# US 10,312,087 B2 · Method to improve adhesion of photoresist on silicon substrate for extreme ultraviolet and electron beam lithography

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- Number: US 10,312,087 B2
- Document ID: US10312087B2
- Status: Granted
- Kind: B2
- Application number: 15/804,568
- Filed: 2017-11-06
- Published: 2018-08-16
- Granted: 2019-06-04
- Earliest claimed: 2017-02-15
- Assignees: International Business Machines Corporation
- Applicants: International Business Machines Corporation
- Inventors: Martin Glodde; Dario L. Goldfarb
- Web page: https://patentgrep.com/patent/US10312087B2

## CPC

- H10P 76/4088: {Processes for improving the resolution of the masks}
- G03F 7/0751: {used as adhesion-promoting additives or as means to improve adhesion}
- 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 7/70016: {by discharge lamps}
- G03F 7/70033: {by plasma extreme ultraviolet [EUV] sources}
- H10P 76/2041: {Photolithographic processes}
- H10P 76/405: {characterised by their composition, e.g. multilayer masks}
- H10P 76/4083: {characterised by their behaviours during the lithography processes, e.g. soluble masks or redeposited masks}
- H10P 76/4085: {characterised by the processes involved to create the masks}
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- 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

An etch process that includes removing an oxide containing surface layer from a semiconductor surface to be etched by applying a hydrofluoric (HF) based chemistry, wherein the hydrofluoric (HF) based chemistry terminates the semiconductor surface to be etched with silicon-hydrogen bonds, and applying a vapor priming agent bearing chemical functionality based on the group consisting of alkynes, alcohols and a combination thereof to convert the silane terminated surface to a hydrophobic organic surface. The method continues with forming a photoresist layer on the hydrophobic organic surface; and patterning the photoresist layer. Thereafter, the patterned portions of the photoresist are developed to provide an etch mask. The portions of the semiconductor surface exposed by the etch mask are then etched.

## Claims

### Claim 1

An etch process comprising:
providing a semiconductor surface to be etched;
removing an oxide containing surface layer from the semiconductor surface to be etched by applying a hydrofluoric (HF) based chemistry, wherein the hydrofluoric (HF) based chemistry terminates the semiconductor surface to be etched with silicon-hydrogen bonds;
applying a vapor priming agent bearing chemical functionality based on the group consisting of alkynes, alcohols and a combination thereof to convert the silane terminated surface to a hydrophobic organic surface;
forming a photoresist layer on the hydrophobic organic surface;
patterning the photoresist layer;
developing patterned portions of the photoresist layer to provide an etch mask; and
etching the portions of the semiconductor surface exposed by the etch mask, while the portions of the semiconductor surface that are underlying the mask are not etched.

### Claim 2 (depends on 1)

The method of claim 1, wherein said patterning is a lithography method selected from the group consisting of EUV lithography, E-beam lithography and combinations thereof.

### Claim 3 (depends on 1)

The method of claim 1, wherein the hydrofluoric (HF) based chemistry is dilute hydrofluoric acid.

### Claim 4 (depends on 1)

The method of claim 1, wherein said vapor priming agent bearing chemical functionality based on alkynes to convert the silane terminated surface to a hydrophobic organic surface comprises said alcohol selected from the group consisting of 2-Propyn-1-ol, 3-Butyn-1-ol, 4-Pentyn-1-ol, 1-Hexyn-3-ol, 4-Pentyn-2-ol, 1-Pentyn-3-ol, 4-Methyl-1-heptyn-3-ol, 5-Hexyn-3-ol, 1-Octyn-3-ol, 3-Butyn-2-ol, 3,5-Dimethyl-1-hexyn-3-ol, 2-Methyl-3-butyn-2-ol, 3-Methyl-1-pentyn-3-ol, 3-Ethyl-1-pentyn-3-ol, 1-Ethynylcyclopentanol and combinations thereof.

### Claim 5 (depends on 1)

The method of claim 1, wherein said vapor priming agent bearing chemical functionality based on alkynes to convert the silane terminated surface to a hydrophobic organic surface comprises said alkyne selected from the group consisting of 5-chloro-1-pentyne, Propargyl ether, Iodo-1-pentyne, 5-Hexynoic acid, 1,7-Octadiyne, Ethyl propiolate, Dimethyl propargylmalonate, Methyl propiolate, 1-Hexyne, 1-Octyne, 3-Chloro-1-propanol and combinations thereof.