxide from the
semiconductor surface.
28. The method of claim 27, wherein the post clean composition
further comprises between 0.01% and 10% by weight of a
chelator.
29. The method of claim 25, wherein the surface tension of the post
clean composition is approximately 70 dynes/cm or less.
Description
CROSS-REFERENCE TO ELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional
Application No. 61/000,727, filed Oct. 29, 2007, and U.S.
Provisional Application No. 61/006,225, filed Dec. 31, 2007, both
of which are incorporated herein by reference in their
entirety.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to compositions and methods
for removal of chemical residues from metal or dielectric surfaces
or for chemical mechanical polishing of a copper or aluminum
surface including an aqueous solution comprising an amidoxime
complex applied for a time sufficient to remove the chemical
residues.
[0003] The National Technology Roadmap for the Semiconductor
Industries (1994) indicated that the current computer chips with
0.35 micron feature sizes will be reduced to 0.18 micron feature
size in 2001. The DRAM chip will have a memory of 1 gigabit, and
typical CPU will have 13 million transistors per cm.sup.2
(currently they only contain about 4 million). The number of metal
layers (the "wires") will increase from the current 2-3 to 5-6 and
the operating frequency, which is currently 200 MHZ, will increase,
for example, to 500 ME. This will increase the need for a three
dimensional construction on the wafer chip to reduce delays of the
electrical signals. Currently there are about 840 meters of
"wires"/chip, but with progressed needs (without any significant
design changes) the typical chip would need 10,000 or more meters
of wire. This length of wire would severely compromise the chip's
speed performance without design changes.
[0004] The manufacturing of electronic wafer chips involves a step
wherein semiconductor work-pieces are cleaned with a liquid
solution during or after Chemical Mechanical Planarization (CMP). A
"semiconductor work-piece" is a microelectronic device, which has
not completed the fabrication process, typically a silicon wafer
with active regions formed in or on the surface of the silicon
wafer. Connections to the active regions are made using multiple
layers of metal, typically copper and tungsten, which has been
deposited on the silicon substrate. When copper is used as the
interconnect material, a damascene process is used whereby the
copper is deposited into lines etched into the inter-layer
dielectric and then the excess copper is removed and the surface
planarized using a CMP process, followed by a cleaning step. The
goal of the cleaning process ("Post-C cleaning") is to remove
residues left by the CMP step from the semiconductor work-piece
surface without significantly etching the metal, leaving deposits
on the surface, or imparting significant organic (such as carbon)
contamination to the semiconductor work-piece. Furthermore, it is
desirable to protect the metal surfaces from corrosion by various
mechanisms such as chemical etching, galvanic corrosion or
photo-induced corrosion. Corrosion of the metal surfaces results in
metal recess and thinning of the metal lines. Acidic cleaning
solutions are often quite efficient at removing organic
contamination from the wafer surface and complexing residual
copper. Thus, it is desirable to have a cleaning solution that is
effective in the moderate to low pH regime. Acidic chemistries are
typically utilized in a brush scrubber or megasonic cleaning unit
for Post-CMP cleaning.
[0005] A cleaning solution may contain various chemicals that
perform different functions during the cleaning process. A cleaning
solution must contain a "cleaning agent." A "cleaning agent" is the
component of solution that removes residual CMP slurry particles,
typically particles of metal, from the surface of the semiconductor
work-piece. A cleaning solution may also contain "chelating
agents," "corrosion-inhibiting compounds," and/or "surface-active
agents." A "chelating agent" helps prevent re-deposition of removed
metal onto the semiconductor work-piece by complexing the metal in
the cleaning solution. A "corrosion-inhibiting compound" is the
component of the cleaning solution that protects the metal surface
from attack by mechanisms such as the aggressive nature of the
cleaning solution, oxidation, post cleaning corrosion, galvanic
attack, or photo-induced attack. A "surface-active agent" is a
component of the cleaning solution that modifies the wetting
characteristics and prevents watermark formation.
[0006] U.S. Pat. Nos. 6,194,366, 6,200,947, 6,436,302, 6,492,308,
6,546,939, 6,673,757 and U.S. Patent Publication 2001/0004633
disclose information relevant to Post-CMP cleaning solutions.
However, these references suffer from one or more of the
disadvantages discussed below. Indeed, there has been a long felt
need in the industry for cleaning solutions that address these
disadvantages such that the solutions do not suffer from one or
more of these disadvantages.
[0007] It is highly advantageous to use a cleaning solution protect
the metal surfaces of the semiconductor device from having a high
static etch rate and from oxidation of the metal surfaces by
forming a protective film on the surface. The metal surfaces of the
semiconductor work-piece are typically copper and form the
conducting paths of the semiconductor wafer. Due to the very small
size of features on semiconductor wafers, the metal lines are as
thin as possible while still carrying the desired electric current.
Any oxidation or corrosion on the surface or recess of the metal
causes thinning of the lines (dissolution) and results in poor
performance or failure of the semiconductor device. Therefore, it
is important to protect the metal surfaces from corrosion by
forming a suitable corrosion resistant film on the surface of the
metal. Many cleaning solutions available in the art do not provide
a film forming agent, and thus suffer from a high static etch rate
and/or high RMS value.
[0008] The cleaning solution's corrosion preventing abilities are
quantified by measuring the static etch rate or the surface
roughness (quantified by RMS, root mean square, value) of a metal
surface that has been cleaned with the subject solution. A high
static etch rate indicates dissolution of the metal surface is
occurring. A high RMS value indicates a rough surface caused by
attack of the metal. An effective protective film reduces the
corrosion of the metal as indicated by static etch rate and RMS
values after cleaning. The corrosion resistance of a cleaning
solution can also be directly measured using electrochemical means
known to those skilled in the art.
[0009] One preferred method of protecting the metal surface from
oxidation corrosion is by passivating the metal surface after or
during cleaning. Some existing acidic cleaning chemistries do not
passivate the metal, resulting in corrosion during and after the
cleaning step by oxidation of the metal surface.
[0010] It is also desirable to clean and protect the semiconductor
surface in a single step. Planarizing a wafer surface usually
includes a cleaning step followed by an additional step of rinsing
with water or an inhibitor solution. Some rinsing agents can leave
deposits on the surface of the work-piece, thus contaminating the
wafer. Adding a second step is also a drawback due to the fact that
it lengthens the manufacturing process, complicates the process by
having to handle more chemicals and more steps, and provides one
more possible source of contamination or other quality control
problems. Clearly, a process that cleans and protects the surface
of the semiconductor work-piece is desirable.
[0011] The ability of the cleaning chemistry to remove residual
metals and retain them in the cleaning solution is also an
important characteristic of a Post-CMP cleaning solution. Chemicals
that can complex the residual metals in the cleaning solution are
effective cleaning solutions because the residual metals are not
re-deposited on the semiconductor work-piece after they are
removed. These complexing chemicals are referred to as "chelating
agents." Cleaning solutions using chemistry that cannot complex the
residual metals typically perform poorly at the desired cleaning
task. Thus, it is desirable to have a cleaning solution capable of
removing and complexing the dissolved metal in the cleaning
solution.
[0012] Another common problem with cleaning semiconductor surfaces
is the deposition of contaminants on the surface of the
semiconductor device. Any cleaning solutions that deposit even a
few molecules of undesirable composition, such as carbon, will
adversely affect the performance of the semiconductor device.
Cleaning solutions that require a rinsing step can also result in
depositing contaminants on the surface. Thus, it is desirable to
use a cleaning chemistry that is will leave little to no residue on
the semiconductor surface.
[0013] It may also be desirable to have a surface wetting agent in
the cleaning solution. Surface wetting agents prevent contamination
of the semiconductor work-piece by helping to stop spotting of the
surface caused by droplets clinging to the surface, Spotting (also
called watermarks) on the surface can saturate metrology tools that
measure light point defects, thus masking defects in the
semiconductor work-piece.
[0014] As indicated above, the available cleaning solutions do not
adequately meet all of the requirements of post-CMP cleaning. The
chemistry of the current invention makes use of multiple additives
to provide a solution that is not sensitive to oxygen, removes
particles efficiently, removes metal from the dielectric surface,
is in the neutral to low pH range, protects the metal from
corrosion and dissolution, and does not contaminate the semi
conductor surface.
[0015] In some cases, the biodegradability is also unsatisfactory.
Thus, EDTA proves to have inadequate biodegradability in
conventional tests, as does PDTA or HPDTA and corresponding
aminomethylenephosphonates which, moreover, are often undesirable
because of their phosphorus content. Phosphorus is also a dopant in
semiconductor devices, therefore it is desirable to have CMP and
post-CMP cleaning solutions with non-phosphor containing
compounds.
[0016] Further, most formulations being used in post-CMP cleaning,
and other semiconductor applications, contain complexing agents,
sometimes called chelating agents. Much metal-chelating
functionality is known, a metal ion being attached by coordination
links to two or more nonmetal atoms (ligands) in the same molecule.
Heterocyclic rings are formed with the central (metal) atom as part
of each ring. When the complex becomes more soluble in the
solution, it functions as a cleaning process. If the complexed
product is not soluble in the solution, it becomes a passivating
agent by forming an insoluble film on top of the metal surface. The
current complexing agents in use, such as, glycolic acid, glyoxylic
acid, lactic acid, phosphonic acid, are acidic in nature and have a
tendency to attack the residue and remove both metals and metal
oxides, such as copper and copper oxide. This presents a problem
for formulators where a chelating function is sought but only
selectively to metal oxide and not the metal itself, e.g. in an
application involving metal, such as copper. Accordingly, there is
a need for complexing agents that are not aggressive toward metal
substrates, while effectively providing for the chelation of metal
ions residue created during the manufacturing processes.
[0017] The present invention addresses these problems.
SUMMARY OF THE INVENTION
[0018] The present invention provides a method of solving one or
more of the following problems common with prior art compositions
and methods: reducing or eliminating corrosion problems;
eliminating substantial use of flammable solvents; eliminating SARA
Title III chemistries; and lowering mobile and transition metal
ions.
[0019] One embodiment, in accordance with the present invention, is
a method for the removal of residues from metal or dielectric
surfaces after chemical mechanical polishing (commonly refers to
post CMP clean or PCMP) of a copper or aluminum surface using an
aqueous solution comprising at least one compound with one or more
amidoxime functional groups. Such compound is believed to act as a
chelating compound. The composition optionally contains a basic
compound, and optionally an acid.
[0020] pH
[0021] Another embodiment, in accordance with the present
invention, is a method of chemical mechanical polishing a copper or
aluminum surface by applying the above composition to the copper or
aluminum surface, and polishing the surface in the presence of the
composition. In a preferred embodiment, the copper or aluminum
surface is chemical mechanical polished by applying an aqueous
composition having a pH between about 3 and about 10 to the copper
or aluminum surface, and polishing the surface in the presence of
the composition.
[0022] The invention also relates to a method for removal of
chemical residues from a metal or dielectric surface after chemical
mechanical polishing, by contacting the metal or dielectric surface
with an aqueous composition having a pH between about 2 and about
11 for a time sufficient to remove the chemical residues.
[0023] In another embodiment, the invention relates to a method for
chemical mechanical polishing of a copper surface by applying an
aqueous composition having a pH between about 3.7 and about 7 to
the copper surface, and polishing the surface in the presence of
the composition. Surprisingly, the formulations of the present
invention are effective in both an acidic and basic pH range,
allowing for customization of the pH based on the needs of the
application, not on the effectiveness of the CMP or post-CMP
cleaning compositions.
[0024] In another embodiment, the invention relates to method for
the chemical mechanical polishing of an aluminum surface by
applying an aqueous composition having a pH between about 3.7 and
about 7 to the aluminum surface, and polishing the surface in the
presence of the composition.
[0025] Organic Acid and/or Basic Component
[0026] In embodiments of the present invention, the aqueous
composition may include: a) a monofunctional, difunctional or
trifunctional organic acid; and/or b) a buffering amount of one or
more basic compounds selected from quaternary amines,
hydroxylamine, hydroxylamine derivatives (including salts),
hydrazine or hydrazine salt base, ammonium compounds, and one or
more alkanolamines.
[0027] In another embodiment, the composition contains at least one
alkaline (basic) compound that is an alkanolamine. Preferred
alkanolamines are monoethanolamine,
2-(2-hydroxylethylamino)ethanol, 2-(2-aminoethoxy)ethanol
N,N,N-tris(2-hydroxyethyl)-ammonia, isopropanolamine,
3-amino-1-propanol, 2-amino-1-propanol, 2-(N-methylaminoethanol,
2-(2-aminoethylamino)ethanol, tris(hydroxymethyl)aminoethane and
mixtures thereof.
[0028] Suitable organic acids include methanesulfonic acid, oxalic
acid, lactic acid, citric acid, xylenesulfonic acid,
toluenesulfonic acid, formic acid, tartaric acid, propionic acid,
benzoic acid, ascorbic acid, gluconic acid, malic acid, malonic
acid, succinic acid, gallic acid, butyric acid, trifluoracetic
acid, glycolic, and mixtures thereof.
[0029] Chelating Agent
[0030] In another alternative or additional embodiment, the aqueous
composition can include a chelation agent that will complex with
transition metal ions and mobile ions. In a preferred embodiment,
the chelation agent includes ethylene diamine tetraacetic acid
(EDTA), an oxime, 8-hydroxy quinoline, a polyalkylenepolyamine or
crown ether.
[0031] Oxidizing Agent
[0032] In another alternative or additional embodiment, the aqueous
composition can include an oxidizing agent that will maintain metal
film oxide layers. In a preferred embodiment, the oxidizing agent
includes ammonium peroxydisulfate, peracetic acid, urea
hydroperoxide, sodium percarbonate or sodium perborate. The
cleaning agents of the current invention are also chelating agents.
The cleaning action of the current invention efficiently removes
residual particles from the surface of the semiconductor work-piece
and also complexes the metal that is removed in solution. Thus the
cleaning efficiency is improved by presenting metal from
re-depositing on the semiconductor work-piece surface.
[0033] The corrosion-inhibiting compound of the current invention
protects the metal of the semiconductor work-piece from oxidation,
and corrosion. The corrosion-inhibiting compounds are effective at
forming a film on the metal of the semiconductor work-piece that
protects metal surfaces from chemical, galvanic and photo-induced
attack during and after the cleaning step. One preferred embodiment
forms a protective film by reducing the surface of the metal. By
protecting the metal surface from attack, the metal retains its
desired thickness and electrical carrying capacity. The cleaning
solution of the current invention is not highly sensitive to oxygen
because it does not contain any oxygen sensitive compounds. Because
the cleaning solution is not highly sensitive to oxygen the
performance of the cleaning solution is not affected by the
presence of air in the cleaning equipment. Thus, the cleaning
solution of the current invention can be used without extra
precautions to purge the storage, transfer and cleaning equipment
of essentially all air.
[0034] The cleaning solution of the current invention cleans the
semiconductor work-piece and forms a corrosion-inhibiting film on
the metal surfaces in the same step. Because the cleaning and
corrosion inhibiting is accomplished in a single step, there is
less likelihood of accidental contamination by handling a
completely separate solution. Furthermore, valuable processing time
is saved by not having to add an additional inhibiting step. Some
preferred embodiments of the cleaning solution include a
surface-active agent, also referred to as a surface-wetting agent.
The surface-active agent helps prevent spotting (watermarks) on the
surface that can be a source of contamination or hide defects in
the semiconductor work-piece.
[0035] Post CMP Cleaner
[0036] One embodiment of the present invention involves the use of
an aqueous composition comprising an amidoxime compound containing
one or more amidoxime functional group in a semiconductor
application wherein the amidoxime compound complexes with metal (or
metal oxide) on a surface, in a residue, or both. Optionally, the
composition contains one or more organic solvents. Optionally, the
composition contains one or more surfactants. Optionally, the
composition contains one or more additional compounds that contain
functional groups which complex or chelate with metals or metal
oxides. Optionally, the composition contains a compound which has
oxidation and reduction potentials, such as a hydroxylamine or
hydroxylamine derivative, such as a salt, and hydrogen
peroxide.
[0037] The composition may contain from about 0.1% to about 99.9%
water and from about 0.01% to about 99.9% of one or more compounds
with one or more amidoxime functional groups.
[0038] The composition may also include a surfactant.
[0039] The methods of the present invention may also use
compositions that are substantially free from fluoride-containing
compounds, acid compounds, organic solvents, alkanolamines,
quaternary ammonium compounds, hydroxylamine and hydroxylamine
derivatives, non-hydroxyl-containing amines, alkanolamines, none
amidoxime group chelating agents, and surfactants.
[0040] The compositions herein may contain substantially no
additional components.
[0041] A preferred source of the amidoxime group is from a nitrile
compound that is derived from the cyanoethylation of a compound
selected from the group consisting of sugar alcohols, hydroxy
acids, sugar acids, monomeric polyols, polyhydric alcohols, glycol
ethers, polymeric polyols, polyethylene glycols, polypropylene
glycols, amines, amides, imides, amino alcohols, and synthetic
polymers.
[0042] The reaction of nitrile-containing compounds with
hydroxylamine are as follows, for example:
##STR00001##
[0043] The amidoxime structure can be represented in their
resonance form as illustrated below
##STR00002##
[0044] Amidoximes are made by the reaction of hydroxylamine with
nitrile compounds. The most preferred compounds which undergo
cyanoethylation include the following. [0045] Compounds containing
one or more --OH or --SH groups, such as water, alcohols, phenols,
oximes, hydrogen sulphide and thiols. [0046] Compounds containing
one or more --NH-- groups, e.g., ammonia, primary and secondary
amines, hydrazines, and amides. [0047] Ketones or aldehydes
possessing a --CH--, --CH2-, or CH3 group adjacent to the carbonyl
group. [0048] Compounds such as malonic esters, malonamide and
cyanoacetamide, in which a --CH-- or --CH2- group is situated
between. --CO2R, --CN, or --CONH-- groups.
[0049] A list of the above compounds can be found in the CRC
Handbook--Table for Organic Compound Identification, 3rd Ed.
Published by The Chemical Rubber Company, such Table is
incorporated herein by reference.
[0050] Formulations containing amidoximes may optionally include
other complexing agents and the amidoxime compound could have other
functional groups that have a chelate functionality within the
molecule itself.
[0051] The compositions of the present application include
semiconductor processing compositions comprising water and at least
one compound containing at least one amidoxime functional group. It
a preferred embodiment the at least one amidoxime functional groups
are derived from a nitrile compound.
[0052] In some embodiments the nitrile compound is derived from the
cyanoethylation of a compound selected from the group consisting of
sugar alcohols, hydroxy acids, sugar acids, monomeric polyols,
polyhydric alcohols, glycol ethers, polymeric polyols, polyethylene
glycols, polypropylene glycols, amines, amides, imides, amino
alcohols, and synthetic polymers.
[0053] One embodiment of the present invention is a method for
removal of chemical residues from a metal or dielectric surface,
which comprises: providing a semiconductor surface, wherein said
surface comprises at least one metal or metal oxide and has
undergone chemical mechanical polishing by contacting the metal or
dielectric surface with a cleaning composition comprising: at least
about 10% by weight of a mixture of water and optionally an organic
solvent; from about 0.1% to about 35% by weight of at least one
compound containing at least one amidoxime functional group,
optionally one or more other organic acid compounds.
[0054] In another embodiment, the composition includes between 0.1%
to 45% by weight of one or more organic acids selected from the
group consisting of monofunctional, difunctional or trifunctional
organic acid and between 0.5% and 30% by weight of an oxidizing
agent. The one or more oxidizing agents may be selected from the
group consisting of hydrogen peroxide, ammonium peroxydisulfate,
peracetic acid, urea hydroperoxide, sodium percarbonate, sodium
perboraten and mixtures thereof.
[0055] Optionally, the cleaning composition may contain a buffering
amount of at least one basic compounds such as e.g., an ammonium
compound, hydroxylamine, a hydroxylamine derivative, an
alkanolamine and mixtures thereof. In one embodiment, the cleaning
composition contains at least at least hydroxylamine or a
hydroxylamine derivative as a basic component, which may be present
in an amount from about 0.3% to about 15% by weight. In another
embodiment, the composition contains ammonium component (such as
e.g. tetraalkylammonium hydroxide, TMAH pentahydrate, BTMAH
(benzyltetramethylammonium hydroxide), TBAH, choline, or THEMAH
(Tris(2-hydroxyethyl)methylammonium hydroxide)), preferably present
in an amount from about 0.1% to about 50% by weight. In yet another
embodiment, the composition contains an alkanolamine component
including but not limited to monoethanolamine,
2-(2-hydroxylethylamino)ethanol, 2-(2-aminoethoxy)ethanol,
N,N,N-tris(2-hydroxyethyl)-ammonia, isopropanolamine,
3-amino-1-propanol, 2-amino-1-propanol, 2-(N-methylamino)ethanol,
2-(2-aminoethylamino)ethanol, tris(hydroxymethyl)aminoethane, or
mixtures thereof.
[0056] In some embodiments, the cleaning composition neutralizes
and removes amines and/or hydroxylamines in the residual processing
formulation and wherein said contacting removes metal or metal
oxide of the semiconductor surface at a rate less than about 17
Angstroms/min.
[0057] In a preferred embodiment, the cleaning composition includes
a buffering amount of at least one basic compound selected from the
group consisting of: an ammonium compound; hydroxylamine; a
hydroxylamine derivative; and one or more alkanolamines. A
buffering amount is, for example, from about 0.1% to about 5% by
weight of the basic compound. One preferred basic compound is
choline. Another is hydroxylamine.
[0058] In some embodiments, the cleaning (e.g. post-CMP)
composition includes one or more organic acid compounds, which can
be, for example methanesulfonic acid, oxalic acid, lactic acid,
citric acid, xylenesulfonic acid, toluenesulfonic acid, formic
acid, tartaric acid, propionic acid, benzoic acid, ascorbic acid,
gluconic acid, malic acid, malonic acid, succinic acid, gallic
acid, butyric acid, trifluoracetic acid, glycolic acid,
methanesulfonic acid, oxalic acid, lactic acid, citric acid, and
mixtures thereof. The one or more organic acid compounds may be
present in an amount from about 0.2% to about 45% by weight.
[0059] The composition may further contain an organic solvent or
surface active agent.
[0060] In some embodiments the organic solvent, which is miscible
with water, is in an amount from about 5% to about 15% by weight.
Other preferred embodiments contain a surface active agent, such
as: (a) non-ionic; (b) anionic; (c) cationic; (d) zwitterionic; (e)
amphoteric surfactants; (f) and mixtures thereof.
[0061] Another embodiment of the present invention is a method for
the cleaning of a semiconductor work-piece after the Chemical
Mechanical Planarization (CMP) of the wafer during the
manufacturing of semiconductor devices; the method comprising the
steps of: (a) providing a semiconductor work-piece, wherein said
semiconductor workpiece comprises: (i) a metal line, wherein said
metal line comprises copper or aluminum; (ii) a barrier material,
wherein said barrier materials can be selected from the group
consisting of a). tantalum (Ta), b). tantalum nitride (TaN), c).
titanium (Ti), d). Titanium nitride (TiN), e) tungsten (W), and f).
tungsten nitride (WN); and (iii) a dielectric (b) contacting said
semiconductor work-piece with a cleaning solution comprising a
cleaning agent, wherein said cleaning agent comprises: (i) water;
and (ii) one or more amidoxime compounds.
[0062] In some embodiments, the cleaning agent further comprises a
surface-active agent which can be selected from the group
consisting of: (a) non-ionic; (b) anionic; (c) cationic; (d)
zwitterionic; (e) amphoteric surfactants; (f) and mixtures thereof.
Optionally the cleaning agent contains at least one basic compound
which includes one or more alkanolamines selected from the group
consisting of monoethanolamine, 2-(2-hydroxylethylamino)ethanol,
2-(2-aminoethoxy)ethanol, N,N,N-tris(2-hydroxyethyl)-ammonia,
isopropanolamine, 3-amino-1-propanol, 2-amino-1-propanol,
2-(N-methylamino)ethanol, 2-(2-aminoethylamino)ethanol,
tris(hydroxymethyl)aminoethane and mixtures thereof. The cleaning
agent may be present in an amount from about 0.5% to about 50% by
weight.
[0063] In some embodiments, the cleaning agent (post-CMP cleaner)
is substantially free from fluoride-containing compounds, acid
compounds, organic solvents, alkanolamines, quaternary ammonium
compounds, hydroxylamine and hydroxylamine derivatives,
non-hydroxyl-containing amines, alkanolamines, non-amidoxime group
chelating agents, and surfactants.
[0064] In one embodiment, the amidoxime group is derived from a
nitrile compound that is derived from the cyanoethylation of a
compound selected from the group consisting of sugar alcohols,
hydroxy acids, sugar acids, monomeric polyols, polyhydric alcohols,
glycol ethers, polymeric polyols, polyethylene glycols,
polypropylene glycols, amines, amides, imides, amino alcohols, and
synthetic polymers.
[0065] The cleaning agent may be further diluted with e.g. water
prior to contacting the semiconductor work-piece. In other
embodiments the cleaning agent or compositions are diluted before
use or replenished during or after use where up to 500 parts water
is added to said composition within about one day prior to
contacting the resulting mixture to a substrate. At some times the
up to 500 parts water is added to the composition within about one
hour prior to contacting the resulting mixture to a substrate. In
one embodiment, the dilution factor is from about 10 to about
500.
[0066] The cleaning solution may have (1) another chelating agent
which does not contain an amidoxime functional group, such as e.g.
ethylene diamine tetraacetic acid, hydroxamic acid, an oxime,
8-hydroxy quinoline, a polyalkylenepolyamine, triazole, a crown
ether, and mixtures thereof and/or (2) an oxidizing agent, such as
e.g. ammonium peroxydisulfate, peracetic acid, urea hydroperoxide,
sodium percarbonate, organic peroxide, sodium perborate and
mixtures thereof.
[0067] Another embodiment of the invention is a method for the
removal of residues and contaminants from a metal or dielectric
surface. The method has at least the steps of (1) providing a
semiconductor surface, wherein said surface comprises at least one
metal or metal oxide and has thereon a cleaning formulation
comprising amines, hydroxylamines, or mixtures thereof; (2)
contacting the metal or dielectric surface with a post-cleaning
composition containing one or more amidoxime compounds, water,
between 1 to 25% by weight of one or more organic acids selected
from the group consisting of monofunctional, difunctional and
trifunctional organic acids, and between 0.5% and 30% by weight of
an oxidizing agent, for a time sufficient to remove the residual
cleaning formulation. The post cleaning (post-clean) composition
has a pH between about 3.5 and about 7, and the contacting removes
metal or metal oxide of the semiconductor surface at a rate less
than about 17 Angstroms/min.
[0068] In one embodiment of the invention, the semiconductor
surface comprises a metal comprising Al, an Al/(0.5%)Cu alloy, Ti,
W, Ta, or alloys thereof, and wherein the contacting step removes
less than about 1 Angstrom/min of metal or metal oxide from the
semiconductor surface. In another embodiment of the invention, the
contacting step of the method removes less than about 17
Angstroms/min of Cu metal or Cu oxide from the semiconductor
surface, Optionally, the post-clean composition may also contain
between 0.01% and 10% by weight of a chelator. In another
embodiment, the post clean composition has a surface tension of
approximately 70 dynes/cm or less. The methods and compositions of
the present invention can remove chemical residues form both metals
and dielectric surfaces. In some cases the residues are from a
liquid residual CMP or etching residue remover formulation
comprising, for example amines, hydroxylamines, or mixture thereof.
The chemical residues are removed by contacting the metal or
dielectric surface with a post-etch cleaning composition
comprising: one or more compounds with at least one amidoxime
functional group, water, between 1% to 25% by weight of one or more
organic acids selected from the group consisting of monofunctional,
difunctional or trifunctional organic acid; between 0.5% and 30% by
weight of an oxidizing agent; and water, wherein the post clean
composition has a pH between about 3.5 and about 7, for a time
sufficient to remove the residual processing formulation, wherein
the post clean composition neutralizes and removes amines and/or
hydroxylamines in the residual processing formulation, wherein said
contacting removes copper or copper oxide from the semiconductor
surface at a rate less than about 17 Angstroms/min or in other
embodiments, the semiconductor surface has a metal comprising Al,
an Al/(0.5%)Cu alloy, Ti, W, Ta, or alloys thereof, and wherein
contacting such metals, the post-etch cleaning composition removes
less than about 1 A/min of metal or metal oxide from the
semiconductor surface. Some of these formulations may also have
between 0.01% and 10% by weight of a chelator, which may help
reduce redeposition and aid in removal. In some cases the surface
tension of the post clean composition is approximately 70 dynes/cm
or less.
[0069] The post-CMP cleaning chemistries herein are capable of
being used without a rinse step and in some embodiments; the method
of post-CMP cleaning is done without a rinse step, unlike many
current post-CMP cleaners.
[0070] Chemical Mechanical Planarization
[0071] The present invention also applies to a method for the
chemical mechanical planarization of a semiconductor work-piece;
the method comprising the steps of: (a) providing a semiconductor
work-piece, wherein said semiconductor workpiece comprises: (i) a
metal line, wherein said metal line comprises copper or aluminum;
(ii) a barrier material, wherein said barrier materials can be
selected from the group consisting of a). Tantalum (Ta), b).
Tantalum nitride (TaN), c). Titanium (Ti), d). Titanium nitride
(TiN), e). Tungsten (W), and f). Tungsten nitride (WN); and (iii) a
dielectric (b) contacting said semiconductor work-piece with a
cleaning solution comprising a cleaning agent, wherein said
cleaning agent comprises: (i) water; (ii) one or more compounds
containing at least one amidoxime functional group.
[0072] In use in CMP applications, the cleaning agent may further
include one or more oxidizers and one or more surface-active
agents, such as a surfactant in the classes disclosed herein
(anionic surfactants, Zweitter-ionic surfactants, multi-ionic
surfactants, or combinations thereof). Examples of such surfactants
are: sodium salts of polyacrylic acid, potassium oleate,
sulfosuccinates, sulfosuccinate derivatives, sulfonated amines,
sulfonated amides, sulfates of alcohols, alkylanyl sulfonates,
carboxylated alcohols, alkylamino propionic acids,
alkyliminodipropionic acids, and combinations thereof and wherein
the surfactant comprises between about 0.001 to about 10 percent by
weight of the composition.
[0073] In CMP applications the pH may be adjusted to between about
2 and about 11. Preferable additives for pH adjustment are acetic
acid, phosphoric acid, oxalic acid, and combinations thereof and
wherein the composition has a pH between about 2 and about II.
[0074] Such chemistries in CMP applications may be slurries
including abrasive particles comprising about 35 wt. % or less of
the composition and wherein the abrasive particles comprise
materials selected from the group of silica, alumina, titanium
oxide, zirconium oxide, cerium oxide, and combinations thereof. The
chemistries may also comprise one or more corrosion inhibitors,
water, and combinations thereof. In some embodiments the one or
more compounds containing at least one amidoxime group in situ with
a first CMP composition between about 30 seconds and about 300
seconds after the first CMP composition is delivered to the
polishing pad.
[0075] In another embodiment, the compositions herein are diluted
prior to use in an amount of up to about 1000 parts water by weight
to about 1 part of the composition by weight, more preferably up to
about 500 parts water by weight to about 1 part of the composition,
or up to about 100 parts water by weight to about 1 part of the
composition or up to about 10 parts water by weight to about 1 part
of the composition, or 1 part water to about 1 part of the
composition, including ratios in between. The dilution is done
prior to use in some embodiments and after use in another
embodiment. When done prior to use, the water is added, for
example, within about one week, or about one day, or about one
hour. It has been found that the fresh dilution is more effective
than if said dilution occurred greater than about one week from
use. By use, for example, the mixture is contacted with a
substrate.
BRIEF DESCRIPTION OF THE FIGURES
[0076] FIG. 1 illustrates the surface chemistry concept of a
contact angle and its importance in semiconductor cleaning.
[0077] FIG. 2 shows the unexpected results of an amidoxime compound
inhibiting copper oxidation in the presence of strong oxidizer,
such as hydrogen peroxide.
[0078] FIG. 3 provides ESCA analysis data which show the presence
of Cu(II) oxide in a copper substrate prior to the cleaning
step.
[0079] FIG. 4 provides ESCA analysis data which show that all of
the Cu(II) oxide has been removed by the amidoxime solution of the
invention. The cleaning process also inhibits the oxidation of the
copper surface after two hours exposure to an ambient
environment.
[0080] FIG. 5 provides ESCA analysis data which show only a small
amount of Cu(II) oxide growth after exposure to an ambient
environment for 10 days. The cleaning process using a composition
comprising an amidoxime compound inhibited the growth of Cu(II)
oxide.
[0081] FIG. 6 is the Auger depth profile analysis of the copper
surface treated by cleaning; the result suggests that, after
exposure to an ambient environment for 10 days, Cu(I) and Cu(II)
oxide did not increase significantly after the cleaning process
using a composition comprising an amidoxime compound.
[0082] FIG. 7 shows a Copper Pourbaix diagram indicating that
copper oxide/hydroxide are insoluble in water at high pH.
[0083] FIG. 8 is a graph depicting amidoxime solution (DS6-10),
which effectively removes particles from a thermal oxide surface.
It is also effective at a dilution factor of 10.
[0084] FIG. 9 is a graph showing amidoxime solution (DS6-10), which
effectively removes particles from a copper surface. It is also
effective at a dilution factor of 10.
