# US 2024/0201595 A1 · Compound For Forming Metal-Containing Film, Composition For Forming Metal-Containing Film, And Patterning Process

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- Number: US 2024/0201595 A1
- Document ID: US20240201595A1
- Status: Published application
- Kind: A1
- Application number: 18/501,027
- Filed: 2023-11-03
- Published: 2024-06-20
- Earliest claimed: 2022-11-08
- Assignees: Shin-Etsu Chemical Co., Ltd.
- Applicants: Shin-Etsu Chemical Co., Ltd.
- Inventors: Naoki KOBAYASHI; Nobuhiro NAGAMACHI; Daisuke KORI
- Web page: https://patentgrep.com/patent/US20240201595A1

## CPC

- G03F 7/11: having cover layers or intermediate layers, e.g. subbing layers {(G03F7/091 - G03F7/093, B41N3/03 take precedence)}
- C07F 7/00: Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F 7/28: Titanium compounds
- G03F 7/0752: {in non photosensitive layers or as additives, e.g. for dry lithography}
- G03F 7/0757: {Macromolecular compounds containing Si-O, Si-C or Si-N bonds (G03F7/0752 takes precedence)}
- G03F 7/094: {Multilayer resist systems, e.g. planarising layers}
- 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)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

The present invention is a compound for forming a metal-containing film to be contained in a composition for forming a metal-containing film used in manufacturing a semiconductor, where the compound is represented by the following general formula (A). This provides: a compound for forming a metal-containing film having better dry etching resistance than conventional resist underlayer film materials and also having high filling and planarizing properties; a composition for forming a metal-containing film containing the compound; and a patterning process in which the composition is used as a resist underlayer film material.

## Claims

### Claim 1

A compound for forming a metal-containing film to be contained in a composition for forming a metal-containing film used in manufacturing a semiconductor, wherein
the compound is represented by the following general formula (A),
wherein M represents Ti, Zr, or Hf; Ra1, Ra2, Ra3, and Ra4 each represent an organic group of the following general formula (1), a silicon-containing organic group of the following general formula (2), or an alkyl group having 1 to 10 carbon atoms, at least one of Ra1, Ra2, Ra3, and Ra4 being an organic group of the following general formula (1) and at least one of Ra1, Ra2, Ra3, and Ra4 being a silicon-containing organic group of the following general formula (2); and “n” represents 1 to 30,
wherein “p” represents 0 or 1; “*” represents an attachment point to an oxygen atom; when “p” represents 1 and W represents an alkoxy group having 1 to 10 carbon atoms, X represents an unsaturated divalent organic group having 2 to 20 carbon atoms; when “p” represents 1 and W represents the following general formula (1A), X represents a saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms; and when “p” represents 0, X represents a monovalent organic group having 2 to 30 carbon atoms and containing a crosslinking group having a structure represented by one of the following general formulae (b-1) and (b-2),
wherein Y represents a saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms; RA represents a structure represented by one of the following general formulae (a-1) to (a-3); “h” represents 1 to 6; and “*” represents an attachment point to a carbon atom of a carbonyl group,
wherein each R1 independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms; each “q” independently represents 0 or 1; and “*” represents an attachment point to Y,
wherein each R2 independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms; each “q” independently represents 0 or 1; and “*” represents an attachment point,
wherein R3A, R3B, and R3C each represent an organic group selected from an organic group having 2 to 30 carbon atoms and containing a crosslinking group having a structure represented by one of the following general formulae (c-1) to (c-3), a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms; when the “p” in the general formula (1) represents 1 and the W represents an alkoxy group having 1 to 10 carbon atoms, at least one of R3A, R3B, and R3C represents an organic group having 2 to 30 carbon atoms and containing a crosslinking group having a structure represented by one of the following general formulae (c-1) to (c-3); and “*” represents an attachment point to an oxygen atom,
wherein each R3 independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms; each “q” independently represents 0 or 1; and “*” represents an attachment point.

