# US 12,601,976 B2 · All-in-one dry development for metal-containing photoresist

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- Number: US 12,601,976 B2
- Document ID: US12601976B2
- Status: Granted
- Kind: B2
- Application number: 18/850,628
- Filed: 2024-07-26
- Published: 2025-02-20
- Granted: 2026-04-14
- Earliest claimed: 2023-07-27
- Assignees: Lam Research Corporation
- Applicants: Lam Research Corporation
- Inventors: Da Li; Ji Yeon Kim; Younghee Lee; Hongxiang Zhao; Yisi Zhu; Samantha S.H. Tan; Mengnan Zou; Zhiwei Sun; Jun Xue
- Web page: https://patentgrep.com/patent/US12601976B2

## CPC

- G03F 7/36: Imagewise removal not covered by groups G03F7/30 - G03F7/34, e.g. using gas streams, using plasma
- H10P 72/0454: {surrounding a central transfer chamber}
- G03F 7/0042: {with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists (G03F7/075 takes precedence)}
- G03F 7/0043: {Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof (G03F7/0044 takes precedence)}
- G03F 7/40: Treatment after imagewise removal, e.g. baking
- G03F 7/405: {Treatment with inorganic or organometallic reagents after imagewise removal}
- H10P 72/0468: {comprising a chamber adapted to a particular process}
- H10P 72/0606: {Position monitoring, e.g. misposition detection or presence detection}
- H10P 72/3306: {Horizontal transfer of a single workpiece}
- 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

Process condition management facilitates the combination of dry development and post-development treatment into a single process chamber, eliminating the necessity for a post-dry development bake step in a separate chamber during semiconductor manufacturing. Thermal dry development and plasma dry development may be performed in the same chamber. Thermal dry development, plasma dry development and passivation such as an O2 flash treatment; or thermal dry development, plasma dry development, passivation and hardening operations are enabled without wafer transfer.

## Claims

### Claim 1

A method for performing dry development, the method comprising:
performing, in a process chamber, a thermal dry development on a semiconductor substrate comprising an EUV-sensitive photoresist film using a halogen-containing gas in a plasma-free process, wherein the EUV-sensitive photoresist film comprises EUV-exposed portions and unexposed portions, wherein the thermal dry development selectively removes unexposed portions relative to the EUV-exposed portions to form a patterned photoresist mask; and
performing, in the process chamber after performing the thermal dry development, a plasma dry development on the semiconductor substrate by forming plasma with at least one reactive gas to descum, wherein the plasma dry development removes residues including byproducts of thermal dry development relative to the EUV-exposed portions, the byproducts having a different composition than the unexposed portions and the exposed portions of the EUV-sensitive photoresist film.

### Claim 2 (depends on 1)

The method of claim 1, wherein the at least one reactive gas comprises one or more halogen-containing gases, one or more hydrogen-containing gases, or a combination thereof.

### Claim 3 (depends on 1)

The method of claim 1, wherein the at least one reactive gas comprises one or more hydrogen-containing gases, wherein the one or more hydrogen-containing gases comprises CH4.

### Claim 4 (depends on 1)

The method of claim 1, wherein the at least one reactive gas comprises multiple halogen-containing gases, each of the halogen-containing gases selected from the group consisting of: HBr, HCl, Cl2, and BCl3.

### Claim 5 (depends on 4)

The method of claim 4, wherein the at least one reactive gas comprises HBr and Cl2, HBr and HCl, HBr and BCl3, or BCl3 and Cl2.

### Claim 6 (depends on 1)

The method of claim 1, wherein the at least one reactive gas comprises a combination of one halogen-containing gas selected from HBr, HCl, Cl2, and BCl3, and one hydrogen-containing gas selected from H2 and CH4.

### Claim 7 (depends on 6)

The method of claim 6, wherein the at least one reactive gas comprises HBr and H2, BCl3 and CH4, Cl2 and CH4, HCl and CH4, or HBr and CH4.

### Claim 8 (depends on 1)

The method of claim 1, wherein performing plasma dry development by forming plasma with at least one reactive gas comprises forming plasma with at least one reactive gas and at least one non-reactive gas, wherein the non-reactive gas is selected from the group consisting of: N2, He, Ne, Ar, Kr, and Xe.

### Claim 9 (depends on 8)

The method of claim 8, wherein the at least one reactive gas comprises HBr and the at least one non-reactive gas comprises N2.

### Claim 10 (depends on 8)

The method of claim 8, wherein the at least one reactive gas comprises Cl2 and the at least one non-reactive gas comprises N2.

