U.S. patent application number 13/562993 was filed with the patent office on 2012-11-22 for composition for removing photoresist and/or etching residue from a substrate and use thereof.
This patent application is currently assigned to Air Products and Chemicals, Inc.. Invention is credited to Matthew I. Egbe, Denise Geitz.
Application Number | 20120295828 13/562993 |
Document ID | / |
Family ID | 34937875 |
Filed Date | 2012-11-22 |
United States Patent
Application |
20120295828 |
Kind Code |
A1 |
Egbe; Matthew I. ; et
al. |
November 22, 2012 |
Composition for Removing Photoresist and/or Etching Residue From a
Substrate and Use Thereof
Abstract
Compositions containing certain organic solvents comprising at
least 50% by weight of a glycol ether and a quaternary ammonium
compound are capable of removing residues such as photoresist
and/or etching residue from an article.
Inventors: |
Egbe; Matthew I.; (West
Norriton, PA) ; Geitz; Denise; (Bethlehem,
PA) |
Assignee: |
Air Products and Chemicals,
Inc.
Allentown
PA
|
Family ID: |
34937875 |
Appl. No.: |
13/562993 |
Filed: |
July 31, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10896589 |
Jul 22, 2004 |
|
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13562993 |
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Current U.S.
Class: |
510/176 |
Current CPC
Class: |
G03F 7/425 20130101;
H01L 21/02071 20130101; H01L 21/02063 20130101; H01L 21/31133
20130101 |
Class at
Publication: |
510/176 |
International
Class: |
G03F 7/42 20060101
G03F007/42 |
Claims
1. A composition for removing residue, the composition comprising:
a) at least about 50% by weight of an organic solvent wherein at
least about 50% of the organic solvent is a glycol ether; b) at
least about 0.5% by weight of a quaternary ammonium compound; and
c) a positive amount up to about 20% by weight of a corrosion
inhibitor.
2. The composition of claim 1 wherein the glycol ether comprises a
glycol mono (C.sub.1-C.sub.6) alkyl ether.
3. The composition of claim 1 wherein the glycol ether comprises a
(C.sub.1-C.sub.20) alkanediol, a (C.sub.1-C.sub.6) alkyl ether, or
a (C.sub.1-C.sub.20) alkanediol di(C.sub.1-C.sub.6) alkyl
ether.
4. The composition of claim 1 wherein the glycol ether is selected
from ethylene glycol monomethyl ether, ethylene glycol monoethyl
ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl
ether, ethylene glycol diethyl ether, diethylene glycol monomethyl
ether, diethylene glycol monoethyl ether, diethylene glycol
monopropyl ether, diethylene glycol monoisopropyl ether diethylene
glycol monobutyl ether, diethylene glycol monoisobutyl ether,
diethylene glycol monobenzyl ether, diethylene glycol dimethyl
ether, diethylene glycol diethyl ether, triethylene glycol
monomethyl ether, triethylene glycol dimethyl ether, polyethylene
glycol monomethyl ether, diethylene glycol methyl ethyl ether,
triethylene glycol ethylene glycol monomethyl ether acetate,
ethylene glycol monoethyl ether acetate, propylene glycol
monomethyl ether, propylene glycol dimethyl ether, propylene glycol
monobutyl ether, propylene glycol, monoproply ether, dipropylene
glycol monomethyl ether, dipropylene glycol monopropyl ether,
dipropylene glycol monoisopropyl ether, dipropylene monobutyl
ether, dipropylene glycol diisopropyl ether, tripropylene glycol
monomethyl ether, 1-methoxy-2-butanol, 2-methoxy-1-butanol,
2-methoxy-2-methylbutanol, 1,1-dimethoxyethane, and
2-(2-butoxyethoxy)ethanol.
5. The composition of claim 1 wherein the glycol ether is selected
from the group consisting of propylene glycol monomethyl ether,
propylene glycol monopropyl ether, tri(propylene glycol)monomethyl
ether, and 2(2-butoxyethoxy)ethanol.
6. The composition of claim 1 wherein the quaternary ammonium
compound comprises a C.sub.1-C.sub.4 quaternary ammonium
compound.