### Claim 2 (depends on 1)

The compound for forming a metal-containing film according to claim 1, wherein in the general formula (1), “p” represents 1, X represents a saturated divalent organic group having 1 to 20 carbon atoms or an unsaturated divalent organic group having 2 to 20 carbon atoms, and W represents either structure represented by the following general formulae (1B),
wherein RA1 represents a structure represented by the general formula (a-1); each RA2 independently represents a structure represented by one of the general formulae (a-2) and (a-3); Z represents an oxygen atom or a secondary amine; L represents a divalent hydrocarbon group having 1 to 10 carbon atoms; each RA3 independently represents a saturated monovalent organic group having 1 to 20 carbon atoms or an unsaturated monovalent organic group having 2 to 20 carbon atoms; “t” represents 1 to 6 and “s” represents 0 to 5, provided that t+s is 1 or more and 6 or less; “r” represents 1 to 10; “u” represents 0 or 1; “m” represents 0 or 1; and “*” represents an attachment point to a carbon atom of a carbonyl group.

### Claim 3 (depends on 1)

The compound for forming a metal-containing film according to claim 1, wherein in the general formula (1), “p” represents 1, W represents an alkoxy group having 1 to 10 carbon atoms, and X represents any structure represented by the following formulae (1C),
wherein “*” represents an attachment point to a carbon atom of a carbonyl group.

### Claim 4 (depends on 1)

The compound for forming a metal-containing film according to claim 1, wherein in the general formula (1), “p” represents 0 and X represents a structure represented by the following formula (1D),
wherein each RD2 independently represents a structure represented by one of the general formulae (b-1) and (b-2); each RD1 independently represents a saturated monovalent organic group having 1 to 20 carbon atoms or an unsaturated monovalent organic group having 2 to 20 carbon atoms; “t′” represents 1 to 6 and “s′” represents 0 to 5, provided that t′+s′ is 1 or more and 6 or less; “u′” represents 0 or 1; and “*” represents an attachment point to a carbon atom of a carbonyl group.

### Claim 5 (depends on 1)

The compound for forming a metal-containing film according to claim 1, wherein the silicon-containing organic group of the general formula (2) has any structure represented by the following formulae (2A),
wherein R3D and R3E each independently represent an organic group selected from a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms; R3 is as defined above; “s” represents 1 to 10; and “*” represents an attachment point to an oxygen atom.

### Claim 6 (depends on 1)

A composition for forming a metal-containing film used in manufacturing a semiconductor, the composition comprising: (A) the compound for forming a metal-containing film according to claim 1; and (B) an organic solvent.

### Claim 7 (depends on 6)

The composition for forming a metal-containing film according to claim 6, further comprising one or more of (C) a crosslinking agent and (E) a surfactant.

### Claim 8 (depends on 6)

The composition for forming a metal-containing film according to claim 6, wherein the organic solvent (B) contains, as (B1) a high-boiling-point solvent, one or more kinds of organic solvent having a boiling point of 180° C. or higher.

### Claim 9 (depends on 6)

The composition for forming a metal-containing film according to claim 6, further comprising (F) metal oxide nanoparticles having an average primary particle size of 100 nm or less.

### Claim 10 (depends on 9)

The composition for forming a metal-containing film according to claim 9, wherein the metal oxide nanoparticles (F) are selected from the group consisting of zirconium oxide nanoparticles, hafnium oxide nanoparticles, titanium oxide nanoparticles, tin oxide nanoparticles, and tungsten oxide nanoparticles.

### Claim 11 (depends on 6)

The composition for forming a metal-containing film according to claim 6, further comprising (BP) a flowability accelerator having any organic group represented by the following general formulae (3) and an aromatic ring,
wherein “*” represents an attachment point to an oxygen atom; RB represents a divalent organic group having 1 to 10 carbon atoms; and RA represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.