[0085] FIG. 10 is a graph depicting amidoxime solution (DS6-10),
which effectively removes particles from low k dielectric
BlackDiamond.TM. (BDI) surface. It is also effective at a dilution
factor of 10.
[0086] FIG. 11 shows the zeta potential of conventional CMP
slurries at various pH's. Slurry systems are stable above or below
its isoelectric point.
[0087] FIG. 12 shows the zeta potential of amidoxime solution
(DS6-10) at various pH's. It has a high negative Zeta Potential,
which suggests good property for removal slurry particles.
[0088] FIG. 13 provides SEM images using different cleaning
chemicals. Amidoxime solution (DS6-10) of the invention effectively
removes particles and copper oxide from the surface without
damaging the copper surface. It is also effective at a dilution
factor of 10.
[0089] FIG. 14 presents SEM images of amidoxime solution DS6-10)
which, after exposure to the solution at 60.degree. C. up to 4
hours, effectively remove particles and copper oxide from the
surface without damaging the copper surface. The images are
compared to those for EKC5510 from EKC Technology under the same
conditions.
[0090] FIG. 15 shows there was no k value shift for
BlackDiamond.TM. (BDI) from Applied Materials. This suggests that
amidoxime solution (DS6-10) of the invention is compatible with
carbon doped low k dielectric.
[0091] FIG. 16 shows the process flow for post CMP clean tool from
EBARA EPO222D. After polishing, the wafer is transferred to a brush
unit capable of dispensing cleaning chemistries and DI water, and
then the wafer is moved to a pencil unit for DI rinse with high
pressure jet spray water to the wafer surface.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0092] The present invention is a cleaning solution for cleaning a
semiconductor work-piece. The composition of the cleaning solution
comprises at least one compound containing at least one amidoxime
functional group. The CMP and post-CMP cleaning solution may be
supplied in concentrated form, or diluted with water or other
suitable diluents known to one skilled in the art and in
concentrations as provided herein.
[0093] Post-Chemical Mechanical Planarization Clean Processes
[0094] Both the interdielectric layers and metal polishing
processes for chemical mechanical planarization (CMP) processes
must eventually pass through a final cleaning step to remove traces
of slurry and the chemistry. Though the process appears to be
simple, i.e., a brush scrub and a rinse cycle, considerable effort
is being expended to determine if the process should involve single
side or double-sided scrubbing, single wafer or batch processing,
spray tools or immersion tanks. Wafer cleanliness from slurry and
pad particles and metallic contamination is the most important
issue in the post-clean step; process reliability and defect
metrology are two other important areas of concerns.
[0095] Residual particle levels must be <0.05 particle/cm2, and
90% of these particles with less than 0.2 micron size. Line widths
of 0.35 micron will require the removal of particles down to 0.035
micron or less to avoid failures. Incomplete particle removal will
decrease wafer yield. Low defect (scratches) levels and acceptable
planarity will also be very important.
[0096] Most fabrication facilities (fabs) have developed their own
in-house technology for the post-clean CMP steps. Most of the
"chemistries" involve deionized (DI) water with either added
ammonium hydroxide or hydrofluoric acid (HF) while some fabs are
using the standard RCA SC-1 (NH.sub.4OH:H.sub.2O.sub.2:H.sub.2O)
and SC-2 (HCl: H.sub.2O.sub.2:H.sub.2O) cleaning steps
traditionally used in the front end process.
[0097] There are five mechanisms for removing impurities (particles
and/or ions) from the wafer surfaces: (1) Physical desorption by
solvents: Replacing a small number of strongly absorbed material
with a large volume of weakly absorbed solvent (changing the
interaction of the surface charges). (2) Change the surface charge
with either acids or bases. The Si--OH group can be protonated
(made positive) in acid or made negative with bases by removing the
proton. (3) Ion complexion: Removing adsorbed metal ions by adding
acid (i.e., ion exchange). (4) Oxidation or decomposition of
impurities: Oxidation of metals, organic materials or the surface
of slurry particles will change the chemical forces between the
impurities and substrate surface. (The chemical reaction can either
be through redox chemistry or free radicals), (5) Etching the
surface: The impurity and a certain thickness of the substrate
surface are dissolved.
[0098] Amidoxime Chemistry
[0099] Amidoxime compound can be used in the invention is derived
from the reaction of a nitrile compound with hydroxylamine.
##STR00003##
The formation of compounds with amidomime functional groups is
detailed herein.
[0100] Silicon Oxide Chemistry
[0101] The mechanism for dielectric polishing is still being
developed, but the polishing process appears to involve two
concurrent processes; a mechanical process involving plastic
deformation of the surface and, chemical attack by hydroxide (OH)
to form silanol bonds.
SiO.sub.2+2H.sub.2O.revreaction.Si(OH).sub.4(aq) pH<9 Log
K3=-2.7
Si(OH).sub.4(aq+OH.revreaction.SiO(OH).sub.3+2H.sub.2O pH>9 Log
K3=-1.7
SiO(OH).sub.3.revreaction.Polynuclear species pH>10.5
Si(OH).sub.4+O2.revreaction.(HO)3Si --O--Si(OH)3+H2O
[0102] In a slurry (colloidal suspension), the pH is important and
for the silicon oxide system it needs to be in the 10 to 11.5
range. Currently CMP users are using silicon oxide-based slurries
which were "buffered" with sodium hydroxide but now are being
formulated with potassium or ammonium hydroxide solutions. Etch
rates can be in the range of 1700 A/min.
[0103] If the pH is too high the polynuclear species may start to
precipitate in an unpredictable manner. There is also the
possibility of an oxidation process to form Si--O--Si bonds.
[0104] There are other important features of the silicon surface
that will influence the etch rates and final surface conditions
(metal contamination and possibly micro scratches). As mentioned
above, the typical silicon surface is terminated (covered) with
--OH groups under neutral or basic conditions. The silicon surface
is hydrophilic, meaning the surface is "wettable". These groups
activate the surface to a number of possible chemical or
physioabsorbtion phenomena. The Si--OH groups impair a weak acid
effect which allows for the formation of salts and to exchange the
proton (H+) for various metals (similar to the ion exchange
resins). These SiO-- and Si--OH groups can also act as ligands for
complexing Al, Fe, Cu, Sn and Ca. Of course the surface is very
dipolar and so electrostatic charges can accumulate or be
dissipated depending on the bulk solution's pH, ion concentration
or charge. This accumulated surface charge can be measured as the
Zeta potential.
[0105] Factors Affecting Zeta Potential
[0106] pH In aqueous media, the pH of the sample is one of the most
important factors that affects its zeta potential. A zeta potential
value on its own without defining the solution conditions is a
virtually meaningless number. Imagine a particle in suspension with
a negative zeta potential. If more alkali is added to this
suspension then the particles tend to acquire more negative charge.
If acid is added to this suspension then a point will be reached
where the charge will be adsorption where they have no effect on
the isoelectric point. (ii) specific ion neutralised. Further
addition of acid will cause a build up of positive charge.
Therefore a zeta potential versus pH curve will be positive at low
pH and lower or negative at high pH. There may be a point where the
plot passes through zero zeta potential. This point is called the
isoelectric point and is very important from a practical
consideration. It is normally the point where the colloidal system
is least stable. A typical plot of zeta potential versus pH is
shown in FIG. 8. In this example, the isoelectric point of the
sample is at approximately pH 5.5. In addition, the plot can be
used to predict that the sample should be stable at pH values less
than 4 (sufficient positive charge is present) and greater than pH
7.5 (sufficient negative charge is present). Problems with
dispersion stability would be expected at pH values between 4 and
7.5 as the zeta potential values are between +30 and -30 mV.
[0107] Conductivity
[0108] The thickness of the double layer (K-1) depends upon the
concentration of ions in solution and can be calculated from the
ionic strength of the medium. The higher the ionic strength, the
more compressed the double layer becomes. The valency of the ions
will also influence double layer thickness. A trivalent ion such as
Al.sup.3+ will compress the double layer to a greater extent in
comparison with a monovalent ion such as Na.sup.+. Inorganic ions
can interact with charged surfaces in one of two distinct ways (i)
non-specific ion adsorption, which will lead to a change in the
value of the isoelectric point. The specific adsorption of ions
onto a particle surface, even at low concentrations, can have a
dramatic effect on the zeta potential of the particle dispersion.
In some cases, specific ion adsorption can lead to charge reversal
of the surface.
[0109] Concentration of a Formulation Component
[0110] The effect of the concentration of a formulation component
on the zeta potential can give information to assist in formulating
a product to give maximum stability. The influence of known
contaminants on the zeta potential of a sample can be a powerful
tool in formulating the product to resist flocculation for
example.
[0111] If the silicon (Si) surface underneath the oxide layer is
exposed because of an over aggressive polishing process, this could
cause electrochemical problems because silicon has a modest redox
potential which will allow Cu, Au, Pt, Pb, Hg and Ag to "plate on"
the silica surface. Exposure to light will also effect the redox
reaction for Cu. The light will "generate" electrons in the
semiconductor Si material which then reduces the copper ion to
Cu(0).
[0112] CMP Metal Chemistry
[0113] It has also been determined that these Post Clean Treatment
solutions can be used to perform CMP planarization of copper or
aluminum metal films. This type of polishing relies on the
oxidation of the metal surface and the subsequent abrasion of the
oxide surface with emulsion slurry. In this mechanism, the
chemistry's pH is important. The general equations are (M=metal
atom):
M.sup.0.fwdarw.M.sup.n++ne.sup.-
M.sup.n++[O.sub.x].sub.y.fwdarw.MO.sub.x or [M(OH).sub.x]
[0114] Under ideal conditions the rate of metal oxide (MOx)
formation (Vf) will equal the rate of oxide polishing (Vp),
(Vf=Vp). If the pH is too low (acidic) then the chemistry can
rapidly penetrate the oxide and attack the metal (Vf<Vp), thus
exposing the metal without any further oxide formation. This means
that all metal surfaces, at high points and in valleys, are removed
at the same rate. Planarization of the surface is not achieved.
This could cause metal plug connectors to be recessed below
("dishing") the planarization surface which will lead eventually to
poor step coverage and possible poor contact resistance.
[0115] When the pH is too high (caustic), then the oxide layer may
become impenetrable to the chemistry and the metal becomes passive,
(Vf>Vp) and the metal polishing rate becomes slow. Metal
polishing selectively to oxide generally ranges from 20 to 100:1,
depending on the metal type. Tungsten metal should have
selectivities >50:1 for the metal to oxide, and copper could
have >140:1 metal to oxide selectivity. Etch rates can be up to
7000 A/min. The chemical diffusion rate and the type of metal oxide
surface are important to the successful planarization process. A
detailed mechanism has been proposed by Kaufman, F.; J.
Electrochem. Soc; 138 (11) p. 3460, 1991.
[0116] Copper films present a difficult problem because copper is a
soft metal and is easily damaged by slurry particles. The Post
Clean Treatment solutions can be very useful for removing these
imperfections.
[0117] Aluminum is also a soft metal and is easily damaged by
slurry particles. However, Aluminum differs from copper in its
ability to self-passivate. Copper in its natural state does not
easily form an oxide film on its surface. It is believed that the
Post Clean Treatment solution can successfully polish copper in
part because copper does not easily form a protective oxide layer.
In contrast, Aluminum does self-passivate relatively easily. In
spite of this tendency to form a protective oxide layer, we have
surprisingly found that the Post Clean Treatment solutions can also
be used to successfully polish aluminum films.
[0118] Contact angle measurement characterizes the interfacial
tension between a solid and a liquid drop. The technique provides a
simple method to generate a great amount of information for surface
analysis. And because the technique is extremely surface sensitive,
it can be used in semiconductor cleaning applications Contact angle
measurement is a simplified method of characterizing the
interfacial tension present between a solid, a liquid, and a vapor.
When a droplet of a high surface tension liquid rests on a solid of
low surface energy, the liquid surface tension will cause the
droplet to form a spherical shape (lowest energy shape).
Conversely, when the solid surface energy exceeds the liquid
surface tension, the droplet is a flatter, lower profile shape.
[0119] Types of Chemicals
[0120] In addition to water and at least one compound having one or
more amidoxime functional groups, a variety of chemicals can be
used in these Post Clean Treatment formulations.
[0121] Acids
[0122] There are a variety of organic acids that can be used in the
Post Clean Treatment chemistries. The type of organic acid is very
important. Some possible acids and their pKa's are as follows:
TABLE-US-00001 pK.sub.a1 pK.sub.a2 pK.sub.a3 Monobasic Formic 3.8
Acetic 4.8 Propionic 4.9 n-Butyric 4.9 Isobutyric 4.8 Benzoic 4.2
Dibasic Ascorbic 4.2 11.6 Gluconic 3.5 4.7 Malic 3.4 5.1 Malonic
2.8 5.7 Oxalic 1.3 4.3 Succinic 4.1 5.6 Tartaric 2.9 4.2 Tribasic
Citric 3.1 4.8 6.9 Gallic 4.2 8.9
[0123] General Structure for the Acid
##STR00004##
[0124] X=--OH. --NHR, --H, -Halogen, --CO.sub.2H and
--CH.sub.2COOH, --CH(OH)--COOH
[0125] R=generally aliphatic, H or aromatic
[0126] Concentrations can vary from 1 to 25 wt %. The important
factor is the solubility of the acid and base products with any
additional agents in the aqueous solutions.
[0127] Bases Component
[0128] A caustic component can be used to adjust the pH of the
buffer Post CMP cleaning composition. Although the pH adjustment
can be achieved with any common base, i.e. sodium, potassium,
magnesium etc. hydroxides, such bases introduce mobile ions into
the final formulation. Mobile ions can easily destroy computer
chips being produced today in the semiconductor industry.
Accordingly, embodiments of the present invention are free of bases
that introduce mobile ions. In such embodiments, other bases are
used, including organic amines, hydroxylamine, quaternary amines
such as tetramethylammonium hydroxide (TMAH) or choline or THEMAH
or ammonium hydroxide.
[0129] Other Chelators
[0130] An added feature for this invention is to add small
quantities of metal ion chelators which could include di-, tri-,
tetra-functional groups, i.e., EDTA, citric acid, oximes, lactic
acid, 8-hydroxy quinoline and other well known agents that will
chelate with metal ions under acid conditions. Other possible
agents are polyethylene oxide, polyethyleneimine and crown ethers.
These latter two compounds have varying affinity for mobile ions
(Li, Na, K, and certain alkaline earth ions). Concentrations
preferably vary from 0.01 to 10 wt %.
[0131] Corrosion Inhibitor
[0132] Preferred corrosion-inhibiting compounds are ascorbic acid,
benzotriazole, caffeic acid, cinnamic acid, cysteine, glucose,
imidazole, mercaptothiazoline, mercaptoethanol, mercaptopropionic
acid, mercaptobenzothiazole, mercaptomethylimidazole, tannic acid,
thioglycerol, thiosalicylic acid, triazole, vanillin, vanillic
acid, or mixtures thereof.
[0133] Surfactants
[0134] One preferred cleaning solution of the present invention
includes a surface-active agent to promote even wetting of the
semiconductor surface. Preferred embodiments include, but are not
limited to, non-ionic, anionic, cationic, zwitterionic or
amphoteric surfactants or mixtures thereof. Surfactants (nonionics,
anionics and cationics) can be included in these formulations.
Though the surface tensions for the Post Clean Treatment solutions
will be .about. 70 dynes/cm, there may be special situations were
the surface tension needs to be reduced.
[0135] A key component of the formulations of the present invention
is the presence of one or more compounds with at least one
amidoxime functional group. Without being bound to any particular
theory, it is understood that the multidentate complexing agents
disclosed above complex with substrate surfaces to remove
contaminants on such surfaces. Amidoxime molecule can be designed
to function as passivation on metal surface by rendering insoluble
metal complex or as cleaning agent by rendering the metal
containing residue more soluble.
[0136] Amidoxime copper complexes have shown to be readily soluble
in water under basic condition while less soluble under acidic
condition. Accordingly, the passivating/cleaning effect of the
amidoxime chemistry can be affected by altering the pH.
[0137] U.S. Pat. No. 6,166,254, for example, discusses the
formation of amidoximes from aqueous hydroxylamine freebase and
nitriles, such as the reaction of acetonitrile with aqueous
hydroxylamine at ambient temperature to yield high purity
acetamidoxime.
[0138] It will be obvious to those skills of the art that other
nitriles will react with hydroxylamine freebase in similar
manners.
[0139] Amidoximes have been shown to complex with metals, such as
copper. Amidoximes of cyanoethylated cellulose have also been shown
to complex with copper and other metal ions. (See, Altas H. Basta,
International Journal of Polymeric Materials, 42, 1-26 (1998)).
[0140] One preferred embodiment of the present invention is to
compositions, and method of use thereof, containing a group of
higher pH range chelating compounds comprising at least two
functional groups where at least one such group is an amidoxime.
The other groups or complexing compounds may be selected as may be
beneficial for the application, the chemistry, and/or the
conditions. Examples of other complexing groups include hydroxamic
acid, thiohydroxamic acid, N-hydroxyurea, N-hydroxycarbamate, and
N-nitroso-alkyl-hydroxylamine. These groups offer synergistic
advantages when used with amidoximes of removing metal oxide, such
as copper oxide, residue by rendering such oxides soluble in
aqueous solutions. As with amidoximes, these functional groups can
be formed by reaction with hydroxylamine or hydroxylamine
derivatives.
[0141] Regarding other complexing agents that may optionally be
used with amidoximes in the compositions of the present
application, complexing agents may be purchased commercially or
prepared by known methods. A non-exhaustive list has been
previously presented.
[0142] One example of a synergistic functional group is a
hydroxamic acid group. Such groups are well known (H. L. Yale, "The
Hydroxamic Acids", Chem. Rev., 209-256 (1943)), Polymers containing
hydroxamic acid groups are known and can be prepared by addition of
hydroxylamine to anhydride groups of anhydride-containing
copolymers, such as styrene-maleic anhydride copolymer or
poly(vinylmethylether/maleic anhydride) copolymers, or by reaction
of hydroxylamine with ester groups. Hydroxamic acid-containing
polymers can also be prepared by acid-catalyzed hydrolysis of
polymers that contain amidoxime groups (U.S. Pat. No.
3,345,344).
[0143] U.S. Pat. No. 6,259,353, for example, discusses the
formation of high purity oximes from aqueous hydroxylamine and
ketones reacted at ambient temperature without addition of
impurities such as salts or acids.
[0144] Thiohydroxamic acids are another synergistic type of
functional groups with amidoximes and can be prepared by addition
of hydroxylamine to dithiocarboxylic acids (H. L. Yale, Chem. Rev.,
33, 209-256 (1943)).
[0145] N-hydroxyureas are another synergistic type of functional
groups with amidoximes and can be prepared by reaction of
hydroxylamine with an isocyanate (A. O. Ilvespaa et al., Chime
(Switz.) 18, 1-16 (1964)).
[0146] N-Hydroxycarbamates are another synergistic type of
functional groups with amidoximes and can be prepared by reaction
of hydroxylamine with either a linear or cyclic carbonate (A. O.
Ilvespaa et al., Chimia (Switz.) 18, 1-16 (1964)).
[0147] N-Nitroso-alkyl-hydroxylamines are another synergistic type
of functional groups with amidoximes and can be prepared by
nitrosation of alkyl hydroxylamines (M. Shiino et al., Bioorganic
and Medicinal Chemistry 95, 1233-1240 (2001)).
[0148] One embodiment of the present invention involves methods of
precleaning substrates or removing stripping or ashing residues
using aqueous cleaning solutions which comprise at least one
chelating compound with one or more amidoxime functional group.
##STR00005##
[0149] The amidoximes can be prepared by the reaction of
nitrile-containing compounds with hydroxylamine.
##STR00006##
[0150] A convenient route to the formation of amidoxime chelating
compounds is by adding hydroxylamine to the corresponding nitrile
compound. There are several methods known for preparing
nitrile-containing compounds, including cyanide addition reactions
such as hydrocyanation, polymerization of nitrile-containing
monomers to form polyacrylonitrile or copolymers of acrylonitrile
with vinyl monomers, and dehydration of amides. Typical procedures
for the syntheses of nitriles may be found in J. March, Advanced
Organic Chemistry, 4th ed., John Wiley and Sons, NY, (1992).
[0151] Nitriles compounds listed in the CRC Handbook (pages
344-368) can be used in this invention include but are not limited
to the followings: Cyanoacetylene, Cyanoacetaldehyde,
Acrylonitrile, Fluoroacetonitrile, Acetonitrile (or Cyanomethane),
Trichloroacetonitrile, Methacrylonitrile (or
.alpha.-Methylacrylonitrile), Proionitrile (or Cyanoethane),
Isobutyronitrile, Trimethylacetonitrile (or tert-Butylcyanide),
2-Ethyacrylonitrile, Dichloroacetonitrile, .alpha.
Chloroisobutyronitrile, n-Butyronitrile (or 1-Cyanopropane),
trans-Crotononitrile, Allycyanide, Methoxyacetonitrile,
2-Hydroxyisobutyronitrile (or Acetone cyanohydrins),
3-Hydroxy-4-methoxybenzonitrile, 2-Methylbutyronitrile,
Chloroacetonitrile, Isovaleronitrile, 2,4-Pentadienonitrile,
2-Chlorocrotononitrile, Ethoxyacetonitrile, 2-Methycrotononitrile,
2-Bromoisobutyronitrile, 4-Pentenonitrile,
Thiophene-2,3-dicarbonitrile (or 2,3-Dicyanothiophene),
3,3-Dimethylacrylonitrile, Valeronitrile (or 1 Cyanobutane),
2-Chlorobutyronitrile, Diethylacetonitrile, 2-Furanecarbonitrile
(or beta-Furonitrile; 2 Cyanofuran), 2-Methylacetoacetonitrile,
Cyclobutanecarbonitrile (or Cyanocyclobutane),
2-Chloro-3-methylbutyronitrile, Isocapronitrile (or
4-Methylpentanonitrile), 2,2-Dimethylacetoacetonitrile,
2-Methylhexanonitrile, 3-Methoxypropionitrile, n-Capronitrile
(n-Hexanonitrile), Ethylamino) acetonitrile (or
N-Ethylglycinonitrile), d,l-3-Methylhexanonitrile,
Chlorofumaronitrile, 2-Acetoxypropionitrile (or
O-Acetyllactonitrile), 3-Ethoxypropionitrile,
3-Chlorobutyronitrile, 3-Chloropropionitrile, Indole-3-carbonitrile
(or 3-Cyanoindole), 5-Methylhexanonitrile, Thiophene-3-carbonitrile
(or 3-Cyanothiophene), d,l-4-Methylhexanonitrile, d,l-Lactonitrile
(or Acetaldehydecyanohydrin), Glycolnitrile (or
Formaldehydecyanohydrin), Heptanonitrile, 4-Cyanoheptane,
Benzonitrile, Thiophene-2-carbonitrile (or 2-Cyanothiophene),
2-Octynonitrile, 4-Chlorobutyronitrile, Methyl cyanoacetate,
Dibenzylacetonitrile, 2-Tolunitrile (or 2-Methoxybenzonitrile),
2,3,3-Trimethyl-1-cyclopentene-1-carbonitrile (or
.quadrature.-Campholytonitrile), Caprylonitrile (or Octanonitrile),
1,1-Dicyanopropane (or Ethylmalononitrile), Ethyl cyanoacetate,
1,1-Dicyanobutane (or Propylmalononitrile), 3-Tolunitrile (or
3-Methylbenzonitrile), Cyclohexylacetonitrile, 4,4-Dicyano-1-butene
(or Allylmalononitrile),
3-Isopropylidene-1-methyl-cyclopentane-1-carbonitrile (or .beta.
Fencholenonitrile), 3-Hydroxypropionitrile,
1,1-Dicyano-3-methylbutane (or Isobutylmalononitrile),
Nonanonitrile, 2-Phenylcrotononitrile, Ethylenecyanohydrin,
2-Phenylpropionitrile, Phenylacetonitrile (or Benzylcyanide),
Phenoxyacetonitrile, 4-Hydroxy-butyronitrile, (3-Tolyl)acetonitrile
(or m-Xylycyanide), (4-Tolyl)acetonitrile (or p-Xylycyanide),
4-Isopropylbenzonitrile, (2-Tolyl)acetonitrile (or o-Xylycyanide),
Decanonitrile, 3-Methyl-2-phenyl butyronitrile, 1,2-Dicyanopropane,
1-Undecanonitrile (or 1-Hendecanonitrile), 2-Phenylvaleronitrile,
10-Undecenonitrile (or 10 Hendecenonitrile), 3-Phenylpropionitrile,
2-Cyanobenzalchloride (or .alpha.,.alpha. Dichloro-o-tolunitrile),
N-Methylanilinonitrile (or N-Cyano-N-methylamine),
3-(2-Chlorophenyl)propionitrile, 1,3-Dicyano-2-methylpropane (or
2-Methylglutaronitrile), O-Benzoyl lactonitrile (or Lactonitrile
benzoate), 3-Cyanobenzatchloride (or
.alpha.,.alpha.-Dichloro-m-tolunitrile), 4-Cyanobenzalchloride (or
.alpha.,.alpha.-Dichloro-p-tolunitrile), Dodecanonitrile (or
Lauronitrile), 1,3-Dicyanopropane (or Glutaronitrile),
4-Methoxyhydrocinnamonitrile (or
3-(4-Methoxyphenyl)-propionitrile), 1,4-Dicyanobutane
(Adiponitrile), 1,2,2,3-Tetramethyl-3-cyclopentene-1-acetonitrile
(or 5-Methyl-.alpha.-campholenonitrile), 1-Cyanocyclohexene,
2-Hydroxybutyronitrile (or Propanalcyanohydrin), Hydnocarponitrile,
.alpha.-Chloro-.alpha.-phenyl acetonitrile, Butyl cyanoacetate,
3-Bromopropionitrile, 2,4-Diphenylbutyronitrile,
Thiophene-2-acetonitrile, Trans-4-Chlorocrotononitrile,
2-Cyanopentanoic acid, Azelaonitrile (or 1,7-Dicyanoheptane),
3-Chloro-2-hydroxy-2-methylpropionitrile (or Chloroacetone
cyanohydrins), 1,11-Dicyanoundecane (or 1,11-Dicyanohendecane),
2-Cyanobutyric acid, 2-Cyanobiphenyl, 1,12-Dicyanodedecane (or
.alpha.,.omega.-Dodecane dicyanide),
1-Cyano-4-isopropenylcyclohexene, Sebaconitrile (or
1,8-Dicyanooctane), Suberonitrile (or 1,6-Dicyanohexane),
3-Cyanoindene (or Indene-3-carbonitrile), Aminoacetonitrile (or
Glycinonitrile), 2-Cyanodiphenylmethane, N-Piperidinoacetonitrile,
3-Chloro-2-tolunitrile, Tetradecanonitrile, Cinnamonitrile,
Trichloroacrylonitrile, DL-Mandelonitrile (or Benzaldehyde
cyanohydrins), Pentadecanonitrile, 2-Methoxybenzonitrile,
(2-Chlorophenyl)acetonitrile (or 2-Chlorobenzylcyanide),
1,1-Dicyanoethane (or Methylmalononitrile), 2-Cyanopyridine (or
2-Pyridinecarbonitrile; Picolinonitrile), 4-tolunitrile (or
4-Methylbenzonitrile), D-Mandelonitrile,
d,l-(2-Bromophenyl)acetonitrile (or 2-Bromobenzyl cyanide), (4
Chlorophenyl)acetonitrile (or 4-Chlorobenzyl cyanide),
Malononitrile (or Methylene cyanide), Hexadecanonitrile,
Maleonitrile (or cis-1,2-Dicyanoethylene), 2,2-Dicyanopropane (or
Dimethylmalononitrile), tert-Butylacetonitrile (or Neopentyl
cyanide), 1-Naphthylacetonitrile, 4,4-Dicyanoheptane (or
Dipropylmalononitrile), Heptadecanonitrile, t-Naphthonitrile (or
1-Cyanonapthalene), 2-Cyanopropionic acid, 4-Fluorobenzonitrile,
Coumarilonitrile (or Coumarin-2-carbonitrile),
Indole-3-acetonitrile, 3-Bromobenzonitrile,
2-(N-Anilino)-butyronitrile, Trans-o-Chlorocinnamonitrile,
Octadecanonitrile, 3-Chlorobenzonitrile, 2-Chlorobenzonitrile,
4-Chloromandelonitrile, Nonadecanonitrile, 2-Bromo-4-tolunitrile,
3,3-Dicyanopentane (or Diethylmalononitrile), 4-Cyanobutyric acid,
5-Chloro-2-tolunitrile, (4-Aminophenyl)acetonitrile (or
4-Aminobenzyl cyanide), meso-2,3-Dimethyl-succinonitrile,
3-Bromo-4-tolunitrile, (4-Bromophenyl)acetonitrile (or
4-Bromobenzyl cyanide), N-Anilinoacetonitrile, 3-Cyanopropionic
acid, 3-Chloro-4-tolunitrile, 3,3-Diphenylacrylonitrile
(.beta.-Phenylcinnamonitrile), 3-Bromo-2-hydroxy benzonitrile,
4,4-Dicyanoheptane (or Dipropylmalononitrile), trans-2,3-Diphenyl
acrylonitrile, Eicosanonitrile, 3-Cyanopyridine (or
Nicotinonitrile), (4-Iodophenyl)acetonitrile (or 4-Iodobenzyl
cyanide), 4-Cyanodiphenyl methane, 2-(N-Anilino) valeronitrile,
2-Aminobenzonitrile (or Anthranilonitrile), 2-Bromobenzonitrile,
5-Cyanothiazole, 3-Aminobenzonitrile, 2-Quinolinoacetonitrile,
2-Iodobenzonitrile, 2,4,6-Trimethylbenzonitrile,
.alpha.-Aminobenzyl cyanide, Cyanoform (or Tricyanomethane),
Succinonitrile, 2-Iodo-4-tolunitrile (2-Iodo-4-methylbenzonitrile),
2,6-Dinitrobenzonitrile, d,l-2,3-Dimethylsuccinonitrile,
2-Chloro-4-tolunitrile, 4-Methoxybenzonitrile,
2,4-Dichlorobenzonitrile, 4-Methoxycinnamonitrile,
3,5-Dichlorobenzonitrile, cis-1,4-Dicyanocyclohexane,
Bromomalononitrile, 2-Naphthonitrile (or 2-Cyanonaphthalene),
Cyanoacetic acid, 2-Cyano-2-ethylbutyric acid (or
Diethylcyanoacetic acid), 2,4-Diphenylglutaronitrile,
beta-Chloro-3-tolunitrile, 4-Chloro-2-tolunitrile,
1-Cyanoacenaphthene (or Acenaphthene-1-carbonitrile),
Phenylmalononitrile (.beta.-Cyanobenzyl cyanide).,
6-Nitro-2-tolunitrile, (4-Hydroxyphenyl)acetonitrile (or
4-Hydroxybenzyl cyanide), 5-Bromo-2-tolunitrile,
.beta.-Bromo-2-tolunitrile., 2,2-Diphenylglutaronitrile,
(2-Aminophenyl)acetonitrile (or 2-Aminobenzyl cyanide),
3,4-Dichlorobenzonitrile,
1,2,2,3-Tetramethylcyclopentene-1-carbonitrile (or Campholic
nitrile), Dicyanodimethylamine (or Bis(cyanomethyl) amine),
Diphenylacetonitrile (.beta.-Phenylbenzyl cyanide),
4-Cyano-N,N-dimethylaniline, 1-Cyanoisoquinoline, 4-Cyanopyridine,
.beta.-Chloro-4-tolunitrile (or 4-Cyanobenzyl chloride),
2,5-Diphenylvaleronitrile, 3-Cyanobenzaldehyde (or
3-Formylbenzonitrile), 6-Nitro-3-tolunitrile, Benzoylacetonitrile,
6-Chloro-2-tolunitrile, 8-Cyanoquinoline, 2-Nitro-3-tolunitrile,
2,3,4,5-Tetrachlorobenzonitrile, 4-Cyanobiphenyl,
2-Naphthylacetonitrile, cis-2,3-Diphenylacrylonitrile,
4-Aminobenzonitrile (or 4-Cyanoaniline),
1-Cyano-2-phenylacrylonitrile (or Benzalmalononitrile),
5-Bromo-2,4-dimethyl-benzonitrile, 2-Cyanotripbenylmethane,
5-Cyanoquinoline, 2,6-Dimethylbenzonitrile, Phenylcyanoacetic
acid., 2-(N-Anilino)-propionitrile, 2,4-Dibromobenzonitrile,
.beta.-(2-Nitrophenyl)-acrylonitrile,
5-Chloro-2-nitro-4-tolunitrile, .beta.Bromo-3-tolunitrile (or
3-Cyanobenzyl bromide), 4-Nitro-3-tolunitrile,
2-(N-Anilino)-isobutyronitrile, 2-Cyanoquinoline, 4-Cyanovaleric
acid (or 2-Methylglutaromononitrile), Fumaronitrile,
4-Chlorobeuzonitrile, 9-Phenanthrylacetonitrile,
3,5-Dibromobenzonitrile, 2-Chloro-3-nitrobenzonitrile,
2-Hydroxybenzonitrile (or 2-Cyanophenol),
4-Chloro-2-nitrobenzonitrile, 4-Cyanotriphenylmethane,
4-Chloro-3-nitrobenzonitrile, 3-Nitro-4-tolunitrile,
2-Cyano-3-phenylpropionic acid, 3-Cyanophenanthrene,
2,3,3-Triphenylpropionitrile, 4-Cyanoquinoline,
4-Bromo-1-naphthonitrile (or 1-Bromo-4-cyanonaphthalene),
4-Bromo-2,5-dimethylbenzonitrile, 5-Nitro-3-tolunitrile,
2,4-Dinitrobenzonitrile, 4-Nitro-2-tolunitrile,
6-Chloro-3-nitrobenzonitrile, 5-Bromo-3-nitro-2-tolunitrile,
2-Nitro-4-tolunitrile, 9-Cyanophenanthrene, 3-Cyanoquinoline,
2-Cyanophenanthrene, 3-Nitro-2-tolunitrile, 2-Nitrobenzonitrile,
4-Chloro-1-naphthonitrile (or 1-Chloro-4-cyanonaphthalene),
5-Cyanoacenaphthene (or Acenaphthene-5-carbonitrile),
4-Bromobenzonitrile, 2,4,5-Trimethoxybenzonitrile,
4-Hydroxybenzonitrile (or 4-Cyanophenol),
2,3-Diphenylvaleronitrile, .beta.Bromo-4-tolunitrile (or
4-Cyanobenzylbromide), (4-Nitrophenyl)aceto nitrile (or
4-Nitrobenzylcyanide), 6-Bromo-3-nitrobenzonitrile,
(2-Hydroxyphenyl)acetonitrile (or 2-Hydroxybenzyl cyanide),
3-Nitrobenzonitrile, 4-Bromo-3-nitrobenzonitrile,
4-Cyanoazobenzene, Dipicolinonitrile (or 2,6-Dicyanopyridine),
2-Cyanohexanoic acid, Dibromomalononitrile (or
Bromodicyanomethane), 1-Cyanoanthracene,
2,2,3-Triphenylpropionitrile, 1-Cyanophenanthrene,
2,3-Diphenylbutyronitrile, 5-Bromo-3nitro-4-tolunitrile,
2,5-Dichlorobenzonitrile, 2,5-Dibromobenzonitrile,
5-Bromo-2-nitro-4-tolunitrile, 2-Hydroxy-3-nitrobenzonitrile (or
2-Cyano-6-nitrophenol), 4-Nitro-1-naphthonitrile (or
1-Cyano-4-nitronaphthalene), 4-Acetamidobenzonitrile,
6-Cyanoquinoline, Apiolonitrile (or
2,5-Dimethoxy-3,4-methylenedioxybenzonitrile),
1-Nitro-2-naphthonitrile (or 2-Cyano-1-nitronaphthalene),
3,5-Dichloro-2-hydroxybenzonitrile, trans-1,4-Dicyanocyclohexane,
3,3,3-Triphenylpropionitrile, 4-Cyano-2-phenylquinoline (or
2-Phenyl-4quinolinonitrile), Phthalonitrile (or o-Dicyanobenzene),
8-Nitro-2-naphthonitrile (or 2-Cyano-8-nitronaphthalene),
5-Chloro-2-naphthonitrile (or 5-Chloro-2cyanonaphthalene),
5-Chloro-1-naphthonitrile (or 5-Chloro-1-cyanonaphthalene),
3,5-Dichloro-4-hydroxybenzonitrile, 4-Nitrobenzonitrile,
5-Bromo-1-naphthonitrile (or 1-Bromo-5cyanonaphthalene),
5-Iodo-2-naphthonitrile (or 2-Cyano-5-iodonaphthalene),
3-Cyano-3-phenylpropionic Acid, 2-Cyano-2-propylvaleramide (or
Dipropylcyanoacetamide), 2,6-Dibromobenzonitrile,
3-Chloro-4-hydroxybenzonitrile, 5-Chloro-2,4-dinitrobenzonitrile,
4-Benzamidobenzonitrile (or N-Benzoylanthranilonitrile),
5-Bromo-2-hydroxybenzonitrile, d,l-2,3-Diphenylsuccinonitrile,
Isophthalonitrile (or m-Dicyanobenzene),
2-Hydroxy-4-nitrohenzonitrile (or 2-Cyano-5-nitrophenol),
d,l-4-Cyano-3,4-diphenylbutyric acid (or
d,l-2,3-Diphenylglutaromononitrile),
d-3-Carboxy-2,2,3-trimethyicyclopentylacetonitrile.,
5-Chloro-2-hydroxyhenzonitrile (or 4-Chloro-2-cyanophenol),
2,3-Diphenylcinnamonitrile (or Cyanotriphenylethylene),
1,7-Dicyanonaphthalene, 4,4'-Dicyanodiphenylmethane, 2,2'-Diphenic
acid mononitrile (or 2-Carboxy-2'-cyanobiphenyl).,
5-Nitro-2-naphthonitrile (or 2-Cyano-5-nitronaphthalene),
9-Cyanoanthracene (or 9-Anthracenecarbonitrile),
2,3-Dicyanopyridine, 1,3-Dicyanonaphthalene, 3-Cyanocoumarin,
2-Cyanocinnamic acid, 2-Cyanobenzoic acid, 1,2-Dicyanonaphthalene,
2-Hydroxy-5-nitrobenzonitrile (or 2-Cyano-4-nitrophenol) 7
Tetracyanoethylene, 5-Nitro-1-naphthonitrile (or
1-Cyano-5-nitronaphthalene), 1,4-Dicyanonaphthalene,
1,6-Dicyanonaphthalene, 1,5-Dicyanonaphthalene, 3-Cyanobenzoic
acid, 4-Cyanobenzoic acid, Terephthalonitrile (or
p-Dicyanobenzene), 1,8-Dicyanonaphthalene, 4,4'-Dicyanobiphenyl,
1-2,3-Diphenylsuccinonitrile, 1-Cyano-9,10-anthraquinone,
2,3-Dicyanonaphthalene, 2,7-Dicyanonaphthalene,
2,6-Dicyanonaphthalene.
