# US 2019/0378754 A1 · Doping control of metal nitride films

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- Number: US 2019/0378754 A1
- Document ID: US20190378754A1
- Status: Published application
- Kind: A1
- Application number: 16/545,340
- Filed: 2019-08-20
- Published: 2019-12-12
- Earliest claimed: 2013-02-01
- Assignees: Applied Materials, Inc.
- Applicants: Applied Materials, Inc.
- Inventors: Annamalai Lakshmanan; Ben-Li Sheu; Guodan Wei; Nicole Lundy; Paul F. Ma
- Web page: https://patentgrep.com/patent/US20190378754A1

## CPC

- H10W 20/048: {by using plasmas or gaseous environments, e.g. by nitriding}
- H10P 14/432: {using selective deposition}
- H10W 20/032: {of conductive barrier, adhesion or liner layers}
- H10W 20/033: {in openings in dielectrics}
- H10W 20/034: {bottomless barrier, adhesion or liner layers}
- H10W 20/0523: {by irradiating with ultraviolet or particle radiation}
- H10W 20/055: {by formation methods other than physical vapour deposition [PVD], chemical vapour deposition [CVD] or liquid deposition}
- H10W 20/0552: {by diffusing metallic dopants to react with dielectrics}
- H10W 20/076: {in via holes or trenches}
- H10W 20/425: {Barrier, adhesion or liner layers}
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

Described are methods for controlling the doping of metal nitride films such as TaN, TiN and MnN. The temperature during deposition of the metal nitride film may be controlled to provide a film density that permits a desired amount of doping. Dopants may include Ru, Cu, Co, Mn, Mo, Al, Mg, Cr, Nb, Ta, Ti and V. The metal nitride film may optionally be exposed to plasma treatment after doping.

## Claims

### Claim 1

A method for depositing a doped metal nitride film on a substrate, the method comprising:
depositing a metal nitride film on the substrate at a temperature selected to provide a film having a predetermined film density; and
exposing the metal nitride film to a dopant metal precursor to form a doped metal nitride film.

### Claim 2 (depends on 1)

The method of claim 1, wherein the metal nitride film comprises one or more of TaN, TiN and MnN.

### Claim 3 (depends on 1)

The method of claim 1, wherein the metal nitride film is doped with one or more of Ru, Cu, Co, Mn, Mo, Al, Mg, Cr, Nb, Ta, Ti and V.

### Claim 4 (depends on 1)

The method of claim 1, wherein the metal nitride film is deposited at a temperature less than or equal to about 350° C.

### Claim 5 (depends on 1)

The method of claim 1, wherein the metal nitride film comprises one or more of MnN doped with Ru, TaN doped with Mn, MnN doped with Cu or combinations thereof.

### Claim 6 (depends on 1)

The method of claim 1, wherein the predetermined film density is less than or equal to about 8.5 g/cm3.

### Claim 7 (depends on 1)

The method of claim 1, further comprising exposing the metal nitride film to plasma treatment after forming the doped metal nitride film.

### Claim 8 (depends on 1)

The method of claim 1, wherein the doped metal nitride film comprises 0.01 to 30 wt. % dopant.

### Claim 9

A method for controlling doping of a metal nitride film, the method comprising:
controlling temperature during deposition of a metal nitride film to control density of the metal nitride film; and
exposing the metal nitride film to a dopant metal precursor to form a doped metal nitride film.

### Claim 10 (depends on 9)

The method of claim 9, wherein the metal nitride film comprises one or more of TaN, TiN and MnN.

### Claim 11 (depends on 9)

The method of claim 9, wherein the metal nitride film is doped with one or more of Ru, Cu, Co, Mn, Mo, Al, Mg, Cr, Nb, Ta, Ti and V.

### Claim 12 (depends on 9)

The method of claim 9, wherein temperature is controlled such that temperature during deposition of the metal nitride film does not exceed about 350° C.

### Claim 13 (depends on 9)

The method of claim 9, wherein the metal nitride film is deposited via atomic layer deposition.

### Claim 14 (depends on 9)

The method of claim 9, further comprising exposing the metal nitride film to plasma treatment after doping.

### Claim 15 (depends on 9)

The method of claim 9, wherein the doped metal nitride film comprises 0.01 to 30 wt. % dopant.

### Claim 16

A method for depositing a barrier film, the method comprising:
depositing a metal nitride film on a dielectric film on a substrate surface, wherein temperature during deposition of the metal nitride film is controlled to control density of the metal nitride film;
doping the metal nitride film with one or more dopants; and
diffusing one or more of the dopants through the metal nitride film to the dielectric film.

### Claim 17 (depends on 16)

The method of claim 16, wherein the one or more dopants and the dielectric film react to provide a metal oxide film or a metal silicate film.

### Claim 18 (depends on 17)

The method of claim 17, wherein the one or more dopants comprises one or more of Al and Mn and the metal oxide film or metal silicate film comprises one or more of Al2O3, MnO and MnSiOx.

### Claim 19 (depends on 16)

The method of claim 16, wherein temperature during deposition of the metal nitride film is selected to provide a desired amount of doping for the metal nitride film.

### Claim 20 (depends on 16)

The method of claim 16, wherein the one or more dopants has a concentration in a range of 0.01 to 30 wt. %.