# US 2014/0193757 A1 · Compositon for forming metal oxide-containing film and patterning process > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2014/0193757 A1 - Document ID: US20140193757A1 - Status: Published application - Kind: A1 - Application number: 14/107,500 - Filed: 2013-12-16 - Published: 2014-07-10 - Earliest claimed: 2013-01-08 - Assignees: Shin-Etsu Chemical Co., Ltd. - Applicants: Shin-Etsu Chemical Co., Ltd. - Inventors: Tsutomu OGIHARA; Takafumi UEDA; Seiichiro TACHIBANA; Yoshinori TANEDA - Web page: https://patentgrep.com/patent/US20140193757A1 ## CPC - G03F 7/094: {Multilayer resist systems, e.g. planarising layers} - G03F 7/0752: {in non photosensitive layers or as additives, e.g. for dry lithography} - 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) ## Abstract The invention provides a composition for forming a metal oxide-containing film comprising, as a component (A), a metal oxide-containing compound A1 obtained by hydrolysis and/or condensation of one or more kinds of hydrolysable metal compounds shown by the following general formula (A-1), as a component (B), an aromatic compound shown by the following general formula (B-1), the compound generating a hydroxyl group by thermal and/or an acid. There can be provided a composition for a resist lower layer film, which has high etching selectivity, capable of subjecting to stripping under mild conditions than the conventional process, has excellent pattern adhesiveness, and fine pattern formation can be performed. ## Claims ### Claim 1 A composition for forming a metal oxide-containing film comprising: as a component (A), a metal oxide-containing compound A1 obtained by hydrolysis and/or condensation of one or more kinds of hydrolysable metal compounds shown by the following general formula (A-1), L(OROA)a0(OR1A)a1(O)a2 (A-1) wherein, R0A and R1A represent an organic group having 1 to 30 carbon atoms; a0, a1 and a2 represent an integer of 0 or more and a0+a1+2×a2 is the same number as the number determined by valency of L; L is any of aluminum, gallium, yttrium, titanium, zirconium, hafnium, bismuth, tin, vanadium, and tantalum, as a component (B), an aromatic compound shown by the following general formula (B-1), the compound generating a hydroxyl group by thermal and/or an acid, wherein, d1 and d3 represent an integer of 1, 2 or 3; d2 represents an integer of 0, 1 or 2; E and G represent a single bond or a divalent organic group composed of one or more of carbon, oxygen and hydrogen atom; each D1, D2 and D3 may be the same or different and represents an organic group shown by the following general formula (B-1a) or (B-1b), wherein, each R1, R2 and R3 may be the same or different and represents an organic group shown by the following general formula (B-1c), (B-1d) or (B-1e); each R4, R5 and R6 may be the same or different and represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and two alkyl groups may be bonded to form a cyclic substituent. wherein, Q1B to Q4B represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and two substituents arbitrarily selected from Q1B to Q4B may be bonded to form a cyclic substituent; Q5B to Q7B represent an alkyl group having 1 to 20 carbon atoms, and two substituents arbitrarily selected from Q5B to Q7B may be bonded to form a cyclic substituent; and Q8B and Q9B represent an alkyl group having 1 to 20 carbon atoms, and Q8B and Q9B may be bonded each other to form a cyclic substituent. ### Claim 2 (depends on 1) The composition for forming a metal oxide-containing film according to claim 1, wherein the component (A) contains a metal oxide-containing compound A2 obtained by hydrolysis and/or condensation of one or more kinds of hydrolysable metal compounds shown by the general formula (A-1) and one or more kinds of hydrolysable metal compounds shown by the following general formula (A-2), M(OR3A)a3(OR4A)a4(O)a5 (A-2) wherein, R3A and R4A represent an organic group having 1 to 10 carbon atoms; a3, a4 and a5 represent an integer of 0 or more, and a3+a4+2×a5 is the same number as the number determined by valency of M; and the M is an element belonging to groups of III, IV, or V in a periodic table except for carbon and is an element different from L. ### Claim 3 (depends on 2) The composition for forming a metal oxide-containing film according to claim 2, wherein the component (A) is a mixture of the metal oxide-containing compound A1 and the metal oxide-containing compound