[0152] The present invention further include the "nitrile
quaternaries", cationic nitrites of the formula
##STR00007##
in which R.sub.1 is --H, --CH.sub.3, a C.sub.2-24-alkyl or -alkenyl
radical, a substituted C.sub.2-24-alkyl or -alkenyl radical with at
least one substituent from the group --Cl, --Br, --OH, --NH.sub.2,
--CN, an alkyl- or alkenylaryl radical with a C1-24-alkyl group, or
is a substituted alkyl- or alkenylaryl radical with a
C.sub.1-24-alkyl group and at least one further substituent on the
aromatic ring, R.sub.2 and R.sub.3, independently of one another,
are chosen from CH.sub.2--CN, --CH.sub.3, --CH.sub.2--CH.sub.3,
--CH.sub.2--CH.sub.2--CH.sub.3, --CH(CH.sub.3)--CH.sub.3,
--CH.sub.2--OH, --CH.sub.2--CH.sub.2--OH, --CH(OH)--CH.sub.3,
--CH.sub.2--CH.sub.2--CH.sub.2--OH, --CH.sub.2--CH(OH)--CH.sub.3,
--CH(OH)--CH.sub.2--CH.sub.3, --CH.sub.2CH.sub.2--O).sub.nH where
n=1, 2, 3, 4, 5 or 6 and X is an anion.
[0153] The general formula covers a large number of cationic
nitrites which can be used within the scope of the present
invention. With particular advantage, the detergent and cleaner
according to the invention comprise cationic nitrites in which
R.sub.1 is methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl,
n-octyl, n-decyl, n-dodecyl, n-tetradecyl, nhexadecyl or
n-octadecyl radical. R.sub.2 and R.sub.3 are preferably chosen from
methyl, ethyl, propyl, isopropyl and hydroxyethyl, where one or
both of the radicals may advantageously also be a cyanomethylene
radical.
[0154] For reasons of easier synthesis, preference is given to
compounds in which the radicals R1 to R3 are identical, for example
(CH.sub.3).sub.3N(+)CH.sub.2--CN(X--),
(CH.sub.3CH.sub.2).sub.3N(+)CH.sub.2--CNX--,
(CH.sub.3CH.sub.2CH.sub.2).sub.3N(+)CH.sub.2--CNX--,
(CH.sub.3CH(CH.sub.3)).sub.3N(+)CH.sub.2--CNX-- or
(HO--CH.sub.2--CH.sub.2).sub.3N(+)CH.sub.2--CNX--, where X-- is
preferably an anion which is chosen from the group consisting of
hydroxide, chloride, bromide, iodide, hydrogensulfate,
methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate.
[0155] Examples of typical acrylonitrile polymeric materials, which
serve as precursors for preparing our polyamidoximes, are listed
below. The figures are the percents by weight of each monomer in
the polymer.
TABLE-US-00002 90% acrylonitrile 10% vinylacetonitrile 50%'
acrylonitrile 50% methacrylonitrile 97% acrylonitrile 3% vinyl
acetate 50% acrylonitrile 50% vinyl acetate 95% acrylonitrile 5%
methyl methacrylate 65% acrylonitrile 35% methyl acrylate 45%
acrylonitrile 10% methyl acrylate 45% vinyl acetate 44%
acrylonitrile 44% vinyl chloride 12% methyl acrylate 93%
acrylonitrile 7% 2-vinyl pyridine 26% acrylonitrile 74% butadiene
40% 1 acrylonitrile 60% butadiene 33% acrylonitrile 67% styrene
100% acrylonitrile
[0156] Several of the polymers are available commercially, such
as:
TABLE-US-00003 Product Manufacturer Composition Orion DuPont de
Nemours 90% Acrylonitriles Acrilan Chemstrand 90% Acrylonitriles
Creslan American Cyanamid 95-96% Acrylonitriles Zefran Dow Chemical
Co., 90% Acrylonitriles Verel Eastman About 50% acrylonitrile Dyrel
Carbide &Carbon 40% acrylonitrile-60% Vinyl chloride Chemical
Darlan B.F Goodrich 50 Mole percent vinylidene cyanide - 50 Mole
percent Vinyl acetate
[0157] A particularly useful route to nitrites is termed
"cyanoethylation", in which acrylonitrile undergoes a conjugate
addition reaction with protic nucleophiles such as alcohols and
amines. Other unsaturated nitrites can also be used in place of
acrylonitrile.
##STR00008##
[0158] Preferred amines for the cyanoethylation reaction are
primary amines and secondary amines having 1 to 30 carbon atoms,
and polyethylene amine. Alcohols can be primary, secondary, or
tertiary. The cyanoethylation reaction (or "cyanoalkylation" using
an unsaturated nitrile other than acrylonitrile) is preferably
carried out in the presence of a cyanoethylation catalyst.
Preferred cyanoethylation catalysts include lithium hydroxide,
sodium hydroxide, potassium hydroxide and metal ion free bases from
tetraalkylammonium hydroxide, such as tetramethylammonium
hydroxide, TMAH pentahydrate, BTMAH (benzyltetramethylammonium
hydroxide), TBAH, choline, and THEMAH
(Tris(2-hydroxyethyl)methylammonium hydroxide). The amount of
catalyst used is typically between 0.05 mol % and 15 mol %, based
on unsaturated nitrile.
[0159] Preferrably, the cyanolates are derived from the following
groups: arabitol, erythritol, glycerol, isomalt, lactitol,
maltitol, mannitol, sorbitol, xylitol, sucrose and hydrogenated
starch hydrosylate (HSH).
[0160] From the group of hydroxy acids: hydroxyphenylacetic acid
(mandelic acid), 2-hydroxypropionic acid (lactic acid), glycolic
acid, hydroxysuccinic acid (malic acid), 2,3-dihydroxybutanedioic,
acid (tartaric acid), 2-hydroxy-1,2,3-propanetricarboxylic, acid
(citric acid), ascorbic acid, 2-hydroxybenzoic, acid (salicylic
acid), 3,4,5-trihydroxybenzoic acid (gallic acid).
[0161] From the group of sugar acids: galactonic acid, mannonic,
acid, fructonic acid, arabinonic acid, xylonic acid, ribonic, acid,
2-deoxyribonic acid, and alginic acid.
[0162] From the group of amino acids: alanine, valine, leucine,
isoleucine, proline, tryptophan, phenylalanine, methionine,
glycine, serine, tyrosine, threonine, cysteine, asparagine,
glutamine, aspartic acid, glutamic acid, lysine, arginine, and
histidine.
[0163] From the group of monomeric polyols- or polyhydric alcohols,
or glycol ethers, chosen from ethanol, n- or isopropanol, butanols,
glycol, propane- or butanediol, glycerol, diglycol, propyl or butyl
diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene
glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol
mono-n-butyl ether, diethylene glycol methyl ether, diethylene
glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether,
dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxy
triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol,
propylene glycol t-butyl ether, and pentaerythritol.
[0164] From the group of polymeric polyols, chosen from the group
of polyethylene glycols and polypropylene glycols:
[0165] Polyethylene glycols (abbreviation PEGS) PEGs are polymers
of ethylene glycol which satisfy the general formula
##STR00009##
where n can assume values between 1 (ethylene glycol, see below)
and about 16. Polyethylene glycols are commercially available, for
example under the trade names Carbowax. RTM. PEG 200 (Union
Carbide), Emkapol.RTM. 200 (ICI Americas), Lipoxol.RTM. 200 MED
(HOLS America), Polyglycol.RTM. E-200 (Dow Chemical), Alkapol.RTM.
PEG 300 (Rhone-Poulenc), Lutrol.RTM. E300 (BASF), and the
corresponding trade names with higher numbers.
[0166] Polypropylene glycols (PPGs) which can be used according to
the invention are polymers of propylene glycol which satisfy the
general formula
##STR00010##
where n can assume values between 1 (propylene glycol) and about
12. Of industrial significance here are, in particular, di-, tri-
and tetrapropylene glycol, i.e. the representatives where n=2, 3
and 4 in the above formula.
[0167] From the group of organic nitrogen compounds:
[0168] Amines: Amines are organic compounds and a type of
functional group that contain nitrogen as the key atom.
Structurally amines resemble ammonia, wherein one or more hydrogen
atoms are replaced by organic substituents such as alkyl, aryl and
cyclic groups. Compounds containing one or more --NH-- groups of
the formula:
##STR00011##
[0169] Amides--an amide is an amine where one of the nitrogen
substituent is an acyl group; it is generally represented by the
formula: R.sub.1(CO)R.sub.2R.sub.3, where either or both R2 and R3
may be hydrogen. Specifically, an amide can also be regarded as a
derivative of a carboxylic acid in which the hydroxyl group has
been replaced by an amine or ammonia, in which a --CH-- or
--CH.sub.2-- group is situated between --CONH-- groups.
##STR00012##
[0170] Imides--imide is a functional group consisting of two
carbonyl groups bound to a primary amine or ammonia. The structure
of the imide moiety is as shown, which possessing a --CH--,
--CH.sub.2--, or --CH3 group adjacent to the carbonyl group.
##STR00013##
[0171] From the group of amino alcohol (or alkanolamine)--Amino
alcohols are organic compounds that contain both an amine
functional group and an alcohol functional, where the amine can be
primary or secondary amines of the formula, wherein X is
independently selected from alkylene, heteroalkylene, arylene,
heteroarylene, alkylene-heteroaryl, or alkylene-aryl group.
##STR00014##
[0172] From the group of synthetic polymers: Synthetic polymers
such as acetone-formaldehyde condensate, acetone-isobutyraldehyde
condensate, methyl ethyl ketone-formaldehyde condensate, poly(allyl
alcohol), poly(crotyl alcohol), poly(3-chloroallyl alcohol),
ethylene-carbon monoxide copolymers, polyketone from propylene,
ethylene and carbon monoxide, poly(methallyl alcohol, poly(methyl
vinyl ketone, and poly(vinyl alcohol).
[0173] Synthetic polymers such as acetone-formaldehyde condensate,
acetone-isobutyraldehyde condensate, methyl ethyl
ketone-formaldehyde condensate, poly(allyl alcohol), poly(crotyl
alcohol), poly(3-chloroallyl alcohol), ethylene-carbon monoxide
copolymers, polyketone from propylene, ethylene and carbon
monoxide, poly(methallyl alcohol, poly(methyl vinyl ketone, and
poly(vinyl alcohol) have also been cyanoethylated and can also
serve as platforms for further modification into metal-binding
polymers.
[0174] The nitrile groups of these cyanoethylates or cyanoalkylates
can be reacted with hydroxylamine to form the amidoxime. In the
process described herein for preparing amidoxime groups,
hydroxylamine, hydroxylamine hydrochloride, and hydroxylamine
sulfate are suitable sources of hydroxylamine. If hydroxylamine
salt is used instead of hydroxylamine freebase, a base such as
sodium hydroxide, sodium carbonate or metal ion free base such
ammonium hydroxide, tetraalkylammonium hydroxide should be used to
release hydroxylamine as freebase for the reaction.
[0175] Metal ion freebase, such as ammonium hydroxide or a group of
tetraalkylammonium hydroxide, such as tetramethylammonium
hydroxide, TMAH pentahydrate, BTMAH (benzyltetramethylammonium
hydroxide), TBAH, choline, and TEMAH
(Tris(2-hydroxyethyl)methylammonium hydroxide) are preferred.
[0176] Metals, such as copper and others, complex strongly with
molecules containing amidoxime groups, for example amidoximes of
sucrose and sorbitol, to bind metal contaminant residues.
[0177] The present invention offers the benefit of binding to the
metal oxide surface to create an oxidation barrier, particularly
where the amidoxime is derived from functionalized amidoxime
polymer, such as from polyvinylalcohol, polyacrylonitriles and its
copolymers.
[0178] The present invention utilizes the cyanoethylated compounds
referenced in "The Chemistry of Acrylonitrile, 2nd ed." as starting
materials for synthesis of amidoximes, such reference is
incorporated herein to the extent of the cyanoethylated compounds
disclosed therein. The most preferred staring materials for
synthesis of amidoximes are those prepared from cyanoethylated
sugar alcohols, like sucrose, or reduced sugar alcohols, like
sorbitol.
[0179] The present invention further offers the benefit of
increasing the bulk removal of metal during the CMP process when a
chelating agent disclosed herein (e.g.,
(1,2,3,4,5,6-(hexa-(2-amidoximo)ethoxy)hexane) combined with a
compound with oxidation and reduction potentials such as
hydroxylamine and its salts, hydrogen peroxide, hydrazines.
[0180] Because the chelating agents disclosed herein are not
carboxylic acid based but are instead contain multiple ligand
sites, the present invention further offers the benefit of more
efficient and effective binding to metal ions found in
semiconductor manufacturing processes, such as residue after plasma
etching particularly with leading edge technology where copper is
used as conducting metal.
[0181] Another advantage of the chelating agents disclosed herein
is that such chelating agent could be used in dilution as a
Post-copper CMP clean because these groups of compounds are less
acidic than organic acid and less basic than ammonia, choline
hydroxide and THEMAH.
[0182] Because the chelating agents disclosed herein are not
carboxylic acid based but are instead contain multiple ligand
sites, the present invention further offers the benefit of more
efficient and effective binding to metal ions found in
semiconductor manufacturing processes, such as residue after plasma
etching particularly with leading edge technology where copper is
used as conducting metal.
[0183] Another advantage of the chelating agents disclosed herein
is that such chelating agent could be used in dilution as a
Post-copper CMP clean because these groups of compounds are less
acidic than organic acid and less basic than ammonia, choline
hydroxide and THEMAH.
##STR00015##
[0184] General Procedures on Preparation of Amidoxime
[0185] Examples of cyanoethylation to produce nitrile
compounds;
Preparation of .beta.-Ethoxypropionitrile,
C.sub.2H.sub.5--O--CH.sub.2--CH.sub.2--CN
[0186] Place 25 ml of 2 percent aqueous sodium hydroxide and 26 g.
(33 ml.) of ethyl alcohol in a 250 ml. reagent bottle, add 26.5 g.
(33 ml.) of acrylonitrile and close the mouth of the bottle with a
tightly-fitting cork. Shake the resulting clear homogeneous liquid
in a shaking machine for 2 hours. During the first 15 minutes the
temperature of the mixture rises 15.degree. C. to 20.degree. C. and
thereafter falls gradually to room temperature; two liquid layers
separate after about 10 minutes. Remove the upper layer and add
small quantities of 5 percent acetic acid to it until neutral to
litmus; discard the lower aqueous layer. Dry with anhydrous
magnesium sulfate, distil and collect the
.beta.-Ethoxypropionitrile at 172-174.degree. C. The yield is 32
g.
.beta.-n-Propoxypropionitrile,
C.sub.3H.sub.7.alpha.--O--CH.sub.2--CH.sub.2--CN
[0187] Introduce 0.15 g of potassium hydroxide and 33 g. (41 ml) of
dry n-propyl alcohol into a 150 ml. bolt-head flask, warm gently
until the solid dissolves, and then cool to room temperature. Clamp
the neck of the flask and equip it with a dropping funnel, a
mechanical stirrer and a thermometer (suitably supported in
clamps). Introduce from the dropping funnel, with stirring, 26.5 g.
(33 ml) of pure acrylonitrile over a period of 2.5-30 minutes (1
drop every ca. 2 seconds). Do not allow the temperature of the
mixture to rise above 35-45.degree. C.; immerse the reaction flask
in a cold water bath, when necessary. When all the acrylonitrile
has been added, heat under reflux in a boiling water bath for 1
hour; the mixture darkens. Cool, filter and distil. Collect the
O-n-Propoxypropionitrile at 187-189.degree. C. The yield is 38
g.
.beta.-Diethylaminopropionitrile,
(C.sub.2H.sub.5).sub.2N--CH.sub.2CH.sub.2--CN
[0188] Mix 42.5 g (60 ml) of freshly-distilled diethylamine and
26.5 g. (33 ml) of pure acrylonitrile in a 250 ml round-bottomed
flask fitted with a reflux condenser. Heat at 50.degree. C. in a
water bath for 10 hours and then allow to stand at room temperature
for 2 days. Distil off the excess of diethylamine on a water bath,
and distil the residue from a Claisen flask under reduced pressure.
Collect the .beta.-Diethylaminopropionitrile at 75-77.degree. C./11
mm. The yield is 54 g.
.beta.-Di-n-butylaminopropionitrile,
(C.sub.4H.sub.9.alpha.).sub.2N--CH.sub.2--CH.sub.2--CN
[0189] Proceed as for the diethyl compound using 64.5 g. (85 ml) of
redistilled di-n-butylamine and 26.5 g. (33 ml.) of pure
acrylonitrile. After heating at 50.degree. C. and standing for 2
days, distil the entire product under diminished pressure (air
bath); discard the low boiling point fraction containing unchanged
di-n-butylamine and collect the .beta.-Di-n-butylaminopropionitrile
at 120-122-122.degree. 110 mm. The yield is 55 g.
Ethyl n-propyl-2-cyanoethylmalonate
[0190] Add 8.0 g (10.0 ml) of redistilled acrylonitrile to a
stirred solution of ethyl n-propyl malonate (30.2 g.) and of 30
percent methanolic potassium hydroxide (4.0 g.) in tert-butyl
alcohol (100 g.). Keep the reaction mixture at
30.degree.-35.degree. C. during the addition and stir for a further
3 hours. Neutralize the solution with dilute hydrochloric acid
(1:4), dilute with water and extract with ether. Dry the ethereal
extract with anhydrous magnesium sulfate and distil off the ether:
the residue (ethyl n-propyl-2-cyanoethylmalonate; 1 g) solidifies
on cooling in ice, and melts at 31-32.degree. C. after
recrystallization from ice-cold ethyl alcohol.
[0191] Preparation of Cyanoethylated Compound
[0192] A cyanoethylated diaminocyclohexane is prepared according to
U.S. Pat. No. 6,245,932, which is incorporated herein by reference,
with cyanoethylated methylcyclohexylamines are readily prepared in
the presence of water.
##STR00016##
[0193] Analysis shows that almost no compounds exhibiting secondary
amine hydrogen reaction and represented by structures C and D are
produced when water alone is used as the catalytic promoter.
[0194] Examples of reaction of nitrile compound with hydroxylamine
to form amidoxime compound
[0195] Preparation and analysis of polyamidoxime (See, U.S. Pat.
No. 3,345,344)
[0196] 80 parts by weight of polyacrylonitrile of molecular weight
of about 130,000 in the form of very fine powder (-300 mesh) was
suspended in a solution of 300 parts by weight of hydroxylammonium
sulfate, 140 parts by weight of sodium hydroxide and 2500 parts by
weight of deionized water. The pH of the solution was 7.6. The
mixture was heated to 90.degree. C. and held at that temperature
for 12 hours, all of the time under vigorous agitation. It was
cooled to 35.degree..alpha.C. and the product filtered off and
washed repeatedly with deionized water. The resin remained
insoluble throughout the reaction, but was softened somewhat by the
chemical and heat. This caused it to grow from a very fine powder
to small clusters of 10 to 20 mesh. The product weighed 130 grams.
The yield 40 is always considerably more than theoretical because
of firmly occluded salt. The product is essentially a polyamidoxime
having the following reoccurring unit.
[0197] The mixture of hydroxylamine sulfate and sodium hydroxide
can be replaced with equal molar of hydroxylamine freebase
solution.
##STR00017##
[0198] Portions of this product were then analyzed for total
nitrogen and for oxime nitrogen by the well-known Dumas and Raschig
methods and the following was found,
TABLE-US-00004 Percent Total nitrogen (Dumas method) 22.1 Oxime
nitrogen (Raschig method) 6.95 Amidoxime nitrogen (twice the amount
of oxime nitrogen) 13.9 (calculated) Nitrile nitrogen (difference
between the total nitrogen and 8.2 amidoxime nitrogen)
(calculated)
[0199] Conversion of reacted product from cyanoethylation of
cycloaliphatic vicinal primary amines (See, U.S. Pat. No.
6,245,932),
[0200] For example, Cyanoethylated methylcyclohexylamines
##STR00018##
[0201] Due to large number of the amidoxime compounds are not
commercially available. The amidoxime chelating compound can also
prepare in-situ while blending the cleaning formulation.
[0202] The following are photoresist stripper formulations that can
be used with the amidoximes compounds of the present invention:
TABLE-US-00005 Start After Step 1 After Step 2 End Stripper
Ingredient MW mole Wt mole Wt mole Wt mole Wt Composition Step
Amine 2-Pyrolidone 85.11 1.00 85.11 0.00 0.00 0.00 0.00 0.00 0.00
0% 1 Nitrile Acrylonitrile 53.00 1.00 53.00 0.00 0.00 0.00 0.00
0.00 0.00 0% Metal Ion free TMAH 91.00 0.05 4.55 0.05 4.55 0.05
4.55 0.05 4.55 2% base Water 18.00 0.76 13.65 0.76 13.65 0.76 13.70
0.76 13.68 6% Cyanoethylated 137.10 0.00 0.00 1.00 137.10 0.00 0.00
0.00 0.00 0% Compound Step Oxidizing/ Hydroxylamine 31.00 1.00
31.00 0.00 0.00 0.00 0.00 0.00 0.00 0% 2 Reducing compound Water
Water 18.00 1.72 31.00 0.00 0.00 1.72 31.00 1.72 31.00 14%
Amidoxime Amidoxime 170.00 0.00 0.00 0.00 0.00 1.00 170.00 1.00
170.00 78% ##STR00019## 219.20 100%
[0203] Stripping Composition
TABLE-US-00006 Ingredient Stripper Composition Metal Ion free base
TMAH 2% Water Water 20% Amidoxime ##STR00020## 78% 100%
[0204] Example of Amidoxime Derived from Ammonia
TABLE-US-00007 ##STR00021## ##STR00022## H.sub.2N--OH R.sub.1
R.sub.2 R.sub.3 Nitrile Amidoxime --H --H --H ##STR00023##
##STR00024## CH.sub.3CH.sub.2 H H ##STR00025## ##STR00026##
CH.sub.3CH.sub.2 CH.sub.3CH.sub.2 H ##STR00027## ##STR00028##
[0205] Amidoxime Derived from Citric Acid
TABLE-US-00008 ##STR00029## Reactants ##STR00030## CA:AN:HA 1:1:1
##STR00031## CA:AN:HA 1:1:1 ##STR00032## CA:AN:HA 1:1:1
##STR00033## CA:AN:HA 1:1:1 ##STR00034##
[0206] Amidoxime Derived from Lactic Acid
TABLE-US-00009 ##STR00035## ##STR00036## Amidoxime Compounds --
##STR00037## ##STR00038## ##STR00039##
[0207] Amidoxime Derived from Propylene Glycol
TABLE-US-00010 ##STR00040## Amidoxime Compounds Reactant PG:AN:HA
1:1:1 PG:AN:HA 1:2:1 PG:AN:HA 1:2:2 ##STR00041## ##STR00042##
##STR00043## ##STR00044##
[0208] Amidoxime Derived from Pentaerythritol--DS1
TABLE-US-00011 ##STR00045## ##STR00046## H.sub.2N--OH Amidoxime
Compounds ##STR00047## 1 ##STR00048##
[0209] Amidoxime Derived from Pentaerythritol--DS2
TABLE-US-00012 ##STR00049## ##STR00050## H.sub.2N--OH Amidoxime
Compounds ##STR00051## 1 ##STR00052## 2 ##STR00053##
[0210] Amidoxime Derived from Pentaerythritol--DS3
TABLE-US-00013 ##STR00054## ##STR00055## H.sub.2N--OH Amidoxime
Compounds ##STR00056## 1 ##STR00057## 2 ##STR00058## 3
##STR00059##
[0211] Amidoxime Derived from Pentaerythritol--DS4
TABLE-US-00014 ##STR00060## ##STR00061## H.sub.2N--OH Amidoxime
Compounds ##STR00062## 1 ##STR00063## 2 ##STR00064## 3 ##STR00065##
4 ##STR00066##
[0212] .alpha.-Substituted Acetic Acid
TABLE-US-00015 R ##STR00067## --CH.sub.3 Acetic Acid --CH.sub.2OH
Glycolic Acid --CH.sub.2NH.sub.2 Glycine --CHO Glyoxylic Acid
TABLE-US-00016 ##STR00068## H.sub.2N--OH R ##STR00069## 1 2 3
--CH.sub.3 ##STR00070## --CH.sub.2OH ##STR00071## ##STR00072##
##STR00073## --CH.sub.2NH.sub.2 ##STR00074## ##STR00075##
##STR00076## --CH.sub.2NH.sub.2 ##STR00077## ##STR00078##
##STR00079## ##STR00080## --CHO ##STR00081## ##STR00082##
##STR00083##
[0213] Amidoxime Derived from Iminodiacetic Acid
TABLE-US-00017 ##STR00084## Reactants ##STR00085## H.sub.2N--OH
##STR00086## H.sub.2N--OH ##STR00087## H.sub.2N--OH 1 1 1 1 2 1 3
##STR00088## ##STR00089## ##STR00090## ##STR00091##
[0214] Amidoxime Derived from 2,5-piperazinedione
TABLE-US-00018 Reactants ##STR00092## H.sub.2N--OH ##STR00093##
H.sub.2N--OH ##STR00094## H.sub.2N--OH 1 1 1 2 1 2 2 ##STR00095##
##STR00096## ##STR00097## ##STR00098##
[0215] Amidoxime Derived from Cyanopyridine
TABLE-US-00019 Reactants H.sub.2N--OH 1594-57-6 ##STR00099##
##STR00100## ##STR00101## 2,3 or 4 Cyanopyridine 2, 3 or 4
Amidoxime 4-Amidoxime-pyridine pyridine
[0216] Reactions to Produce Nitrile Precursors to Amidoxime
Compounds
[0217] Cyanoethylation of Diethylaminexine
##STR00102##
[0218] A solution of diethylamine (1 g, 13.67 mmol) and
acrylonitrile (0.798 g, 15 mmol, 1.1 eq) in water (10 cm.sup.3) was
stirred at room temperature for 3 hours, after which the mixture
was extracted with dichloromethane (2.times.50 cm.sup.3). The
organic extracts were evaporated under reduced pressure to give the
pure cyanoethylated compound 3-(diethylamino)propanenitrile (1.47
g, 85.2%) as an oil.
[0219] Monocyanoethylation of Glycine
##STR00103##
[0220] Glycine (5 g, 67 mmol) was suspended in water (10 cm.sup.3)
and TMAH (25% in water 24.3 g, 67 mmol) was added slowly, keeping
the temperature at <30.degree. C. with an ice-bath. The mixture
was then cooled to 10.degree. C. and acrylonitrile (3.89 g, 73
mmol) was added. The mixture was stirred overnight, and allowed to
warm to room temperature slowly. The mixture was then neutralized
with HCl (6M, 11.1 cm.sup.3), concentrated to 15 cm.sup.3 and
diluted to 100 cm.sup.3 with EtOH. The solid precipitated was
collected by filtration, dissolved in hot water (6 cm.sup.3-) and
reprecipitated with EtOH (13 cm.sup.3) to give
2-(2-cyanoethylamino)acetic acid (5.94 g, 69.6%) as a white solid,
mp 192.degree. C. (lit mp 190-191.degree. C.).
[0221] Cyanoethylation of Piperazinexine
##STR00104##
[0222] A solution of piperazine (1 g, 11.6 mmol) and acrylonitrile
(1.6 g, 30.16 mmol, 2.6 eq) in water (10 cm.sup.3) were stirred at
room temperature for 5 hours, after which the mixture was extracted
with dichloromethane (2.times.50 cm.sup.3). The organic extracts
were evaporated under reduced pressure to give the pure doubly
cyanoethylated compound 3,3'-(piperazine-1,4-diyl)dipropanenitrile
(2.14 g, 94.7%) as a white solid, mp 66-67.degree. C.
