U.S. patent application number 15/115165 was filed with the patent office on 2016-11-24 for post chemical mechanical polishing formulations and method of use.
The applicant listed for this patent is ADVANCED TECHNOLOGY MATERIALS, INC., ATMI TAIWAN CO., LTD.. Invention is credited to Jeffrey A. BARNES, Shrane Ning JENQ, Jun LIU, Steven MEDD, Laisheng SUN, Peng ZHANG.
Application Number | 20160340620 15/115165 |
Document ID | / |
Family ID | 53757723 |
Filed Date | 2016-11-24 |
United States Patent
Application |
20160340620 |
Kind Code |
A1 |
SUN; Laisheng ; et
al. |
November 24, 2016 |
POST CHEMICAL MECHANICAL POLISHING FORMULATIONS AND METHOD OF
USE
Abstract
A cleaning composition and process for cleaning post-chemical
mechanical polishing (CMP) residue and contaminants from a
microelectronic device having said residue and contaminants
thereon. The cleaning compositions are substantially devoid of
alkali hydroxides, alkaline earth metal hydroxides, and
tetramethylammonium hydroxide. The composition achieves highly
efficacious cleaning of the post-CMP residue and contaminant
material from the surface of the microelectronic device without
compromising the low-k dielectric material or the copper
interconnect material.
Inventors: |
SUN; Laisheng; (Danbury,
CT) ; ZHANG; Peng; (Montvale, NJ) ; LIU;
Jun; (Brookfield, CT) ; MEDD; Steven;
(Danbury, CT) ; BARNES; Jeffrey A.; (Danielsville,
PA) ; JENQ; Shrane Ning; (Hsin-chu, TW) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ADVANCED TECHNOLOGY MATERIALS, INC.
ATMI TAIWAN CO., LTD. |
Danbury
Hsin-chu |
CT |
US
TW |
|
|
Family ID: |
53757723 |
Appl. No.: |
15/115165 |
Filed: |
January 29, 2015 |
PCT Filed: |
January 29, 2015 |
PCT NO: |
PCT/US2015/013521 |
371 Date: |
July 28, 2016 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61933015 |
Jan 29, 2014 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01L 21/02063 20130101;
H01L 21/02065 20130101; C11D 7/32 20130101; C11D 11/0047 20130101;
C11D 3/0073 20130101; C23G 1/20 20130101; C11D 3/30 20130101; C11D
7/3209 20130101; C11D 1/62 20130101; H01L 21/02074 20130101 |
International
Class: |
C11D 11/00 20060101
C11D011/00; H01L 21/02 20060101 H01L021/02; C11D 3/30 20060101
C11D003/30; C11D 1/62 20060101 C11D001/62; C11D 3/00 20060101
C11D003/00 |
Claims
1. A cleaning composition comprising at least one quaternary base,
at least one organic amine, at least one corrosion inhibitor, and
at least one solvent, wherein the corrosion inhibitor is selected
from the group consisting of 4-methylpyrazole, pyrazole,
2-amino-thiazole, 2-amino-1,3,4-thiadiazole, pterine, pyrazine,
cytosine, pyridazine, derivatives thereof, and combinations
thereof, and wherein the cleaning composition is substantially
devoid of alkali hydroxides, alkaline earth metal hydroxides, and
tetramethylammonium hydroxide.
2. The cleaning composition of claim 1, wherein the at least one
organic amine comprises a species selected from the group
consisting of aminoethylethanolamine, N-methylaminoethanol,
aminoethoxyethanol, dimethylaminoethoxyethanol, diethanolamine,
N-methyldiethanolamine, monoethanolamine, triethanolamine,
1-amino-2-propanol, 3-amino-1-propanol, diisopropylamine,
isopropylamine, 2-amino-1-butanol, isobutanolamine, other
C.sub.1-C.sub.8 alkanolamines, triethylenediamine, ethylenediamine,
hexamethylenediamine, diethylenetriamine, triethylamine,
trimethylamine, 1-methoxy-2-aminoethane, tetraethylenepentamine
(TEPA), 4-(2-hydroxyethyl)morpholine (HEM), N-aminoethylpiperazine
(N-AEP), ethylenediaminetetraacetic acid (EDTA),
1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid (CDTA),
glycine/ascorbic acid, iminodiacetic acid (IDA),
2-(hydroxyethyl)iminodiacetic acid (HIDA), nitrilotriacetic acid,
thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, glycine,
alanine, arginine, asparagine, aspartic acid, cysteine, glutamic
acid, glutamine, histidine, isoleucine, leucine, lysine,
methionine, phenylalanine, piperadine, N-(2-aminoethyl) piperadine,
proline, pyrrolidine, serine, threonine, tryptophan, tyrosine,
valine, and combinations thereof.
3. The cleaning composition of claim 1, wherein the at least one
quaternary base comprises a species selected from the group
consisting of tetraethylammonium hydroxide (TEAH),
tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide
(TBAH), tributylmethylammonium hydroxide (TBMAH),
benzyltrimethylammonium hydroxide (BTMAH), choline hydroxide,
tris(2-hydroxyethyl)methyl ammonium hydroxide,
diethyldimethylammonium hydroxide, choline hydroxide, and
combinations thereof.
4. The cleaning composition of claim 1, further comprising at least
one complexing agent, wherein the at least one complexing agent
comprises a species selected from the group consisting of acetic
acid, acetone oxime, acrylic acid, adipic acid, alanine, arginine,
asparagine, aspartic acid, betaine, dimethyl glyoxime, formic acid,
fumaric acid, gluconic acid, glutamic acid, glutamine, glutaric
acid, glyceric acid, glycerol, glycolic acid, glyoxylic acid,
histidine, iminodiacetic acid, isophthalic acid, itaconic acid,
lactic acid, leucine, lysine, maleic acid, maleic anhydride, malic
acid, malonic acid, mandelic acid, 2,4-pentanedione, phenylacetic
acid, phenylalanine, phthalic acid, proline, propionic acid,
pyrocatecol, pyromellitic acid, quinic acid, serine, sorbitol,
succinic acid, tartaric acid, terephthalic acid, trimellitic acid,
trimesic acid, tyrosine, valine, xylitol, ethylenediamine, oxalic
acid, tannic acid, benzoic acid, ammonium benzoate, catechol,
pyrogallol, resorcinol, hydroquinone, cyanuric acid, barbituric
acid, 1,2-dimethylbarbituric acid, pyruvic acid, phosphonic acid,
1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), propanethiol,
benzohydroxamic acids, salts and derivatives thereof, and
combinations thereof.
5. The cleaning composition of claim 1, wherein the solvent
comprises water.
6. The cleaning composition of claim 1, further comprising residue
and contaminants, wherein the residue comprises post-CMP residue,
post-etch residue, post-ash residue, or combinations thereof.
7. (canceled)
8. (canceled)
9. The cleaning composition of claim 1, wherein the composition is
substantially devoid of at least one of oxidizing agents;
fluoride-containing sources; abrasive materials; and combinations
thereof.
10. A method of removing residue and contaminants from a
microelectronic device having said residue and contaminants
thereon, said method comprising contacting the microelectronic
device with a cleaning composition of claim 1 for sufficient time
to at least partially clean said residue and contaminants from the
microelectronic device.
11. A cleaning composition comprising at least one cleaning
additive, at least one complexing agent, and at least one basic
compound, wherein the composition is substantially devoid of
amines, alkali hydroxides, alkaline earth metal hydroxides, and
tetramethylammonium hydroxide.
12. (canceled)
13. The cleaning composition of claim 11, wherein the at least one
basic compound is a species selected from the group consisting of
(NR.sup.1R.sup.2R.sup.3R.sup.4)OH,
(PR.sup.1R.sup.2R.sup.3R.sup.4)OH,
(R.sup.1R.sup.2N)(R.sup.3R.sup.4N)C.dbd.NR.sup.5, and any
combination thereof, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 may be the same as or different from one another and are
selected from the group consisting of hydrogen, straight-chained
C.sub.1-C.sub.6 alkyl, branched C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkanol, substituted C.sub.6-C.sub.10 aryl,
unsubstituted C.sub.6-C.sub.10 aryl,
CH.sub.2CH.sub.2CH.sub.2C(H)NH.sub.2COOH, and any combination
thereof, with the proviso that when the basic compound is
(NR.sup.1R.sup.2R.sup.3R.sup.4)OH, R.sup.1, R.sup.2, R.sup.3 and
R.sup.4 cannot simultaneously be methyl.