### Claim 11 (depends on 1)

The method of claim 1, wherein the halogen-containing gas comprises a hydrogen halide.

### Claim 12 (depends on 1)

The method of claim 1, wherein the halogen-containing gas comprises hydrogen bromide (HBr).

### Claim 13 (depends on 1)

The method of claim 1, wherein performing the thermal dry development occurs at a first pressure in the process chamber, and wherein performing the plasma dry development occurs at a second pressure that is lower than the first pressure in the same process chamber, wherein transitioning in the process chamber from the first pressure to the second pressure occurs in ten seconds or less.

### Claim 14 (depends on 1)

The method of claim 1, wherein performing the thermal dry development and performing the plasma dry development occur at a temperature between about −60° C. and about 120° C.

### Claim 15 (depends on 1)

The method of claim 1, wherein performing the thermal dry development and performing the plasma dry development are repeated alternatingly in the same process chamber.

### Claim 16 (depends on 1)

The method of claim 1, wherein the plasma dry development is a cyclic plasma dry development, direct plasma dry development, remote plasma dry development, or continuous plasma dry development.

### Claim 17 (depends on 16)

The method of claim 16, wherein the plasma dry development is continuous plasma dry development, and the continuous plasma dry development is performed at variable power, at constant power and pulsing bias, or at variable power and pulsing bias.

### Claim 18

An apparatus for performing dry development, the apparatus comprising:
a process chamber;
a controller having at least one processor and a memory, wherein the controller is configured with instructions to perform the following operations:
perform a thermal dry development in the process chamber on a semiconductor substrate comprising an EUV-sensitive photoresist film using a halogen-containing gas in a plasma free process, wherein the EUV-sensitive photoresist film comprises EUV-exposed portions and unexposed portions, wherein the thermal dry development selectively removes unexposed portions relative to the EUV-exposed portions to form a patterned photoresist mask; and
perform a plasma dry development after the thermal dry development in the same process chamber on the semiconductor substrate by forming a plasma of at least one reactive gas to descum, wherein the plasma dry development removes residues including byproducts of thermal dry development relative to the EUV-exposed portions, the byproducts having a different composition than the unexposed portions and the exposed portions of the EUV-sensitive photoresist film.

### Claim 19 (depends on 18)

The apparatus of claim 18, wherein the at least one reactive gas comprises one or more halogen-containing gases, one or more hydrogen-containing gases, or a combination thereof.

### Claim 20 (depends on 18)

The apparatus of claim 18, wherein the at least one reactive gas comprises multiple halogen-containing gases, each of the halogen-containing gases selected from the group consisting of: HBr, HCl, Cl2, and BCl3.

### Claim 21 (depends on 18)

The apparatus of claim 18, wherein the at least one reactive gas comprises a combination of one halogen-containing gas selected from HBr, HCl, Cl2, and BCl3, and one hydrogen-containing gas selected from H2 and CH4.

### Claim 22 (depends on 18)

The apparatus of claim 18, wherein the controller configured with instructions to perform plasma dry development by forming plasma with at least one reactive gas is configured with instructions to form plasma with at least one reactive gas and at least one non-reactive gas, wherein the non-reactive gas is selected from the group consisting of: N2, He, Ne, Ar, Kr, and Xe.

### Claim 23 (depends on 18)

The apparatus of claim 18, wherein the halogen-containing gas comprises a hydrogen halide.

### Claim 24 (depends on 18)

The apparatus of claim 18, wherein the halogen-containing gas comprises hydrogen bromide (HBr).

### Claim 25 (depends on 18)

The apparatus of claim 18, further comprising:
one or more pressure-regulating devices; and
one or more pumps fluidly coupled with the one or more pressure-regulating devices, wherein the thermal dry development is performed at a first pressure and the plasma dry development is performed at a second pressure that is less than the first pressure.

### Claim 26 (depends on 18)

The apparatus of claim 18, wherein the controller configured with instructions to perform thermal dry development and plasma dry development is configured with instructions to perform thermal dry development and plasma dry development at a temperature between about −60° C. and about 120° C.

### Claim 27 (depends on 18)

The apparatus of claim 18, wherein the controller is further configured with instructions to repeat alternatingly the thermal dry development and the plasma dry development.

### Claim 28 (depends on 18)

The apparatus of claim 18, wherein the plasma dry development is a cyclic plasma dry development, direct plasma dry development, remote plasma dry development, or continuous plasma dry development.

### Claim 29 (depends on 28)

The method of claim 28, wherein the plasma dry development is continuous plasma dry development, and the continuous plasma dry development is performed at variable power, at constant power and pulsing bias, or at variable power and pulsing bias.