# US 2014/0154624 A1 · Positive working photosensitive material

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- Number: US 2014/0154624 A1
- Document ID: US20140154624A1
- Status: Published application
- Kind: A1
- Application number: 13/693,496
- Filed: 2012-12-04
- Published: 2014-06-05
- Earliest claimed: 2012-12-04
- Assignees: Az Electronic Materials (Luxembourg) S.A.R.L.
- Inventors: Weihong LIU; Ping-Hung LU; Medhat TOUKHY; SookMee LAI; Yoshiharu SAKURAI; Aritaka HISHIDA
- Web page: https://patentgrep.com/patent/US20140154624A1

## CPC

- G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors}
- G03F 7/0392: {the macromolecular compound being present in a chemically amplified positive photoresist composition}
- G03F 7/0397: {the macromolecular compound having an alicyclic moiety in a side chain}
- 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

Disclosed herein is a photosensitive composition comprising a heterocyclic thiol compound or tautomeric form thereof and its method of use on a substrate, which may include a chalcophile substrate.

## Claims

### Claim 1

A positive working photosensitive composition comprising:
a. at least one photoacid generator;
b. at least one polymer, comprising one or more (meth)acrylate repeat units and further comprising one or more repeat units with at least one acid cleavable group having formula (5),
wherein R8-R12 are, independently, —H, F or —CH3, A is a linear or branched C1-C10 allylene group, B is a C1-C12 alkyl or alicyclic group, D is a linking group that may be a chemical bond, a carboxylate group, wherein the carbonyl carbon is bonded to the polymer backbone, or a —COOCH2— group, wherein the carbonyl carbon is bonded to the polymer backbone, Ar is a substituted or unsubstituted aromatic group or heteroaromatic group, E is a linear or branched C2-C10 alkylene group, G is an acid cleavable group, and further where v is 0-10 mole %, w is 0 mole %-20 mole %, x is 14 mole %-80 mole %, y is 0 mole %-40 mole % and z is 20 mole %-50 mole %;
c. at least one heterocyclic thiol compound comprising a ring structure chosen from the general formulas:
or tautomers thereof, wherein the ring structure is a single ring structure having 4-8 atoms, or a multi ring structure having 5-20 atoms, and wherein the single ring structure or the multi ring structure is chosen from the group consisting of an aromatic ring, a non aromatic ring, and a heteroaromatic ring, and wherein X is coupled into the ring by a single bond and is chosen from the group consisting of CR1R2, O, S, Se, Te, and NR3, or X is coupled into the ring by a double bond and is chosen from CR1 or N, and Y is chosen from CR1 or N, and wherein R1, R2, and R3 are independently selected from a group consisting of H, a substituted alkyl group having 1-8 carbon atoms, unsubstituted alkyl group having 1-8 carbon atoms, a substituted alkenyl group having 1-8 carbon atoms, unsubstituted alkenyl group having 1-8 carbon atoms, a substituted alkynyl group having 1-8 carbon atoms, unsubstituted alkynyl group having 1-8 carbon atoms, a substituted aromatic group having 1-20 carbon atoms, a substituted heteroaromatic group having 1-20 carbon atoms, unsubstituted aromatic group having 1-20 carbon atoms and unsubstituted heteroaromatic group having 1-20 carbon atoms and further wherein the ring structures of the heterocyclic thiol compound may be unsubstituted or substituted with substituents chosen from the group consisting of saturated hydrocarbon groups, unsaturated hydrocarbon groups, aromatic rings, aliphatic alcohols, aromatic alcohols, heteroaromatic alcohols, amines, amides, imides carboxylic acids, esters, ethers, and halides.

