U.S. patent application number 13/718830 was filed with the patent office on 2013-05-02 for composition and process for post-etch removal of photoresist and/or sacrificial anti-reflective material deposited on a substrate.
This patent application is currently assigned to ADVANCED TECHNOLOGY MATERIALS, INC.. The applicant listed for this patent is ADVANCED TECHNOLOGY MATERIALS, INC.. Invention is credited to Thomas H. Baum, David D. Bernhard, Michael B. Korzenski, David Minsek, Melissa K. Rath.
Application Number | 20130109605 13/718830 |
Document ID | / |
Family ID | 34911755 |
Filed Date | 2013-05-02 |
United States Patent
Application |
20130109605 |
Kind Code |
A1 |
Rath; Melissa K. ; et
al. |
May 2, 2013 |
COMPOSITION AND PROCESS FOR POST-ETCH REMOVAL OF PHOTORESIST AND/OR
SACRIFICIAL ANTI-REFLECTIVE MATERIAL DEPOSITED ON A SUBSTRATE
Abstract
A composition and process for removing photoresist and/or
sacrificial anti-reflective coating (SARC) materials from a
substrate having such material(s) thereon. The composition includes
a base component, such as a quaternary ammonium base in combination
with an alkali or alkaline earth base, or alternatively a strong
base in combination with an oxidant. The composition may be
utilized in aqueous medium, e.g., with chelator, surfactant, and/or
co-solvent species, to achieve high-efficiency removal of
photoresist and/or SARC materials in the manufacture of integrated
circuitry, without adverse effect on metal species on the
substrate, such as copper, aluminum and/or cobalt alloys, and
without damage to SiOC-based dielectric materials employed in the
semiconductor architecture.
Inventors: |
Rath; Melissa K.; (Danbury,
CT) ; Bernhard; David D.; (Kooskia, ID) ;
Minsek; David; (New Milford, CT) ; Korzenski; Michael
B.; (Danbury, CT) ; Baum; Thomas H.; (New
Fairfield, CT) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
ADVANCED TECHNOLOGY MATERIALS, INC.; |
Danbury |
CT |
US |
|
|
Assignee: |
ADVANCED TECHNOLOGY MATERIALS,
INC.
Danbury
CT
|
Family ID: |
34911755 |
Appl. No.: |
13/718830 |
Filed: |
December 18, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10792038 |
Mar 3, 2004 |
8338087 |
|
|
13718830 |
|
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Current U.S.
Class: |
510/176 ; 134/2;
510/175 |
Current CPC
Class: |
C11D 3/3947 20130101;
G03F 7/423 20130101; G03F 7/425 20130101; C11D 11/0047 20130101;
C11D 7/06 20130101; C11D 3/30 20130101; C11D 3/044 20130101 |
Class at
Publication: |
510/176 ;
510/175; 134/2 |
International
Class: |
C11D 3/04 20060101
C11D003/04; C11D 7/06 20060101 C11D007/06 |
Claims
1. A cleaning composition useful for removing photoresist and/or
sacrificial anti-reflective coating (SARC) materials from a
substrate having such material(s) thereon, said composition
comprising potassium hydroxide in combination with an oxidant.
2.-8. (canceled)
9. The cleaning composition of claim 1, which includes an aqueous
solution of at least one oxidant, potassium hydroxide, optionally a
chelator and optionally a co-solvent and/or a surfactant.
10. (canceled)
11. The cleaning composition of claim 1 including the following
components: 0.1-30 wt % potassium hydroxide strong base; 0.01-30 wt
% oxidant; 0-10 wt % chelator; 0-5 wt % surfactant; 0-50 wt %
co-solvent; and 20-98.9 wt % deionized water, wherein percentages
of the components are percentages by weight, based on total weight
of the composition, and wherein the total of the weight percentages
of such components of the composition does not exceed 100 weight
%.
12. (canceled)
13. The cleaning composition of claim 1 wherein the oxidant
comprises an oxidant species selected from the group consisting of
hydrogen peroxide, amine-N-oxides, perborate salts, persulfate
salts, and combinations of two or more of the foregoing.
14. The cleaning composition of claim 1, including a chelator.
15. (canceled)
16. The cleaning composition of claim 14, wherein the chelator
comprises a chelator species selected from the group consisting of:
1,2,4-triazole; benzotriazole; tolyltriazole;
5-phenyl-benzotriazole; 5-nitro-benzotriazole;
4-methyl-2-phenylimidazole; 2-mercaptothiazoline;
1-amino-1,2,4-triazole; hydroxybenzotriazole;
2-(5-amino-pentyl)-benzotriazole; 1-amino-1,2,3-triazole;
1-amino-5-methyl-1,2,3-triazole; 3-amino-1,2,4-triazole;
3-mercapto-1,2,4-triazole; 3-amino-5-mercapto-1,2,4-triazole,
3-isopropyl-1,2,4-triazole; 5-phenylthiol-benzotriazole;
halo-benzotriazoles wherein halo is selected from the group
consisting of F, Cl, Br and I; naphthotriazole;
2-mercaptobenzoimidizole; 2-mercaptobenzothiazole;
5-aminotetrazole; 5-amino-1,3,4-thiadiazole-2-thiol;
2,4-diamino-6-methyl-1,3,5-triazine; thiazole; triazine;
methyltetrazole; 1,3-dimethyl-2-imidazolidinone;
1,5-pentamethylenetetrazole; 1-phenyl-5-mercaptotetrazole;
diaminomethyltriazine; mercaptobenzothiazole; imidazoline thione;
mercaptobenzimidazole ; 4-methyl-4H-1,2,4-triazole-3-thiol; 5-amino
-1,3,4 -thiadiazole-2-thiol; benzothiazole; tritolyl phosphate;
indiazole; guanine; adenine; glycerol; thioglycerol;
nitrilotriacetic acid; salicylamide; iminodiacetic acid;
benzoguanamine; melamine; thiocyranuric acid; anthranilic acid;
gallic acid; ascorbic acid; salicylic acid; 8-hydroxyquinoline;
5-carboxylic acid-benzotriazole; 3-mercaptopropanol; boric acid;
and iminodiacetic acid.
17. The cleaning composition of claim 1, comprising a surfactant
wherein the surfactant comprises a surfactant species selected from
the group consisting of: fluoroalkyl surfactants; polyethylene
glycols; polypropylene glycols; polyethylene glycol ethers;
polypropylene glycol ethers; carboxylic acid salts;
dodecylbenzenesulfonic acid and salts thereof; polyacrylate
polymers; dinonylphenyl polyoxyethylene; silicone polymers;
modified silicone polymers; acetylenic diols; modified acetylenic
diols, alkylammonium salts; modified alkylammonium salts; and
combinations of two or more of the foregoing.