A2. ### Claim 4 (depends on 1) The composition for forming a metal oxide-containing film according to claim 1, wherein the component (A) is a mixture of the metal oxide-containing compound A1 and a metal oxide-containing compound A3 obtained by hydrolysis and/or condensation of one or more kinds of hydrolysable metal compounds shown by the general formula (A-2). ### Claim 5 (depends on 1) The composition for forming a metal oxide-containing film according to claim 1, wherein the composition for forming a metal oxide-containing film further comprises, as a component (C), a silicon-containing compound obtained by hydrolysis and/or condensation of one or more kinds of silicon compounds shown by the following general formula (C-1), R1Cc1R2Cc2R3Cc3Si(OR0C)(4-c1-c2-c3) (C-1) wherein, R0C represents a hydrocarbon group having 1 to 6 carbon atoms; R1C, R2C and R3C represent a hydrogen atom or an organic group having 1 to 30 carbon atoms; and c1, c2 and c3 represent 0 or 1 and satisfy 1≦c1+c2+c3≦3. ### Claim 6 (depends on 2) The composition for forming a metal oxide-containing film according to claim 2, wherein the composition for forming a metal oxide-containing film further comprises, as a component (C), a silicon-containing compound obtained by hydrolysis and/or condensation of one or more kinds of silicon compounds shown by the following general formula (C-1), R1Cc1R2Cc2R3Cc3Si(OR0C)(4-c1-c2-c3) (C-1) wherein, R0C represents a hydrocarbon group having 1 to 6 carbon atoms; R1C, R2C and R3C represent a hydrogen atom or an organic group having 1 to 30 carbon atoms; and c1, c2 and c3 represent 0 or 1 and satisfy 1≦c1+c2+c3≦3. ### Claim 7 (depends on 3) The composition for forming a metal oxide-containing film according to claim 3, wherein the composition for forming a metal oxide-containing film further comprises, as a component (C), a silicon-containing compound obtained by hydrolysis and/or condensation of one or more kinds of silicon compounds shown by the following general formula (C-1), R1Cc1R2Cc2R3Cc3Si(OR0C)(4-c1-c2-c3) (C-1) wherein, R0C represents a hydrocarbon group having 1 to 6 carbon atoms; R1C, R2C and R3C represent a hydrogen atom or an organic group having 1 to 30 carbon atoms; and c1, c2 and c3 represent 0 or 1 and satisfy 1≦c1+c2+c3≦3. ### Claim 8 (depends on 4) The composition for forming a metal oxide-containing film according to claim 4, wherein the composition for forming a metal oxide-containing film further comprises, as a component (C), a silicon-containing compound obtained by hydrolysis and/or condensation of one or more kinds of silicon compounds shown by the following general formula (C-1), R1Cc1R2Cc2R3Cc3Si(OR0C)(4-c1-c2-c3) (C-1) wherein, R0C represents a hydrocarbon group having 1 to 6 carbon atoms; R1C, R2C and R3C represent a hydrogen atom or an organic group having 1 to 30 carbon atoms; and c1, c2 and c3 represent 0 or 1 and satisfy 1≦c1+c2+c3≦3. ### Claim 9 (depends on 5) The composition for forming a metal oxide-containing film according to claim 5, wherein the component (C) is a silicon-containing compound obtained by hydrolysis and/or condensation of a mixture containing one or more kinds of silicon compounds shown by the general formula (C-1) and one or more kinds of silicon compounds shown by the following general formula (C-2), Si(OR4C)4 (C-2) wherein, R4C represents a hydrocarbon group having 1 to 6 carbon atoms. ### Claim 10 (depends on 6) The composition for forming a metal oxide-containing film according to claim 6, wherein the component (C) is a silicon-containing compound obtained by hydrolysis and/or condensation of a mixture containing one or more kinds of silicon compounds shown by the general formula (C-1) and one or more kinds of silicon compounds shown by the following general formula (C-2), Si(OR4C)4 (C-2) wherein, R4C represents a hydrocarbon group having 1 to 6 carbon atoms. ### Claim 11 (depends on 7) The composition for forming a metal oxide-containing film according to claim 7, wherein the component (C) is a silicon-containing compound obtained by hydrolysis and/or condensation of a mixture containing one or more kinds of silicon compounds shown by the general formula (C-1) and one or more kinds of silicon compounds shown by the following general formula (C-2), Si(OR4C)4 (C-2) wherein, R4C represents a hydrocarbon group having 1 to 6 carbon atoms. ### Claim 12 (depends on 8) The composition for forming a metal oxide-containing film according to claim 