US2009186793A1PendingUtilityA1
Dynamic multi-purpose composition for the removal of photoresists and method for its use
Est. expiryOct 28, 2025(expired)· nominal 20-yr term from priority
Inventors:Michael T. PhenisLauri JohnsonRaymond ChanDiane Marie ScheeleKimberly Dona PollardGene Goebel
C11D 3/26C11D 7/3218C11D 3/43G03F 7/425C11D 7/5009C11D 3/30C11D 7/32C11D 1/004G03F 7/426G03F 7/32C11D 2111/22
51
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Claims
Abstract
Improved dry stripper solutions for removing one, two or more photoresist layers from substrates are provided. The stripper solutions comprise dimethyl sulfoxide, a quaternary ammonium hydroxide, and an alkanolamine, an optional secondary solvent and less than about 3 wt. % water and/or a dryness coefficient of at least about 1. Methods for the preparation and use of the improved dry stripping solutions are additionally provided.
Claims
exact text as granted — not AI-modified1 . A stripper solution for removing a photoresist from a substrate comprising dimethyl sulfoxide, a quaternary ammonium hydroxide, and an alkanolamine having at least two carbon atoms, at least one amino substituent and at least one hydroxyl substituent, the amino and hydroxyl substituents attached to different carbon atoms.
2 . The solution of claim 1 , wherein the quaternary ammonium hydroxide has substituents that are (C 1 -C 8 )alkyl, arylalkyl or combinations thereof.
3 . The solution of claim 2 , wherein the dimethyl sulfoxide comprises from about 20% to about 90% of the composition; the quaternary ammonium hydroxide comprises from about 1% to about 7% of the composition; the alkanolamine comprises from about 1% to about 75% of the composition.
4 . The solution of claim 1 , wherein the alkanolamine is a compound of the formula:
where R 1 is H, C 1 -C 4 alkyl, or C 1 -C 4 alkylamino.
5 . The solution of claim 4 , wherein R 1 is H.
6 . The solution of claim 5 , further comprising a surfactant.
7 . The solution of claim 6 , wherein the surfactant is DuPont Zonyl® FSO fluorosurfactant.
8 . The solution of claim 7 , wherein the quaternary ammonium hydroxide is tetramethylammonium hydroxide.
9 . The solution of claim 1 , additionally comprising 2 to 75% of a secondary solvent.
10 . The solution of claim 9 , wherein the alkanolamine is:
where R 1 is H, C 1 -C 4 alkyl, or C 1 -C 4 alkylamino.
11 . The solution of claim 10 , wherein the secondary solvent is a glycol ether.
12 . The solution of claim 11 wherein the glycol ether is diethyleneglycol monomethyl ether.
13 . The solution of claim 12 , wherein R 1 is CH 2 CH 2 NH 2 .
14 . The solution of claim 13 , further comprising a surfactant.
15 . The solution of claim 14 , wherein the surfactant is DuPont Zonyl® FSO fluorosurfactant.
16 . The solution of claim 15 , wherein the quaternary ammonium hydroxide is tetramethylammonium hydroxide.
17 . A method for removing a photoresist from a substrate comprising:
(a) selecting a substrate having a photoresist thereon; (b) contacting the substrate with a stripper solution for a time sufficient to remove a desired amount of photoresist; (c) removing the substrate from the stripping solution; and (d) rinsing the stripper solution from the substrate with a solvent, wherein the stripping solution: (i) comprises dimethyl sulfoxide, a quaternary ammonium hydroxide, and an alkanolamine having at least two carbon atoms, at least one amino substituent and at least one hydroxyl substituent, the amino and hydroxyl substituents attached to different carbon atoms.
18 . The method of claim 17 , wherein the quaternary ammonium hydroxide has substitutents that are (C 1 -C 8 )alkyl, arylalkyl or combinations thereof.
19 . The method of claim 18 , wherein the dimethyl sulfoxide comprises from about 20% to about 90% of the composition; the quaternary ammonium hydroxide comprises from about 1% to about 7% of the composition; the alkanolamine comprises from about 1% to about 75% of the composition.
20 . The method of claim 19 , wherein the alkanolamine is a compound of the formula:
where R 1 is H, (C 1 -C 4 )alkyl, or (C 1 -C 4 )alkylamino.
21 . The method of claim 20 , wherein R 1 is CH 2 CH 2 NH 2 .