18. (canceled)
19. The cleaning composition of claim 9, comprising a
co-solvent.
20. (canceled)
21. The composition of claim 19, wherein the co-solvent comprises a
co-solvent species selected from the group consisting of:
dimethyldiglycolamine; 1,8-diazabicyclo[5.4.0]undecene;
aminopropylmorpholine; triethanolamine; methylethanolamine;
diethylene glycol; propylene glycol; neopentyl glycol;
hydroxyethylmorpholine; aminopropylmorpholine; di(ethylene
glycol)monoethyl ether; di(propylene glycol)propyl ether; ethylene
glycol phenyl ether; di(propylene glycol) butyl ether; butyl
carbitol; polyglycol ethers; and combinations of two or more of the
foregoing.
22. (canceled)
23. (canceled)
24. A method of removing photoresist and/or SARC material from a
substrate having said material thereon, said method comprising
contacting the substrate with a cleaning composition for sufficient
time to at least partially remove said material from the substrate,
wherein the cleaning composition comprises potassium hydroxide in
combination with an oxidant.
25. The method of claim 24, wherein the substrate comprises a
semiconductor device structure.
26.-28. (canceled)
29. The method of claim 24, wherein said contacting is carried out
for a time of from about 10 to about 45 minutes, and at temperature
in a range of from about 50.degree. C. to about 80.degree. C.
30.-37. (canceled)
38. The method of claim 24, wherein the cleaning composition
includes an aqueous solution of at least one oxidant, potassium
hydroxide, optionally a chelator and optionally a co-solvent and/or
a surfactant.
39. (canceled)
40. The method of claim 24, wherein the cleaning composition
includes the following components: 0.1-30 wt % potassium hydroxide
strong base; 0.01-30 wt % oxidant; 0-10 wt % chelator; 0-5 wt %
surfactant; 0-50 wt % co-solvent; and 20-98.9 wt % deionized water,
wherein percentages of the components are percentages by weight,
based on total weight of the composition, and wherein the total of
the weight percentages of such components of the composition does
not exceed 100 weight %.
41. (canceled)
42. The method of claim 24, wherein the oxidant comprises an
oxidant species selected from the group consisting of hydrogen
peroxide, organic peroxides, amine-N-oxides, perborate salts,
persulfate salts, and combinations of two or more of the
foregoing.
43. The method of claim 24, including a chelator.
44. (canceled)
45. The method of claim 43, wherein the chelator comprises a
chelator species selected from the group consisting of:
1,2,4-triazole; benzotriazole; tolyltriazole;
5-phenyl-benzotriazole; 5-nitro-benzotriazole;
1-amino-1,2,4-triazole; hydroxybenzotriazole;
2-(5-amino-pentyl)-benzotriazole; 1-amino-1,2,3-triazole;
4-methyl-2phenylimidazole; 2-mercaptothiazoline;
1-amino-5-methyl-1,2,3-triazole; 3-amino-1,2,4-triazole;
3-amino-5-mercapto-1,2,4-triazole, 3-mercapto-1,2,4-triazole;
3-isopropyl-1,2,4-triazole; 5-phenylthiol-benzotriazole;
halo-benzotriazoles wherein halo is selected from the group
consisting of F, Cl, Br and I; naphthotriazole;
2-mercaptobenzoimidizole; 2-mercaptobenzothiazole;
5-aminotetrazole; 5-amino-1,3,4-thiadiazole-2-thiol;
2,4-diamino-6-methyl-1,3,5-triazine; thiazole; triazine;
methyltetrazole; 1,3-dimethyl-2-imidazolidinone;
1,5-pentamethylenetetrazole; 1-phenyl-5-mercaptotetrazole;
diaminomethyltriazine; mercaptobenzothiazole; imidazoline thione;
mercaptobenzimidazole; 4-methyl-4H-1,2,4-triazole-3-thiol;
5-amino-1,3,4-thiadiazole-2-thiol; benzothiazole; tritolyl
phosphate; indiazole; guanine; adenine; glycerol; thioglycerol;
nitrilotriacetic acid; salicylamide; iminodiacetic acid;
benzoguanamine; melamine; thiocyranuric acid; anthranilic acid;
gallic acid; ascorbic acid; salicylic acid; 8-hydroxyquinoline;
5-carboxylic acid-benzotriazole; 3-mercaptopropanol; boric acid;
and iminodiacetic acid.
46. The method of claim 24, wherein the cleaning composition
comprises a surfactant, wherein the surfactant comprises a
surfactant species selected from the group consisting of:
fluoroalkyl surfactants; polyethylene glycols; polypropylene
glycols; polyethylene glycol ethers; polypropylene glycol ethers;
carboxylic acid salts; dodecylbenzenesulfonic acid and salts
thereof; polyacrylate polymers; dinonylphenyl polyoxyethylene;
silicone polymers; modified silicone polymers; acetylenic diols;
modified acetylenic diols, alkylammonium salts; modified
alkylammonium salts; and combinations of two or more of the
foregoing.
47. (canceled)
48. The method of claim 24, wherein the cleaning composition
includes a co-solvent.
49. (canceled)
50. The method of claim 48, wherein the co-solvent comprises a
co-solvent species selected from the group consisting of:
dimethyldiglycolamine; 1,8-diazabicyclo[5.4.0]undecene;
methyldiethanolamine; aminopropylmorpholine; triethanolamine;
methylethanolamine; diethylene glycol; propylene glycol; neopentyl
glycol; hydroxyethylmorpholine; aminopropylmorpholine; di(ethylene
glycol)monoethyl ether; di(propylene glycol)propyl ether; ethylene
glycol phenyl ether; di(propylene glycol) butyl ether; butyl
carbitol; polyglycol ethers; and combinations of two or more of the
foregoing.
51. (canceled)
52. (canceled)
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a composition and process
useful for removal of post-etch photoresist and/or sacrificial
anti-reflective coating material from a substrate or article having
such material deposited thereon.
[0003] 2. Description of the Related Art
[0004] Semiconductor integration as currently evolving requires (i)
use of antireflective coatings, (ii) minimization of
etch/ash-induced damage to low k dielectric material, (iii)
minimization of effective k values for dielectric/etch stop
interconnect layers and (iv) wide process latitude in terms of
permissible conditions and variation of integration techniques.