14. The cleaning composition of claim 11, wherein the at least one
basic compound is selected from the group consisting of
tetrabutylphosphonium hydroxide (TBPH), tetramethylphosphonium
hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium
hydroxide, benzyltriphenylphosphonium hydroxide, methyl
triphenylphosphonium hydroxide, ethyl triphenylphosphonium
hydroxide, N-propyl triphenylphosphonium hydroxide,
tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide
(TPAH), tetrabutylammonium hydroxide (TBAH), trimethylethylammonium
hydroxide, diethyldimethylammonium hydroxide,
tributylmethylammonium hydroxide (TBMAH), benzyltrimethylammonium
hydroxide (BTMAH), choline hydroxide, tetrabutylphosphonium
hydroxide, guanidine acetate, 1,1,3,3-tetramethyl guanidine,
guanidine carbonate, arginine, and combinations thereof.
15. The cleaning composition of claim 11, wherein the complexing
agent comprises at least one species selected from the group
consisting of ethylenediaminetetraacetic acid (EDTA),
1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid (CDTA),
4-(2-hydroxyethyl)morpholine (HEM), N-aminoethylpiperazine (N-AEP),
glycine, ascorbic acid, iminodiacetic acid (IDA),
2-(hydroxyethyl)iminodiacetic acid (HIDA), nitrilotriacetic acid,
alanine, arginine, asparagine, aspartic acid, cysteine, glutamic
acid, glutamine, histidine, isoleucine, leucine, lysine,
methionine, phenylalanine, proline, serine, threonine, tryptophan,
tyrosine, valine, gallic acid, boric acid, acetic acid, acetone
oxime, acrylic acid, adipic acid, betaine, dimethyl glyoxime,
formic acid, fumaric acid, gluconic acid, glutaric acid, glyceric
acid, glycolic acid, glyoxylic acid, isophthalic acid, itaconic
acid, lactic acid, maleic acid, maleic anhydride, malic acid,
malonic acid, mandelic acid, 2,4-pentanedione, phenylacetic acid,
phthalic acid, proline, propionic acid, pyrocatecol, pyromellitic
acid, quinic acid, sorbitol, succinic acid, tartaric acid,
terephthalic acid, trimellitic acid, trimesic acid, tyrosine,
xylitol,
1,5,9-triazacyclododecane-N,N',N''-tris(methylenephosphonic acid)
(DOTRP),
1,4,7,10-tetraazacyclododecane-N,N',N'',N'''-tetrakis(methylenep-
hosphonic acid) (DOTP), nitrilotris(methylene)triphosphonic acid,
diethylenetriaminepenta(methylenephosphonic acid) (DETAP),
aminotri(methylenephosphonic acid),
1-hydroxyethylidene-1,1-diphosphonic acid (HEDP),
bis(hexamethylene)triamine phosphonic acid,
1,4,7-triazacyclononane-N,N',N''-tris(methylenephosphonic acid
(NOTP), dimercaprol, 1,2-propanedithiol, 1,2-dimercaptopropane,
Ethanol, 2,2-dimercapto-(9CI), salts and derivatives thereof, and
combinations thereof, preferably cysteine.
16. The cleaning composition of claim 11, wherein the at least one
cleaning additive comprises a species selected from the group
consisting of citric acid, ethylenediaminetetraacetic acid (EDTA),
1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), glutamic acid,
iminodiacetic acid, sulfosalicylic acid, methanesulfonic acid,
salicylic acid, phthalic acid, benzene sulfonic acid, oxalic acid,
lactic acid, and combinations thereof.
17. The cleaning composition of claim 11, wherein the composition
further comprises at least one metal corrosion inhibitor selected
from the group consisting of adenosine, adenine, pyrazole,
1,2,4-triazole, 1,2,3-triazole, imidazole, 3-amino-1,2,4-triazole
1H-pyrazole-4-carboxylic acid, 3-amino-5-tert-butyl-1H-pyrazole,
5-amino-1H-tetrazole, 4-methylpyrazole, derivatives thereof, and
combinations thereof.
18. The cleaning composition of claim 11, wherein the composition
further comprises at least one reducing agent selected from the
group consisting of ascorbic acid, L(+)-ascorbic acid, isoascorbic
acid, ascorbic acid derivatives, gallic acid, formamidinesulfinic
acid, uric acid, tartaric acid, and any combination thereof,
preferably ascorbic acid, tartaric acid, or a combination
thereof.
19. The cleaning composition of claim 11, wherein the composition
further comprises at least one surfactant selected from the group
consisting of SURFONYL.RTM. 104, TRITON.RTM. CF-21, TRITON.RTM.
CF-10, TRITON.RTM. X-100, ZONYL.RTM. UR, ZONYL.RTM. FSO-100,
ZONYL.RTM. FSN-100, PLURONIC F-127, 3M Fluorad fluorosurfactants,
dioctylsulfosuccinate salt, 2,3-dimercapto-1-propanesulfonic acid
salt, polyethylene glycols, polypropylene glycols, polyethylene
glycol ethers, polypropylene glycol ethers, carboxylic acid salts,
alkyl benzene sulfonic acids, amphiphilic fluoropolymers,
C.sub.8-C.sub.18 alkyl phosphate ethers, carboxylic acid salts,
dodecylbenzenesulfonic acid, alkylaryl phosphonic acids,
polyacrylate polymers, dinonylphenyl polyoxyethylene,
polyethoxylated sorbitans, sorbitans, silicone polymers, modified
silicone polymers, acetylenic diols, modified acetylenic diols,
alkylammonium salts, modified alkylammonium salts, sodium dodecyl
sulfate, perfluoropolyether surfactants, 2-sulfosuccinate salts,
phosphate-based surfactants, sulfur-based surfactants,
acetoacetate-based polymers, and combinations thereof.
20. The cleaning composition of claim 11, wherein the cleaning
composition comprises water.
21. The cleaning composition of claim 11, further comprising
residue and contaminants, wherein the residue comprises post-CMP
residue, post-etch residue, post-ash residue, or combinations
thereof.
22. (canceled)
23. (canceled)
24. The cleaning composition of claim 11, wherein the composition
is substantially devoid of at least one of oxidizing agents;
fluoride-containing sources; abrasive materials; and combinations
thereof.
25. A method of removing residue and contaminants from a
microelectronic device having said residue and contaminants
thereon, said method comprising contacting the microelectronic
device with a cleaning composition of claim 11 for sufficient time
to at least partially clean said residue and contaminants from the
microelectronic device.
Description
FIELD
[0001] The present invention relates generally to compositions
including corrosion inhibitors for cleaning residue and/or
contaminants from microelectronic devices having same thereon.
DESCRIPTION OF THE RELATED ART
[0002] Microelectronic device wafers are used to form integrated
circuits. The microelectronic device wafer includes a substrate,
such as silicon, into which regions are patterned for deposition of
different materials having insulative, conductive or
semi-conductive properties.
[0003] In order to obtain the correct patterning, excess material
used in forming the layers on the substrate must be removed.
Further, to fabricate functional and reliable circuitry, it is
important to prepare a flat or planar microelectronic wafer surface
prior to subsequent processing. Thus, it is necessary to remove
and/or polish certain surfaces of a microelectronic device
wafer.
[0004] Chemical Mechanical Polishing or Planarization ("CMP") is a
process in which material is removed from a surface of a
microelectronic device wafer, and the surface is polished (more
specifically, planarized) by coupling a physical process such as
abrasion with a chemical process such as oxidation or chelation. In
its most rudimentary form, CMP involves applying slurry, e.g., a
solution of an abrasive and an active chemistry, to a polishing pad
that buffs the surface of a microelectronic device wafer to achieve
the removal, planarization, and polishing processes. It is not
desirable for the removal or polishing process to be comprised of
purely physical or purely chemical action, but rather the
synergistic combination of both in order to achieve fast, uniform
removal. In the fabrication of integrated circuits, the CMP slurry
should also be able to preferentially remove films that comprise
complex layers of metals and other materials so that highly planar
surfaces can be produced for subsequent photolithography, or
patterning, etching and thin-film processing.
