# US 10,370,529 B2 · Method of manufacturing patterned substrate

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- Number: US 10,370,529 B2
- Document ID: US10370529B2
- Status: Granted
- Kind: B2
- Application number: 15/514,929
- Filed: 2015-09-30
- Published: 2017-07-27
- Granted: 2019-08-06
- Earliest claimed: 2014-09-30
- Assignees: LG Chem, Ltd.
- Applicants: LG Chem, Ltd.
- Inventors: Se Jin Ku; Mi Sook Lee; Hyung Ju Ryu; Jung Keun Kim; Sung Soo Yoon; No Jin Park; Je Gwon Lee; Eun Young Choi
- Web page: https://patentgrep.com/patent/US10370529B2

## 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 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 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

Provided is a method of manufacturing a patterned substrate. The method may be applied to a process of manufacturing a device such as an electronic device or integrated circuit, or another use, for example, to manufacture an integrated optical system, a guidance and detection pattern of a magnetic domain memory, a flat panel display, a LCD, a thin film magnetic head or an organic light emitting diode, and used to construct a pattern on a surface to be used to manufacture a discrete tract medium such as an integrated circuit, a bit-patterned medium and/or a magnetic storage device such as a hard drive.

## Claims

### Claim 1

A method of manufacturing a patterned substrate, comprising:
forming a polymer film on a surface of an oxygen plasma-treated substrate, wherein the polymer film comprises a block copolymer that includes a first block and a second block, and the block copolymer forms a self-assembly structure, where an interface between a domain formed by the first block and a domain formed by the second block is vertical to a surface of the substrate, and wherein the first block includes a ring structure substituted with a side chain having 8 or more chain-forming atoms, and the ring structure is linked to a main chain of the first block as a side chain, wherein the ring structure is directly linked or is linked to the main chain via a linker and the linker is an oxygen atom, a sulfur atom, —S(═O)2—, a carbonyl group, —C(═O)—X1— or —X1—C(═O)—, where the X1 is an oxygen atom or a sulfur atom.

### Claim 2 (depends on 1)

The method of claim 1, wherein the substrate is a metal substrate.

### Claim 3 (depends on 1)

The method of claim 1, wherein the substrate includes one or more metals selected from the group consisting of gold, copper, titanium, nickel, silver, aluminum, germanium, tungsten, tin, antimony, indium, cadmium, palladium, lead and platinum, or an oxide, nitride or sulfide of the one or more metals.

### Claim 4 (depends on 1)

The method of claim 1, wherein the oxygen plasma is applied with RF power of 30 to 2000 W, a process pressure of 5 to 300 mTorr and an oxygen flow rate of 20 to 100 sccm.

### Claim 5 (depends on 1)

The method of claim 1, wherein the polymer film is formed in contact with the surface of the oxygen plasma-treated substrate.

### Claim 6 (depends on 1)

The method of claim 1, wherein the self-assembly structure is a lamellar structure.

### Claim 7 (depends on 1)

The method of claim 1, wherein the second block is different from the first block, in which
the first block shows a peak at an azimuthal angle of −90 to −70 degrees or 70 to 90 degrees of a diffraction pattern of a scattering vector of 12 to 16 nm−1 in a GIWAXS spectrum.

### Claim 8 (depends on 1)

The method of claim 1, wherein the second block has a different chemical structure from the first block,
in which the first block shows a melting transition peak or isotropic transition peak in a range of −80 to 200° C. through differential scanning calorimetry (DSC) analysis.

### Claim 9 (depends on 1)

The method of claim 1, wherein the second block has a different chemical structure from the first block,
in which the first block shows a peak having a full width at half maximum (FWHM) of 0.2 to 0.9 nm−1 in a scattering vector (q) range of 0.5 to 10 nm−1 through XRD analysis.