[0005] The foregoing requirements can be accommodated by use of
etching operations without ashing, using a dielectric patterning
process that employs a sacrificial antireflective coating, in
combination with a liquid cleaning chemistry that removes the
post-etch photoresist and SARC in a single process step.
[0006] Current photolithography processes used in semiconductor
manufacturing require use of a UV/light-absorbing coating below the
photoresist layer to prevent reflection of the stepper UV light.
Without this coating, significant amounts of light are reflected
off the underlying substrate. Such reflected light, in turn, can
create defects during the photolithographic process, such as
photoresist notching resulting from constructive and destructive
interference, non-uniform photospeed, occurrence of gross
photolithographic pattern defects, loss of critical dimensioning
capability, and the like.
[0007] Several approaches exist for attaining high absorbance of UV
light in photolithographic processes, including use of bi- and
tri-layer photoresists, use of bottom antireflective coatings
(BARCs) and sacrificial antireflective coatings (SARCs). All of
these approaches incorporate a UV chromophore into a spin-on
polymer matrix that absorbs incident light. All of these
antireflective coatings also have a planarizing effect on
topological wafer surfaces encountered in typical dual damascene
integration.
[0008] When SiOC-based dielectric materials are employed in the
semiconductor integration, however, the use of SARCs has two
important advantages over the other approaches mentioned above.
[0009] First, since SARC materials are based on
tetraethylorthosilicate (TEOS), they are etchable in a similar
manner and at similar rate to SiOC-based dielectric material. This
allows a very high level of etch uniformity and etch control to be
achieved, to such extent that trench etch stop layers are not
required, and via etch stop layers can be reduced in thickness by
up to 50%, in relation to the aforementioned alternative
approaches.
[0010] Second, etched SARCs can be removed by liquid
cleaner/etchant compositions, since etched SARCs do not
significantly increase their degree of cross-linking after etch, in
relation to organic-based photoresists and BARCs.
[0011] When a cleaner/etchant composition is used in
back-end-of-line (BEOL) applications to process aluminum or copper
interconnected wires, separated by low capacitance (low k)
insulating material, or dielectric, it is important that the
composition used to remove photoresist residue and SARCs possess
good metal compatibility, e.g., a low etch rate on copper,
aluminum, cobalt, etc.
[0012] Untreated photoresist possesses solubility in strong aqueous
alkaline solutions as well as solutions of select organic solvents.
However, photoresist that has been exposed to gas-phase plasma
etching, such is typically used for etching of dielectric
materials, will develop a hardened crust on the surface of the
material. The hardened crust is composed of cross-linked organic
polymer and may contain small amounts of silicon or metal atoms.
Fluorine-based plasma etches as used in dual damascene processes
may deposit fluorine atoms in the photoresist crust, which may
decrease its solubility and increase its resistance to chemical
removal.
[0013] The photoresist and crust can be removed by gas phase ashing
where the substrate is exposed to an oxidative or reductive plasma
etch, but these plasma ashing techniques can cause damage to the
dielectric, especially porous, organosilicate or organic low k
materials, causing an unacceptable increase in k value. The
semiconductor features of the structure being fabricated may
contain metals vital to the operation of the eventual product chip,
such as copper, aluminum and alloys of cobalt.
[0014] Hydroxylamine solutions have been utilized in the art for
photoresist removal, but such solutions have associated corrosion,
toxicity and reactivity problems that limit their use, with adverse
corrosion effects being particularly problematic when copper is
employed in the integrated circuitry.
SUMMARY OF THE INVENTION
[0015] The present invention in one aspect relates to a cleaning
composition useful for removing photoresist and/or sacrificial
anti-reflective coating (SARC) materials from a substrate having
such material(s) thereon. The composition includes an active
cleaning combination (ACC) selected from the group consisting of:
(a) a quaternary ammonium base in combination with at least one of
alkali and alkaline earth base; and (b) a strong base in
combination with an oxidant.
[0016] Another aspect of the invention relates to a method of
removing photoresist and/or SARC material from a substrate having
said material thereon, said method comprising contacting the
substrate with a cleaning composition for sufficient time to at
least partially remove said material from the substrate, wherein
the cleaning composition includes an active cleaning combination
(ACC) selected from the group consisting of: (a) a quaternary
ammonium base in combination with at least one of alkali and
alkaline earth base; and (b) a strong base in combination with an
oxidant.
[0017] Other aspects, features and advantages of the invention will
be more fully apparent from the ensuing disclosure and appended
claims.
DETAILED DESCRIPTION OF THE INVENTION, AND PREFERRED EMBODIMENTS
THEREOF
[0018] The present invention contemplates cleaning compositions
that are useful to remove photoresist and/or sacrificial
anti-reflective coating (SARC) materials from a substrate having
such material(s) thereon.
[0019] The composition includes an active cleaning combination
(ACC) selected from the group consisting of: (a) a quaternary
ammonium base in combination with at least one of alkali and
alkaline earth base; and (b) a strong base in combination with an
oxidant.
[0020] Compositions of the invention may be embodied in a wide
variety of specific formulations, as hereinafter more fully
described.
[0021] 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 0.01
weight percent, based on the total weight of the composition in
which such components are employed.
[0022] The present invention in one aspect thereof relates to a
cleaning composition useful for removal of SARCs and photoresist,
which includes the following components: [0023] 0.1-40.0 weight %
organic quaternary ammonium base [0024] 0.01-5 weight % alkali or
alkaline earth base [0025] 0-80 weight % solvent(s) and/or amine(s)
[0026] 0-5 weight % surfactant [0027] 0-10 weight %
chelator/passivation agent [0028] 0-98 weight % water wherein
percentages of the components are percentages by weight, based on
total weight of the composition, and wherein the total of the
weight percentages of such components of the composition does not
exceed 100 weight %.
[0029] Such composition may optionally include additional
components, including active as well as inactive ingredients, e.g.,
stabilizers, dispersants, anti-oxidants, penetration agents,
adjuvants, additives, fillers, excipients, etc.
[0030] In various embodiments, the composition may variously
comprise, consist of, or consist essentially of, the aforementioned
organic quaternary ammonium base, alkali or alkaline earth base,
solvent(s) and/or amine(s), surfactant, chelator/passivation agent,
and water components.
[0031] In one specific embodiment, the cleaning composition
includes the following components: [0032] 2-15 weight % organic
quaternary ammonium base [0033] .about.0.01-2 weight % alkali or
alkaline earth base [0034] 0-50 weight % solvent(s) and/or amine(s)
[0035] .about.0.01-2 weight % surfactant [0036] 0-5 weight %
chelator/passivation agent [0037] 40-95 weight % water wherein
percentages of the components are percentages by weight, based on
total weight of the composition, and wherein the total of the
weight percentages of such components of the composition does not
exceed 100 weight %.
