# US 12,761,556 B2 · Polymer, photoresist compositions including the same, and pattern formation methods

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 12,761,556 B2
- Document ID: US12761556B2
- Status: Granted
- Kind: B2
- Application number: 18/090,638
- Filed: 2022-12-29
- Published: 2024-07-18
- Granted: 2026-10-13
- Earliest claimed: 2022-12-29
- Assignees: Dupont Electronic Materials International, LLC
- Applicants: Rohm and Haas Electronic Materials LLC
- Inventors: Tomas Marangoni; Huan He; Joshua Kaitz; Li Cui; Yinjie Cen; Emad Aqad; Mingqi Li
- Web page: https://patentgrep.com/patent/US12761556B2

## CPC

- G03F 7/039: Macromolecular compounds which are photodegradable, e.g. positive electron resists (G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023)
- G03F 7/028: with photosensitivity-increasing substances, e.g. photoinitiators
- G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)

## Abstract

A polymer including a first repeating unit comprising an acid labile group; an anionic endgroup selected from a carboxylate group or a sulfamate group; and an organic cation.

## Claims

### Claim 1

A polymer, comprising:
a first repeating unit comprising an acid labile group;
an anionic endgroup selected from a carboxylate group or a sulfamate group; and
an organic cation,
wherein the polymer is a polymerization product of a monomer comprising the acid labile group in the presence of a compound of Formulae (9a) or (9b):
wherein, in Formulae (9a) and (9b),
R10 to R13 are each independently hydrogen, halogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C3-30 heterocycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C3-30 cycloalkenyl, substituted or unsubstituted C3-30 heterocycloalkenyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C2-30 heteroaryl, substituted or unsubstituted C3-30 heteroarylalkyl, or substituted or unsubstituted C3-30 alkylheteroaryl;
provided that at least one of R10 and R11 is not hydrogen, and at least one of R12 and R13 is not hydrogen;
R10 and R11 are optionally bonded together to form a ring, and R12 and R13 are optionally bonded together to form a ring;
X is chlorine, bromine, iodine, or cyano;
L11 is a divalent linking group;
A− is a carboxylate group or a sulfamate group; and
M+ is an organic cation.

### Claim 2 (depends on 1)

The polymer of claim 1, wherein the polymer further comprises a second repeating unit, and wherein the second repeating unit comprises a lactone group, a polar group, or a combination thereof.

### Claim 3 (depends on 1)

The polymer of claim 1, wherein the anionic endgroup is bonded to a backbone of the polymer via an alkylene group, a cycloalkylene group, an arylene group, or a heteroarylene group, each of which may further comprise as part of its structure one or more groups selected from —O—, —C(O)—, —C(O)O—, —S—, —S(O)2—, —N(Rc)—, or —C(O)N(Rc)— wherein Rc is hydrogen, substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C3-20 cycloalkyl, or substituted or unsubstituted C3-20 heterocycloalkyl.

### Claim 4

A polymer, comprising:
a first repeating unit comprising an acid labile group;
an anionic endgroup selected from a carboxylate group or a sulfamate group; and
an organic cation,
wherein the polymer is a polymerization product of a monomer comprising the acid labile group in the presence of a compound of Formulae (10a), (10b), or (10c):
wherein, in Formulae (10a) to (10c),
R14 and R19 are each independently substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C3-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C2-30 heteroaryl, substituted or unsubstituted C3-30 heteroarylalkyl, or substituted or unsubstituted C3-30 alkylheteroaryl;
R15 to R18 are each independently hydrogen, halogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C3-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C2-30 heteroaryl, substituted or unsubstituted C3-30 heteroarylalkyl, or substituted or unsubstituted C3-30 alkylheteroaryl;
R20 and R21 are each independently substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C3-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C2-30 heteroaryl, substituted or unsubstituted C3-30 heteroarylalkyl, or substituted or unsubstituted C3-30 alkylheteroaryl;
L12 is a divalent linking group;
L13 is a single bond or a divalent linking group;
L14 is a divalent linking group;
each A− is a carboxylate group or a sulfamate group; and
each M+ is an organic cation.

