# US 10,308,752 B2 · Block copolymer

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- Number: US 10,308,752 B2
- Document ID: US10308752B2
- Status: Granted
- Kind: B2
- Application number: 15/479,705
- Filed: 2017-04-05
- Published: 2017-07-20
- Granted: 2019-06-04
- Earliest claimed: 2011-11-09
- Assignees: Jsr Corporation
- Applicants: Jsr Corporation
- Inventors: Yuji Namie; Shinya Minegishi; Tomoki Nagai; Takuo Sone
- Web page: https://patentgrep.com/patent/US10308752B2

## CPC

- C08F 297/026: {polymerising acrylic acid, methacrylic acid or derivatives thereof}
- B81C 1/00031: {Regular or irregular arrays of nanoscale structures, e.g. etch mask layer (photomechanical, e.g. photolithographic, production of textured or patterned surfaces G03F7/00; lithographic processes for making patterned surfaces using printing and stamping G03F7/0002)}
- C08L 53/005: {Modified block copolymers}
- G03F 7/0002: {Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping}
- G03F 7/0035: {Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface}
- G03F 7/70: {Microphotolithographic exposure; Apparatus therefor (photo-masks G03F1/00)}
- H10P 50/695: {characterised by the process involved to create the mask, e.g. lift-off masks or sidewalls or to modify the mask}
- H10P 50/71: {using masks for conductive or resistive materials}
- H10P 76/204: {of organic photoresist masks}
- H10P 76/4085: {characterised by the processes involved to create the masks}
- B81C 2201/0149: Forming nanoscale microstructures using auto-arranging or self-assembling material
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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)
- 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)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

A block copolymer includes a polystyrene block including a styrene unit, and a polyalkyl (meth)acrylate block including an alkyl (meth)acrylate unit. The block copolymer includes an organic group that is bound to at least one end of a main chain of the block copolymer and that comprises a hetero atom. A polymerization initiation end of the block copolymer includes a structure derived from an alkyl lithium. The organic group included in the block copolymer includes a nitrogen atom, a sulfur atom, a phosphorus atom, a tin atom, or a combination thereof, or is represented by formula (1). R1 represents a single bond or a divalent organic group having 1 to 30 carbon atoms; and R2 represents a hydrogen atom, an aliphatic linear hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 30 carbon atoms, or the like.

## Claims

### Claim 1

A block copolymer comprising:
a polystyrene block comprising a styrene unit; and
a polyalkyl (meth)acrylate block comprising an alkyl (meth)acrylate unit,
the block copolymer comprising an organic group that is bound to at least one end of a main chain of the block copolymer and that comprises a hetero atom,
wherein a polymerization initiation end of the block copolymer comprises a structure derived from an alkyl lithium,
wherein the organic group included in the block copolymer comprises a nitrogen atom, a sulfur atom, a phosphorus atom, a tin atom, or a combination thereof, or is represented by formula (1):
wherein, in the formula (1), R1 represents a single bond or a divalent organic group having 1 to 30 carbon atoms; and R2 represents a hydrogen atom, an aliphatic linear hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 30 carbon atoms, or a group in which the aliphatic linear hydrocarbon group having 1 to 30 carbon atoms or the alicyclic hydrocarbon group having 3 to 30 carbon atoms comprises a hetero atom between adjacent two carbon atoms, and
wherein the organic group is not a monomeric unit included in the block copolymer.

### Claim 2 (depends on 1)

The block copolymer of claim 1, wherein the block copolymer is a diblock copolymer or a triblock copolymer.

### Claim 3 (depends on 1)

The block copolymer of claim 1, wherein the block copolymer is a diblock copolymer.

### Claim 4 (depends on 1)

The block copolymer of claim 1, wherein the organic group is bound to an end of the main chain of the polyalkyl (meth)acrylate block.

### Claim 5 (depends on 1)

The block copolymer of claim 1, wherein the block copolymer is a diblock copolymer the organic group is bound to an end of the main chain of the polyalkyl (meth)acrylate block.

### Claim 6 (depends on 1)

The block copolymer of claim 1, wherein the alkyl (meth)acrylate unit is a methyl methacrylate unit.

### Claim 7 (depends on 1)

The block copolymer of claim 1, wherein a molar ratio of styrene units to alkyl (meth)acrylate units in the block copolymer is no less than 10/90 and no greater than 90/10.

### Claim 8 (depends on 1)

The block copolymer of claim 1, wherein the organic group included in the block copolymer is derived from an epoxy compound.

### Claim 9 (depends on 1)

The block copolymer of claim 1, wherein the hetero atom is a nitrogen atom, a sulfur atom, a phosphorus atom, a tin atom or a combination thereof.

### Claim 10 (depends on 1)

The block copolymer of claim 1, wherein R1 represents a divalent organic group having 2 to 30 carbon atoms.

### Claim 11 (depends on 1)

The block copolymer of claim 1, wherein R1 represents an aliphatic linear hydrocarbon group having 2 to 30 carbon atoms and optionally comprising a hetero atom between adjacent two carbon atoms, an alicyclic hydrocarbon group having 3 to 30 carbon atoms and optionally comprising a hetero atom between adjacent two carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms and optionally comprising a hetero atom between adjacent two carbon atoms.

### Claim 12 (depends on 1)

The block copolymer of claim 1, wherein the organic group included in the block copolymer is represented by the formula (1).

### Claim 13 (depends on 12)

The block copolymer of claim 12, wherein R1 represents a divalent organic group having 2 to 30 carbon atoms.

### Claim 14 (depends on 12)

The block copolymer of claim 12, wherein R1 represents an aliphatic linear hydrocarbon group having 2 to 30 carbon atoms and optionally comprising a hetero atom between adjacent two carbon atoms, an alicyclic hydrocarbon group having 3 to 30 carbon atoms and optionally comprising a hetero atom between adjacent two carbon atoms, or an aromatic hydrocarbon group having 6 to 30 carbon atoms and optionally comprising a hetero atom between adjacent two carbon atoms.