[0038] In various preferred embodiments, the cleaning composition
is formulated in the following Formulations A-G, wherein all
percentages are by weight, based on the total weight of the
formulation:
Formulation A
[0039] 5.36% benzyltrimethylammonium hydroxide [0040] 0.28%
potassium hydroxide [0041] 3.0% 4-methylmorpholine N-oxide [0042]
0.30% polyoxyethylene(150) dinonylphenyl ether [0043] 0.08%
2-mercaptobenzimidazole [0044] 91.0% water
Formulation B
[0044] [0045] 5.36% benzyltrimethylammonium hydroxide [0046] 0.28%
potassium hydroxide [0047] 3.0% 4-methylmorpholine N-oxide [0048]
0.30% polyoxyethylene(150) dinonylphenyl ether [0049] 0.20%
5-amino-1,3,4-thiadiazole-2-thiol [0050] 90.86% water
Formulation C
[0050] [0051] 3.60% benzyltrimethylammonium hydroxide [0052] 0.27%
potassium hydroxide [0053] 3.5% 4-methylmorpholine N-oxide [0054]
15.0% 4-(3-aminopropyl)morpholine [0055] 0.30% polyoxyethylene(150)
dinonylphenyl ether [0056] 0.08% 2-mercaptobenzimidazole [0057]
77.25% water
Formulation D
[0057] [0058] 5.36% benzyltrimethylammonium hydroxide [0059] 0.28%
potassium hydroxide [0060] 20.0% dimethyl sulfoxide [0061] 0.08%
2-mercaptobenzimidazole [0062] 74.28% water
Formulation E
[0062] [0063] 5.36% benzyltrimethylammonium hydroxide [0064] 0.28%
potassium hydroxide [0065] 10.0% tetramethylene sulfone [0066]
0.30% oxirane, methyl-, polymer with oxirane, ether with
2.2'-(oxidoimino)bis(ethanol) (2:1),
N(-3(C(-11-isoalkyloxy)propyl)derivatives, C.sub.10-rich [0067]
0.08% 2-mercaptobenzimidazole [0068] 83.98% water
Formulation F
[0068] [0069] 5.36% benzyltrimethylammonium hydroxide [0070] 0.28%
potassium hydroxide [0071] 10.0% di(ethyleneglycol)butyl ether
[0072] 10.0% 2-(2-dimethylamino)ethoxy)ethanol [0073] 0.30%
oxirane, methyl-, polymer with oxirane, ether with
2.2'-(oxidoimino)bis(ethanol) (2:1),
N(-3(C(-11-isoalkyloxy)propyl)derivatives, C.sub.10-rich [0074]
74.06% water
Formulation G
[0074] [0075] 5.36% benzyltrimethylammonium hydroxide [0076] 0.28%
potassium hydroxide [0077] 10.0% tetramethylene sulfone [0078]
10.0% di(ethyleneglycol)butyl ether [0079] 0.10% oxirane, methyl-,
polymer with oxirane, mono(octylphenyl)ether [0080] 0.08%
2-mercaptobenzimidazole [0081] 74.18% water
[0082] In another aspect, the present invention relates to a
cleaning composition that is useful for stripping photoresist
and/or photoresist residues from semiconductor substrates and/or
SARCs while maintaining cobalt and copper compatibility. Such
cleaning composition includes an aqueous solution of at least one
oxidant, a strong base, optionally a chelator and optionally a
co-solvent and/or a surfactant. The cleaning composition
effectively removes photoresist from the top of the semiconductor
device without causing damage to the dielectric material and
without causing corrosion of the underlying metal.
[0083] Compositions of such type in which the base component
includes potassium hydroxide are especially advantageous in
achieving high efficiency cleaning without adverse effect on the
dielectric layer.
[0084] Compositions of such type, in one embodiment, include the
following components by weight, based on the total weight of the
composition: [0085] 0.1-30 wt % strong base [0086] 0.01-30 wt %
oxidant [0087] 0-10 wt % chelator [0088] 0-5 wt % surfactant [0089]
0-50 wt % co-solvent [0090] 20-98.9 wt % deionized water
[0091] As used in such context, the term "strong base" means a
cation/anion salt that dissociates in aqueous or partially aqueous
solutions to yield virtually stoichiometric amounts of hydroxide
anions. The strong base can include bases such as potassium
hydroxide and alkylammonium hydroxides such as tetramethylammonium
hydroxide (TMAH), choline hydroxide, benzyltrimethylammonium
hydroxide, etc.
[0092] In one embodiment, the compositions of the invention are
devoid of hydroxylamine.
[0093] The oxidant in such composition can include, without
limitation, inorganic and/or organic oxidizers, such as hydrogen
peroxide, organic peroxides, amine-N-oxides, perborate salts,
persulfate salts, as well as combinations of two or more of the
foregoing.
[0094] The chelator in such composition can be of any suitable
type, and may include, without limitation, triazoles, such as
1,2,4-triazole, or triazoles substituted with substituents such as
C1-C8 alkyl, amino, thiol, mercapto, imino, carboxy and nitro
groups, such as benzotriazole, to lyltriazole,
5-phenyl-benzotriazole, 5-nitro-benzotriazole,
3-amino-5-mercapto-1,2,4-triazole, 1-amino-1,2,4-triazole,
hydroxybenzotriazole, 2-(5-amino-pentyl)-benzotriazole,
1-amino-1,2,3-triazole, 1-amino-5-methyl-1,2,3-triazole,
3-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole,
3-isopropyl-1,2,4-triazole, 5-phenylthiol-benzotriazole,
halo-benzotriazoles (halo=F, Cl, Br or I), naphthotriazole, and the
like, as well as thiazoles, tetrazoles, imidazoles, phosphates,
thiols and azines such as 2-mercaptobenzoimidizole,
2-mercaptobenzothiazole, 4-methyl-2-phenylimidazole,
2-mercaptothiazoline, 5-aminotetrazole,
5-amino-1,3,4-thiadiazole-2-thiol,
2,4-diamino-6-methyl-1,3,5-triazine, thiazole, triazine,
methyltetrazole, 1,3-dimethyl-2-imidazolidinone,
1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole,
diaminomethyltriazine, mercaptobenzothiazole, imidazoline thione,
mercaptobenzimidazole, 4-methyl-4H-1,2,4-triazole-3-thiol,
5-amino-1,3,4-thiadiazole-2-thiol, benzothiazole, tritolyl
phosphate, indiazole, etc. Suitable chelator species further
include glycerols, amino acids, carboxylic acids, alcohols, amides
and quinolines such as guanine, adenine, glycerol, thioglycerol,
nitrilotriacetic acid, salicylamide, iminodiacetic acid,
benzoguanamine, melamine, thiocyranuric acid, anthranilic acid,
gallic acid; ascorbic acid; salicylic acid; 8-hydroxyquinoline,
5-carboxylic acid-benzotriazole, 3-mercaptopropanol, boric acid,
iminodiacetic acid, etc. The chelator is usefully employed to
increase the compatibility of the composition with the metals and
the dielectric materials used in the semiconductor device.