### Claim 5 (depends on 1)

A method of preparing the polymer of claim 1, the method comprising:
polymerizing:
a first monomer comprising the acid labile group; and
a compound comprising a carboxylate group or a sulfamate group.

### Claim 6 (depends on 1)

A photoresist composition, comprising:
a first polymer comprising the polymer of claim 1; and
a solvent.

### Claim 7 (depends on 6)

The photoresist composition of claim 6, further comprising a second polymer, wherein the first polymer and the second polymer are different.

### Claim 8 (depends on 6)

The photoresist composition of claim 6, further comprising a photoacid generator.

### Claim 9 (depends on 6)

A method of forming a pattern, the method comprising:
applying a layer of a photoresist composition of claim 6 on a substrate to form a photoresist composition layer;
pattern-wise exposing the photoresist composition layer with activating radiation to form an exposed photoresist composition layer; and
developing the exposed photoresist composition layer.

### Claim 10

A polymer, comprising:
a first repeating unit comprising an acid labile group;
an anionic endgroup selected from a carboxylate group, a sulfonate group, or a sulfamate group; and
an organic cation,
wherein the polymer is a polymerization product of a monomer comprising the acid labile group in the presence of a compound represented by at least one of Formulae (9c), (10c), or (10d):
wherein, in Formulae (9c), (10c), and (10d),
R22 and R23 are each independently hydrogen, halogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C3-30 heterocycloalkyl, substituted or unsubstituted C2-30 alkenyl, substituted or unsubstituted C3-30 cycloalkenyl, substituted or unsubstituted C3-30 heterocycloalkenyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C2-30 heteroaryl, substituted or unsubstituted C3-30 heteroarylalkyl, or substituted or unsubstituted C3-30 alkylheteroaryl;
provided that at least one of R22 and R23 is not hydrogen;
R22 and R23 are optionally bonded together to form a ring;
R24 and R25 are each independently substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C3-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C2-30 heteroaryl, substituted or unsubstituted C3-30 heteroarylalkyl, or substituted or unsubstituted C3-30 alkylheteroaryl;
R26 to R29 are each independently hydrogen, halogen, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C3-30 heterocycloalkyl, substituted or unsubstituted C6-30 aryl, substituted or unsubstituted C7-30 arylalkyl, substituted or unsubstituted C7-30 alkylaryl, substituted or unsubstituted C2-30 heteroaryl, substituted or unsubstituted C3-30 heteroarylalkyl, or substituted or unsubstituted C3-30 alkylheteroaryl;
X is chlorine, bromine, iodine, or cyano;
L15 and L16 are each independently a divalent linking group;
L17 is a single bond or a divalent linking group;
each A− is a carboxylate group, a sulfamate group, or a sulfonate group; and
each M+ is an organic cation.

### Claim 11 (depends on 10)

The polymer of claim 10, wherein the polymer further comprises a second repeating unit, and wherein the second repeating unit comprises a lactone group, a polar group, or a combination thereof.

### Claim 12 (depends on 10)

The polymer of claim 10, wherein the anionic endgroup is bonded to a backbone of the polymer via an alkylene group, a cycloalkylene group, an arylene group, or a heteroarylene group, each of which may further comprise as part of its structure one or more groups selected from —O—, —C(O)—, —C(O)O—, —S—, —S(O)2—, —N(Rc)—, or —C(O)N(Rc)— wherein Rc is hydrogen, substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C3-20 cycloalkyl, or substituted or unsubstituted C3-20 heterocycloalkyl.

### Claim 13 (depends on 10)

A photoresist composition, comprising:
a first polymer comprising the polymer of claim 10; and
a solvent.

### Claim 14 (depends on 13)

The photoresist composition of claim 13, further comprising a second polymer, wherein the first polymer and the second polymer are different.

### Claim 15 (depends on 13)

The photoresist composition of claim 13, further comprising a photoacid generator.

### Claim 16 (depends on 13)

A method of forming a pattern, the method comprising:
applying a layer of a photoresist composition of claim 13 on a substrate to form a photoresist composition layer;
pattern-wise exposing the photoresist composition layer with activating radiation to form an exposed photoresist composition layer; and
developing the exposed photoresist composition layer.