22 . The method of claim 19 , wherein the contacting further comprises immersing the substrate in the stripping solution.
23 . The method of claim 19 , wherein the contacting includes spraying the stripping solution onto the substrate.
24 . The method of claim 19 , wherein the rinsing is with water.
25 . The method of claim 19 , wherein the rinsing is with a lower alcohol.
26 . The method of claim 25 , wherein the lower alcohol is isopropanol.
27 . The method of claim 20 , wherein the quaternary ammonium hydroxide is tetramethylammonium hydroxide.
28 . The method of claim 27 , wherein the solution further comprises a surfactant.
29 . The method of claim 28 , wherein R 1 is hydrogen.
30 . The method of claim 28 , wherein R 1 is CH 2 CH 2 NH 2 .
31 . The method of claim 17 , wherein the photoresist is a bilayer resist having two polymer layers.
32 . The method of claim 17 , wherein the photoresist is a bilayer resist having one inorganic layer and one polymer layer.
33 . An electronic device prepared according to the method of claim 17 .
34 . A stripper solution for removing a photoresist from a substrate comprising dimethyl sulfoxide, a quaternary ammonium hydroxide base, water, and an alkanolamine, said stripper solution having a dryness coefficient of at least about 1 wherein said dryness coefficient (DC) is defined by the equation:
DC
=
mass
of
base
/
mass
of
solution
tested
mass
of
water
/
mass
of
solution
tested
35 . The solution of claim 34 , wherein said quaternary ammonium hydroxide has substituents that are C x -alkyl, arylalkyl or combinations thereof and x is an integer ranging from about 1 to about 4 and said alkanolamine has at least two carbon atoms, at least one amino substituent and at least one hydroxyl substituent, the amino and hydroxyl substituents attached to different carbon atoms.
36 . The solution of claim 35 , additionally comprising a secondary solvent.
37 . The solution of claim 35 , wherein the alkanolamine is:
where R 1 is H, C 1 -C 4 alkyl, or C 1 -C 4 alkylamino.
38 . The solution of claim 36 , wherein said secondary solvent is a glycol ether.
39 . The solution of claim 38 , wherein said glycol ether is diethylene glycol monomethyl ether.
40 . The solution of claim 39 , wherein the quaternary ammonium hydroxide is tetramethylammonium hydroxide.
41 . The solution of claim 37 , wherein R 1 is CH 2 CH 2 NH 2 .
42 . The solution of claim 41 , having a dryness coefficient of at least about 1.8.
43 . A method for removing a photoresist from a substrate comprising:
(a) selecting a substrate having a photoresist thereon; (b) contacting the substrate with a stripper solution containing a base for a time sufficient to remove a desired amount of photoresist; (c) removing the substrate from the stripping solution; and (d) rinsing the stripper solution from the substrate with a solvent, wherein said stripper solution comprises dimethyl sulfoxide, a quaternary ammonium hydroxide, water, and an alkanolamine wherein said stripper solution has a dryness coefficient (DC) of at least about 1, where said dryness coefficient is defined by the equation:
DC
=
mass
of
base
/
mass
of
solution
tested
mass
of
water
/
mass
of
solution
tested
44 . The method of claim 43 , wherein said contacting involves a stripper solution wherein said quaternary ammonium hydroxide has substituents that are C 1 -C 4 alkyl, arylalkyl or combinations thereof and said alkanolamine has at least two carbon atoms, at least one amino substituent and at least one hydroxyl substituent, the amino and hydroxyl substituents attached to different carbon atoms.
45 . The method of claim 44 , wherein said contacting involves contacting said substrate with a stripper solution further comprising a secondary solvent.
46 . The method of claim 45 , wherein said contacting involves contacting said substrate with a stripper solution having a dryness coefficient of at least about 1.8.
47 . The method of claim 45 , wherein said contacting involves a stripper solution maintained at a temperature of at least about 20° C. during the contacting.
48 . The method of claim 45 , wherein said contacting involves said stripper solution having:
(a) said quaternary ammonium hydroxide having the formula:
where R 2 , R 3 , R 4 and R 5 are independently C 1 -C 4 alkyl, arylalkyl or combinations thereof; and
(b) said alkanolamine having the formula:
where R 1 is H, C 1 -C 4 alkyl, or C 1 -C 4 alkylamino.