### Claim 2 (depends on 1)

The positive working photosensitive composition of claim 1, wherein the heterocyclic thiol is selected from a group consisting of 1H-1,2,4-triazole-3-thiol, 1H-1,2,4-triazole-5-thiol, 1H-benzo[d]imidazole-2-thiol, 1H-imidazole-2-thiol, 1H-imidazole-4-thiol, 1H-imidazole-5-thiol, 2-azabicyclo[2.2.1]hept-2-ene-3-thiol, 2-azabicyclo[3.2.1]oct-2-ene-3-thiol, 2-mercaptopyrimidine-4,6-diol, 3-mercapto-6-methyl-1,2,4-triazin-5-ol, 2-mercaptopyrimidin-4-ol, 2-mercapto-6-methylpyrimidin-4-ol, 1-methyl-1H-imidazole-2-thiol, 1H-indazole-3-thiol, 5-methyl-2-thiouracil, 5,6-dimethyl-2-thiouracil, 6-ethyl-5-methyl-2-thiouracil, 6-methyl-5-n-propyl-2-thiouracil, 5-ethyl-2-thioracil, 5-n-propyl-2-thiouracil, 5-n-butyl-2-thiouracil, 5-n-hexyl-2-thiouracil, 5-n-butyl-6-ethyl-2-thiouracil, 5-hydroxy-2-thiouracil, 5,6-dihydroxy-2-thiouracil, 5-hydroxy-6-n-propyl-2-thiouracil, 5-methoxy-2-thiouracil, 5-n-butoxy-2-thiouracil, 5-methoxy-6-n-propyl-2-thiouracil, 5-bromo-2-thiouracil, 5-chloro-2-thiouracil, 5-fluoro-2-thiouracil, 5-amino-2-thiouracil, 5-amino-6-methyl-2-thiouracil, 5-amino-6-phenyl-2-thiouracil, 5,6-diamino-2-thiouracil, 5-allyl-2-thiouracil, 5-allyl-3-ethyl-2-thiouracil, 5-allyl-6-phenyl-2-thiouracil, 5-benzyl-2-thiouracil, 5-benzyl-6-methyl-2-thiouracil, 5-acetamido-2-thiouracil, 6-methyl-5-nitro-2-thiouracil, 6-amino-2-thiouracil, 6-amino-5-methyl-2-thiouracil, 6-amino-5-n-propyl-2-thiouracil, 6-bromo-2-thiouracil, 6-chloro-2-thiouracil, 6-fluoro-2-thiouracil, 6-bromo-5-methyl-2-thiouracil, 6-hydroxy-2-thiouracil, 6-acetamido-2-thiouracil, 6-n-octyl-2-thiouracil, 6-dodecyl-2-thiouracil, 6-tetradecyl-2-thiouracil, 6-hexadecyl-2-thiouracil, 6-(2-hydroxyethyl)-2-thiouracil, 6-(3-isopropyloctyl)-5-methyl-2-thiouracil, 6-(m-nitrophenyl)-2-thiouracil, 6-(m-nitrophenyl)-5-n-propyl-2-thiouracil, 6-α-naphthyl-2-thiouracil, 6-α-naphthyl-5-t-butyl-2-thiouracil, 6-(p-chlorophenyl)-2-thiouracil, 6-(p-chlorophenyl)-2-ethyl-2-thiouracil, 5-ethyl-6-eicosyl-2-thiouracil, 6-acetamido-5-ethyl-2-thiouracil, 6-eicosyl-5-allyl-2-thiouracil, 5-amino-6-phenyl-2-thiouracil, 5-amino-6-(p-chlorophenyl)-2-thiouracil, 5-methoxy-6-phenyl-2-thiouracil, 5-ethyl-6-(3,3-dimethyloctyl)-2-thiouracil, 6-(2-bromoethyl)-2-thiouracil, tautomers thereof and combinations thereof.

### Claim 3 (depends on 1)

The positive working photosensitive composition of claim 1, wherein the heterocyclic thiol is selected from a group consisting of, 2-mercapto-6-methylpyrimidin-4-ol, 3-mercapto-6-methyl-1,2,4-triazin-5-ol, 2-mercaptopyrimidine-4,6-diol, 1H-1,2,4-triazole-3-thiol, 1H-1,2,4-triazole-5-thiol, 1H-imidazole-2-thiol, 1H-imidazole-5-thiol, 1H-imidazole-4-thiol, 2-azabicyclo[3.2.1]oct-2-ene-3-thiol, 2-azabicyclo[2.2.1]hept-2-ene-3-thiol, -1H-benzo[d]imidazole-2-thiol, 2-mercapto-6-methylpyrimidin-4-ol, 2-mercaptopyrimidin-4-ol, 1-methyl-1H-imidazole-2-thiol, 1H-indazole-3-thiol, tautomers thereof and combinations thereof.

### Claim 4 (depends on 1)

The positive working photosensitive material of claim 1, wherein the at least one photoacid generator is selected from a group consisting of an onium salt, a dicarboximidyl sulfonate ester, an oxime sulfonate ester, a diazo(sulfonyl methyl) compound, a disulfonyl methylene hydrazine compound, a nitrobenzyl sulfonate ester, a biimidazole compound, a diazomethane derivative, a glyoxime derivative, a β-ketosulfone derivative, a disulfone derivative, a sulfonic acid ester derivative, an imidoyl sulfonate derivative, a halogenated triazine compound, a diazonaphthoquinone sulfonate ester and combinations thereof.