### Claim 10 (depends on 1)

The method of claim 1, wherein the second block has a different chemical structure from the first block,
the number of chain-forming atoms (n) of the side chain of the first block and the scattering vector (q) obtained by XRD analysis performed on the first block, satisfy Equation 2:
3 to 5 nm−1=nq/(2×π) [Equation 2]
where n is the number of chain-forming atoms of the side chain of the first block, q is the smallest scattering vector (q) in which a peak is shown through XRD analysis performed on a block including the side chain of the first block, or a scattering vector (q) showing a peak having the largest peak area.

### Claim 11 (depends on 1)

The method of claim 1, wherein the second block has a different chemical structure from the first block, in which the absolute value of a difference in surface energy between the first block and the second block is 10 mN/m or less.

### Claim 12 (depends on 1)

The method of claim 1, wherein the second block has a different chemical structure from the first block, in which the absolute value of a difference in density between the first block and the second block is 0.25 g/cm3 or more.

### Claim 13 (depends on 1)

The method of claim 1, wherein the second block is different from the first block, in which a volume fraction of the first block is in a range of 0.2 to 0.6, and a volume fraction of the second block is in a range of 0.4 to 0.8.

### Claim 14 (depends on 1)

The method of claim 1, wherein the ring structure does not include a halogen atom.

### Claim 15 (depends on 1)

The method of claim 1, wherein the second block of the block copolymer includes 3 or more halogen atoms.

### Claim 16 (depends on 15)

The method of claim 15, wherein the second block includes a ring structure, and the halogen atom is substituted in the ring structure.

### Claim 17 (depends on 1)

The method of claim 1, wherein the first block has the unit represented by Formula 1:
where R is a hydrogen or an alkyl group, X is a single bond, an oxygen atom, a sulfur atom, —S(═O)2—, a carbonyl group, —C(═O)—X1— or —X1—C(═O)—, in which X1 is an oxygen atom, or a sulfur atom, and Y is the ring structure substituted with the side chain having 8 or more chain-forming atoms.

### Claim 18 (depends on 17)

The method of claim 17, wherein Y of Formula 1 is represented by Formula 2:
-P-Q-Z [Formula 2]
where P is an arylene group or a cycloalkylene group, Q is a single bond, an oxygen atom or —NR3—, in which R3 is a hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, and Z is the side chain having 8 or more chain-forming atoms.

### Claim 19 (depends on 18)

The method of claim 18, wherein P of Formula 2 is an arylene group having 6 to 12 carbon atoms.

### Claim 20 (depends on 1)

The method of claim 1, wherein the first block has the unit represented by Formula 3:
where R is a hydrogen or an alkyl group having 1 to 4 carbon atoms, X is a single bond, an oxygen atom, —C(═O)—O— or —O—C(═O)—, P is an arylene group, Q is an oxygen atom or —NR3—, in which R3 is a hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, and Z is a linear chain having 8 or more chain-forming atoms.

### Claim 21 (depends on 1)

The method of claim 1, further comprising:
selectively removing any one block of the block copolymer, which forms a self-assembly structure.

### Claim 22

A method of manufacturing a patterned substrate, comprising:
forming a polymer film on a surface of an oxygen plasma-treated substrate, wherein the polymer film comprises a block copolymer that includes a first block and a second block, and the block copolymer forms a self-assembly structure, where an interface between a domain formed by the first block and a domain formed by the second block is vertical to a surface of the substrate, and wherein the first block includes a ring structure substituted with a side chain having 8 or more chain-forming atoms, and the second block has the unit represented by Formula 5:
where B is a monovalent substituent having an aromatic structure including one or more halogen atoms.

### Claim 23 (depends on 21)

The method of claim 21, further comprising:
etching the substrate, after one block of the block copolymer is selectively removed.

### Claim 24 (depends on 22)

The method of claim 22, further comprising:
selectively removing any one block of the block copolymer, which forms a self-assembly structure.

### Claim 25 (depends on 24)

The method of claim 24, further comprising:
etching the substrate, after one block of the block copolymer is selectively removed.