# US 12,772,764 B2 · Methods of forming conformal silicon oxycarbonitride thin films on high aspect ratio semiconductor structures

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 12,772,764 B2
- Document ID: US12772764B2
- Status: Granted
- Kind: B2
- Application number: 18/602,159
- Filed: 2024-03-12
- Published: 2025-09-18
- Granted: 2026-10-20
- Earliest claimed: 2024-03-12
- Assignees: Applied Materials, Inc.; National University of Singapore
- Applicants: Applied Materials, Inc.; National University of Singapore
- Inventors: Xinke Wang; Lakmal C. Kalutarage; Bhaskar Jyoti Bhuyan; Mark Saly; John Sudijono; SeyedMahmoud Hosseini; Wei Shi; Yuye Kang
- Web page: https://patentgrep.com/patent/US12772764B2

## CPC

- H10P 14/6927: {the material being a silicon oxynitride, e.g. SiON or SiON:H}
- H10D 64/017: {using dummy gates in processes wherein at least parts of the final gates are self-aligned to the dummy gates, i.e. replacement gate processes}
- H10P 14/6306: {of the semiconductor materials}
- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- H10P 14/6529: {by exposure to a gas or vapour}
- H10P 14/6682: {the compound being a silane, e.g. disilane, methylsilane or chlorosilane}
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES

## Abstract

Methods of depositing high-quality conformal silicon oxycarbonitride (SiOCN) films in the formation of semiconductor devices are described. The methods include a first deposition cycle comprising exposing a semiconductor substrate in a semiconductor processing chamber to a first precursor, a first purge gas, a second precursor, and a second purge gas to deposit a conformal silicon carbonitride (SiCN) film, wherein the first precursor is a silicon- and carbon-containing precursor, and the second precursor comprises one or more of ammonia (NH3), a diamine (NH2—R—NH2 wherein R is an alkyl group), hydrazine (N2H4), and diazene (N2H2). The conformal silicon carbonitride (SiCN) film is then oxidized to form a conformal silicon oxycarbonitride (SiOCN) film, and the conformal silicon oxycarbonitride (SiOCN) film is thermally annealed to form a high-quality conformal silicon oxycarbonitride (SiOCN) film.

## Claims

### Claim 1

A method of depositing a film on a semiconductor device, the method comprising:
a first deposition cycle comprising exposing a semiconductor substrate in a semiconductor processing chamber to a first precursor, a first purge gas, a second precursor, and a second purge gas to deposit a conformal silicon carbonitride (SiCN) film, wherein the first precursor is a silicon- and carbon-containing precursor, and the second precursor comprises one or more of ammonia (NH3), a diamine (NH2—R—NH2 wherein R is an alkyl group), hydrazine (N2H4), and diazene (N2H2);
oxidizing the conformal silicon carbonitride (SiCN) film to form a conformal silicon oxycarbonitride (SiOCN) film; and
thermally annealing the silicon oxycarbonitride (SiOCN) film to form a high-quality conformal silicon oxycarbonitride (SiOCN) film having a wet etch rate less than 10 Å/min in 100:1 dilute hydrofluoric acid (DHF).

### Claim 2 (depends on 1)

The method of claim 1, wherein the high-quality conformal silicon oxycarbonitride (SiOCN) film has a dielectric constant is less than 4.5.

### Claim 3 (depends on 1)

The method of claim 1, wherein oxidizing the conformal silicon carbonitride (SiCN) film comprises exposing the silicon carbonitride (SiCN) film to a third precursor, the third precursor comprising one or more of water (H2O) and hydrogen peroxide (H2O2), or an organic oxidizing agent.

### Claim 4 (depends on 1)

The method of claim 1, wherein oxidizing the conformal silicon carbonitride (SiCN) film comprises exposing the conformal silicon carbonitride (SiCN) film to an oxidizing environment of water (H2O) and oxygen (O2).

### Claim 5 (depends on 1)

The method of claim 1, wherein thermally annealing treating the conformal silicon oxycarbonitride (SiOCN) film with one or more of oxygen (O2), ozone (O3), and an inert gas at a temperature greater than 200° C.

