# US 10,372,039 B2 · Resist underlayer film forming composition containing silicon having ester group

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- Number: US 10,372,039 B2
- Document ID: US10372039B2
- Status: Granted
- Kind: B2
- Application number: 14/439,791
- Filed: 2013-10-24
- Published: 2015-11-05
- Granted: 2019-08-06
- Earliest claimed: 2012-10-31
- Assignees: Nissan Chemical Industries, Ltd.
- Applicants: Nissan Chemical Industries, Ltd.
- Inventors: Yuta Kanno; Makoto Nakajima; Satoshi Takeda; Hiroyuki Wakayama
- Web page: https://patentgrep.com/patent/US10372039B2

## CPC

- G03F 7/0757: {Macromolecular compounds containing Si-O, Si-C or Si-N bonds (G03F7/0752 takes precedence)}
- C08G 77/14: containing silicon bound to oxygen-containing groups
- C08G 77/26: nitrogen-containing groups
- C08G 77/28: sulfur-containing groups
- C08G 77/80: {Siloxanes having aromatic substituents, e.g. phenyl side groups}
- C09D 183/06: containing silicon bound to oxygen-containing groups (C09D183/12 takes precedence)
- C09D 183/08: containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
- G03F 7/0752: {in non photosensitive layers or as additives, e.g. for dry lithography}
- G03F 7/091: {characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement}
- G03F 7/094: {Multilayer resist systems, e.g. planarising layers}
- G03F 7/30: Imagewise removal using liquid means
- G03F 7/322: {Aqueous alkaline compositions}
- G03F 7/325: {Non-aqueous compositions}
- G03F 7/36: Imagewise removal not covered by groups G03F7/30 - G03F7/34, e.g. using gas streams, using plasma
- G03F 7/40: Treatment after imagewise removal, e.g. baking
- H10P 14/6342: {Liquid deposition, e.g. spin-coating, sol-gel techniques or spray coating}
- H10P 14/6922: {the material containing Si, O and at least one of H, N, C, F or other non-metal elements, e.g. SiOC, SiOC:H or SiONC}
- H10P 76/405: {characterised by their composition, e.g. multilayer masks}
- 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)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

A resist underlayer film forming composition for lithography for a resist underlayer film usable as a hardmask. A resist underlayer film forming composition for lithography, including: as a silane, a hydrolyzable silane, a hydrolysis product thereof, or a hydrolysis-condensation product thereof, wherein the hydrolyzable silane includes a hydrolyzable silane of Formula (1) or a hydrolyzable silane containing a combination of a hydrolyzable silane of Formula (1) with a hydrolyzable silane of Formula (2), and a content of the hydrolyzable silane of Formula (1) or the hydrolyzable silane containing a combination of a hydrolyzable silane of Formula (1) with a hydrolyzable silane of Formula (2) in all silanes is less than 50% by mole, R1aR2bSi(R3)4−(a+b) Formula (1) R4a1R5b1Si(R6)4−(a1+b1) Formula (2).

