# US 12,119,221 B2 · PEALD nitride films

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- Number: US 12,119,221 B2
- Document ID: US12119221B2
- Status: Granted
- Kind: B2
- Application number: 18/125,509
- Filed: 2023-03-23
- Published: 2023-07-20
- Granted: 2024-10-15
- Earliest claimed: 2019-09-19
- Assignees: Applied Materials, Inc.
- Applicants: Applied Materials, Inc.
- Inventors: Hanhong Chen; Philip A. Kraus; Joseph AuBuchon
- Web page: https://patentgrep.com/patent/US12119221B2

## CPC

- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- C23C 16/34: Nitrides {(C23C16/303 takes precedence)}
- C23C 16/45542: {Plasma being used non-continuously during the ALD reactions}
- H10P 14/432: {using selective deposition}
- H10P 14/6336: {in the presence of a plasma [PECVD]}
- H10P 14/668: {the materials being characterised by the deposition precursor materials}
- H10P 14/6682: {the compound being a silane, e.g. disilane, methylsilane or chlorosilane}
- H10P 14/69394: {the material containing titanium, e.g. TiO2}
- H10P 14/69433: {the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz}
- H10W 20/032: {of conductive barrier, adhesion or liner layers}
- 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)
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10

## Abstract

A method of depositing nitride films is disclosed. Some embodiments of the disclosure provide a PEALD process for depositing nitride films which utilizes separate reaction and nitridation plasmas. In some embodiments, the nitride films have improved growth per cycle (GPC) relative to films deposited by thermal processes or plasma processes with only a single plasma exposure. In some embodiments, the nitride films have improved film quality relative to films deposited by thermal processes or plasma processes with only a single plasma exposure.

## Claims

### Claim 1

A method of depositing a nitride film, the method comprising:
exposing a substrate to a precursor to form a reactive species on the substrate;
exposing the reactive species to a first plasma gas flow formed from a first plasma gas to form an activated species, the first plasma gas comprising N2; and
exposing the activated species to a second plasma gas flow formed from a second plasma gas to form the nitride film, the second plasma gas comprising NH3, wherein the first plasma gas flow and the second plasma gas flow are separated by a purge gas, and the method defines a deposition cycle, and the deposition cycle is repeated until a predetermined thickness of the nitride film has been formed.

### Claim 2 (depends on 1)

The method of claim 1, wherein the nitride film comprises one or more of Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, or W.

### Claim 3 (depends on 2)

The method of claim 2, wherein the nitride film comprises TiN.

### Claim 4 (depends on 3)

The method of claim 3, wherein the precursor consists essentially of TiCl4.

### Claim 5 (depends on 3)

The method of claim 3, wherein the TIN film grows at a rate of greater than or equal to 0.3 Å/cycle.

### Claim 6 (depends on 5)

The method of claim 5, wherein the TIN film has a stress of less than or equal to 800 MPa.

### Claim 7 (depends on 5)

The method of claim 5, wherein the TIN film has a bulk resistivity of less than or equal to 200μΩ·cm.

### Claim 8 (depends on 1)

The method of claim 1, wherein the nitride film comprises one or more of Al, Ga, In, Si, Ge, or Sn.

### Claim 9 (depends on 8)

The method of claim 8, wherein the nitride film comprises SiN.

### Claim 10 (depends on 9)

The method of claim 9, wherein the precursor consists essentially of SiH2Cl2.

### Claim 11 (depends on 9)

The method of claim 9, wherein the SiN film grows at a rate of greater than or equal to 0.5 Å/cycle.

### Claim 12 (depends on 1)

The method of claim 1, wherein NH3 is pulsed into the second plasma gas.

### Claim 13 (depends on 1)

The method of claim 1, wherein the first plasma gas and the second plasma gas comprise Ar.

### Claim 14 (depends on 1)

The method of claim 1, wherein one or both of the first plasma gas flow and the second plasma gas flow are generated by a microwave plasma.

### Claim 15 (depends on 1)

The method of claim 1, wherein one or both of the first plasma gas flow and the second plasma gas flow are generated by a hot wire.

### Claim 16

A method of depositing a silicon nitride film, the method comprising:
exposing a substrate to SiH2Cl2 to form a silicon species on the substrate;
exposing the silicon species to a first plasma gas flow formed from a first plasma gas comprising N2 and Ar to form an activated species; and
exposing the activated species to a second plasma gas flow formed from a second plasma gas comprising NH3 and Ar to form the silicon nitride film, wherein the first plasma gas flow and the second plasma gas flow are separated by a purge gas, the method defines a deposition cycle, and the deposition cycle is repeated to form a silicon nitride film of a predetermined thickness.