[0005] Recently, copper has been increasingly used for metal
interconnects in integrated circuits. In copper damascene processes
commonly used for metallization of circuitry in microelectronic
device fabrication, the layers that must be removed and planarized
include copper layers having a thickness of about 1-1.5 .mu.m and
copper seed layers having a thickness of about 0.05-0.15 .mu.m.
These copper layers are separated from the dielectric material
surface by a layer of barrier material, typically about 50-300
.ANG. thick, which prevents diffusion of copper into the oxide
dielectric material. One key to obtaining good uniformity across
the wafer surface after polishing is to use a CMP slurry that has
the correct removal selectivities for each material.
[0006] The foregoing processing operations, involving wafer
substrate surface preparation, deposition, plating, etching and
chemical mechanical polishing, variously require cleaning
operations to ensure that the microelectronic device product is
free of contaminants that would otherwise deleteriously affect the
function of the product, or even render it useless for its intended
function. Often, particles of these contaminants are smaller than
0.3 .mu.m.
[0007] One particular issue in this respect is the residues that
are left on the microelectronic device substrate following CMP
processing. Such residues include CMP material and corrosion
inhibitor compounds such as benzotriazole (BTA). If not removed,
these residues can cause damage to copper lines or severely roughen
the copper metallization, as well as cause poor adhesion of
post-CMP applied layers on the device substrate. Severe roughening
of copper metallization is particularly problematic, since overly
rough copper can cause poor electrical performance of the product
microelectronic device.
[0008] Another residue-producing process common to microelectronic
device manufacturing involves gas-phase plasma etching to transfer
the patterns of developed photoresist coatings to the underlying
layers, which may consist of hardmask, interlevel dielectric (ILD),
and etch stop layers. Post-gas phase plasma etch residues, which
may include chemical elements present on the substrate and in the
plasma gases, are typically deposited on the back end of the line
(BEOL) structures and if not removed, may interfere with subsequent
silicidation or contact formation. Conventional cleaning
chemistries often damage the ILD, absorb into the pores of the ILD
thereby increasing the dielectric constant, and/or corrode the
metal structures.
[0009] There is a continuing need in the art to provide
compositions and methods that effectively remove residue from a
substrate, e.g., post-CMP residue, post-etch residue, and post-ash
residue. The compositions are more environmentally friendly than
the prior art compositions and can include innovative components
and as such, can be considered an alternative to the compositions
of the prior art.
SUMMARY
[0010] The present invention generally relates to a composition and
process for cleaning residue and/or contaminants from
microelectronic devices having said residue and contaminants
thereon. The cleaning compositions of the invention are
substantially devoid of alkali hydroxides, alkaline earth metal
hydroxides, and tetramethylammonium hydroxide. The residue may
include post-CMP, post-etch, and/or post-ash residue.
[0011] In one aspect, a cleaning composition is described, said
composition comprising at least one quaternary base, at least one
organic amine, at least one corrosion inhibitor, and at least one
solvent, wherein the corrosion inhibitor is selected from the group
consisting of 4-methylpyrazole, pyrazole, 2-amino-thiazole,
2-amino-1,3,4-thiadiazole, pterine, pyrazine, cytosine, pyridazine,
derivatives thereof, and combinations thereof, and wherein the
cleaning composition is substantially devoid of alkali hydroxides,
alkaline earth metal hydroxides, and tetramethylammonium
hydroxide.
[0012] In another aspect, a cleaning composition is described, said
composition comprising at least one cleaning additive, at least one
complexing agent, and at least one basic compound, wherein the
composition is substantially devoid of amines, alkali hydroxides,
alkaline earth metal hydroxides, and tetramethylammonium
hydroxide.
[0013] In still another aspect, a method of removing residue and
contaminants from a microelectronic device having said residue and
contaminants thereon is described, said method comprising
contacting the microelectronic device with a cleaning composition
for sufficient time to at least partially clean said residue and
contaminants from the microelectronic device, wherein said
composition comprises at least one quaternary base, at least one
organic amine, at least one corrosion inhibitor, and at least one
solvent, wherein the corrosion inhibitor is selected from the group
consisting of 4-methylpyrazole, pyrazole, 2-amino-thiazole,
2-amino-1,3,4-thiadiazole, pterine, pyrazine, cytosine, pyridazine,
derivatives thereof, and combinations thereof, and wherein the
cleaning composition is substantially devoid of alkali hydroxides,
alkaline earth metal hydroxides, and tetramethylammonium
hydroxide.
[0014] In yet another aspect, a method of removing residue and
contaminants from a microelectronic device having said residue and
contaminants thereon is described, said method comprising
contacting the microelectronic device with a cleaning composition
for sufficient time to at least partially clean said residue and
contaminants from the microelectronic device, wherein said
composition comprises at least one cleaning additive, at least one
complexing agent, and at least one basic compound, wherein the
composition is substantially devoid of amines, alkali hydroxides,
alkaline earth metal hydroxides, and tetramethylammonium
hydroxide.
[0015] Other aspects, features and advantages will be more fully
apparent from the ensuing disclosure and appended claims.
DETAILED DESCRIPTION, AND PREFERRED EMBODIMENTS THEREOF
[0016] The present invention relates generally to compositions
useful for the removal of residue and contaminants from a
microelectronic device having such material(s) thereon. The
compositions are particularly useful for the removal of post-CMP,
post-etch or post-ash residue.
[0017] For ease of reference, "microelectronic device" corresponds
to semiconductor substrates, flat panel displays, phase change
memory devices, solar panels and other products including solar
substrates, photovoltaics, and microelectromechanical systems
(MEMS), manufactured for use in microelectronic, integrated
circuit, or computer chip applications. Solar substrates include,
but are not limited to, silicon, amorphous silicon, polycrystalline
silicon, monocrystalline silicon, CdTe, copper indium selenide,
copper indium sulfide, and gallium arsenide on gallium. The solar
substrates may be doped or undoped. It is to be understood that the
term "microelectronic device" is not meant to be limiting in any
way and includes any substrate that will eventually become a
microelectronic device or microelectronic assembly.
[0018] As used herein, "residue" corresponds to particles generated
during the manufacture of a microelectronic device including, but
not limited to, plasma etching, ashing, chemical mechanical
polishing, wet etching, and combinations thereof.
[0019] As used herein, "contaminants" correspond to chemicals
present in the CMP slurry, reaction by-products of the polishing
slurry, chemicals present in the wet etching composition, reaction
by products of the wet etching composition, and any other materials
that are the by-products of the CMP process, the wet etching, the
plasma etching or the plasma ashing process.
[0020] As used herein, "post-CMP residue" corresponds to particles
from the polishing slurry, e.g., silica-containing particles,
chemicals present in the slurry, reaction by-products of the
polishing slurry, carbon-rich particles, polishing pad particles,
brush deloading particles, equipment materials of construction
particles, metals, metal oxides, organic residues, and any other
materials that are the by-products of the CMP process. As defined
herein, the "metals" that are typically polished include copper,
aluminum and tungsten.
[0021] As defined herein, "low-k dielectric material" corresponds
to any material used as a dielectric material in a layered
microelectronic device, wherein the material has a dielectric
constant less than about 3.5. Preferably, the low-k dielectric
materials include low-polarity materials such as silicon-containing
organic polymers, silicon-containing hybrid organic/inorganic
materials, organosilicate glass (OSG), TEOS, fluorinated silicate
glass (FSG), silicon dioxide, and carbon-doped oxide (CDO) glass.
It is to be appreciated that the low-k dielectric materials may
have varying densities and varying porosities.
[0022] As defined herein, "complexing agent" includes those
compounds that are understood by one skilled in the art to be
complexing agents, chelating agents and/or sequestering agents.
Complexing agents will chemically combine with or physically hold
the metal atom and/or metal ion to be removed using the
compositions described herein.
[0023] As defined herein, the term "barrier material" corresponds
to any material used in the art to seal the metal lines, e.g.,
copper interconnects, to minimize the diffusion of said metal,
e.g., copper, into the dielectric material. Preferred barrier layer
materials include tantalum, titanium, ruthenium, hafnium, tungsten,
cobalt, and other refractory metals and their nitrides and
silicides.
