# US 10,865,475 B2 · Deposition of metal borides and silicides

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- Number: US 10,865,475 B2
- Document ID: US10865475B2
- Status: Granted
- Kind: B2
- Application number: 15/135,258
- Filed: 2016-04-21
- Published: 2017-10-26
- Granted: 2020-12-15
- Earliest claimed: 2016-04-21
- Assignees: ASM IP Holding B.V.
- Applicants: ASM IP Holding B.V.
- Inventors: Petri Raisanen; Eric Shero; Suvi Haukka; Robert Brennan Milligan; Michael Eugene Givens
- Web page: https://patentgrep.com/patent/US10865475B2

## CPC

- C23C 16/38: Borides
- C23C 16/42: Silicides
- C23C 16/45525: {Atomic layer deposition [ALD]}
- 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 depositing a metal film onto a substrate is disclosed. In particular, the method comprises pulsing a metal halide precursor onto the substrate and pulsing a reducing precursor onto the substrate. A reaction between the metal halide precursor and the reducing precursor forms a metal film. Specifically, the method discloses forming a metal boride or a metal silicide film.

## Claims

### Claim 1

A method of forming a metal boride or a metal silicide comprising:
providing a substrate for processing in a reaction chamber;
performing a metal halide precursor deposition onto the substrate, the performing the metal halide precursor deposition step comprises:
maintaining a metal halide precursor at a first temperature prior to the metal halide entering into the reaction chamber;
pulsing the metal halide precursor onto the substrate; and
purging an excess of the metal halide precursor from the reaction chamber; and
performing a reducing precursor deposition onto the substrate, the performing the reducing precursor deposition step comprises:
maintaining a reducing precursor at a second temperature prior to the reducing precursor entering into the reaction chamber;
pulsing the reducing precursor onto the substrate; and
purging an excess of the reducing precursor from the reaction chamber;
wherein the metal halide precursor comprises one of: niobium tetrabromide (NbBr4), niobium tetraiodide (NbI4), zirconium tetrabromide (ZrBr4), zirconium tetraiodide (ZrI4), molybdenum pentabromide (MoBr5), molybdenum hexabromide (MoBr6), molybdenum pentaiodide (MoI5), or molybdenum hexaiodide (MoI6);
wherein a reaction between the metal halide precursor and the reducing precursor forms a film of: niobium diboride (NbB2), zirconium diboride (ZrB2), molybdenum boride (MoB), niobium silicide (NbSi2), zirconium silicide (ZrSi2), or molybdenum disilicide (MoSi2);
wherein a pressure of the reaction chamber ranges between 0.5 and 8 Torr;
wherein the first temperature is different than the second temperature;
wherein the metal precursor deposition step is repeated a predetermined number of times; and
wherein the reducing precursor deposition step is repeated a predetermined number of times.

### Claim 2 (depends on 1)

The method of claim 1, wherein the reducing precursor comprises at least one of: silane (SiH4), disilane (Si2H6), trisilane (Si3H8), amine boranes, cyclic borides, and borazines.

### Claim 3 (depends on 1)

The method of claim 1, wherein a temperature of the reaction chamber ranges between 200 and 400° C.

### Claim 4 (depends on 1)

The method of claim 1, wherein the reducing precursor comprises borane, diborane, triborane, tetraborane, pentaborane, hexaborane, heptaborane, octaborane, nonaborane, decaborane, or other borane compound that consist of boron and hydrogen, cyclic borides, borazines, and borane compounds that do not include carbon.

### Claim 5 (depends on 1)

The method of claim 1, wherein the first temperature is higher than the second temperature.

### Claim 6 (depends on 1)

The method of claim 1, wherein the film comprises niobium diboride (NbB2), zirconium diboride (ZrB2), or molybdenum boride (MoB).

### Claim 7 (depends on 1)

The method of claim 1, wherein purging the excess of the metal halide precursor comprises purging the reaction chamber with at least one of: nitrogen (N2), argon (Ar), helium (He), hydrogen (H2), or other rare gases.