7. The composition of claim 1 wherein the quaternary ammonium
compound is selected from tetramethylammounium hydroxide,
tetraethylammounium hydroxide, tetrapropylammounium hydroxide,
tetrabutylammounium hydroxide, trimethylethylammonium hydroxide,
(2-hydroxyethyl)trimethylammonium hydroxide,
(2-hydroxyethyl)triethylammonium hydroxide,
(2-hydroxyethyl)tripropylammonium hydroxide, and
(1-hydroxypropyl)trimethylammonium hydroxide.
8. The composition of claim 1 wherein quaternary ammonium compound
comprises tetramethyl ammonium hydroxide.
9. The composition of claim 1 wherein the amount of the glycol
ether is at least 50% by weight of the composition.
10. The composition of claim 1 wherein the amount of the glycol
ether is about 50% to about 70% by weight of the composition.
11. The composition of claim 1 wherein the amount of the glycol
ether is about 50% to about 60% by weight of the composition.
12. The composition of claim 1 wherein the amount of the quaternary
ammonium compound is about 0.5% to about 15% by weight of the
composition.
13. The composition of claim 12 wherein the amount of the
quaternary ammonium compound is about 0.5% to about 5% by
weight.
14. The composition of claim 1 which further comprises an auxiliary
organic solvent.
15. The composition of claim 14 wherein the auxiliary organic
solvent comprises a C.sub.2-C.sub.20 alkane diol or a
C.sub.3-C.sub.20 alkane triol.
16. The composition of claim 14 wherein the auxiliary organic
solvent comprises propylene glycol.
17. The composition of claim 16 wherein the amount of the propylene
glycol is about 0.1 to about 40% of weight.
18. The composition of claim 1 being free from fluoride-containing
compounds.
19. The composition of claim 1 wherein the composition comprises a
fluoride-containing compound.
20. The composition of claim 1 which further comprises up to about
40% by weight of water.
21. The composition of claim 1 which further comprises up to about
20% by weight of a corrosion inhibitor.
22. The composition of claim 21 wherein the corrosion inhibitor
comprises a hydroxylamine, an acid salt thereof; an organic acid,
an acid salt thereof; and mixtures thereof.
23. The composition of claim 21 where the corrosion inhibitor
comprises a hydroxylamine.
24. The composition of claim 23 wherein said hydroxylamine
comprises diethyl hydroxylamine.
25. A method for removing photoresist or etching residue or both
from a substrate wherein comprises contacting said substrate with a
composition comprising: a) at least about 50% by weight of an
organic solvent wherein at least about 50% of said organic solvent
is a glycol ether, and b) at least about 0.5% by weight of a
quaternary ammonium compound.
Description
RELATED APPLICATION
[0001] This application is a continuation of U.S. Ser. No.
10/896,589 (Attorney docket 06586 USA) filed Jul. 22, 2004, having
the same title and inventors, which is incorporated in its entirety
herein by reference.
BACKGROUND OF THE INVENTION
[0002] Numerous steps are involved in the fabrication of
microelectronic structures. Within the manufacturing scheme of
fabricating integrated circuits selective etching of different
surfaces of the semiconductor is sometimes required. Historically,
a number of vastly different types of etching processes, to
selectively remove material, have been successfully utilized to
varying degrees. Moreover, the selective etching of different
layers, within the microelectronic structure, is considered a
critical and crucial step in the integrated circuit fabrication
process.
[0003] Increasingly, reactive ion etching (RIE), is the process of
choice for pattern transfer during via, metal line and trench
formation. For instance, complex semi-conductor devices such as
advanced DRAMS and microprocessors, which require multiple layers
of back end of line interconnect wiring, utilize RIE to produce
vias, metal lines and trench structures. Vias are used, through the
interlayer dielectric, to provide contact between one level of
silicon, silicide or metal wiring and the next level of wiring.
Metal lines are conductive structures used as device interconnects.
Trench structures are used in the formation of metal line
structures. Vias, metal lines and trench structures typically
expose metals and alloys such as Al, Al and Cu alloys, Cu, Ti, TiN,
Ta, TaN, W, TiW, silicon or a silicide such as a silicide of
tungsten, titanium or cobalt. The RIE process typically leaves a
residue (of a complex mixture) that may include re-sputtered oxide
material as well as possibly organic materials from photoresist and
antireflective coating materials used to lithographically define
the vias, metal lines and or trench structures.