[0223] Cyanoethylation of 2-ethoxyethanol
##STR00105##
[0224] To an ice-water cooled mixture of 2-ethoxyethanol (1 g, 11.1
mmol) and Triton B (40% in MeOH, 0.138 g, 0.33 mmol) was added
acrylonitrile (0.618 g, 11.6 mmol) and the mixture was stirred at
room temperature for 24 hours. It was then neutralized with 0.1 M
HCl (3.3 cm.sup.3) and extracted with CH.sub.2Cl.sub.2 (2.times.10
cm.sup.3). The extracts were concentrated under reduced pressure
and the residue was Kugelrohr-distilled to give the product
3-(2-ethoxyethoxy)propanenitrile (1.20 g, 75.5%) as a colourless
oil, bp 100-130.degree. C./20 Torr.
[0225] Cyanoethylation of 2-(2-dimethylaminoethoxy)ethanol
##STR00106##
[0226] To an ice-water cooled mixture of
2-(2-dimethyleminothoxy)ethanol (1 g, 7.5 mmol) and Triton B (40%
in MeOH, 0.094 g, 0.225 mmol) was added acrylonitrile (0.418 g, 7.9
mmol) and the mixture was stirred at room temperature for 24 hours.
It was then neutralized with 0.1 M HCl (2.3 cm.sup.3) and extracted
with CH.sub.2Cl.sub.2 (2.times.10 cm.sup.3). The extracts were
concentrated under reduced pressure and the residue was purified by
column chromatography (silica, Et.sub.2O, 10% CH.sub.2Cl.sub.2,
0-10% EtOH) to give
3-(2-(2-(dimethylamino)ethoxy)ethoxy)propanenitrile as an oil.
[0227] Cyanoethylation of Isobutyraldehyde
##STR00107##
[0228] Isobutyraldehyde (1 g, 13.9 mmol) and acrylonitrile (0.81 g,
15 mmol) were mixed thoroughly and cooled with an ice-bath. Triton
B (40% in MeOH, 0.58 g, 1.4 mmol) was added. The mixture was
stirred at room temperature overnight. It was then neutralized with
0.1 M HCl (14 cm.sup.3) and extracted with C.sub.1H.sub.2Cl.sub.2
(100 cm.sup.3). The extracts were concentrated under reduced
pressure and the residue was Kugelrohr-distilled to give the
product 4,4-dimethyl-5-oxopentanenitrile (0.8 g, 50.7%) as an oil,
bp 125-130.degree. C./20 Torr.
[0229] Cyanoethylation of Aniline
##STR00108##
[0230] Silica was activated by heating it above 100.degree. C. in
vacuum and was then allowed to cool to room temperature under
nitrogen. To the activated silica (10 g) was absorbed aniline (1.86
g, 20 mmol) and acrylonitrile (2.65 g, 50 mmol) and the flask was
capped tightly. The contents were then stirred with a magnetic
stirrer for 6 days at 60.degree. C. After this time the mixture was
cooled to room temperature and extracted with MeOH. The extracts
were evaporated to dryness and the residue was Kugelrohr-distilled
under high vacuum to give the product 3-(phenylamino)propanenitrile
(2.29 g, 78.4%) as an oil which crystallised on standing; bp
120-150.degree. C./1-2 Torr (lit bp 120.degree. C./1 Torr), mp
50.5-52.5.degree. C.
[0231] Cyanoethylation of Ethylenediamine
##STR00109##
[0232] Acrylonitrile (110 g, 137 cm.sup.3, 2.08 mol) was added to a
vigorously stirred mixture of ethylenediamine (25 g, 27.8 cm.sup.3,
0.416 mol) and water (294 cm.sup.3) at 40.degree. C. over 30 min.
During the addition, it was necessary to cool the mixture with a
25.degree. C. water bath to maintain temperature at 40.degree. C.
The mixture was then stirred for an additional 2 hours at
40.degree. C. and 2 hours at 80.degree. C. Excess acrylonitrile and
half of the water were evaporated off and the residue, on cooling
to room temperature, gave a white solid which was recrystallised
from MeOH-water (9:1) to give pure product
3,3',3'',3'''-(ethane-1,2-diylbis(azanetriyl))tetrapropanenitrile
(86.6 g, 76.4%) as white crystals, mp 63-65.degree. C.
[0233] Cyanoethylation of Ethylene Glycol
##STR00110##
[0234] Small scale: Ethylene glycol (1 g, 16.1 mmol) was mixed with
Triton B (40% in MeOH, 0.22 g, 0.53 mmol) and cooled in an ice-bath
while acrylonitrile (1.71 g, 32.2 mmol) was added. The mixture was
stirred at room temperature for 60 hours after which it was
neutralized with 0.1 M HCl (0.6 cm.sup.3) and extracted with
CH.sub.2Cl.sub.2 (80 cm.sup.3). The extracts were concentrated
under reduced pressure and the residue was Kugelrohr-distilled to
give 3,3'-(ethane-1,2-diylbis(oxy))dipropanenitrile (1.08 g, 39.9%)
as a light coloured oil, hp 150-170.degree. C./20 Torr.
[0235] Large scale: Ethylene glycol (32.9 g, 0.53 mol) was mixed
with Triton B (40% in MeOH, 2.22 g, 5.3 mmol) and cooled in an
ice-bath while acrylonitrile (76.2 g, 1.44 mol) was added. The
mixture was allowed to warm slowly to room temperature and stirred
for 60 hours after which it was neutralized with 0.1 M HCl (50
cm.sup.3) and extracted with CH.sub.2Cl.sub.2 (300 cm.sup.3). The
extracts were passed through a silica plug three times to reduce
the brown colouring to give 86 g (quantitative yield) of the
product as an amber coloured oil, pure by .sup.1H-NMR, containing
10 g of water (total weight 96 g, amount of water calculated by
.sup.1H NMR integral sizes).
[0236] Cyanoethylation of Diethyl Malonate
##STR00111##
[0237] To a solution of diethyl malonate (1 g, 6.2 mmol) and Triton
B (40% in MeOH, 0.13 g, 0.31 mmol) in dioxane (1.2 cm.sup.3) was
added dropwise acrylonitrile (0.658 g, 12.4 mmol) and the mixture
was stirred at 60.degree. C. overnight. The mixture was then cooled
to room temperature and neutralized with 0.1 M HCl (3 cm.sup.3) and
poured into ice-water (10 cm.sup.3). Crystals precipitated during
30 min. These were collected by filtration and recrystallised from
EtOH (cooling in freezer before filtering off) to give diethyl
2,2-bis(2-cyanoethyl)malonate (1.25 g, 75.8%) as a white solid, mp
62.2-63.5.degree. C.
[0238] Hydrolysis of diethyl 2,2-bis(2-cyanoethyl)malonate
##STR00112##
[0239] Diethyl 2,2-bis(2-cyanoethyl)malonate (2 g, 7.51 mmol) was
added to TMAH (25% in water, 10.95 g, 30.04 mmol) at room
temperature. The mixture was stirred for 24 hours, and was then
cooled to 0.degree. C. A mixture of 12M HCl (2.69 cm.sup.3, 32.1
mmol) and ice (3 g) was added and the mixture was extracted with
CH.sub.2Cl.sub.2 (5.times.50 cm.sup.3). The extracts were
evaporated under vacuum to give 2,2-bis(2-cyanoethyl)malonic acid
(0.25 g, 15.8%) as colourless very viscous oil (lit decomposed.
158.degree. C.).
[0240] Dicyanoethylation of Glycine to Give
2-(bis(2-cyanoethyl)amino)acetic acid
##STR00113##
[0241] Glycine (5 g, 67 mmol) was suspended in water (10 cm.sup.3)
and TMAH (25% in water, 24.3 g, 67 mmol) was added slowly, keeping
the temperature at <30.degree. C. with an ice-bath. The mixture
was then cooled to 10.degree. C. and acrylonitrile (7.78 g, 146
mmol) was added. The mixture was stirred overnight, and allowed to
warm to room temperature slowly. It was then heated at 50.degree.
C. for 2 hours, using a reflux condenser. After cooling with ice,
the mixture was neutralized with HCl (6M, 11.1 cm.sup.3) and
concentrated to a viscous oil. This was dissolved in acetone (100
cm.sup.3) and filtered to remove NMe.sub.4Cl. The filtrate was
concentrated under reduced pressure to give an oil that was treated
once more with acetone (100 cm.sup.3) and filtered to remove more
NMe.sub.4Cl. Concentration of the filtrate gave
2-bis(2-cyanoethyl)amino)acetic acid (11.99 g, 99.3%) as a
colourless, viscous oil that crystallised over 1 week at room
temperature to give a solid product, mp 73.degree. C. (lit mp
77.8-78.8.degree. C. Duplicate .sup.13C signals indicate a partly
zwitterionic form in CDCl.sub.3 solution.
[0242] When NaOH is used in the literature procedure, the NaCl
formed is easier to remove and only one acetone treatment is
necessary.
[0243] Dicyanoethylation of N-methyldiethanolamine to Give
3,3'-(2,2'-(methylazanediyl)bis(ethane-2,1-diyl)bis(oxy))dipropanenitrile-
.
##STR00114##
[0244] To a cooled, stirred mixture of N-methyldiethanolamine (2 g,
17 mmol) and acrylonitrile (2.33 g, 42 mmol) was added TMAH (25% in
water, 0.25 cm.sup.3, 0.254 g, 7 mmol). The mixture was then
stirred overnight, and allowed to warm to room temperature slowly.
It was then filtered through silica using a mixture of Et.sub.2O
and CH.sub.2Cl.sub.2 (1:1, 250 cm.sup.3) and the filtrated was
evaporated under reduced pressure to give
3,3'-(2,2'-(methylazanediyl)bis(ethane-2,1-diyl)bis(oxy))dipropaneni-
trile (2.85 g, 74.4%) as a colourless oil.
[0245] Dicyanoethylation of Glycine Anhydride
##STR00115##
[0246] Glycine anhydride (2 g, 17.5 mmol) was mixed with
acrylonitrile (2.015 g, 38 mmol) at 0.degree. C. and TMAH (25% in
water, 0.1 cm.sup.3, 0.1 g, 2.7 mmol) was added. The mixture was
then stirred overnight, allowing it to warm to room temperature
slowly. The solid formed was recrystallised from EtOH to give
3,3'-(2,5-dioxopiperazine-1,4-diyl)dipropanenitrile (2.35 g, 61%)
as a white solid, mp 171-173.degree. C. (lit mp 166.degree.
C.).
[0247] N,N-Dicyanoethylation of Acetamide
##STR00116##
[0248] Acetamide (2 g, 33.9 mmol) was mixed with acrylonitrile
(2.26 g, 42.7 mmol) at 0.degree. C. and TMAH (25% in water, 0.06
cm.sup.3, 0.06 g, 1.7 mmol) was added. The mixture was then stirred
overnight, allowing it to warm to room temperature slowly. The
mixture was filtered through a pad of silica with the aid of
Et.sub.2O/CH.sub.2Cl.sub.2 (200 cm.sup.3) and the filtrate was
concentrated under reduced pressure. The product was heated with
spinning in a Kugelrohr at 150.degree. C./2 mmHg to remove side
products and to give N,N-bis(2-cyanoethyl)acetamide (0.89 g, 15.9%)
as a viscous oil.
[0249] The N-substituent in the amides is non-equivalent due to
amide rotation.
[0250] Tricyanoethylation of Ammonia
##STR00117##
[0251] Ammonia (aq 35%, 4.29, 88 mmol) was added dropwise to
ice-cooled AcOH (5.5 g, 91.6 mmol) in water (9.75 cm.sup.3),
followed by acrylonitrile (4.65 g, 87.6 mol). The mixture was
stirred under reflux for 3 days, after which it was cooled with ice
and aq TMAH (25% in water, 10.94 g, 30 mmol) was added. The mixture
was kept cooled with ice for 1 hour. The crystals formed was
collected by filtration and washed with water. The product was
dried in high vacuum to give 3,3',3''-nitrilotripropanenitrile
(2.36 g, 45.8%) as a white solid, mp 59-61.degree. C. (lit mp
59.degree. C.).
[0252] When NaOH was used to neutralise the reaction (literature
procedure), the yield was higher, 54.4%.
[0253] Dicyanoethylation of Cyanoacetamide
##STR00118##
[0254] To a stirred mixture of cyanoacetamide (2.52 g, 29.7 mmol)
and Triton B (40% in MeOH, 0.3 g, 0.7 mmol) in water (5 cm.sup.3)
was added acrylonitrile (3.18 g, 59.9 mmol) over 30 minutes with
cooling. The mixture was then stirred at room temperature for 30
min and then allowed to stand for 1 hours. EtOH (20 g) and 1M HCl
(0.7 cm.sup.3) were added and the mixture was heated until all
solid had dissolved. Cooling to room temperature gave crystals that
were collected by filtration and recrystallised from EtOH to give
2,4-dicyano-2-(2-cyanoethyl)butanamide (4.8 g, 84.7%) as a pale
yellow solid, mp 118-120.degree. C. (lit mp 118.degree. C.).
[0255] N,N-Dicyanoethylation of Anthranilonitrile
##STR00119##
[0256] Anthranilonitrile (2 g, 16.9 mmol) was mixed with
acrylonitrile (2.015 g, 38 mmol) at 0.degree. C. and TMAH (25% in
water, 0.3 cm.sup.3, 0.1 g, 2.7 mmol) was added. The mixture was
then stirred overnight, allowing it to warm to room temperature
slowly. The product was dissolved in CH.sub.2Cl.sub.2 and filtered
through silica using a mixture of Et.sub.2O and CH.sub.2Cl.sub.2
(1:1, 250 cm.sup.3). The filtrate was evaporated to dryness and the
solid product was recrystallised from EtOH (5 cm.sup.3) to give
3,3'-(2-cyanophenylazanediyl)dipropanenitrile (2.14 g, 56.5%) as an
off-white solid, mp 79-82.degree. C.
[0257] Dicyanoethylation of Malononitrile
##STR00120##
[0258] Malononitrile (5 g, 75.7 mmol) was dissolved in dioxane (10
cm.sup.3), followed by trimethylbenzylammonium hydroxide (Triton B,
40% in MeOH, 1.38 g, 3.3 mmol). The mixture was cooled while
acrylonitrile (8.3 g, 156 mmol) was added. The mixture was stirred
overnight, allowing it to warm to room temperature slowly. It was
then neutralized with HCl (1 M, 3.3 cm.sup.3) and poured into
ice-water. The mixture was extracted with CH.sub.2Cl.sub.2 (200
cm.sup.3) and the extracts were evaporated under reduced pressure.
The product was purified by column chromatography (silica, 1:1
EtOAc-petroleum) followed by recrystallisation to give
1,3,3,5-tetracarbonitrile (1.86 g, 14.3%), mp 90-92.degree. C. (lit
mp 92.degree. C.).
[0259] Tetracyanoethylation of Pentaerythritol
##STR00121##
[0260] Pentaerythritol (2 g, 14.7 mmol) was mixed with
acrylonitrile (5 cm.sup.3, 4.03 g, 76 mmol) and the mixture was
cooled in an ice-bath while tetramethylammonium hydroxide (=TMAH,
25% in water, 0.25 cm.sup.3, 0.254 g, 7 mmol) was added. The
mixture was then stirred at room temperature for 20 hours. After
the reaction time, the mixture was filtered through silica using a
mixture of Et.sub.2O and CH.sub.2Cl.sub.2 (1:1, 250 cm.sup.3), and
the filtrated was evaporated under reduced pressure to give
3,3'-(2,2-bis((2-cyanoethoxy)methyl)propane-1,3-diyl)bis(oxy)dipropanenit-
rile (5.12 g, 100%) as a colourless oil.
[0261] Hexacyanoethylation of Sorbitol
##STR00122##
[0262] Sorbitol (2 g, 11 mmol) was mixed with acrylonitrile (7
cm.sup.3, 5.64 g, 106 mmol) and the mixture was cooled in an
ice-bath while tetramethylammonium hydroxide (=TMAH, 25% in water,
0.25 cm.sup.3, 0.254 g, 7 mmol) was added. The mixture was then
stirred at room temperature for 48 hours, adding another 0.25
cm.sup.3 of TMAH after 24 hours. After the reaction time the
mixture was filtered through silica using a mixture of Et.sub.2O
and CH.sub.2Cl.sub.2 (1:1, 250 cm.sup.3) and the filtrate was
evaporated under reduced pressure to give a fully cyanoethylated
product (4.12 g, 75%) as a colourless oil.
[0263] Tricyanoethylation of Diethanolamine to Give
3,3'-(2,2'-(2-cyanoethylazanediyl)bis(ethane-2,1-diyl)bis(oxy))dipropanen-
itrile
##STR00123##
[0264] To an ice-cooled stirred solution of diethanolamine (2 g, 19
mmol) and TMAH (25% in water, 0.34 cm.sup.3, 0.35 g, 9.5 mmol) in
dioxane (5 cm.sup.3) was added acrylonitrile (3.53 g, 66.1 mmol)
dropwise. The mixture was then stirred overnight, and allowed to
warm to room temperature. More acrylonitrile (1.51 g, 28 mmol) and
TMAH (0.25 cm.sup.3, 7 mmol) was added and stirring was continued
for additional 24 h. The crude mixture was filtered through a pad
of silica (Et.sub.2O/CH.sub.2Cl.sub.2 as eluent) and evaporated to
remove dioxane. The residue was purified by column chromatography
(silica, Et.sub.2O to remove impurities followed by EtOAc to elute
product) to give
3,3'-(2,2'-(2-cyanoethylazanediyl)bis(ethane-2,1-diyl)bis(oxy))dipropanen-
itrile (1.67 g, 33%) as an oil.
[0265] Reactions to Produce Amidoxime Compounds
[0266] Reaction of Acetonitrile to Give N'-hydroxyacetimidamide
##STR00124##
[0267] A solution of acetonitrile (0.78 g, 19 mmol) and
hydroxylamine (50% in water, 4.65 cm.sup.3, 5.02 g, 76 mmol, 4 eq)
in EtOH (100 cm.sup.3) was stirred under reflux for 1 hours, after
which the solvent was removed under reduced pressure and the
residue was recrystallised from iPrOH to give the product
N'-hydroxyacetimidamide (0.63 g, 45%) as a solid, mp
134.5-136.5.degree. C.
[0268] Reaction of Octanonitrile to give
N'-hydroxyoctanimidamide
##STR00125##
[0269] Octanonitrile (1 g, 7.99 mmol) and hydroxylamine (50% in
water, 0.74 cm3, 0.79 g, 12 mmol, 1.5 eq) in EtOH (1 cm.sup.3) were
stirred at room temperature for 7 days. Water (10 cm.sup.3) was
then added. This caused crystals to precipitate; these were
collected by filtration and dried in high vacuum line to give the
product N'-hydroxyoctanimidamide (0.94 g, 74.6%) as a white solid,
mp 73-75.degree. C.
[0270] Reaction of Chloroacetonitrile to Give
2-chloro-N'-hydroxyacetimidamide
##STR00126##
[0271] Chloroacetonitrile (1 g, 13 mmol) and hydroxylamine (50% in
water, 0.89 cm.sup.3, 0.96 g, 14.6 mmol, 1.1 eq) in EtOH (1
cm.sup.3) were stirred at 30-50.degree. C. for 30 min. The mixture
was then extracted with Et2O (3.times.50 cm.sup.3). The extracts
were evaporated under reduced pressure to give the product
2-chloro-N'-hydroxyacetimidamide (0.81 g, 57.4%) as a yellow solid,
mp 79-80.degree. C.
[0272] Reaction of ethyl 2-cyanoacetate to Give
3-amino-N-hydroxy-3-(hydroxyimino)propanamide
##STR00127##
[0273] Ethyl cyanoacetate (1 g, 8.84 mmol) and hydroxylamine (50%
in water, 1.19 cm3, 1.29 g, 19.4 mmol, 2.2 eq) in EtOH (1 cm.sup.3)
were allowed to stand at room temperature for 1 hour with
occasional swirling. The crystals formed were collected by
filtration and dried in high vacuum line to give a colourless
solid, 3-amino-N-hydroxy-3-(hydroxyimino)propanamide, mp
158.degree. C. (decomposed) (lit mp 150.degree. C.).
[0274] Reaction of 3-hydroxypropionitrile to Give
N',3-dihydroxypropanimidamide
##STR00128##
[0275] Equal molar mixture of 3-hydroxypropionitrile and
hydroxylamine heated to 40.degree. C. for 8 hours with stirring.
The solution is allowed to stand overnight yielding a fine slightly
off white precipitate. The precipitated solid was filtered off and
washed with iPrOH and dried to a fine pure white crystalline solid
N',3-dihydroxypropanimidamide mp 94.degree. C.
[0276] Reaction of 2-cyanoacetic Acid to Give Isomers of
3-amino-3-(hydroxyimino)propanoic Acid.
##STR00129##
[0277] 2-Cyanoacetic acid (1 g, 11.8 mmol) was dissolved in EtOH
(10 cm.sup.3) and hydroxylamine (50% in water, 0.79 cm3, 0.85 g,
12.9 mmol, 1.1 eq) was added. The mixture was warmed at 40.degree.
C. for 30 min and the crystals formed (hydroxylammonium
cyanoacetate) were filtered off and dissolved in water (5
cm.sup.3). Additional hydroxylamine (50% in water, 0.79 cm3, 0.85
g, 12.9 mmol, 1.1 eq) was added and the mixture was stirred at room
temperature overnight. Acetic acid (3 cm.sup.3) was added and the
mixture was allowed to stand for a few hours. The precipitated
solid was filtered off and dried in high vacuum line to give the
product 3-amino-3-(hydroxyimino)propanoic acid (0.56 g, 40%) as a
white solid, mp 136.5.degree. C. (lit 144.degree. C.) as two
isomers.
[0278] Characterization of the product using FTIR and NMR are as
follows: .nu.max(KBr)/cm-1 3500-3000 (br), 3188, 2764, 1691, 1551,
1395, 1356, 1265 and 1076; .delta.H(300 MHz; DMSO-d6; Me4Si)
10.0-9.0 (br, NOH and COOH), 5.47 (2H, br s, NH2) and 2.93 (2H, s,
CH2); .delta.C(75 MHz; DMSO-d6; Me4Si) 170.5 (COOH minor isomer),
170.2 (COOH major isomer), 152.8 (C(NOH)NH2 major isomer) 148.0
(C(NOH)NH2 minor isomer), 37.0 (CH2 minor isomer) and 34.8 (CH2
major isomer).
[0279] Reaction of Adiponitrile to Give
N'1,N'6-dihydroxyadipimidamide
##STR00130##
[0280] Adiponitrile (1 g, 9 mmol) and hydroxylamine (50% in water,
1.24 cm3, 1.34 g, 20 mmol, 2.2 eq) in EtOH (10 cm3) were stirred at
room temperature for 2 days and then at 80.degree. C. for 8 hours.
The mixture was allowed to cool and the precipitated crystals were
collected by filtration and dried in high vacuum line to give the
product N'1,N'6-dihydroxyadipimidamide (1.19 g, 75.8%) as a white
solid, mp 160.5 (decomposed) (lit decomposed 168-170.degree.
C.).
[0281] Reaction of Sebaconitrile to Give
N'1,N'10-dihydroxydecanebis(imidamide)
##STR00131##
[0282] Sebaconitrile (1 g, 6 mmol) and hydroxylamine (50% in water,
0.85 cm.sup.3, 0.88 g, 13.4 mmol, 2.2 eq) in EtOH (12 cm.sup.3)
were stirred at room temperature for 2 days and then at 80.degree.
C. for 8 h. The mixture was allowed to cool and the precipitated
crystals were collected by filtration and dried in high vacuum line
to give the product N'1,N'10-dihydroxydecanebis(imidamide) (1 g,
72.5%); mp 182.degree. C.
[0283] Reaction of 2-cyanoacetamide to Give
3-amino-3-(hydroxyimino)propanamide
##STR00132##
[0284] 2-Cyanoacetamide (1 g, 11.9 mmol) and hydroxylamine (0.8
cm.sup.3, 13 mmol, 1.1 eq) in EtOH (6 cm.sup.3) were stirred under
reflux for 2.5 hours. The solvents were removed under reduced
pressure and the residue was washed with CH.sub.2Cl.sub.2 to give
the product 3-amino-3-(hydroxyimino)propanamide (1.23 g, 88.3%) as
a white solid, mp 159.degree. C.
[0285] Reaction of Glycolonitrile to Give
N',2-dihydroxyacetimidamide
##STR00133##
[0286] Glycolonitrile (1 g, 17.5 mmol) and hydroxylamine (50% in
water, 2.15 cm.sup.3, 35 mmol, 2 eq) in EtOH (10 cm.sup.3) were
stirred under reflux for 6 hours and then at room temperature for
24 hours. The solvent was evaporated and the residue was purified
by column chromatography (silica, 1:3 EtOH--CH.sub.2Cl.sub.2) to
give the product N',2-dihydroxyacetimidamide (0.967 g, 61.4%) as an
off-white solid, mp 63-65.degree. C.
[0287] Reaction of 5-hexynenitrile to Give
4-cyano-N'-hydroxybutanimidamide
##STR00134##
[0288] A solution of 5-hexynenitrile (0-93 g, 10 mmol) and
hydroxylamine (50% in water, 1.22 cm.sup.3, 20 mmol) was stirred
under reflux for to hours, after which volatiles were removed under
reduced pressure to give the product
4-cyano-N'-hydroxybutanimidamide (1.30 g, 100%) as a white solid,
mp 99.5-101.degree. C.
[0289] Reaction of Iminodiacetonitrile to Give
2,2'-azanediylbis(N'-hydroxyacetimidamide)
##STR00135##
[0290] Commercial iminodiacetonitrile (Alfa-Aesar) was purified by
dispersing the compound in water and extracting with
dichloromethane, then evaporating the organic solvent from the
extracts to give a white solid. Purified iminodiacetonitrile (0.82
g) and hydroxylamine (50% in water, 2.12 ml, 2.28 g, 34.5 mmol, 4
eq) in MeOH (6.9 ml) and water (6.8 ml) were stirred at room
temperature for 48 hours. Evaporation of volatiles under reduced
pressure gave a colorless liquid which was triturated with EtOH
(40.degree. C.) to give 2,2'-azanediylbis(N'-hydroxyacetimidamide)
(1.23 g, 88.7%) as a white solid, mp 135-136.degree. C., (lit mp
138.degree. C.).
[0291] Reaction of 3-methylaminopropionitrile to Give
N'-hydroxy-3-(methylamino)propanimidamide
##STR00136##
[0292] A solution of 3-methylaminopropionitrile (1 g, 11.9 mmol)
and hydroxylamine (50% in water, 0.8 cm3, 0.864 g, 13.1 mmol, 1.1
eq) in EtOH (1 cm.sup.3) was stirred at 30-50.degree. C. for 3
hours and then at room temperature overnight. The solvent was
removed under reduced pressure (rotary evaporator followed by high
vacuum line) to give the product
N'-hydroxy-3-(methylamino)propanimidamide (1.387 g, 99.5%) as a
thick pale yellow oil.
[0293] Reaction of 3-(diethylamino)propanenitrile to Give
3-(diethylamino)-N'-hydroxypropanimidamide
##STR00137##
[0294] A solution of 3-(diethylamino)propanenitrile (1 g, 8 mmol)
and NH.sub.2OH (50% in water, 0.73 cm.sup.3, 11.9 mmol) in EtOH (10
cm.sup.3) were heated to reflux for 24 hours, after which the
solvent and excess hydroxylamine were removed by rotary evaporator.
The residue was freeze-dried and kept in high vacuum line until it
slowly solidified to give 3-(diethylamino)N'-hydroxypropanimidamide
(1.18 g, 92.6%) as a white solid, mp 52-54.degree. C.
[0295] Reaction of 3,3',3''-nitrilotripropanenitrile with
Hydroxylamine to Give
3,3',3''-nitrilotris(N'-hydroxypropanimidamide)
##STR00138##
[0296] A solution of 3,3',3''-nitrilotripropanenitrile (2 g, 11.35
mmol) and hydroxylamine (50% in water, 2.25 g, 34 mmol) in EtOH (25
cm.sup.3) was stirred at 80.degree. C. overnight, then at room
temperature for 24 hours. The white precipitate was collected by
filtration and dried in high vacuum to give
3,3',3''-nitrilotris(,N-hydroxypropanimidamide) (1.80 g, 57.6%) as
a white crystalline solid, mp 195-197.degree. C. (decomposed).
[0297] Reaction of 3-(2-ethoxyethoxy)propanenitrile to Give
3-(2-ethoxyethoxy)-N'-hydroxypropanimidamide
##STR00139##
[0298] A solution of 3-(2-ethoxyethoxy)propanenitrile (1 g, 7 mmol)
and NH.sub.2OH (50% in water, 0.64 cm.sup.3, 10.5 mmol) in EtOH (10
cm.sup.3) were heated to reflux for 24 hours, after which the
solvent and excess hydroxylamine were removed by rotary evaporator.
The residue was freeze-dried and kept in high vacuum line for
several hours to give 3-(2-ethoxyethoxy)-N'-hydroxypropanimidamide
(1.2 g, 97.6%) as a colourless oil.
[0299] Reaction of
3-(2-(2-(dimethylamino)ethoxy)ethoxy)propanenitrile to Give
3-(2-(2-(dimethylamino)ethoxy)ethoxy)-N'-hydroxypropanimidamide
##STR00140##
[0300] A solution of
3-(2-(2-(dimethylamino)ethoxy)ethoxy)propanenitrile (0.5 g, 2.68
mmol) and NH.sub.2OH (50% in water, 0.25 cm.sup.3, 4 mmol) in EtOH
(10 cm.sup.3) were stirred at 80.degree. C. for 24 hours, after
which the solvent and excess hydroxylamine were removed by rotary
evaporator. The residue was freeze-dried and kept in high vacuum
line for several hours to give
3-(2-(2-(dimethylamino)ethoxy)ethoxy)-N'-hydroxypropanimidamide
(0.53 g, 90.1%) as a light yellow oil.
[0301] Reaction of
3,3'-(2,2'-(2-cyanoethylazanediyl)bis(ethane-2,1-diyl)bis(oxy))dipropanen-
itrile with Hydroxylamine to Give
3,3'-(2,2'-(3-amino-3-(hydroxyimino)propylazanediyl)bis(ethane-2,1-diyl))-
bis(oxy)bis(N'-hydroxypropanimidamide).
##STR00141##
[0302] Treatment of
3,3'-(2,2'-(2-cyanoethylazanediyl)bis(ethane-2,1-diyl)bis(oxy))dipropanen-
itrile (0.8 g, 3 mmol) with NH.sub.2OH (0.74 cm.sup.3, 12.1 mmol)
in EtOH (8 cm.sup.3) gave
3,3'-(2,2'-(3-amino-3-(hydroxyimino)propylazanediyl)bis(ethane-2,1-diyl))-
bis(oxy)bis(N'-hydroxypropanimidamide) (1.09 g, 100%) as an
oil.
[0303] Reaction of Iminodipropionitrile to Give
3,3'-azanediylbis(N'-hydroxypropanimidamide)
##STR00142##
[0304] Iminodipropionitrile (1 g, 8 mmol) and hydroxylamine (50% in
water, 1 cm3, 1.07 g, 16 mmol, 2 eq) in EtOH (8 cm.sup.3) were
stirred at room temperature for 2 days and then at 80.degree. C.
for 8 hours. The mixture was allowed to cool and the precipitated
crystals were collected by filtration and dried in high vacuum line
to give the product 3,3'-azanediylbis(N'-hydroxypropanimidamide)
(1.24 g, 82.1%) as a white solid, mp 180.degree. C. (lit
160.degree. C.).
[0305] Reaction of
3,3',3'',3'''-(ethane-1,2-diylbis(azanetriyl))tetrapropanenitrile
to Give
3,3',3'',3'''-(ethane-1,2-diylbis(azanetriyl))tetrakis(N'-hydroxypropanim-
idamide) to Produce EDTA Analogue
##STR00143##
[0306] A solution of
3,3',3'',3'''-(ethane-1,2-diylbis(azanetriyl))tetrapropanenitrile
(1 g, 4 mmol) and NH.sub.2OH (50% in water, 1.1 cm.sup.3, 18.1
mmol) in EtOH (10 cm.sup.3) was stirred at 80.degree. C. for 24
hours and was then allowed to cool to room temperature. The solid
formed was collected by filtration and dried under vacuum to give
3,3',3'',3'''-(ethane
1,2-diylbis(azanetriyl))tetrakis(N'-hydroxypropanimidamide) (1.17
g, 76.4%) as a white solid, mp 191-192.degree. C.
[0307] Reaction of
3,3'-(2,2-bis((2-cyanoethoxy)methyl)propane-1,3-diyl)bis(oxy)dipropanenit-
rile with hydroxylamine to Give
3,3'-(2,2-bis((3-(hydroxyamino)-3-iminopropoxy)methyl)propane-1,3-diyl)bi-
s(oxy)bis(N-hydroxypropanimidamide)
##STR00144##
[0308] To a solution of
3,3'-(2,2-bis((2-cyanoethoxy)methyl)propane-1,3-diyl)bis(oxy)dipropanenit-
rile (1 g, 2.9 mmol) in EtOH (10 ml) was added NH.sub.2OH (50% in
water, 0.88 ml, 0.948 g, 14.4 mmol), the mixture was stirred at
80.degree. C. for 24 hours and was then cooled to room temperature.
