# US 12,001,138 B2 · Composition for forming silicon-containing resist underlayer film and patterning process

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- Number: US 12,001,138 B2
- Document ID: US12001138B2
- Status: Granted
- Kind: B2
- Application number: 17/000,566
- Filed: 2020-08-24
- Published: 2021-03-25
- Granted: 2024-06-04
- Earliest claimed: 2019-09-19
- Assignees: Shin-Etsu Chemical Co., Ltd.
- Applicants: Shin-Etsu Chemical Co., Ltd.
- Inventors: Yusuke Kai; Takeru Watanabe; Yusuke Biyajima; Tsutomu Ogihara
- Web page: https://patentgrep.com/patent/US12001138B2

## CPC

- G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors}
- C08G 77/04: Polysiloxanes
- C08G 77/16: to hydroxy groups
- C08G 77/18: to alkoxy or aryloxy groups
- C08G 77/26: nitrogen-containing groups
- C09D 183/04: Polysiloxanes
- 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 7/004: Photosensitive materials (G03F7/12, G03F7/14 take precedence)
- G03F 7/0755: {Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds (G03F7/0752 takes precedence)}
- G03F 7/0757: {Macromolecular compounds containing Si-O, Si-C or Si-N bonds (G03F7/0752 takes precedence)}
- G03F 7/095: having more than one photosensitive layer (G03F7/075 takes precedence)
- G03F 7/11: having cover layers or intermediate layers, e.g. subbing layers {(G03F7/091 - G03F7/093, B41N3/03 take precedence)}
- H10P 76/2041: {Photolithographic processes}
- H10P 76/405: {characterised by their composition, e.g. multilayer masks}
- H10P 76/4083: {characterised by their behaviours during the lithography processes, e.g. soluble masks or redeposited masks}
- H10P 76/4085: {characterised by the processes involved to create the masks}
- H10P 76/4088: {Processes for improving the resolution of the 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 composition for forming a silicon-containing resist underlayer film contains at least one or more kinds of a quaternary ammonium salt shown by the following general formula (A-1), and a thermally crosslinkable polysiloxane (Sx), where Ar1 represents an aromatic group having 6 to 20 carbon atoms, or a heteroaromatic group having 4 to 20 carbon atoms. R11 represents an alkyl group, alkenyl group, oxoalkyl group, or oxoalkenyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group or aryloxoalkyl group having 7 to 12 carbon atoms. Some or all of hydrogen atoms of these groups are optionally substituted. Z− represents an organic or inorganic anion as a counterion of the quaternary ammonium cation. An object is to provide a silicon-containing resist underlayer film having high effect of suppressing ultrafine pattern collapse and appropriate etching rate in multilayer resist methods.

## Claims

### Claim 1

A composition for forming a silicon-containing resist underlayer film, comprising at least:
one or more kinds of a quaternary ammonium salt having an organic or inorganic anion as a counterion of a quaternary ammonium cation selected from the group consisting of cations shown by the formulae below:
a thermally crosslinkable polysiloxane (Sx); and
an acid generator, wherein the acid generator is a sulfonium salt which is a photoacid generator and generates an acid by an action of a high energy beam.

### Claim 2 (depends on 1)

The composition for forming a silicon-containing resist underlayer film according to claim 1, wherein the thermally crosslinkable polysiloxane (Sx) comprises any one or more of a repeating unit shown by the following general formula (Sx-1), a repeating unit shown by the following general formula (Sx-2), and a partial structure shown by the following general formula (Sx-3):
wherein R1, R2, and R3 are identical to or different from each other and each represent a monovalent organic group having 1 to 30 carbon atoms.

### Claim 3 (depends on 1)

A patterning process comprising steps of:
forming an organic film by using a coating-type organic film material on a body to be processed;
forming a silicon-containing resist underlayer film on the organic film by using the composition for forming a silicon-containing resist underlayer film according to claim 1;
forming a resist upper layer film on the silicon-containing resist underlayer film by using a resist upper layer film composition composed of a photoresist composition;
forming a circuit pattern in the resist upper layer film;
transferring the pattern to the silicon-containing resist underlayer film by etching using the resist upper layer film having the formed circuit pattern as a mask;
transferring the pattern to the organic film by etching using the silicon-containing resist underlayer film having the transferred pattern as a mask; and
transferring the pattern to the body to be processed by etching using the organic film having the transferred pattern as a mask.

### Claim 4 (depends on 1)

A patterning process comprising steps of:
forming a hard mask mainly containing carbon by a CVD method on a body to be processed;
forming a silicon-containing resist underlayer film on the hard mask by using the composition for forming a silicon-containing resist underlayer film according to claim 1;
forming a resist upper layer film on the silicon-containing resist underlayer film by using a resist upper layer film composition composed of a photoresist composition;
forming a circuit pattern in the resist upper layer film;
transferring the pattern to the silicon-containing resist underlayer film by etching using the resist upper layer film having the formed circuit pattern as a mask;
transferring the pattern to the hard mask by dry etching using the silicon-containing resist underlayer film having the transferred pattern as a mask; and
transferring the pattern to the body to be processed by dry etching using the hard mask having the transferred pattern as a mask.

### Claim 5 (depends on 3)

The patterning process according to claim 3, wherein in the step of forming the circuit pattern in the resist upper layer film, the pattern is formed by a photolithography with a wavelength of 10 nm or more and 300 nm or less, direct lithography with electron beam, nanoimprinting, or a combination thereof.

### Claim 6 (depends on 4)

The patterning process according to claim 4, wherein in the step of forming the circuit pattern in the resist upper layer film, the pattern is formed by a photolithography with a wavelength of 10 nm or more and 300 nm or less, direct lithography with electron beam, nanoimprinting, or a combination thereof.

### Claim 7 (depends on 3)

The patterning process according to claim 3, wherein the body to be processed is a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, or a metal oxynitride film.

### Claim 8 (depends on 4)

The patterning process according to claim 4, wherein the body to be processed is a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, or a metal oxynitride film.

### Claim 9 (depends on 5)

The patterning process according to claim 5, wherein the body to be processed is a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, or a metal oxynitride film.

### Claim 10 (depends on 6)

The patterning process according to claim 6, wherein the body to be processed is a semiconductor device substrate, a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, or a metal oxynitride film.

### Claim 11 (depends on 3)

The patterning process according to claim 3, wherein a metal constituting the body to be processed is silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or an alloy thereof.

### Claim 12 (depends on 4)

The patterning process according to claim 4, wherein a metal constituting the body to be processed is silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or an alloy thereof.

### Claim 13 (depends on 5)

The patterning process according to claim 5, wherein a metal constituting the body to be processed is silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or an alloy thereof.

### Claim 14 (depends on 6)

The patterning process according to claim 6, wherein a metal constituting the body to be processed is silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or an alloy thereof.

### Claim 15 (depends on 7)

The patterning process according to claim 7, wherein a metal constituting the body to be processed is silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or an alloy thereof.

### Claim 16 (depends on 8)

The patterning process according to claim 8, wherein a metal constituting the body to be processed is silicon, gallium, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, silver, gold, indium, arsenic, palladium, tantalum, iridium, aluminum, iron, molybdenum, cobalt, or an alloy thereof.