[0024] As defined herein, "post-etch residue" corresponds to
material remaining following gas-phase plasma etching processes,
e.g., BEOL dual damascene processing, or wet etching processes. The
post-etch residue may be organic, organometallic, organosilicic, or
inorganic in nature, for example, silicon-containing material,
carbon-based organic material, and etch gas residue such as oxygen
and fluorine.
[0025] As defined herein, "post-ash residue," as used herein,
corresponds to material remaining following oxidative or reductive
plasma ashing to remove hardened photoresist and/or bottom
anti-reflective coating (BARC) materials. The post-ash residue may
be organic, organometallic, organosilicic, or inorganic in
nature.
[0026] "Substantially devoid" is defined herein as less than 2 wt.
%, preferably less than 1 wt. %, more preferably less than 0.5 wt.
%, and most preferably less than 0.1 wt. %. In one embodiment,
"substantially devoid" corresponds to zero percent.
[0027] As used herein, "about" is intended to correspond to .+-.5%
of the stated value.
[0028] For the purposes of this invention, an "amine" is defined as
at least one primary, secondary, or tertiary amine, and/or ammonia,
with the proviso that (i) an amide group, (ii) species including
both a carboxylic acid group and an amine group, (iii) surfactants
that include amine groups, and (iv) species where the amine group
is a substituent (e.g., attached to an aryl or heterocyclic
moiety), are not considered "amines" according to this definition.
The amine formula can be represented by NR.sup.1R.sup.2R.sup.3,
wherein R.sup.1, R.sup.2 and R.sup.3 can be the same as or
different from one another and are selected from the group
consisting of hydrogen, straight-chained or branched
C.sub.1-C.sub.6 alkyls (e.g., methyl, ethyl, propyl, butyl, pentyl,
hexyl), C.sub.6-C.sub.10 aryls (e.g., benzyl), straight-chained or
branched C.sub.1-C.sub.6 alkanols (e.g., methanol, ethanol,
propanol, butanol, pentanol, hexanol), and combinations thereof,
with the proviso that R.sup.1, R.sup.2 and R.sup.3 cannot all be
hydrogen.
[0029] As defined herein, "reaction or degradation products"
include, but are not limited to, product(s) or byproduct(s) formed
as a result of catalysis at a surface, oxidation, reduction,
reactions with the compositional components, or that otherwise
polymerize; product(s) or byproduct(s) formed formed as a result of
a change(s) or transformation(s) in which a substance or material
(e.g., molecules, compounds, etc.) combines with other substances
or materials, interchanges constituents with other substances or
materials, decomposes, rearranges, or is otherwise chemically
and/or physically altered, including intermediate product(s) or
byproduct(s) of any of the foregoing or any combination of the
foregoing reaction(s), change(s) and/or transformation(s). It
should be appreciated that the reaction or degradation products may
have a larger or smaller molar mass than the original reactant.
[0030] As used herein, "suitability" for cleaning residue and
contaminants from a microelectronic device having said residue and
contaminants thereon corresponds to at least partial removal of
said residue/contaminants from the microelectronic device. Cleaning
efficacy is rated by the reduction of objects on the
microelectronic device. For example, pre- and post-cleaning
analysis may be carried out using an atomic force microscope. The
particles on the sample may be registered as a range of pixels. A
histogram (e.g., a Sigma Scan Pro) may be applied to filter the
pixels in a certain intensity, e.g., 231-235, and the number of
particles counted. The particle reduction may be calculated
using:
Cleaning Efficacy = ( Number of PreClean Objects - Number of
PostClean Objects ) Number of PreClean Objects .times. 100
##EQU00001##
Notably, the method of determination of cleaning efficacy is
provided for example only and is not intended to be limited to
same. Alternatively, the cleaning efficacy may be considered as a
percentage of the total surface that is covered by particulate
matter. For example, AFM's may be programmed to perform a z-plane
scan to identify topographic areas of interest above a certain
height threshold and then calculate the area of the total surface
covered by said areas of interest. One skilled in the art would
readily understand that the less area covered by said areas of
interest post-cleaning, the more efficacious the cleaning
composition. Preferably, at least 75% of the residue/contaminants
are removed from the microelectronic device using the compositions
described herein, more preferably at least 90%, even more
preferably at least 95%, and most preferably at least 99% of the
residue/contaminants are removed.
[0031] Compositions described herein may be embodied in a wide
variety of specific formulations, as hereinafter more fully
described.
[0032] In all such compositions, wherein specific components of the
composition are discussed in reference to weight percentage ranges
including a zero lower limit, it will be understood that such
components may be present or absent in various specific embodiments
of the composition, and that in instances where such components are
present, they may be present at concentrations as low as 0.001
weight percent, based on the total weight of the composition in
which such components are employed.
[0033] In a first aspect, the cleaning compositions include at
least one corrosion inhibitor, where the corrosion inhibitor
component is added to the cleaning composition to lower the
corrosion rate of metals, e.g., copper, aluminum, as well as
enhance the cleaning performance. Corrosion inhibitors contemplated
include, but are not limited to: 4-methylpyrazole, pyrazole,
2-amino-thiazole, adenosine, 2-amino-1,3,4-thiadiazole,
5-amino-1H-tetrazole, adenine, pterine, pyrimidine, pyrazine,
cytosine, pyridazine, 1H-pyrazole-3-carboxylic acid,
1H-pyrazole-4-carboxylic acid, 3-amino-5-hydroxy-1H-pyrazole,
3-amino-5-methyl-1H-pyrazole, 3-amino-5-tert-butyl-1H-pyrazole,
2-amino-methylthiazole, 2-mercaptothiazole,
2,5-dimercapto-1,3,4-thiadiazole,
2-mercapto-5-methyl-1,3,4-thiadiazole,
2-aminothiazole-5-carbonitrile, 2-aminothiazole-5-carboxaldehyde,
ethyl 2-aminothiazole-4-carboxylate, 1,2,3-triazole,
1,2,4-triazole, imidazole, 3-amino-1,2,4-triazole derivatives
thereof, and combinations thereof. Preferably, the corrosion
inhibitors are selected from the group consisting of
4-methylpyrazole, pyrazole, 2-amino-thiazole,
2-amino-1,3,4-thiadiazole, pterine, pyrazine, cytosine, pyridazine,
derivatives thereof, and combinations thereof. Most preferably, the
corrosion inhibitors comprise pyrazole.
[0034] In one embodiment, the cleaning composition of the first
aspect comprises at least one solvent and at least one corrosion
inhibitor. Preferably, the solvent comprises water, and more
preferably deionized water.
[0035] In a further embodiment the cleaning composition of the
first aspect comprises, consists of, or consists essentially of at
least one corrosion inhibitor, at least one quaternary base, at
least one organic amine, at least one solvent (e.g., water), and
optionally at least one complexing agent, wherein the cleaning
composition is substantially devoid of alkali hydroxides, alkaline
earth metal hydroxides, and tetramethylammonium hydroxide.
[0036] In a particularly preferred embodiment, the cleaning
composition of the first aspect comprises, consists of or consists
essentially of at least one quaternary base, at least one organic
amine, at least one corrosion inhibitor, and at least one solvent
(e.g., water), wherein the corrosion inhibitor is selected from the
group consisting of 4-methylpyrazole, pyrazole, 2-amino-thiazole,
2-amino-1,3,4-thiadiazole, pterine, pyrazine, cytosine, pyridazine,
derivatives thereof, and combinations thereof, and wherein the
cleaning composition is substantially devoid of alkali hydroxides,
alkaline earth metal hydroxides, and tetramethylammonium hydroxide.
The cleaning composition of the first aspect may further comprise
at least one complexing agent.
[0037] In another particularly preferred embodiment, the cleaning
composition of the first aspect comprises, consists of or consists
essentially of at least one quaternary base, at least one organic
amine, at least one corrosion inhibitor, at least one complexing
agent, and at least one solvent (e.g., water), wherein the
corrosion inhibitor is selected from the group consisting of
4-methylpyrazole, pyrazole, 2-amino-thiazole,
2-amino-1,3,4-thiadiazole, pterine, pyrazine, cytosine, pyridazine,
derivatives thereof, and combinations thereof, and wherein the
cleaning composition is substantially devoid of alkali hydroxides,
alkaline earth metal hydroxides, and tetramethylammonium
hydroxide.
