# US 2014/0193975 A1 · Composition for forming titanium-containing resist underlayer 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 2014/0193975 A1 - Document ID: US20140193975A1 - Status: Published application - Kind: A1 - Application number: 14/107,841 - 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/US20140193975A1 ## CPC - G03F 7/0752: {in non photosensitive layers or as additives, e.g. for dry lithography} - C08G 77/58: Metal-containing linkages - C09D 183/14: in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms (C09D183/10 takes precedence) - G03F 7/0392: {the macromolecular compound being present in a chemically amplified positive photoresist composition} - G03F 7/0397: {the macromolecular compound having an alicyclic moiety in a side chain} - G03F 7/09: characterised by structural details, e.g. supports, auxiliary layers (supports for printing plates in general B41N) - 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 7/2041: {in the presence of a fluid, e.g. immersion; using fluid cooling 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: 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) ## Abstract The invention provides a composition for forming a titanium-containing resist underlayer film comprising: as component (A), a silicon-containing compound obtained by hydrolysis and/or condensation of one or more kinds of silicon compounds shown by the following general formula (A-I) and, as component (B), a titanium-containing compound obtained by hydrolysis and/or condensation of one or more kinds of hydrolysable titanium compounds shown by the following general formula (B-I). There can be provided a composition for forming a titanium-containing resist underlayer film to form a resist underlayer film having an excellent adhesiveness in fine patterning and an excellent etching selectivity relative to a conventional organic film and a silicon-containing film. ## Claims ### Claim 1 A composition for forming a titanium-containing resist underlayer film comprising: as a component (A), a silicon-containing compound obtained by hydrolysis and/or condensation of one or more kinds of silicon compounds shown by the following general formula (A-I), R1Aa1R2Aa2R3Aa3Si(OR0A)(4-a1-a2-a3) (A-I) wherein, ROA represents a hydrocarbon group having 1 to 6 carbon atoms; R1A, R2A and R3A represent a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms; and a1, a2 and a3 represent 0 or 1 and satisfy 1≦a1+a2+a3≦3, and as a component (B), a titanium-containing compound obtained by hydrolysis and/or condensation of one or more kinds of hydrolysable titanium compounds shown by the following general formula (B-I), Ti(OR0B)4 (B-I) wherein, R0B represents an organic group having 1 to 10 carbon atoms. ### Claim 2 (depends on 1) The composition for forming a titanium-containing resist underlayer film according to claim 1, wherein the component (A) contains a silicon-containing compound obtained by hydrolysis and/or condensation of one or more kinds of silicon compounds shown by the general formula (A-I) and one or more kinds of hydrolysable metal compounds shown by the following general formula (A-II), L(OR4A)a4(OR5A)a5(O)a6 (A-II) wherein, R4A and R5A represent an organic group having 1 to 30 carbon atoms; a4, a5 and a6 represent an integer of 0 or more and a4+a5+2×a6 is the same number as the number determined by valency of L; and L is an element belonging to groups of III, IV, or V in a periodic table except for carbon. ### Claim 3 (depends on 2) The composition for forming a titanium-containing resist underlayer film according to claim 2, wherein L of the general formula (A-II) is any of boron, silicon, aluminum, gallium, yttrium, germanium, titanium, zirconium, hafnium, bismuth, tin, phosphorous, vanadium, arsenic, antimony, niobium, and tantalum. ### Claim 4 (depends on 1) The composition for forming a titanium-containing resist underlayer film according to claim 1, wherein any one or more of R1A, R2A and R3A is an organic group containing a hydroxyl group or a carboxyl group, the groups being substituted with an acid-labile group. ### Claim 5 (depends on 2) The composition for forming a titanium-containing resist underlayer film according to claim 2, wherein any one or more of R1A, R2A and R3A is an organic group containing a hydroxyl group or a carboxyl group, the groups being substituted with an acid-labile group. ### Claim 6 (depends on 3) The composition for forming a titanium-containing resist underlayer film according to claim 3, wherein any one or more of R1A, R2A and R3A is an organic group containing a hydroxyl group or a carboxyl group, the groups being substituted with an acid-labile group. ### Claim 7 (depends on 1) A patterning process, the patterning process to form a pattern on a body to be processed, wherein an organic underlayer film is formed on a body to be processed by using an application-type composition for the organic underlayer film, on this organic underlayer film is formed a titanium-containing resist underlayer film by using the composition for forming the titanium-containing resist underlayer film according to claim 1, on this titanium-containing resist underlayer film is formed a photoresist film by using a chemically amplified resist composition, the photoresist film is exposed to a high energy beam after heat treatment, a positive pattern is formed by dissolving an exposed area of the photoresist film by using an alkaline developer, pattern transfer is made onto the titanium-containing resist underlayer film by using the photoresist film having the positive pattern as a mask, pattern transfer is made onto the organic underlayer film by using the titanium-containing resist underlayer film having the transferred pattern as a mask, and then pattern transfer is made onto the body to be processed by using the organic underlayer film having the transferred pattern as a mask. ### Claim 8 (depends on 1) A patterning process, the patterning process to form a pattern on a body to be processed, wherein an organic hard mask mainly comprising carbon is formed on a body to be processed by a CVD method, on this organic hard mask is formed a titanium-containing resist underlayer film by using the composition for forming the titanium-containing