# US 2014/0154883 A1 · Tungsten nucleation process to enable low resistivity tungsten feature fill

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- Number: US 2014/0154883 A1
- Document ID: US20140154883A1
- Status: Published application
- Kind: A1
- Application number: 14/173,733
- Filed: 2014-02-05
- Published: 2014-06-05
- Earliest claimed: 2009-04-16
- Assignees: Lam Research Corporation
- Applicants: Lam Research Corporation
- Inventors: Raashina Humayun; Sudha Manandhar; Michal Danek
- Web page: https://patentgrep.com/patent/US20140154883A1

## CPC

- H10P 14/43: Chemical deposition, e.g. chemical vapour deposition [CVD]
- C23C 16/0281: {of metallic sub-layers (C23C16/029 takes precedence)}
- 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 14/432: {using selective deposition}
- H10P 72/0468: {comprising a chamber adapted to a particular process}
- H10W 20/045: {for deposition from the gaseous phase, e.g. for chemical vapour deposition [CVD]}
- H10W 20/052: {by treatments not introducing additional elements therein}
- H10W 20/056: {by filling conductive material into holes, grooves or trenches}
- 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

Methods for depositing low resistivity tungsten in features of substrates in semiconductor processing are disclosed herein. Methods involve using a germanium-containing reducing agent during tungsten nucleation layer deposition to achieve thin, low resistivity nucleation layers.

## Claims

### Claim 1

A method of filling a feature on a substrate with tungsten, the method comprising:
prior to depositing a bulk tungsten layer, forming a tungsten nucleation layer by exposing the feature to alternating pulses of a germanium-containing reducing agent and a tungsten-containing precursor.

### Claim 2 (depends on 1)

The method of claim 1, wherein the tungsten nucleation layer is formed to a thickness between about 1 nm and about 20 nm.

### Claim 3 (depends on 1)

The method of claim 1, wherein the tungsten nucleation layer is formed to a thickness less than about 1 nm.

### Claim 4 (depends on 1)

The method of claim 1, wherein the amount of tungsten deposited per cycle is less than about 8 Å.

### Claim 5 (depends on 1)

The method of claim 1, wherein the tungsten nucleation layer is formed in a hydrogen atmosphere.

### Claim 6 (depends on 1)

The method of claim 1, wherein substantially all of the tungsten formed in the feature comprises alpha-tungsten.

### Claim 7 (depends on 1)

The method of claim 1, wherein the germanium-containing reducing agent is germane (GeH4) or digermane (Ge2H6).

### Claim 8 (depends on 1)

The method of claim 1, further comprising depositing a bulk tungsten layer on the tungsten nucleation layer by chemical vapor deposition.

### Claim 9 (depends on 8)

The method of claim 8, wherein grain growth during the bulk tungsten layer deposition extends from a first site where tungsten nucleated to a second site where tungsten nucleated in the feature.

### Claim 10 (depends on 8)

The method of claim 8, wherein substantially all of the tungsten formed in the feature comprises alpha-tungsten.

### Claim 11

A method of filling a feature on a substrate with tungsten, the method comprising:
forming a tungsten nucleation layer, and
after forming the tungsten nucleation layer and prior to depositing a tungsten bulk layer, treating the tungsten nucleation layer to pulses of a germanium-containing reducing agent.

### Claim 12 (depends on 11)

The method of claim 11, wherein no intervening pulses of other precursors are pulsed during the treatment.

### Claim 13 (depends on 11)

The method of claim 11, wherein the treatment further comprises intervening pulses of a tungsten-containing precursor, wherein the amount of the tungsten-containing precursor pulsed during the treatment is less than the amount of the tungsten-containing precursor pulsed during the nucleation layer formation.

### Claim 14 (depends on 11)

The method of claim 11, wherein the treatment further comprises intervening pulses of a tungsten-containing precursor, wherein substantially no tungsten is deposited during the treatment.

### Claim 15 (depends on 11)

The method of claim 11, wherein the germanium-containing reducing agent is germane (GeH4) or digermane (Ge2H6).

### Claim 16

An apparatus for filling a feature on a substrate, the apparatus comprising:
a multi-chamber apparatus comprising a chamber, the chamber comprising a substrate support and one or more gas inlets configured to expose the substrate to gases; and
a controller for controlling the operations in the apparatus, comprising machine-readable instructions for:
exposing the feature to alternating pulses of a germanium-containing reducing agent and a tungsten-containing precursor.

### Claim 17 (depends on 16)

The apparatus in claim 16, wherein the controller further comprises instructions for flowing hydrogen into the chamber while the feature is exposed to the alternating pulses of the germanium-containing reducing agent and the tungsten-containing precursor.

### Claim 18 (depends on 16)

The apparatus in claim 16, wherein the germanium-containing reducing agent is germane (GeH4) or digermane (Ge2H6).

### Claim 19 (depends on 16)

The apparatus in claim 16, wherein the multi-chamber apparatus further comprises a treatment chamber, and the controller further comprises instructions for pulsing a germanium-containing reducing agent without intervening pulses of a tungsten-containing precursor.