[0038] Illustrative organic amines that may be useful in specific
compositions include species having the general formula
NR.sup.1R.sup.2R.sup.3, wherein R.sup.1, R.sup.2 and R.sup.3 may be
the same as or different from one another and are selected from the
group consisting of hydrogen, straight-chained or branched
C.sub.1-C.sub.6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl,
and hexyl), straight-chained or branched C.sub.1-C.sub.6 alcohol
(e.g., methanol, ethanol, propanol, butanol, pentanol, and
hexanol), and straight chained or branched ethers having the
formula R.sup.4--O--R.sup.5, where R.sup.4 and R.sup.5 may be the
same as or different from one another and are selected from the
group consisting of C.sub.1-C.sub.6 alkyls as defined above. Most
preferably, at least one of R.sup.1, R.sup.2 and R.sup.3 is a
straight-chained or branched C.sub.1-C.sub.6 alcohol. Examples
include, without limitation, alkanolamines such as alkanolamines
such as aminoethylethanolamine, N-methylaminoethanol,
aminoethoxyethanol, dimethylaminoethoxyethanol, diethanolamine,
N-methyldiethanolamine, monoethanolamine, triethanolamine,
1-amino-2-propanol, 3-amino-1-propanol, diisopropylamine,
isopropylamine, 2-amino-1-butanol, isobutanolamine, other
C.sub.1-C.sub.8 alkanolamines, and combinations thereof; amines
such as triethylenediamine, ethylenediamine, hexamethylenediamine,
diethylenetriamine, triethylamine, trimethylamine, and combinations
thereof; and combinations of amines and alkanolamines. When the
amine includes the ether component, the amine may be considered an
alkoxyamine, e.g., 1-methoxy-2-aminoethane. Alternatively, or in
addition to the NR.sup.1R.sup.2R.sup.3 amine, the amine may be a
multi-functional amine including, but not limited to,
tetraethylenepentamine (TEPA), 4-(2-hydroxyethyl)morpholine (HEM),
N-aminoethylpiperazine (N-AEP), ethylenediaminetetraacetic acid
(EDTA), 1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid (CDTA),
glycine/ascorbic acid, iminodiacetic acid (IDA),
2-(hydroxyethyl)iminodiacetic acid (HIDA), nitrilotriacetic acid,
thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, glycine,
alanine, arginine, asparagine, aspartic acid, cysteine, glutamic
acid, glutamine, histidine, isoleucine, leucine, lysine,
methionine, phenylalanine, piperadine, N-(2-aminoethyl) piperadine,
proline, pyrrolidine, serine, threonine, tryptophan, tyrosine,
valine, and combinations thereof. Preferably, the amines include at
least one species selected from the group consisting of
monoethanolamine, triethanolamine, cysteine, or a combination
thereof.
[0039] Quaternary bases contemplated herein include compounds
having the formula NR.sup.1R.sup.2R.sup.3R.sup.4OH, wherein
R.sup.1, R.sup.2, R.sup.3 and R.sup.4 may be the same as or
different from one another and are selected from the group
consisting of hydrogen, straight-chained or branched
C.sub.1-C.sub.6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl,
and hexyl), and substituted or unsubstituted C.sub.6-C.sub.10 aryl,
e.g., benzyl, with the proviso that R.sup.1, R.sup.2, R.sup.3, and
R.sup.4 cannot all simultaneously be a methyl group.
Tetraalkylammonium hydroxides that are commercially available
include tetraethylammonium hydroxide (TEAH), tetrapropylammonium
hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH),
tributylmethylammonium hydroxide (TBMAH), benzyltrimethylammonium
hydroxide (BTMAH), choline hydroxide, tris(2-hydroxyethyl)methyl
ammonium hydroxide, diethyldimethylammonium hydroxide, and
combinations thereof, may be used. Tetraalkylammonium hydroxides
which are not commercially available may be prepared in a manner
analogous to the published synthetic methods used to prepare TEAH,
TPAH, TBAH, TBMAH, and BTMAH, which are known to one ordinary of
skill in the art. Another widely used quaternary ammonium base is
choline hydroxide. Although not a quaternary base, it is
contemplated that the bases potassium hydroxide, cesium hydroxide
or rubidium hydroxide may be used in the absence of or the presence
of the above-identified quaternary bases. Preferably, the
quaternary base comprises TEAH, BTMAH, or a combination of TEAH and
BTMAH.
[0040] The optional complexing agents contemplated herein include,
but are not limited to, acetic acid, acetone oxime, acrylic acid,
adipic acid, alanine, arginine, asparagine, aspartic acid, betaine,
dimethyl glyoxime, formic acid, fumaric acid, gluconic acid,
glutamic acid, glutamine, glutaric acid, glyceric acid, glycerol,
glycolic acid, glyoxylic acid, histidine, iminodiacetic acid,
isophthalic acid, itaconic acid, lactic acid, leucine, lysine,
maleic acid, maleic anhydride, malic acid, malonic acid, mandelic
acid, 2,4-pentanedione, phenylacetic acid, phenylalanine, phthalic
acid, proline, propionic acid, pyrocatecol, pyromellitic acid,
quinic acid, serine, sorbitol, succinic acid, tartaric acid,
terephthalic acid, trimellitic acid, trimesic acid, tyrosine,
valine, xylitol, ethylenediamine, oxalic acid, tannic acid, benzoic
acid, ammonium benzoate, catechol, pyrogallol, resorcinol,
hydroquinone, cyanuric acid, barbituric acid and derivatives such
as 1,2-dimethylbarbituric acid, alpha-keto acids such as pyruvic
acid, phosphonic acid and derivatives thereof such as
1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), propanethiol,
benzohydroxamic acids, salts and derivatives thereof, and
combinations thereof. In a preferred embodiment, preferably the
complexing agent comprises HEDP, tartaric acid, or a combination
thereof.
[0041] In one aspect, the composition for cleaning post-CMP residue
and contaminants comprises, consists of, or consists essentially of
at least one quaternary base, at least one organic amine, at least
one corrosion inhibitor, at least one solvent (e.g., water), and
optional at least one complexing agent, wherein the corrosion
inhibitor is selected from the group consisting of
4-methylpyrazole, pyrazole, 2-amino-thiazole,
2-amino-1,3,4-thiadiazole, pterine, pyrazine, cytosine, pyridazine,
derivatives thereof, and combinations thereof, and wherein the
cleaning composition is substantially devoid of alkali hydroxides,
alkaline earth metal hydroxides, and tetramethylammonium hydroxide,
present in the following range of weight percents, based on the
total weight of the composition:
TABLE-US-00001 component weight percent range preferred wt. % range
quaternary base(s) about 0.001 to about 15 about 0.001 to about 10
amine(s) about 0.001 to about 10 about 0.001 to about 7 corrosion
about 0.0001 to about 2 about 0.0001 to about inhibitor(s) 0.5
optional complexing 0 to about 10 0.001 to about 5 (when agent(s)
present) solvent(s) balance balance
[0042] In a particularly preferred embodiment, the cleaning
composition of the first aspect comprises, consists of, or consists
essentially of tetraethylammonium hydroxide, at least one amine, at
least one corrosion inhibitor, at least one complexing agent, and
water. Preferably, the corrosion inhibitor is selected from the
group consisting of 4-methylpyrazole, pyrazole, 2-amino-thiazole,
2-amino-1,3,4-thiadiazole, pterine, pyrazine, cytosine, pyridazine,
derivatives thereof, and combinations thereof, and the cleaning
composition is substantially devoid of alkali hydroxides, alkaline
earth metal hydroxides, and tetramethylammonium hydroxide. For
example, the cleaning composition of the first aspect can comprise,
consist of or consist essentially of TEAH, at least one
alkanolamine, pyrazole, at least one complexing agent, and water,
preferably TEAH, monoethanolamine (MEA), pyrazole, HEDP and water.
Preferably, a concentrate of the cleaning composition of the first
aspect comprises, consists of, or consists essentially of about 6%
to about 10% by weight TEAH, about 2% to about 7% by weight MEA,
about 1% to about 4% by weight HEDP, and about 0.05% to about 0.3%
by weight pyrazole.
