# US 12,222,653 B2 · Method for forming semiconductor structure

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- Number: US 12,222,653 B2
- Document ID: US12222653B2
- Status: Granted
- Kind: B2
- Application number: 17/320,754
- Filed: 2021-05-14
- Published: 2021-09-16
- Granted: 2025-02-11
- Earliest claimed: 2017-09-22
- Assignees: Taiwan Semiconductor Manufacturing Company, Ltd.
- Applicants: Taiwan Semiconductor Manufacturing Company, Ltd.
- Inventors: Ming-Hui Weng; An-Ren Zi; Ching-Yu Chang; Chin-Hsiang Lin; Chen-Yu Liu
- Web page: https://patentgrep.com/patent/US12222653B2

## CPC

- G03F 7/30: Imagewise removal using liquid means
- G03F 7/0047: {characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing}
- G03F 7/027: Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds (G03F7/075 takes precedence)
- G03F 7/038: Macromolecular compounds which are rendered insoluble or differentially wettable (G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021)
- G03F 7/11: having cover layers or intermediate layers, e.g. subbing layers {(G03F7/091 - G03F7/093, B41N3/03 take precedence)}
- G03F 7/325: {Non-aqueous compositions}
- G03F 7/40: Treatment after imagewise removal, e.g. baking
- H10P 14/6334: {using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition (deposition by physical ablation of a target H10P14/6329)}
- H10P 14/6342: {Liquid deposition, e.g. spin-coating, sol-gel techniques or spray coating}
- H10P 30/40: into insulating materials
- H10P 50/283: {by chemical means}
- H10P 76/20: of masks comprising organic materials
- H10P 76/405: {characterised by their composition, e.g. multilayer masks}
- 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 method for forming a semiconductor device structure is provided. The method includes forming a resist layer over a material layer, the resist layer includes an inorganic material. The inorganic material includes a plurality of metallic cores and a plurality of first linkers bonded to the metallic cores. The method includes forming a modified layer over the resist layer, and the modified layer includes an auxiliary. The method includes performing an exposure process on the modified layer and the resist layer, and removing a portion of the modified layer and a first portion of the resist layer by a first developer. The first developer includes a ketone-based solvent having a substituted or unsubstituted C6-C7 cyclic ketone, an ester-based solvent having a formula (b), or a combination thereof.

## Claims

### Claim 1

A method for forming a semiconductor structure, comprising:
forming a material layer over a substrate;
forming a resist layer over the material layer, wherein the resist layer comprises an inorganic material, the inorganic material comprises a plurality of metallic cores and a plurality of first linkers bonded to the metallic cores;
forming a modified layer over the resist layer, wherein the modified layer comprises an auxiliary;
performing an exposure process on the modified layer and the resist layer;
removing a portion of the modified layer and a first portion of the resist layer by a first developer, wherein the first developer comprises a ketone-based solvent having a substituted or unsubstituted C6-C7 cyclic ketone, an ester-based solvent having a formula (b), or a combination thereof:
wherein R3 is linear or branched C1-C5 alkyl, or linear or branched C2 alkoxy, and R4 is linear or branched C2-C6 alkyl, or linear or branched C3-C6 alkoxy; and
removing a second portion of the resist layer to expose a top surface of the material layer and to form a patterned resist layer, wherein the top surface of the material layer is in direct contact with a bottom surface of the patterned resist layer.

### Claim 2 (depends on 1)

The method for forming the semiconductor structure as claimed in claim 1, wherein the auxiliary comprises a plurality of second linkers, and the second linkers react with the first linkers during the exposure process to form a plurality of chemical bonds between the auxiliary and the inorganic material.

### Claim 3 (depends on 1)

The method for forming the semiconductor structure as claimed in claim 1, wherein the top surface of the material layer is covered by the second portion of the resist layer before removing the second portion of the resist layer.

### Claim 4 (depends on 1)

The method for forming the semiconductor structure as claimed in claim 1, wherein the metallic cores comprise tin (Sn), indium (In), antimony (Sb).

### Claim 5 (depends on 1)

The method for forming the semiconductor structure as claimed in claim 1, wherein the first developer includes 3-heptanone, 4-heptanone, 2-octanone, 5-methyl-2-hexanone, 2-4-dimethyl-3-pentanone, or a combination thereof.

### Claim 6 (depends on 1)

The method for forming the semiconductor structure as claimed in claim 1, wherein the first developer includes butyl acetate and 1-methoxy-2-propanol acetate.

### Claim 7 (depends on 1)

The method for forming the semiconductor structure as claimed in claim 1, further comprising:
forming a compound in the resist layer during the exposure process, wherein the compound is closer to an interface between the modified layer and the resist layer than the metallic cores.

