# US 12,014,956 B2 · Tungsten gapfill using molybdenum co-flow

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- Number: US 12,014,956 B2
- Document ID: US12014956B2
- Status: Granted
- Kind: B2
- Application number: 17/488,275
- Filed: 2021-09-28
- Published: 2023-04-06
- Granted: 2024-06-18
- Earliest claimed: 2021-09-28
- Assignees: Applied Materials, Inc.
- Applicants: Applied Materials, Inc.
- Inventors: Xi Cen; Kai Wu
- Web page: https://patentgrep.com/patent/US12014956B2

## CPC

- H10W 20/056: {by filling conductive material into holes, grooves or trenches}
- H10W 20/057: {by selectively depositing, e.g. by using selective CVD or plating}
- 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 16/08: from metal halides
- C23C 16/52: Controlling or regulating the coating process {(C23C16/45557, C23C16/279 take precedence)}
- H10P 14/43: Chemical deposition, e.g. chemical vapour deposition [CVD]
- H10W 20/033: {in openings in dielectrics}
- H10W 20/045: {for deposition from the gaseous phase, e.g. for chemical vapour deposition [CVD]}
- H10W 20/4441: {the principal metal being a refractory metal}
- 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

Some embodiments of the disclosure relate to methods for forming a bottom-up tungsten gapfill. Some embodiments of the disclosure relate to methods for reducing the deposition rate of tungsten by chemical vapor deposition. A molybdenum halide precursor is added to a tungsten halide precursor and a reductant. The co-flow of tungsten halide and molybdenum halide demonstrates either reduced or eliminated tungsten growth.

## Claims

### Claim 1

A method of forming bottom-up tungsten gapfill, the method comprising simultaneously exposing a substrate with a feature therein to flows of a tungsten halide, a molybdenum halide and a reductant, the tungsten halide comprising WF6 and the molybdenum halide comprising MoF6, and a ratio of a flow rate of WF6:MoF6 is in a range of 5:1 to 100:1, the feature defined by a depth from a top surface of the substrate to a bottom and width between two sidewalls, wherein tungsten is formed on the bottom without substantial deposition on the top surface of the substrate.

### Claim 2 (depends on 1)

The method of claim 1, wherein the feature has an aspect ratio of greater than or equal to 20:1.

### Claim 3 (depends on 1)

The method of claim 1, wherein the tungsten halide and the molybdenum halide comprise the same halogen.

### Claim 4 (depends on 1)

The method of claim 1, wherein the reductant comprises H2.

### Claim 5 (depends on 1)

The method of claim 1, wherein the substrate is maintained at a temperature in a range of 350° C. to 550° C.

### Claim 6 (depends on 1)

The method of claim 1, wherein a processing pressure is maintained in a range of 3 Torr to 90 Torr.

### Claim 7 (depends on 1)

The method of claim 1, wherein the feature is lined with a barrier layer.

### Claim 8 (depends on 7)

The method of claim 7, wherein the barrier layer comprises TiN.

### Claim 9 (depends on 1)

The method of claim 1, wherein the tungsten gapfill is formed on a nucleation layer.

### Claim 10 (depends on 9)

The method of claim 9, wherein the nucleation layer is deposited by sequentially exposing the feature to WF6 and a reductant comprising one or more of B2H6, SiH4 or H2.

### Claim 11 (depends on 1)

The method of claim 1, further comprising exposing the substrate to a nitrogen-treatment before forming the forming the tungsten gapfill.

### Claim 12 (depends on 11)

The method of claim 11, wherein the nitrogen treatment comprises one or more of nitrogen radicals, nitrogen ions or thermal ammonia.