[0043] In another particularly preferred embodiment, the cleaning
composition of the first aspect comprises, consists of, or consists
essentially of benzyltrimethylammonium hydroxide, at least one
amine, at least one corrosion inhibitor, at least one complexing
agent, and water. Preferably, the corrosion inhibitor is selected
from the group consisting of 4-methylpyrazole, pyrazole,
2-amino-thiazole, 2-amino-1,3,4-thiadiazole, pterine, pyrazine,
cytosine, pyridazine, derivatives thereof, and combinations
thereof, and the cleaning composition is substantially devoid of
alkali hydroxides, alkaline earth metal hydroxides, and
tetramethylammonium hydroxide. For example, the cleaning
composition of the first aspect can comprise, consist of or consist
essentially of BTMAH, at least one alkanolamine, pyrazole, at least
one complexing agent, and water, preferably BTMAH,
monoethanolamine, pyrazole, HEDP and water. Preferably, the
cleaning composition of the first aspect comprises, consists of, or
consists essentially of about 7% to about 11% by weight BTMAH,
about 2% to about 7% by weight MEA, about 1% to about 4% by weight
HEDP, and about 0.05% to about 0.3% by weight pyrazole.
[0044] In a second aspect, the cleaning compositions generally are
aqueous and include at least one cleaning additive, at least one
complexing agent, and at least one basic compound, wherein the
composition is substantially devoid of amines, alkali hydroxides,
alkaline earth metal hydroxides, and tetramethylammonium hydroxide.
In one embodiment, the cleaning compositions of the second aspect
include at least one cleaning additive, at least one complexing
agent, at least one basic compound, and water, wherein the
composition is substantially devoid of amines, alkali hydroxides,
alkaline earth metal hydroxides, and tetramethylammonium hydroxide.
The compositions of the second aspect are useful for removing
residue selected from the group consisting of post-CMP residue,
post-etch residue, post-ash residue and combinations thereof.
Preferably, the compositions of the second aspect are used to
remove post-CMP residue. The at least one basic compound can be a
species selected from the group consisting of
(NR.sup.1R.sup.2R.sup.3R.sup.4)OH,
(PR.sup.1R.sup.2R.sup.3R.sup.4)OH,
(R.sup.1R.sup.2N)(R.sup.3R.sup.4N)C.dbd.NR.sup.5, and any
combination thereof, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4 and
R.sup.5 may be the same as or different from one another and are
selected from the group consisting of hydrogen, straight-chained
C.sub.1-C.sub.6 alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl,
hexyl), branched C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkanol
(e.g., methanol, ethanol, propanol, butanol, pentanol, hexanol),
substituted C.sub.6-C.sub.10 aryl, unsubstituted C.sub.6-C.sub.10
aryl (e.g., benzyl), CH.sub.2CH.sub.2CH.sub.2C(H)NH.sub.2COOH, and
any combination thereof, with the proviso that when the basic
compound is (NR.sup.1R.sup.2R.sup.3R.sup.4)OH, R.sup.1, R.sup.2,
R.sup.3 and R.sup.4 cannot simultaneously be methyl. Basic
compounds include tetrabutylphosphonium hydroxide (TBPH),
tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide,
tetrapropylphosphonium hydroxide, benzyltriphenylphosphonium
hydroxide, methyl triphenylphosphonium hydroxide, ethyl
triphenylphosphonium hydroxide, N-propyl triphenylphosphonium
hydroxide, tetraethylammonium hydroxide (TEAH), tetrapropylammonium
hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH),
trimethylethylammonium hydroxide, diethyldimethylammonium
hydroxide, tributylmethylammonium hydroxide (TBMAH),
benzyltrimethylammonium hydroxide (BTMAH), choline hydroxide,
tris(2-hydroxyethyl)methyl ammonium hydroxide,
diethyldimethylammonium hydroxide, guanidine acetate,
1,1,3,3-tetramethyl guanidine, guanidine carbonate, arginine, and
combinations thereof, may be used. Preferably, the basic compound
comprises TBPH, TEAH, BTMAH, 1,1,3,3-tetramethyl guanidine, or any
combination thereof. In one preferred embodiment, the basic
compound comprises 1,1,3,3-tetramethyl guanidine.
[0045] The at least one complexing agent of the compositions of the
second aspect include, but are not limited to,
ethylenediaminetetraacetic acid (EDTA),
1,2-cyclohexanediamine-N,N,N',N'-tetraacetic acid (CDTA),
4-(2-hydroxyethyl)morpholine (HEM), N-aminoethylpiperazine (N-AEP),
glycine, ascorbic acid, iminodiacetic acid (IDA),
2-(hydroxyethyl)iminodiacetic acid (HIDA), nitrilotriacetic acid,
alanine, arginine, asparagine, aspartic acid, cysteine, glutamic
acid, glutamine, histidine, isoleucine, leucine, lysine,
methionine, phenylalanine, proline, serine, threonine, tryptophan,
tyrosine, valine, gallic acid, boric acid, acetic acid, acetone
oxime, acrylic acid, adipic acid, betaine, dimethyl glyoxime,
formic acid, fumaric acid, gluconic acid, glutaric acid, glyceric
acid, glycolic acid, glyoxylic acid, isophthalic acid, itaconic
acid, lactic acid, maleic acid, maleic anhydride, malic acid,
malonic acid, mandelic acid, 2,4-pentanedione, phenylacetic acid,
phthalic acid, proline, propionic acid, pyrocatecol, pyromellitic
acid, quinic acid, sorbitol, succinic acid, tartaric acid,
terephthalic acid, trimellitic acid, trimesic acid, tyrosine,
xylitol,
1,5,9-triazacyclododecane-N,N',N''-tris(methylenephosphonic acid)
(DOTRP),
1,4,7,10-tetraazacyclododecane-N,N',N'',N'''-tetrakis(methylenep-
hosphonic acid) (DOTP), nitrilotris(methylene)triphosphonic acid,
diethylenetriaminepenta(methylenephosphonic acid) (DETAP),
aminotri(methylenephosphonic acid),
1-hydroxyethylidene-1,1-diphosphonic acid (HEDP),
bis(hexamethylene)triamine phosphonic acid,
1,4,7-triazacyclononane-N,N',N''-tris(methylenephosphonic acid
(NOTP), dimercaprol, 1,2-propanedithiol, 1,2-dimercaptopropane,
Ethanol, 2,2-dimercapto-(9CI), salts and derivatives thereof, and
combinations thereof. Preferably, the at least one complexing agent
comprises cysteine.
[0046] The at least one cleaning additive preferably is capable of
both acting as a complexing agent and a buffer and can include at
least one species selected from the group consisting of citric
acid, ethylenediaminetetraacetic acid (EDTA),
1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), glutamic acid,
iminodiacetic acid, sulfosalicylic acid, methanesulfonic acid,
salicylic acid, phthalic acid, benzene sulfonic acid, oxalic acid,
lactic acid, and combinations thereof. In a preferred embodiment,
the cleaning additive comprises citric acid.
[0047] The cleaning compositions of the second aspect can further
comprise at least one reducing agent, at least one metal corrosion
inhibitor, at least one surfactant, or any combination thereof. In
one embodiment, the cleaning composition of the second aspect
comprises, consists of, or consists essentially of at least one
cleaning additive, at least one complexing agent, at least one
basic compound, and water, wherein the composition is substantially
devoid of amines, alkali hydroxides, alkaline earth metal
hydroxides, and tetramethylammonium hydroxide. In another
embodiment, the cleaning composition of the second aspect
comprises, consists of, or consists essentially of at least one
cleaning additive, at least one complexing agent, at least one
basic compound, water, and at least one reducing agent, wherein the
composition is substantially devoid of amines, alkali hydroxides,
alkaline earth metal hydroxides, and tetramethylammonium hydroxide.
