# US 9,040,231 B2 · Pattern forming method, multi-layered resist pattern, multi-layered film for organic solvent development, manufacturing method of electronic device, and electronic device > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,040,231 B2 - Document ID: US9040231B2 - Status: Granted - Kind: B2 - Application number: 14/257,314 - Filed: 2014-04-21 - Published: 2014-08-14 - Granted: 2015-05-26 - Earliest claimed: 2011-10-27 - Assignees: FUJIFILM Corporation - Applicants: FUJIFILM Corporation - Inventors: Keita Kato; Michihiro Shirakawa; Tadahiro Odani; Atsushi Nakamura; Hidenori Takahashi; Kaoru Iwato - Web page: https://patentgrep.com/patent/US9040231B2 ## CPC - G03F 7/094: {Multilayer resist systems, e.g. planarising layers} - G03F 7/095: having more than one photosensitive layer (G03F7/075 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 7/091: {characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement} - G03F 7/2041: {in the presence of a fluid, e.g. immersion; using fluid cooling means} - G03F 7/325: {Non-aqueous compositions} - G03F 7/20: Exposure; Apparatus therefor (photographic printing apparatus for making copies G03B27/00) - 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 A pattern forming method contains: (i) a step of forming a bottom anti-reflective coating on a substrate by using a first resin composition (I), (ii) a step of forming a resist film on the bottom anti-reflective coating by using a second resin composition (II), (iii) a step of exposing a multi-layered film having the bottom anti-reflective coating and the resist film, and (iv) a step of developing the bottom anti-reflective coating and the resist film in the exposed multi-layered film by using an organic solvent-containing developer to form a negative pattern. ## Claims ### Claim 1 A pattern forming method comprising: (i) a step of forming a bottom anti-reflective coating on a substrate by using a first resin composition (I), (ii) a step of forming a resist film on the bottom anti-reflective coating by using a second resin composition (II), (iii) a step of exposing a multi-layered film having the bottom anti-reflective coating and the resist film, and (iv) a step of developing the bottom anti-reflective coating and the resist film in the exposed multi-layered film by using an organic solvent-containing developer to form a negative pattern, wherein the first resin composition (I) contains a first resin capable of increasing the polarity by the action of an acid to decrease the solubility for an organic solvent-containing developer, the second resin composition (II) contains a second resin capable of increasing the polarity by the action of an acid to decrease the solubility for an organic solvent-containing developer, at least either one of the first resin composition (I) and the second resin composition (II) contains a compound capable of generating an acid upon irradiation with an actinic ray or radiation, the first resin in the first resin composition (I) is a resin containing a repeating unit having an aromatic ring or the first resin composition (I) further contains an aromatic compound, and an amount of the organic solvent used in the organic developer in step (iv) is from 90 to 100 mass%, based on the entire amount of the developer. ### Claim 2 (depends on 1) The pattern forming method according to claim 1, wherein the content of a crosslinking agent selected from the group consisting of a crosslinking agent capable of crosslinking the first resin by the action of an acid to form a crosslinked product and a crosslinking agent capable of crosslinking to another crosslinking agent by the action of an acid to form a crosslinked product is 1 mass% or less based on the entire solid content of the first resin composition (I). ### Claim 3 (depends on 1) The pattern forming method according to claim 1, wherein the first resin composition (I) does not contain a crosslinking agent selected from the group consisting of a crosslinking agent capable of crosslinking the first resin by the action of an acid to form a crosslinked product and a crosslinking agent capable of crosslinking to another crosslinking agent by the action of an acid to form a crosslinked product. ### Claim 4 (depends on 1) The pattern forming method according to claim 1, wherein the weight average molecular weight of the first resin is from 1,000 to 200,000. ### Claim 5 (depends on 1) The pattern forming method according to claim 1, wherein the first resin composition (I) does not contain the compound capable of generating an acid upon irradiation with an actinic ray or radiation. ### Claim 6 (depends on 1) The pattern forming method according to claim 1, wherein the exposure in the step (iii) is exposure to an ArF excimer laser. ### Claim 7 (depends on 1) The pattern forming method according to claim 1, wherein the exposure in the step (iii) is exposure to a KrF excimer laser, and the first resin in the first resin composition (I) is a resin containing a repeating unit having a polycyclic aromatic group or the first resin composition (I) further contains a polycyclic aromatic compound. ### Claim 8 (depends on 1) The pattern forming method according to claim 1, wherein the organic solvent-containing developer is a developer containing at least one kind of an organic solvent selected from the group consisting of a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amide-based solvent and an ether-based solvent. ### Claim 9 (depends on 1) The pattern forming method according to claim 1, wherein a water content ratio in the entire developer is less than 10 mass%. ### Claim 10 (depends on 1) The pattern forming method according to claim 1, wherein the developer contains substantially no water. ### Claim 11 (depends on 1) The pattern forming method according to claim 1, wherein the organic solvent-containing developer is a developer containing at least one kind of an organic solvent selected from the group consisting of a ketone-based solvent, an ester-based solvent, an amide-based solvent and an ether-based solvent. ### Claim 12 (depends on 1) The pattern forming method according to claim 1, wherein at least either one of the first resin composition (I) and the second resin composition (II) contains a basic compound. ### Claim 13 (depends on 12) The pattern forming method according to claim 12, wherein the first resin composition (I) contains a basic compound. ### Claim 14 (depends on 13) The pattern forming method according to claim 13, wherein the second resin composition (II) contains a basic compound. ### Claim 15 (depends on 1) The pattern forming method according to claim 1, wherein the solvent contained in the second resin composition (II) is an alcohol not having an oxygen atom except for a hydroxyl group, an ester compound having a carbon number of 7 or more, or an ether compound not having an oxygen atom except for an ether bond. ### Claim 16 (depends on 1) A multi-layered resist pattern formed by the pattern forming method according to claim 1. ### Claim 17 A multi-layered film for organic solvent development, comprising: a bottom anti-reflective coating formed on a substrate by using a first resin composition (I), and a resist film formed on the bottom anti-reflective coating by using a second resin composition (II), wherein the first resin composition (I) contains a first resin capable of increasing the polarity by the action of an acid to decrease the solubility for an organic solvent-containing developer, the second resin composition (II) contains a second resin capable of increasing the polarity by the action of an acid to decrease the solubility for an organic solvent-containing developer, at least either one of the first resin composition (I) and the second resin composition (II) contains a compound capable of generating an acid upon irradiation with an actinic ray or radiation, and the first resin in the first resin composition (I) is a resin containing a repeating unit having an aromatic ring or the first resin composition (I) further contains an aromatic compound. ### Claim 18 (depends on 1) A manufacturing method of an electronic device, comprising the pattern forming method according to claim 1. ### Claim 19 (depends on 18) An electronic device manufactured by the manufacturing method of an electronic device according to claim 18.