Evaporation of the solvent and excess NH.sub.2OH in the rotary
evaporator followed by high vacuum for 12 hours gave
3,3'-(2,2-bis((3-(hydroxyamino)-3-iminopropoxy)methyl)propane-1,3-diyl)bi-
s(oxy)bis(N-hydroxypropanimidamide) (0.98 g, 70.3%) as a white
solid, mp 60.degree. C.
[0309] Reaction of 3,3'-(2-cyanophenylazanediyl)dipropanenitrile
with hydroxylamine to Give
3,3'-(2-(N'-hydroxycarbamimidoyl)phenylazanediyl)bis(N'-hydroxypropanimid-
amide)
##STR00145##
[0310] Treatment of 3,3'-(2-cyanophenylazanediyl)dipropanenitrile
(1 g, 4.46 mmol) with NH.sub.2OH (1.23 ml, 20 mmol) in EtOH (10 ml)
gave a crude product that was triturated with CH.sub.2Cl.sub.2 to
give
3,3'-(2-(N'-hydroxycarbamimidoyl)phenylazanediyl)bis(N'-hydroxypropanimid-
amide) (1.44 g, 100%) as a solid, decomposed. 81.degree. C.
[0311] Reaction of N,N-bis(2-cyanoethyl)acetamide with
hydroxylamine to give
N,N-bis(3-amino-3-(hydroxyimino)propyl)acetamide
##STR00146##
[0312] Treatment of N,N-bis(2-cyanoethyl)acetamide (0.5 g, 3.03
mmol) with NH.sub.2OH (0.56 ml, 9.1 mmol) in EtOH (5 ml) gave
N,N-bis(3-amino-3-(hydroxyimino)propyl)acetamide (0.564 g, 100%) as
a white solid, mp 56.4-58.degree. C.
[0313] Reaction of
3,3'-(2,2'-(methylazanediyl)bis(ethane-2,1-diyl)bis(oxy))dipropanenitrile
with hydroxylamine to Give
3,3'-(2,2'-(methylazanediyl)bis(ethane-2,1-diyl)bis(oxy))bis(N'-hydroxypr-
opanimidamide)
##STR00147##
[0314] Treatment of
3,3'-(2,2'-(methylazanediyl)bis(ethane-2,1-diyl)bis(oxy))dipropanenitrile
(1 g, 4.4 mmol) with NH.sub.2OH (0.82 ml, 13.3 mmol) in EtOH (10
ml) gave
3,3'-(2,2'-(methylazanediyl)bis(ethane-2,1-diyl)bis(oxy))bis(N'-hydroxypr-
opanimidamide) (1.28 g, 100%) as an oil.
[0315] Reaction of Glycol Derivative
3,3'-(ethane-1,2-diylbis(oxy))dipropanenitrile to Give
3,3'-(ethane-1,2-diylbis(oxy))bis(N'-hydroxypropanimidamide)
##STR00148##
[0316] A solution of 3,3'-(ethane-1,2-diylbis(oxy))dipropanenitrile
(1 g, 5 mmol) and NH.sub.2OH (50% in water, 0.77 cm.sup.3, 12.5
mmol) in EtOH (10 cm.sup.3) was stirred at 80.degree. C. for 24
hours and then at room temperature for 24 hours. The solvent and
excess NH.sub.2OH were evaporated off and the residue was
freeze-dried to give
3,3'-(ethane-1,2-diylbis(oxy))bis(N'-hydroxypropanimidamide) (1.33
g, 100%) as a viscous oil.
[0317] Reaction of 3,3'-(piperazine-1,4-diyl)dipropanenitrile to
Give 3,3'-(piperazine-1,4-diyl)bis(N'-hydroxypropanimidamide)
##STR00149##
[0318] A solution of 3,3'-(piperazine-1,4-diyl)dipropanenitrile (1
g, 5.2 mmol) and NH.sub.2OH (50% in water, 0.96 cm.sup.3, 15.6
mmol) in EtOH (10 cm.sup.3) were heated to reflux for 24 hours,
after which the mixture was allowed to cool to room temperature.
The solid formed was collected by filtration and dried in high
vacuum line to give
3,3'-(piperazine-1,4-diyl)bis(N'-hydroxypropanimidamide) (1.25 g,
93.3%) as a white solid, deep 238.degree. C. (brown colouration at
>220.degree. C.
[0319] Reaction of Cyanoethylated Sorbitol Compound with
hydroxylamine to Give
1,2,3,4,5,6-hexakis-O-[3-(hydroxyamino)-3-iminopropyl Hexitol
##STR00150##
[0320] A solution of cyanoethylated product of sorbitol (0.48 g,
0.96 mmol) and NH.sub.2OH (50% in water, 0.41 ml, 0.44 g, 6.71
mmol) in EtOH (5 ml) was stirred at 80.degree. C. for 24 hours.
Evaporation of solvent and NMR analysis of the residue showed
incomplete conversion. The product was dissolved in water (10 ml)
and EtOH (100 ml) and NH.sub.2OH (0.5 g, 7.6 mmol) was added. The
mixture was stirred at 80.degree. C. for a further 7 hours. Removal
of all volatiles after the reaction gave
1,2,3,4,5,6-hexakis-O-[3-(hydroxyamino)-3-iminopropyl Hexitol,
(0.67 g, 100%) as a white solid, mp 92-94.degree. C.
(decomposed).
[0321] Reaction of Benzonitrile to Give N'-hydroxybenzimidamide
##STR00151##
[0322] Benzonitrile (0.99 cm.sup.3, 1 g, 9.7 mmol) and
hydroxylamine (50% in water, 0.89 cm.sup.3, 0.96 g, 14.55 mmol, 1.5
eq) were stirred under reflux in EtOH (10 cm.sup.3) for 48 hours.
The solvent was evaporated under reduced pressure and water (10
cm.sup.3) was added to the residue. The mixture was extracted with
dichloromethane (100 cm.sup.3) and the organic extract was
evaporated under reduced pressure. The residue was purified by
column chromatography to give the product N'-hydroxybenzimidamide
(1.32 g, 100%) as a white crystalline solid, mp 79-81.degree. C.
(lit 79-80.degree. C. This procedure is suitable for all starting
materials bearing a benzene ring.
[0323] Reaction of 3-phenylpropionitrile to Give
N'-hydroxy-3-phenylpropanimidamide
##STR00152##
[0324] Phenylpropionitrile (1 g, 7.6 mmol) was reacted with
hydroxylamine (50% in water, 0.94 cm.sup.3, 15.2 mmol, 2 eq) in
EtOH (7.6 cm.sup.3) in the same manner as in the preparation of
N'-hydroxybenzimidamide (EtOAc used in extraction) to give the
product N'-hydroxy-3-phenylpropanimidamide (0.88 g, 70.5%) as a
white solid, mp 42-43.degree. C.
[0325] Reaction of m-tolunitrile to Give
N'-hydroxy-3-methylbenzimidamide
##STR00153##
[0326] The reaction of m-tolunitrile (1 g, 8.54 mmol) and
hydroxylamine (0.78 cm.sup.3, 12.8 mmol, 1.5 eq) in EtOH (8.5
cm.sup.3) was performed in the same manner as in the preparation of
N'-hydroxybenzimidamide, to give the product
N'-hydroxy-3-methylbenzimidamide (1.25 g, 97.7%) as a white solid,
mp 92.degree. C. (lit 88-90.degree. C.).
[0327] Reaction of Benzyl Cyanide to Give
N'-hydroxy-2-phenylacetimidamide
##STR00154##
[0328] Benzyl cyanide (1 g, 8.5 mmol) and hydroxylamine (50% in
water, 1.04 cm.sup.3, 17 mmol, 2 eq) in EtOH (8.5 cm.sup.3) were
reacted in the same manner as in the preparation of
N'-hydroxybenzimidamide (EtOAc used in extraction) to give the
product N'-hydroxy-2-phenylacetimidamide (1.04 g, 81.9%) as a pale
yellow solid, mp 63.5-64.5.degree. C. (lit 57-59.degree. C.).
[0329] Reaction of Anthranilonitrile to Give
2-amino-N'-hydroxybenzimidamide
##STR00155##
[0330] Anthranilonitrile (1 g, 8.5 mmol) and hydroxylamine (50% in
water, 0.57 cm.sup.3, 9.3 mmol, 1.1 eq) in EtOH (42.5 cm.sup.3)
were stirred under reflux for 24 hours, after which the volatiles
were removed under reduced pressure and residue was partitioned
between water (5 cm.sup.3) and CH.sub.2Cl.sub.2 (100 cm.sup.3). The
organic phase was evaporated to dryness in the rotary evaporator
followed by high vacuum line to give the product
2-amino-N'-hydroxybenzimidamide (1.16 g, 90.3%) as a solid, mp
85-86.degree. C.
[0331] Reaction of Phthalonitrile to Give isoindoline-1,3-dione
Dioxime
##STR00156##
[0332] Phthalonitrile (1 g, 7.8 mmol) and hydroxylamine (1.9
cm.sup.3, 31.2 mmol, 4 eq) in EtOH (25 cm.sup.3) were stirred under
reflux for 60 hours, after which the volatiles were removed under
reduced pressure and the residue was washed with EtOH (2 cm.sup.3)
and CH.sub.2Cl.sub.2 (2 cm.sup.3) to give the cyclised product
isoindoline-1,3-dione dioxime (1.18 g, 85.4%) as a pale yellow
solid, mp 272-275.degree. C. (decomposed) (lit 271.degree. C.).
[0333] Reaction of 2-cyanophenylacetonitrile to Give the Cyclised
Product 3-aminoisoquinolin-1(4H)-one Oxime or
3-(hydroxyamino)-3,4-dihydroisoquinolin-1-amine
##STR00157##
[0334] A solution of 2-cyanophenylacetonitrile (1 g, 7 mmol) and
hydroxylamine (1.7 cm.sup.3, 28.1 mmol, 4 eq) in EtOH (25 cm.sup.3)
were stirred under reflux for 60 hours, after which the volatiles
were removed under reduced pressure. The residue was recrystallised
from EtOH-water (1:4, 15 cm.sup.3) to give the cyclised product
3-aminoisoquinolin-1(4H)-one oxime or
3-(hydroxyamino)-3,4-dihydroisoquinolin-1-amine (1.15 g, 85.9%) as
a solid, mp 92.5-94.5.degree. C.
[0335] Reaction of Cinnamonitrile to Give
N'-hydroxycinnamimidamide
##STR00158##
[0336] Cinnamonitrile (1 g, 7.74 mmol) and hydroxylamine (0.71
cm.sup.3, 11.6 mmol, 1.5 eq) were reacted in EtOH (7 cm.sup.3) as
described for AO6 (two chromatographic separations were needed in
purification) to give N'-hydroxycinnamimidamide (0.88 g, 70%) as a
light orange solid, mp 85-87.degree. C. (lit 93.degree. C.).
[0337] Reaction of 5-cyanophthalide to Give the Product
N'-hydroxy-1-oxo-1,3-dihydroisobenzofuran-5-carboximidamide
##STR00159##
[0338] A solution of 5-cyanophthalide (1 g, 6.28 mmol) and
hydroxylamine (50% in water, 0.77 cm.sup.3, 0.83 g, 12.6 mmol, 2
eq) in EtOH (50 cm.sup.3) was stirred at room temperature for 60
hours and then under reflux for 3 hours. After cooking to room
temperature and standing overnight, the solid formed was collected
by filtration and dried in high vacuum line to give the product
N'-hydroxy-1-oxo-1,3-dihydroisobenzofuran-5-carboximidamide (1.04
g, 86.2%) as a white solid, mp 223-226.degree. C. (decomposed).
[0339] Reaction of 4-chlorobenzonitrile to Give the Product
4-chloro-N'-hydroxybenzimidamide
##STR00160##
[0340] A solution of 4-chlorobenzonitrile (1 g, 7.23 mmol) and
hydroxylamine (50% in water, 0.67 cm.sup.3, 10.9 mmol, 1.5 eq) in
EtOH (12.5 cm.sup.3) was stirred under reflux for 48 hours. The
solvent was removed under reduced pressure and the residue was
washed with CH.sub.2Cl.sub.2 (10 cm.sup.3) to give the product
4-chloro-N'-hydroxybenzimidamide (0.94 g, 76%) as a white solid, mp
133-135.degree. C.
[0341] Reaction of 3-(phenylamino)propanenitrile to Give
N'-hydroxy-3-(phenylamino)propanimidamide
##STR00161##
[0342] A solution of 3-(phenylamino)propanenitrile (1 g, 6.84 mmol)
and NH.sub.2OH (50% in water, 0.63 cm.sup.3, 10.26 mmol) in EtOH
(10 cm.sup.3) were heated to reflux for 24 hours, after which the
solvent and excess hydroxylamine were removed by rotary evaporator.
To the residue was added water (10 cm.sup.3) and the mixture was
extracted with CH.sub.2Cl.sub.2 (100 cm.sup.3). The extracts were
concentrated under reduced pressure and the residue was purified by
column chromatography (silica, Et.sub.2O) to give
N'-hydroxy-3-(phenylamino)propanimidamide (0.77 g, 62.8%) as a
white solid, mp 93-95.degree. C. (lit mp 91-91.5.degree. C.).
[0343] Reaction of 4-pyridinecarbonitrile to Give the Product
N'-hydroxyisonicotinimidamide
##STR00162##
[0344] Pyridinecarbonitrile (1 g, 9.6 mmol) and hydroxylamine (50%
in water, 0.88 cm.sup.3, 14.4 mmol, 1.5 eq) in EtOH (10 cm.sup.3)
were stirred under reflux for 18 hours, after which the volatiles
were removed under reduced pressure and the residue was
recrystallised from EtOH to give the product
N'-hydroxyisonicotinimidamide (1.01 g, 76.7%) as a solid, mp
203-205.degree. C.
[0345] Cyanoethylation of Sorbitol to Produce Multi
Substituted-(2-amidoximo)ethoxy)hexane.
[0346] 1. A one-liter three-necked round-bottomed flask was
equipped with a mechanical stirrer, reflux condenser, thermometer,
and 100 ml addition funnel under nitrogen. Lithium hydroxide
monohydrate (1.0 g, 23.8 mmol, 0.036 eq) dissolved in water (18.5
ml) was added to the flask, followed by the addition of sorbitol
(120 g, 659 mmol) in one portion, and then water (100 ml). The
solution was warned to 42.degree. C. in a water bath and treated
with acrylonitrile (43.6 ml, 659 mmol, and 1.0 eq) drop-wise via
the addition funnel for a period of 2 hr., while maintaining the
temperature at 42.degree. C. After the addition was complete, the
solution was warmed to 50-55.degree. C. for 4 hr. and then allowed
to cool to room temperature. The reaction was neutralized by
addition of acetic acid (2.5 ml) and allowed to stand overnight at
room temperature. The solution was evaporated under reduced
pressure to give the product as a clear, viscous oil (155.4 g).
[0347] Tetramethylammonium hydroxide can be used to substitute
lithium hydroxide.
[0348] Elemental analysis: Found, 40.95% C; 3.85% N. The IR
spectrum showed a nitrile peak at 2255 cm-1 indicative of the
nitrile group.
[0349] 2. A one liter three-neck round-bottomed flask was equipped
with a mechanical stirrer, reflux condenser, thermometer, and 100
ml addition funnel under nitrogen. Lithium hydroxide (1.0 g, 23.8
mmol, 0.036 eq) dissolved in water (18.5 ml) was added to the
flask, followed by the addition of the first portion of sorbitol
(60.0 g, 329 mmol) and then water (50 ml). The solution was warmed
to 42.degree. C. in a water bath and treated with acrylonitrile (42
ml, 633 mmol, 0.96 eq) drop-wise via the addition funnel for a
period of 1 hr. while maintaining the temperature at 42.degree. C.
The second portion of sorbitol (60 g, 329 mmol) and water (50 ml)
were added to the flask. The second portion of the acrylonitrile
(89.1 ml, 1.344 mol, 2.04 eq) was added in a drop-wise fashion over
a period of 1 hr. After the addition was complete, the solution was
warmed to 50-55.degree. C. for 4 hr. and then allowed to cool to
room temperature. The reaction was neutralized by addition of
acetic acid (2.5 ml) and allowed to stand overnight at room
temperature. The solution was evaporated under reduced pressure to
give the product as a clear, viscous oil (228.23 g).
[0350] Tetramethylammonium hydroxide can be used to substitute
lithium hydroxide.
[0351] Elemental analysis: Found: 49.16% C; 10.76% N. The IR
spectrum showed a nitrile peak at 2252 cm-1 indicative of the
nitrile group.
[0352] 3. A 1000 ml 3-necked round-bottomed flask equipped with an
mechanical stirrer, reflux condenser, nitrogen purge, dropping
funnel, and thermometer was charged with water (18.5 ml) and
lithium hydroxide monohydrate (1.75 g) and the first portion of
sorbitol (44.8 g). The solution was heated to 42.degree. C. with a
water bath with stirring and the second portion of sorbitol (39.2
g) was added directly to the reaction flask. The first portion of
acrylonitrile (100 ml) was then added to the reaction drop-wise via
a 500 ml addition funnel over a period of 2 hr. The reaction was
slightly exothermic, raising the temperature to 51.degree. C. The
final portion of sorbitol (32 g) was added for a total of 0.638
moles followed by a final portion of acrylonitrile (190 ml) over
2.5 hr. keeping the reaction temperature below 60.degree. C. (A
total of 4.41 moles of acrylonitrile was used.) The reaction
solution was then heated to 50-55.degree. C. for 4 hr. The solution
was then allowed to cool to room temperature and the reaction was
neutralized by addition of acetic acid (2.5 ml). Removal of the
solvent under reduced pressure gave the product as a clear, viscous
oil (324 g).
[0353] Tetramethylammonium hydroxide can be used to substitute
lithium hydroxide.
[0354] The IR spectrum showed a nitrile peak at 2251 cm-1,
indicative of the nitrile group.
[0355] 4. Preparation of
(1,2,3,4,5,6-(hexa-(2-amidoximo)ethoxy)hexane Hexitol.
##STR00163##
[0356] A 1000 mL three-necked round-bottomed flask was equipped
with a mechanical stirrer, condenser, and addition funnel under
nitrogen. CE-Sorb6 (14.77 g, 29.5 mmol) and water (200 mL) were
added to the flask and stirred. In a separate 500 mL Erlenmeyer
flask, hydroxylamine hydrochloride (11.47 g, 165 mmol, 5.6 eq) was
dissolved in water (178 mL) and then treated with ammonium
hydroxide (22.1 mL of 28% solution, 177 mmol, 6.0 eq) for a total
volume of 200 ml. The hydroxylamine solution was then added in one
portion directly to the mixture in the round-bottomed flask at room
temperature. The stirred mixture was heated at 80.degree. C. for 2
hr., pH=8-9, and then allowed to cool to room temperature.
[0357] Hydroxylamine freebase (50%) aqueous solution can be used to
replace the solution by blending hydroxylamine chloride and
ammonium hydroxide.
[0358] The IR spectrum indicated loss of most of the nitrile peak
at 2250 cm-1 and the appearance of a new peak at 1660 cm-1,
indicative of the amidoxime or hydroxamic acid.
[0359] Preparation and analysis of polyamidoxime is essentially
that described in U.S. Pat. No. 3,345,344, which is incorporated
herein by reference in its entirety. In that process 80 parts by
weight of polyacrylonitrile of molecular weight of about 130,000 in
the form of very fine powder (-300 mesh) was suspended in a
solution of 300 parts by weight of hydroxylammonium sulfate, 140
parts by weight of sodium hydroxide and 2500 parts by weight of
deionized water. The pH of the solution was 7.6. The mixture was
heated to 90.degree. C. and held at that temperature for 12 hours,
all of the time under vigorous agitation. It was cooled to
35.degree. C. and the product filtered off and washed repeatedly
with deionized water. The resin remained insoluble throughout the
reaction, but was softened somewhat by the chemical and heat. This
caused it to grow from a very fine powder to small clusters of 10
to 20 mesh. The product weighed 130 grams. The yield is always
considerably more than theoretical because of fumly occluded salt.
The product is essentially a poly-amidoxime having the following
reoccurring unit
##STR00164##
[0360] The following depicts metalcomplexing using amidoxime
compounds.
##STR00165##
[0361] Amidoxime chelating agents can substitute for organic
carboxylic acids, organic carboxylic ammonium salt or an amine
carboxylates being used in cleaning formulations and processes.
##STR00166##
[0362] With reference to the present invention, as hereinafter more
fully described, the claimed compounds can be applied to
applications in the state of the art forming a background to the
present invention includes the following U.S. patents, the
disclosures of which hereby are incorporated herein, in their
respective entireties.
EXAMPLES OF EMBODIMENTS OF THE PRESENT INVENTION
[0363] Note that all patents cited in the examples are incorporated
herein by reference regarding the proportions, amounts and support
for the compositions and methods described in the examples.
Example 1
[0364] The patents referred to in the examples herein and elsewhere
in the description and summary are each hereby incorporated by
reference in their entirety. One embodiment involves a method for
removing organometallic and organosilicate residues remaining after
a dry etch process from semiconductor substrates. The substrate is
exposed to a conditioning solution of phosphoric acid, hydrofluoric
acid, and a carboxylic acid, such as acetic acid, which removes the
remaining dry etch residues while minimizing removal of material
from desired substrate features. The approximate proportions of the
conditioning solution are typically 80 to 95 percent by weight
amidoxime compound and acetic acid, 1 to 15 percent by weight
phosphoric acid, and 0.01 to 5.0 percent by weight hydrofluoric
acid. See, U.S. Pat. No. 7,261,835.
[0365] Another embodiment includes from about 0.5% to about 24% by
weight of complexing agents with amidoxime functional groups with
an method having a pH between about 1.5 and about 6 and comprising:
at least about 75% by weight of a mixture of water and an organic
solvent; from about 0.5% to about 10% by weight phosphoric acid;
optionally one or more other acid compounds; optionally one or more
fluoride-containing compounds; and at least one alkaline compound
selected from the group consisting of: a trialkylammonium hydroxide
and/or a tetraalkylammonium hydroxide; a hydroxylamine derivative;
and one or more alkanolamines.
Example 2
[0366] Table 1 lists other embodiments of the present invention
where the formulations additionally include from about 0.5% to
about 24% by weight of compounds with amidoxime functional groups
in methods. Such formulations may contain additional components
consistent with this application such as surfactants, alkaline
components, and organic solvents.
TABLE-US-00020 TABLE 1 Examples of Useful Formulations with
Chelating Agents for Use with Amidoxime Compounds of the Present
Invention H.sub.3PO.sub.4 (wt %) Other Acid wt % 2 methanesulfonic
1.47 2 pyrophosphoric acid (PPA) 3.0 2 Fluorosicilic 0.24 2 Oxalic
2.0 4 Oxalic 2.0 6 Glycolic 1.0 3 Oxalic 2.0 3 Lactic 2.0 4 Lactic
2.0 3 Citric 2.0 4 Citric 2.0 3 PPA 0.5 3 Glycolic 2.0 6 Glycolic
2.0 3 PPA 2.0 3 PPA 4.0
Example 3
[0367] Another embodiment is a composition for cleaning or etching
a semiconductor substrate and method for using the same. The
compositions include from about 0.01% to about 50%, more preferably
about 0.5% to about 24% by weight of compounds with amidoxime
functional groups may include a fluorine-containing compound as an
active agent such as a quaternary ammonium fluoride, a quaternary
phosphonium fluoride, sulfonium fluoride, more generally an -onium
fluoride or "multi" quaternary-onium fluoride that includes two or
more quaternary-onium groups linked together by one or more
carbon-containing groups. The composition may further include a pH
adjusting acid such as a mineral acid, carboxylic acid,
dicarboxylic acid, sulfonic acid, or combination thereof to give a
pH of about 2 to 9. The composition can be anhydrous and may
further include an organic solvent such as an alcohol, amide,
ether, or combination thereof. The composition is useful for
obtaining improved etch rate, etch selectivity, etch uniformity and
cleaning criteria on a variety of substrates.
Example 4
[0368] In another embodiment, the present invention can be used
with methods and compositions for removing silicon-containing
sacrificial layers from Micro Electro Mechanical System (MEMS) and
other semiconductor substrates having such sacrificial layers is
described. The etching compositions include a supercritical fluid
(SCF), an etchant species, a co-solvent, chelating agent containing
at least one amidoxime group, and optionally a surfactant. Such
etching compositions overcome the intrinsic deficiency of SCFs as
cleaning reagents, viz., the non-polar character of SCFs and their
associated inability to solubilize polar species that must be
removed from the semiconductor substrate. The resultant etched
substrates experience lower incidents of stiction relative to
substrates etched using conventional wet etching techniques. See
U.S. Pat. No. 7,160,815.
Example 5
[0369] In another embodiment, the invention uses a supercritical
fluid (SFC)-based composition, comprising at least one co-solvent,
at least one etchant species, and optionally at least one
surfactant, wherein said at least one etchant comprises an alkyl
phosphonium difluoride and wherein said SFC-based composition is
useful for etching sacrificial silicon-containing layers, said
compositions containing from about 0.01% to about 50% by weight,
preferably about 0.5% to about 24%, of compounds with one or more
chelating group, at least one being an amidoxime functional groups.
In another embodiment the surfactant comprises at least one
nonionic or anionic surfactant, or a combination thereof, and the
surfactant is preferably a nonionic surfactant selected from the
group consisting of fluoroalkyl surfactants, polyethylene glycols,
polypropylene glycols, polyethylene ethers, polypropylene glycol
ethers, carboxylic acid salts, dodecylbenzenesulfonic acid;
dodecylbeuzenesulfonic salts, polyaciylate polymers, dinonylphenyl
polyoxyethylene, silicone polymers, modified silicone polymers,
acetylenic diols, modified acetylenic diols, alkylammonium salts,
modified alkylammonium salts, and combinations comprising at least
one of the foregoing.
Example 6
[0370] Another embodiment of the present invention is a composition
for use in semiconductor processing wherein the composition
comprises water, phosphoric acid, and an organic acid; wherein the
organic acid is ascorbic acid or is an organic acid having two or
more carboxylic acid groups (e.g., citric acid). The said
compositions containing from about 0.01% to about 50% by weight,
preferably about 0.5% to about 24%, of compounds with one or more
chelating groups/agents, at least one being an amidoxime functional
group/compound and such compounds can be in addition to, part of,
or in substitution of the organic acid. The water can be present in
about 40 wt. % to about 85 wt, % of the composition, the phosphoric
acid can be present in about 0.01 wt. % to about 10 wt. % of the
composition, and the organic acid can be present in about 10 wt. %
to about 60 wt. % of the composition. The composition can be used
for cleaning various surfaces, such as, for example, patterned
metal layers and vias by exposing the surfaces to the composition.
See U.S. Pat. No. 7,135,444.
Example 7
[0371] The present invention can also be used with a polishing
liquid composition for polishing a surface, with one embodiment
comprising an insulating layer and a metal layer, the polishing
liquid composition comprising a compound having six or more carbon
atoms and a structure in which each of two or more adjacent carbon
atoms has a hydroxyl group in a molecule, and water, wherein the
compound having a structure in which each of two or more adjacent
carbon atoms has a hydroxyl group in a molecule is represented by
the formula (I): R1-X--(CH.sub.2)q-[CH(OH)].sup.n--CH.sub.2OH (I)
wherein R1 is a hydrocarbon group having 1 to 12 carbon atoms; X is
a group represented by (CH.sub.2).sub.m, wherein m is 1, oxygen
atom, sulfur atom, COO group, OCO group, a group represented by
NR.sub.2 or O(R.sub.2O)P(O)O, wherein R.sub.2 is hydrogen atom or a
hydrocarbon group having 1 to 24 carbon atoms; q is 0 or 1; and n
is an integer of 1 to 4, further comprising from about 0.01% to
about 50% by weight, preferably about 0.5% to about 24%, of
compounds with one or more chelating groups/agents, at least one
being an amidoxime functional group/compound and such compounds can
be in addition to, part of, or in substitution of an organic acid.
Some embodiments include an abrasive. See U.S. Pat. No.
7,118,685.
Example 8
[0372] Another embodiment of the present invention is a composition
for use in semiconductor processing wherein the composition
comprises water, phosphoric acid, and an organic acid; wherein the
organic acid is ascorbic acid or is an organic acid having two or
more carboxylic acid groups (e.g., citric acid), further comprising
from about 0.01% to about 50% by weight, preferably about 0.5% to
about 24%, of compounds with one or more chelating groups/agents,
at least one being an amidoxime functional group/compound and such
compounds can be in addition to, part of, or in substitution of the
organic acid. The water can be present in about 40 wt. % to about
85 wt. % of the composition, the phosphoric acid can be present in
about 0.01 wt. % to about 10 wt. % of the composition, and the
organic acid can be present in about 10 wt. % to about 60 wt. % of
the composition. The composition can be used for cleaning various
surfaces, such as, for example, patterned metal layers and vias by
exposing the surfaces to the composition. See U.S. Pat. Nos.
7,087,561, 7,067,466, and 7,029,588.
Example 9
[0373] In another embodiment of the present invention, from about
0.01% to about 50% by weight, preferably about 0.5% to about 24%,
of compounds with one or more chelating groups/agents, at least one
being an amidoxime functional group/compound can be used with an
oxidizing solution and process for the in situ oxidation of
contaminants, including hydrocarbon, organic, bacterial, phosphonic
acid, and other contaminants, the contaminants being found in
various surfaces and media, including soil, sludge, and water. In a
preferred embodiment, the solution further includes a peroxygen
compound, such as hydrogen peroxide, in solution with a pre-mixed
solution of a carboxylic acid and a halogen salt, such as glycolic
acid and sodium bromide, respectively.
Example 10
[0374] In another embodiment of the present invention from about
0.01% to about 5% by weight, preferably about 0.01 to about 0.1% of
compounds with one or more chelating groups/agents, at least one
being an amidoxime functional group/compound can be used with a
chemical mechanical polishing slurry that is free of heteropolyacid
and consisting essentially of about 3 to about 5 percent abrasive,
about 3 to about 5 percent hydrogen peroxide, about 0.05 to about
0.1 percent citric acid, about 0.05 to about 0.5 percent
iminodiacetic acid, about 0.005 to about 0.02 percent ammonia, and
about 85-90 percent water, wherein the abrasive consists
essentially of polymethylmethacrylate. See U.S. Pat. No.
7,029,373.
Example 11
[0375] In another embodiment, the present invention includes a
non-corrosive cleaning composition for removing residues from a
substrate comprising: (a) water; (b) at least one hydroxylammonium
compound; (c) at least one basic compound, preferably selected from
the group consisting of amines and quaternary ammonium hydroxides;
(d) at least one organic carboxylic acid; (e) from about 0.01% to
about 50% by weight, preferably about 0.5% to about 24%, of
compounds with one or more chelating groups/agents, at least one
being an amidoxime functional group/compound and such compounds can
be in addition to, part of, or in substitution of the organic acid;
and (f) optionally, a polyhydric compound. The pH of the
composition is preferably between about 2 to about 6. See U.S. Pat.
No. 7,001,874, which is incorporated herein by reference.
Example 12
[0376] The present invention may also be used with a cleaning
solution where the cleaning solution also contains one of
polyvalent carboxylic acid and its salt, such as where the
polyvalent carboxylic acid contains at least one selected from the
group consisting of oxalic acid, citric acid, malic acid, maleic
acid, succinic acid, tartaric acid, and malonic acid, wherein the
cleaning solution contains from about 0.01% to about 50% by weight,
preferably about 0.5% to about 24%, of compounds with one or more
chelating groups/agents, at least one being an amidoxime functional
group/compound and such compounds can be in addition to, part of,
or in substitution of the organic acid, which can be used in
addition to, as part of, or in substitution of the polyvalent
carboxylic acid. In another embodiment, the cleaning solution
further contains a polyamino carboxylic acid and its salt. See U.S.
Pat. No. 6,998,352.
Example 13
[0377] A further embodiment of the present invention is to a method
of chemically-mechanically polishing a substrate, which method
comprises: (i) contacting a substrate comprising at least one layer
of ruthenium and at least one layer of copper with a polishing pad
and a chemical-mechanical polishing composition comprising: (a) an
abrasive consisting of .alpha.-alumina treated with a
negatively-charged polymer or copolymer, (b) hydrogen peroxide, (c)
from about 0.01% to about 50% by weight, preferably about 0.5% to
about 24% of compounds with one or more chelating groups/agents, at
least one being an amidoxime functional group/compound; (d) at
least one heterocyclic compound, wherein the at least one
heterocyclic compound comprises at least one nitrogen atom, (e) a
phosphonic acid, and (f) water, (ii) moving the polishing pad
relative to the substrate, and (iii) abrading at least a portion of
the substrate to polish the substrate, wherein the pH of the water
and any components dissolved or suspended therein is about 6 to
about 12, wherein the at least one layer of ruthenium and at least
one layer of copper are in electrical contact and are in contact
with the polishing composition, wherein the difference between the
open circuit potential of copper and the open circuit potential of
ruthenium in the water and any components dissolved or suspended
therein is about 50 mV or less, and wherein a selectivity for
polishing copper as compared to ruthenium is about 2 or less.
