# US 2014/0193752 A1 · Stabilized acid amplifiers

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- Number: US 2014/0193752 A1
- Document ID: US20140193752A1
- Status: Published application
- Kind: A1
- Application number: 14/008,475
- Filed: 2012-03-28
- Published: 2014-07-10
- Earliest claimed: 2011-04-01
- Assignees: The Research Foundation of State University of New York
- Inventors: Robert L. Brainard; Brian Cardineau
- Web page: https://patentgrep.com/patent/US20140193752A1

## CPC

- G03F 7/027: Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds (G03F7/075 takes precedence)
- C07C 309/65: of a saturated carbon skeleton
- C07C 309/70: of a carbon skeleton substituted by carboxyl groups
- C07C 309/73: to carbon atoms of non-condensed six-membered aromatic rings
- C07D 317/18: Radicals substituted by singly bound oxygen or sulfur atoms
- C07D 317/72: spiro-condensed with carbocyclic rings
- C07D 319/06: not condensed with other rings
- C07D 319/08: condensed with carbocyclic rings or ring systems
- C07C 2601/14: The ring being saturated
- 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)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)

## Abstract

There are disclosed sulfonic acid precursor compositions, as are methods of using these compositions in, for example, photolithography. Other embodiments are also disclosed.

## Claims

### Claim 1

A compound of formula I
wherein
G1 is selected from —N+(CH3)3, —(CH2)—N+(CH3)3, —(CH2)—NO2, —CH2(CN), —CH(CN)2, —(CH2)0-1SO2(C1-C8)hydrocarbon, —C6F5, —Si(CH3)3, halogen, —CiHj(halogen)k, and CsHt(halogen)u-E, wherein i is 1-2, j is 0-3, k is 1-5, and the sum of j plus k is 2i+1; and wherein s is 1-2, t is 0-2, u is 1-4, and the sum of t plus u is 2s;
E is selected from —(C1-C6)alkyl, aryl, (C1-C6)haloalkyl, haloaryl, haloaryl(C1-C2)alkyl, and aryl(Ct—C2)alkyl;
G2 is selected from hydrogen, —CF3, —N+(CH3)3, halogen and (C1-C10)hydrocarbon;
A is selected from the following moieties:
wherein
M is —O—, —S— or —NR90—;
R10 is chosen from (C1-C8)saturated hydrocarbon; (C1-C8)saturated hydrocarbon substituted with halogen, cyano or nitro; (C1-C8)silaalkane; —O—(C1-C8)saturated hydrocarbon; —O—(C1-C8)saturated hydrocarbon substituted with halogen, cyano or nitro; —S—(C1-C8)saturated hydrocarbon; —S—(C1-C8)saturated hydrocarbon substituted with halogen, cyano or nitro; and optionally substituted phenyl;
R20 is chosen from H, (C1-C6) hydrocarbon and (C1-C6) hydrocarbon substituted with nitro or cyano, or taken together with the carbon to which they are attached, R10 and R20 form a three- to eight-membered ring;
R40 is chosen from H, (C1-C6)alkyl, —C(═O)(C1-C6)alkyl, —C(═O)(C1-C6)alkenyl, —C(═O)(C1-C6)haloalkyl, benzyl, substituted benzyl, —C(═O)phenyl, —C(═O)substituted phenyl, —SO2-phenyl, —SO2(substituted)phenyl and Q; or, when M is O or S, R10 and R40 together with the carbons to which they are attached form a four- to eight-membered ring optionally substituted with one or more (C1-C6) hydrocarbon groups;