8, wherein the component (C) is a silicon-containing compound obtained by hydrolysis and/or condensation of a mixture containing one or more kinds of silicon compounds shown by the general formula (C-1) and one or more kinds of silicon compounds shown by the following general formula (C-2), Si(OR4C)4 (C-2) wherein, R4C represents a hydrocarbon group having 1 to 6 carbon atoms. ### Claim 13 (depends on 5) The composition for forming a metal oxide-containing film according to claim 5, wherein any one or more of R1C, R2C and R3C in the general formula (C-1) is an organic group containing a hydroxyl group or a carboxyl group, the groups being substituted with an acid-labile group. ### Claim 14 (depends on 6) The composition for forming a metal oxide-containing film according to claim 6, wherein any one or more of R1C, R2C and R3C in the general formula (C-1) is an organic group containing a hydroxyl group or a carboxyl group, the groups being substituted with an acid-labile group. ### Claim 15 (depends on 7) The composition for forming a metal oxide-containing film according to claim 7, wherein any one or more of R1C, R2C and R3C in the general formula (C-1) is an organic group containing a hydroxyl group or a carboxyl group, the groups being substituted with an acid-labile group. ### Claim 16 (depends on 8) The composition for forming a metal oxide-containing film according to claim 8, wherein any one or more of R1C, R2C and R3C in the general formula (C-1) is an organic group containing a hydroxyl group or a carboxyl group, the groups being substituted with an acid-labile group. ### Claim 17 (depends on 1) The composition for forming a metal oxide-containing film according to claim 1, wherein the composition for forming a metal oxide-containing film further comprises an acid and/or a thermal acid generator. ### Claim 18 (depends on 2) The composition for forming a metal oxide-containing film according to claim 2, wherein the composition for forming a metal oxide-containing film further comprises an acid and/or a thermal acid generator. ### Claim 19 (depends on 3) The composition for forming a metal oxide-containing film according to claim 3, wherein the composition for forming a metal oxide-containing film further comprises an acid and/or a thermal acid generator. ### Claim 20 (depends on 4) The composition for forming a metal oxide-containing film according to claim 4, wherein the composition for forming a metal oxide-containing film further comprises an acid and/or a thermal acid generator. ### Claim 21 (depends on 1) A patterning process, the patterning process to form a pattern on a body to be processed, wherein, a metal oxide-containing film is formed on a body to be processed by using the composition for forming a metal oxide-containing film according to claim 1, a resist upper layer film is formed on the metal oxide-containing film by using a resist upper layer film composition, the resist upper layer film is exposed to form a resist pattern, pattern transfer of the resist pattern is made onto the metal oxide-containing film, and then the body to be processed which is under the metal oxide-containing film is processed by etching by using the metal oxide-containing film having the transferred pattern as an etching mask. ### Claim 22 (depends on 1) A patterning process, the patterning process to form a pattern on a body to be processed, wherein, a silicon-containing film is formed on a body to be processed by using a silicon-containing film composition, a metal oxide-containing film is formed on the silicon-containing film by using the composition for forming the metal oxide-containing film according to claim 1, a resist upper layer film is formed on the metal oxide-containing film by using a resist upper layer film composition, the resist upper layer film is exposed to form a resist pattern, pattern transfer of the resist pattern is made onto the metal oxide-containing film, pattern transfer is made onto the silicon-containing film which is under the metal oxide-containing film having the transferred pattern by dry or wet etching, and then the body to be processed is processed by etching by using the silicon-containing film having the transferred pattern as an etching mask. ### Claim 23 (depends on 1) A patterning process, the patterning process to form a pattern on a body to be processed, wherein, an organic film is formed on a body to be processed by using an organic film composition, a metal