Example 14
[0378] Another embodiment of the present invention is to a
semiconductor wafer cleaning formulation, including 1-21% wt.
fluoride source, 20-55% wt. organic amine(s), 0.5-40% wt.
nitrogenous component, e.g., a nitrogen-containing carboxylic acid
or an imine, 23-50% wt. water, and 0-21% wt. of compounds with one
or more chelating groups/agents, at least one being an amidoxime
functional group/compound. The formulations are useful to remove
residue from wafers following a resist plasma ashing step, such as
inorganic residue from semiconductor wafers containing delicate
copper interconnecting structures. See U.S. Pat. No. 6,967,169.
Example 15
[0379] The present invention also includes a method for chemical
mechanical polishing copper, barrier material and dielectric
material, the method comprises the steps of: a) providing a first
chemical mechanical polishing slurry comprising (i) 1-10 wt. %
silica particles, (ii) 1-12 wt. % oxidizing agent, and (iii) 0-2
wt. % corrosion inhibitor and cleaning agent, wherein said first
slurry has a higher removal rate on copper relative to a lower
removal rate on said barrier material; b) chemical mechanical
polishing a semiconductor wafer surface with said first slurry; c)
providing a second chemical mechanical polishing slurry comprising
(i) 1-10 wt. % silica particles, (ii) 0.1-1.5 wt. % oxidizing
agent, and (iii) 0.1-2 wt. % carboxylic acid, having a pH in a
range from about 2 to about 5, wherein the amount of (ii) is not
more than the amount of (iii), and wherein said second slurry has a
higher removal rate on said barrier material relative to a lower
removal rate on said dielectric material and an intermediate
removal rate on copper; and d) chemical mechanical polishing said
semiconductor wafer surface with said second slurry, wherein either
or both slurries contains from about 0.01% to about 50% by weight,
preferably about 0.5% to about 24%, of compounds with one or more
chelating groups/agents, at least one being an amidoxime functional
group/compound. See U.S. Pat. No. 6,936,542.
Example 16
[0380] The present invention further includes a method for cleaning
a surface of a substrate, which comprises at least the following
steps (1) and (2), wherein the step (2) is carried out after
carrying out the step (1): Step (1): A cleaning step of cleaning
the surface of the substrate with an alkaline cleaning agent
containing a complexing agent, and Step (2): A cleaning step
employing a cleaning agent having a hydrofluoric acid content C (wt
%) of from 0.03 to 3 wt %, the complexing agent is from about 0.01%
to about 50% by weight, preferably about 0.5% to about 24%, of
compounds with one or more chelating groups/agents, at least one
being an amidoxime functional group/compound. See U.S. Pat. No.
6,896,744.
Example 17
[0381] Another embodiment of the present invention includes a
cleaning gas that is obtained by vaporizing a carboxylic acid
and/or a compound with one or more chelating groups/agents, at
least one being an amidoxime functional group/compound which is
supplied into a treatment chamber having an insulating substance
adhering to the inside thereof, and the inside of the treatment
chamber is evacuated. When the cleaning gas supplied into the
treatment chamber comes in contact with the insulating substance
adhering to an inside wall and a susceptor in the treatment
chamber, the insulating substance is turned into a complex, so that
the complex of the insulating substance is formed. The complex of
the insulating substance is easily vaporized due to its high vapor
pressure. The vaporized complex of the insulating substance is
discharged out of the treatment chamber by the evacuation. See U.S.
Pat. No. 6,893,964.
Example 18
[0382] The present invention includes a method for rinsing
metallized semiconductor substrates following treatment of the
substrates with an etch residue removal chemistry, the method
comprising the steps of: providing at least one metallized
semiconductor substrate, the substrate having etch residue removal
chemistry thereon, wherein the etch residue removal chemistry
includes N-methylpyrrolidinone; rinsing the etch residue removal
chemistry from the substrate and minimizing metal corrosion of the
substrate by rinsing the substrate with an aqueous medium
comprising an anti-corrosive agent including an organic acid
selected from the group consisting of mono- and polycarboxylic
acids in an amount effective to minimize metal corrosion; removing
the aqueous medium from the process vessel; and introducing a
drying vapor into the process vessel which the substrate remains
substantially stationary within the process vessel, wherein the
remover includes from about 0.01% to about 50% by weight,
preferably about 0.5% to about 24%, of compounds with one or more
chelating groups/agents, at least one being an amidoxime functional
group/compound, which can be in addition to, part of, or in
substitution of the organic acid. The composition may further
include acetic acid. See U.S. Pat. No. 6,878,213.
Example 19
[0383] The present invention may also be used with the compositions
of U.S. Pat. No. 6,849,200 wherein the iminodiacetic acid component
is supplemented by or substituted with compounds with one or more
chelating groups/agents, at least one being an amidoxime functional
group/compound.
Example 20
[0384] The present invention also includes a method of cleaning a
surface of a copper-containing material by exposing the surface to
an acidic mixture comprising NO3-, F--, and one or more compounds
with one or more chelating groups/agents, at least one being an
amidoxime functional group/compound. The mixture may also include
one or more organic acids to remove at least some of the particles.
See U.S. Pat. No. 6,835,668.
Example 21
[0385] The present invention also includes a cleaning composition
comprising at least one of fluoride salts and hydrogendifluoride
salts; an organic solvent having a hetero atom or atoms; optionally
one or more surfactants in an amount of from 0.0001 to 10.0%; water
and from about 0.01% to about 50% by weight, preferably about 0.5%
to about 24%, of compounds with one or more chelating
groups/agents, at least one being an amidoxime functional
group/compound. See U.S. Pat. No. 6,831,048.
Example 22
[0386] The present invention further includes a glycol-free
composition for cleaning a semiconductor substrate, the composition
consisting essentially of: a. an acidic buffer solution having an
acid selected from a carboxylic acid and a polybasic acid and an
ammonium salt of the acid in a molar ratio of acid to ammonium salt
ranging from 10:1 to 1:10 and wherein the acidic buffer solution is
present in an amount sufficient to maintain a pH of the composition
from about 3 to about 6, b. from 30% by weight to 90% by weight of
an organic polar solvent that is miscible in all proportion in
water, c. from 0.1% by weight to 20% by weight of fluoride, d. from
0.5% by weight to 40% by weight of water, and e. optionally up to
15% by weight of a corrosion inhibitor. The composition further
contains from about 0.01% to about 50% by weight, preferably about
0.5% to about 24%, of compounds with one or more chelating
groups/agents, at least one being an amidoxime functional
group/compound or such compounds may be used in place of the
corrosion inhibitor. See U.S. Pat. No. 6,828,289.
Example 23
[0387] The present invention further includes compositions
containing AEEA and or AEEA derivatives which can be present in an
amount ranging from about 1% to about 99%, though in most instances
the amount ranges from about 10% to about 85%. For each AEEA range
given for various compositions described herein, there is a
"high-AEEA" embodiment where the amount of AEEA is in the upper
half of the range, and a "low-AEEA" embodiment where AEEA is
present in an amount bounded by the lower half of the range.
Generally, the higher AEEA embodiments exhibit lower etch rates
than the low AEEA embodiments for selected substrates, the
embodiments further include from about 0.01% to about 50% by
weight, preferably about 0.5% to about 24%, of compounds with one
or more chelating groups/agents, at least one being an amidoxime
functional group/compound. In most embodiments, these compositions
also include other compounds, particularly polar organic solvents,
water, alkanolamines, hydroxylamines, additional chelating agents,
and/or corrosion inhibitors. See U.S. Pat. No. 6,825,156.
Example 24
[0388] A composition for the stripping of photoresist and the
cleaning of residues from substrates, and for silicon oxide etch,
comprising from about 0.01 percent by weight to about 10 percent by
weight of one or more fluoride compounds, from about 10 percent by
weight to about 95% by weight of a sulfoxide or sulfone solvent,
and from about 20 percent by weight to about 50 percent by weight
water, further including from about 0.01% to about 50% by weight,
preferably about 0.5% to about 24%, of compounds with one or more
chelating groups/agents, at least one being an amidoxime functional
group/compound. The composition may contain corrosion inhibitors,
chelating agents, co-solvents, basic amine compounds, surfactants,
acids and bases. See U.S. Pat. No. 6,777,380.
Example 25
[0389] A polishing composition for polishing a semiconductor
substrate has a pH of under 5.0 and comprises (a) a carboxylic acid
polymer comprising polymerized unsaturated carboxylic acid monomers
having a number average molecular weight of about 20,000 to
1,500,000 or blends of high and low number average molecular weight
polymers of polymerized unsaturated carboxylic acid monomers, (b) 1
to 15% by weight of an oxidizing agent, (c) up to 3.0% by weight of
abrasive particles, (d) 50-5,000 ppm (parts per million) of an
inhibitor, (e) up to 3.0% by weight of a complexing agent, such as,
malic acid, and (f) 0.1 to 5.0% by weight of a surfactant, from
about 0.01% to about 50% by weight, preferably about 0.5% to about
24%, of compounds with one or more chelating groups/agents, at
least one being an amidoxime functional group/compound. See U.S.
Pat. No. 6,679,928.
Example 26
[0390] Particulate and metal ion contamination is removed from a
surface, such as a semiconductor wafer containing copper damascene
or dual damascene features, employing aqueous composition
comprising a fluoride containing compound; a dicarboxylic acid
and/or salt thereof; and a hydroxycarboxylic acid and/or salt
thereof, the composition contains from about 0.01% to about 50% by
weight, preferably about 0.5% to about 24%, of compounds with one
or more chelating groups/agents, at least one being an amidoxime
functional group/compound. See U.S. Pat. No. 6,673,757.
Example 27
[0391] A semiconductor wafer cleaning formulation, including 2-98%
wt. organic amine, 0-50% wt. water, 0.1-60% wt. 1,3-dicarbonyl
compound chelating agent, 0-25% wt. of additional different
chelating agent(s), 0.5-40% wt. nitrogen-containing carboxylic acid
or an imine, and 2-98% wt polar organic solvent. The formulations
are useful to remove residue from wafers following a resist plasma
ashing step, such as inorganic residue from semiconductor wafers
containing delicate copper interconnecting structures.
Example 28
[0392] Another embodiment of the present invention relates to a
method useful in removing etch residue from etcher equipment parts.
The compositions used are aqueous, acidic compositions containing
fluoride and polar, organic solvents. The compositions are free of
glycols and hydroxylamine and have a low surface tension and
viscosity and further include from about 0.01% to about 50% by
weight, preferably about 0.5% to about 24%, of compounds with one
or more chelating groups/agents, at least one being an amidoxime
functional group/compound. See U.S. Pat. No. 6,656,894.
Example 29
[0393] The invention includes a method of cleaning a surface of a
copper-containing material by exposing the surface to an acidic
mixture comprising NO3-, F-- and from about 0.01% to about 50% by
weight, preferably about 0.5% to about 24%, of compounds with one
or more chelating groups/agents, at least one being an amidoxime
functional group/compound and/or one or more organic acid anions
having carboxylate groups. The invention also includes an improved
semiconductor processing method of forming an opening to a
copper-containing material. A mass is formed over a
copper-containing material within an opening in a substrate. The
mass contains at least one of an oxide barrier material and a
dielectric material. A second opening is etched through the mass
into the copper-containing material to form a base surface of the
copper-containing material that is at least partially covered by
particles comprising at least one of a copper oxide, a silicon
oxide or a copper fluoride. The base surface is cleaned with a
solution comprising nitric acid, hydrofluoric acid and one or more
organic acids to remove at least some of the particles.
[0394] One or more organic acids may be used in the composition of
this example. An exemplary composition includes an acetic acid
solution (99.8%, by weight in water), an HF solution (49%, by
weight in water), an HNO3 solution (70.4%, by weight in water), and
H2O the resulting cleaning mixture being: from about 3% to about
20% compounds with one or more chelating groups/agents, at least
one being an amidoxime functional group/compound, by weight: from
about 0.1% to about 2.0% HNO3 by weight; and from about 0.05% to
about 3.0% HF, by weight. See U.S. Pat. No. 6,589,882.
Example 30
[0395] Another embodiment of the present invention is a composition
for selective etching of oxides over a metal. The composition
contains water, hydroxylammonium salt, one or more compounds with
one or more chelating groups/agents, at least one being an
amidoxime functional group/compound, a fluorine containing
compound, and optionally, a base. The pH of the composition is
about 2 to 6. See U.S. Pat. No. 6,589,439.
Example 31
[0396] Another embodiment of the present invention is an etching
treatment comprising a combination including hydrofluoric acid of
15 percent by weight to 19 percent by weight, one or more compounds
with one or more chelating groups/agents, at least one being an
amidoxime functional group/compound of 0.5 percent by weight to 24
percent by weight and ammonium fluoride of 12 percent by weight to
42 percent by weight, said combination having a hydrogen ion
concentration of 10-6 mol/L to 10-1.8, further comprising a
surfactant of 0.001 percent by weight to 1 percent by weight. See
U.S. Pat. No. 6,585,910.
Example 32
[0397] Another embodiment of the present invention includes a
semiconductor wafer cleaning formulation, including 2-98% wt.
organic amine, 0-50% wt, water, 0.1-60% wt. one or more compounds
with one or more chelating groups/agents, at least one being an
amidoxime functional group/compound, 0-25% wt. of additional
different chelating agent(s), 0.1-40% wt. nitrogen-containing
carboxylic acid or an imine, optionally 1,3-dicarbonyl compound
chelating agent, and 2-98% wt polar organic solvent. The
formulations are useful to remove residue from wafers following a
resist plasma ashing step, such as inorganic residue from
semiconductor wafers containing delicate copper interconnecting
structures. See U.S. Pat. No. 6,566,315.
Example 33
[0398] An alternative embodiment of the present invention is a
method for removing organometallic and organosilicate residues
remaining after a dry etch process from semiconductor substrates.
The substrate is exposed to a conditioning solution of a fluorine
source, a non-aqueous solvent, a complementary acid, and a surface
passivation agent. The fluorine source is typically hydrofluoric
acid. The non-aqueous solvent is typically a polyhydric alcohol
such as propylene glycol. The complementary acid is typically
either phosphoric acid or hydrochloric acid. The surface
passivation agent is one or more compounds with one or more
chelating groups/agents, at least one being an amidoxime functional
group/compound, and may optionally include a carboxylic acid such
as citric acid. Exposing the substrate to the conditioning solution
removes the remaining dry etch residues while minimizing removal of
material from desired substrate features. See U.S. Pat. No.
6,562,726.
Example 34
[0399] Another embodiment of the present invention is a stripping
and cleaning composition for the removal of residue from metal and
dielectric surfaces in the manufacture of semi-conductors and
microcircuits. The composition is an aqueous system including
organic polar solvents including corrosive inhibitor component from
one or more compounds with one or more chelating groups/agents, at
least one being an amidoxime functional group/compound and
optionally a select group of aromatic carboxylic acids used in
effective inhibiting amounts. A method in accordance with this
invention for the removal of residues from metal and dielectric
surfaces comprises the steps of contacting the metal or dielectric
surface with the above inhibited compositions for a time sufficient
to remove the residues. See U.S. Pat. No. 6,558,879.
Example 35
[0400] Another embodiment of the present invention is a homogeneous
non-aqueous composition containing a fluorinated solvent, ozone,
one or more compounds with one or more chelating groups/agents, at
least one being an amidoxime functional group/compound, and
optionally a co-solvent and the use of these compositions for
cleaning and oxidizing substrates is described. See U.S. Pat. No.
6,537,380.
Example 36
[0401] The present invention also includes a chemical mechanical
polishing slurry and method for using the slurry for polishing
copper, barrier material and dielectric material that comprises a
first and second slurry. The first slurry has a high removal rate
on copper and a low removal rate on barrier material. The second
slurry has a high removal rate on barrier material and a low
removal rate on copper and dielectric material. The first and
second slurries at least comprise silica particles, an oxidizing
agent, one or more compounds with one or more chelating
groups/agents, at least one being an amidoxime functional
group/compound, optionally a corrosion inhibitor, and a cleaning
agent. See, U.S. Pat. No. 6,527,819.
Example 37
[0402] Another embodiment of the present invention also includes a
method for removing organometallic and organosilicate residues
remaining after a dry etch process from semiconductor substrates.
The substrate is exposed to a conditioning solution of phosphoric
acid, hydrofluoric acid, and one or more compounds with one or more
chelating groups/agents, at least one being an amidoxime functional
group/compound, and optionally a carboxylic acid, such as acetic
acid, which removes the remaining dry etch residues while
minimizing removal of material from desired substrate features. The
approximate proportions of the conditioning solution are typically
80 to 95 percent by weight one or more compounds with one or more
chelating groups/agents, at least one being an amidoxime functional
group/compound and carboxylic acid, 1 to 15 percent by weight
phosphoric acid, and 0.01 to 5.0 percent by weight hydrofluoric
acid. U.S. Pat. No. 6,517,738.
Example 38
[0403] Another embodiment of the present invention is a composition
for use in semiconductor processing wherein the composition
comprises water, phosphoric acid, and one or more compounds with
one or more chelating groups/agents, at least one being an
amidoxime functional group/compound, and optionally an organic
acid; wherein the organic acid is ascorbic acid or is an organic
acid having two or more carboxylic acid groups (e.g., citric acid).
The water can be present in about 40 wt. % to about 85 wt. % of the
composition, the phosphoric acid can be present in about 0.01 wt. %
to about 10 wt. % of the composition, and the one or more compounds
with one or more chelating groups/agents, at least one being an
amidoxime functional group/compound and organic acid can be present
in about 10 wt, % to about 60 wt. % of the composition. The
composition can be used for cleaning various surfaces, such as, for
example, patterned metal layers and vias by exposing the surfaces
to the composition. See U.S. Pat. No. 6,486,108.
Example 39
[0404] Another embodiment of the present invention is a method for
removing organometallic and organosilicate residues remaining after
a dry etch process from semiconductor substrates. The substrate is
exposed to a conditioning solution of phosphoric acid, hydrofluoric
acid, and one or more compounds with one or more chelating
groups/agents, at least one being an amidoxime functional
group/compound, and optionally a carboxylic acid, such as acetic
acid, which removes the remaining dry etch residues while
minimizing removal of material from desired substrate features. The
approximate proportions of the conditioning solution are typically
80 to 95 percent by weight one or more compounds with one or more
chelating groups/agents, at least one being an amidoxime functional
group/compound and acetic acid, 1 to 15 percent by weight
phosphoric acid, and 0.01 to 5.0 percent by weight hydrofluoric
acid. See U.S. Pat. No. 6,453,914.
Example 40
[0405] Another example of the present invention is show in cleaning
a substrate which has a metal material and a semiconductor material
both exposed at the surface and which has been subjected to a
chemical mechanical polishing treatment, the substrate is first
cleaned with a first cleaning solution containing ammonia water,
etc. and then with a second cleaning solution containing (a) a
first complexing agent capable of easily forming a complex with the
oxide of said metal material, etc. and (b) an anionic or cationic
surfactant. See U.S. Pat. No. 6,444,583.
Example 41
[0406] The present invention is also exemplified by a cleaning
agent for semiconductor parts, which can decrease a load on the
environment and has a high cleaning effect on CMP (chemical
mechanical polishing) abrasive particles, metallic impurities and
other impurities left on the semiconductor parts such as
semiconductor substrates after the Cam, comprising a (co)polymer
having one or more compounds with one or more chelating
groups/agents, at least one being an amidoxime functional
group/compound, and optionally at least one kind of group selected
from the group consisting of sulfonic acid (salt) groups and
carboxylic acid (salt) groups, the cleaning agent further
containing a phosphonic acid (salt) group-containing (co)polymer, a
phosphonic acid compound or a surfactant as needed; and a method
for cleaning semiconductor parts with the above cleaning agent. See
U.S. Pat. No. 6,440,856.
Example 42
[0407] The present invention also includes a non-corrosive cleaning
composition for removing residues from a substrate. The composition
comprises: (a) water; (b) at least one hydroxylammonium compound;
(c) at least one basic compound, preferably selected from the group
consisting of amines and quaternary ammonium hydroxides; (d) one or
more compounds with one or more chelating groups/agents, at least
one being an amidoxime functional group/compound, (e) optionally at
least one organic carboxylic acid; and (f) optionally, a polyhydric
compound. The pH of the composition is preferably between about 2
to about 6. See U.S. Pat. No. 6,413,923.
Example 43
[0408] Another embodiment of the present invention is a composition
comprising a slurry having an acidic pH and a corrosion inhibitor
with one or more compounds with one or more chelating
groups/agents, at least one being an amidoxime functional
group/compound, and optionally a carboxylic acid corrosion
inhibitor, wherein said carboxylic acid is selected from the group
consisting of: glycine, oxalic acid, malonic acid, succinic acid
and nitrilotriacetic acid. U.S. Pat. No. 6,409,781.
Example 44
[0409] An alternative embodiment of the present invention is a
chemical formulation consisting of a chelating agent, wherein said
chelating agent is one or more compounds with one or more chelating
groups/agents, at least one being an amidoxime functional
group/compound, and optionally one or more additional chelating
agents selected from the group consisting of iminodiacetic,
malonic, oxalic, succinic, boric and malic acids and 2,4
pentanedione; a fluoride; and a glycol solvent, wherein said
chelating agents consist of approximately 0.1-10% by weight of the
formulation; and wherein said fluoride consists of a compound
selected from the group consisting of ammonium fluoride, an organic
derivative of ammonium fluoride, and a organic derivative of a
polyammonium fluoride; and wherein said fluoride consists of
approximately 1.65-7% by weight of the formulation; and wherein
said glycol solvent consists of approximately 73-98.25% by weight
of said formulation, further comprising: an amine, wherein said
amine consists of approximately 0.1-10% by weight of said
formulation. The chelating agents generally contain one or more
compounds with one or more chelating groups/agents, at least one
being an amidoxime functional group/compound, and optionally
contain two carboxylic acid groups or two hydroxyl groups or two
carbonyl groups such that the two groups in the chelating agent are
in close proximity to each other. Other chelating agents which are
also weakly to moderately acidic and are structurally similar to
those claimed are also expected to be suitable. See U.S. Pat. No.
6,383,410.
Example 45
[0410] Another embodiment of the present invention is a cleaning
composition comprising a partially fluorinated solvent, a
co-solvent, one or more compounds with one or more chelating
groups/agents, at least one being an amidoxime functional
group/compound, and ozone, wherein said fluorinated solvent
comprises hydrofluoroethers, wherein said co-solvent is selected
from the group consisting of ethers, esters, tertiary alcohols,
carboxylic acids, ketones and aliphatic hydrocarbons. See U.S. Pat.
No. 6,372,700.
Example 46
[0411] Yet another embodiment of the present invention is a
combination of one or more compounds with one or more chelating
groups/agents, at least one being an amidoxime functional
group/compound and optionally a carboxylic acid corrosion
inhibitor. The combination of corrosion inhibitors can effectively
inhibit metal corrosion of aluminum, copper, and their alloys.
Suitable carboxylic acids include monocarboxylic and polycarboxylic
acids. For example, the carboxylic acid may be, but is not limited
to, formic acid, acetic acid, propionic acid, valeric acid,
isovaleric acid, oxalic acid, malonic acid, succinic acid, glutaric
acid, maleic acid, filmaric acid, phthalic acid,
1,2,3-benzenetricarboxylic acid, glycolic acid, lactic acid, citric
acid, salicylic acid, tartaric acid, gluconic acid, and mixtures
thereof. The preferred carboxylic acid is citric acid.
Example 47
[0412] Another example of the present invention is a composition
for selective etching of oxides over a metal comprising: (a) water;
(b) hydroxylammonium salt in an amount about 0.1 wt. % to about 0.5
wt. % of said composition; (c) one or more compounds with one or
more chelating groups/agents, at least one being an amidoxime
functional group/compound; (d) optionally a carboxylic acid
selected from the group consisting of: formic acid, acetic acid,
propionic acid, valeric acid, isovaleric acid, oxalic acid, malonic
acid, succinic acid, glutaric acid, maleic acid, filmaric acid,
phthalic acid, 1,2,3-benzenetricarboxylic acid, glycolic acid,
lactic acid, citric acid, salicylic acid, tartaric acid, gluconic
acid, and mixtures thereof; (e) a fluorine-containing compound; and
(e) optionally, base. See U.S. Pat. No. 6,361,712.
Example 48
[0413] In a further aspect, the invention relates to a
semiconductor wafer cleaning formulation for use in post plasma
ashing semiconductor fabrication, comprising the following
components in the percentage by weight (based on the total weight
of the formulation) ranges shown:
TABLE-US-00021 Organic amine(s) 2-98% by weight Water 0-50% by
weight amidoxime chelating agent 0.1-60% by weight Complexing agent
0-25% by weight Nitrogen-containing carboxylic 0.5-40% by weight
acid or imine polar organic solvent 2-98% by weight.
Example 49
[0414] Another example of the present invention includes an
essentially anhydrous cleaning composition comprising 88 weight
percent or more of a fluorinated solvent, from 0.005 to 2 weight
percent of hydrogen fluoride or complex thereof, and from 0.01 to 5
weight percent of a co-solvent, wherein said co-solvent is selected
from one or more compounds with one or more chelating
groups/agents, at least one being an amidoxime functional
group/compound, ethers, polyethers, carboxylic acids, primary and
secondary alcohols, phenolic alcohols, ketones, aliphatic
hydrocarbons and aromatic hydrocarbons. See U.S. Pat. No.
6,310,018.
Example 50
TABLE-US-00022 [0415] A. Amidoxime compound 2.5% by weight
Tetramethylammonium fluoride 4.5% by weight Ethylene glycol 93% by
weight B. Amidoxime compound 1.3% by weight
Pentamethyldiethylenetriammonium 4.6% by weight trifluoride
Ethylene glycol 94.1% by weight C. Amidoxime compound 1.25% by
weight Triethanolammonium fluoride 5% by weight Ethylene glycol
93.75% by weight D. Amidoxime compound 2.8% by weight
Tetramethylammonium fluoride 5.1% by weight Ethylene glycol 92.1%
by weight E. Amidoxime compound 2% by weight Ammonium fluoride 7%
by weight Ethylene glycol 91% by weight F. Amidoxime compound 2.8%
by weight Ammonium fluoride 5% by weight Ethylene glycol 92.2% by
weight
Example 51
[0416] Another embodiment of the present invention includes a
chelating agent, a fluoride salt, and a glycol solvent, wherein
said chelating agent is weakly to moderately acidic, and consists
of approximately 0.1-10% by weight of the formulation; and wherein
said fluoride salt consists of a compound selected from the group
consisting of ammonium fluoride, an organic derivative of ammonium
fluoride, and a organic derivative of a polyammonium fluoride; and
wherein said fluoride salt consists of approximately 1.65-7% by
weight of the formulation; and wherein said glycol solvent consists
of 73-98.25% by weight of said formulation; and further including
an amine, wherein said amine consists of approximately 0.1-10% by
weight of said formulation; and wherein said chelating agent is an
amidoxime or hydroxamic acid. See U.S. Pat. No. 6,280,651.
Example 52
[0417] Another example of the present invention is a cleaning agent
for use in producing semiconductor devices, which consists
essentially of an aqueous solution containing (A) 0.1 to 15% by
weight based on the total amount of the cleaning agent of at least
one fluorine-containing compound selected from the group consisting
of hydrofluoric acid, ammonium fluoride, ammonium hydrogen
fluoride, acidic ammonium fluoride, methylamine salt of hydrogen
fluoride, ethylamine salt of hydrogen fluoride, propylamine salt of
hydrogen fluoride and tetramethylammonium fluoride, (B) 0.1 to 15%
by weight based on the total amount of the cleaning agent of a salt
of boric acid and (C) 0.5 to 50% by weight of one or more compounds
with one or more chelating groups/agents, at least one being an
amidoxime functional group/compound; and (d) 5 to 80% by weight
based on the total amount of the cleaning agent of a water-soluble
organic solvent, and optionally further containing at least one of
a quaternary ammonium salt, an ammonium salt of an organic
carboxylic acid, an amine salt of an organic carboxylic acid and a
surfactant. See U.S. Pat. No. 6,265,309.
Example 53
[0418] Another embodiment of the present invention includes a
cleaning liquid in the form of an aqueous solution for cleaning a
semiconductor device during production of a semiconductor device,
which comprises (A) a fluorine-containing compound; (B) a
water-soluble or water-miscible organic solvent; (C) one or more
compounds with one or more chelating groups/agents, at least one
being an amidoxime functional group/compound; (D) optionally, an
organic acid; and (E) a quaternary ammonium salt. In some
embodiments the cleaning solution also contains a surfactant. The
organic acid is typically selected from the group consisting of
formic acid, acetic acid, propionic acid, butyric acid, isobutyric
acid, valeric acid, isovaleric acid, heptanoic acid, lauric acid,
palmitic acid, stearic acid, acrylic acid, crotonic acid,
methacrylic acid, oxalic acid, malonic acid, maleic acid, succinic
acid, adipic acid, azelaic acid, sebacic acid, benzoic acid, toluic
acid, phthalic acid, trimellitic acid, pyromellitic acid,
benzenesulfonic acid, toluenesulfonic acid, salicylic acid and
phthalic anhydride. See U.S. Pat. No. 5,972,862.
Example 54
[0419] Another embodiment is a method for semiconductor processing
comprising etching of oxide layers, especially etching thick SiO2
layers and/or last step in the cleaning process wherein the oxide
layers are etched in the gas phase with a mixture of hydrogen
fluoride, one or more compounds with one or more chelating
groups/agents, at least one being an amidoxime functional
group/compound, and optionally one or more carboxylic acids,
eventually in admixture with water. See U.S. Pat. No.
5,922,624.
Example 55
[0420] The complexing agents of the present invention may also be
added to the rinse containing a peroxide of U.S. Pat. No.
5,911,836.
Example 56
[0421] Copper blanket wafer is immersed in the following solutions
at room temperature for 15 and 30 minutes to observe the copper
thickness changes. The amidoxime compound is
1,2,3,4,5,6-hexakis-O-[3-(hydroxyamino)-3-iminopropyl Hexitol
TABLE-US-00023 H.sub.2O.sub.2 H.sub.2O.sub.2/AO AO Hydrogen
Peroxide 3% 3% 0 1,2,3,4,5,6-hexakis-O- 0 1% 1%
[3-(hydroxyamino)-3-iminopropyl Hexitol Water Balance Balance
Balance Copper Thickness Lost 15 minutes 97 16 22 30 minutes 120 13
48
[0422] Hydrogen peroxide attacks the copper surface and changed
into copper oxide resulting in the reduction of copper thickness.
It resulted a lost of 120 .ANG. in 30 minutes of immersion.
Amidoxime etches copper slightly in 30 minutes to remove about 50
.ANG.. It is unexpected to see the mixture of the two components
inhibits the oxidation of the copper surface.
Example 57
[0423] Copper blanket wafer is immersed in the following solutions
at room temperature for 30 minutes at various temperatures to
observe the copper thickness changes.
TABLE-US-00024 Hydroxyl- Hydroxylamine amine (50%) (50%)/AO AO
Hydroxylamine (50%) 10% 10% 0 1,2,3,4,5,6-hexakis-O-[3- 0 10% 10%
(hydroxyamino)-3-iminopropyl Hexitol Water Balance Balance Balance
Copper Thickness Lost RT 2.88 9.76 4.08 .ANG./min 40.degree. C.
5.27 32.68 5.83 60.degree. C. 7.95 61.68 4.39
The copper static etch rate, when
1,2,3,4,5,6-hexakis-O-[3-(hydroxyamino)-3-iminopropyl Hexitol is
mixed with hydroxylamine (50%) increases the etch rates
exponentially from about 8 .ANG./min to 62 .ANG./min. This
indicates the combination of amidoxime compound with hydroxylamine
to improve copper and copper oxide debries removal from the CMP
processes in the manufacturing of semiconductor devices.
Example 58
[0424] A sample coupon of the electroplated copper wafer was
immersed in 10% of amidoxime in water at 30.degree. C. for 30
minutes. The sample is then rinsed in DI water for 5 minutes and
blow dried with nitrogen gas. The sample is then sent to Evan
Laboratory for ESCA and Auger analysis.
[0425] The sample is then re-analyzed again after 10 days of
exposure to normal storage condition.
[0426] Even the surface analysis were done on the same day, there
was a gap of two hours due to transportation to Evan Laboratory.
Therefore, there is two hours as "queue time" for standard wafer
fab processes for re-growth of copper oxide.
[0427] As opposed to the solubility of Cu(II) oxide, as shown in
this Pourbaix diagram, the Cu--H2O system forms insoluble oxides
and hydroxides at a pH of 7-12. (Ref: M. J. N. Pourbaix, Atlas of
Chemical Equlibria in Aqueous Solutions, National Assoc. of
Corrosion Engineers, Houston, Tex., 1974.). The amidoxime removes
Cu(II) oxide effectively at pH of 9-11.
