# US 11,908,736 B2 · Methods for depositing a molybdenum metal film over a dielectric surface of a substrate by a cyclical deposition process and related semiconductor device structures

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- Number: US 11,908,736 B2
- Document ID: US11908736B2
- Status: Granted
- Kind: B2
- Application number: 17/700,635
- Filed: 2022-03-22
- Published: 2022-07-07
- Granted: 2024-02-20
- Earliest claimed: 2017-08-30
- Assignees: ASM IP Holding B.V.
- Applicants: ASM IP Holding B.V.
- Inventors: Bhushan Zope; Kiran Shrestha; Shankar Swaminathan; Chiyu Zhu; Henri Jussila; Qi Xie
- Web page: https://patentgrep.com/patent/US11908736B2

## CPC

- H10W 20/045: {for deposition from the gaseous phase, e.g. for chemical vapour deposition [CVD]}
- C23C 16/0272: {Deposition of sub-layers, e.g. to promote the adhesion of the main coating}
- C23C 16/045: {Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates}
- C23C 16/14: Deposition of only one other metal element
- C23C 16/45525: {Atomic layer deposition [ALD]}
- H10P 14/412: {Deposition of metallic or metal-silicide materials}
- H10P 14/418: {the conductive layers comprising transition metals}
- H10P 14/432: {using selective deposition}
- H10W 20/056: {by filling conductive material into holes, grooves 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
- 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)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

Methods for depositing a molybdenum metal film over a dielectric surface of a substrate by a cyclical deposition process are disclosed. The methods may include: providing a substrate comprising a dielectric surface into a reaction chamber; depositing a nucleation film directly on the dielectric surface; and depositing a molybdenum metal film directly on the nucleation film, wherein depositing the molybdenum metal film includes: contacting the substrate with a first vapor phase reactant comprising a molybdenum halide precursor; and contacting the substrate with a second vapor phase reactant comprising a reducing agent precursor. Semiconductor device structures including a molybdenum metal film disposed over a surface of a dielectric material with an intermediate nucleation film are also disclosed.

## Claims

### Claim 1

A method for depositing a molybdenum metal film over a dielectric surface of a substrate by a cyclical deposition process, the method comprising:
providing a substrate comprising a dielectric surface into a reaction chamber;
depositing a nucleation film comprising a silicon compound material directly on the dielectric surface, wherein depositing the nucleation film comprises repeating unit cycles of the cyclical deposition process to form the nucleation film having a thickness of less than 10 Angstroms, wherein at least one of the unit cycles comprises:
contacting the substrate with a first vapor phase reactant comprising a silicon precursor; and
contacting the substrate with a second vapor phase reactant comprising at least one of a nitrogen precursor, an oxygen precursor, or a carbon precursor, wherein the nitrogen precursor comprises at least one of ammonia, hydrazine, triazane, tertbutylhydrazine, methylhydrazine, dimethylhydrazine, or a nitrogen plasma, wherein the oxygen precursor comprises at least one of water, hydrogen peroxide, ozone, or an oxide of nitrogen comprising at least one of nitrogen monoxide, nitrous oxide, or nitrogen dioxide, and wherein the carbon precursor comprises a hydrocarbon; and
depositing a molybdenum metal film directly on the nucleation film, wherein depositing the molybdenum metal film comprises:
contacting the substrate with a first vapor phase reactant comprising a molybdenum halide precursor; and
contacting the substrate with a second vapor phase reactant comprising a reducing agent precursor.

### Claim 2 (depends on 1)

The method of claim 1, wherein the silicon compound material comprises a silicon binary compound material.

### Claim 3 (depends on 2)

The method of claim 2, wherein the silicon binary compound material comprises at least one of a silicon nitride, a silicon carbide, or a silicon oxide.

### Claim 4 (depends on 1)

The method of claim 1, wherein the molybdenum metal film has a r.m.s. surface roughness (Ra) of less than 5 percent of the total thickness of the molybdenum metal film.

### Claim 5 (depends on 1)

The method of claim 1, wherein depositing the molybdenum metal film further comprises heating the substrate to substrate temperature of less than 600° C.

### Claim 6 (depends on 1)

The method of claim 1, wherein depositing the molybdenum metal film further comprises heating the substrate to substrate temperature of between 400° C. and 700° C.

### Claim 7 (depends on 1)

The method of claim 1, wherein the molybdenum halide precursor comprises a molybdenum chalcogenide halide.

### Claim 8 (depends on 7)

The method of claim 7, wherein the molybdenum chalcogenide halide comprises a molybdenum oxyhalide selected from the group comprising: a molybdenum oxychloride, a molybdenum oxyiodide, or a molybdenum oxybromide.

### Claim 9 (depends on 8)

The method of claim 8, wherein the molybdenum oxychloride comprises molybdenum (IV) dichloride dioxide (MoO2Cl2).

### Claim 10 (depends on 1)

The method of claim 1, wherein the molybdenum metal film is a crystalline film.

### Claim 11 (depends on 1)

The method of claim 1, wherein the dielectric surface comprises a gap feature and the molybdenum metal film fills the gap feature without the formation of a seam.

### Claim 12 (depends on 1)

The method of claim 1, wherein the molybdenum halide precursor is selected from the group consisting of a molybdenum chalcogenide halide and a molybdenum oxyhalide.

### Claim 13 (depends on 1)

The method of claim 1, wherein the nucleation film is a discontinuous film.

### Claim 14 (depends on 1)

The method of claim 1, wherein depositing molybdenum metal film comprises repeating unit cycles of the cyclical deposition process to form the molybdenum metal film having a thickness of between 50 Angstroms and 200 Angstroms.

### Claim 15 (depends on 1)

The method of claim 1, wherein providing the substrate comprises providing an engineered substrate, wherein the dielectric surface is disposed over a bulk support with an intervening buried oxide (BOX) layer disposed therebetween.

### Claim 16 (depends on 1)

The method of claim 1, wherein the thickness of the nucleation film is less than 5 Angstroms.

### Claim 17 (depends on 1)

The method of claim 1, wherein the thickness of the nucleation film is less than 3 Angstroms.