# US 12,000,044 B2 · Catalyzed deposition of metal films

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- Number: US 12,000,044 B2
- Document ID: US12000044B2
- Status: Granted
- Kind: B2
- Application number: 16/448,449
- Filed: 2019-06-21
- Published: 2019-12-26
- Granted: 2024-06-04
- Earliest claimed: 2018-06-22
- Assignees: Applied Materials, Inc.
- Applicants: Applied Materials, Inc.
- Inventors: Sang Ho Yu; Seshadri Ganguli; Byunghoon Yoon; Wei Min Chen
- Web page: https://patentgrep.com/patent/US12000044B2

## CPC

- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- C23C 16/06: characterised by the deposition of metallic material
- C23C 16/45544: {characterized by the apparatus}
- 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

Methods of depositing a metal film with high purity are discussed. Some embodiments utilize a thermal ALD process comprising an alkyl halide and a metal precursor. Some embodiments selectively deposit a metal film with high purity on a metal surface over a dielectric surface. Some embodiments selectively deposit a metal film with high purity on a dielectric surface over a metal surface. Some embodiments deposit a metal film with greater than 99% metal atoms on an atomic basis.

## Claims

### Claim 1

A ruthenium deposition method comprising: maintaining a substrate having a dielectric surface and a metal surface at a deposition temperature while sequentially exposing the substrate to an alkyl halide, the alkyl halide adsorbing to a surface of the substrate to form an activated substrate surface, then exposing the activated substrate surface to a ruthenium precursor to selectively form a ruthenium film on the metal surface over the dielectric surface, the ruthenium precursor having a decomposition temperature above the deposition temperature, and the alkyl halide comprising bromine or iodine, wherein the method is performed without the use of an oxygen-containing reactive gas.

### Claim 2 (depends on 1)

The method of claim 1, wherein the ruthenium precursor comprises a ruthenium atom bonded to one or more of an optionally alkyl substituted benzene ring and an open or closed diene.

### Claim 3 (depends on 1)

The method of claim 1, wherein the alkyl halide consists essentially of iodoethane or diiodomethane.

### Claim 4 (depends on 1)

The method of claim 1, wherein exposing the substrate to the ruthenium precursor and the alkyl halide comprises a cycle, and the ruthenium film is deposited at a rate of greater than or equal to about 0.2 Å/cycle.

### Claim 5 (depends on 1)

The method of claim 1, wherein the ruthenium film has a surface roughness of less than or equal to about 10% of a thickness of the ruthenium film.

### Claim 6 (depends on 1)

The method of claim 1, wherein the ruthenium film has a carbon content less than or equal to about 2% carbon on an atomic basis.

### Claim 7 (depends on 1)

The method of claim 1, wherein the ruthenium film has a purity of greater than or equal to about 97% ruthenium.

### Claim 8 (depends on 1)

The method of claim 1, wherein the halogen of the alkyl halide is insoluble in the ruthenium film.

### Claim 9 (depends on 1)

The method of claim 1, wherein exposing the substrate to the ruthenium precursor and the alkyl halide comprises a cycle, and the ruthenium film is deposited at a rate of greater than or equal to about 0.5 Å/cycle.

### Claim 10

A ruthenium deposition method comprising:
exposing a substrate at a deposition temperature to an alkyl halide (R—X) to adsorb R and X on the substrate;
desorbing R in the form of R—R or R;
exposing the substrate to a ruthenium precursor (M—L);
reacting M—L with the adsorbed X to form M—X; and
reacting M—X with M—X to form M—M,
wherein M—L is thermally stable at the deposition temperature, X is insoluble within M, the bond strength of M—L is less than M—X is less than M—M, and the deposited ruthenium has a purity of greater than or equal to about 97% ruthenium on an atomic basis.

### Claim 11 (depends on 10)

The method of claim 10, wherein R—X is thermally stable at the deposition temperature.

### Claim 12

A method of selectively depositing a ruthenium film, the method comprising:
sequentially exposing a substrate having a first dielectric surface and a second metal surface to a ruthenium precursor and an alkyl halide while the substrate is maintained at a deposition temperature, the alkyl halide comprising bromine or iodine, and both the ruthenium precursor and the alkyl halide having a decomposition temperature above the deposition temperature, wherein a ruthenium film is selectively deposited on the second metal surface over the first dielectric surface.

### Claim 13 (depends on 12)

The method of claim 12, wherein the ruthenium precursor comprises a ruthenium atom bonded to one or more of an optionally alkyl substituted benzene ring and an open or closed diene.

### Claim 14 (depends on 12)

The method of claim 12, wherein the halogen of the alkyl halide is insoluble in the ruthenium film.

### Claim 15 (depends on 12)

The method of claim 12, wherein the alkyl halide consists essentially of iodoethane.

### Claim 16 (depends on 12)

The method of claim 12, wherein exposing the substrate to the ruthenium precursor and the alkyl halide comprises a cycle, and the ruthenium film is deposited at a rate of greater than or equal to about 0.2 Å/cycle.

### Claim 17 (depends on 12)

The method of claim 12, wherein the ruthenium film has a surface roughness of less than or equal to about 10% of thickness.

### Claim 18 (depends on 12)

The method of claim 12, wherein the ruthenium film has a carbon content less than 2% carbon on an atomic basis.

### Claim 19 (depends on 12)

The method of claim 12, wherein the ruthenium film has a purity of greater than or equal to about 97% ruthenium.

### Claim 20 (depends on 12)

The method of claim 12, wherein maintaining the substrate at a deposition temperature below the decomposition temperature of the ruthenium precursor and alkyl halide provides selective deposition of the ruthenium film on the second metal surface without a blocking layer.