# US 2017/0285477 A1 · Photosensitive resin composition, cured film, element provided with cured film, and method for manufacturing semiconductor device

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- Number: US 2017/0285477 A1
- Document ID: US20170285477A1
- Status: Published application
- Kind: A1
- Application number: 15/509,171
- Filed: 2015-09-18
- Published: 2017-10-05
- Earliest claimed: 2014-09-30
- Assignees: Toray Industries, Inc.
- Applicants: Toray Industries, Inc.
- Inventors: Yugo TANIGAKI; Takenori FUJIWARA
- Web page: https://patentgrep.com/patent/US20170285477A1

## CPC

- G03F 7/095: having more than one photosensitive layer (G03F7/075 takes precedence)
- C08K 3/36: Silica
- C08K 5/28: Azides
- C08L 83/06: containing silicon bound to oxygen-containing groups (C08L83/12 takes precedence)
- G03F 7/0042: {with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists (G03F7/075 takes precedence)}
- G03F 7/0047: {characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing}
- G03F 7/0233: {characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides}
- G03F 7/032: with binders
- G03F 7/039: Macromolecular compounds which are photodegradable, e.g. positive electron resists (G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023)
- G03F 7/0758: {with silicon- containing groups in the side chains}
- G03F 7/40: Treatment after imagewise removal, e.g. baking
- H10P 50/242: {of Group IV materials}
- H10P 76/00: Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
- 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)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

To provide a photosensitive resin composition which is capable of forming a pattern with high resolution and obtaining a cured film having excellent heat resistance and cracking resistance, and is also alkali developable; and a method capable of shortening the step required to remove a cured film of the composition after formation of an impurity region on a semiconductor substrate; and a method for manufacturing a semiconductor device using the same. Disclosed is a photosensitive resin composition including a polysiloxane (A), wherein the polysiloxane (A) is a polysiloxane represented by the general formula (1), and wherein (X) and (Y) are represented by the general formulas (4) to (6). 7.5≦(X)≦75 (4) 2.5≦(Y)≦40 (5) 1.5×(Y)≦(X)≦3×(Y) (6)

## Claims

### Claim 1

A photosensitive resin composition comprising a polysiloxane (A), wherein
the polysiloxane (A) is a polysiloxane represented by the general formula (1):
wherein R1 to R3, in the general formula (1), each independently represents hydrogen, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, R7 to R9, Y1, and Y2 each independently represents hydrogen, an alkyl group, an acyl group, an aryl group, a polymer chain of the polysiloxane, or a substituent represented by the general formula (7), n and m each independently represents an integer of 1 or more, and l represents an integer of 0 or more:
wherein R4 to R6, in the general formula (7), each independently represents hydrogen, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group; and
wherein the content ratio of an organosilane unit represented by the general formula (2) in the polysiloxane (A) is (X) mol % in terms of a molar ratio of Si atoms, and the content ratio of an organosilane unit represented by the general formula (3) is (Y) mol % in terms of a molar ratio of Si atoms:
wherein R1 and R2, in the general formula (2), each independently represents hydrogen, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group;
wherein R7 and R8, in the general formula (3), each independently represents hydrogen, an alkyl group, an acyl group, an aryl group, a polymer chain of the polysiloxane, or a substituent represented by the general formula (7); and
wherein (X) and (Y) are represented by the general formulas (4) to (6).
7.5≦(X)≦75 (4)
2.5≦(Y)≦40 (5)
1.5×(Y)≦(X)≦3×(Y) (6)

### Claim 2 (depends on 1)

The photosensitive resin composition according to claim 1, wherein the polysiloxane (A) has a weight average molecular weight of 500 to 100,000.

### Claim 3 (depends on 1)

The photosensitive resin composition according to claim 1, wherein the polysiloxane (A) includes an organosilane unit having an aromatic group, and the content ratio of the organosilane unit having an aromatic group in the polysiloxane (A) is 15 to 80 mol % in terms of a molar ratio of Si atoms.

### Claim 4 (depends on 3)

The photosensitive resin composition according to claim 3, wherein the organosilane unit having an aromatic group is one or more unit(s) selected from the group consisting of an organosilane unit represented by the general formula (4a), an organosilane unit represented by the general formula (4b), and an organosilane unit represented by the general formula (4c):
wherein R61, in the general formula (4a), represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and p represents an integer of 0 to 7;
wherein R62 and R63, in the general formula (4b), represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an aryl group having 6 to 15 carbon atoms, q represents an integer of 0 to 7, w represents an integer of 1 to 2, x represents an integer of 0 to 1, and w+x=2; and
wherein R64 and R65, in the general formula (4c), represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an aryl group having 6 to 15 carbon atoms, r represents an integer of 0 to 7, y represents an integer of 1 to 3, z represents an integer of 0 to 2, and y+z=3.