R50 is chosen from H, (C1-C6) hydrocarbon, nitro, cyano, (C1-C6) hydrocarbon substituted with nitro or cyano, and (C1-C6)silaalkane, or together with the carbons to which they are attached, R10 and R50 form a (C3-C8) hydrocarbon ring; or, when M is O or S, R20 and R50 together with the carbons to which they are attached form a three- to eight-membered ring optionally substituted with one or more (C1-C6) hydrocarbon groups;
R90 is chosen from H, (C1-C6)alkyl, —C(═O)(C1-C6)alkyl and phenyl, or together with the nitrogen to which they are attached, R40 and R90 may form a nitrogen heterocycle, with the proviso that one of R40 and R90 must be an acyl, and when R40 and R90 together with the nitrogen to which they are attached form a heterocycle, the heterocyle must contain one or two α-oxo substituents; and
wherein
Rw, Rx and Ry are chosen independently in each instance from hydrogen, (C1-C10) hydrocarbon and (C1-C8) silaalkane;
R100 is chosen from hydrogen and (C1-C20) hydrocarbon; or
any two of R100, Rw, Rx, Ry and G2, taken together with the carbons to which they are attached, form a (C5-C8) hydrocarbon ring which may be substituted with (C1-C8)hydrocarbon, with the proviso that the C═C double bond above is not contained within a phenyl ring; or
G1 and A, together with the carbon to which they are attached, can form a non-aromatic, 5- or 6-membered ring D:
wherein Rg represents one or two substituents independently selected in each instance from hydrogen, -M-R40, (C1-C10)hydrocarbon, hydroxyl and RhCH2COO—, wherein Rh is chosen from halogen, hydroxyl, a polymer and an oligomer; and wherein G3 is selected from —N+(CH3)2, —(CH)—NO2, —CH(CN), —C(CN)2, —Si(CH3)2—, —CiHj(halogen)k, and CsHt(halogen)u-E, wherein i is 1-2, j is 0-3, k is 1-5, and the sum of j plus k is 2i; and wherein s is 1-2, t is 0-2, u is 1-4, and the sum of t plus u is 2s minus 1; and wherein RA and RB can each be selected independently from hydrogen, (C1-C6)alkyl and benzyl;
R30 is chosen from
(a) —CnHmFp wherein n is 1-8, m is 0-16, p is 1-17 and the sum of m plus p is 2n+1;
(b) —CH2C(═O)-Q;
(c) —CF2CH2OQ;
(d) —CF2C(═O)-Q;
(e) —CF2CH2C(═O)—R31, wherein R31 is selected from CH═CH2, CCH3═CH2, CHQCH2Q and CCH3QCH2Q;
wherein Z is a direct bond, CH2, CHF or CF2;
R60 is chosen from —CF3, —OCH3, —NO2, F, Cl, Br, —CH2Br, —CH═CH2, —OCH2CH2Br, -Q, —O-Q, —OCH2CH2-Q, —OCH2CH2O-Q, —CH(O)CH2-Q, —OC═OCH═CH2, —OC═OCCH3═CH2, —OC═OCHQCH2Q, and —OC═OCCH3QCH2Q;
R70 represents from one to four substituents chosen independently in each instance from H, —CF3, —OCH3, —CH3, —NO2, F, Br, Cl, —CiHj(halogen)k, and CsHt(halogen)u-E, wherein i is 1-2, j is 0-3, k is 1-5, and the sum of j plus k is 2i+1; and wherein s is 1-2, t is 0-2, u is 1-4, and the sum of t plus u is 2s;
E is selected from —(C1-C6)alkyl, aryl, (C1-C6)haloalkyl, haloaryl, haloaryl(C1-C2)alkyl, and aryl(C1-C2)alkyl;
(g) —(CH2)qCl, wherein q is an integer from 1 to 8;
(h) —CF2C(═O)NHC6H4R60;
(i) —CH2C(═O)NHC6H4R60; and
(j) —CHFC(═O)NHC6H4R60;
and
Q is a polymer or oligomer.