[0004] It would therefore be desirable to provide a selective
cleaning composition and process capable of removing residues such
as, for example, remaining photoresist and/or processing residues,
such as for example, residues resulting from selective etching
using plasmas and/or RIE. Moreover, it would be desirable to
provide a selective cleaning composition and process, capable of
removing residues such as photoresist and etching residue, that
exhibits high selectivity for the residue as compared to metals,
high k dielectric materials, silicon, silicide and/or interlevel
dielectric materials including low k dielectric materials such as
deposited oxides that might also be exposed to the cleaning
composition. It would be desirable to provide a composition that is
compatible with and can be used with such sensitive low-k films as
HSQ, MSQ, FOx, black diamond and TEOS (tetraethylsilicate).
SUMMARY OF THE INVENTION
[0005] The composition disclosed herein is capable of selectively
removing residue such as photoresist and processing residue from a
substrate without attacking to any undesired extent metal, low k,
and/or high k dielectric materials that might also be exposed to
the composition. In addition, the composition disclosed herein may
exhibit minimal etch rates of certain dielectric materials such as
silicon oxide.
[0006] In one aspect, there is provided a composition for removing
residues comprising at least about 50% by weight of an organic
solvent; wherein at least about 50% of the organic solvent
contained therein is a glycol ether; and at least about 0.5% by
weight of a quaternary ammonium compound.
[0007] In another aspect, the composition may further include an
auxiliary organic solvent that includes at least one of a dihydric
alcohol and/or a polyhydric alcohol. In still a further aspect, the
composition may comprise water and optionally a corrosion
inhibitor.
[0008] Also disclosed herein is a method for removing residues
including photoresist and/or etching residue from a substrate that
comprises contacting the substrate with the above-disclosed
composition.
BEST AND VARIOUS MODES FOR CARRYING OUT INVENTION
[0009] A composition and process comprising same for selectively
removing residues such as, for example, photoresist and/or
processing residues such as the residues generated by etching
particularly reactive ion etching. In a cleaning process involving
articles such as substrates useful for microelectronic devices,
typical contaminants to be removed may include, for example,
organic compounds such as exposed photoresist material, photoresist
residue, UV- or X-ray-hardened photoresist, C-F-containing
polymers, low and high molecular weight polymers, and other organic
etch residues; inorganic compounds such as metal oxides, ceramic
particles from CMP slurries and other inorganic etch residues;
metal containing compounds such as organometallic residues and
metal organic compounds; ionic and neutral, light and heavy
inorganic (metal) species, moisture, and insoluble materials,
including particles generated by processing such as planarization
and etching processes. In one particular embodiment, residues
removed are processing residues such as those created by reactive
ion etching.
[0010] Moreover, the photoresist and/or processing residues are
typically present in an article that also includes metal, silicon,
silicate and/or interlevel dielectric material such as deposited
silicon oxides and derivitized silicon oxides such as HSQ, MSQ,
FOX, TEOS and Spin-On Glass, and/or high-k materials such as
hafnium silicate, hafnium oxide, barium strontium titanium (BST),
Ta.sub.2O.sub.5, and TiO.sub.2, wherein both the photoresist and/or
residues and the metal, silicon, silicide, interlevel dielectric
materials and/or high-k materials will come in contact with the
cleaning composition. The composition and method disclosed herein
provides for selectively removing residues without significantly
attacking the metal, silicon, silicon dioxide, interlevel
dielectric materials, and/or high-k materials. In one embodiment,
the composition disclosured herein may be suitable for structures
containing sensitive low k-films. In certain embodiments, the
substrate may contain a metal, such as, but not limited to, copper,
copper alloy, titanium, titanium nitride, tantalum, tantalum
nitride, tungsten, titanium/tungsten, aluminum and/or aluminum
alloys. The compositions disclosed herein may comprise at least
about 50% by weight of an organic solvent wherein at least about
50% of the organic solvent contained therein is a glycol ether and
at least about 0.5% by weight of a quaternary ammonium compound. In
certain embodiments, the composition may contain from about 50 to
about 70% of the glycol ether, or from about 50 to about 60% of the
glycol ether.
[0011] The glycol ethers are typically water miscible and may
include glycol mono(C.sub.1-C.sub.6)alkyl ethers and glycol
di(C.sub.1-C.sub.6)alkyl ethers, such as but not limited to,
(C.sub.1-C.sub.20)alkane diols, (C.sub.1-C.sub.6)alkyl ethers, and
(C.sub.1-C.sub.20)alkane diol di(C.sub.1-C.sub.6)alkyl ethers.