### Claim 5 (depends on 1)

The photosensitive resin composition according to claim 1, further comprising (F) a dissolution accelerating crosslinking agent and the dissolution accelerating crosslinking agent (F) is one or more compound(s) selected from the group consisting of a compound represented by the general formula (14), a compound represented by the general formula (15), and a compound represented by the general formula (16):
wherein R35 and R36, in the general formula (14), each independently represents hydrogen or an alkyl group having 1 to 6 carbon atoms, R37 and R38 each independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a hydroxy group, X1 represents a direct bond or an alkylene chain having 1 to 6 carbon atoms, when X1 is a direct bond, a, b, x, and y are 0, when X1 is not a direct bond, X2 and X3 each independently represents a direct bond or an alkylene chain having 1 to 6 carbon atoms, R31 and R32 each independently represents hydrogen, an alkyl halide group having 1 to 6 carbon atoms, or a halogen atom, R33 and R34 each independently represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, c and d represent an integer of 0 to 2, and when X1 is not a direct bond, x and y represent 1, and a and b represent an integer of 1 to 6; and
wherein R39, in the general formula (15), represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, R49 and R41 each independently represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and e represents an integer of 0 to 3; and
wherein X17 and X18, in the general formula (16), each independently represents a direct bond or an alkylene chain having 1 to 6 carbon atoms, R65 to R67 each independently represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms, R68 and R69 each independently represents hydrogen or an alkyl group having 1 to 6 carbon atoms, R79 and R71 each independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a hydroxy group, X11 and X12 each independently represents a direct bond or an alkylene chain having 1 to 6 carbon atoms, when X11 is a direct bond, f, g, p, and q are 0, when X12 is a direct bond, h, i, r, and s are 0, when X11 or X12 is not a direct bond, X13, X14, X15, and X16 each independently represents a direct bond or an alkylene chain having 1 to 6 carbon atoms, R61 to R64 each independently represents hydrogen, an alkyl halide group having 1 to 6 carbon atoms, or a halogen atom, j, k, and 1 represent an integer of 0 to 2, when X11 and X12 are not direct bonds, p, q, r, and s are 1, and f, g, h, and i represent an integer of 1 to 6.

### Claim 6 (depends on 1)

The photosensitive resin composition according to claim 1, wherein (X) and (Y) are represented by the general formulas (4′) to (6′).
24≦(X)≦75 (4′)
8≦(Y)≦40 (5′)
1.5×(Y)≦(X)≦3×(Y) (6′)

### Claim 7 (depends on 1)

The photosensitive resin composition according to claim 1, further comprising (B) inorganic particles.

### Claim 8 (depends on 7)

The photosensitive resin composition according to claim 7, wherein the inorganic particles (B) are silica particles.

### Claim 9 (depends on 7)

The photosensitive resin composition according to claim 7, wherein the polysiloxane (A) is (A1) inorganic particle-containing polysiloxane including an organosilane unit to which the inorganic particles (B) are bonded.

### Claim 10 (depends on 1)

The photosensitive resin composition according to claim 1, further comprising one or more compound(s) selected from the group consisting of (C) a compound having a naphthoquinone diazide structure, (D) a photopolymerization initiator, (E1) a photoacid generator, and (E2) a photobase generator.

### Claim 11 (depends on 1)

The photosensitive resin composition according to claim 1, further comprising (G) a dissolution accelerator, the (G) dissolution accelerator being (G1) a compound represented by the general formula (17) or a compound represented by the general formula (18), and/or (G2) an acrylic resin including a structural unit represented by the general formula (19):
wherein X4 and X5, in the general formula (17), each independently represents a direct bond, an alkylene chain having 1 to 10 carbon atoms, a cycloalkylene chain having 4 to 10 carbon atoms, or an arylene chain having 6 to 15 carbon atoms, X6 represents a direct bond or a methylene chain, Y3 represents a direct bond or an oxygen atom, R42 represents hydrogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms, R43 and R44 each independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and f represents an integer of 0 to 2;
wherein X7, in the general formula (18), represents a direct bond, an alkylene chain having 1 to 10 carbon atoms, a cycloalkylene chain having 4 to 10 carbon atoms, or an arylene chain having 6 to 15 carbon atoms, X8 and X9 each independently represents an alkylene chain having 1 to 6 carbon atoms, Y4 represents a direct bond or an oxygen atom, R45 and R46 each independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, and g represents an integer of 0 to 2; and
wherein R47 and R48, in the general formula (19), represent hydrogen or an alkyl group having 1 to 4 carbon atoms, R49 and R59 represent an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms, each including a structural unit represented by the general formula (20), X10 represents a direct bond, an alkylene chain having 1 to 6 carbon atoms, a cycloalkylene chain having 4 to 7 carbon atoms, or an arylene chain having 6 to 10 carbon atoms:
wherein R51, in the general formula (20), represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms which has a hydroxy group, R52 represents hydrogen or an alkyl group having 1 to 4 carbon atoms which has a hydroxy group, h represents an integer of 1 to 4, i represents an integer of 0 to 30, and j represents an integer of 1 to 100.

