# US 8,785,114 B2 · Method for manufacturing micro-structure

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- Number: US 8,785,114 B2
- Document ID: US8785114B2
- Status: Granted
- Kind: B2
- Application number: 13/157,460
- Filed: 2011-06-10
- Published: 2011-12-15
- Granted: 2014-07-22
- Earliest claimed: 2010-06-11
- Assignees: Shin-Etsu Chemical Co., Ltd.
- Applicants: Hideto Kato; Hiroshi Kanbara; Tomoyoshi Furihata; Yoshinori Hirano
- Inventors: Hideto Kato; Hiroshi Kanbara; Tomoyoshi Furihata; Yoshinori Hirano
- Web page: https://patentgrep.com/patent/US8785114B2

## CPC

- C09D 163/04: Epoxynovolacs
- B81C 1/00619: {Forming high aspect ratio structures having deep steep walls}
- G03F 7/0226: {characterised by the non-macromolecular additives}
- G03F 7/0236: {Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins}
- G03F 7/30: Imagewise removal using liquid means
- G03F 7/40: Treatment after imagewise removal, e.g. baking
- G03F 7/70466: {Multiple exposures, e.g. combination of fine and coarse exposures, double patterning or multiple exposures for printing a single feature (stitching G03F7/70475)}
- B81C 2201/0108: Sacrificial polymer, ashing of organics
- 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)
- 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)
- 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)

## Abstract

A micro-structure is manufactured by patterning a sacrificial film, forming an inorganic material film on the pattern, providing the inorganic material film with an aperture, and etching away the sacrificial film pattern through the aperture to define a space having the contour of the pattern. The patterning stage includes the steps of (A) forming a sacrificial film using a composition comprising a cresol novolac resin and a crosslinker, (B) exposing patternwise the film to first high-energy radiation, (C) developing, and (D) exposing the sacrificial film pattern to second high-energy radiation and heat treating for thereby forming crosslinks within the cresol novolac resin.

## Claims

### Claim 1

A method for manufacturing a micro-structure comprising the stages of (i) processing a sacrificial film on a substrate to form a sacrificial film pattern, (ii) forming an inorganic material film on the sacrificial film pattern, (iii) providing a portion of the inorganic material film with an aperture for etching, and (iv) etching away the sacrificial film pattern through the aperture to define a space having the contour of the sacrificial film pattern, wherein
the stage (i) of forming a sacrificial film pattern includes the steps of:
(A) forming an optically patternable sacrificial film of 2 to 20 μm thick using a sacrificial film-forming composition comprising:
(i) component (A-1), (A-2), or (A-3); and
(ii) a crosslinker;
wherein component (A-1) is (i) a cresol novolac resin having some or all phenolic hydroxyl groups esterified with 1,2-naphthoquinonediazidosulfonyl halide, or (ii) a mixture of a cresol novolac resin having some or all phenolic hydroxyl groups esterified with 1,2-naphthoquinonediazidosulfonyl halide and a cresol novolac resin having phenolic hydroxyl groups non-esterified,
wherein component (A-2) is the novolac resin (i) or the novolac resin mixture (ii) of (A-1) and a 1,2-naphthoquinonediazidosulfonic acid ester,
wherein component (A-3) is a cresol novolac resin having phenolic hydroxyl groups non-esterified and a 1,2-naphthoquinonediazidosulfonic acid ester,
wherein the crosslinker is selected from the group consisting of melamines, alkoxymethylureas, and alkoxymethylglycolurils,
(B) exposing patternwise the optically patternable sacrificial film to first high-energy radiation,
(C) developing the sacrificial film with an alkaline developer to form a positive sacrificial film pattern, and
(D) exposing the sacrificial film pattern to second high-energy radiation, and then heating the sacrificial film pattern at a temperature of 100 to 220° C., for thereby forming crosslinks within the cresol novolac resin in the sacrificial film pattern.

### Claim 2 (depends on 1)

The method of claim 1 wherein said crosslinker is a melamine compound and said sacrificial film-forming composition comprises 2 to 30% by weight of the melamine compound in the total solids weight of the composition.

### Claim 3 (depends on 2)

The method of claim 2 wherein the melamine compound comprises at least 80% by weight of a hexamethoxymethylol melamine monomer.

### Claim 4 (depends on 1)

The method of claim 1 wherein the cresol novolac resin used in said sacrificial film-forming composition or a cresol novolac resin from which the cresol novolac resin having phenolic hydroxyl groups esterified is derived is a cresol novolac resin containing at least 40 mol % of p-cresol and having a weight average molecular weight of 2,000 to 30,000 and a melting temperature of at least 130° C.

### Claim 5 (depends on 1)

The method of claim 1 wherein the cresol novolac resin having some or all phenolic hydroxyl groups esterified with 1,2-naphthoquinonediazidosulfonyl halide is a cresol novolac resin in which 1 to 30 mol % of phenolic hydroxyl groups are esterified with 1,2-naphthoquinonediazidosulfonyl halide.

### Claim 6 (depends on 1)

The method of claim 1 wherein the content of component (A-1), (A-2) or (A-3) is 45 to 98% by weight in the total solids weight of the sacrificial film-forming composition, and the total amount of the esterized cresol novolac resin and the non-esterized cresol novolac resin is at least 67% by weight in component (A-1), (A-2) or (A-3).

### Claim 7 (depends on 1)

The method of claim 1 wherein the second high-energy radiation is ultraviolet radiation with a wavelength of at least 350 nm.

### Claim 8 (depends on 1)

The method of claim 1 wherein said sacrificial film-forming composition is such that the sacrificial film pattern resulting from the pattern forming step has a side wall which is forward tapered at an angle from 80° to less than 90° relative to the substrate.