# US 10,310,378 B2 · Block copolymer

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 10,310,378 B2
- Document ID: US10310378B2
- Status: Granted
- Kind: B2
- Application number: 15/514,939
- Filed: 2015-09-30
- Published: 2017-08-31
- Granted: 2019-06-04
- Earliest claimed: 2014-09-30
- Assignees: LG Chem, Ltd.
- Applicants: LG Chem, Ltd.
- Inventors: Eun Young Choi; No Jin Park; Jung Keun Kim; Je Gwon Lee; Se Jin Ku; Mi Sook Lee; Hyung Ju Ryu; Sung Soo Yoon
- Web page: https://patentgrep.com/patent/US10310378B2

## CPC

- B81C 1/00428: {Etch mask forming processes not provided for in groups B81C1/00396 - B81C1/0042}
- B05D 1/005: {Spin coating}
- B05D 3/007: {After-treatment}
- C08F 2/14: Organic medium
- C08F 32/06: having two or more carbon-to-carbon double bonds
- C08F 212/08: Styrene
- C08F 216/12: by an ether radical
- C08F 220/10: Esters
- C08F 220/26: Esters containing oxygen in addition to the carboxy oxygen
- C08F 293/00: Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule (on to polymers modified by introduction of unsaturated end groups C08F290/02)
- C08F 293/005: {using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent}
- C08F 299/024: {the unsaturation being in acrylic or methacrylic groups}
- C08G 61/08: of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
- C08G 61/12: Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08J 5/18: Manufacture of films or sheets
- C08J 7/123: {Treatment by wave energy or particle radiation (C08J7/18 takes precedence)}
- C08L 53/00: Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L 53/005: {Modified block copolymers}
- C08L 53/02: of vinyl-aromatic monomers and conjugated dienes
- 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}
- G03F 7/0046: {with perfluoro compounds, e.g. for dry lithography (G03F7/0048 takes precedence)}
- G03F 7/039: Macromolecular compounds which are photodegradable, e.g. positive electron resists (G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023)
- G03F 7/091: {characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement}
- G03F 7/16: Coating processes; Apparatus therefor (applying coatings to base materials in general B05; applying photosensitive compositions to base for photographic purposes G03C1/74)
- G03F 7/162: {Coating on a rotating support, e.g. using a whirler or a spinner}
- G03F 7/165: {Monolayers, e.g. Langmuir-Blodgett}
- G03F 7/2004: {characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light}
- G03F 7/30: Imagewise removal using liquid means
- H10P 50/73: {using masks for insulating materials}
- H10P 76/204: {of organic photoresist masks}
- H10P 95/064: {the removal being chemical etching}
- H10P 95/066: {the removal being a selective chemical etching step, e.g. selective dry etching through a mask}
- H10P 95/08: {Planarisation of organic insulating materials}
- B81C 2201/0149: Forming nanoscale microstructures using auto-arranging or self-assembling material
- B82Y 40/00: Manufacture or treatment of nanostructures
- C01P 2002/70: defined by measured X-ray, neutron or electron diffraction data
- C07B 2200/00: Indexing scheme relating to specific properties of organic compounds
- C08F 212/20: {Fluorine}
- C08F 220/301: {and one oxygen in the alcohol moiety}
- 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]
- C08G 2261/1424: containing ether groups, including alkoxy
- C08G 2261/1426: containing carboxy groups (COOH) and/or -C(=O)O-moieties
- C08G 2261/332: containing only carbon atoms
- C08G 2261/3324: derived from norbornene
- C08G 2261/40: Polymerisation processes
- C08G 2261/418: Ring opening metathesis polymerisation [ROMP]
- 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
- B81C: PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS (making microcapsules or microballoons B01J13/02; processes or apparatus specially adapted for the manufacture or treatment of piezoelectric, electrostrictive or magnetostrictive elements per se H10N30/01)
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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)
- 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
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C07B: GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR (preparation of carboxylic acid esters by telomerisation C07C67/47; telomerisation C08F)

## Abstract

The present application relates to a block copolymer and uses thereof. The present application can provide a block copolymer—which exhibits an excellent self-assembling property and thus can be used effectively in a variety of applications—and uses thereof.