[0012] Examples of glycol ethers are ethylene glycol monomethyl
ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl
ether, ethylene glycol dimethyl ether, ethylene glycol diethyl
ether, diethylene glycol monomethyl ether, diethylene glycol
monoethyl ether, diethylene glycol monopropyl ether, diethylene
glycol monoisopropyl ether diethylene glycol monobutyl ether,
diethylene glycol monoisobutyl ether, diethylene glycol monobenzyl
ether, diethylene glycol dimethyl ether, diethylene glycol diethyl
ether, triethylene glycol monomethyl ether, triethylene glycol
dimethyl ether, polyethylene glycol monomethyl ether, diethylene
glycol methyl ethyl ether, triethylene glycol ethylene glycol
monomethyl ether acetate, ethylene glycol monoethyl ether acetate,
propylene glycol monomethyl ether, propylene glycol dimethyl ether,
propylene glycol monobutyl ether, propylene glycol, monoproply
ether, dipropylene glycol monomethyl ether, dipropylene glycol
monopropyl ether, dipropylene glycol monoisopropyl ether,
dipropylene monobutyl ether, dipropyllene glycol diisopropyl ether,
tripropylene glycol monomethyl ether, 1-methoxy-2-butanol,
2-methoxy-1-butanol, 2-methoxy-2-methylbutanol, 1,1-dimethoxyethane
and 2-(2-butoxyethoxy)ethanol.
[0013] More typical examples of glycol ethers are propylene glycol
monomethyl ether, propylene glycol monopropyl ether, tri(propylene
glycol)monomethyl ether and 2-(2-butoxyethoxy)ethanol.
[0014] As mentioned previously, the composition further includes
one or more quaternary ammonium compound. Examples of quaternary
ammonium compounds include lower-alkyl (e.g. (C.sub.1-C.sub.4)
quaternary ammonium compounds and include tetramethylammounium
hydroxide (TMAH), tetraethylammounium hydroxide, tetrabutylammonium
hydroxide, tetrapropylammounium hydroxide, trimethylethylammonium
hydroxide, (2-hydroxyethyl)trimethylammonium hydroxide,
(2-hydroxyethyl)triethylammonium hydroxide,
(2-hydroxyethyl)tripropylammonium hydroxide, and
(1-hydroxypropyl)trimethylammonium hydroxide. In certain
embodiments, the quaternary ammonium compounds are added to the
compositions in the free base or hydroxide form. The quaternary
ammonium compounds are present in an amount ranging from about 0.5%
to 15%. In certain embodiments, the compositions may contain from
about 0.5% to about 5% or from about 1% to about 5%.
[0015] In certain embodiments, the composition may contain one or
more auxiliary organic solvent. In these embodiments, the organic
solvent may be water miscible and includes dihydric and polyhydric
alcohols such as diols and polyols such as (C.sub.2-C.sub.20)
alkane diols and (C.sub.3-C.sub.20) alkane triols, cyclic alcohols
and substituted alcohols. Particular examples of these auxiliary
organic solvents are propylene glycol, tetrahydrofurfuryl alcohol,
diacetone alcohol and 1,4-cyclohexanedimethanol. In these
embodiments, the auxiliary organic cosolvent is present in amounts
ranging from 0.1 to about 40% or from 0.1 to 20% by weight.
[0016] The composition may optionally contain up to about 40% by
weight of water, or up to about 35% by weight of water or up to
about 10% by weight of water. In embodiments wherein water is added
to the composition, the water is deionized water.
[0017] The compositions of the present disclosure can also
optionally contain up to about 20% by weight, or about 0.2 to about
19% by weight of a corrosion inhibitor. Examples of corrosion
inhibitors include, but are not limited to, organic acids, organic
acid salts, catechol, gallic acid, benzotriazole (BZT), resorcinol,
other phenols, acids or triazoles, and more typically
hydroxylamines or acid salts thereof. Preferred hydroxylamines are
diethylhydroxylamine and the lactic acid and citric acid salts
thereof. Ordinarily, hydroxylamines are not considered as being
compatible with copper because of their ability to etch. However,
in the composition of the present disclosure they surprisingly
inhibit copper corrosion.
