# US 9,751,984 B2 · Polyimide precursor, photosensitive resin composition containing said polyimide precursor, and cured-pattern-film manufacturing method and semiconductor device using said photosensitive resin composition

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- Number: US 9,751,984 B2
- Document ID: US9751984B2
- Status: Granted
- Kind: B2
- Application number: 14/654,758
- Filed: 2013-12-19
- Published: 2015-12-10
- Granted: 2017-09-05
- Earliest claimed: 2012-12-21
- Assignees: Hitachi Chemical Dupont Microsystems, Ltd.
- Applicants: Hitachi Chemical DuPont MicroSystems, Ltd.
- Inventors: Tetsuya Enomoto; Keishi Ono; Masayuki Ohe; Keiko Suzuki; Kazuya Soejima; Etsuharu Suzuki
- Web page: https://patentgrep.com/patent/US9751984B2

## CPC

- C08G 73/1007: {from tetracarboxylic acids or derivatives and diamines}
- C08F 290/14: Polymers provided for in subclass C08G
- C08G 73/1039: {comprising halogen-containing substituents}
- C08G 73/1042: {Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds}
- C08G 73/1053: {with oxygen only in the tetracarboxylic moiety}
- C08G 73/1067: {Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound}
- C08G 73/1071: {Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain}
- C08G 73/16: Polyester-imides
- C08K 5/33: Oximes
- C09D 179/08: Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- G03F 7/031: Organic compounds not covered by group G03F7/029
- G03F 7/037: the binders being polyamides or polyimides
- G03F 7/0387: {Polyamides or polyimides}
- G03F 7/0388: {with ethylenic or acetylenic bands in the side chains of the photopolymer}
- G03F 7/168: {Finishing the coated layer, e.g. drying, baking, soaking}
- G03F 7/20: Exposure; Apparatus therefor (photographic printing apparatus for making copies G03B27/00)
- G03F 7/32: Liquid compositions therefor, e.g. developers
- G03F 7/40: Treatment after imagewise removal, e.g. baking
- H10P 14/683: {carbon-based polymeric organic materials, e.g. polyimides, poly cyclobutene or PVC}
- H10P 50/28: of insulating materials
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- 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)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

A polyimide precursor including a structural unit represented by the following general formula (1) in a ratio of 50 mol % or more based on the total structural units. In the general formula (1), A is a tetravalent organic group represented by the following general formula (2a), a tetravalent organic group represented by the following general formula (2b), or a tetravalent organic group represented by the following general formula (2c), and B is a divalent organic group represented by the following general formula (3).

## Claims

### Claim 1

A photosensitive resin composition comprising:
(a) a polyimide precursor comprising
(a1) a structural unit represented by a general formula (1) in a ratio of 50 mol % or more based on total structural units, and
(a2) a structural unit represented by a general formula (4),
wherein A is a tetravalent organic group represented by a formula (2a), a tetravalent organic group represented by a formula (2b), or a tetravalent organic group represented by a general formula (2c),
B is a divalent organic group represented by a general formula (3), and
R1 and R2 are independently a hydrogen atom or a monovalent organic group,
wherein X and Y are independently a divalent group that is not conjugated with benzene rings bonded thereto, or a single bond,
wherein R3 to R10 are independently a hydrogen atom or a monovalent group, at least one of R3 to R10 being a trifluoromethyl group,
wherein D is a tetravalent organic group represented by a general formula (5), and B, R1 and R2 are the same as defined above in connection with the general formula (1), and
wherein Z is an ether bond (—O—) or a sulfide bond (—S—);
(b) a compound that generates radicals when irradiated with active rays;
(c) a solvent; and
(d) a tetrazole, a tetrazole derivative, benzotriazole, or a benzotriazole derivative.

### Claim 2 (depends on 1)

The photosensitive resin composition according to claim 1, wherein the molar ratio of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (4) is 5/5 to 9/1.

### Claim 3 (depends on 1)

The photosensitive resin composition according to claim 1, wherein R1 or R2 in the general formula (1) is a monovalent organic group that comprises a carbon-carbon unsaturated double bond.

### Claim 4 (depends on 1)

The photosensitive resin composition according to claim 1, wherein the component (b) comprises an oxime ester compound.

### Claim 5 (depends on 4)

The photosensitive resin composition according to claim 4, wherein the oxime ester compound is a compound represented by a general formula (22), a compound represented by a general formula (23), or a compound represented by a general formula (24),
wherein R11 and R12 are independently an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or a phenyl group, and R13 is —H, —OH, —COOH, —O(CH2)OH, —O(CH2)2OH, —COO(CH2)OH, or —COO(CH2)2OH,
wherein R14 are independently an alkyl group having 1 to 6 carbon atoms, R15 is NO2 or ArCO (wherein Ar is an aryl group), and R16 and R17 are independently an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group,
wherein R18 is an alkyl group having 1 to 6 carbon atoms, R19 is an organic group that comprises an acetal bond, and R20 and R21 are independently an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group.

### Claim 6 (depends on 1)

A cured film obtained by heating the photosensitive resin composition according to claim 1.

### Claim 7 (depends on 1)

A patterned cured film obtained by heating the photosensitive resin composition according to claim 1.

### Claim 8 (depends on 1)

A method for producing a patterned cured film, the method comprising the steps of:
applying the photosensitive resin composition according to claim 1 to a substrate, and drying the applied photosensitive resin composition to form a film;
exposing the film in a pattern by applying active rays to the film;
removing an unexposed area of the film by development to obtain a patterned resin film; and
heating the patterned resin film.

### Claim 9 (depends on 8)

A semiconductor device comprising a patterned cured film obtained using the method for producing a patterned cured film according to claim 8.

### Claim 10 (depends on 1)

The photosensitive resin composition according to claim 1, wherein the polyimide precursor additionally comprises an addition-polymerizable compound.

### Claim 11 (depends on 1)

The photosensitive resin composition according to claim 1, wherein the polyimide precursor additionally comprises a tetrazole or a tetrazole derivative selected from the group consisting of 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, 5,5′-bis-1H-tetrazole, 1-methyl-5-ethyltetrazole, 1-methyl-5-mercaptotetrazole, and 1-carboxymethyl-5-mercaptotetrazole.

### Claim 12 (depends on 1)

The photosensitive resin composition according to claim 1, wherein the polyimide precursor additionally comprises a benzotriazole or a benzotriazole derivative selected from the group consisting of benzotriazole, 1H-benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, 1H-benzotriazole-1-methanol, carboxybenzotriazole, and mercaptobenzoxazole.

### Claim 13 (depends on 1)

The photosensitive resin composition according to claim 1, wherein the tetravalent organic group that produces the structure represented in formula (1) by A is one or more selected from the group consisting of pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and the tetracarboxylic dianhydrides respectively represented by the following formulas (6) to (12),