# US 11,299,596 B2 · Laminate > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,299,596 B2 - Document ID: US11299596B2 - Status: Granted - Kind: B2 - Application number: 16/463,624 - Filed: 2017-11-29 - Published: 2019-12-12 - Granted: 2022-04-12 - Earliest claimed: 2016-11-30 - Assignees: LG Chem, Ltd. - Applicants: LG Chem, Ltd. - Inventors: Mi Sook Lee; Se Jin Ku; No Jin Park; Jung Keun Kim; Je Gwon Lee; Eun Young Choi; Hyung Ju Ryu; Sung Soo Yoon - Web page: https://patentgrep.com/patent/US11299596B2 ## CPC - C08J 5/18: Manufacture of films or sheets - C08F 293/005: {using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent} - C08L 33/06: of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical - G03F 1/66: Containers specially adapted for masks, mask blanks or pellicles; Preparation thereof - G03F 1/76: Patterning of masks by imaging - G03F 1/80: Etching - C08F 2438/03: Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX] - C08J 2353/00: Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - 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 present application relates to a block copolymer and a use thereof. The present application can provide a laminate which is capable of forming a highly aligned block copolymer on a substrate and thus can be effectively applied to production of various patterned substrates, and a method for producing a patterned substrate using the same. ## Claims ### Claim 1 A laminate comprising a block copolymer film which comprises a block copolymer comprising a polymer segment A satisfying one or more of Conditions 1 to 3 below and a polymer segment B different from the polymer segment A and having an absolute value of a difference in surface energy with the polymer segment A of 10 mN/m or less; and a random copolymer film which is formed in contact with the block copolymer film and comprises a random copolymer comprising a monomer unit of Formula 1 below and a monomer unit of Formula 3 below, wherein in the random copolymer, the monomer unit of Formula 3 has a volume fraction in a range of 0.45 to 0.65 and the sum of volume fraction of the monomer unit of Formula 1 and the volume fraction of the monomer unit of Formula 3 is 1: Condition 1: it exhibits a melting transition peak or an isotropic transition peak in a range of −80° C. to 200° C. in a differential scanning calorimetry (DSC) analysis, Condition 2: it exhibits a peak having a half-value width in a range of 0.2 to 0.9 nm−1 within a scattering vector (q) range of 0.5 nm−1 to 10 nm−1 in an X-ray diffraction (XRD) analysis, Condition 3: it comprises a side chain, which satisfies Equation 1 below: 3 nm−1 to 5 nm−1=nq/(2×π) [Equation 1] wherein, n is a number of chain-forming atoms in the side chain and q is the smallest scattering vector in which a peak is observed in the XRD analysis for the block copolymer or the scattering vector in which a peak of the largest peak area is observed, wherein, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is a single bond, an oxygen atom, a sulfur atom, —S(═O)2—, a carbonyl group, an alkylene group, an alkenylene group, an alkynylene group, —C(═O)—X1— or —X1—C(═O)—, where X1 is an oxygen atom, a sulfur atom, —S(═O)2—, an alkylene group, an alkenylene group or an alkynylene group, and Y is a monovalent substituent comprising a ring structure to which a side chain having 8 or more chain-forming atoms is linked, wherein, X2 is a single bond, an oxygen atom, a sulfur atom, —S(═O)2—, an alkylene group, an alkenylene group, an alkynylene group, —C(═O)—X1— or —X1—C(═O)—, where X1 is a single bond, an oxygen atom, a sulfur atom, —S(═O)2—, an alkylene group, an alkenylene group or an alkynylene group, and W is an aryl group containing at least one halogen atom. ### Claim 2 (depends on 1) The laminate according to claim 1, further comprising a substrate in which a trench having a bottom portion and two sidewalls is formed by mesa structures disposed at a distance from each other on the a surface, wherein the block copolymer film is formed in contact with the random copolymer film in the trench. ### Claim 3 (depends on 1) The laminate according to claim 1, wherein the block copolymer film forms a lamellar structure. ### Claim 4 (depends on 3) The laminate according to claim 3, wherein the block copolymer film has a thickness in a range of 1 L to 10 L, where L is a pitch of the lamellar structure. ### Claim 5 (depends on 1) The laminate according to claim 1, wherein the polymer segment A comprises a side chain having 8 or more chain-forming atoms. ### Claim 6 (depends on 5) The laminate according to claim 5, wherein the polymer segment A comprises a ring structure and the side chain is substituted on the ring structure directly or via a linker. ### Claim 7 (depends on 5) The laminate according to claim 5, wherein the polymer segment B comprises three or