[0018] In certain embodiments, the composition may include a
fluoride containing compound. Fluoride containing compounds may
include those of the general formula R.sub.1R.sub.2R.sub.3R.sub.4NF
where R.sub.1, R.sub.2, R.sub.3, and R.sub.4 are each independently
hydrogen, an alcohol group, an alkoxy group, an alkyl group and
mixtures thereof. Examples of such compositions are ammonium
fluoride, tetramethyl ammonium fluoride and tetraethyl ammonium
fluoride. Still further examples of fluoride-containing compounds
include fluoroboric acid, hydrofluoric acid, and choline fluoride.
In these embodiments, the fluoride containing compound or mixture
thereof is present in amounts of from 0.1% by weight to 20% or from
0.1 to 10% by weight based on the total weight of the composition.
In certain embodiments, the fluoride compound is added to the
compositions in the form of a fluoride salt.
[0019] The composition may also include one or more of the
following additives: surfactants, chelating agents, chemical
modifiers, dyes, biocides, and other additives. Some examples of
representative include acetylenic alcohols and derivatives thereof,
acetylenic diols (non-ionic alkoxylated and/or self-emulsifiable
acetylenic diol surfactants) and derivatives thereof, alcohols,
quaternary amines and di-amines, amides (including aprotic solvents
such as dimethyl formamide and dimethyl acetamide), alkyl
alkanolamines (such as diethanolethylamine), and chelating agents
such as beta-diketones, beta-ketoimines, carboxylic acids, mallic
acid and tartaric acid based esters and diesters and derivatives
thereof, and tertiary amines, diamines and triamines.
[0020] Compositions disclosed herein are compatible with low-k
films such as HSQ (FOx), MSQ, SILK, etc. including those containing
a fluoride. The formulations are also effective in stripping
photoresists including positive and negative photoresists and
plasma etch residues such as organic residues, organometallic
residues, inorganic residues, metallic oxides, or photoresist
complexes at low temperatures with very low corrosion of aluminum,
copper, titanium containing substrates. Moreover, the compositions
are compatible with a variety of high dielectric constant
materials.
[0021] During the manufacturing process, a photoresist layer is
coated on the substrate. Using photolithographic process, a pattern
is defined on the photoresist layer. The patterned photoresist
layer is thus subjected to plasma etch by which the pattern is
transferred to the substrate. Etch residues are generated in the
etch stage. Some of the substrates used in this invention are ashed
while some are not ashed. When the substrates are ashed the main
residues to be cleaned are etchant residues. If the substrates are
not ashed, then the main residues to be cleaned or stripped are
both etch residues and photoresists.
[0022] The composition disclosed herein are used to remove post
etch and ash, organic and inorganic residues as well as polymeric
residues from semiconductor substrates at low temperatures with low
corrosion. In general, the stripping and cleaning processes using
the composition disclosed herein are carried out by immersing a
substrate in the stripper/cleaner composition at one or more
temperatures ranging from 25.degree. C. to 85.degree. C. for a
period of time ranging from 3 minutes to 1 hour. However, the
composition can be used in any method known in the art that
utilizes a cleaning fluid for the removal of photoresist, ash or
etch residues and/or residues.
[0023] The following non-limiting examples are presented to further
illustrate the present disclosure.
[0024] The photoresists in the following examples undergo one of
the processes as discussed below.
[0025] A positive photoresist is a spin-coated on to a substrate.
The positive photoresist comprises diazonaphthoquinone and novolak
resin. The photoresist after being coated is baked at about
90.degree. C. for about 90 seconds. A pattern is defined on the
photoresist by exposure, through a patterned mask, to i-line (365
nm) rays followed by development. The pattern is then transferred
via plasma etch to the substrate.
[0026] A negative photoresist is spin-coated on to a substrate. The
photoresist after being coated is baked at about 90.degree. C. for
about 90 seconds. A pattern is defined on the photoresist by
exposure, through a patterned mask, to i-line (365 nm) rays
followed by development. The pattern is then transferred via plasma
etch to the substrate.
[0027] A positive photoresist is spin-coated on to a substrate. The
photoresist coated is baked at 90.degree. C. for 90 seconds. A
pattern is defined on the photoresist by exposure, through a
patterned mask, to deep ultra-violet (248 nm) rays followed by
development. The pattern is then transferred via plasma etch to the
substrate.
[0028] The stripper and cleaner compositions of the present
invention are typically prepared by mixing the components together
in a vessel at room temperature until all solids have dissolved.