Example 59
Particle Performance Comparison
Particle Performance on Thermal Oxide
TABLE-US-00025 [0428] DS6-10 + PCMP5500 PCMP 5510 Glycolic (EKC
Clean Dilution DIW (EKC Technology) DS6-10 Acid Technology) 100
ratio -- 1 10 25 50 100 1 10 10 50 30 0.1up 334 456 531 362 141 81
170 154 89 190 194 0.12up 234 325 426 270 114 54 126 108 65 147 137
0.14up 263 243 368 218 91 44 97 67 45 115 102 0.17up 229 168 319
180 72 32 76 44 20 80 70 0.2up 99 126 273 153 58 27 60 35 24 60 50
0.3up 51 52 183 109 48 17 36 11 10 41 32 0.5up 17 18 109 68 23 17
22 4 4 26 18
Example 60
Particle Performance Comparison
Particle Performance Cu Blanket
TABLE-US-00026 [0429] PCMP5500 PCMP 5510 (EKC Clean Dilution DIW
(EKC Technology) DS6-10 Technology) 100 ratio -- 1 10 25 50 100 1
10 50 30 LPD 136 101 74 80 77 65 124 164 120 38 count Area 44 17 21
12 14 14 24 43 4 11 count defect 0.513 0.381 0.279 0.302 0.291
0.245 0.468 0.618 0.452 0.143 density
Example 61
Particle Performance Comparison
Particle Performance on BlackDiamond.TM. (BD1)
TABLE-US-00027 [0430] DS6-10 + PCMP5500 PCMP 5510 (Glycolic (EKC
Clean (EKC Technology) DS6-10 Acid Technology) 100 Dilution ratio 1
10 25 50 100 1 10 10 50 30 0.1up 446 938 693 600 2273 168 66 1124
80 693 0.12up 308 777 492 230 1453 122 44 791 56 427 0.14up 231 677
317 125 1053 82 33 645 41 272 0.17up 175 563 192 61 758 64 25 506
29 141 0.2up 136 481 137 50 618 51 21 422 25 90 0.3up 55 285 41 32
379 33 11 316 14 37 0.5up 24 159 12 15 241 16 9 174 8 14
Example 62 Zeta Potential of Amidoxime Solution
TABLE-US-00028 [0431] EKC PCMP5510 .TM.- DS6- dilution ratio pH
Silica Alumina pH Silica Alumina 1 7.62 9.75 10 7.46 -28 -45 9.37
-70 -35 25 7.45 -33 -48 9.34 -65 -31 50 7.45 -47 -49 9.27 -58 -31
100 7.45 -57 -50 9.29 -50 -30
Example 63 Metal Contamination Thermal Oxide
TABLE-US-00029 [0432] K Ca Cr Mn Fe Co Ni Cu Zn DIW 4.7 ND <1
<1 2.0 <1 ND <1 ND EKC5510 4.2 ND <1 <1 <1 <1
ND 4.0 ND (EKC Technology, Inc.) Dil 10 <1 ND <1 <1 <1
ND ND 5.1 ND Dil 25 ND ND 1.0 <1 4.5 <1 <1 4.6 ND Dil 50
3.8 ND <1 ND 1.0 <1 ND 4.3 ND Dil 100 <1 ND <1 <1
<1 <1 ND 4.2 ND DS6-10 4.0 <1 <1 <1 <1 ND ND 2.0
ND Dil 10 2.8 <1 <1 ND 1.6 <1 ND <1 ND DS6 + Glycolic
Acid 1.9 <1 <1 <1 <1 ND ND 5.4 ND EKC5500 2.6 <1
<1 <1 <1 <1 ND <1 ND (EKC Technology, Inc.) dil 50
Clean100 dil 30 <1 ND <1 <1 1.9 <1 ND 6.3 ND
Example 64 Metal Contamination BD1
TABLE-US-00030 [0433] K Ca Cr Mn Fe Co Ni Cu Zn DIW 1.2 ND <1 ND
<1 ND ND <1 ND EKC5510 12.6 ND <1 <1 1.6 ND ND 18.0 ND
(EKC Technology, Inc.) Dil 10 21.3 ND <1 <1 1.7 <1 ND 19.8
ND Dil 25 17.6 <1 <1 <1 1.7 <1 ND 21.4 ND Dil 50 14.2
ND <1 ND 1.3 <1 ND 18.8 ND Dil 100 16.5 ND <1 <1 1.2
<1 ND 18.1 ND DS6-10 7.1 ND <1 <1 1.5 <1 ND 9.6 ND Dil
10 3.1 1.0 <1 <1 1.3 <1 ND 4.4 ND DS6 + Glycolic Acid 51.5
<1 ND ND 1.9 <1 ND 58.2 ND EKC5500 dil 50 21.3 ND <1 <1
<1 ND ND 1.9 ND Clean100 dil 30 38.9 <1 <1 <1 2.4 <1
ND 57.1 ND
Example 65
[0434] Evaluation of various PCMP cleaning chemistries with the
EBARA EPO222D CMP tool, following standard CMP processes steps
follows. The process flow for post CMP clean tool from EBARA
EPO222D is as follows:
[0435] After polishing, the wafer is transferred to a brush unit
capable of dispensing cleaning chemistries and DI water, and then
the wafer is moved to a pencil unit for DI rinse with high pressure
jet spray water to the wafer surface.
[0436] 1. Process
1. Step 1: Bulk Copper Removal--Standard post CMP clean using
process of record 2. Step 2--Barrier metal removal.fwdarw.PCMP
Clean evaluation with various chemistries
[0437] 2. PCMP Clean recipe
TABLE-US-00031 Brush Wafer Chemical/ Speed Rotation Flow Time
Module DI Water (RPM) (RPM) (ml) (sec) 1 Brush Chemical 100 20 600
40 2 DI Water 100 20 600 20 3 Pencil DI Water Center to edge scan -
4 times 4 2000
[0438] 3. Inspection/Measurement Using Hitachi S-5200--SEM images
of Line/Space (L/S) pattern
[0439] When copper oxide remained on the surface, one cannot
observe the copper grain boundaries. As indicated, the wafer has
been processed only with DI water. The copper grain boundaries are
seen after processed through various PCMP cleaning chemistries,
which suggests copper oxides are removed from the surface. The
results show that the amidoxime solution (D56-10) of the invention
effectively removes particles and copper oxide from the surface
without damaging the copper surface. It is also effective at a
dilution factor of 10. While other chemistries, such as EKC5500
from EKC Technology and Clean 100 from supplier D, are capable of
removing copper oxide, their use leaves white particle residues on
the copper surface. Both chemistries have low a pH.
Example 66
Acceleration Copper Corrosion Test
[0440] Wafer samples from Example 65 are immersed in the cleaning
solutions at 60.degree. C. for 1 and 4 hours. The samples are then
inspected using a Hitachi S-5200 Scanning Electron Microscope. The
results from the SEM pictures show that approximately 25 nm of
copper has been eroded using the amidoxime solution of the
invention, compared to 130 nm lost in PCMP EKC5510 from EKC
Technology, Inc.
Example 67
[0441] Experiment to show compatibility with low k dielectric
material k value shift Tool: CVmap3092-A/Four Dimensions, Inc.
Example 68
Comparison to Other PCMP Cleaning Solutions
TABLE-US-00032 [0442] Components Vendor Product Quaternary Amine
Acid Additive Dilution pH A 1 TMAH MEA Gallic acid (GA) 30-100:1 12
2 TMAH MEA Ascorbic acid (AA) 30-60:1 12 3 TMAH MEA Gallic acid
&Ascorbic 30-60:1 12 acid 4 TMAH TEA Gallic acid &Ascorbic
30-60:1 10 acid 5 TMAH TEA Gallic acid &Ascorbic 30-60:1 8 acid
5 TMAH MEA Ascorbic Acid 1,2,4 triazole 20-30:1 12 B 7 NH3/HF
Citric Acid 10-30:1 4 8 NH3 TAZ 1-5:1 10 9 Maleic acid (MA),
20-60:1 4 Oxalic acid (OA), Citric acid (CA) 10 MA, CA, OA
Surfactant 20-60:1 4 C 11 NH3 Oxalic Acid Mannose, 20-60:1 4
surfactant D 12 NH3 OA DDBSA 20-100:1 4
[0443] In examining commercial available PCMP cleaning solutions,
they all contain quaternary ammonium compound, amine and carboxylic
acids with corrosion inhibitors. The pHs of these solutions are
adjusted by varying the acid and organic base component.
Example 69
[0444] Cleaning Copper Surface Passivated by BTA
[0445] Benzotriazole is commonly used as corrosion inhibitor in CMP
slurry mixtures to protect the surface from erosion and dishing. It
is highly desirable to remove this BTA/copper complex layer during
the post CMP cleaning step. Experiments are carried out to compare
the efficacy of amidoxime containing solution to commercial
available PCMP5510 solution from EKC Technology. A blanket copper
wafer is immersed in 0.2% BTA solution for 30 sec. The BTA treated
wafer is then processed through AmiSorb.TM. DS6 (AmiSorb.TM. DS6 is
60% 1,2,3,4,5,6-hexakis-O-[3-(hydroxyamino)-3-iminopropyl Hexitol
in water) and EKC PCMP5510.
[0446] The results show that the amidoxime solution reduces the
surface contact angle much better than PCMP5510, a product from EKC
Technology. This indicates a clean copper surface with low contact
angle measurement. Amidoxime is capable to remove the BTA/complex
by displacing the BTA and form a water soluble complex.
TABLE-US-00033 Total Contact Angle Contact Angle Time Thickness
using H2O using H2O Dilution (min) Loss (.ANG.) (Before) (After)
0.2% BTA Cu treated wafer 100 10 39.261 50.03 22.56 process in
AmiSorb .TM. 20 21.688 49.35 17.41 DS6-10% solution 50 10 10.731
46.22 22.12 20 48.825 46.86 17.61 10 10 65.213 47.39 21.43 20
38.106 48.33 19.35 0.2% BTA Cu treated wafer 100 10 8.609 57.15
51.67 process in 20 4.404 56.75 50.49 PCMP5510 50 10 13.931 57.14
52.48 20 3.347 55.96 50.04 10 10 8.234 57.3 51.73 20 62.133 58.25
32.37
Example 70
Amidoxime Inhibits Copper Corrosion
TABLE-US-00034 [0447] Cu Etch Lactic Citric Rate ID THEMAH Acid
Acid DS6 DI Water (.ANG./Min) pH 5510C 44% 4.5% 18.9% -- 32.6 31.5
9.0 5510- 44% 4.5% 18.9% 5% 27.6 0.2 9.5 RS- SB6-5
[0448] Adding a composition comprising 5% of amidoxime into a PCMP
cleaning formulation decreases the copper etch rate from about 32
.ANG./Min to 0.2 .ANG./Min. This suggests the amidoxime solution of
the invention inhibits copper corrosion in an existing PCMP
cleaning formulation.
Example 71
[0449] Another example of the present invention is a method and
apparatus for increasing the deposition of ions onto a surface,
such as the adsorption of uranium ions on the detecting surface of
a radionuclide detector. The method includes the step of exposing
the surface to one or more compounds with one or more chelating
groups/agents, at least one being an amidoxime functional
group/compound, and optionally, a phosphate ion solution, which has
an affinity for the dissolved species to be deposited on the
surface. This provides, for example, enhanced sensitivity of the
radionuclide detector. See U.S. Pat. No. 5,652,013.
Example 72
[0450] Another embodiment of the present invention is a stripping
and cleaning agent for removing dry-etching photoresist residues,
and a method for forming aluminum based line pattern using the
stripping and cleaning agent. The stripping and cleaning agent
contains (a) from 5 to 50% by weight of one or more compounds with
one or more chelating groups/agents, at least one being an
amidoxime functional group/compound; (b) from 0.5 to 15% by weight
of a fluorine compound; and (c) a solvent, including water. The
inventive method is advantageously applied to treating a dry-etched
semiconductor substrate with the stripping and cleaning agent. The
semiconductor substrate comprises a semiconductor wafer having
thereon a conductive layer containing aluminum. The conductive
layer is dry-etched through a patterned photoresist mask to form a
wiring body having etched side walls. The dry etching forms a side
wall protection film on the side walls. In accordance with the
inventive method, the side wall protection film and other resist
residues are completely released without corroding the wiring body.
See, U.S. Pat. No. 5,630,904.
Example 73
[0451] U.S. Pat. No. 6,927,176 describes the effectiveness of
chelating compound due to their binding sites and is illustrated in
FIGS. 2a and 2b in U.S. Pat. No. 6,927,176. It highlights there are
6 binding sites
##STR00167##
[0452] 6 binding sites
[0453] By the same principal applying to a amidoxime from the
conversion of a cyanoethylation compound of ethylenediamine, it
results a total of 14 binding sites, as depicted in the
following
##STR00168## [0454] 14 binding sites
(1,2,3,4,5,6-(hexa-(2-amidoximo)ethoxy)hexane
##STR00169##
[0455] has a total of 18 binding sites. The claimed amidoxime
chelating agent can substitute in application to replace
polyacrylates, carbonates, phosphonates, and gluconates,
ethylenediaminetetraacetic acid (EDTA),
N,N'-bis(2-hydroxyphenyl)ethylenediiminodiacetic acid (HPED),
triethylenetetranitrilohexaacetic acid (TTHA), desferriferrioxamin
B,N,N',N''-tris[2-(N-hydroxycarbonyl)ethyl]-1,3,5-benzenetricarboxamide
(BAMTPH), and ethylenediaminediorthohydroxyphenylacetic acid
(EDDHA).
[0456] Cleaning solutions of the present application include
compositions comprising
[0457] A) An organic compound with one or more amidoxime functional
group
##STR00170##
or salts thereof.
[0458] Firstly considering the amidoxime functional group itself,
in one embodiment, R.sub.a and R.sub.b are independently hydrogen,
alkyl, hetero-alkyl, alkyl-aryl, or alkyl-heteroaryl groups. R is
independently selected from alkyl, alkyl-aryl, or alkyl-heteroaryl
groups. In these two embodiments, chelation of the amidoxime to
metal centres may be favoured because, in reaction with a metal
centre, a proton can be lost from NR.sub.aR.sub.b so as to form a
nominally covalent bond with the metal centre.
[0459] In another embodiment, NR.sub.aR.sub.b is further
substituted with R.sub.c so the amidoxime has the following
chemical formula:
##STR00171##
In this case, a counter-ion balances the positive charge on the
nitrogen atom. Any counter-ion may be used, for example chloride,
bromide, iodide, a SO.sub.4 ion, a PF.sub.6 ion or a ClO.sub.4 ion.
R.sub.c may be hydrogen, alkyl, alkyl-aryl, or alkyl-heteroaryl
group.
[0460] It is noted that R.sub.a, R.sub.b and/or R.sub.c can join
onto one another and/or join onto R so as to form one or more
cycles.
[0461] It is also noted that amidoxime can exist as their
tautomers:
##STR00172##
[0462] Compounds that exist mainly or wholly in this tautomeric
form are included within the scope of the present invention.
[0463] Accordingly, the amidoxime functional group includes the
following functionalities and their tautomers:
##STR00173##
wherein R may be connected to one or more of R.sub.a, R.sub.b and
R.sub.c.
[0464] For example, the amidoxime functional group includes within
its scope:
##STR00174##
wherein Alk is an alkyl group as defined below. The three alkyl
groups may be independently selected or may be the same. In one
embodiment, the alkyl group is methyl or ethyl.
[0465] Turning now to the R group, R may be an alkyl group (in
other words, a group containing carbon and hydrogen). The alkyl
group may be completely saturated or may contain unsaturated groups
(i.e. may contain alkene and alkyne functional groups, so the term
"alkyl" encompasses the terms "alkylene" and "alkylyne" within its
scope). The alkyl group may be straight-chained or branched.
[0466] The alkyl group may contain any number of carbon and
hydrogen atoms. While alkyl groups having a lesser number of carbon
atoms tend to be more soluble in polar solvents such as DMSO and
water, alkyl groups having a greater number of carbons can have
other advantageous properties, for example surfactant properties.
Therefore, in one embodiment, the alkyl group contains 1 to 10
carbon atoms, for example the alkyl group is a lower alkyl group
containing 1 to 6 carbon atoms. In another embodiment, the alkyl
group contains 10 or more carbon atoms, for example 10 to 24 carbon
atoms.
[0467] The alkyl group may be unsubstituted (i.e. the alkyl group
contains only carbon and hydrogen). The unsubstituted alkyl group
may be unsaturated or saturated. Examples of possible saturated
unsubstituted alkyl groups include methyl, ethyl, n-propyl,
sec-propyl, cyclopropyl, n-butyl, sec-butyl, tert-butyl,
cyclobutyl, pentyl (branched or unbranched), hexyl (branched or
unbranched), heptyl (branched or unbranched), octyl (branched or
unbranched), nonyl (branched or unbranched), and decyl (branched or
unbranched). Saturated unsubstituted alkyl groups having a greater
number of carbons may also be used. Cyclic alkyl groups may also be
used, so the alkyl group may comprise, for examples a cyclopropyl
group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group,
a cycloheptyl group, a cyclooctyl group, a cyclononyl group and/or
a cyclodecyl group. These cyclic alkyl groups may directly append
the amidoxime group or may be joined to the amidoxime through one
or more carbon atoms.
[0468] Examples of amidoxime compounds containing unsubstituted
saturated alkyl groups include:
##STR00175## ##STR00176##
[0469] Examples further include:
##STR00177##
wherein Alk is methyl or ethyl and R is an alkyl group, typically
but not necessarily straight chained. R may be for example an alkyl
group containing 8 to 25 carbon atoms. If the alkyl group is
substituted, it may for example be substituted at the opposite end
of the alkyl group to the amidoxime group. For example, it may be
substituted antipodally to the amidoxime group by one or more
halogens, for example fluorine. Examples further include alkyl
groups appending two or more amidoxime functional groups.
[0470] For example, the amidoxime may be:
##STR00178##
where R is an alkyl group. For example, R is independently selected
from alkylene, heteroalkylene, arylene, heteroarylene,
alkylene-heteroaryl, or alkylene-aryl group. Examples of suitable
groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,
octyl, nonyl and decyl.
[0471] Specific examples of unsubstituted saturated alkyl
amidoximes are:
##STR00179##
[0472] If the alkyl group is unsaturated, it may be any of the
groups just listed except for having one or more unsaturated
carbon-carbon bonds (so it may contain one or more alkene and/or
alkyne groups). These unsaturated group(s) may optionally be in
conjugation with the amidoxime group. A specific example of an
unsubstituted unsaturated alkyl amidoxime molecules is:
##STR00180##
[0473] The alkyl group may also be substituted with one or more
hetero-atoms or group of hetero-atoms. If more than one
hetero-substituent is present, the substituents are independently
selected from one another unless they form a part of a particular
functional group (e.g. an amide group). (Groups containing
hetero-atoms joined to carbon atoms are contained within the scope
of the term "heteroalklyl" as discussed below). One or more of the
substituents may be a halogen atom, including fluorine, chlorine,
bromine or iodine, --OH, .dbd.O, --NH.sub.2, .dbd.NH, --NHOH,
.dbd.NOH, --OPO(OH).sub.2, --SH, .dbd.S or --SO.sub.2OH. In one
embodiment, the substituent is an oxime group (.dbd.NOH). The alkyl
group may also be itself substituted with one or more amidoxime
functional groups.
[0474] If the alkyl group is substituted with .dbd.O, the alkyl
group may comprise an aldehyde, a ketone, a carboxylic acid or an
amide. Preferably, there is an enolizable hydrogen adjacent to the
.dbd.O, .dbd.NH or .dbd.NOH (i.e. there is a hydrogen in the alpha
position to the carbonyl). The alkyl group may comprise the
following functionality: -(CZ.sub.1)-CH--(CZ.sub.2)-, wherein
Z.sub.1 and Z.sub.2 are independently selected from O, NH and NOH.
The CH in this group is further substituted with hydrogen or an
alkyl group or joined to the amidoxime functional group.
[0475] Thus, an alkyl group appending an amidoxime group may simply
be substituted with, for example one or more independently-selected
halogens, for example fluorine, chlorine, bromine or iodine. In one
embodiment, the halogens are substituted at the antipodal (i.e.
opposite) end of the alkyl group to the amidoxime group. This can
for example provide surfactant activity, in particular for example
if the halogen is fluorine.
[0476] A specific example of an amidoxime group substituted with a
substituted alkyl group is:
##STR00181##
[0477] Details of the characterization of this molecule are given
in the examples.
[0478] Compounds that are substituted in a .beta. position are
conveniently synthesized from readily-available starting
materials.
[0479] Examples of such compounds include:
##STR00182##
wherein R.sub.1 and R.sub.2 are independently-selected alkyl groups
or hydrogen atoms.
[0480] Specific examples of substituted alkyl amidoxime molecules
are:
##STR00183##
It should be noted that some of these molecules can exist as
different isomers. For example:
##STR00184##
The different isomers can be differentiated by carbon-13 NMR.
Characterization of this isomer is provided in the example.
[0481] R may be a heteroalkyl group. The term heteroalkyl refers to
optionally a first alkyl group connected to one or more
independently-selected hetero-atoms or groups of hetero-atoms,
which itself is substituted with one or more independently-selected
groups containing one or more carbon atoms. The presence of the
first alkyl group is optional because the amidoxime group may be
attached directly to the one or more heteroatoms. As an
illustrative example, an alkyl group substituted with an ether
group is a heteroalkyl group because the alkyl group is substituted
with oxygen, which itself is substituted with a second alkyl group.
Alternatively, an --O--CH.sub.3 group is an example of a
heteroalkyl group.
[0482] When R is a heteroalkyl group, the amidoxime may have the
following chemical structure:
##STR00185##
where "n" varies from 1 to N and y varies from 1 to Y.sub.n; N
varies from 0 to 3: Y.sub.n varies from 0 to 5. In this formula,
R.sub.1 is independently-selected alkylene groups; R.sub.y is
independently selected from alkyl, or hetero-alkyl groups, or
adjoins R.sub.1 so to form a heterocycle with the directly
appending X.sub.n. R.sub.1 may also be a direct bond, so that the
amidoxime group is connected directly to the one or more
heteroatoms. X.sub.n is a heteroatom or a group of heteroatoms
selected from boron, nitrogen, oxygen, silicon, phosphorus and
sulphur. Each heteroatom or group of heteroatoms and each alkyl
group is independently selected from one another. The above formula
includes an amidoxime group directly bearing an alkyl group. The
alkyl group is substituted with N independently-selected
heteroatoms or groups of heteroatoms. Each heteroatom or group of
heteroatoms is itself substituted with one or more
independently-selected alkyl groups or hetero-alkyl groups.
[0483] X is one or more hetero-atoms. For example, X may be or may
comprise boron, nitrogen, oxygen, silicon, phosphorus or sulphur.
In one embodiment, X is oxygen. In this case, X may be part of an
ether group (--O--), an ester (--O--CO--), --O--CO--O--,
--O--CO--NH--, --O--CO--NR.sub.2--, --O--CNH--, --O--CNH--O--,
--O--CNH--NH--, --O--CNH--NR.sub.2--, --O--CNOH--, --O--CNOH--O--,
--O--CNOH--NH-- or --O--CNOH--NR.sub.2--, wherein R.sub.2 is
independently selected alkyl group, hetero-alkyl group, or
hetero-aryl group. In another embodiment, X is a nitrogen atom. In
this case, X may be part of one of the following groups:
--NR.sub.2H, --NR.sub.2--, --NR.sub.2R.sub.3-- (with an appropriate
counter-ion), --NHNH--, --NH--CO--, --NR2-CO--, --NH--CO--O--,
--NH--CO--NH--, --NH--CO--NR.sub.2--, --NR.sub.2--CO--NH--,
--NR.sub.2--CO--NR.sub.3--, --NH--CNH--, --NR2-CNH--,
--NH--CNH--O--, --NH--CN --NH--, --NH--CNH--NR.sub.2--,
--NR.sub.2--CNH--NH--, --NR.sub.2--CNH--NR.sub.3--, --NH--CNOH--,
--NR2-CNOH--, --NH--CNOH--O--, --NH--CNOH--NH--,
--NH--CNOH--NR.sub.2--, --NR.sub.2--CNOH--NH--,
--N.sub.2--CNOH--NR.sub.3--. R.sub.2 to R.sub.3 are independently
selected alkyl groups, hetero-alkyl groups, or hetero-aryl groups,
wherein the heteroalkyl group and hetero-aryl group may be
unsubstituted or substituted with one or more heteroatoms or group
of heteroatoms or itself be substituted with another heteroalkyl
group. If more than one hetero-substituent is present, the
substituents are independently selected from one another unless
they form a part of a particular functional group (e.g., an amide
group).
[0484] In another embodiment, X comprises boron. In this case, X
may also comprise oxygen. In another embodiment, X comprises
phosphorus. In this case, X may also comprise oxygen, for example
in an --OPO(OH)(OR.sub.2) group or an --OPO(OHR.sub.2)(OR.sub.3)
group. In another embodiment, X comprises sulphur, for example as a
thiol ether or as a sulphone.
[0485] The term heteroalkyl also includes within its scope cyclic
alkyl groups containing a heteroatom. If X is N or O, examples of
such groups include a lactone, lactam or lactim. Further examples
of heteroalkyl groups include azetidines, oxetane, thietane,
dithietane, dihydrofuran, tetrahydrofuran, dihydrothiophene,
tetrahydrothiophene, piperidine, pyrroline, pyrrolidine,
tetrahydropyran, dihydropyran, thiane, piperazine, oxazine,
dithiane, dioxane and morpholine. These cyclic groups may be
directly joined to the amidoxime group or may be joined to the
amidoxime group through an alkyl group.
[0486] The heteroalkyl group may be unsubstituted or substituted
with one or more hetero-atoms or group of hetero-atoms or itself be
substituted with another heteroalkyl group. If more than one
hetero-substituent is present, the substituents are independently
selected from one another unless they form a part of a particular
functional group (e.g. an amide group). One or more of the
substituents may be a halogen atom, including fluorine, chlorine,
bromine or iodine, --OH, .dbd.O, --NH.sub.2, .dbd.NH, --NHOH,
.dbd.NOH, --OPO(OH).sub.2, --SH, .dbd.S or --SO.sub.2OH. In one
embodiment, the substituent is an oxime group (.dbd.NOH). The
heteroalkyl group may also be itself substituted with one or more
amidoxime functional groups.
[0487] If the heteroalkyl group is substituted with .dbd.O, the
heteroalkyl group may comprise an aldehyde, a ketone, a carboxylic
acid or an amide. Preferably, there is an enolizable hydrogen
adjacent to the .dbd.O, .dbd.NH or .dbd.NOH (i.e. there is a
hydrogen in the alpha position to the carbonyl). The heteroalkyl
group may comprise the following functionality:
-(CZ.sub.1)-CH-(CZ.sub.2)-, wherein Z.sub.1 and Z.sub.2 are
independently selected from O, NH and NOH. The CH in this group is
further substituted with hydrogen or an alkyl group or heteroalkyl
group or joined to the amidoxime functional group.
[0488] Amines are particularly versatile functional groups for use
in the present invention, in part because of their ease of
preparation. For example, by using acrylonitrile as described
later, a variety of functionalized amines can be synthesized.
[0489] Examples include:
##STR00186##
R may itself be an alkylene group or a heteroatom or group of
heteroatoms. The heteroatoms may be unsubstituted or substituted
with one or more alkyl groups.
[0490] R may itself be a hetero-atom or group of heteroatoms. The
heteroatoms may be unsubstituted or substituted with one or more
alkyl groups. For example, R may be H, NH.sub.2, NHR.sub.1,
OR.sub.1, or NR.sub.1R.sub.2, wherein R.sub.1 and R.sub.2 are
independently-selected alkyl groups.
[0491] R may be an aryl group. The term "aryl" refers to a group
comprising an aromatic cycle. A particular example of an aryl
substituent is a phenyl group. The aryl group may be unsubstituted.
A specific example of an amidoxime bearing an unsubstituted aryl
is:
##STR00187##
The aryl group may also be substituted with one or more alkyl
groups, heteroalkyl groups or heteroatom substituents. If more than
one substituent is present, the substituents are independently
selected from one another.
[0492] Specific examples of amidoximes comprising a heteroalkyl
group include:
##STR00188##
Experimental details of these molecules are given in the
examples.
[0493] The term "aryl" refers to a group comprising an aromatic
cycle. The cycle is made from carbon atoms. The cycle itself may
contain any number of atoms, for example 3 to 10 atoms. For the
sake of convenient synthesis, cycles comprising 5 or 6 atoms have
been found to be particularly useful. An example of an aryl
substituent is a phenyl group.
[0494] The aryl group may be unsubstituted. A specific example of
an amidoxime bearing an unsubstituted aryl is:
##STR00189##
[0495] The aryl group may also be substituted with one or more
alkyl groups, heteroalkyl groups or hetero-atom substituents. If
more than one substituent is present, the substituents are
independently selected from one another.
[0496] One or more of the hetero-atom substituents may be for
example, a halogen atom, including fluorine, chlorine, bromine or
iodine, --OH, .dbd.O, --NH.sub.2, .dbd.NH, --NHOH, .dbd.NOH,
--OPO(OH).sub.2, --SH, .dbd.S or --SO.sub.2OH. In one embodiment,
the substituent is an oxime group (.dbd.NOH).
[0497] The one or more alkyl groups are the alkyl groups defined
previously and the one or more heteroalkyl groups are the
heteroalkyl groups defined previously. Specific examples of
substituted aryl amidoxime molecules are:
##STR00190##
[0498] R may also be hetero-aryl. The term hetero-aryl refers to an
aryl group containing one or more hetero-atoms in its aromatic
cycle. The one or more hetero-atoms are independently-selected
from, for example, boron, nitrogen, oxygen, silicon, phosphorus and
sulfur. Examples of hetero-aryl groups include pyrrole, furan,
thiophene, pyridine, melamine, pyran, thiine, diazine and
thiazine.
[0499] The hetero-aryl group may be unsubstituted. A specific
example of an unsubstituted heteroaryl amidoxime molecule is:
##STR00191##
[0500] It should be noted that the heteroaryl group may be attached
to the amidoxime group through its heteroatom, for example (the
following molecule being accompanied by a counter anion):
##STR00192##
[0501] The hetero-aryl group may be substituted with one or more
alkyl groups, heteroalkyl groups or hetero-atom substituents. If
more than one substituent is present, the substituents are
independently selected from one another.
[0502] One or more of the hetero-atom substituents may be, for
example, a halogen atom, including fluorine, chlorine, bromine or
iodine, --OH, .dbd.O, --NH.sub.2, .dbd.NH, --NHOH, .dbd.NOH,
--OPO(OH).sub.2, --SH, .dbd.S or --SO.sub.2OH. The one or more
alkyl groups are the alkyl groups defined previously and the one or
more heteroalkyl groups are the heteroalkyl groups defined
previously.
[0503] Within the scope of the term aryl are alkyl-aryl groups. The
term "alkyl-aryl" refers to an amidoxime group bearing (i.e.
directly joined to) an alkyl group. The alkyl group is then itself
substituted with an aryl group. Correspondingly, within the scope
of the term heteroaryl are alkyl-heteroaryl groups.
[0504] The alkyl group may be any alkyl group previously defined.
The aryl/heteroaryl group may also be any aryl group previously
defined.
[0505] Both the alkyl group and the aryl/heteroalkyl group may be
unsubstituted. Specific examples of unsubstituted alkyl-aryl
amidoxime molecules are:
##STR00193##
[0506] Alternatively, one or both of the alkyl group and the
aryl/heteroalkyl group may be substituted. If the alkyl group is
substituted, it may be substituted with one or more hetero-atoms or
groups containing hetero-atoms. If the aryl/heteroalkyl group is
substituted, it may be substituted with one or more alkyl groups,
heteroalkyl groups or hetero-atom substituents. If more than one
substituent is present, the substituents are independently selected
from one another.
[0507] One or more of the hetero-atom substituents may be, for
example, a halogen atom, including fluorine, chlorine, bromine or
iodine, --OH, .dbd.O, --NH.sub.2, .dbd.NH, --NHOH, .dbd.NOH,
--OPO(OH).sub.2, --SH, .dbd.S or --SO.sub.2OH. In one embodiment,
the substituent is an oxime group (.dbd.NOH). The alkyl group may
also be itself substituted with one or more amidoxime functional
groups.
[0508] If the alkyl group is substituted with .dbd.O, the alkyl
group may comprise an aldehyde, a ketone, a carboxylic acid or an
amide. Preferably, there is an enolizable hydrogen adjacent to the
.dbd.O, .dbd.NH or .dbd.NOH (i.e. there is a hydrogen in the alpha
position to the carbonyl). The alkyl group may comprise the
following functionality: -(CZ.sub.1)-CH-(CZ.sub.2)-, wherein
Z.sub.1 and Z.sub.2 are independently selected from O, NH and NOH.
The CH in this group is further substituted with hydrogen or an
alkyl group or heteroalkyl group or joined to the amidoxime
functional group.
[0509] Within the scope of the term aryl are also heteroalkyl-aryl
groups. The term "heteroalkyl-aryl" refers to an amidoxime group
bearing (i.e. directly joined to) an heteroalkyl group. The
heteroalkyl group is then itself substituted with an aryl group.
Correspondingly, within the scope of the term heteroaryl are also
heteroalkyl-aryl groups.
[0510] The heteroalkyl group may be any alkyl group previously
defined. The aryl/heteroaryl group may also be any aryl group
previously defined.
[0511] Both the heteroalkyl group and the aryl/heteroaryl group may
be unsubstituted. Alternatively, one or both of the heteroalkyl
group and the aryl/heteroaryl group may be substituted. If the
heteroalkyl group is substituted, it may be substituted with one or
more hetero-atoms or groups containing hetero-atoms. If the
aryl/heteroaryl group is substituted, it may be substituted with
one or more alkyl groups, heteroalkyl groups or hetero-atom
substituents. If more than one substituent is present, the
substituents are independently selected from one another.
[0512] One or more of the hetero-atom substituents may be, for
example, a halogen atom, including fluorine, chlorine, bromine or
iodine, --OH, .dbd.O, --NH.sub.2, .dbd.NH, --NHOH, .dbd.NOH,
--OPO(OH).sub.2, --SH, .dbd.S or --SO.sub.2OH. In one embodiment,
the substituent is an oxime group (.dbd.NOH). The alkyl group may
also be itself substituted with one or more amidoxime functional
groups.