## Claims

### Claim 1

A resist underlayer film forming composition for lithography, comprising:
as a silane, a hydrolyzable silane, a hydrolysis product thereof, or a hydrolysis-condensation product thereof, wherein
the hydrolyzable silane contains:
a hydrolyzable silane containing a combination of a hydrolyzable silane of Formula (1) with a hydrolyzable silane of Formula (2), and
an other hydrolyzable silane,
wherein the other hydrolyzable silane is at least one organic silicon compound selected from the group consisting of:
a compound of Formula (3):
R7a2Si(R8)4−a2 Formula (3)
where in Formula (3), R7 is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group, and is bonded to a silicon atom through a Si—C bond; R8 is an alkoxy group, an acyloxy group, or a halogen group; and a2 is an integer of 0 to 3,
and a compound of Formula (4):
[R9cSi(R10)3−c]2Yb2 Formula (4)
where in Formula (4), R9 is an alkyl group and is bonded to a silicon atom through a Si—C bond; R10 is an alkoxy group, an acyloxy group, or a halogen group; Y is an alkylene group or an arylene group; b2 is an integer of 0 or 1; and c is an integer of 0 or 1, and
the other hydrolyzable silane contains a substituted phenyl silane and a methyl silane, and
a content of the hydrolyzable silane containing a combination of a hydrolyzable silane of Formula (1) with a hydrolyzable silane of Formula (2) in all silanes is 10 to 20% by mole,
R1aR2bSi(R3)4−(a+b) Formula (1)
where in Formula (1), R1 is a monovalent organic group containing a group of Formula (1-1), Formula (1-2), Formula (1-3), Formula (1-4), or Formula (1-5):
where in Formula (1-1), Formula (1-2), Formula (1-3), Formula (1-4), and Formula (1-5), each of T1 and T7 is an alkylene group, a cyclic alkylene group, an alkenylene group, an arylene group, a sulfur atom, an oxygen atom, an oxycarbonyl group, an amido group, a secondary amino group, or a combination of these groups and atoms; T2 is an alkyl group; each of T3 and T5 is an aliphatic ring or an aromatic ring; T4 is a cyclic alkylene group, an alkenylene group, an arylene group, a sulfur atom, an oxygen atom, an oxycarbonyl group, an amido group, a secondary amino group, or a combination of these groups and atoms; each of T6 and T8 is a lactone ring; and n is an integer of 1 or 2, and R1 is bonded to a silicon atom through a Si—C bond; R2 is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, or a cyano group, and is bonded to a silicon atom through a Si—C bond; R3 is an alkoxy group, an acyloxy group, or a halogen group; and a is an integer of 1, b is an integer of 0 or 1, and a+b is an integer of 1 or 2,
R4a1R5b1Si(R6)4−(a1+b1) Formula (2)
where in Formula (2), R4 is a monovalent organic group containing a group of Formula (2-1), Formula (2-2), or Formula (2-3):
and R4 is bonded to a silicon atom through a Si—C bond; R5 is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, or a cyano group, and is bonded to a silicon atom through a Si—C bond; R6 is an alkoxy group, an acyloxy group, or a halogen group; and a1 is an integer of 1, b1 is an integer of 0 or 1, and a1+b1 is an integer of 1 or 2; wherein
the hydrolyzable silane does not contain:
a combination of a hydrolyzable silane of Formula (1) in which R1 is a monovalent organic group containing Formula (1-1) with a hydrolyzable silane of Formula (2) in which R4 is a monovalent organic group containing Formula (2-3),
a combination of a hydrolyzable silane of Formula (1) in which R1 is a monovalent organic group containing Formula (1-4) with a hydrolyzable silane of Formula (2) in which R4 is a monovalent organic group containing Formula (2-3), and
a combination of a hydrolyzable silane of Formula (1) in which R1 is a monovalent organic group containing Formula (1-5) with a hydrolyzable silane of Formula (2) in which R4 is a monovalent organic group containing Formula (2-3).

### Claim 2 (depends on 1)

The resist underlayer film forming composition according to claim 1, wherein
a hydrolyzable silane of Formula (2) is a hydrolyzable silane in which R4 is an organic group containing a group of Formula (2-1), a hydrolyzable silane in which R4 is an organic group containing a group of Formula (2-2), a hydrolyzable silane in which R4 is an organic group containing a group of Formula (2-3), or a mixture of these hydrolyzable silanes.

### Claim 3 (depends on 1)

The resist underlayer film forming composition according to claim 1, wherein
a hydrolyzable silane containing a combination of a hydrolyzable silane of Formula (1) with a hydrolyzable silane of Formula (2) contains a hydrolyzable silane of Formula (1) and a hydrolyzable silane of Formula (2) in a molar ratio of 1:0.01 to 1:10.

### Claim 4 (depends on 1)

A resist underlayer film forming composition comprising:
a hydrolysis product of a hydrolyzable silane containing a combination of a hydrolyzable silane of Formula (1) with a hydrolyzable silane of Formula (2), and a hydrolyzable silane of Formula (3) as claimed in claim 1, as a polymer,
wherein the hydrolyzable silane containing a combination of a hydrolyzable silane of Formula (1) with a hydrolyzable silane of Formula (2) contains a hydrolyzable silane of Formula (1) and a hydrolyzable silane of Formula (2) in a molar ratio of 1:0.01 to 1:10.