### Claim 8 (depends on 1)

The method of claim 1, wherein purging the excess of the reducing precursor comprises purging the reaction chamber with at least one of: nitrogen (N2), argon (Ar), helium (He), hydrogen (H2), or other rare gases.

### Claim 9

A method of forming a metal boride or a metal silicide for NMOS applications comprising:
providing a substrate for processing in a reaction chamber;
performing a metal halide precursor deposition onto the substrate, the performing the metal halide precursor deposition step comprises:
maintaining a metal halide precursor at a first temperature prior to the metal halide entering into the reaction chamber;
pulsing the metal halide precursor onto the substrate; and
purging an excess of the metal halide precursor from the reaction chamber; and
performing a reducing precursor deposition onto the substrate, the performing the reducing precursor deposition step comprises:
maintaining a reducing precursor at a second temperature prior to the reducing precursor entering into the reaction chamber;
pulsing the reducing precursor onto the substrate; and
purging an excess of the reducing precursor from the reaction chamber;
wherein a temperature of the reaction chamber ranges between 200° C. and 400° C.;
wherein the first temperature is different than the second temperature;
wherein the metal halide precursor comprises one of: niobium tetrabromide (NbBr4), niobium tetraiodide (NbI4), zirconium tetrabromide (ZrBr4), zirconium tetraiodide (ZrI4), molybdenum pentabromide (MoBr5), molybdenum hexabromide (MoBr6), molybdenum pentaiodide (MoI5), or molybdenum hexaiodide (MoI6); and
wherein a reaction between the metal halide precursor and the reducing precursor forms a film of: niobium diboride (NbB2), zirconium diboride (ZrB2), molybdenum boride (MoB), niobium silicide (NbSi2), zirconium silicide (ZrSi2), or molybdenum disilicide (MoSi2).

### Claim 10 (depends on 9)

The method of claim 9, wherein the reducing precursor comprises at least one of: silane (SiH4), disilane (Si2H6), trisilane (Si3H8), borane (BH3), diborane (B2H6), triborane (B3H8), tetraborane (B4H10), pentaborane, hexaborane, heptaborane, octaborane, nonaborane, decaborane, borane compounds that consist of only boron and hydrogen, amine boranes, cyclic borides, borazines, and borane compounds that do not include carbon, and other boron-containing precursors.

### Claim 11 (depends on 9)

The method of claim 9, wherein the film comprises zirconium diboride (ZrB2), zirconium silicide (ZrSi2), or molybdenum disilicide (MoSi2).

### Claim 12 (depends on 9)

The method of claim 9, wherein a pressure of the reaction chamber ranges between 0.5 and 8 Torr.

### Claim 13 (depends on 9)

The method of claim 9, wherein the pulsing the metal halide precursor has a duration of 0.1 and 10 seconds.

### Claim 14 (depends on 9)

The method of claim 9, wherein the film niobium diboride (NbB2), zirconium diboride (ZrB2), or molybdenum boride (MoB).

### Claim 15 (depends on 9)

The method of claim 9, further comprising repeating the step of performing a metal halide precursor deposition prior to the step of performing a reducing precursor deposition.

### Claim 16 (depends on 9)

The method of claim 9, further comprising, after the step of performing a reducing precursor deposition, repeating the step of performing a reducing precursor deposition prior to a step of repeating the step of performing a metal halide precursor deposition.

### Claim 17 (depends on 9)

The method of claim 9, wherein the film has a concentration of Boron or Silicon from about 30 to about 80 at. %.

### Claim 18 (depends on 9)

The method of claim 9, wherein the film has a concentration of a metal from about 20 to about 70 at. %.

### Claim 19 (depends on 9)

The method of claim 9, wherein the film has a concentration of Oxygen of less than 5 at. %.

### Claim 20 (depends on 9)

The method of claim 9, wherein the film has a concentration of Hydrogen of less than 5 at. %.

### Claim 21 (depends on 9)

The method of claim 9, wherein the film has a concentration of a halide of less than 5 at. %.