[0513] If the heteroalkyl group is substituted with .dbd.O, the
heteroalkyl group may comprise an aldehyde, a ketone, a carboxylic
acid or an amide. Preferably, there is an enolizable hydrogen
adjacent to the .dbd.O, .dbd.NH or .dbd.NOH (i.e. there is a
hydrogen in the alpha position to the carbonyl). The heteroalkyl
group may comprise the following functionality:
-(CZ.sub.1)-CH-(CZ.sub.2)-, wherein Z.sub.1 and Z.sub.2 are
independently selected from O, NH and NOH. The CH in this group is
further substituted with hydrogen or an alkyl group or heteroalkyl
group or joined to the amidoxime functional group
[0514] A preferred substituent to any type of R group is a
tetra-valent nitrogen. In other words, any of the above groups may
be substituted with --NR.sub.aR.sub.bR.sub.cR.sub.d where R.sub.a
to R.sub.d are independently-selected R groups as defined herein.
In one embodiment, R.sub.a to R.sub.d are unsubstituted saturated
alkyl groups having 1 to 6 carbon atoms. For example, one or more
of (for example all of) R.sub.a to R.sub.d are methyl and/or ethyl.
With this substituent, the tetra-valent nitrogen is preferably
substituted in an antipodal position to the amidoxime group. For
example, if R is a straight-chained unsubstituted saturated alkyl
group of the form (CH.sub.2).sub.n, then the tetra-valent nitrogen
is at one end of the alkyl group and the amidoxime group is at the
other end. In this embodiment, n is preferably 1, 2, 3, 4, 5 or
6.
[0515] In one embodiment, the present invention provides an
amidoxime molecule that contains only one amidoxime functional
group. In another embodiment, the present invention provides an
amidoxime molecule containing two or more amidoxime functional
groups. In fact, a large number of functional groups can be
contained in a single molecule, for example if a polymer has
repeating units having appending amidoxime functional groups.
Examples of amidoxime compounds that contain more than one
amidoxime functional groups have been described previously
throughout the specification.
[0516] Amidoximes may be conveniently prepared from
nitrile-containing molecules as follows:
##STR00194##
[0517] Typically, to prepare a molecule having
R.sub.a.dbd.R.sub.b.dbd.H, hydroxylamine is used. If one or both of
R.sub.a and R.sub.b in the desired amidoxime is not hydrogen, the
amidoxime can be prepared either using the corresponding
hydroxylamine or by further reacting the amidoxime once it has been
formed. This may, for example, occur by intra-molecular reaction of
the amidoxime.
[0518] Accordingly, amidoxime molecules containing more than one
amidoxime functional groups can be conveniently prepared from
precursors having more than one nitrile group. Specific amidoxime
molecules having two amidoxime functional groups which have been
synthesised in this way include:
##STR00195##
[0519] One preferred method of forming the nitrile precursors to
the amidoximes of the present invention is by nucleophilic
substitution of a leaving group with a nucleophile. Nucleophiles
are well known to the person skilled in the art, see for example
the Guidebook to Mechanism in Organic Chemistry by Peter Sykes.
Examples of suitable nucleophiles are molecules having an OH, SH,
NH-- or a suitable CH-- group, for example one having a low
pK.sub.a (for example below about 15). For OH, SH and NH--, the
hydrogen is optionally removed before acting as a nucleophile in
order to augment its nucleophilicity. For CH--, they hydrogen is
usually removed with a suitable base so that it can act as a
nucleophile.
[0520] Leaving groups are well known to the person skilled in the
art, see for example the Guidebook to Mechanism in Organic
Chemistry by Peter Sykes. Examples of suitable leaving groups
include Cl, Br, I, O-tosyl, O-mesolate and other leaving group well
known to the person skilled in the art. The ability to act as a
leaving group may be enhanced by adding an acid, either protic or
Lewis.
[0521] For example, a nitrile can be formed accordingly:
##STR00196##
In this example, R.sub.3 is independently selected from alkylene,
heteroalkylene, arylene, heteroarylene, alkylene-heteroaryl, or
alkylene-aryl group. R.sub.n is independently selected from
hydrogen, alkyl, heteroalkyl, aryl, heteroaryl, alkyl-heteroaryl,
or alkyl-aryl group. X may be any a nucleophile selected from O, S,
N, and suitable C. N varies from 1 to 3. Y is a leaving group.
[0522] For X.dbd.NH--, the may be part of a primary or secondary
amine (i.e. NH.sub.2 or NHR.sub.5), NH--CO--, NH--CNH--, NH--CHOH--
or --NHNR.sub.5R.sub.6 (wherein R.sub.5 and R.sub.6 are
independently-selected alkyl, heteroalkyl, aryl, heteroaryl or
alkyl-aryl).
[0523] For XH.dbd.CH--, wherein a stabilized anion may be formed.
XH may be selected from but not limited to --CHCO--R.sub.5,
--CHCOOH, --CHCN, --CHCO--OR.sub.5, --CHCO--NR.sub.5R.sub.6,
--CHCNH--R.sub.5, --CHCNH--OR.sub.5, --CHCNH--NR.sub.5R.sub.6,
--CHCNOH--R.sub.5, --CHCNOH--OR.sub.5 and
--CHCNOH--NR.sub.5R.sub.6.
[0524] A preferred example is:
##STR00197##
for example
##STR00198##
wherein R.sub.5 and R.sub.6 are independently-selected alkyl,
heteroalkyl, aryl, heteroaryl or alkyl-aryl or a heteroatom
optionally substituted with any of these groups. In one embodiment,
either one or both of R.sub.5 and R.sub.6 are oxygen or nitrogen
atoms optionally independently substituted with alkyl, heteroalkyl,
aryl, heteroaryl or alkyl-aryl groups, for example:
##STR00199##
[0525] The compounds may also be formed by any type of nucleophilic
reaction using any of the above nucleophiles.
[0526] The inventors have found one reaction in particular to be
particularly versatile for producing nitrile precursors for
amidoxime compounds:
##STR00200##
[0527] In this example, X bears N independently-selected
substituents. Each R.sub.a is independently chosen from hydrogen,
alkyl, heteroalkyl, aryl, heteroaryl and alkylaryl as previously
defined. X is a nucleophile as previously defined. The
acrylonitrile may be substituted as desired.
[0528] For example, the acrylonitrile may have the following
formula:
##STR00201##
wherein R.sub.4, R.sub.5 and R.sub.6 are independently selected
from hydrogen, heteroatoms, heterogroups, alkyl, heteroalkyl, aryl
and heteroaryl.
[0529] Accordingly, the present invention also relates to amidoxime
compounds for use in semiconductor processing prepared by the
addition of a nucleophile to an unsubstituted or substituted
acrylonitrile. Once nucleophilic addition to the acrylonitrile has
occurred, the intermediate can be functionalized using standard
chemistry known to the person skilled in the art:
##STR00202##
where Y is a leaving group as previously defined.
[0530] Examples of simple nucleophiles with show the adaptability
of this reaction include:
##STR00203##
[0531] This reaction is particularly versatile, especially when
applied to the synthesis of multidentate amidoxime compounds (i.e.
molecules containing two or more amidoxime functional groups). For
example, it can be used to functionalize compounds having two or
more NH groups. In one example, the reaction can be used to
functionalize a molecule containing two or more primary amines.
[0532] For example:
##STR00204##
where n is 1 or more, for example 1 to 24.
[0533] Further functionalization of a primary amine is possible.
For example, a tetradentate amidoxime, for example the functional
equivalent of EDTA, may be conveniently formed:
##STR00205##
wherein R.sub.10 is alkyl, heteroalkyl, aryl or heteroaryl. In an
alternative conceived embodiment, R.sub.10 is nothing: the starting
material is hydrazine. An example of this reaction where R.sub.10
is CH.sub.2CH.sub.2 is provided in the examples.
[0534] In a related embodiment, a molecule having two or more
secondary amines can be functionalized:
##STR00206##
where R.sub.10 is defined as above and R.sub.11 and R.sub.12 are
independently selected alkyl, heteroalkyl, aryl or heteroaryl.
Again, an embodiment where R.sub.10 is nothing is contemplated.
[0535] For example, the secondary amines can be part of a cyclic
system:
##STR00207##
where R.sub.10 and R.sub.11 are defined above. For example, common
solvent used in semiconductor processing can be functionalized with
amidoxime functional groups. For example.
##STR00208##
Details of these reactions are contained in the examples.
[0536] Similarly, an oxygen nucleophile may be used to provide
nitrile precursors to amidoxime molecules. In one embodiment, the
nucleophile is an alcohol.
##STR00209##
where R.sub.3 is alkyl, heteroalkyl, aryl or heteroaryl.
[0537] For example, polyalcohol compounds may be functionalized.
Poly-alcohols are molecules that contain more than one alcohol
functional group. As an example, the following is a
polyalcohol.
##STR00210##
wherein n is 0 or more, for example 0 to 24. In one example, n is 0
(glycol). In another example, n is 6 (sorbitol).
[0538] In another example, the polyalcohol forms part of a polymer.
For example, reaction may be carried out with a polymer comprising
polyethylene oxide. For example, the polymer may contain just
ethylene oxide units, or may comprise polyethylene oxide units as a
copolymer (i.e. with one or more other monomer units). For example,
the polymer may be a block copolymer comprising polyethylene oxide.
For copolymers, especially block copolymers, the polymer may
comprise a monomer unit not containing alcohol units. For example,
the polymer may comprise blocks of polyethylene glycol (PEG).
Copolymer (e.g. block copolymers) of polyethylene oxide and
polyethylene glycol may be advantageous because the surfactant
properties of the blocks of polyethylene glycol can be used and
controlled.
[0539] Carbon nucleophiles can also be used. Many carbon
nucleophiles are known in the art. For example, an enol group can
act as a nucleophile. Harder carbon-based nucleophiles can be
generated by deprotonation of a carbon. While many carbons bearing
a proton can be deprotonated if a strong enough base is provided,
it is often more convenient to be able to use a weak base to
generate a carbon nucleophile, for example NaOEt or LDA. As a
result, in one embodiment, a CH group having a pK.sub.a of 20 or
less, for example 15 or less, is deprotonated to form the
carbon-based nucleophile.
[0540] An example of a suitable carbon-based nucleophile is a
molecule having the beta-diketone functionality (it being
understood that the term beta-diketone also covers aldehydes,
esters, amides and other C.dbd.O containing functional groups.
Furthermore, one or both of the C.dbd.O groups may be replaced by
NH or NOH).
[0541] For example:
##STR00211##
where R.sub.1 and R.sub.2 are independently selected alkyl groups,
heteroalkyl groups, aryl groups, heteroaryl groups and
heteroatoms.
[0542] A specific example of this reaction sequence where
R.sub.1.dbd.R.sub.2=OEt is given in the examples.
[0543] Nitrile groups themselves act to lower the pK.sub.a of
hydrogens in the alpha position. This in fact means that sometimes
control of reaction conditions is preferably used to prevent a
cyano compound, once formed by reaction of a nucleophile with
acrylonitrile, from deprotonating at its alpha position and
reacting with a second acrylonitrile group. For example, selection
of base and reaction conditions (e.g. temperature) can be used to
prevent this secondary reaction. However, this observation can be
taken advantage of to functionalize molecules that already contain
one or more nitrile functionalities. For example, the following
reaction occurs in basic conditions:
##STR00212##
[0544] The cyanoethylation process usually requires a strong base
as a catalyst. Most often such bases are alkali metal hydroxides
such as, e.g., sodium oxide, lithium hydroxide, sodium hydroxide
and potassium hydroxide. These metals, in turn, can exist as
impurities in the amidoxime compound solution. The existence of
such metals in the amidoxime compound solution is not acceptable
for use in electronic, and more specifically, semiconductor
manufacturing processes and as stabilizer for hydroxylamine
freebase and other radical sensitive reaction chemicals.
[0545] Preferred alkali bases are metal ion free organic ammonium
hydroxide compound, such as tetramethylammonium hydroxide,
trimethylbenzylammonium hydroxide and the like.
[0546] Water
[0547] Within the scope of this invention, water may be introduced
into the composition essentially only in chemically and/or
physically bound form or as a constituent of the raw materials or
compounds.
[0548] The composition further comprises chemicals from one or more
groups selecting from the following:
[0549] Solvent--From about 1% to 99% by weight.
[0550] The compositions of the present invention also include 0% to
about 99% by weight and more typically about 1% to about 80% by
weight of a water miscible organic solvent.where the solvent(s)
is/are preferably chosen from the group of water miscible organic
solvents.
[0551] Examples of water miscible organic solvents include, but are
not limited to, dimethylacetamide (DMAC), N-methylpyrrolidinone
(NMP), N-Ethyl pyrrolidone (NEP), N-Hydroxyethyl Pyrrolidone (HEP),
N-Cyclohexyl Pyrrolidone (CHP) dimethylsulfoxide (DMSO), Sulfolane,
dimethylformamide (DMF), N-methylformamide (NMF), formamide,
Monoethanol amine (MEA), Diglycolamine, dimethyl-2-piperidone
(DMPD), morpholine, N-morpholine-N-Oxide (NMNO), tetrahydrofurfuryl
alcohol, cyclohexanol, cyclohexanone, polyethylene glycols and
polypropylene glycols, glycerol, glycerol carbonate, triacetin,
ethylene glycol, propylene glycol, propylene carbonate, hexylene
glycol, ethanol and n-propanol and/or isopropanol, diglycol, propyl
or butyl diglycol, hexylene glycol, ethylene glycol methyl ether,
ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene
glycol mono-n-butyl ether, diethylene glycol methyl ether
diethylene glycol ethyl ether, propylene glycol methyl, ethyl or
propyl ether, dipropylene glycol methyl or ethyl ether, methoxy,
ethoxy or butoxy triglycol, I-butoxyethoxy-2-propanol,
3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, and
other amides, alcohols or pyrrolidones, ketones, sulfoxides, or
multifunctional compounds, such as hydroxyamides or aminoalcohols,
and mixtures of these solvents thereof. The preferred solvents,
when employed, are dimethyl acetamide and dimethyl-2-piperidone,
dimethylsufoxide and N-methylpyrrolidinone, diglycolamine, and
monoethanolamine.
[0552] Acids--From about 0.001% to 15% by weight
[0553] Possible acids are either inorganic acids or organic acids
provided these are compatible with the other ingredients.
[0554] Inorganic acids include hydrochloric acid, hydrofluoric
acid, sulfuric acid, phosphoric acid, phosphorous acid,
hypophosphorous acid, phosphonic acid, nitric acid, and the
like.
[0555] Organic acids include monomeric and/or polymeric organic
acids from the groups of unbranched saturated or unsaturated
monocarboxylic acids, of branched saturated or unsaturated
monocarboxylic acids, of saturated and unsaturated dicarboxylic
acids, of aromatic mono-, di- and tricarboxylic acids, of sugar
acids, of hydroxy acids, of oxo acids, of amino acids and/or of
polymeric carboxylic acids are preferred.
[0556] From the group of unbranched saturated or unsaturated
monocarboxylic acids: methanoic acid (formic acid), ethanoic acid
(acetic acid), propanoic acid (propionic acid), pentanoic acid
(valeric acid), hexanoic acid (caproic acid), heptanoic acid
(enanthic acid), octanoic acid (caprylic acid), nonanoic acid
(pelargonic acid), decanoic acid (capric acid), undecanoic acid,
dodecanoic acid (lauric acid), tridecanoic acid, tetradecanoic acid
(myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic
acid), heptadecanoic acid (margaric acid), octadecanoic acid
(stearic acid), eicosanoic acid (arachidic acid), docosanoic acid
(behenic acid), tetracosanoic acid (lignoceric acid), hexacosanoic
acid (cerotic acid), triacontanoic acid (melissic acid),
9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid
(petroselic acid), 6t-octadecenoic acid (petroselaidic acid),
9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid (elaidic
acid), 9c,12c-octadecadienoic acid (linoleic acid),
9t,12t-octadecadienoic acid (linolaidic acid) and
9c,12c,15c-octadecatrienoic acid (linolenic acid).
[0557] From the group of branched saturated or unsaturated
monocarboxylic acids: 2-methylpentanoic acid, 2-ethylhexanoic acid,
2-propylheptanoic acid, 2-butyloctanoic acid, 2-pentylnonanoic
acid, 2-hexyldecanoic acid, 2-heptylundecanoic acid,
2-octyldodecanoic acid, 2-nonyltridecanoic acid,
2-decyltetradecanoic acid, 2-undecylpentadecanoic acid,
2-dodecylhexadecanoic acid, 2-tridecylheptadecanoic acid,
2-tetradecyloctadecanoic acid, 2-pentadecylnonadecanoic acid,
2-hexadecyleicosanoic acid, 2-heptadecylheneicosanoic acid.
[0558] From the group of unbranched saturated or unsaturated di- or
tricarboxylic acids: propanedioic acid (malonic acid), butanedioic
acid (succinic acid), pentanedioic acid (glutaric acid),
hexanedioic acid (adipic acid), heptanedioic acid (pimelic acid),
octanedioic acid (suberic acid), nonanedioic acid (azelaic acid),
decanedioic acid (sebacic acid), 2c-butenedioic acid (maleic acid),
2t-butenedioic acid (fumaric acid), 2-butynedicarboxylic acid
(acetylenedicarboxylic acid).
[0559] From the group of aromatic mono-, di- and tricarboxylic
acids: benzoic acid, 2-carboxybenzoic acid (phthalic acid),
3-carboxybenzoic acid (isophthalic acid), 4-carboxybenzoic acid
(terephthalic acid), 3,4-dicarboxybenzoic acid (trimellitic acid),
and 3,5-dicarboxybenzoic acid (trimesionic acid).
[0560] From the group of sugar acids, galactonic acid, mannonic
acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid,
2-deoxyribonic acid, alginic acid.
[0561] From the group of hydroxy acids: hydroxyphenylacetic acid
(mandelic acid), 2-hydroxypropionic acid (lactic acid),
hydroxysuccinic acid (malic acid), 2,3-dihydroxybutanedioic acid
(tartaric acid), 2-hydroxy-1,2,3-propanetricarboxylic acid (citric
acid), ascorbic acid, 2-hydroxybenzoic acid (salicylic acid), and
3,4,5-trihydroxybenzoic acid (gallic acid).
[0562] From the group of oxo acids: 2-oxopropionic acid (pyruvic
acid) and 4-oxopentanoic acid (levulinic acid).
[0563] From the group of amino acids: alanine, valine, leucine,
isoleucine, proline, tryptophan, phenylalanine, methionine,
glycine, serine, tyrosine, threonine, cysteine, asparagine,
glutamine, aspartic acid, glutamic acid, lysine, arginine, and
histidine.
[0564] Bases--from about 1% to 45% by weight
[0565] Possible bases are either inorganic bases or organic bases
provided these are compatible with the other ingredients.
[0566] Inorganic bases include sodium hydroxide, lithium hydroxide,
potassium hydroxide, ammonium hydroxide and the like.
[0567] Organic bases including organic amines, and quaternary
alkylammonium hydroxide which may include, but are not limited to,
tetramethylammonium hydroxide (TMAH), TMAH pentahydrate,
benzyltetramethylammonium hydroxide (BTMAH), TBAH, choline, and
Tris(2-hydroxyethyl)methylammonium hydroxide (TEMAH).
[0568] Activator--from about 0.001% to 25% by weight
[0569] According to the present invention, the cleaning
compositions comprise one or more substances from the group of
activators, in particular from the groups of polyacylated
alkylenediamines, in particular tetraacetylethylenediamine (TAED),
N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated
phenolsulfonates, in particular n-nonanoyl- or
isononanoyloxybenzenesulfonate (n- or iso-NOBS) and
n-methylmorpholiniumacetonitrile, methylsulfate (MMA), and "nitrile
quaternary" compound in amounts of from 0.1 to 20% by weight,
preferably from 0.5 to 15% by weight and in particular from 1 to
10% by weight, in each case based on the total composition to
enhance the oxidation/reduction performance of the cleaning
solutions. The "nitrile quats", cationic nitrites has the
formula,
##STR00213##
[0570] Compounds having oxidation and reduction potential--From
about 0.001% to 25% by weight.
[0571] These compounds include hydroxylamine and its salts, such as
hydroxylamine chloride, hydroxylamine nitrate, hydroxylamine
sulfate, hydroxylamine phosphate or its derivatives, such as
N,N-diethylhydroxylamine, N-Phenylhydroxylamine.
[0572] Hydrazine and its derivatives; hydrogen peroxide; persulfate
salts of ammonium, potassium and sodium, permanganate salt of
potassium, sodium; and other sources of peroxide are selected from
the group consisting of: perborate monohydrate, perborate
tetrahydrate, percarbonate, salts thereof, and combinations
thereof. For environmental reasons, hydroxylamine phosphate is not
preferred.
[0573] Other compounds which may be used as ingredients within the
scope of the present invention are the diacyl peroxides, such as,
for example, dibenzoyl peroxide. Further typical organic compounds
which have oxidation/reduction potentials are the peroxy acids,
particular examples being the alkyl peroxy acids and the aryl
peroxy acids. Preferred representatives are (a) peroxybenzoic acid
and its ring substituted derivatives, such as alkylperoxybenzoic
acids, but also peroxy-a-naphthoic acid and magnesium
monoperphthalate, (b) the aliphatic or substituted aliphatic peroxy
acids, such as peroxylauric acid, peroxystearic acid,
c-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid
(PAP)], o-carboxybenzamidoperoxycaproic acid,
N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and
(c) aliphatic and araliphatic peroxydicarboxylic acids, such as
1,2-diperoxycarhoxylic acid, 1,9-diperoxyazelaic acid,
diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic
acids, 2-decyldiperoxybutane-1,4-dioic acid,
N,N-terephthaloyldi(6-aminopercaproic acid) may be used.
[0574] Other Chelating agents--Preferably, the cleaning composition
comprises (by weight of the composition) from 0.0% to 15% of
additional one or more chelant.
[0575] A further possible group of ingredients are the chelate
complexing agents. Chelate complexing agents are substances which
form cyclic compounds with metal ions, where a single ligand
occupies more than one coordination site on a central atom, i.e. is
at least "bidentate". In this case, stretched compounds are thus
normally closed by complex formation via an ion to give rings. The
number of bonded ligands depends on the coordination number of the
central ion.
[0576] Complexing groups (ligands) of customary complex forming
polymers are iminodiacetic acid, hydroxyquinoline, thiourea,
guanidine, dithiocarbamate, hydroxamic acid, amidoxime,
aminophosphoric acid, (cycl.) polyamino, mercapto, 1,3-dicarbonyl
and crown ether radicals, some of which have very specific
activities toward ions of different metals.
[0577] For the purposes of the present invention, it is possible to
use complexing agents of the prior art. These may belong to
different chemical groups. Preferred chelating/complexing agents
include the following, individually or in a mixture with one
another:
[0578] 1) polycarboxylic acids in which the sum of the carboxyl and
optionally hydroxyl groups is at least 5, such as gluconic
acid.
[0579] 2) nitrogen-containing mono- or polycarboxylic acids, such
as ethylenediaminetetraacetic acid (EDTA),
N-hydroxyethylethylenediaminetriacetic acid,
diethylenetriaminepentaacetic acid, hydroxy-ethyliminodiacetic
acid, nitridodiacetic acid-3-propionic acid, isoserinediacetic
acid, N,N-di(.beta.-hydroxyethyl)glycine,
N-(1,2-dicarboxy-2-hydroxyethyl)glycine,
N-(1,2-dicarboxy-2-hydroxyethyl)-aspartic acid or nitrilotriacetic
acid (NTA),
[0580] 3) geminal diphosphonic acids, such as
1-hydroxyethane-1,1-diphosphonic acid (HEDP), higher homologs
thereof having up to 8 carbon atoms, and hydroxy or amino
group-containing derivatives thereof and
1-aminoethane-1,1-diphosphonic acid, higher homologs thereof having
up to 8 carbon atoms, and hydroxy or amino group-containing
derivatives thereof,
[0581] 4) aminophosphonic acids, such as
ethylenediamine-tetra(methylenephosphonic acid),
diethylenetriaminepenta (methylenephosphonic acid) or
nitrilotri(methylenephosphonic acid),
[0582] 5) phosphonopolycarboxylic acids, such as
2-phosphonobutane-1,2,4-tricarboxylic acid, and
[0583] f) cyclodextrins.
[0584] Surfactants--From about 10 ppm to 5%.
[0585] The compositions according to the invention may thus also
comprise anionic, cationic, and/or amphoteric surfactants as
surfactant component.
[0586] Source of fluoride ions--From an amount about 0.001% to
10%.
[0587] Sources of fluoride ions include, but are not limited to,
ammonium bifluoride, ammonium fluoride, hydrofluoric acid, sodium
hexafluorosilicate, fluorosilicic acid and tetrafluoroboric
acid.
[0588] The components of the claimed compositions can be metered
and mixed in situ just prior dispensing to the substrate surface
for treatment. Furthermore, analytical devices can be installed to
monitor the composition and chemical ingredients can be
re-constituted to mixture to the specification to deliver the
cleaning performance. Critical parameters that can be monitored
includes physical and chemical properties of the composition, such
as pH, water concentration, oxidation/reduction potential and
solvent components.
[0589] The composition claims a range at point of use and also as
mixtures which can be diluted to meet the specific cleaning
requirements.
[0590] Summary of preferred amidoxime compounds from nitriles and
not limited to
TABLE-US-00035 Nitrile (N) Amidoxime (AO) 3 3-hydroxypropionitrile
N',3-dihydroxypropanimidamide 4 Acetonitrile
NN'-hydroxyacetimidamide 5 3-
N'-hydroxy-3-(methylamino)propanimidamide methylaminopropionitrile
6 Benzonitrile N'-hydroxybenzimidamide 8 3,3' iminodipropionitrile
3,3'-azanediylbis(N'-hydroxypropanimidamide) 9 octanonitrile
N'-hydroxyoctanimidamide 10 3-phenylpropionitrile
N'-hydroxy-3-phenylpropanimidamide 11 ethyl 2-cyanoacetate
3-amino-N-hydroxy-3-(hydroxyimino)propanamide 12 2-cyanoacetic acid
3-amino-3-(hydroxyimino)propanoic acid 13 2-cyanoacetamide
3-amino-3-(hydroxyimino)propanamide 15 adiponitrile
N'1,N'6-dihydroxyadipimidamide 16 sebaconitrile
N'1,N'10-dihydroxydecanebis(imidamide) 17 4-pyridinecarbonitrile
N'-hydroxyisonicotinimidamide 18 m-tolunitrile
N'-hydroxy-3-methylbenzimidamide 19 phthalonitrile
isoindoline-1,3-dione dioxime 20 glycolonitrile
N',2-dihydroxyacetimidamide 21 chloroacetonitrile
2-chloro-N'-hydroxyacetimidamide 22 benzyl cyanide product
N'-hydroxy-2-phenylacetimidamide 24 Anthranilonitrile
2-amino-N'-hydroxybenzimidamide 25 3,3' iminodiacetonitrile
2,2'-azanediylbis(N'-hydroxyacetimidamide) 26 5-cyanophthalide
N'-hydroxy-1-oxo-1,3-dihydroisobenzofuran-5-carboximidamide 27
2-cyanophenylacetonitrile 3-aminoisoquinolin-1(4H)-one oxime or
3-(hydroxyamino)-3,4- dihydroisoquinolin-1-amine 29 cinnamonitrile
N'-hydroxycinnamimidamide 30 5-hexynenitrile
4-cyano-N'-hydroxybutanimidamide 31 4-chlorobenzonitrile
4-chloro-N'-hydroxybenzimidamide
[0591] For example, N3 represents 3-hydroxypropionitrile and AO3 is
N',3-dihydroxypropanimidamide from reacting 3-hydroxypropionitrile
with hydroxylamine to form its corresponding amidoxime
[0592] Summary of preferred amidoxime compounds from nitriles by
cyanoethylation of nucleophilic compounds and not limited to the
list below:
TABLE-US-00036 Nucleophilic Cyanoethylated Compounds Amidoxime from
cyanoethylated ID compounds (CE) compounds (AO) 01 Sorbitol
1,2,3,4,5,6-hexakis-O-(2-
1,2,3,4,5,6-hexakis-O-[3-(hydroxyamino)-3- cyanoetyl)hexitol
iminopropyl Hexitol, 07 ethylenediamine 3,3',3'',3'''-(ethane-1,2-
3,3',3'',3'''-(ethane-1,2- diylbis(azanetriyl))tetrapropanenitrile
diylbis(azanetriyl))tetrakis(N'- hydroxypropanimidamide) 28
ethylene glycol 3,3'-(ethane-1,2-
3,3'-(ethane-1,2-diylbis(oxy))bis(N'- diylbis(oxy))dipropanenitrile
hydroxypropanimidamide) 34 diethylamine 3-(diethylamino)propane
nitrile 3-(diethylamino)-N'- hydroxypropanimidamide 35 piperazine
3,3'-(piperazine-1,4- 3,3'-(piperazine-1,4-diyl)bis(N'-
diyl)dipropanenitrile hydroxypropanimidamide) 36 2-ethoxyethanol
3-(2-ethoxyethoxy) 3-(2-ethoxyethoxy)-N'- propanenitrile
hydroxypropanimidamide 37 2-(2- 3-(2-(2-(dimethylamino)
3-(2-(2-(dimethylamino)ethoxy)ethoxy)-N'- dimethylamino
ethoxy)ethoxy) propanenitrile hydroxypropanimidamide ethoxy)ethanol
38 isobutyraldehyde 4,4-dimethyl-5-oxo N'-hydroxy-4,4-dimethyl-5-
pentanenitrile oxopentanimidamide 39 diethyl malonate diethyl
2,2-bis(2-cyanoethyl) 2,2-bis(3-amino-3- malonate
(hydroxyimino)propyl)malonic acid 40 aniline 3-(phenylamino)
propanenitrile N'-hydroxy-3-(phenylamino) propanimidamide 41
ammonia 3,3',3''-nitrilotri propanenitrile 3,3',3''-nitrilotris(N'-
hydroxypropanimidamide) 42 diethyl malonate 2,2-bis(2-cyanoethyl)
malonic 2,2-bis(3-amino-3- acid (hydroxyimino)propyl)malonic acid
43 Glycine (Mono 2-(2-cyanoethylamino)acetic 2-(3-amino-3-
cyanoethylated) acid (hydroxyimino)propylamino)acetic acid 44
Glycine 2-(bis(2-cyanoethyl)amino) 2-(bis(3-amino-3-
(Dicyanothylated) acetic acid (hydroxyimino)propyl)amino)acetic
acid 45 malononitrile propane-1,1,3-tricarbonitrile
N1,N'1,N'3-trihydroxypropane-1,1,3- tris(carboximidamide) 46
cyanoacetamide 2,4-dicyano-2-(2- 5-amino-2-(3-amino-3-
cyanoethyl)butanamide (hydroxyimino)propyl)-2-(N'-
hydroxycarbamimidoyl)-5- (hydroxyimino)pentanamide 47
Pentaerythritol 3,3'-(2,2-bis((2-cyanoethoxy)
3,3'-(2,2-bis((3-(hydroxyamino)-3- methyl) propane-1,3-
iminopropoxy)methyl)propane-1,3- diyl)bis(oxy) dipropanenitrile
diyl)bis(oxy)bis(N- hydroxypropanimidamide) 48 N-methyl
3,3'-(2,2'-(methylazanediyl)
3,3'-(2,2'-(methylazanediyl)bis(ethane-2,1- diethanol amine
bis(ethane-2,1-diyl) diyl)bis(oxy))bis(N'- bis(oxy)dipropanenitrile
hydroxypropanimidamide) 49 glycine anhydride
3,3'-(2,5-dioxopiperazine-1,4-
3,3'-(2,5-dioxopiperazine-1,4-diyl)bis(N'- diyl)dipropanenitrile
hydroxypropanimidamide) 50 acetamide N,N-bis(2-cyanoethyl)acetamide
N,N-bis(3-amino-3- (hydroxyimino)propyl)acetamide 51
anthranilonitrile 3,3'-(2-cyanophenylazanediyl) 3,3'-(2-N'-
dipropanenitrile hydroxycarbamimidoyl)phenylazanediyl)bis
(N'-hydroxypropanimidamide) 52 diethanolamine 3,3'-(2,2'-(2-
3,3'-(2,2'-(3-amino-3- cyanoethylazanediyl)bis(ethane-
(hydroxyimino)propylazanediyl)bis(ethane-
2,1-diyl)bis(oxy))dipropane 2,1-diyl))bis(oxy)bis(N'- nitrile
hydroxypropanimidamide)
[0593] For example, CE36 represents cyanoethylated product of
ethylene glycol and AO36 is from reacting 3-(2-ethoxyethoxy)
propanenitrile with hydroxylamine to form its corresponding
amidoxime.
[0594] While the invention has been described and illustrated
herein by references to various specific materials, procedures and
examples, it is understood that the invention is not restricted to
the particular combinations of materials and procedures selected
for that purpose. Numerous variations of such details can be
implied as will be appreciated by those skilled in the art. It is
intended that the specification and examples be considered as
exemplary, only, with the true scope and spirit of the invention
being indicated by the following claims. All references, patents,
and patent applications referred to in this application are herein
incorporated by reference in their entirety.
* * * * *