# US 2020/0401043 A1 · Pattern forming method and developer > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2020/0401043 A1 - Document ID: US20200401043A1 - Status: Published application - Kind: A1 - Application number: 17/010,895 - Filed: 2020-09-03 - Published: 2020-12-24 - Earliest claimed: 2018-03-08 - Assignees: Jsr Corporation - Applicants: Jsr Corporation - Inventors: Ryo KAWAJIRI; Noboru OOTSUKA; Makoto SHIMIZU - Web page: https://patentgrep.com/patent/US20200401043A1 ## CPC - G03F 7/038: Macromolecular compounds which are rendered insoluble or differentially wettable (G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021) - G03F 7/325: {Non-aqueous compositions} - G03F 7/0397: {the macromolecular compound having an alicyclic moiety in a side chain} - G03F 7/2041: {in the presence of a fluid, e.g. immersion; using fluid cooling means} - G03F 7/32: Liquid compositions therefor, e.g. developers - G03F 7/70025: {by lasers} - H01S 3/225: comprising an excimer or exciplex - 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) - H01S: DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL ## Abstract A pattern forming method includes applying a photoresist composition onto a substrate to form a resist film. The resist film is exposed to an ArF excimer laser. The exposed resist film is developed with a developer. the photoresist composition includes a polymer and a radiation-sensitive acid generator. The polymer has a structural unit having an acid-dissociable group, does not have a phenolic hydroxyl group and exhibits decreased solubility in the developer by dissociation of the acid-dissociable group. The developer includes a nitrogen-containing compound, and the nitrogen-containing compound is at least one of: a condensed ring compound or bridged cyclic compound including at least two nitrogen atoms as ring-forming atoms, a compound having a nitrogen-containing aromatic heterocyclic structure and an acyclic tertiary amine structure in a molecule thereof, an onium salt compound represented by Formula (A-1), or a compound represented by Formula (A-2). ## Claims ### Claim 1 A pattern forming method comprising: applying a photoresist composition onto a substrate to form a resist film; exposing the resist film to an ArF excimer laser; and developing the exposed resist film with a developer comprising an organic solvent, wherein the photoresist composition comprises: [A] a polymer that has a structural unit (I) having an acid-dissociable group to be dissociated by action of an acid, does not have a phenolic hydroxyl group and exhibits decreased solubility in the developer by dissociation of the acid-dissociable group; and [B] a radiation-sensitive acid generator, the developer comprises a nitrogen-containing compound, and the nitrogen-containing compound is at least one of (i) a condensed ring compound or bridged cyclic compound comprising at least two nitrogen atoms as ring-forming atoms, (ii) a compound having a nitrogen-containing aromatic heterocyclic structure and an acyclic tertiary amine structure in a molecule thereof, (iii) an onium salt compound represented by Formula (A-1), or (iv) a compound represented by Formula (A-2): wherein, in Formula (A-1), R1 is an aliphatic hydrocarbon group having 1 to 12 carbon atoms or a group obtained by substituting a part or all of hydrogen atoms contained in an aliphatic hydrocarbon group having 1 to 12 carbon atoms with a fluorine atom, R2 is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a branched hydrocarbon group having 3 to 12 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and Z+ is a monovalent onium cation, wherein, in Formula (A-2), R3, R4, and R5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or any one of R3 to R5 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and remaining two of R3 to R5 are combined with each other to be a part of a 3 to 6-membered ring structure that is formed together with the nitrogen atom to which the remaining two of R3 to R5 are bonded, provided that the 3 to 6-membered ring is unsubstituted except the any one of R3 to R5, and that R3 to R5 are not all hydrogen atoms. ### Claim 2 (depends on 1) The pattern forming method according to claim 1, wherein the nitrogen-containing compound is the condensed ring compound containing at least two nitrogen atoms as ring-forming atoms. ### Claim 3 (depends on 2) The pattern forming method according to claim 2, wherein the condensed ring compound comprises two tertiary nitrogen atoms as ring-forming atoms, and the two tertiary nitrogen atoms are directly bonded to each other or the two tertiary nitrogen atoms are bonded to each other via one carbon atom. ### Claim 4 (depends on 1) The pattern forming method according to claim 1, wherein each ring that forms the condensed ring compound is a 6-membered or higher ring. ### Claim 5 (depends on 1) The pattern forming method according to claim 1, wherein one of atoms forming a bond shared by rings to be condensed of the condensed ring compound is a nitrogen atom. ### Claim 6 (depends on 1) The pattern forming method according to claim 1, wherein a ring-forming atom of the nitrogen-containing aromatic heterocyclic structure is directly bonded to a nitrogen atom of the acyclic tertiary amine structure. ### Claim 7 (depends on 1) The pattern forming method according to claim 1, wherein a content of the nitrogen-containing compound in the developer is less than 0.1% by mass. ### Claim 8 (depends on 1) The pattern forming method according to claim 1, wherein the organic solvent is at least one selected from the group consisting of an ether-based solvent, a ketone-based solvent, and an ester-based solvent. ### Claim 9 A developer which is capable of developing an exposed resist film, the developer comprising an organic solvent and a nitrogen-containing compound, wherein the nitrogen-containing compound is at least one of (i) a condensed ring compound or bridged compound comprising at least two nitrogen atoms as ring-forming atoms, (ii) a compound having a nitrogen-containing aromatic heterocyclic structure and an acyclic tertiary amine structure in a molecule thereof, (iii) an onium salt compound represented by Formula (A-1), or (iv) a compound represented by Formula (A-2): wherein, in Formula (A-1), R1 is an aliphatic hydrocarbon group having 1 to 12 carbon atoms or a group obtained by substituting a part or all of hydrogen atoms contained in an aliphatic hydrocarbon group having 1 to 12 carbon atoms with a fluorine atom, R2 is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a branched hydrocarbon group having 3 to 12 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms, and Z is a monovalent onium cation, wherein, in Formula (A-2), R3, R4, and R5 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or any one of R3 to R5 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and remaining two of R3 to R5 are combined with each other to be a part of a 3 to 6-membered ring structure that is formed together with the nitrogen atom to which the remaining two of R3 to R5 are bonded, provided that the 3 to 6-membered ring is unsubstituted except the any one of R3 to R5, and that R3 to R5 are not all hydrogen atoms. ### Claim 10 (depends on 9) The developer according to claim 9, wherein a content of the nitrogen-containing compound in the developer is less than 0.1% by mass. ### Claim 11 (depends on 9) The developer according to claim 9, wherein the condensed ring compound comprises two tertiary nitrogen atoms as ring-forming atoms, and the two tertiary nitrogen atoms are directly bonded to each other or the two tertiary nitrogen atoms are bonded to each other via one carbon atom.