# US 12,222,643 B2 · Method of manufacturing a semiconductor device and pattern formation method

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- Number: US 12,222,643 B2
- Document ID: US12222643B2
- Status: Granted
- Kind: B2
- Application number: 17/971,552
- Filed: 2022-10-22
- Published: 2023-03-09
- Granted: 2025-02-11
- Earliest claimed: 2020-07-02
- Assignees: Taiwan Semiconductor Manufacturing Company, Ltd.
- Applicants: Taiwan Semiconductor Manufacturing Company, Ltd.
- Inventors: Chih-Cheng Liu; Ming-Hui Weng; Jr-Hung Li; Yahru Cheng; Chi-Ming Yang; Tze-Liang Lee; Ching-Yu Chang
- Web page: https://patentgrep.com/patent/US12222643B2

## CPC

- G03F 7/0042: {with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists (G03F7/075 takes precedence)}
- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- C23C 16/56: After-treatment
- G03F 7/167: {from the gas phase, by plasma deposition (G03F7/2035 takes precedence)}
- G03F 7/168: {Finishing the coated layer, e.g. drying, baking, soaking}
- G03F 7/2004: {characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light}
- G03F 7/38: Treatment before imagewise removal, e.g. prebaking {(G03F7/265 takes precedence)}
- H10P 76/2041: {Photolithographic processes}
- H10P 76/40: of masks comprising inorganic materials
- 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)
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

A method of manufacturing a semiconductor device includes forming a photoresist layer over a substrate. A first precursor and a second precursor are combined. The first precursor is an organometallic having a formula: MaRbXc, where M is one or more of Sn, Bi, Sb, In, and Te, R is one or more of a C7-C11 aralkyl group, a C3-C10 cycloalkyl group, a C2-C10 alkoxy group, and a C2-C10 alkylamino group, X is one or more of a halogen, a sulfonate group, and an alkylamino group, and 1≤a≤2, b≥1, c≥1, and b+c≤4, and the second precursor is one or more of water, an amine, a borane, and a phosphine. The photoresist layer is selectively exposed to actinic radiation to form a latent pattern. The latent pattern is developed by applying a developer to the selectively exposed photoresist layer.

## Claims

### Claim 1

A method of manufacturing a semiconductor device, comprising:
forming a photoresist layer over a substrate,
wherein the forming the photoresist layer comprises:
combining a first precursor and a second precursor to form a photoresist material,
wherein the first precursor is an organometallic selected from the group consisting of
and
the second precursor is one or more selected from the group consisting of water, an amine, a borane, and a phosphine; and
depositing the photoresist layer over the substrate;
selectively exposing the photoresist layer to actinic radiation to form a latent pattern; and
developing the latent pattern by applying a developer to the selectively exposed photoresist layer to form a pattern in the photoresist layer.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the actinic radiation is extreme ultraviolet radiation.

### Claim 3 (depends on 1)

The method according to claim 1, further comprising after selectively exposing the photoresist layer to actinic radiation to form a latent pattern and before developing the latent pattern, heating the photoresist layer at a temperature ranging from 50° C. to 300° C.

### Claim 4 (depends on 1)

The method according to claim 1, wherein the photoresist material is deposited over the substrate by atomic layer deposition (ALD) or chemical vapor deposition (CVD).

### Claim 5 (depends on 1)

The method according to claim 1, wherein the developer is a dry developer.

### Claim 6 (depends on 5)

The method according to claim 5, wherein the developer is a plasma or a chemical vapor.

### Claim 7 (depends on 1)

The method according to claim 1, further comprising before selectively exposing the photoresist layer to actinic radiation to form a latent pattern, heating the photoresist layer at a temperature ranging from 40° C. to 120° C.

### Claim 8 (depends on 1)

The method according to claim 1, wherein the second precursor is ammonia.

### Claim 9 (depends on 1)

The method according to claim 1, wherein the second precursor is hydrazine.

### Claim 10

A method of manufacturing a semiconductor device, comprising:
combining a first precursor and a second precursor in a vapor state to form a photoresist material,
wherein the first precursor is selected from the group consisting of
and
the second precursor is one or more selected from the group consisting of water, an amine, a borane, and a phosphine;
depositing the photoresist material over a target layer to be patterned to form a photoresist layer;
selectively exposing the photoresist layer to actinic radiation; and
applying a developer to the selectively exposed photoresist layer to form a pattern in the photoresist layer.

### Claim 11 (depends on 10)

The method according to claim 10, wherein the second precursor is ammonia.

### Claim 12 (depends on 10)

The method according to claim 10, wherein the actinic radiation is extreme ultraviolet radiation.

### Claim 13 (depends on 10)

The method according to claim 10, further heating the photoresist layer at a temperature ranging from 50° C. to 300° C. after selectively exposing the photoresist layer to actinic radiation and before applying the developer.

### Claim 14 (depends on 10)

The method according to claim 10, wherein the photoresist material is deposited over the target layer to be patterned by atomic layer deposition (ALD) or chemical vapor deposition (CVD).

### Claim 15 (depends on 10)

The method according to claim 10, wherein the developer is plasma or a chemical vapor.

### Claim 16

A method of manufacturing a semiconductor device, comprising:
forming a resist layer over a target layer to be patterned,
wherein the resist layer comprises a reaction product of a first precursor and a second precursor,
wherein the first precursor is selected from the group consisting of
and
the second precursor is one or more selected from the group consisting of water, an amine, a borane, and a phosphine; and
patterning the resist layer.

### Claim 17 (depends on 16)

The method according to claim 16, further comprising before patterning the resist layer, heating the resist layer at a temperature ranging from 40° C. to 120° C.

### Claim 18 (depends on 16)

The method according to claim 16, wherein the second precursor is water vapor.

### Claim 19 (depends on 16)

The method according to claim 16, wherein the resist layer is deposited over target layer by atomic layer deposition (ALD) or chemical vapor deposition (CVD).

### Claim 20 (depends on 16)

The method according to claim 16, wherein the patterning the resist layer further comprises:
patternwise exposing the resist layer to actinic radiation to form a latent pattern; and
applying a developer to the latent pattern to form a pattern in the resist layer.