more halogen atoms. ### Claim 8 (depends on 7) The laminate according to claim 7, wherein the polymer segment B comprises a ring structure and the halogen atoms are substituted on the ring structure. ### Claim 9 (depends on 2) The laminate according to claim 2, wherein the ratio of the distance between the mesa structures and the height of each of the mesa structures is in a range of 0.1 to 10, and the ratio of the distance between the mesa structures and the width of each of the mesa structures is in a range of 0.5 to 10. ### Claim 10 (depends on 6) The laminate according to claim 6, wherein the ring structure in the polymer segment A is an aromatic or an alicyclic ring, and no halogen atom is present on the ring structure. ### Claim 11 (depends on 8) The laminate according to claim 8, wherein the ring structure in the polymer segment B comprises is an aromatic or an alicyclic ring. ### Claim 12 (depends on 5) The laminate according to claim 5, wherein the chain-forming atoms are each independently a carbon, an oxygen, a nitrogen or a sulfur atom. ### Claim 13 (depends on 6) The laminate according to claim 6, wherein the linker is an oxygen atom, a sulfur atom, —NR1—, —S(═O)2—, a carbonyl group, an alkylene group, an alkenylene group, an alkynylene group, —C(═O)—X1— or —X1—C(═O)—, wherein R1 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, and X1 is a single bond, an oxygen atom, a sulfur atom, —NR2—, —S(═O)2—, an alkylene group, an alkenylene group or an alkynylene group, where R2 is hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group. ### Claim 14 (depends on 3) The laminate according to claim 3, wherein the random copolymer film has a thickness in a range of 0.5 nm to 10 nm. ### Claim 15 A method for producing a patterned substrate comprising forming a random copolymer film which comprises a random copolymer comprising a monomer unit of Formula 1 below and a monomer unit of Formula 3 below on a substrate, wherein in the random copolymer, the monomerunit of Formula 3 has a volume fraction in a range of 0.45 to 0.65 and the sum of volume fraction of the monomer unit of Formula 1 and the volume fraction of the monomer unit of Formula 3 is 1, and forming a self-assembled block copolymer film in contact with the random copolymer film, wherein the block copolymer film comprises a block copolymer which comprises a polymer segment A satisfying one or more of Conditions 1 to 3 below and a polymer segment B different from the polymer segment A and having an absolute value of a difference in surface energy with the polymer segment A of 10 mN/m or less: Condition 1: it exhibits a melting transition peak or an isotropic transition peak in a range of −80° C. to 200° C. in a differential scanning calorimetry (DSC) analysis, Condition 2: it exhibits a peak having a half-value width in a range of 0.2 to 0.9 nm−1 within a scattering vector (q) range of 0.5 nm−1 to 10 nm−1 in an X-ray diffraction (XRD) analysis, Condition 3: it comprises a side chain, which satisfies Equation 1 below: 3 nm−1 to 5 nm−1=nq/(2×π) [Equation 1] wherein, n is a number of the-chain-forming atoms in the side chain and q is the smallest scattering vector in which a peak is observed in the XRD analysis for the block copolymer or the scattering vector in which a peak of the largest peak area is observed, wherein, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is a single bond, an oxygen atom, a sulfur atom, —S(═O)2—, a carbonyl group, an alkylene group, an alkenylene group, an alkynylene group, —C(═O)—X1— or —X1—C(═O)—, where X1 is an oxygen atom, a sulfur atom, —S(═O)2—, an alkylene group, an alkenylene group or an alkynylene group, and Y is a monovalent substituent comprising a ring structure to which a side chain having 8 or more chain-forming atoms is linked, wherein, X2 is a single bond, an oxygen atom, a sulfur atom, —S(═O)2—, an alkylene group, an alkenylene group, an alkynylene group, —C(═O)—X1— or —X1—C(═O)—, where X1 is a single bond, an oxygen atom, a sulfur atom, —S(═O)2—, an alkylene group, an alkenylene group or an alkynylene group, and W is an aryl group containing at least one halogen atom. ### Claim 16 (depends on 15) The method for producing a patterned substrate according to claim 15, wherein a trench having a bottom portion and two sidewalls is formed by mesa structures disposed at a distance from each other on a surface of the substrate, and the random copolymer film is formed on all the two sidewalls and the bottom portion of the trench. ### Claim 17 (depends on 15) The method for producing a patterned substrate according to claim 15, further performing steps of selectively removing any one polymer segment of the block copolymer film on which a self-assembled structure is formed; and etching the substrate using the block copolymer, from which the polymer segment is removed, as a mask.