# US 12,772,807 B2 · Method of manufacturing a semiconductor device

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- Number: US 12,772,807 B2
- Document ID: US12772807B2
- Status: Granted
- Kind: B2
- Application number: 18/123,095
- Filed: 2023-03-17
- Published: 2024-03-21
- Granted: 2026-10-20
- Earliest claimed: 2022-08-31
- Assignees: Taiwan Semiconductor Manufacturing Company, Ltd.
- Applicants: Taiwan Semiconductor Manufacturing Company, Ltd.
- Inventors: Chieh-Hsin Hsieh; Wei-Han Lai; Ching-Yu Chang
- Web page: https://patentgrep.com/patent/US12772807B2

## CPC

- H10P 76/2041: {Photolithographic processes}
- G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors}
- G03F 7/0757: {Macromolecular compounds containing Si-O, Si-C or Si-N bonds (G03F7/0752 takes precedence)}
- G03F 7/162: {Coating on a rotating support, e.g. using a whirler or a spinner}
- G03F 7/168: {Finishing the coated layer, e.g. drying, baking, soaking}
- H10P 50/692: {characterised by their composition, e.g. multilayer masks or materials}
- H10P 50/71: {using masks for conductive or resistive materials}
- H10P 50/73: {using masks for insulating materials}
- H10P 76/2043: {using an anti-reflective coating}
- 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

A method of manufacturing a semiconductor device includes forming a first layer comprising an organic material over a substrate. A second layer is formed over the first layer, wherein the second layer includes a silicon-containing material and one or more selected from the group consisting of a photoacid generator, an actinic radiation absorbing additive including an iodine substituent, and a silicon-containing monomer having iodine or phenol group substituents. A photosensitive layer is formed over the second layer, and the photosensitive layer is patterned.

## Claims

### Claim 1

A method of manufacturing a semiconductor device, comprising:
forming a first layer comprising an organic material over a substrate;
forming a second layer over the first layer, wherein the second layer comprises a silicon-containing material and a silicon-containing monomer having iodine or phenol group substituents,
wherein the forming the second layer comprises:
applying a mixture comprising the silicon-containing material and the silicon-containing monomer containing over the first layer; and
crosslinking the mixture by heating the mixture at a temperature ranging from 150° C. to 400° C. after applying the mixture over the first layer,
wherein the applying the mixture comprises spin coating the mixture, and during the spin coating the silicon-containing monomer at least partially separates from the mixture forming an upper second layer and a lower second layer, wherein the upper second layer has a higher concentration of the silicon-containing monomer than the lower second layer;
forming a photosensitive layer over the second layer; and
patterning the photosensitive layer.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the silicon-containing material is a siloxane or a spin-on-glass.

### Claim 3 (depends on 1)

The method according to claim 1, wherein the second layer includes a photoacid generator, and the photoacid generator includes a sulfonium or an iodonium cation.

### Claim 4 (depends on 1)

The method according to claim 1, wherein the second layer includes a photoacid generator is-bound to the silicon-containing material.

### Claim 5 (depends on 1)

The method according to claim 1, wherein the mixture further comprises:
one or more of a photoacid generator and an actinic radiation absorbing additive having an iodine substituent.

### Claim 6 (depends on 1)

The method according to claim 1, wherein during the crosslinking the mixture, the silicon-containing monomer in the upper second layer is crosslinked.

### Claim 7

A method of manufacturing a semiconductor device, comprising:
forming a bottom anti-reflective coating layer over a substrate;
forming a middle layer over the bottom anti-reflective coating layer, wherein the middle layer comprises a silicon-containing material and a silicon-containing monomer having iodine or phenol group substituents,
wherein the silicon-containing monomer has a structure
where Z and D are independently a substituted or unsubstituted C1-C20 alkyl group, C3-C20 cycloalkyl group, C1-C20 hydroxyalkyl group, C2-C20 alkoxy group, C3-C20 alkoxyalkyl group, C2-C20 acetyl group, C3-C20 acetyl alkyl group, C1-C20 carboxyl group, C2-C20 alkyl carboxyl group, C1-C20 alkyl fluoride group, C6-C20 aryl group, C7-C20 aralkyl group, or adamantyl group, wherein Z and D independently include 1-10 iodine or 1-10 phenolic OH groups, or Z is a single bond, or D is H; R4, R5, and R6 are respectively H or a substituted or unsubstituted C6-C20 aryl group, C7-C20 aralkyl group, C3-C20 cycloalkyl group, C1-C20 hydroxyalkyl group, C2-C20 alkoxy group, C3-C20 alkoxy alkyl group, C2-C20 acetyl group, C3-C20 acetyl alkyl group, C1-C20 carboxyl group, C2-C20 alkyl carboxyl group, or C4-C20 cycloalkyl carboxyl group;
forming a photosensitive layer over the middle layer;
selectively exposing the photosensitive layer to actinic radiation to form a latent pattern; and
developing the selectively exposed photosensitive layer to form a pattern in the photosensitive layer.

