# US 2018/0323056 A1 · Methods for forming a silicon nitride film on a substrate and related semiconductor device structures

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

- Number: US 2018/0323056 A1
- Document ID: US20180323056A1
- Status: Published application
- Kind: A1
- Application number: 15/589,861
- Filed: 2017-05-08
- Published: 2018-11-08
- Earliest claimed: 2017-05-08
- Assignees: ASM IP Holding B.V.
- Applicants: ASM IP Holding B.V.
- Inventors: Jacob Huffman Woodruff; Bed Sharma; Eric James Shero
- Web page: https://patentgrep.com/patent/US20180323056A1

## CPC

- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- C23C 16/345: {Silicon nitride}
- C23C 16/4554: {Plasma being used non-continuously in between ALD reactions (C23C16/56 takes precedence)}
- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- H10P 14/6336: {in the presence of a plasma [PECVD]}
- H10P 14/6532: {by exposure to a plasma}
- H10P 14/6682: {the compound being a silane, e.g. disilane, methylsilane or chlorosilane}
- H10P 14/69433: {the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz}
- H10P 50/283: {by chemical means}
- H10P 76/405: {characterised by their composition, e.g. multilayer masks}
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)

## Abstract

A method for forming a silicon nitride film on a substrate is disclosed. The method may include; forming a cyclical silicon nitride film on the substrate by a cyclical deposition process, wherein the cyclical deposition process comprises at least one of; contacting the substrate with a first reactant comprising a silicon halide source and contacting the substrate with a second reactant comprising a nitrogen source. The method may also include exposing the cyclical silicon nitride film to a plasma. Semiconductor device structures comprising a silicon nitride film are also disclosed.

## Claims

### Claim 1

A method for forming a silicon nitride film on a substrate, the method comprising:
forming a cyclical silicon nitride film on the substrate by a cyclical deposition process, wherein the cyclical deposition process comprises at least one cycle of;
contacting the substrate with a first reactant comprising a silicon halide source, and
contacting the substrate with a second reactant comprising a nitrogen source,
exposing the cyclical silicon nitride film to a plasma; and
passivating a surface of the silicon nitride film.

### Claim 2 (depends on 1)

The method of claim 1, wherein the method comprises at least one complete deposition cycle comprising forming the cyclical silicon nitride film on the substrate by a cyclical deposition process and exposing the cyclical silicon nitride film to the plasma.

### Claim 3 (depends on 2)

The method of claim 2, wherein the complete deposition cycle is repeated two or more times.

### Claim 4 (depends on 1)

The method of claim 1, wherein forming the cyclical silicon nitride film on the substrate by the cyclical deposition process comprises forming the cyclical silicon nitride film with a thickness of between approximately 5 Angstroms and approximately 30 Angstroms.

### Claim 5 (depends on 1)

The method of claim 1, wherein the step of passivating comprises contacting the silicon nitride film with a nitrogen precursor prior to removing the silicon nitride film from a semiconductor processing apparatus.

### Claim 6 (depends on 1)

The method of claim 1, further comprising selecting the silicon halide source to comprise at least one of silicon tetraiodide (SiI4), silicon tetrabromide (SiBr4), silicon tetrachloride (SiCl4), hexaiododisilane (Si2I6), or octoiodotrisilane (Si3I8).

### Claim 7 (depends on 1)

The method of claim 1, further comprising selecting the nitrogen source to comprise an alkyl-hydrazine.

### Claim 8 (depends on 1)

The method of claim 1, wherein exposing the cyclical silicon nitride film to a plasma comprises exposing the cyclical silicon nitride to a plasma for a time period of less than approximately 90 seconds.

### Claim 9 (depends on 1)

The method of claim 1, wherein exposing the cyclical silicon nitride film to the plasma source comprises exposing the cyclical silicon nitride film to a plasma source comprising at least one of nitrogen (N2), helium (He), hydrogen (H2), and argon (Ar).

### Claim 10 (depends on 9)

The method of claim 9, wherein exposing the cyclical silicon nitride film to a plasma source comprises exposing the cyclical silicon nitride film to plasma source comprising helium (He) and nitrogen (N2).

### Claim 11 (depends on 10)

The method of claim 10, wherein exposing the cyclical silicon nitride film to a plasma source comprising helium (He) and nitrogen (N2) comprises a 50%:50% ratio of helium (He) to nitrogen (N2).

### Claim 12 (depends on 1)

The method of claim 1, further comprising heating the substrate to a temperature of less than approximately 250° C.

### Claim 13 (depends on 12)

The method of claim 12, wherein the silicon nitride film has an atomic percentage of hydrogen of less than 15%.

### Claim 14 (depends on 1)

The method of claim 1, wherein the silicon nitride film has a wet etch rate in a 2000:1 H2O:HF solution of approximately less than 5 Angstroms/minute.

### Claim 15 (depends on 1)

The method of claim 1, wherein forming the cyclical silicon nitride film on the substrate by a cyclical deposition process and exposing the cyclical silicon nitride film to a plasma are performed within the same semiconductor processing apparatus.

### Claim 16 (depends on 1)

The method of claim 1, further comprising exposing the substrate to a plasma source prior to forming a cyclical silicon nitride film on the substrate by a cyclical deposition process.

### Claim 17 (depends on 1)

The method of claim 1, wherein exposing the cyclical silicon nitride to a plasma further comprises altering the stress in the silicon nitride layer.

### Claim 18 (depends on 17)

The method of claim 17, wherein altering the stress in the silicon nitride layer further comprises altering the stress from a tensile state to a compressive state.

### Claim 19 (depends on 1)

The method of claim 1, wherein exposing the cyclical silicon nitride to a plasma further comprises altering the degree of bow in the substrate.

### Claim 20 (depends on 1)

The method of claim 1, wherein the step of passivating comprises contacting the silicon nitride film with a nitrogen precursor comprising at least one of ammonia or nitrogen gas plasma prior to removing the silicon nitride film from a semiconductor processing apparatus.

### Claim 21 (depends on 20)

The method of claim 20, wherein the at least one or ammonia or a nitrogen plasma are formed using a remote plasma.

### Claim 22 (depends on 1)

A semiconductor device structure comprising the silicon nitride layer formed by the method of claim 1.

### Claim 23 (depends on 1)

A reaction system configured to perform the method of claim 1.