[0095] The surfactant employed in the composition can be of any
suitable type, e.g., nonionic surfactants such as fluoroalkyl
surfactants, polyethylene glycols, polypropylene glycols,
polyethylene or polypropylene glycol ethers, carboxylic acid salts,
dodecylbenzenesulfonic acid or salts thereof, polyacrylate
polymers, dinonylphenyl polyoxyethylene, or other substituted
phenyl polyoxyethylenes, silicone or modified silicone polymers,
acetylenic diols or modified acetylenic diols, alkylammonium or
modified alkylammonium salts, as well as combinations of two or
more of the foregoing.
[0096] Suitable co-solvent species for such composition include,
without limitation, amines such as dimethyldiglycolamine,
1,8-diazabicyclo[5.4.0]undecene, aminopropylmorpholine,
triethanolamine, methylethanolamine, methyldiethanolamine, etc. or
glycols such as ethylene or polyethylene, propylene glycol,
neopentyl glycol, etc., amines such as hydroxyethylmorpholine,
aminopropylmorpholine, etc. or glycol ethers such as di(ethylene
glycol)monoethyl ether, di(propylene glycol)propyl ether, ethylene
glycol phenyl ether, di(propylene glycol) butyl ether, butyl
carbitol, etc., or polyglycol ethers.
[0097] Specific embodiments of such composition are set out as
Formulations H-S below, wherein all percentages are by weight,
based on the total weight of the composition.
Formulation H
TABLE-US-00001 [0098] tetramethylammonium hydroxide, 25% aqueous
solution 14.7% N-methylmorpholine oxide, 50% aqueous solution 7.0%
dinonylphenol polyoxyethylene, 7% aqueous solution 4.3%
3-amino-5-mercapto-1,2,4-triazole 0.1% water 73.9%
Formulation I
TABLE-US-00002 [0099] tetramethylammonium hydroxide, 25% aqueous
solution 14.7% N-methylmorpholine oxide, 50% aqueous solution 7.0%
dinonylphenol polyoxyethylene, 7% aqueous solution 4.3% ammonium
tetrathiomolybdate 0.1% water 73.9%
Formulation J
TABLE-US-00003 [0100] tetramethylammonium hydroxide, 25% aqueous
solution 14.7% N-methylmorpholine oxide, 50% aqueous solution 7.0%
dinonylphenol polyoxyethylene, 7% aqueous solution 4.3%
2-mercaptobenzimidazole 0.1% aminopropylmorpholine 20.0% water
53.9%
Formulation K
TABLE-US-00004 [0101] tetramethylammonium hydroxide, 25% aqueous
solution 14.7% N-methylmorpholine oxide, 50% aqueous solution 7.0%
dinonylphenol polyoxyethylene, 7% aqueous solution 4.3%
2-mercaptobenzimidazole 0.1% N-ethylmorpholine 20.0% water
53.9%
Formulation L
TABLE-US-00005 [0102] tetramethylammonium hydroxide, 25% aqueous
solution 14.7% N-methylmorpholine oxide, 50% aqueous solution 7.0%
dinonylphenol polyoxyethylene, 7% aqueous solution 4.3%
2-mercaptobenzimidazole 0.1% aminoethylpiperidine 20.0% water
53.9%
Formulation M
TABLE-US-00006 [0103] tetramethylammonium hydroxide, 25% aqueous
solution 14.7% N-methylmorpholine oxide, 50% aqueous solution 7.0%
dinonylphenol polyoxyethylene, 7% aqueous solution 4.3%
3-amino-5-1,2,4-triazole 0.1% aminopropylmorpholine 20.0% water
53.9%
Formulation N
TABLE-US-00007 [0104] tetramethylammonium hydroxide, 25% aqueous
solution 14.7% N-methylmorpholine oxide, 50% aqueous solution 7.0%
dinonylphenol polyoxyethylene, 7% aqueous solution 4.3%
3-amino-5-1,2,4-triazole 0.1% aminopropylmorpholine 10.0% water
63.9%
Formulation O
TABLE-US-00008 [0105] tetramethylammonium hydroxide, 25% aqueous
solution 14.7% N-methylmorpholine oxide, 50% aqueous solution 7.0%
dinonylphenol polyoxyethylene, 7% aqueous solution 4.3%
2-mercaptobenzimidazole 0.1% aminopropylmorpholine 20.0% water
53.9%
Formulation P
TABLE-US-00009 [0106] tetramethylammonium hydroxide, 25% aqueous
solution 14.7% N-methylmorpholine oxide, 50% aqueous solution 7.0%
dinonylphenol polyoxyethylene 7% aqueous solution 4.3%
2-mercaptobenzimidazole 0.1% aminopropylmorpholine 10.0% water
63.9%
Formulation Q
TABLE-US-00010 [0107] benzyltrimethylammonium hydroxide, 40%
aqueous solution 9.0% potassium hydroxide, 45% aqueous solution
0.6% N-methylmorpholine oxide, 50% aqueous solution 7.0%
dinonylphenol polyoxyethylene, 7% aqueous solution 4.3%
2-mercaptobenzimidazole 0.1% aminopropylmorpholine 20.0% water
59.02%
Formulation R
TABLE-US-00011 [0108] benzyltrimethylammonium hydroxide, 40%
aqueous solution 9.0% potassium hydroxide, 45% aqueous solution
0.6% N-methylmorpholine oxide, 50% aqueous solution 7.0%
dinonylphenol polyoxyethylene, 7% aqueous solution 4.3%
2-mercaptobenzimidazole 0.1% aminopropylmorpholine 15.0% water
64.02%
Formulation S
TABLE-US-00012 [0109] benzyltrimethylammonium hydroxide, 40%
aqueous solution 9.0% potassium hydroxide, 45% aqueous solution
0.6% N-methylmorpholine oxide, 50% aqueous solution 7.0%
dinonylphenol polyoxyethylene, 7% aqueous solution 4.3%
2-mercaptobenzimidazole 0.1% aminopropylmorpholine 10.0% water
69.02%
[0110] In another aspect, the invention contemplates cleaning
compositions that include the following components by weight, based
on the total weight of the composition: [0111] 0.1-30 wt % strong
base [0112] 2-30 wt % oxidant [0113] 0-10 wt % chelator [0114] 0-5
wt % surfactant [0115] 0-50 wt % co-solvent [0116] 20-98 wt %
deionized water
[0117] The strong base, oxidant, chelator, co-solvent and
surfactant species in such composition may be of same or
corresponding species to those discussed illustratively
hereinabove.