Examples of the aqueous stripper and cleaner compositions are set
forth in Table I. The summary of etch rate data and cleaning data
are provided in Tables II and III, respectively.
[0029] During the manufacturing process, a photoresist layer is
coated on the substrate. Using photolithographic process, a pattern
is defined on to the photoresist layer. The patterned photoresist
layer is thus subjected to plasma etch by which the pattern is
transferred to the substrate. Etch residues are generated in the
etch stage. Some of the substrates used in this disclosure are
ashed while some are not ashed. When the substrates are ashed the
main residues to be cleaned are etch residues. If the substrates
are not ashed, then the main residues to be cleaned or stripped are
both etch residues and photoresists.
[0030] All of the examples from the Table I were very effective in
stripping and cleaning photoresists, etch and ashed residues. The
process temperature is typically 40.degree. C. or less and each of
the examples can be used in batch cleaning process, spray tools and
single wafer tools.
[0031] For the following tables, all amounts are given in weight
percent and add up to 100 weight percent unless otherwise noted.
Metal etch rates were determined using a CDE ResMap 273 Four Point
Probe (E-M-DGLAB-0007). 500 mls of test solution was placed in a
600 ml beaker with stirring and heated, if required to the
specified temperature. If the metal to be tested was titanium, an
initial dip in phosphoric acid was required. The initial thickness
of a wafer was determined using the CDE ResMap 273 Four Point
Probe. After determining the initial thickness, test wafers were
immersed in the test solution. If only one test wafer was being
examined, a dummy wafer was added to the solution. After five
minutes the test wafers were removed from the test solution, rinsed
for three minutes with deionized water and completely dried under
nitrogen. If a negative stripper solution was used, an intermediate
rinse of the test wafer in a solvent such as DMAC or IPA (isopropyl
alcohol) was performed for three minutes prior to the water wash.
The thickness of each wafer was measured and if necessary the
procedure was repeated on the test wafer.
[0032] Oxide etch rates were determined using a Nanospec AFT 181
(E-M-DGLAB-0009). 200 mls of a test solution was placed in a 250 ml
beaker with stirring and heated, if required, to the specified
temperature. Three circles were scribed on each of the wafers to be
tested. The marked areas on each wafer were the areas in which
measurements would be taken. Initial measurements of each wafer
were taken. After the initial measurements the wafers were immersed
in the test solution for five minutes. If only one wafer was placed
in a beaker containing solution a dummy wafer was placed in the
beaker. After five minutes each test wafer was washed with
deionized water for three minutes and dried under nitrogen. If a
negative stripper solution was used DMAC, IPA or another suitable
solvent was used to rinse the test wafers for three minutes prior
to the water rinse. Measurements of the scribed areas on each wafer
were taken and if necessary the procedure was repeated.
TABLE-US-00001 TABLE I Sample Formulations Example A Example B
Example C Example A1 BEE 92 BEE 89 THFA 48 PGME 57.6 TBAH 0.6 TBAH
0.6 TMAH 5 Water 20.9 p-TSA 2.8 p-TSA 2.8 p-TSA 2.8 TBAH 1.1 MEA 1
MEA 1 MEA 1 TEA/p-TSA 2.4 Water 3.6 Water 3.6 Water 13.2 DEHA 5 3
PGME 30 Resorcinol 3 Example D Example E Example F Example A2 PGME
92 PGME 75 PGME 76 PGME 62.7 TBAH 0.6 TMAH 5.5 TMAH 5.5 DI Water 25
p-TSA 2.8 p-TSA 2.8 p-TSA 4 TMAF 1 MEA 1 MEA 1 MEA 1.4 lactic acid
3 Water 3.6 water 15.7 Water 10.1 TEAH 8.3 Citric acid 3 Example G
Example H Example I Example A3 PGME 55 PGME 69 PGME 80 PGPE 36 TBAH