## Claims

### Claim 1

A block copolymer comprising a first block and a second block different from the first block, wherein X of Equation 1below ranges from 2.5 to 10:
X=1+(D×M)/(K×L) [Equation 1]
where in the Equation 1, D represents a ratio (D2/D1) of a density (D2) of the second block to a density (D1) of the first block;
M represents a ratio (M1/M2) of a molar mass (M1) of the first block to a molar mass (M2) of the second block;
K represents a ratio (A2/A1) in a 1H-NMR spectrum of an area (A2) of a peak that is produced based on the second block to an area (A1) of a peak that is produced based on the first block; and
L represents a ratio (H1/H2) of a number (H1) of hydrogen atoms in 1 mole of a repeat unit of the first block to a number (H2) of hydrogen atoms in 1 mole of a repeat unit of the second block,
wherein the first block includes an aromatic structure that connects to a main chain of the first block by a linker and the linker is 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)—, wherein the X1 represents an oxygen atom, a sulfur atom, —S(═O)2—, an alkylene group, an alkenylene group or an alkynylene group.

### Claim 2

A block copolymer comprising a first block and a second block different from the first block, wherein X of Equation 1below ranges from 1.1 to 1.7:
X=1+(D×M)/(K×L) [Equation 1]
where in the Equation 1 , D represents a ratio (D2/D1) of a density (D2) of the second block to a density (D1) of the first block;
M represents a ratio (M1/M2) of a molar mass (M1) of the first block to a molar mass (M2) of the second block;
K represents a ratio (A2/A1) in a 1H-NMR spectrum of an area (A2) of a peak that is produced based on the second block to an area (A1) of a peak that is produced based on the first block; and
L represents a ratio (H1/H2) of a number (H1) of hydrogen atoms in 1 mole of a repeat unit of the first block to a number (H2) of hydrogen atoms in 1 mole of a repeat unit of the second block,
wherein the first block includes an aromatic structure that connects to a main chain of the first block by a linker and the linker is 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)—, wherein the X1 represents an oxygen atom, a sulfur atom, —S(═O)2—, an alkylene group, an alkenylene group or an alkynylene group.

### Claim 3 (depends on 1)

The block copolymer of claim 1, wherein it forms a cylindrical structure.

### Claim 4 (depends on 1)

The block copolymer of claim 1, wherein the second block includes an aromatic structure.

### Claim 5 (depends on 1)

The block copolymer of claim 1, wherein the first block includes a side chain that is connected to the aromatic structure of the first block.

### Claim 6 (depends on 5)

The block copolymer of claim 5, wherein the side chain is connected to the aromatic structure of the first block by an oxygen atom or a nitrogen atom.

### Claim 7 (depends on 1)

The block copolymer of claim 1, wherein the first block includes a side chain that includes 8 or more chain-forming atoms.

### Claim 8 (depends on 1)

The block copolymer of claim 1, wherein the first block includes a side chain that is connected to the aromatic structure of the first block, and the second block includes an aromatic structure that includes one or more halogen atoms.

### Claim 9 (depends on 1)

The block copolymer of claim 1, wherein the first block includes a structural unit represented by Structural Formula 1 below:
where in the Structural Formula 1, R represents a hydrogen atom or an alkyl group with 1 to 4 carbons;
X represents 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)—, wherein the X1 represents an oxygen atom, a sulfur atom, —S(═0)2—, an alkylene group, an alkenylene group or an alkynylene group; and
Y represents a monovalent substituent that includes an aromatic structure to which a side chain including 8 or more chain-forming atoms is connected.

### Claim 10 (depends on 1)

The block copolymer of claim 1, wherein the second block includes a structural unit represented by Structural Formula 3 below:
where in the Structural Formula 3 , X2represents 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)—, wherein the X1 represents a single bond, an oxygen atom, a sulfur atom, —S(═O)2—, an alkylene group, an alkenylene group or an alkynylene group; and
W represents an aryl group that includes at least one halogen atom.

### Claim 11 (depends on 1)

The block copolymer of claim 1 having a number average molecular weight ranging from 3,000 to 300,000.

### Claim 12 (depends on 1)

The block copolymer of claim 1 comprising a polydispersity (Mw/Mn) ranging from 1.01 to 1.60.

### Claim 13 (depends on 1)

A polymer film comprising the block copolymer of claim 1, wherein the block copolymer is self-assembled.

### Claim 14 (depends on 1)

A method of forming a polymer film comprising:
depositing the of claim 1 or coating the block copolymer of claim 1 on a substrate to form a layer, and
annealing the layer.

### Claim 15 (depends on 1)

A method of forming a pattern, the method comprising:
forming a polymer film containing the block copolymer of claim 1 on a substrate, removing the first block or second block of the block copolymer from the polymer film, and
etching the substrate.