### Claim 5 (depends on 1)

The positive working photosensitive composition of claim 1, wherein the acid cleavable group G is selected from a group consisting of a t-butyl group, a tetrahydropyran-2-yl group, a tetrahydrofuran-2-yl group, a 4-methoxytetrahydropyran-4-yl group, a 1-ethoxyethyl group, a 1-butoxyethyl group, a 1-propoxyethyl group, a 3-oxocyclohexyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a 8-methyl-8-tricyclo[5.2.1.0 2,6]decyl group, a 1,2,7,7-tetramethyl-2-norbornyl group, a 2-acetoxymenthyl group, a 2-hydroxymethyl group a 1-methyl-1-cyclohexylethyl group, a 4-methyl-2-oxotetrahydro-2H-pyran-4-yl group, a 2,3-dimethylbutan-2-yl group, a 2,3,3-trimethylbutan-2-yl group, a 1-methyl cyclopentyl group, a 1-ethyl cyclopentyl group, a 1-methyl cyclohexyl group, 1-ethyl cyclohexyl group, a 1,2,3,3-tetramethylbicyclo[2.2.1]heptan-2-yl group, a 2-ethyl-1,3,3-trimethylbicyclo[2.2.1]heptan-2-yl group, a 2,6,6-trimethylbicyclo[3.1.1]heptan-2-yl group, a 2,3-dimethylpentan-3-yl group, or a 3-ethyl-2-methylpentan-3-yl group.

### Claim 6 (depends on 1)

The positive working photosensitive composition of claim 1, wherein the polymer further comprises one or more repeat units selected from a group consisting of (meth)acrylic acid, 2-methoxyethyl(meth)acrylate, 2-ethoxyethyl(meth)acrylate, benzyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 4-hydroxybenzyl(meth)acrylate, 2-isobornyl methacrylate, 3-isobornyl(meth)acrylate, 1-adamantyl(meth)acrylate, styrene, 4-hydroxystyrene, tert-butyl 4-vinylphenyl carbonate, mevalonic lactone methacrylate, 2-oxotetrahydrofuran-3-yl(meth)acrylate, 2-oxotetrahydro-2H-pyran-3-yl(meth)acrylate, and 2-oxooxepan-3-yl(meth)acrylate.

### Claim 7 (depends on 1)

The positive working photosensitive composition of claim 1, wherein the polymer further comprises one or more styrenic repeat units having the structure
where R4 is chosen from H, Cl or CH3 and R5 and R6 can be the same or different, and are chosen from H, OH, OCOOC(CH3)3, or OCOCOO(CH3)3.

### Claim 8 (depends on 1)

A method of forming a positive relief image comprising:
a. forming a photosensitive layer by applying the positive working photosensitive composition of claim 1 to a substrate;
b. image-wise exposing the photosensitive layer to actinic radiation to form a latent image;
c. developing the latent image in a developer,
d. wherein the image-wise exposed photosensitive layer is optionally thermally treated.

### Claim 9 (depends on 8)

The method of claim 8 wherein the substrate comprises a chalcophile.

### Claim 10 (depends on 8)

The method of claim 8 wherein the substrate is copper.

### Claim 11 (depends on 1)

The positive working photosensitive composition of claim 1 further comprising an alkali-soluble novolak polymer.

### Claim 12 (depends on 11)

The positive working photosensitive composition of claim 11 where the novolak has a dissolution rate in 2.38% aqueous tetramethylammonium hydroxide between 10 Å/sec to 15,000 Å/sec.

### Claim 13 (depends on 11)

The positive working photosensitive composition of claim 11 where the novolak polymer comprises 20% to 80% w/w of the total polymer loading.

### Claim 14 (depends on 11)

The positive working photosensitive composition of claim 11 where the novolak polymer comprises 30% to 75% w/w of the total polymer loading.

### Claim 15 (depends on 11)

The positive working photosensitive composition of claim 11 were the polymer comprising one or more (meth)acrylate repeat units having formula 5 is a copolymer of methacrylic acid, benzyl methacrylate, hydroxypropyl methacrylate, and tert-butyl acrylate

