# US 12,006,384 B2 · Random copolymer and pinning composition comprising the same

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- Number: US 12,006,384 B2
- Document ID: US12006384B2
- Status: Granted
- Kind: B2
- Application number: 16/652,565
- Filed: 2018-10-29
- Published: 2020-07-30
- Granted: 2024-06-11
- Earliest claimed: 2017-10-27
- Assignees: LG Chem, Ltd.
- Applicants: LG Chem, Ltd.
- Inventors: Se Jin Ku; Mi Sook Lee; Na Na Kang; Eung Chang Lee; Sung Soo Yoon; No Jin Park; Je Gwon Lee; Eun Young Choi; Hyung Ju Ryu; Yoon Hyung Hur
- Web page: https://patentgrep.com/patent/US12006384B2

## CPC

- C08F 212/20: {Fluorine}
- B32B 27/28: comprising synthetic resins not wholly covered by any one of the sub-groups {B32B27/30 - B32B27/42}
- C08F 220/301: {and one oxygen in the alcohol moiety}
- C08F 220/44: Acrylonitrile
- C08F 230/02: containing phosphorus
- C08F 293/005: {using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent}
- C08L 33/14: of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C09D 5/002: {Priming paints (C09D5/08 takes precedence)}
- C09D 133/20: Homopolymers or copolymers of acrylonitrile (C09D155/02 takes precedence)
- C09D 143/02: Homopolymers or copolymers of monomers containing phosphorus
- C09D 153/00: Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- G03F 7/0002: {Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping}
- H10P 76/20: of masks comprising organic materials
- C08F 220/325: {containing glycidyl radical, e.g. glycidyl (meth)acrylate}
- 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]
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- 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)
- 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)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

The present application relates to a pinning composition, a laminate comprising the same, and a method for producing the same. The pinning composition of the present application can impart directionality and location selection properties to a polymer membrane comprising a self-assembly structure of a block copolymer. The pinning composition of the present application exhibits excellent reaction selectivity, whereby it can form a vertical lamella structure with a high degree of alignment. In addition, the pinning composition of the present application may be suitable for application to low temperature processes.

## Claims

### Claim 1

A random copolymer comprising a unit represented by Formula 1 below and a unit represented by Formula 3-1 or 4 below:
wherein, in Formula 1, R is hydrogen or an alkyl group, A is an oxygen atom, a sulfur atom, —S(═O)2—, a carbonyl group, —C(═O)—X1— or —X1—C(═O)—, where X1 is an oxygen atom or a sulfur atom, B is an alkylene group, an alkenylene group or an alkynylene group, and C is represented by Formula 2 below,
wherein, L is a single bond or an oxygen atom,
wherein, in Formula 3-1, R is hydrogen or an alkyl group, X is a single bond, R1 to R5 are each independently hydrogen, an alkyl group, a haloalkyl group or a halogen atom, and at least one halogen atom is included in at least one of R1, R2, R3, R4, or R5,
wherein, in Formula 4, R is hydrogen or an alkyl group, and X is a single bond, an oxygen 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, an alkylene group, an alkenylene group or an alkynylene group, and Y is a monovalent substituent including a ring structure to which a linear chain having eight or more chain-forming atoms is linked.

### Claim 2 (depends on 1)

The random copolymer according to claim 1, wherein in Formula 3-1, at least one fluorine atom is included in at least one of R1, R2, R3, R4, or R5.

### Claim 3 (depends on 1)

The random copolymer according to claim 1, wherein in Formula 4, the ring structure of Y is an aromatic ring structure or an alicyclic ring structure.

### Claim 4 (depends on 1)

The random copolymer according to claim 1, wherein the unit represented by Formula 3-1 or 4 is contained in the entire random copolymer in a ratio of 80 wt % to 99.9 wt %.

### Claim 5 (depends on 1)

The random copolymer according to claim 1, which the unit represented by Formula 1 is contained in an amount of 1 part by weight to 30 parts by weight relative to 100 parts by weight of the unit represented by Formula 3-1 or 4.

### Claim 6 (depends on 1)

A pinning composition comprising the random copolymer of claim 1.

### Claim 7 (depends on 6)

The pinning composition according to claim 6, wherein the random copolymer is contained in a ratio of 0.1 wt % to 20 wt %.

### Claim 8 (depends on 1)

A substrate comprising a base layer; and a pinning layer present on the surface of the base layer, wherein the pinning layer comprises the random copolymer of claim 1.

### Claim 9 (depends on 8)

The substrate according to claim 8, wherein the pinning layer forms a stripe pattern on the surface of the base layer.

### Claim 10 (depends on 8)

The substrate according to claim 8, further comprising a neutral layer present on the surface of the base layer, wherein the neutral layer and the pinning layer form alternately repeated stripe patterns.

### Claim 11 (depends on 8)

The substrate according to claim 8, further comprising a polymer membrane formed on the pinning layer or the pinning layer and the neutral layer, wherein the polymer membrane comprises a block copolymer including a first block and a second block different from the first block.

### Claim 12 (depends on 11)

The substrate according to claim 11, wherein the block copolymer forms a sphere, cylinder, gyroid or lamella structure.

### Claim 13 (depends on 11)

The substrate according to claim 11, wherein the first block or the second block of the block copolymer comprises the unit of Formula 3 or the unit of Formula 4.

### Claim 14 (depends on 6)

A method for producing a patterned substrate comprising a step of coating the pinning composition of claim 6 on a base layer and annealing it at a temperature of less than 130° C. to form a pinning layer.

### Claim 15 (depends on 14)

The method for producing a patterned substrate according to claim 14, wherein a neutral layer is formed on the base layer to be annealed.

### Claim 16 (depends on 14)

The method for producing a patterned substrate according to claim 14, further comprising a step of forming a polymer membrane, which comprises a block copolymer including a first block and a second block different from the first block, in a self-assembled state on the pinning layer.

### Claim 17 (depends on 16)

The method for producing a patterned substrate according to claim 16, further comprising a step of selectively removing the first block or the second block of the block copolymer from the polymer membrane.

### Claim 18 (depends on 10)

The substrate according to claim 10, wherein the neutral layer comprises a random copolymer including a unit represented by Formula 3 below and a unit represented by Formula 4 below:
wherein, in Formula 3 and 4, R is hydrogen or an alkyl group, and X is a single bond, an oxygen 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, an alkylene group, an alkenylene group or an alkynylene group, and in Formula 3, W is an aryl group containing at least one halogen atom, and in Formula 4, Y is a monovalent substituent including a ring structure to which a linear chain having eight or more chain-forming atoms is linked.

### Claim 19 (depends on 18)

The substrate according to claim 18, wherein the random copolymer contained in the neutral layer comprises the unit represented by Formula 4 in a ratio of 9 mol% to 32 mol%.

### Claim 20 (depends on 18)

The substrate according to claim 18, wherein the ratio (B/A) of the mole number (B) of the unit represented by Formula 3 to the mole number (A) of the unit represented by Formula 4 is in a range of 2 to 10.