In yet another embodiment, the cleaning composition of the second
aspect comprises, consists of, or consists essentially of at least
one cleaning additive, at least one complexing agent, at least one
basic compound, water, and at least one metal corrosion inhibitor,
wherein the composition is substantially devoid of amines, alkali
hydroxides, alkaline earth metal hydroxides, and
tetramethylammonium hydroxide. In still another embodiment, the
cleaning composition of the second aspect comprises, consists of,
or consists essentially of at least one cleaning additive, at least
one complexing agent, at least one basic compound, water, and at
least one surfactant, wherein the composition is substantially
devoid of amines, alkali hydroxides, alkaline earth metal
hydroxides, and tetramethylammonium hydroxide. In another
embodiment, the cleaning composition of the second aspect
comprises, consists of, or consists essentially of at least one
cleaning additive, at least one complexing agent, at least one
basic compound, water, at least one reducing agent, and at least
one metal corrosion inhibitor, wherein the composition is
substantially devoid of amines, alkali hydroxides, alkaline earth
metal hydroxides, and tetramethylammonium hydroxide. In yet another
embodiment, the cleaning composition of the second aspect
comprises, consists of, or consists essentially of at least one
cleaning additive, at least one complexing agent, at least one
basic compound, water, at least one reducing agent, and at least
one surfactant, wherein the composition is substantially devoid of
amines, alkali hydroxides, alkaline earth metal hydroxides, and
tetramethylammonium hydroxide. In still another embodiment, the
cleaning composition of the second aspect comprises, consists of,
or consists essentially of at least one cleaning additive, at least
one complexing agent, at least one basic compound, water, at least
one metal corrosion inhibitor, and at least one surfactant, wherein
the composition is substantially devoid of amines, alkali
hydroxides, alkaline earth metal hydroxides, and
tetramethylammonium hydroxide. In another embodiment, the cleaning
composition of the second aspect comprises, consists of, or
consists essentially of at least one cleaning additive, at least
one complexing agent, at least one basic compound, water, at least
one reducing agent, at least one metal corrosion inhibitor, and at
least one surfactant, wherein the composition is substantially
devoid of amines, alkali hydroxides, alkaline earth metal
hydroxides, and tetramethylammonium hydroxide.
[0048] When present, the at least one metal corrosion inhibitor is
added to the cleaning composition of the second aspect to lower the
corrosion rate of metals, e.g., copper, aluminum, as well as
enhance the cleaning performance. Corrosion inhibitors contemplated
include, but are not limited to: adenosine, adenine, pyrazole,
1,2,4-triazole, 1,2,3-triazole, imidazole, 3-amino-1,2,4-triazole,
1H-pyrazole-4-carboxylic acid, 3-amino-5-tert-butyl-1H-pyrazole,
5-amino-1H-tetrazole, 4-methylpyrazole, derivatives thereof, and
combinations thereof. In a preferred embodiment, the metal
corrosion inhibitor comprises adenine.
[0049] Reducing agents contemplated include ascorbic acid,
L(+)-ascorbic acid, isoascorbic acid, ascorbic acid derivatives,
gallic acid, formamidinesulfinic acid, uric acid, tartaric acid,
and any combination thereof, preferably ascorbic acid, tartaric
acid, or a combination thereof.
[0050] Surfactants for use in the compositions of the second aspect
include, but are not limited to, amphoteric salts, cationic
surfactants, anionic surfactants, fluoroalkyl surfactants,
non-ionic surfactants, and combinations thereof including, but not
limited to, SURFONYL.RTM. 104, TRITON.RTM. CF-21, TRITON.RTM.
CF-10, TRITON.RTM. X-100, ZONYL.RTM. UR, ZONYL.RTM. FSO-100,
ZONYL.RTM. FSN-100, PLURONIC F-127, 3M Fluorad fluorosurfactants
(i.e., FC-4430 and FC-4432), dioctylsulfosuccinate salt,
2,3-dimercapto-1-propanesulfonic acid salt, polyethylene glycols
(e.g., PEG 400), polypropylene glycols, polyethylene or
polypropylene glycol ethers, carboxylic acid salts, R.sub.1 benzene
sulfonic acids or salts thereof (where the R.sub.1 is a
straight-chained or branched C.sub.8-C.sub.18 alkyl group),
amphiphilic fluoropolymers, C.sub.8-C.sub.18 alkyl phosphate
ethers, carboxylic acid salts, alkylaryl sulfonic acids where the
alkyl group is a C.sub.8-C.sub.18 alkyl such as
dodecylbenzenesulfonic acid, alkylaryl phosphonic acids where the
alkyl group is a C.sub.8-C.sub.18 alkyl, polyacrylate polymers,
dinonylphenyl polyoxyethylene, polyethoxylated sorbitans (e.g.,
polysorbate 80), sorbitans (e.g., sorbitan oleate), silicone or
modified silicone polymers, acetylenic diols or modified acetylenic
diols, alkylammonium or modified alkylammonium salts, as well as
combinations comprising at least one of the foregoing surfactants,
sodium dodecyl sulfate, zwitterionic surfactants, aerosol-OT (AOT)
and fluorinated analogues thereof, alkyl ammonium,
perfluoropolyether surfactants, 2-sulfosuccinate salts,
phosphate-based surfactants, sulfur-based surfactants, and
acetoacetate-based polymers.
[0051] In one embodiment, the cleaning compositions of the second
aspect are formulated in the following embodiments, wherein all
percentages are by weight, based on the total weight of the
formulation:
TABLE-US-00002 more preferably (% by component of % by weight
preferably (% by weight) weight) cleaning additive(s) about 0.001%
to about about 0.001% to about 5% about 0.001% to about 10% 4%
complexing agent(s) about 0.001% to about about 0.001% to about
about 0.001% to about 25% 20% 17% basic compound(s) about 0.001% to
about about 0.001% to about about 0.001% to about 40% 30% 25% water
balance balance balance reducing agent(s) 0 to about 10% 0 to about
5% 0 to about 5% corrosion inhibitor(s) 0 to about 5% 0 to about 1%
0 to about 0.5% surfactant(s) 0 to about 5% 0 to about 1% 0 to
about 0.5%
When present, the lower limit of the reducing agent and surfactant
in the composition is about 0.0001%. When present, the lower limit
of corrosion inhibitor in the composition is about 0.001%.
[0052] The cleaning compositions of either aspect are particularly
useful for cleaning residue and contaminants, e.g., post-CMP
residue, post-etch residue, post-ash residue, and contaminants from
a microelectronic device structure. Regardless of the embodiment,
the cleaning compositions of either aspect are preferably
substantially devoid of at least one of oxidizing agents (e.g.,
hydrogen peroxide); fluoride-containing sources; abrasive
materials; alkali and/or alkaline earth metal bases;
tetramethylammonium hydroxide; and combinations thereof, prior to
removal of residue material from the microelectronic device. In
addition, the cleaning compositions should not solidify to form a
polymeric solid, for example, photoresist.
[0053] The pH of the cleaning compositions of either aspect is
greater than 7, preferably in a range from about 10 to greater than
14, most preferably in a range from about 12 to about 14.
[0054] The range of weight percent ratios of the components will
cover all possible concentrated or diluted embodiments of the
compositions of either aspect. Towards that end, in one embodiment,
a concentrated cleaning composition is provided that can be diluted
for use as a cleaning solution. A concentrated cleaning
composition, or "concentrate," advantageously permits a user, e.g.
CMP process engineer, to dilute the concentrate to the desired
strength and pH at the point of use. Dilution of the concentrated
cleaning composition may be in a range from about 1:1 to about
2500:1, preferably about 5:1 to about 200:1, and most preferably
about 10:1 to about 50:1, wherein the cleaning composition is
diluted at or just before the tool with solvent, e.g., deionized
water. It is to be appreciated by one skilled in the art that
following dilution, the range of weight percent ratios of the
components disclosed herein should remain unchanged.
[0055] The compositions of either aspect may have utility in
applications including, but not limited to, post-etch residue
removal, post-ash residue removal surface preparation, post-plating
cleaning and post-CMP residue removal. In addition, it is
contemplated that the cleaning compositions of either aspect may be
useful for the cleaning and protection of other metal (e.g.,
copper-containing) products including, but not limited to,
decorative metals, metal wire bonding, printed circuit boards and
other electronic packaging using metal or metal alloys.
[0056] In yet another preferred embodiment, the cleaning
compositions of either aspect further include residue and/or
contaminants. The residue and contaminants may be dissolved in the
compositions. Alternatively, the residue and contaminants may be
suspended in the compositions. Preferably, the residue includes
post-CMP residue, post-etch residue, post-ash residue,
contaminants, or combinations thereof.
