Photoresist pattern trimming compositions and pattern formation methods
Photoresist pattern trimming compositions comprise a polymer, an aromatic sulfonic acid, and an organic-based solvent system, wherein the polymer comprises polymerized units of general formulas (I) and (II): wherein: X independently represents a halogen atom; Q represents a single bond, —O—, or —C(O)O—; R 1 independently represents hydrogen, a halogen atom, C1-C12 alkyl or C1-C12 fluoroalkyl; R 2 represents C1-C3 alkyl or C1-C3 fluoroalkyl; and m is an integer from 0 to 4; and wherein the polymerized units of general formula (I) are present in the polymer in an amount of 10 to 90 mol % and the polymerized units of general formula (II) are present in the polymer in an amount from 10 to 60 mol %, based on total polymerized units of the polymer. The photoresist pattern trimming compositions and their use in pattern formation methods find particular applicability in the manufacture of semiconductor devices.
1. A photoresist pattern trimming composition, comprising a polymer, an aromatic sulfonic acid, and an organic-based solvent system, wherein the polymer comprises polymerized units of general formulas (I) and (II):
wherein: X independently represents a halogen atom; Q represents a single bond, —O—, or —C(O)O—; R 1 independently represents hydrogen, a halogen atom, C1-C12 alkyl or C1-C12 fluoroalkyl, wherein the alkyl or fluoroalkyl is unsubstituted or substituted with a hydroxy group; R 2 represents hydrogen, C1-C3 alkyl or C1-C3 fluoroalkyl; and m is an integer from 0 to 4; and wherein the polymerized units of general formula (I) are present in the polymer in an amount of from 10 to 90 mol % and the polymerized units of general formula (II) are present in the polymer in an amount from 10 to 60 mol %, based on total polymerized units of the polymer, wherein a weight average molecular weight of the polymer is from 3,000 to 50,000.
2. The photoresist pattern trimming composition of claim 1 , wherein the polymer further comprises polymerized units of general formula (III):
wherein: R 3 represents hydrogen, a halogen atom, C1-C3 alkyl or C1-C3 fluoroalkyl; W represents O or NR, wherein R represents hydrogen or C1-C6 alkyl; and R 4 represents substituted or unsubstituted C1-C20 alkyl or C1-C20 hetero alkyl.
3. The photoresist pattern trimming composition of claim 2 , wherein the polymerized units of general formula (III) are present in the polymer in an amount from 1 to 50 mol %, based on total polymerized units of the polymer.
4. The photoresist pattern trimming composition of claim 1 , wherein the aromatic sulfonic acid is of general formula V:
wherein: R 5 independently represents a halogen atom, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted carbocyclic aryl, substituted or unsubstituted heterocyclic aryl, substituted or unsubstituted alkoxy, or a combination thereof, wherein adjacent R 5 groups together optionally form a fused ring with the aromatic group; and a represents an integer of from 0 to 5.
5. The photoresist pattern trimming composition of claim 1 , wherein the organic-based solvent system comprises a monoether.
6. The photoresist pattern trimming composition of claim 5 , wherein the organic-based solvent system further comprises an alcohol or an ester.
7. The photoresist pattern trimming composition of claim 1 , wherein Q is a single bond or —O— and R 1 is C1-C12 alkyl.
8. A pattern formation method, comprising:
(a) providing a semiconductor substrate;
(b) forming a photoresist pattern over the semiconductor substrate, wherein the photoresist pattern is formed from a photoresist composition comprising a polymer comprising an acid labile groups and a photoacid generator;
(c) coating a pattern trimming composition of claim 1 over the photoresist pattern;
(d) heating the coated photoresist pattern; and
(e) rinsing the heated photoresist pattern with a rinsing agent to remove residual pattern treatment composition.
9. The pattern formation method of claim 8 , wherein the rinsing agent is an aqueous tetramethylammonium hydroxide solution.
10. The pattern formation method of claim 8 , wherein the photoresist pattern is formed by deep-UV or EUV lithography.
11. The pattern formation method of claim 8 , wherein the polymer further comprises polymerized units of general formula (III):
wherein: R 3 represents hydrogen, a halogen atom, C1-C3 alkyl or C1-C3 fluoroalkyl; W represents O or NR, wherein R represents hydrogen or C1-C6 alkyl; and R 4 represents substituted or unsubstituted C1-C20 alkyl or C1-C20 hetero alkyl.
12. The pattern formation method of claim 11 , wherein the polymerized units of general formula (III) are present in the polymer in an amount from 1 to 50 mol %, based on total polymerized units of the polymer.
13. The pattern formation method of claim 8 , wherein the aromatic sulfonic acid is of general formula V:
wherein: R 5 independently represents a halogen atom, hydroxy, substituted or unsubstituted alkyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted carbocyclic aryl, substituted or unsubstituted heterocyclic aryl, substituted or unsubstituted alkoxy, or a combination thereof, wherein adjacent R 5 groups together optionally form a fused ring with the aromatic group; and a represents an integer of from 0 to 5.
14. The pattern formation method of claim 8 , wherein the organic-based solvent system comprises a monoether.
15. The pattern formation method of claim 14 , wherein the organic-based solvent system further comprises an alcohol or an ester.
16. The pattern formation method of claim 8 , wherein Q is a single bond or —O— and R 1 is C1-C12 alkyl.