### Claim 8 (depends on 7)

The method according to claim 7, wherein the silicon-containing material is a polysiloxane.

### Claim 9 (depends on 7)

The method according to claim 7, wherein the middle layer includes a photoacid generator, and the photoacid generator includes a sulfonium cation or an iodonium cation.

### Claim 10 (depends on 7)

The method according to claim 7, wherein the middle layer includes a photoacid generator, and the photoacid generator is comprised of an anion selected from the group consisting of
and
a cation selected from the group consisting of

### Claim 11 (depends on 7)

The method according to claim 7, wherein the middle layer includes an actinic radiation absorbing additive having an iodine substituent, and the additive has a structure In—R1, where n=1-10 and R1 is selected from the group consisting of substituted or unsubstituted C1-C10 alkyl groups, C6-C10 aryl groups, C1-C10 aralkyl groups, C3-C10 cycloalkyl groups, C1-C10 hydroxyalkyl groups, C2-C10 alkoxyalkyl groups, C2-C10 acetyl groups, C3-10 acetyl alkyl groups, C1-C10 carboxyl groups, C2-C10 alkyl carboxyl groups, C3-C10 cycloalkyl carboxyl groups, or adamantyl groups.

### Claim 12 (depends on 7)

The method according to claim 7, wherein the middle layer includes an actinic radiation absorbing additive having an iodine substituent, and the additive is selected from the group consisting of:

### Claim 13 (depends on 7)

The method according to claim 7, wherein the silicon-containing monomer is selected from the group consisting of

### Claim 14 (depends on 7)

The method according to claim 7, wherein;
the silicon-containing monomer includes a photoacid generator substituent, and is selected from the group consisting of

### Claim 15

A composition, comprising:
a silicon-containing material and a silicon-containing monomer having iodine or phenol group substituents,
the silicon-containing monomer has a structure
where Z and D are independently a substituted or unsubstituted C1-C20 alkyl group, C3-C20 cycloalkyl group, C1-C20 hydroxyalkyl group, C2-C20 alkoxy group, C3-C20 alkoxyalkyl group, C2-C20 acetyl group, C3-C20 acetyl alkyl group, C1-C20 carboxyl group, C2-C20 alkyl carboxyl group, C1-C20 alkyl fluoride group, C6-C20 aryl group, C7-C20 aralkyl group, or adamantyl group, wherein Z and D independently include 1-10 iodine or 1-10 phenolic OH groups, or Z is a single bond, or D is H; R4, R5, and R6 are respectively H or a substituted or unsubstituted C6-C20 aryl group, C7-C20 aralkyl group, C3-C20 cycloalkyl group, C1-C20 hydroxyalkyl group, C2-C20 alkoxy group, C3-C20 alkoxy alkyl group, C2-C20 acetyl group, C3-C20 acetyl alkyl group, C1-C20 carboxyl group, C2-C20 alkyl carboxyl group, or C4-C20 cycloalkyl carboxyl group.

### Claim 16 (depends on 15)

The composition of claim 15, wherein the silicon-containing material is a siloxane or a spin-on-glass.

### Claim 17 (depends on 15)

The composition of claim 15, wherein the silicon-containing material is a polysiloxane.

### Claim 18 (depends on 15)

The composition of claim 15, further comprising a photoacid generator.

### Claim 19 (depends on 18)

The composition of claim 18, wherein the photoacid generator is comprised of an anion selected from the group consisting of
a cation selected from the group consisting of

### Claim 20 (depends on 15)

The composition of claim 15, further comprising an actinic radiation absorbing additive having an iodine substituent has a structure In—R1,
where n=1-10 and R1 is selected from the group consisting of substituted or unsubstituted C1-C10 alkyl groups, C6-C10 aryl groups, C1-C10 aralkyl groups, C3-C10 cycloalkyl groups, C1-C10 hydroxyalkyl groups, C2-C10 alkoxyalkyl groups, C2-C10 acetyl groups, C3-10 acetyl alkyl groups, C1-C10 carboxyl groups, C2-C10 alkyl carboxyl groups, C3-C10 cycloalkyl carboxyl groups, or adamantyl groups.