[0118] Specific embodiments of such composition are set out as
Formulations T, U, V, W, X, Y, Z, A.sup.2, B.sup.2, C.sup.2,
D.sup.2, E.sup.2, F.sup.2, G.sup.2, H.sup.2, I.sup.2, J.sup.2,
K.sup.2 and L.sup.2 below, wherein all percentages are by weight,
based on the total weight of the composition.
Formulation T
TABLE-US-00013 [0119] benzyltrimethylammonium hydroxide, 40%
aqueous solution 13.4% N-methylmorpholine oxide, 50% aqueous
solution 7.0% Potassium hydroxide, 45% aqueous solution 0.6%
2-mercaptobenzimidazole 0.08% dinonylphenol polyoxyethylene 0.3%
water 78.62%
Formulation U
TABLE-US-00014 [0120] benzyltrimethylammonium hydroxide, 40%
aqueous solution 13.4% N-methylmorpholine oxide, 50% aqueous
solution 7.0% Potassium hydroxide, 45% aqueous solution 1.2%
2-mercaptobenzimidazole 0.08% dinonylphenol polyoxyethylene 0.3%
water 78.02%
Formulation V
TABLE-US-00015 [0121] tetramethylammonium hydroxide, 25% aqueous
solution 5.85% N-methylmorpholine oxide, 50% aqueous solution 7.0%
Potassium hydroxide, 45% aqueous solution 1.2%
2-mercaptobenzimidazole 0.08% dinonylphenol polyoxyethylene 0.3%
water 85.57%
Formulation W
TABLE-US-00016 [0122] tetramethylammonium hydroxide, 25% aqueous
solution 2.93% N-methylmorpholine oxide, 50% aqueous solution 7.0%
Potassium hydroxide, 45% aqueous solution 1.2%
2-mercaptobenzimidazole 0.08% dinonylphenol polyoxyethylene 0.3%
water 88.49%
Formulation X
TABLE-US-00017 [0123] benzyltrimethylammonium hydroxide, 40%
aqueous solution 7.2% N-methylmorpholine oxide, 50% aqueous
solution 7.0% Potassium hydroxide, 45% aqueous solution 0.6%
2-mercaptobenzimidazole 0.08% dinonylphenol polyoxyethylene 0.3%
water 84.82%
Formulation Y
TABLE-US-00018 [0124] benzyltrimethylammonium hydroxide, 40%
aqueous solution 3.6% N-methylmorpholine oxide, 50% aqueous
solution 7.0% Potassium hydroxide, 45% aqueous solution 1.2%
2-mercaptobenzimidazole 0.08% dinonylphenol polyoxyethylene 0.3%
water 87.82%
Formulation Z
TABLE-US-00019 [0125] benzyltrimethylammonium hydroxide, 40%
aqueous solution 3.6% N-methylmorpholine oxide, 50% aqueous
solution 7.0% Potassium hydroxide, 45% aqueous solution 0.6%
2-mercaptobenzimidazole 0.08% dinonylphenol polyoxyethylene 0.3%
water 88.42%
Formulation A.sup.2
TABLE-US-00020 [0126] benzyltrimethylammonium hydroxide, 40%
aqueous solution 7.2% N-methylmorpholine oxide, 50% aqueous
solution 7.0% Potassium hydroxide, 45% aqueous solution 0.3%
2-mercaptobenzimidazole 0.08% dinonylphenol polyoxyethylene 0.3%
water 85.12%
Formulation B.sup.2
TABLE-US-00021 [0127] benzyltrimethylammonium hydroxide, 40%
aqueous solution 22.26% Potassium hydroxide, 45% aqueous solution
0.6% 2-mercaptobenzimidazole 0.08% methyldiethanolamine 2.33%
phosphoric acid (86%) 1.69% 3-amino-5-mercapto-1,2,4-triazole 1.0%
water 72.04%
Formulation C.sup.2
TABLE-US-00022 [0128] benzyltrimethylammonium hydroxide, 40%
aqueous solution 22.26% Potassium hydroxide, 45% aqueous solution
0.6% 2-mercaptobenzimidazole 0.08% methyldiethanolamine 2.33%
phosphoric acid (86%) 1.69% 4-methyl-2-phenyl-imidazole 1.0% water
72.04%
Formulation D.sup.2
TABLE-US-00023 [0129] benzyltrimethylammonium hydroxide, 40%
aqueous solution 22.26% Potassium hydroxide, 45% aqueous solution
0.6% 2-mercaptobenzimidazole 0.08% methyldiethanolamine 2.33%
phosphoric acid (86%) 1.69% 2-mercaptothiazoline 1.0% water
72.04%
Formulation E.sup.2
TABLE-US-00024 [0130] benzyltrimethylammonium hydroxide, 40%
aqueous solution 22.26% Potassium hydroxide, 45% aqueous solution
0.6% 2-mercaptobenzimidazole 0.08% methyldiethanolamine 2.33%
phosphoric acid (86%) 1.69% 8-hydroxyquinoline 1.0% water
72.04%
Formulation F.sup.2
TABLE-US-00025 [0131] benzyltrimethylammonium hydroxide, 40%
aqueous solution 22.26% Potassium hydroxide, 45% aqueous solution
0.6% 2-mercaptobenzimidazole 0.08% methyldiethanolamine 2.33%
phosphoric acid (86%) 1.69% 1-phenyl-2-tetrazoline-5-thione 1.0%
water 72.04%
Formulation G.sup.2
TABLE-US-00026 [0132] benzyltrimethylammonium hydroxide, 40%
aqueous solution 22.26% Potassium hydroxide, 45% aqueous solution
0.6% 2-mercaptobenzimidazole 0.08% methyldiethanolamine 2.33%
phosphoric acid (86%) 1.69% gallic acid 1.0% water 72.04%
Formulation H.sup.2
TABLE-US-00027 [0133] benzyltrimethylammonium hydroxide, 40%
aqueous solution 22.26% Potassium hydroxide, 45% aqueous solution
0.6% 2-mercaptobenzimidazole 0.08% methyldiethanolamine 2.33%
phosphoric acid (86%) 1.69% salicylic acid 1.0% water 72.04%
Formulation I.sup.2
TABLE-US-00028 [0134] benzyltrimethylammonium hydroxide, 40%
aqueous solution 22.26% Potassium hydroxide, 45% aqueous solution
0.6% 2-mercaptobenzimidazole 0.08% methyldiethanolamine 2.33%
phosphoric acid (86%) 1.69% ascorbic acid 1.0% water 72.04%
Formulation J.sup.2
TABLE-US-00029 [0135] benzyltrimethylammonium hydroxide, 40%
aqueous solution 7.2% Potassium hydroxide, 45% aqueous solution
0.6% 2-mercaptobenzimidazole 0.08% aminopropyl morpholine 10%
4-methyl-2-phenyl-imidazole 1.0% water 81.12%
Formulation K.sup.2
TABLE-US-00030 [0136] benzyltrimethylammonium hydroxide, 40%
aqueous solution 7.2% Potassium hydroxide, 45% aqueous solution
0.6% 2-mercaptobenzimidazole 0.08% aminopropyl morpholine 10%
4-methyl-2-phenyl-imidazole 0.5% water 81.62%
Formulation L.sup.2
