# US 2014/0193754 A1 · Compositions of neutral layer for directed self assembly block copolymers and processes thereof

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

- Number: US 2014/0193754 A1
- Document ID: US20140193754A1
- Status: Published application
- Kind: A1
- Application number: 14/180,848
- Filed: 2014-02-14
- Published: 2014-07-10
- Earliest claimed: 2011-09-23
- Assignees: Az Electronic Materials (Luxembourg) S.A.R.L.
- Inventors: Hengpeng WU; Yi CAO; SungEun HONG; Jian YIN; Margareta PAUNESCU; Mark O. NEISSER; Guanyang LIN
- Web page: https://patentgrep.com/patent/US20140193754A1

## CPC

- G03F 7/20: Exposure; Apparatus therefor (photographic printing apparatus for making copies G03B27/00)
- B82Y 10/00: Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
- B82Y 40/00: Manufacture or treatment of nanostructures
- C08F 212/08: Styrene
- C08F 212/32: containing two or more rings
- C08F 220/14: Methyl esters {, e.g. methyl (meth)acrylate}
- 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)
- 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
- C09D 125/14: with unsaturated esters
- C09D 125/16: Homopolymers or copolymers of alkyl-substituted styrenes
- G03F 7/0002: {Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping}
- G03F 7/2037: {Exposure with X-ray radiation or corpuscular radiation, through a mask with a pattern opaque to that radiation}
- 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)
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- 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)
- 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)

## Abstract

The present invention relates to novel neutral layer compositions and methods for using the neutral layer compositions for aligning microdomains of directed self-assembling block copolymers (BCP). The compositions and processes are useful for fabrication of electronic devices. The neutral layer composition comprises at least one random copolymer having at least one unit of structure (1), at least one unit of structure (2) and at least one unit of structure (3) where R1 is selected from the group consisting of a C1-C8 alkyl, C1-C8 fluoroalkyl moiety, C1-C8 partially fluorinated alkyl, C4-C8 cycloalkyl, C4-C8 cyclofluoroalkyl, C4-C8 partially fluorinated cycloalkyl, and a C2-C8 hydroxyalkyl; R2, R3 and R5 are independently selected from a group consisting of H, C1-C4 alkyl, CF3 and F; R4 is selected from the group consisting of H, C1-C8 alkyl, C1-C8 partially fluorinated alkyl and C1-C8 fluoroalkyl, n ranges from 1 to 5, R6 is selected from the group consisting of H, F, C1-C8 alkyl and a C1-C8 fluoroalkyl and m ranges from 1 to 3.

## Claims

### Claim 1

A process for forming an image by graphoepitaxy comprising:
a) forming a coating of the neutral layer on a substrate;
b) heating the neutral layer to form a crosslinked neutral layer;
c) providing a coating of a photoresist layer over the crosslinked neutral layer;
d) forming a pattern in the photoresist;
e) applying a block copolymer comprising an etch resistant block and highly etchable block over the photoresist pattern and annealing until directed self assembly occurs; and,
f) etching the block copolymer, thereby removing the highly etchable block of the copolymer and forming a pattern.

### Claim 2 (depends on 1)

The process of claim 1 where the photoresist pattern is formed by imaging lithography selected from a group consisting of e-beam, broadband, 193 nm immersion lithography, 13.5 nm, 193 nm, 248 nm, 365 nm and 436 nm.

### Claim 3 (depends on 1)

The process of claim 1, where the photoresist is a positive or negative tone developable photoresist.

### Claim 4

A process for forming an image by chemoepitaxy comprising:
a) forming a coating of a neutral layer on a substrate;
b) heating the neutral layer to form a crosslinked neutral layer;
c) providing a coating of a photoresist layer over the crosslinked neutral layer;
d) forming a pattern in the photoresist layer to remove the unexposed photoresist, thereby forming an uncovered crosslinked neutral layer region;
e) treating the uncovered crosslinked neutral layer region,
f) removing the photoresist,
g) applying a block copolymer comprising an etch resistant block and highly etchable block over the neutral layer and annealing until directed self assembly occurs; and,
h) etching the block copolymer, thereby removing the highly etchable block of the copolymer and forming a pattern.

### Claim 5 (depends on 4)

The process of claim 4 where the photoresist pattern is formed by imaging lithography selected from a group consisting of e-beam, 193 nm immersion lithography, broadband, 13.5 nm, 193 nm, 248 nm, 365 nm and 436 nm.

### Claim 6 (depends on 4)

The process of claim 4, where the photoresist is a negative or positive tone developable photoresist.

### Claim 7

A process for forming an image by chemoepitaxy comprising:
a) forming a coating of the neutral layer on a substrate;
b) heating the neutral layer to form a crosslinked neutral layer;
c) providing a coating of a photoresist layer over the crosslinked neutral layer;
d) forming a pattern in the photoresist layer;
e) applying a block copolymer comprising an etch resistant block and highly etchable block over the photoresist pattern and annealing until directed self assembly occurs; and,
f) etching the block copolymer with a plasma, thereby removing the highly etchable block of the copolymer and forming a pattern.

### Claim 8 (depends on 7)

The process of claim 7 where the photoresist pattern is formed by imaging lithography selected from a group consisting of e-beam, broadband, 193 nm immersion lithography, 13.5 nm, 193 nm, 248 nm, 365 nm and 436 nm.

### Claim 9 (depends on 7)

The process of claim 7, where the photoresist is a negative or positive photoresist.