oxide-containing film is formed on the organic film by using the composition for forming a metal oxide-containing film according to claim 1, a resist upper layer film is formed on the metal oxide-containing film by using a resist upper layer film composition, the resist upper layer film is exposed to form a resist pattern, pattern transfer of the resist pattern is made onto the metal oxide-containing film, pattern transfer is made onto the organic film which is under the metal oxide-containing film having the transferred pattern by dry or wet etching, and then the body to be processed is processed by etching by using the organic film having the transferred pattern as an etching mask. ### Claim 24 (depends on 1) A patterning process, the patterning process to form a pattern on a body to be processed, wherein, an inorganic-carbon film is formed on a body to be processed by using an inorganic-carbon film composition, a metal oxide-containing film is formed on the inorganic-carbon film by using the composition for forming a metal oxide-containing film according to claim 1, a resist upper layer film is formed on the metal oxide-containing film by using a resist upper layer film composition, the resist upper layer film is exposed to form a resist pattern, pattern transfer of the resist pattern is made onto the metal oxide-containing film, pattern transfer is made onto the inorganic-carbon film which is under the metal oxide-containing film having the transferred pattern by dry or wet etching, and then the body to be processed is processed by etching by using the inorganic-carbon film having the transferred pattern as an etching mask. ### Claim 25 (depends on 21) The patterning process according to claim 21, wherein the resist upper layer film is exposed by the method of photolithography with the wavelength of 300 nm or less or an EUV beam, by the method of a direct drawing with an electron beam, or by the method of nanoimprint lithography. ### Claim 26 (depends on 22) The patterning process according to claim 22, wherein the resist upper layer film is exposed by the method of photolithography with the wavelength of 300 nm or less or an EUV beam, by the method of a direct drawing with an electron beam, or by the method of nanoimprint lithography. ### Claim 27 (depends on 23) The patterning process according to claim 23, wherein the resist upper layer film is exposed by the method of photolithography with the wavelength of 300 nm or less or an EUV beam, by the method of a direct drawing with an electron beam, or by the method of nanoimprint lithography. ### Claim 28 (depends on 24) The patterning process according to claim 24, wherein the resist upper layer film is exposed by the method of photolithography with the wavelength of 300 nm or less or an EUV beam, by the method of a direct drawing with an electron beam, or by the method of nanoimprint lithography. ### Claim 29 (depends on 21) The patterning process according to claim 21, wherein the patterning process contains, after pattern transfer is made onto the layer which is under the metal oxide-containing film having the transferred pattern, a step of removing the metal oxide-containing film by using aqueous ammonia containing hydrogen peroxide or hydrochloric acid containing hydrogen peroxide. ### Claim 30 (depends on 22) The patterning process according to claim 22, wherein the patterning process contains, after pattern transfer is made onto the layer which is under the metal oxide-containing film having the transferred pattern, a step of removing the metal oxide-containing film by using aqueous ammonia containing hydrogen peroxide or hydrochloric acid containing hydrogen peroxide. ### Claim 31 (depends on 23) The patterning process according to claim 23, wherein the patterning process contains, after pattern transfer is made onto the layer which is under the metal oxide-containing film having the transferred pattern, a step of removing the metal oxide-containing film by using aqueous ammonia containing hydrogen peroxide or hydrochloric acid containing hydrogen peroxide. ### Claim 32 (depends on 24) The patterning process according to claim 24, wherein the patterning process contains, after pattern transfer is made onto the layer which is under the metal oxide-containing film having the transferred pattern, a step of removing the metal oxide-containing film by using aqueous ammonia containing hydrogen peroxide or hydrochloric acid containing hydrogen peroxide.