TABLE-US-00031 [0137] benzyltrimethylammonium hydroxide, 40%
aqueous solution 7.2% Potassium hydroxide, 45% aqueous solution
0.6% 2-mercaptobenzimidazole 0.08% aminopropyl morpholine 10%
4-methyl-2-phenyl-imidazole 1.0% water 81.02% dinonylphenol
polyoxyethylene 0.1%
Still other formulations within the broad scope of the present
invention, which are suitable for stripping photoresist and/or
photoresist residues from semiconductor substrates, while
maintaining cobalt and copper compatibility, include the
formulations M.sup.2, N.sup.2, O.sup.2, P.sup.2, Q.sup.2 .sub.and
R.sup.2 whose compositions are set out below.
Formulation M.sup.2
TABLE-US-00032 [0138] tetramethylammonium hydroxide, 25% aqueous
4.0% solution hydrogen peroxide, 30% aqueous solution 2.0%
5-aminotetrazole 0.1% water 93.9%
Formulation N.sup.2
TABLE-US-00033 [0139] tetramethylammonium hydroxide, 25% aqueous
4.0% solution hydrogen peroxide, 30% aqueous solution 2.0%
2,4-diamino-6-methyl-1,3,5-triazine 0.1% water 93.9%
Formulation O.sup.2
TABLE-US-00034 [0140] tetramethylammonium hydroxide, 25% aqueous
4.0% solution hydrogen peroxide, 30% aqueous solution 2.0%
5-amino-1,3,4-thiadiazole-2-thiol 0.1% water 93.9%
[0141] Formulation P.sup.2
TABLE-US-00035 tetramethylammonium hydroxide, 25% aqueous 4.0%
solution hydrogen peroxide, 30% aqueous solution 2.0%
1,2,4-triazole 0.1% water 93.9%
[0142] Formulation Q.sup.2
TABLE-US-00036 tetramethylammonium hydroxide, 25% aqueous 4.0%
solution hydrogen peroxide, 30% aqueous solution 2.0%
2,4-dihydroxy-6-methylpyrimidine 0.1% water 93.9%
[0143] Formulation R.sup.2
TABLE-US-00037 tetramethylammonium hydroxide, 25% aqueous 4.0%
solution hydrogen peroxide, 30% aqueous solution 2.0%
8-hydroxyquinoline 0.1% water 93.9%
[0144] The cleaning compositions of the invention are easily
formulated by simple addition of the respective ingredients and
mixing to homogeneous condition.
[0145] In cleaning application, the cleaning composition is applied
in any suitable manner to the material to be cleaned, e.g., by
spraying the cleaning composition on the surface of the material to
be cleaned, by dipping (in a volume of the cleaning composition) of
the material or article including the material to be cleaned, by
contacting the material or article to be cleaned with another
material, e.g., a pad, or fibrous sorbent applicator element, that
is saturated with the cleaning composition, or by any other
suitable means, manner or technique, by which the cleaning
composition is brought into cleaning contact with material to be
cleaned.
[0146] As applied to semiconductor manufacturing operations, the
cleaning compositions of the present invention are usefully
employed to remove photoresist and/or SARC materials from
substrates and semiconductor device structures on which such
material(s) have been deposited.
[0147] The compositions of the present invention, by virtue of
their selectivity for such photoresist and/or SARC materials,
relative to other materials that may be present on the
semiconductor substrate and exposed to the cleaning composition,
such as ILD structures, metallization, barrier layers, etc.,
achieve removal of the photoresist and/or SARC material(s) in a
highly efficient manner.
[0148] In use of the compositions of the invention for removing
photoresist and/or SARC materials from semiconductor substrates
having same thereon, the cleaning composition typically is
contacted with the substrate for a time of from about 10 to about
45 minutes, at temperature in a range of from about 50.degree. C.
to about 80.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 remove the photoresist and/or SARC material from the
substrate, within the broad practice of the invention.
[0149] Following the achievement of the desired cleaning action,
the cleaning composition is readily removed from the substrate or
article to which it has previously been applied, e.g., by rinse,
wash, or other removal step(s), as may be desired and efficacious
in a given end use application of the compositions of the present
invention.
[0150] The features and advantages of the invention are more fully
illustrated by the following non-limiting examples, wherein all
parts and percentages are by weight, unless otherwise expressly
stated.
Example 1
[0151] Samples of Formulations A, B, C, D, E, F and G, having the
respective compositions described hereinabove, were prepared.
[0152] The efficacy of these formulations for removing photoresist
and SARC from a substrate containing same coated thereon, while
maintaining a low etching action on copper metallization on such
substrate, was evaluated in corresponding tests in which the
cleaning composition of the particular formulation was contacted
with the substrate for 6-15 minutes at 60-70.degree. C. followed by
rinsing of the substrate with deionized water. The substrate was a
post-etch structure on a silicon wafer containing patterned
organosilicate dielectric and SARC structures underneath patterned
photoresist. The photoresist was a standard commercially available
chemically amplified resist for 193 or 248 nm lithography. The SARC
material was a commercially available spin-on polysiloxane material
layer incorporating a dye material that strongly absorbs light at
the frequency used for lithography.