### Claim 8 (depends on 7)

The method for forming the semiconductor structure as claimed in claim 7, wherein the compound is not removed by the first developer.

### Claim 9

A method for forming a semiconductor structure, comprising:
forming a material layer over a substrate;
forming a bottom layer over the material layer;
forming a middle layer over the bottom layer, wherein the middle layer comprises an auxiliary, and the auxiliary comprises a plurality of second linkers;
forming a resist layer over the middle layer, wherein the resist layer comprises an inorganic material, the inorganic material comprises a plurality of first linkers bonded to a plurality of metallic cores;
exposing a portion of the resist layer by performing an exposure process, wherein the second linkers of the auxiliary bond to the metallic cores through the first linkers during the exposure process; and
removing a portion of the resist layer to form a patterned resist layer by using an ester-based solvent having a formula (b):
wherein R3 is linear or branched C1-C5 alkyl, or linear or branched C2 alkoxy, and R4 is linear or branched C2-C6 alkyl, or linear or branched C3-C6 alkoxy, wherein a sidewall surface of the middle layer extends beyond a sidewall surface of the patterned resist layer.

### Claim 10 (depends on 9)

The method for forming the semiconductor structure as claimed in claim 9, wherein the second linkers react with the first linkers during the exposure process to form a plurality of chemical bonds between the auxiliary and the inorganic material.

### Claim 11 (depends on 9)

The method for forming the semiconductor structure as claimed in claim 9, wherein the metallic cores comprise tin (Sn), indium (In), antimony (Sb).

### Claim 12 (depends on 9)

The method for forming the semiconductor structure as claimed in claim 9, further comprising:
removing a portion of the middle layer by using the patterned resist layer as a mask to form a patterned middle layer; and
removing a portion of the bottom layer by using the patterned middle layer as a mask to form a patterned bottom layer.

### Claim 13 (depends on 9)

The method for forming the semiconductor structure as claimed in claim 9, further comprising:
after using the ester-based solvent, performing a rinse process on the resist layer, wherein the rinse process comprises a rinse solvent, and the rinse solvent includes the ester-based solvent and an additive.

### Claim 14 (depends on 13)

The method for forming the semiconductor structure as claimed in claim 13, wherein the additive comprises formic acid, acetic acid, propanoic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, butyric acid, pentanoic acid, ethanedioic acid, maleic acid, acrylic acid, hydrochloric acid, nitric acid, boric acid, sulfuric acid, carbonic acid, phosphoric acid, hydrofluoric acid, hypochlorous acid, trifluoroacetic acid or a combination thereof.

### Claim 15 (depends on 9)

The method for forming the semiconductor structure as claimed in claim 9, wherein a topmost surface of the middle layer is in direct contact with a bottommost surface of the resist layer.

### Claim 16

A method for forming a semiconductor structure, comprising:
forming a material layer over a substrate;
forming a bottom layer over the material layer;
forming a middle layer over the bottom layer;
forming a resist layer over the middle layer, wherein the resist layer comprises an inorganic material, and the inorganic material comprises a plurality of metallic cores and a plurality of first linkers bonded to the metallic cores;
forming a modified layer over the resist layer, wherein the modified layer comprises an auxiliary;
exposing a portion of the resist layer by performing an exposure process; and
developing the resist layer to form a patterned resist layer to expose a topmost surface of the middle layer which is directly below the patterned resist layer, wherein developing the resist layer is by using cycloheptanone, butyl butyrate, isopropyl butyrate, propyl isobutyrate, butyl 2-methylbutyrate, ethyl trimethylacetate, ethyl valerate, ethyl isovalerate, ethyl 2-methylbutyrate, or methyl 4-methylvalerate.

### Claim 17 (depends on 16)

The method for forming the semiconductor structure as claimed in claim 16, further comprising:
forming a compound in the resist layer during the exposure process, wherein the compound is made of the metallic cores, the second linkers and the first linkers.

### Claim 18 (depends on 17)

The method for forming the semiconductor structure as claimed in claim 17, wherein the compound is not removed by cycloheptanone, butyl butyrate, isopropyl butyrate, propyl isobutyrate, butyl 2-methylbutyrate, ethyl trimethylacetate, ethyl valerate, ethyl isovalerate, ethyl 2-methylbutyrate, or methyl 4-methylvalerate.

### Claim 19 (depends on 16)

The method for forming the semiconductor structure as claimed in claim 16, wherein the metallic cores comprise tin (Sn), indium (In), antimony (Sb).

### Claim 20 (depends on 16)

The method for forming the semiconductor structure as claimed in claim 16, wherein a topmost surface of the middle layer is in direct contact with a bottommost surface of the resist layer.