# US 11,440,060 B2 · Method for cleaning substrate

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- Number: US 11,440,060 B2
- Document ID: US11440060B2
- Status: Granted
- Kind: B2
- Application number: 16/828,743
- Filed: 2020-03-24
- Published: 2021-04-01
- Granted: 2022-09-13
- Earliest claimed: 2019-09-27
- Assignees: Taiwan Semiconductor Manufacturing Company, Ltd.
- Applicants: Taiwan Semiconductor Manufacturing Company Ltd.
- Inventors: Hao-Ming Chang; Chia-Shih Lin
- Web page: https://patentgrep.com/patent/US11440060B2

## CPC

- B08B 3/08: the liquid having chemical or dissolving effect
- B08B 3/12: by sonic or ultrasonic vibrations
- G03F 1/24: Reflection masks; Preparation thereof
- G03F 1/82: Auxiliary processes, e.g. cleaning or inspecting
- H10P 70/23: {during, before or after processing of insulating materials}
- H10P 70/27: {during, before or after processing of conductive materials, e.g. polysilicon or amorphous silicon layers}
- B08B 2203/005: the liquid being ozonated
- B08B: CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- 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 cleaning a substrate includes receiving a photomask substrate comprising a multilayered reflective structure disposed over a surface of the photomask substrate, a capping layer disposed on the multilayered reflective structure and an absorber, wherein the photomask substrate has a plurality of conductive nanoparticles disposed over the surface; applying a first mixture comprising a SC1 solution, a DI water and O3 to the photomask substrate to remove the conductive nanoparticles; and applying a DI water to rinse the photomask substrate. A removal rate of the conductive nanoparticles is greater than approximately 90%.

## Claims

### Claim 1

A method for cleaning a substrate, comprising:
receiving a photomask substrate with a multilayered reflective structure disposed over a surface of the photomask substrate, a capping layer disposed on the multilayered reflective structure, and an absorber, wherein the photomask substrate has a plurality of conductive nanoparticles disposed over a surface of the multilayered reflective structure;
applying a first mixture comprising an SC1 solution, deionized (DI) water, and ozone (O3) to the photomask substrate to remove the conductive nanoparticles, wherein a temperature of the first mixture is between approximately 20° C. and 40° C.;
applying a second mixture to the photomask substrate, wherein the second mixture comprises DI water and H2; and
applying DI water to rinse the photomask substrate,
wherein the applying of the first mixture further comprises a mega sonic agitation, and a frequency of the mega sonic agitation is greater than 3 MHz,
wherein a flow rate of the first mixture is between approximately 1000 ml/min and approximately 5000 ml/min, a flow rate of the second mixture is between approximately 1000 ml/min and approximately 3000 ml/min, and a removal rate of the conductive nanoparticles over a duration including the applying of the first mixture and the applying of the DI water is greater than approximately 90%.

### Claim 2 (depends on 1)

The method of claim 1, wherein the multilayered reflective structure comprises a Ru/Si multilayered reflective structure, a Mo/Be multilayered reflective structure, a Mo compound/Si compound multilayered reflective structure, a Si/Mo/Ru multilayered reflective structure, a Si/Mo/Ru/Mo multilayered reflective structure or a Si/Ru/Mo/Ru multilayered reflective structure.

### Claim 3 (depends on 1)

The method of claim 1, wherein the capping layer comprises a Ru-containing layer.

### Claim 4 (depends on 1)

The method of claim 1, wherein the conductive nanoparticles comprise noble metals.

### Claim 5 (depends on 1)

The method of claim 1, further comprising performing a spin respectively after the applying of the first mixture and the applying of the DI water.