### Claim 2 (depends on 1)

A compound according to claim 1 wherein A is

### Claim 3 (depends on 2)

A compound according to claim 2 wherein R100, Rw, Rx, Ry and G2 are chosen independently in each instance from hydrogen, (C1-C10)alkyl, (C2-C10)alkenyl, and a saturated or unsaturated cyclic (C4-C8)hydrocarbon optionally linked by a methylene.

### Claim at position 4

4-10. (canceled)

### Claim 11 (depends on 1)

A compound according to claim 1 wherein A is

### Claim 12 (depends on 11)

A compound according to claim 11 wherein
R10 is chosen from methyl, propenyl, propynyl, dimethylbutynyl, cyclopropyl, trimethylsilylmethyl, phenyl, nitrophenyl, nitromethyl and cyanomethyl; and
R20 is chosen from H and methyl.

### Claim at position 7

13-14. (canceled)

### Claim 15 (depends on 1)

A compound according to claim 1 wherein R10 and R50 taken together form a cyclopentyl or cyclohexyl ring.

### Claim 16 (depends on 11)

A compound according to claim 11 wherein M is oxygen.

### Claim 17 (depends on 16)

A compound according to claim 16 wherein R40 is chosen from H, methyl, ethyl, isopropyl, t-butyl, benzyl, acetyl, chloroacetyl, dichloroacetyl, trichloroacetyl, benzoyl, 4-(trifluoromethyl)benzoyl, 4-nitrobenzoyl, 4-carboxybenzoyl, 4-methoxybenzoyl, benzenesulfonyl, 4-(trifluoromethyl)benzenesulfonyl, 4-nitrobenzenesulfonyl, 4-carboxybenzenesulfonyl and 4-methoxybenzenesulfonyl.

### Claim at position 11

18-22. (canceled)

### Claim 23 (depends on 1)

A compound according to claim 1 wherein G1 and A, together with the carbon to which they are attached, form a non-aromatic, 5- or 6-membered ring D:

### Claim at position 13

24-32. (canceled)

### Claim 33 (depends on 1)

A compound according to claim 1 wherein R30 is selected from

### Claim at position 15

34-37. (canceled)

### Claim 38

A compound of formula
wherein
G1 is selected from —N+(CH3)3, —(CH2)—N+(CH3)3, —(CH2)—NO2, —CH2(CN), —CH(CN)2, —(CH2)0-1SO2(C1-C8)hydrocarbon, —C6F5, —Si(CH3)3, halogen, —CiHj(halogen)k, and CsHt(halogen)u-E, wherein i is 1-2, j is 0-3, k is 1-5, and the sum of j plus k is 2i+1; and wherein s is 1-2, t is 0-2, u is 1-4, and the sum of t plus u is 2s;
E is selected from —(C1-C6)alkyl, aryl, (C1-C6)haloalkyl, haloaryl, haloaryl(C1-C2)alkyl, and aryl(C1-C2)alkyl;
R10 is chosen from (C1-C8)saturated hydrocarbon; (C1-C8)saturated hydrocarbon substituted with halogen, cyano or nitro; (C1-C8)silaalkane and optionally substituted phenyl;
R20 is chosen from H, (C1-C6) hydrocarbon and (C1-C6) hydrocarbon substituted with nitro or cyano, or taken together with the carbon to which they are attached, R10 and R20 form a (C3-C8) hydrocarbon ring;
R50 is chosen from H, (C1-C6) hydrocarbon, nitro, cyano, (C1-C6) hydrocarbon substituted with nitro or cyano, and (C1-C6)silaalkane, or together with the carbons to which they are attached, R10 and R50 form a (C3-C8) hydrocarbon ring;
R30a is chosen from H, F and (C1-C6) hydrocarbon; and
R30b is chosen from H and F.

### Claim 39 (depends on 1)

A compound according to claim 1 of formula
wherein
R10 is (C1-C8)saturated hydrocarbon;
R20 is chosen from H and (C1-C6) hydrocarbon;
G1 is selected from —N+(CH3)3, —(CH2)—N+(CH3)3, —(CH2)—NO2, —CH2(CN), —CH(CN)2, —(CH2)0-1SO2(C1-C8)hydrocarbon, —C6F5, —Si(CH3)3, halogen, —CiHj(halogen)k, and CsHt(halogen)u-E, wherein i is 1-2, j is 0-3, k is 1-5, and the sum of j plus k is 2i+1; and wherein s is 1-2, t is 0-2, u is 1-4, and the sum of t plus u is 2s;
E is selected from —(C1-C6)alkyl, aryl, (C1-C6)haloalkyl, haloaryl, haloaryl(C1-C2)alkyl, and aryl(C1-C2)alkyl.

### Claim 40

(canceled)

### Claim 41 (depends on 1)

A compound according to claim 1 selected from the group consisting of
wherein R35 is selected from hydrogen, (C1-C6)alkyl and benzyl.

### Claim 42 (depends on 1)

A compound according to claim 1 wherein G1 is —CF3 and R30 is

### Claim 43 (depends on 42)

A compound according to claim 42 selected from the group consisting of

### Claim at position 22

44-46. (canceled)

### Claim 47 (depends on 1)

A composition for photolithography comprising:
(a) a photolithographic polymer; and
(b) a compound according to claim 1.

### Claim 48 (depends on 1)

A photoresist composition comprising:
(a) a photoresist polymer; and
(b) a compound according to claim 1.

### Claim 49 (depends on 48)

A photoresist substrate which is coated with a photoresist composition according to claim 48.

### Claim 50 (depends on 48)

A method for preparing a substrate for photolithography, comprising coating said substrate with a composition according to claim 48.

### Claim 51 (depends on 48)

A method for conducting photolithography on a substrate, comprising (a) providing a substrate, (b) coating said substrate with a composition according to claim 48, and (c) irradiating the coated substrate through a photomask.

### Claim 52

(canceled)