# US 2019/0375904 A1 · Laminate

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- Number: US 2019/0375904 A1
- Document ID: US20190375904A1
- Status: Published application
- Kind: A1
- Application number: 16/463,624
- Filed: 2017-11-29
- Published: 2019-12-12
- 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/US20190375904A1

## 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:
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 2)

The laminate according to claim 2, 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.

### Claim 4 (depends on 1)

The laminate according to claim 1, wherein the block copolymer film forms a lamellar structure.

### Claim 5 (depends on 4)

The laminate according to claim 4, 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 6 (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 7 (depends on 6)

The laminate according to claim 6, 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 8 (depends on 6)

The laminate according to claim 6, wherein the polymer segment B comprises three or more halogen atoms.

### Claim 9 (depends on 8)

The laminate according to claim 8, wherein the polymer segment B comprises a ring structure and the halogen atoms are substituted on the ring structure.

### Claim 10

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 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 11 (depends on 10)

The method for producing a patterned substrate according to claim 10, 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 12 (depends on 10)

The method for producing a patterned substrate according to claim 10, wherein in the random copolymer, the monomer unit of Formula 3 have 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.

### Claim 13 (depends on 10)

The method for producing a patterned substrate according to claim 10, 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.

### Claim 14 (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 15 (depends on 7)

The laminate according to claim 7, 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 16 (depends on 9)

The laminate according to claim 9, wherein the ring structure in the polymer segment B comprises is an aromatic or an alicyclic ring.

### Claim 17 (depends on 6)

The laminate according to claim 6, wherein the chain-forming atoms are each independently a carbon, an oxygen, a nitrogen or a sulfur atom.

### Claim 18 (depends on 7)

The laminate according to claim 7, 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 19 (depends on 4)

The laminate according to claim 4, wherein the random copolymer film has a thickness in a range of 0.5 nm to 10 nm.