### Claim 12 (depends on 1)

The photosensitive resin composition according to claim 1, wherein the polysiloxane (A) is a polysiloxane including an organosilane unit having an acidic group.

### Claim 13 (depends on 7)

The photosensitive resin composition according to claim 7, wherein the inorganic particles (B) have a number average particle diameter of 20 to 55 nm.

### Claim 14

A photosensitive resin composition comprising a polysiloxane (A), wherein
the polysiloxane (A) is a polysiloxane obtained by hydrolyzing an organosilane, followed by condensation, and the organosilane includes an organosilane represented by the general formula (21) and an organosilane represented by the general formula (22):
wherein R53 and R54, in the general formula (21), each independently represents hydrogen, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group, and R55 and R56 each independently represents hydrogen, an alkyl group, an acyl group, or an aryl group;
wherein R57 to R60, in the general formula (22), each independently represents hydrogen, an alkyl group, an acyl group, or an aryl group, and q represents an integer of 1 to 10; and
wherein the content ratio of an organosilane unit represented by the general formula (2) in the polysiloxane (A) is (X) mol % in terms of a molar ratio of Si atoms, and the content ratio of an organosilane unit represented by the general formula (3) is (Y) mol % in terms of a molar ratio of Si atoms:
wherein R1 and R2, in the general formula (2), each independently represents hydrogen, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group;
wherein R7 and R8, in the general formula (3), each independently represents hydrogen, an alkyl group, an acyl group, an aryl group, a polymer chain of the polysiloxane, or a substituent represented by the general formula (7);
wherein R4 to R6, in the general formula (7), each independently represents hydrogen, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group; and
wherein
(X) and (Y) are represented by the general formulas (4) to (6):
7.5≦(X)≦75 (4)
2.5≦(Y)≦40 (5)
1.5×(Y)≦(X)≦3×(Y) (6)

### Claim 15 (depends on 1)

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

### Claim 16 (depends on 1)

An element comprising a cured film obtained by curing the photosensitive resin composition according to claim 1.

### Claim 17 (depends on 1)

A semiconductor device comprising a cured film obtained by curing the photosensitive resin composition according to claim 1.

### Claim 18 (depends on 1)

A method for manufacturing a semiconductor device, which comprises the steps of:
(1) obtaining, on a substrate, a pattern of the photosensitive resin composition according to claim 1 or a cured product thereof,
(2) forming an impurity region on the substrate formed with the pattern and/or patterning on the substrate formed with the pattern, and
(3) removing the pattern, and
which comprises, as the step (2), one or more steps selected from the group consisting of the steps of:
(2-A) implanting ions into the substrate formed with the pattern,
(2-B) exposing the substrate formed with the pattern to dopants,
(2-C) patterning on the substrate formed with the pattern by dry etching, and
(2-D) patterning on the substrate formed with the pattern by wet etching.

### Claim 19 (depends on 18)

The method for manufacturing a semiconductor device according to claim 18, which comprises, as the step (1), the step of (1-1) heating the pattern of the photosensitive resin composition to 150 to 1,500° C.

### Claim 20 (depends on 18)

The method for manufacturing a semiconductor device according to claim 18, which comprises, as the step (2), one or more steps selected from the group consisting of the steps of:
(2-A1) implanting ions into the substrate while heating the substrate formed with the pattern to 200 to 1,000° C.,
(2-B1) exposing the substrate to dopants while heating the substrate formed with the pattern to 200 to 1,500° C.,
(2-C1) patterning by dry etching while heating the substrate formed with the pattern to 100 to 400° C., and
(2-D1) patterning by wet etching while heating the substrate formed with the pattern to 100 to 400° C.

### Claim 21 (depends on 19)

The method for manufacturing a semiconductor device according to claim 19, wherein the step (1-1) is the step of (1-1a) heating a pattern of the photosensitive resin composition to 500 to 1,500° C.

### Claim 22 (depends on 21)

The method for manufacturing a semiconductor device according to claim 21, wherein the step (3) is the step of (3-A) treating the pattern at from 0° C. to lower than 300° C.

### Claim 23 (depends on 18)

The method for manufacturing a semiconductor device according to claim 18, wherein the substrate is a substrate including one or more compound(s) selected from the group consisting of silicon, silicon dioxide (SiO2), silicon nitride (Si3N4), silicon carbide (SiC), gallium nitride (GaN), gallium phosphide (GaP), gallium arsenide (GaAs), aluminum gallium arsenide (GaAlAs), gallium indium nitrogen arsenide (GaInNAs), indium nitride (InN), indium phosphide (InP), indium tin oxide (ITO), indium zinc oxide (IZO), indium gallium arsenide (InGaAs), aluminium indium gallium phosphide (InGaAlP), indium zinc gallium oxide (IGZO), diamond, sapphire (Al2O3), aluminum zinc oxide (AZO), aluminum nitride (AlN), zinc oxide (ZnO), zinc selenide (ZnSe), cadmium sulfide (CdS), and cadmium telluride (CdTe).