### Claim 12 (depends on 11)

The composition for forming a metal-containing film according to claim 11, wherein the flowability accelerator (BP) has at least one constitutional unit represented by the following general formulae (BP-1), (BP-2), (BP-3), (BP-4), and (BP-5),
wherein W1 and W2 each independently represent a benzene ring or a naphthalene ring, part of hydrogen atoms in the benzene ring and the naphthalene ring optionally being substituted with a hydrocarbon group having 1 to 6 carbon atoms; Ra represents either group represented by the following formulae (4); Y′ represents any group represented by the following formulae (5); each “n1” independently represents 0 or 1; each “n2” independently represents 1 or 2; and each V independently represents a hydrogen atom or an attachment point,
wherein Z1 represents any group represented by the following general formulae (6); each Ra independently represents either group represented by the following formulae (4); each “n4” independently represents 0 or 1; each “n5” independently represents 1 or 2; and each V independently represents a hydrogen atom or an attachment point,
wherein “*” represents an attachment point to an oxygen atom,
wherein “*” represents an attachment point,
wherein W1, W2, Y′, and “n1” are as defined above; and “*” represents an attachment point,
wherein “m3” and “m4” represent 1 or 2; Z′ represents a single bond or any structure represented by the following general formulae (7); and Rx represents any structure represented by the following general formulae (8),
wherein “*” represents an attachment point; “l” represents an integer of 0 to 3; Ra to Rf each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and optionally having a substituent fluorine atom, a phenyl group, or a phenylethyl group, Ra and Rb optionally being bonded to each other to form a cyclic compound,
wherein “*” represents an attachment point to an aromatic ring; and each Q1 independently represents a linear saturated hydrocarbon group having 1 to 30 carbon atoms or a structure represented by the following general formula (9),
wherein “*” represents an attachment point to a carbon atom of a carbonyl group; each Ri independently represents either group represented by the formulae (4); each Rj independently represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an amino group, a nitrile group, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an alkanoyloxy group having 1 to 10 carbon atoms; “n3” and “n4” each represent a number of substituents on an aromatic ring, the number each representing an integer of 0 to 7, provided that n3+n4 is 0 or more and 7 or less; and “n5” represents 0 to 2,
wherein each R1 independently represents a saturated monovalent organic group having 1 to 30 carbon atoms or an unsaturated monovalent organic group having 2 to 30 carbon atoms; X′ represents a divalent organic group having 1 to 30 carbon atoms; each Ra independently represents either group represented by the formulae (4); “p” represents an integer of 0 to 5 and “q1” represents an integer of 1 to 6, provided that p+q1 is an integer of 1 or more and 6 or less; and “q2” represents 0 or 1.

### Claim 13 (depends on 6)

A patterning process for forming a pattern in a substrate to be processed, comprising the steps of:
(I-1) applying the composition for forming a metal-containing film according to claim 6 onto a substrate to be processed, followed by heating to form a metal-containing film;
(I-2) forming a resist upper layer film on the metal-containing film by using a photoresist material;
(I-3) subjecting the resist upper layer film to pattern exposure and then development with a developer to form a pattern in the resist upper layer film;
(I-4) transferring the pattern to the metal-containing film by dry etching while using the resist upper layer film having the formed pattern as a mask; and
(I-5) processing the substrate to be processed while using the metal-containing film having the formed pattern as a mask to form the pattern in the substrate to be processed.

### Claim 14 (depends on 6)

A patterning process for forming a pattern in a substrate to be processed, comprising the steps of:
(II-1) applying the composition for forming a metal-containing film according to claim 6 onto a substrate to be processed, followed by heating to form a metal-containing film;
(II-2) forming a silicon-containing resist middle layer film on the metal-containing film;
(II-3) forming a resist upper layer film on the silicon-containing resist middle layer film by using a photoresist material;
(II-4) subjecting the resist upper layer film to pattern exposure and then development with a developer to form a pattern in the resist upper layer film;
(II-5) transferring the pattern to the silicon-containing resist middle layer film by dry etching while using the resist upper layer film having the formed pattern as a mask;
(II-6) transferring the pattern to the metal-containing film by dry etching while using the silicon-containing resist middle layer film having the transferred pattern as a mask; and
(II-7) processing the substrate to be processed while using the metal-containing film having the formed pattern as a mask to form the pattern in the substrate to be processed.