### Claim 16

A positive working photosensitive composition comprising:
a. at least one photoacid generator;
b. at least one polymer, comprising one or more (meth)acrylate repeat units and further comprising one or more repeat units with at least one acid cleavable group having formula (5),
wherein R8-R12 are, independently, —H, F or —CH3, A is a linear or branched C1-C10 alkylene group, B is a C1-C12 alkyl or alicyclic group, D is a linking group that may be a chemical bond, a carboxylate group, wherein the carbonyl carbon is bonded to the polymer backbone, or a —COOCH2— group, wherein the carbonyl carbon is bonded to the polymer backbone, Ar is a substituted or unsubstituted aromatic group or heteroaromatic group, E is a linear or branched C2-C10 alkylene group, G is an acid cleavable group, and further where v is 0-10 mole %, w is 0 mole %-20 mole %, x is 14 mole %-80 mole %, y is 0 mole %-40 mole % and z is 20 mole %-50 mole %;
c. at least one heterocyclic thiol compound chosen from the group consisting of 1H-1,2,4-triazole-3-thiol, 1H-1,2,4-triazole-5-thiol, 1H-benzo[d]imidazole-2-thiol, 1H-imidazole-2-thiol, 1H-imidazole-4-thiol, 1H-imidazole-5-thiol, 2-azabicyclo[2.2.1]hept-2-ene-3-thiol, 2-azabicyclo[3.2.1]oct-2-ene-3-thiol, 2-mercaptopyrimidine-4,6-diol, 3-mercapto-6-methyl-1,2,4-triazin-5-ol, 2-mercaptopyrimidin-4-ol, 2-mercapto-6-methylpyrimidin-4-ol, 1-methyl-1H-imidazole-2-thiol, 1H-indazole-3-thiol, 5-methyl-2-thiouracil, 5,6-dimethyl-2-thiouracil, 6-ethyl-5-methyl-2-thiouracil, 6-methyl-5-n-propyl-2-thiouracil, 5-ethyl-2-thioracil, 5-n-propyl-2-thiouracil, 5-n-butyl-2-thiouracil, 5-n-hexyl-2-thiouracil, 5-n-butyl-6-ethyl-2-thiouracil, 5-hydroxy-2-thiouracil, 5,6-dihydroxy-2-thiouracil, 5-hydroxy-6-n-propyl-2-thiouracil, 5-methoxy-2-thiouracil, 5-n-butoxy-2-thiouracil, 5-methoxy-6-n-propyl-2-thiouracil, 5-bromo-2-thiouracil, 5-chloro-2-thiouracil, 5-fluoro-2-thiouracil, 5-amino-2-thiouracil, 5-amino-6-methyl-2-thiouracil, 5-amino-6-phenyl-2-thiouracil, 5,6-diamino-2-thiouracil, 5-allyl-2-thiouracil, 5-allyl-3-ethyl-2-thiouracil, 5-allyl-6-phenyl-2-thiouracil, 5-benzyl-2-thiouracil, 5-benzyl-6-methyl-2-thiouracil, 5-acetamido-2-thiouracil, 6-methyl-5-nitro-2-thiouracil, 6-amino-2-thiouracil, 6-amino-5-methyl-2-thiouracil, 6-amino-5-n-propyl-2-thiouracil, 6-bromo-2-thiouracil, 6-chloro-2-thiouracil, 6-fluoro-2-thiouracil, 6-bromo-5-methyl-2-thiouracil, 6-hydroxy-2-thiouracil, 6-acetamido-2-thiouracil, 6-n-octyl-2-thiouracil, 6-dodecyl-2-thiouracil, 6-tetradecyl-2-thiouracil, 6-hexadecyl-2-thiouracil, 6-(2-hydroxyethyl)-2-thiouracil, 6-(3-isopropyloctyl)-5-methyl-2-thiouracil, 6-(m-nitrophenyl)-2-thiouracil, 6-(m-nitrophenyl)-5-n-propyl-2-thiouracil, 6-α-naphthyl-2-thiouracil, 6-α-naphthyl-5-t-butyl-2-thiouracil, 6-(p-chlorophenyl)-2-thiouracil, 6-(p-chlorophenyl)-2-ethyl-2-thiouracil, 5-ethyl-6-eicosyl-2-thiouracil, 6-acetamido-5-ethyl-2-thiouracil, 6-eicosyl-5-allyl-2-thiouracil, 5-amino-6-phenyl-2-thiouracil, 5-amino-6-(p-chlorophenyl)-2-thiouracil, 5-methoxy-6-phenyl-2-thiouracil, 5-ethyl-6-(3,3-dimethyloctyl)-2-thiouracil, 6-(2-bromoethyl)-2-thiouracil, tautomers thereof and combinations thereof.

### Claim 17 (depends on 16)

The positive working photosensitive composition of claim 16 further comprising an alkali-soluble novolak polymer.

### Claim 18 (depends on 17)

The positive working photosensitive composition of claim 17 where the novolak has a dissolution rate in 2.38% aqueous tetramethylammonium hydroxide between 10 Å/sec to 15,000 Å/sec.

### Claim 19 (depends on 17)

The positive working photosensitive composition of claim 17 where the novolak polymer comprises 20% to 80% w/w of the total polymer loading.

### Claim 20 (depends on 17)

The positive working photosensitive composition of claim 17 where the novolak polymer comprises 30% to 75% w/w of the total polymer loading.