### Claim 6

A method for cleaning a substrate, comprising:
receiving a photomask substrate with a phase-shifting layer disposed over a surface of the photomask substrate and a shielding layer disposed on the phase-shifting layer, wherein the photomask substrate has a plurality of conductive nanoparticles disposed over a surface of shielding layer;
applying a first mixture comprising an SC1 solution, deionized (DI) water, and ozone (O3) to the substrate to remove the conductive nanoparticles, wherein a temperature of the first mixture is between approximately 20° C. and 40° C.;
applying a second mixture to the photomask substrate, wherein the second mixture comprises DI water and H2; and
applying a DI water to rinse the photomask substrate,
wherein the applying of the first mixture further comprises a mega sonic agitation, and a frequency of the mega sonic agitation is greater than approximately 3 MHz,
wherein a flow rate of the first mixture is between approximately 1000 ml/min and approximately 5000 ml/min, a flow rate of the second mixture is between approximately 1000 ml/min and approximately 3000 ml/min, and a removal rate of the conductive nanoparticles over a duration including the applying of the first mixture and the applying of the DI water is greater than approximately 90%.

### Claim 7 (depends on 6)

The method of claim 6, wherein the phase-shifting layer comprises molybdenum silicide (MoSi), molybdenum-silicide-nitride (MoSiN), molybdenum silicide oxynitride (MoSiON), titanium nitride, titanium silicon nitride or silicon nitride.

### Claim 8 (depends on 6)

The method of claim 6, wherein the shielding layer comprises chromium (Cr), chromium oxide, chromium nitride and chromium oxynitride.

### Claim 9

A method for cleaning a substrate, comprising:
receiving a semiconductor substrate having a surface and a plurality of patterns disposed on the surface, wherein the semiconductor substrate has a plurality of conductive nanoparticles disposed over the surface of the semiconductor substrate;
applying a first mixture comprising an SC1 solution, deionized (DI) water, and ozone (O3) to the semiconductor substrate to remove the conductive nanoparticles, wherein a temperature of the first mixture is between approximately 20° C. and 40° C.;
applying a second mixture to the semiconductor substrate, wherein the second mixture comprises DI water and H2; and
applying a DI water to rinse the semiconductor substrate,
wherein the applying of the first mixture further comprises a mega sonic agitation, and a frequency of the mega sonic agitation is greater than approximately 3 MHz,
wherein a flow rate of the first mixture is between approximately 1000 ml/min and approximately 5000 ml/min, a flow rate of the second mixture is between approximately 1000 ml/min and approximately 3000 ml/min, and a removal rate of the conductive nanoparticles over a duration including the applying of the first mixture and the applying of the DI water is greater than approximately 90%.

### Claim 10 (depends on 9)

The method of claim 9, wherein the patterns comprise insulative materials.

### Claim 11 (depends on 10)

The method of claim 10, wherein a duration of the applying of the first mixture is less than approximately 10 minutes.

### Claim 12 (depends on 1)

The method of claim 1, wherein the conductive nanoparticles are in a scale of approximately 1 nanometer to approximately 100 nanometers in size.

### Claim 13 (depends on 6)

The method of claim 6, wherein the conductive nanoparticles comprise noble metals.

### Claim 14 (depends on 1)

The method of claim 1, wherein the frequency of the mega sonic agitation is between greater than 3 MHz and approximately 10 MHz.

### Claim 15 (depends on 6)

The method of claim 6, wherein the frequency of the mega sonic agitation is between greater than 3 MHz and approximately 10 MHz.

### Claim 16 (depends on 9)

The method of claim 9, wherein the frequency of the mega sonic agitation is between greater than 3 MHz and approximately 10 MHz.

### Claim 17 (depends on 1)

The method of claim 1, wherein a duration of the applying of the first mixture is between approximately 8 minutes and approximately 15 minutes.

### Claim 18 (depends on 1)

The method of claim 1, wherein a temperature of the second mixture is between approximately 20° C. and 40° C.

### Claim 19 (depends on 1)

The method of claim 1, wherein a duration of the applying of the second mixture is between approximately 5 minutes and approximately 15 minutes.

### Claim 20 (depends on 6)

The method of claim 6, wherein a temperature of the second mixture is between approximately 20° C. and 40° C.