resist underlayer film according to claim 1, on this titanium-containing resist underlayer film is formed a photoresist film by using a chemically amplified resist composition, the photoresist film is exposed to a high energy beam after heat treatment, a positive pattern is formed by dissolving an exposed area of the photoresist film by using an alkaline developer, pattern transfer is made onto the titanium-containing resist underlayer film by using the photoresist film having the positive pattern as a mask, pattern transfer is made onto the organic hard mask by using the titanium-containing resist underlayer film having the transferred pattern as a mask, and then pattern transfer is made onto the body to be processed by using the organic hard mask having the transferred pattern as a mask. ### Claim 9 (depends on 1) A patterning process, the patterning process to form a pattern on a body to be processed, wherein an organic underlayer film is formed on a body to be processed by using an application-type composition for the organic underlayer film, on this organic underlayer film is formed a titanium-containing resist underlayer film by using the composition for forming the titanium-containing resist underlayer film according to claim 1, on this titanium-containing resist underlayer film is formed a photoresist film by using a chemically amplified resist composition, the photoresist film is exposed to a high energy beam after heat treatment, a negative pattern is formed by dissolving an unexposed area of the photoresist film by using an organic solvent developer, pattern transfer is made onto the titanium-containing resist underlayer film by using the photoresist film having the negative pattern as a mask, pattern transfer is made onto the organic underlayer film by using the titanium-containing resist underlayer film having the transferred pattern as a mask, and then pattern transfer is made onto the body to be processed by using the organic underlayer film having the transferred pattern as a mask. ### Claim 10 (depends on 1) A patterning process, the patterning process to form a pattern on a body to be processed, wherein an organic hard mask mainly comprising carbon is formed on a body to be processed by a CVD method, on this organic hard mask is formed a titanium-containing resist underlayer film by using the composition for forming the titanium-containing resist underlayer film according to claim 1, on this titanium-containing resist underlayer film is formed a photoresist film by using a chemically amplified resist composition, the photoresist film is exposed to a high energy beam after heat treatment, a negative pattern is formed by dissolving an unexposed area of the photoresist film by using an organic solvent developer, pattern transfer is made onto the titanium-containing resist underlayer film by using the photoresist film having the negative pattern as a mask, pattern transfer is made onto the organic hard mask by using the titanium-containing resist underlayer film having the transferred pattern as a mask, and then pattern transfer is made onto the body to be processed by using the organic hard mask having the transferred pattern as a mask. ### Claim 11 (depends on 7) The patterning process according to claim 7, wherein the body to be processed is a semiconductor substrate coated, as a layer to be processed, with any of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film. ### Claim 12 (depends on 8) The patterning process according to claim 8, wherein the body to be processed is a semiconductor substrate coated, as a layer to be processed, with any of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film. ### Claim 13 (depends on 9) The patterning process according to claim 9, wherein the body to be processed is a semiconductor substrate coated, as a layer to be processed, with any of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film. ### Claim 14 (depends on 10) The patterning process according to claim 10, wherein the body to be processed is a semiconductor substrate coated, as a layer to be processed, with any of a metal film, a metal carbide film, a metal oxide film, a metal nitride film, a metal oxycarbide film, and a metal oxynitride film. ### Claim 15 (depends on 11) The patterning process according to claim 11, wherein the metal that constitutes the body to be processed is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum or an alloy of these metals. ### Claim 16 (depends on 12) The patterning process according to claim 12, wherein the metal that constitutes the body to be processed is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum or an alloy of these metals. ### Claim 17 (depends on 13) The patterning process according to claim 13, wherein the metal that constitutes the body to be processed is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum or an alloy of these metals. ### Claim 18 (depends on 14) The patterning process according to claim 14, wherein the metal that constitutes the body to be processed is silicon, titanium, tungsten, hafnium, zirconium, chromium, germanium, copper, aluminum, indium, gallium, arsenic, palladium, iron, tantalum, iridium, molybdenum or an alloy of these metals. ### Claim 19 (depends on 7) The patterning process according to claim 7, wherein the photoresist film is exposed by the method of photolithography with the wavelength of 300 nm or less or an EUV beam or by the method of a direct drawing with an electron beam. ### Claim 20 (depends on 8) The patterning process according to claim 8, wherein the photoresist film is exposed by the method of photolithography with the wavelength of 300 nm or less or an EUV beam or by the method of a direct drawing with an electron beam. ### Claim 21 (depends on 9) The patterning process according to claim 9, wherein the photoresist film is exposed by the method of photolithography with the wavelength of 300 nm or less or an EUV beam or by the method of a direct drawing with an electron beam. ### Claim 22 (depends on 10) The patterning process according to claim 10, wherein the photoresist film is exposed by the method of photolithography with the wavelength of 300 nm or less or an EUV beam or by the method of a direct drawing with an electron beam.