[0153] Following such contacting and rinse steps, the percentage
removal of photoresist, the percentage removal of SARC, and the
copper etch rate, in Angstroms per minute (.ANG./min), were
determined. The corresponding data are set out in Table 1
below.
TABLE-US-00038 TABLE 1 Percentage Photoresist Removal, Percentage
SARC Removal and Cu Etch Rate (.ANG./min) of Formulations A-G
Photoresist SARC Cu Etch Rate Formulation Removal, % Removal, %
(.ANG./min) A 100 100 0.77 B 100 100 1.3 C 100 100 2.5 D 99 100 --
E 99 100 0.42 F 85 100 1.3 G 100 100 0.70
Example 2
[0154] Samples of Formulations H, I, J, K, L, M, N, O, P, Q, R and
S, having the respective compositions described hereinabove, were
prepared.
[0155] The efficacy of these formulations for removing photoresist
residues from a semiconductor substrate having photoresist, copper
and cobalt metal thereon, while maintaining a low etching action on
the copper and cobalt on such substrate, was evaluated in
corresponding tests in which the cleaning composition of the
particular formulation was contacted with the substrate at
60-70.degree. C. following by rinsing of the substrate with
deionized water. The substrate was a post-etch structure on a
silicon wafer containing patterned organosilicate dielectric and
SARC structures underneath patterned photoresist. The photoresist
was a standard commercially available chemically amplified resist
for 193 or 248 nm lithography. Substantial cleaning is defined as
greater than 80% removal of the photoresist from the semiconductor
device, as determined by optical microscopy.
[0156] Data are set out in Table 2 below.
TABLE-US-00039 TABLE 2 Cleaning Performance of Formulations H-S
Con- % Temper- tact Copper Cleaning Formu- ature, Time, Cobalt Com-
of lation .degree. C. Min. Compatibility patibility Photoresist H
70 30 slight etch rate of 100 roughening of 0.62 .ANG./min surface
I 70 20 slight incompatible 100 roughening of surface J 70 30 good
good 100 K 70 30 some surface good 100 deposition, no thickness
change L 70 30 good good 100 M 70 30 good good 100 N 70 30 good
good 100 O 70 30 good good 100 P 70 30 good good 100 Q 60 30 good
good 100 R 60 30 good good 100 S 60 30 good good 100
Example 3
[0157] Samples of Formulations T, U, V, W, X, Y, Z, A.sup.2,
B.sup.2, C.sup.2, D.sup.2, E.sup.2, F.sup.2, G.sup.2, H.sup.2,
I.sup.2, J.sup.2, K.sup.2 and L.sup.2, having the respective
compositions described hereinabove, were prepared.
[0158] The efficacy of these formulations, for removing photoresist
residues from a semiconductor substrate having photoresist thereon,
was evaluated in corresponding tests in which the cleaning
composition of the particular formulation was contacted with the
substrate for 12 minutes at 70.degree. C. following by rinsing of
the substrate with deionized water. The substrate was a post-etch
structure on a silicon wafer containing patterned organosilicate
dielectric and SARC structures underneath patterned photoresist.
The photoresist was a standard commercially available chemically
amplified resist for 193 or 248 nm lithography. Substantial
cleaning is defined as greater than 80% removal of the photoresist
from the semiconductor device, as determined by optical
microscopy.
[0159] Results are set out in Tables 3 and 4 below.
TABLE-US-00040 TABLE 3 Percentage Photoresist Removal of
Formulations T-A.sup.2 Percentage Removal of Formulation
Photoresist From Substrate T 100 U 100 V 100 W 100 X 100 Y 95 Z 95
A.sup.2 100
TABLE-US-00041 TABLE 4 Cleaning Performance of Formulations
B.sup.2-L.sup.2 Contact Temperature Time, Cobalt % Cleaning of
Formulation .degree. C. Min. Compatibility Photoresist B.sup.2 60
60 good 100 C.sup.2 60 60 good 100 D.sup.2 60 60 good 100 E.sup.2
60 60 good 100 F.sup.2 60 60 good 100 G.sup.2 60 60 good 100
H.sup.2 60 60 good 100 I.sup.2 60 60 good 100 J.sup.2 60 60 decent
100 K.sup.2 60 60 decent 100 L.sup.2 60 60 decent 100
Example 4
[0160] Samples of Formulations M.sup.2, N.sup.2, O.sup.2, P.sup.2,
Q.sup.2 and R.sup.2, having the respective compositions described
hereinabove, were prepared.
[0161] The efficacy of these formulations for removing photoresist
residues from a semiconductor substrate having photoresist, copper
and cobalt metal thereon, while maintaining a low etching action on
the copper and cobalt on such substrate, was evaluated in
corresponding tests in which the cleaning composition of the
particular formulation was contacted with the substrate at
70.degree. C. followed by rinsing of the substrate with deionized
water. The substrate was a post-etch structure on a silicon wafer
containing patterned organosilicate dielectric and SARC structures
underneath patterned photoresist. The photoresist was a standard
commercially available chemically amplified resist for 193 or 248
nm lithography. Substantial cleaning is defined as greater than 80%
removal of the photoresist from the semiconductor device, as
determined by optical microscopy.
[0162] Data are set out in Table 5 below.
TABLE-US-00042 TABLE 5 Cleaning Performance of Formulations
M.sup.2-R.sup.2 Cobalt Contact Etch % Cleaning Temperature Time,
Cobalt Rate, Copper Etch of Formulation .degree. C. Min.
Compatibility .ANG./min Rate, .ANG./min Photoresist M.sup.2 70 30
good 0.048 0.84 100 N.sup.2 70 30 good 0.16 0.52 100 O.sup.2 70 30
good 0.21 0.72 100 P.sup.2 70 30 good -- incompatible 100 Q.sup.2
70 30 good -- 2.55 100 R.sup.2 70 30 good -- incompatible 100
[0163] The foregoing examples demonstrate that the cleaning
compositions of the invention are useful for removal of photoresist
and/or SARCs from semiconductor substrates having same coated
thereon. Further, such compositions can be employed without adverse
effect on metallization on the substrate, e.g., copper, aluminum
and cobalt alloys.
[0164] Further, the cleaning compositions of the invention are
readily formulated with suitable solvent systems, e.g., aqueous and
semi-aqueous solvent systems, conferring low toxicity and low
combustibility characteristics to such compositions.
[0165] Accordingly, the cleaning compositions of the present
invention achieve a substantial advance in the art of removing
photoresist and/or SARC materials, in the manufacture of integrated
circuit devices.
[0166] 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.
* * * * *