# US 2018/0323055 A1 · Methods for selectively forming a silicon nitride film on a substrate and related semiconductor device structures

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- Number: US 2018/0323055 A1
- Document ID: US20180323055A1
- Status: Published application
- Kind: A1
- Application number: 15/589,849
- Filed: 2017-05-08
- Published: 2018-11-08
- Earliest claimed: 2017-05-08
- Assignees: ASM IP Holding B.V.
- Applicants: ASM IP Holding B.V.
- Inventors: Jacob Huffman Woodruff; Bed Sharma
- Web page: https://patentgrep.com/patent/US20180323055A1

## CPC

- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- C23C 16/04: Coating on selected surface areas, e.g. using masks
- C23C 16/345: {Silicon nitride}
- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- C23C 16/56: After-treatment
- H10P 14/6682: {the compound being a silane, e.g. disilane, methylsilane or chlorosilane}
- H10P 14/69433: {the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz}
- H10W 20/077: {on sidewalls or on top surfaces of conductors (H10W20/076 takes precedence)}
- H10W 99/00: Subject matter not provided for in other groups of this subclass
- 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 for selectively forming a silicon nitride film on a substrate comprising a first metallic surface and a second dielectric surface by a cyclical deposition process is disclosed. The method may comprise contacting the substrate with a first reactant comprising a silicon halide source and contacting the substrate with a second reactant comprising a nitrogen source, wherein the incubation period for the first metallic surface is less than the incubation period for the second dielectric surface. Semiconductor device structures comprising a selective silicon nitride film are also disclosed.

## Claims

### Claim 1

A method for selectively forming a silicon nitride film on a substrate comprising a first metallic surface and a second dielectric surface by a cyclical deposition process, the method comprising:
contacting the substrate with a first reactant comprising a silicon halide source, and
contacting the substrate with a second reactant comprising a nitrogen source,
wherein the incubation period for the first metallic surface is less than the incubation period for the second dielectric surface.

### Claim 2 (depends on 1)

The method of claim 1, wherein the nucleation rate of the silicon nitride film is higher on the first metallic surface than on the second dielectric surface.

### Claim 3 (depends on 1)

The method of claim 1, further comprising heating the substrate in a reaction chamber to a temperature of between approximately 225° C. and approximately 280° C.

### Claim 4 (depends on 3)

The method of claim 3, further comprising heating the substrate in the reaction chamber to a temperature of between approximately 225° C. and approximately 250° C.

### Claim 5 (depends on 1)

The method of claim 1, wherein the cyclical deposition process comprises atomic layer deposition.

### Claim 6 (depends on 1)

The method of claim 1, wherein the cyclical deposition process comprises cyclical chemical vapor deposition.

### Claim 7 (depends on 1)

The method of claim 1, wherein the method comprises at least one deposition cycle in which the substrate is alternately and sequentially contacted with the first reactant and the second reactant.

### Claim 8 (depends on 7)

The method of claim 7, wherein the deposition cycle is repeated two or more times.

### Claim 9 (depends on 1)

The method of claim 1, further comprising selecting the silicon halide source to comprise at least one of silicon tetraiodide (SiI4), silicon tetrabromide (SiBr4), silicon tetrachloride (SiCl4), hexachlorodisilane (Si2Cl6), hexaiododisilane (Si2I6) or octoiodotrisilane (Si3I8).

### Claim 10 (depends on 1)

The method of claim 1, further comprising selecting the nitrogen source to comprise at least one of ammonia (NH3), hydrazine (N2H4) or an alkyl-hydrazine.

### Claim 11 (depends on 1)

The method of claim 1, wherein the incubation period for the second dielectric surface is approximately less than 100 cycles.

### Claim 12 (depends on 1)

The method of claim 1, wherein the incubation period for the first metallic surface is approximately less than 20 cycles.

### Claim 13 (depends on 1)

The method of claim 1, further comprising selecting the first metallic surface to comprise at least one of titanium nitride (TiN), titanium silicon nitride (TiSiN), tantalum nitride (TaN), tantalum silicon nitride (TaSiN), tungsten (W), molybdenum (Mo), silicon (Si), silicon germanium (SiGe), germanium antimony tellurium (GeSbTe), cobalt (Co), tantalum silicide (TaSi), titanium silicide (TiSi), gallium arsenide (GaAs) or gallium nitride (GaN).

### Claim 14 (depends on 1)

The method of claim 1, further comprising selecting the second dielectric surface to comprise at least one of a silicon oxide (SiO), a silicon nitride (SiN), a silicon oxynitride (SiON), carbon (C), hafnium oxide (HfO), zirconium oxide (ZrO), aluminum oxide (AlO), titanium oxide (TiO) or silicon oxycarbide (SiOC).

### Claim 15 (depends on 1)

The method of claim 1, further comprising forming the silicon nitride film to a first thickness over the first metallic surface and forming the silicon nitride film to a second thickness over the second dielectric surface, wherein the first thickness is greater than the second thickness.

### Claim 16 (depends on 15)

The method of claim 15, further comprising etching the silicon nitride film over the second dielectric surface until it is substantially removed and simultaneously etching the silicon nitride film over the first metallic surface until it is partially removed.

### Claim 17 (depends on 16)

The method of claim 16, wherein etching comprises atomic layer etching.

### Claim 18 (depends on 17)

The method of claim 17, wherein the forming of the silicon nitride film and the atomic layer etching are performed in a cluster tool.

### Claim 19 (depends on 16)

The method of claim 16, wherein the processes of etching and selectively forming a silicon nitride film are repeated two or more times.

### Claim 20 (depends on 1)

The method of claim 1, further comprising preheating the silicon halide source to a temperature of approximately less than 100° C.

### Claim 21 (depends on 1)

A semiconductor device structure comprising the silicon nitride film formed by the method of claim 1.

### Claim 22 (depends on 1)

A reaction system configured to perform the method of claim 1.