5.5 TBAH 5.5 TMAH 5.5 PGME 31 p-TSA 4 p-TSA 4 water 5.5 water 21.3
MEA 1.4 MEA 1.4 citric acid 2 TBAH 1.7 water 14.1 water 10.1 DEHA 7
MEA/p-TSA 2 PGPE 20 DEHA 10 DEHA 5 Resorcinol 3 Example J Example K
Example L Example A4 PGPE 66 PGPE 56 PGPE 56 PGME 54.7 PG 10 t-PGME
39 t-PGME 35.5 DI Water 29 TMAH 5.5 water 0.4 water 0 TMAF 1 DEHA 7
TBAH 0.6 TBAH 0.5 TES-tos 4 p-TSA 3 p-TSA 3 p-TSA 6 lacic acid 3
lactic acid 2 MEA 1 MEA 2 TEAH 8.3 MEA 1 Water 5.5 Example M
Example N Example O Example A5 t-PGME 91.5 PGPE 66 PGPE 66 PGME 57
water 0.2 PG 10 PG 13 TMAH 6 TBAH 0.3 TMAH 5.5 TMAH 5.5 DEHA 4
p-TSA 6 DEHA 8 DEHA 8 water 31 MEA 2 p-TSA 3 Water 5.5 lactic acid
2 lactic acid 2 lactic acid 2 Water 5.5 Example P Example Q Example
R Example S t-PGME 66 Water 0.9 t-PGME 43 PGPE 58 PG 13 t-PGME 80
DI Water 32.2 PG 23 TMAH 5.5 t-BA 10 Amm. Fluoride 0.8 TMAH 2.5
DEHA 8 TBAH 1.1 PG 15 DEHA 8 water 5.5 p-TSA 6 DEHA 8 TMAF 0.8
lactic acid 2 MEA 2 TMAH 1 lactic acid 2 DI water 5.7
[0033] The following are the acronyms used in Table I:
TABLE-US-00002 PGME Propylene glycol methyl ether THFA
Tetrahydrofurfuryl alcohol PG Propylene glycol BEE
2-(2-Butoxy)ethanol PGPE Propylene glycol methyl ether DEHA
Dihydroxyamine t-BA tributyl amine t-PGME Tri(propylene glycol)
TMAH tetramethylammonium methyl ether hydroxide TBAH
tetrabutylammonium p-TSA p-toluenesulfonic acid hydroxide TMAF
tetramethylammonium MEA ethanolamine fluoride TEAH
tetraethylammonium TEA/p-TSA triethanolammonium Hydroxide
p-tosylate MEA/p-TSA ethanolammonium p-tosylate
Example A
[0034] As Table I illustrates, the composition of example A
consists of 92 weight % of BEE, 0.6 weight % of TBAH, 3.6 weight %
of deionized water, 2.8 weight % of p-TSA and 1 weight % of MEA.
Example A is a cleaning and stripping composition for removing etch
residues and photoresists from metal lines as well as vias.
Example C
[0035] The composition of example C consists of 48 weight % of
THFA, 5 weight % of TMAH, 30 weight % of PGME, 2.8 weight % of
p-TSA, 1 weight % of MEA and 13.2 weight % of deionized water.
Example C is a cleaning and stripping composition for removing etch
residue and photoresists from transition metal substrates as well
as high-k materials.
Example E
[0036] The composition of example E consists of 75 weight % of
PGME, 5.5 weight % of TBAH, 2.8 weight % of p-TSA, 1 weight % of
MEA and 13.2 weight % of deionized water. Example E is a cleaning
and stripping composition for removing etch residue and
photoresists from transition metal substrates as well as high-k
materials.
Example H
[0037] The composition of example H consists of 69 weight % of
PGME, 5.5 weight % of TBAH, 10 weight % of DEHA, 4 weight % of
p-TSA, 1.4 weight % of MEA and 10.1 weight % of deionized water.
Example H is a cleaning and stripping composition for removing etch
residue and photoresists from transition metal substrates as well
as high-k materials.
Example K
[0038] The composition of example K consists of 56 weight % of
PGPE, 0.6 weight % of TBAH, 39 weight % of t-PGME, 3 weight % of
p-TSA, 1 weight % of MEA and 0.4 weight % of deionized water.
Example K is a cleaning and stripping composition for removing etch
residue and photoresists from transition metal substrates as well a
high-k materials.
Example N
[0039] The composition of example N consists of 66 weight % of
PGPE, 5.5 weight % of TMAH, 10 weight % of PG, 3 weight % of p-TSA,
8 weight % of DEHA, 2 weight % of lactic acid and 5.5 weight % of
deionized water. Example N is a cleaning and stripping composition
for removing etch residue and photoresists from transition metal
substrates as well as high-k materials.
Example O
[0040] The composition of example O consists of 66 weight % of
PGPE, 5.5 weight % of TMAH, 13 weight % of PG, 8 weight % of DEHA,
2 weight % of lactic acid and 5.5 weight % of deionized water.