### Claim 6 (depends on 1)

The method of claim 1, wherein the first deposition cycle is repeated n number of times, wherein n is an integer in a range of from 1 to 1000.

### Claim 7 (depends on 1)

The method of claim 1, wherein the first deposition cycle, the oxidizing, and the thermally annealing form a first super cycle that is repeated m number of times, wherein m is an integer in a range of from 1 to 1000.

### Claim 8 (depends on 1)

The method of claim 1, wherein the first deposition cycle and the oxidizing form a second super cycle that is repeated p number of times, wherein p is an integer in a range of from 1 to 1000.

### Claim 9 (depends on 1)

The method of claim 1, wherein the first deposition cycle is performed at a temperature in a range of from 200° C. to 550° C.

### Claim 10 (depends on 1)

The method of claim 1, wherein the first purge gas and the second purge gas are independently selected from argon (Ar), helium (He), and nitrogen (N2).

### Claim 11

A method of manufacturing a gate-all-around device, the method comprising:
in a first deposition cycle, exposing a substrate comprising a dummy gate structure on a top surface of a superlattice structure in a semiconductor processing chamber to a first precursor comprising a silicon- and carbon-containing precursor, a first purge gas, a second precursor comprising one or more of ammonia (NH3), a diamine (NH2—R—NH2 wherein R is an alkyl group), hydrazine (N2H4), and diazene (N2H2), and a second purge gas to deposit a conformal silicon carbonitride (SiCN) film as an inner spacer on the superlattice structure, the superlattice structure including a plurality of semiconductor material layers and a corresponding plurality of release layers alternatingly arranged in a plurality of stacked pairs;
oxidizing the conformal silicon carbonitride (SiCN) film to form a silicon oxycarbonitride (SiOCN) film; and
thermally annealing the conformal silicon oxycarbonitride (SiOCN) film to form a high-quality conformal silicon oxycarbonitride (SiOCN) film having a wet etch rate less than 10 Å/min in 100:1 dilute hydrofluoric acid (DHF).

### Claim 12 (depends on 11)

The method of claim 11, wherein the high-quality conformal silicon oxycarbonitride (SiOCN) film has a dielectric constant is less than 4.5.

### Claim 13 (depends on 11)

The method of claim 11, wherein oxidizing the conformal silicon carbonitride (SiCN) film comprises exposing the conformal silicon carbonitride (SiCN) film to a third precursor, the third precursor comprising one or more of water (H2O) and hydrogen peroxide (H2O2), or an organic oxidizing agent.

### Claim 14 (depends on 11)

The method of claim 11, wherein oxidizing the conformal silicon carbonitride (SiCN) film comprises exposing the conformal silicon carbonitride (SiCN) film to an oxidizing environment of water (H2O) and oxygen (O2).

### Claim 15 (depends on 11)

The method of claim 11, wherein thermally annealing treating the conformal silicon oxycarbonitride (SiOCN) film with one or more of oxygen (O2), ozone (O3), and an inert gas at a temperature greater than 200° C.

### Claim 16 (depends on 11)

The method of claim 11, wherein the first deposition cycle is repeated n number of times, wherein n is an integer in a range of from 1 to 1000.

### Claim 17 (depends on 11)

The method of claim 11, wherein the first deposition cycle, the oxidizing, and the thermally annealing form a first super cycle that is repeated m number of times, wherein m is an integer in a range of from 1 to 1000.

### Claim 18 (depends on 11)

The method of claim 11, wherein the first deposition cycle and the oxidizing form a second super cycle that is repeated p number of times, wherein p is an integer in a range of from 1 to 1000.

### Claim 19 (depends on 11)

The method of claim 11, wherein the first deposition cycle is performed at a temperature in a range of from 200° C. to 550° C.

### Claim 20 (depends on 11)

The method of claim 11, wherein the first purge gas and the second purge gas are independently selected from argon (Ar), helium (He), and nitrogen (N2).