### Claim 15 (depends on 6)

A patterning process for forming a pattern in a substrate to be processed, comprising the steps of:
(III-1) applying the composition for forming a metal-containing film according to claim 6 onto a substrate to be processed, followed by heating to form a metal-containing film;
(III-2) forming an inorganic hard mask middle layer film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film on the metal-containing film;
(III-3) forming an organic thin film on the inorganic hard mask middle layer film;
(III-4) forming a resist upper layer film on the organic thin film by using a photoresist material;
(III-5) subjecting the resist upper layer film to pattern exposure and then development with a developer to form a pattern in the resist upper layer film;
(III-6) transferring the pattern to the organic thin film and the inorganic hard mask middle layer film by dry etching while using the resist upper layer film having the formed pattern as a mask;
(III-7) transferring the pattern to the metal-containing film by dry etching while using the inorganic hard mask middle layer film having the transferred pattern as a mask; and
(III-8) processing the substrate to be processed while using the metal-containing film having the formed pattern as a mask to form the pattern in the substrate to be processed.

### Claim 16 (depends on 15)

The patterning process according to claim 15, wherein the inorganic hard mask middle layer film is formed by a CVD method or an ALD method.

### Claim 17 (depends on 6)

A patterning process for forming a pattern in a substrate to be processed, comprising the steps of:
(IV-1) applying the composition for forming a metal-containing film according to claim 6 onto a substrate to be processed, followed by heating to form a metal-containing film;
(IV-2) forming a resist underlayer film on the metal-containing film;
(IV-3) forming a silicon-containing resist middle layer film or a combination of an inorganic hard mask middle layer film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the resist underlayer film;
(IV-4) forming a resist upper layer film on the silicon-containing resist middle layer film or the organic thin film by using a photoresist material;
(IV-5) subjecting the resist upper layer film to pattern exposure and then development with a developer to form a pattern in the resist upper layer film;
(IV-6) transferring the pattern to the silicon-containing resist middle layer film or the organic thin film and the inorganic hard mask middle layer film by dry etching while using the resist upper layer film having the formed pattern as a mask;
(IV-7) transferring the pattern to the resist underlayer film by dry etching while using the silicon-containing resist middle layer film or the inorganic hard mask middle layer film having the transferred pattern as a mask;
(IV-8) transferring the pattern to the metal-containing film by dry etching while using the resist underlayer film having the transferred pattern as a mask; and
(IV-9) processing the substrate to be processed while using the metal-containing film having the formed pattern as a mask to form the pattern in the substrate to be processed.

### Claim 18 (depends on 6)

A tone-reversal patterning process for forming a pattern in a substrate to be processed, comprising the steps of:
(V-1) forming a resist underlayer film on a substrate to be processed;
(V-2) forming a resist middle layer film or a combination of an inorganic hard mask middle layer film selected from a silicon oxide film, a silicon nitride film, and a silicon oxynitride film and an organic thin film on the resist underlayer film;
(V-3) forming a resist upper layer film on the resist middle layer film or the combination of the inorganic hard mask middle layer film and the organic thin film by using a photoresist material;
(V-4) subjecting the resist upper layer film to pattern exposure and then development with a developer to form a pattern in the resist upper layer film;
(V-5) transferring the pattern to the resist middle layer film or the organic thin film and the inorganic hard mask middle layer film by dry etching while using the resist upper layer film having the formed pattern as a mask;
(V-6) transferring the pattern to the resist underlayer film by dry etching while using the resist middle layer film or the inorganic hard mask middle layer film having the transferred pattern as a mask;
(V-7) applying the composition for forming a metal-containing film according to claim 6 onto the resist underlayer film having the formed pattern, followed by heating to cover the resist underlayer film with a metal-containing film, thereby filling a space between the resist underlayer film patterns with the metal-containing film;
(V-8) etching back the metal-containing film covering the resist underlayer film having the formed pattern by a chemical stripper or dry etching to expose an upper surface of the resist underlayer film having the formed pattern;
(V-9) removing the resist middle layer film or the inorganic hard mask middle layer film remaining on the upper surface of the resist underlayer film by dry etching;
(V-10) removing the resist underlayer film having the formed pattern with its surface exposed by dry etching to form a reverse pattern of an original pattern on the metal-containing film; and
(V-11) processing the substrate to be processed while using the metal-containing film having the formed reverse pattern as a mask to form the reverse pattern in the substrate to be processed.