49 . The method of claim 48 , wherein said contacting involves a stripper solution wherein said secondary solvent is a glycol ether.
50 . The method of claim 49 wherein said contacting involves said stripper solution having said glycol ether that is diethylene glycol monomethyl ether.
51 . The method of claim 50 , wherein said photoresist is a bilayer resist having one inorganic layer and one polymer layer.
52 . The method of claim 50 , wherein said photoresist is a bilayer resist having two polymer layers.
53 . The method of claim 50 , wherein said contacting involves said stripper solution having said alkanolamine wherein said R 1 is CH 2 CH 2 NH 2 and wherein said quaternary ammonium hydroxide is tetramethylammonium hydroxide.
54 . The method of claim 50 , wherein said contacting involves said stripper solution having an alkanolamine wherein said R 1 is hydrogen and wherein said quaternary ammonium hydroxide is tetramethylammonium hydroxide.
55 . A method for providing a dry composition containing a quaternary ammonium hydroxide and at least one solvent, the method comprising:
(a) selecting a solution comprising said quaternary ammonium hydroxide, water, and at least one solvent selected from the group consisting of dimethyl sulfoxide and a glycol ether; (b) contacting said solution with sufficient drying agent for a sufficient time to provide said dry composition.
56 . The method of claim 55 , wherein said contacting involves a drying agent that includes molecular sieves.
57 . The method of claim 55 , wherein said contacting involves a drying agent that includes calcium hydride.
58 . The method of claim 56 , wherein said contacting provides a dry composition containing a base, said composition having a dryness coefficient of at least about 1 where said dryness coefficient (DC) is defined by the equation:
DC
=
mass
of
base
/
mass
of
solution
tested
mass
of
water
/
mass
of
solution
tested
59 . The method of claim 58 , wherein said contacting involves contacting said solution with at least about 2 grams of molecular sieves for each gram of water in said solution.
60 . The method of claim 55 , wherein said selecting involves selecting dimethyl sulfoxide as the solvent.
61 . The method of claim 55 , wherein said selecting involves selecting a glycol ether as the solvent.
62 . The method of claim 61 , wherein said selecting involves selecting diethylene glycol monomethyl ether.
63 . The method of claim 55 , wherein said selecting involves selecting dimethyl sulfoxide and a glycol ether.
64 . The method of claim 55 , wherein said selecting involves selecting a solution further comprising an alkanolamine.
65 . A method for reducing the water content of a quaternary ammonium hydroxide to a desired lower level, comprising:
(a) selecting a solution containing said quaternary ammonium hydroxide and said water dissolved in a sacrificial solvent; (b) subjecting said solution to a vacuum of at least about 30 mmhg; (c) maintaining said solution at a temperature of at least about 25° C. until said water content reaches said desired lower level.
66 . The method of claim 65 , wherein said selecting involves selecting a solution of said quaternary ammonium hydroxide and said water dissolved in an alcohol.
67 . The method of claim 66 , wherein said selecting involves selecting a solution of said quaternary ammonium hydroxide and said water dissolved in methanol.
68 . The method of claim 67 , wherein said subjecting involves subjecting said solution to a vacuum of from about 0.01 mmhg to about 10 mmhg.
69 . The method of claim 68 , wherein said maintaining involves maintaining said solution at a temperature of from about 30° C. to about 35° C. until said water content reaches said desired lower level.
70 . The method of claim 69 , wherein said maintaining involves maintaining said solution at said temperature and said pressure for at least about 3 hours.
71 . The method of claim 70 , wherein said selecting involves selecting a quaternary ammonium hydroxide which is tetramethylammonium hydroxide.
72 . A method for maintaining a low water content for a dry stripper solution containing a base, said method comprising:
(a) selecting a dry stripper solution having a dryness coefficient (DC) of at least about 1; (b) establishing contact with said stripper solution and molecular sieves; and (c) maintaining said contact, wherein said dryness coefficient is defined by the equation:
DC
=
mass
of
base
/
mass
of
solution
tested
mass
of
water
/
mass
of
solution
tested
73 . The method of claim 72 , wherein said selecting involves selecting a stripper solution having a dryness coefficient of at least 1.8.
74 . The method of claim 72 , wherein said establishing contact involves establishing contact with 3A molecular sieves.
75 . An integrated circuit device obtainable in part according to the method of claim 43 .Join the waitlist — get patent alerts
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