### Claim 5 (depends on 1)

The resist underlayer film forming composition according to claim 1, further comprising an acid as a hydrolysis catalyst.

### Claim 6 (depends on 1)

The resist underlayer film forming composition according to claim 1, further comprising water.

### Claim 7 (depends on 1)

A resist underlayer film obtained by applying the resist underlayer film forming composition as claimed in claim 1 onto a semiconductor substrate, and baking the composition.

### Claim 8 (depends on 1)

A method for producing a semiconductor device, the method comprising:
applying the resist underlayer film forming composition as claimed in claim 1 onto a semiconductor substrate and baking the composition to form a resist underlayer film;
applying a composition for a resist onto the underlayer film to form a resist film;
exposing the resist film to light;
developing the resist after the exposure to obtain a resist pattern;
etching the resist underlayer film using the resist pattern; and
processing the semiconductor substrate using the patterned resist and the patterned resist underlayer film.

### Claim 9 (depends on 1)

A method for producing a semiconductor device, the method comprising:
forming an organic underlayer film on a semiconductor substrate;
applying the resist underlayer film forming composition as claimed in claim 1, onto the organic underlayer film and baking the composition to form a resist underlayer film;
applying a composition for a resist onto the resist underlayer film to form a resist film;
exposing the resist film to light;
developing the resist after the exposure to obtain a resist pattern;
etching the resist underlayer film using the resist pattern;
etching the organic underlayer film using the patterned resist underlayer film; and
processing the semiconductor substrate using the patterned organic underlayer film.

### Claim 10

A resist underlayer film forming composition for lithography, comprising:
as a silane, a hydrolyzable silane, a hydrolysis product thereof, or a hydrolysis-condensation product thereof, wherein
the hydrolyzable silane contains:
a hydrolyzable silane of Formula (1), and
an other hydrolyzable silane,
wherein the other hydrolyzable silane is at least one organic silicon compound selected from the group consisting of:
a compound of Formula (3):
R7a2Si(R8)4−a2 Formula (3)
where in Formula (3), R7 is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, or a cyano group, and is bonded to a silicon atom through a Si—C bond; R8 is an alkoxy group, an acyloxy group, or a halogen group; and a2 is an integer of 0 to 3,
and a compound of Formula (4):
[R9cSi(R10)3−c]2Yb2 Formula (4)
where in Formula (4), R9 is an alkyl group and is bonded to a silicon atom through a Si—C bond; R10 is an alkoxy group, an acyloxy group, or a halogen group; Y is an alkylene group or an arylene group; b2 is an integer of 0 or 1; and c is an integer of 0 or 1, and
the other hydrolyzable silane contains a substituted phenyl silane and a methyl silane, and
a content of the hydrolyzable silane of Formula (1) in all silanes is 10 to 20% by mole,
R1aR2bSi(R3)4−(a+b) Formula (1)
where in Formula (1),
R1 is a monovalent organic group containing a group of Formula (1-1), Formula (1-2), or Formula (1-3):
where in Formula (1-1), Formula (1-2), and Formula (1-3), T1 an alkylene group, a cyclic alkylene group, an alkenylene group, an arylene group, a sulfur atom, an oxygen atom, an oxycarbonyl group, an amido group, a secondary amino group, or a combination of these groups and atoms; T2 is an alkyl group; T3 is an aliphatic ring or an aromatic ring; T4 is a cyclic alkylene group, an alkenylene group, an arylene group, a sulfur atom, an oxygen atom, an oxycarbonyl group, an amido group, a secondary amino group, or a combination of these groups and atoms; and n is an integer of 1 or 2;
R1 is bonded to a silicon atom through a Si—C bond;
R2 is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, or a cyano group, and is bonded to a silicon atom through a Si—C bond;
R3 is an alkoxy group, an acyloxy group, or a halogen group; and
a is an integer of 1, b is an integer of 0 or 1, and a+b is an integer of 1 or 2.