[0057] The cleaning compositions of either aspect are easily
formulated by simple addition of the respective ingredients and
mixing to homogeneous condition. Furthermore, the compositions of
either aspect may be readily formulated as single-package
formulations or multi-part formulations that are mixed at or before
the point of use, e.g., the individual parts of the multi-part
formulation may be mixed at the tool or in a storage tank upstream
of the tool. The concentrations of the respective ingredients may
be widely varied in specific multiples of the composition, i.e.,
more dilute or more concentrated, and it will be appreciated that
the compositions described herein can variously and alternatively
comprise, consist or consist essentially of any combination of
ingredients consistent with the disclosure herein.
[0058] Accordingly, another aspect relates to a kit including, in
one or more containers, one or more components adapted to form the
cleaning compositions described herein. The kit may include, in one
or more containers, at least one corrosion inhibitor, at least one
quaternary base, at least one organic amine, and optionally at
least one solvent and at least one complexing agent, for combining
with solvent, e.g., water, at the fab or the point of use.
Alternatively, the kit may include, in a first container at least
one corrosion inhibitor, and in a second container at least one
quaternary base, at least one organic amine, and optionally at
least one solvent and at least one complexing agent, for combining
with each other and solvent, e.g., water, at the fab or the point
of use. In still another alternative, the kit includes, in one or
more containers, at least one cleaning additive, at least one
complexing agent, at least one basic compound, optionally at least
one reducing agent, optionally at least one metal corrosion
inhibitor, and optionally at least one surfactant, for combining
with solvent, e.g., water, at the fab or the point of use. The
containers of the kit must be suitable for storing and shipping
said cleaning compositions, for example, NOWPak.RTM. containers
(Advanced Technology Materials, Inc., Danbury, Conn., USA). The kit
containers preferably are substantially devoid of alkali
hydroxides, alkaline earth metal hydroxides, and
tetramethylammonium hydroxide.
[0059] As applied to microelectronic manufacturing operations, the
cleaning compositions of either aspect are usefully employed to
clean post-CMP residue and/or contaminants from the surface of the
microelectronic device. The cleaning compositions do not damage
low-k dielectric materials or corrode metal interconnects on the
device surface. Preferably the cleaning compositions of either
aspect remove at least 85% of the residue present on the device
prior to residue removal, more preferably at least 90%, even more
preferably at least 95%, and most preferably at least 99%.
[0060] In post-CMP residue and contaminant cleaning application,
the cleaning composition of either aspect may be used with a large
variety of conventional cleaning tools such as megasonics and brush
scrubbing, including, but not limited to, Verteq single wafer
megasonic Goldfinger, OnTrak systems DDS (double-sided scrubbers),
SEZ or other single wafer spray rinse, Applied Materials
Mirra-Mesa.TM./Reflexion.TM./Reflexion LK.TM., and Megasonic batch
wet bench systems.
[0061] In use of the compositions of either aspect for cleaning
post-CMP residue, post-etch residue, post-ash residue and/or
contaminants from microelectronic devices having same thereon, the
cleaning composition typically is contacted with the device for a
time of from about 5 sec to about 10 minutes, preferably about 1
sec to 20 min, preferably about 15 sec to about 5 min at
temperature in a range of from about 20.degree. C. to about
90.degree. C., preferably about 20.degree. C. to about 50.degree.
C. Such contacting times and temperatures are illustrative, and any
other suitable time and temperature conditions may be employed that
are efficacious to at least partially clean the post-CMP
residue/contaminants from the device, within the broad practice of
the method. "At least partially clean" and "substantial removal"
both correspond to at removal of at least 85% of the residue
present on the device prior to residue removal, more preferably at
least 90%, even more preferably at least 95%, and most preferred at
least 99%
[0062] Following the achievement of the desired cleaning action,
the cleaning compositions may be readily removed from the device to
which it has previously been applied, as may be desired and
efficacious in a given end use application of the compositions
described herein. Preferably, the rinse solution includes deionized
water. Thereafter, the device may be dried using nitrogen or a
spin-dry cycle.
[0063] Yet another aspect relates to the improved microelectronic
devices made according to the methods described herein and to
products containing such microelectronic devices.
[0064] Another aspect relates to a recycled cleaning composition,
wherein the cleaning composition may be recycled until residue
and/or contaminant loading reaches the maximum amount the cleaning
composition may accommodate, as readily determined by one skilled
in the art.
[0065] A still further aspect relates to methods of manufacturing
an article comprising a microelectronic device, said method
comprising contacting the microelectronic device with a cleaning
composition for sufficient time to clean post-CMP residue and
contaminants from the microelectronic device having said residue
and contaminants thereon, and incorporating said microelectronic
device into said article, using a cleaning composition described
herein.
[0066] In another aspect, a method of removing post-CMP residue and
contaminants from a microelectronic device having same thereon is
described, said method comprising: [0067] polishing the
microelectronic device with a CMP slurry; [0068] contacting the
microelectronic device with a cleaning composition comprising at
least one corrosion inhibitor, for a sufficient time to remove
post-CMP residue and contaminants from the microelectronic device
to form a post-CMP residue-containing composition; and [0069]
continuously contacting the microelectronic device with the
post-CMP residue-containing composition for a sufficient amount of
time to effect substantial cleaning of the microelectronic device,
wherein the at least one corrosion inhibitor comprises a species
selected from the group consisting of 4-methylpyrazole, pyrazole,
1,2,4-triazole, 1,2,3-triazole, imidazole, 3-amino-1,2,4-triazole,
2-amino-thiazole, 2-amino-1,3,4-thiadiazole, pterine, pyrazine,
cytosine, pyridazine, derivatives thereof, and combinations
thereof.
[0070] In still another aspect, a method of removing post-CMP
residue and contaminants from a microelectronic device having same
thereon is described, said method comprising: [0071] polishing the
microelectronic device with a CMP slurry; and [0072] contacting the
microelectronic device with a cleaning composition comprising at
least one cleaning additive, at least one complexing agent, at
least one basic compound, and water, for a sufficient time to
remove post-CMP residue and contaminants from the microelectronic
device to form a post-CMP residue-containing composition, wherein
the cleaning composition is substantially devoid of amines, alkali
hydroxides, alkaline earth metal hydroxides, and
tetramethylammonium hydroxide.
[0073] Another aspect relates to an article of manufacture
comprising a cleaning composition, a microelectronic device wafer,
and material selected from the group consisting of residue,
contaminants and combinations thereof, wherein the cleaning
composition comprises at least one solvent, at least one corrosion
inhibitor, at least one amine, at least one quaternary base, and
optionally at least one complexing agent, wherein the at least one
corrosion inhibitor comprises a species selected from the group
consisting of 4-methylpyrazole, pyrazole, 2-amino-thiazole,
2-amino-1,3,4-thiadiazole, pterine, pyrazine, cytosine, pyridazine,
1,2,4-triazole, 1,2,3-triazole, imidazole, 3-amino-1,2,4-triazole,
derivatives thereof, and combinations thereof, the cleaning
composition is substantially devoid of alkali hydroxides, alkaline
earth metal hydroxides, and tetramethylammonium hydroxide, and the
residue comprises at least one of post-CMP residue, post-etch
residue and post-ash residue.
[0074] Another aspect relates to an article of manufacture
comprising a cleaning composition, a microelectronic device wafer,
and material selected from the group consisting of residue,
contaminants and combinations thereof, wherein the cleaning
composition comprises at least one cleaning additive, at least one
complexing agent, at least one basic compound, and water, wherein
the composition is substantially devoid of amines, alkali
hydroxides, alkaline earth metal hydroxides, and
tetramethylammonium hydroxide, and the residue comprises at least
one of post-CMP residue, post-etch residue and post-ash
residue.
[0075] Although the invention has been variously disclosed herein
with reference to illustrative embodiments and features, it will be
appreciated that the embodiments and features described hereinabove
are not intended to limit the invention, and that other variations,
modifications and other embodiments will suggest themselves to
those of ordinary skill in the art, based on the disclosure herein.
The invention therefore is to be broadly construed, as encompassing
all such variations, modifications and alternative embodiments
within the spirit and scope of the claims hereafter set forth.
* * * * *