Example O is a cleaning and stripping composition for removing etch
residue and photoresists from transition metal substrates as well
as a high-k materials.
Example P
[0041] The composition of example P consists of 66 weight % of
PGPE, 5.5 weight % of TMAH, 13 weight % of PG, 8 weight % of DEHA,
2 weight % of lactic acid and 5.5 weight % of deionized water.
Example P is a cleaning and stripping composition for removing etch
residue and photoresists from transition metal substrates as well
as a high-k materials.
Example Q
[0042] The composition of example Q consists of 80 weight % of
t-PGME, 1.1 weight % of TBAH, 10 weight % of t-BA, 6 weight % of
p-TSA, 2 weight % of MEA and 0.9 weight % of deionized water.
Example Q is a cleaning and stripping composition for removing etch
residue and photoresists metal lines as well as a vias.
Example A1
[0043] The composition of example Al consists of 57.6 weight % of
PGME, 1.1 weight % of TBAH, 2.4 weight % of triethanolammonium
p-tosylate, 5 weight % of DEHA, 3 weight % of resorcinol and 20.9
weight % of deionized water. Example A1 is a cleaning and stripping
composition for removing etch residue and photoresists metal
substrates, low-k materials as well as a high-k materials.
Example A2
[0044] The composition of example A2 consists of 62.7 weight % of
PGME, 1.6 weight of TEAH, 1 weight % of tetramethylammonium
fluoride, 3 weight % of lactic acid and 31.7 weight % of deionized
water. Example A2 is a cleaning and stripping composition for
removing etch residue and photoresists metal substrates, low-k
materials as well as a high-k materials.
Example A5
[0045] The composition of example A5 consists of 57 weight % of
PGME, 6 weight % of TMAH, 4 weight % of DEHA, 2 weight % of lactic
acid and 31 weight % of deionized water. Example A5 is a cleaning
and stripping composition for removing etch residue and
photoresists metal substrates, low-k materials as well as a high-k
materials.
TABLE-US-00003 TABLE II Summary of etch rate data Exam- Temperature
Al (.ANG./ Cu (.ANG./ Ti (.ANG./ W (.ANG./ ples (.degree. C.)
minute) minute) minute) minute) A 65 <1 Nt ~1 Nt B 65 <1 Nt
~1 Nt C 65 >500 nt Nt Nt D 65 ~1 ~8 Nt Nt E 65 >500 ~5 Nt Nt
F 65 >500 Nt Nt Nt G 65 >500 Nt Nt Nt H 65 >500 ~5 Nt Nt I
65 >500 ~5 Nt Nt J 65 ~20 ~2 Nt Nt K 65 ~10 ~7 Nt Nt L 65 ~1 ~5
Nt Nt M 65 ~3 ~7 Nt Nt N 65 >500 ~2 Nt Nt O 65 >500 ~1 Nt Nt
P 65 >500 ~2 Nt Nt Q 65 ~3 ~9 Nt Nt R 25 >500 ~7 Nt Nt S 40
>500 ~3 Nt Nt A1 65 ~1 ~9 <1 ~2 A2 25 >500 ~2 ~1 <1 A2
50 >1000 ~6 >100 ~7 A3 65 Nt ~4 Nt Nt A4 25 >500 Nt Nt Nt
A5 65 >500 ~5 Nt Nt
TABLE-US-00004 TABLE III Summary of cleaning data Substrate A
Substrate B Exam- Temp Com- Temp Un- com- ples (.degree. C.) Lines
Vias ments (.degree. C.) Ashed ashed ments A 50 X Part. Nt nt Corr.
B Nt Nt 60 X C 50 X Nt Nt D 55 X Nt Nt E Nt Nt 60 F Nt Nt 60 X G Nt
Nt 60 X H Nt Nt 60 X K 50 Corr. 65 X X N Nt Nt 65 Nt Nt 75 O nt nt
65 Nt Nt 75 Nt Nt 85 P Nt Nt 65 X Q 55 X X Nt Nt A1 55 Nt Nt A1 65
Nt Nt A2 Nt Nt 40 X A5 Nt Nt 65 Corr. Nt = not tested; Part. Corr.
= partial metal corrosion; Corr. = metal corrosion; = partially
cleaned; = completely cleaned; X = not cleaned.
* * * * *