# US 10,483,102 B2 · Surface modification to improve amorphous silicon gapfill

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- Number: US 10,483,102 B2
- Document ID: US10483102B2
- Status: Granted
- Kind: B2
- Application number: 15/936,740
- Filed: 2018-03-27
- Published: 2018-10-11
- Granted: 2019-11-19
- Earliest claimed: 2017-04-07
- Assignees: Applied Materials, Inc.
- Applicants: Applied Materials, Inc.
- Inventors: Pramit Manna; Shishi Jiang; Abhijit Basu Mallick
- Web page: https://patentgrep.com/patent/US10483102B2

## CPC

- H10P 14/3411: {Silicon, silicon germanium or germanium}
- C23C 16/045: {Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates}
- C23C 16/24: Deposition of silicon only
- C23C 16/505: using radio frequency discharges
- H10P 14/24: using chemical vapour deposition [CVD]
- H10P 14/3238: {being insulating materials}
- H10P 14/3454: {Amorphous}
- H10P 14/36: {characterised by treatments done before the formation of the materials}
- H10W 10/014: {using trench refilling with dielectric materials, e.g. shallow trench isolations}
- H10W 10/17: formed using trench refilling with dielectric materials, e.g. shallow trench isolations
- C23C 16/0245: {by etching with a plasma}
- H10P 14/2925: {Surface structures}
- H10P 14/38: {characterised by treatments done after the formation of the materials}
- 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 gapfilling semiconductor device features, such as high aspect ratio trenches, with amorphous silicon (a-Si) film that involves pretreating the surface of the substrate to modify the underlying hydroxy-terminated silicon (Si—OH) or hydrogen-terminated silicon (Si—H) surface to oxynitride-terminated silicon (Si—ON) or nitride-terminated silicon (Si—N) and enhance the subsequent a-Si deposition are provided. First, a substrate having features formed in a first surface of the substrate is provided. The surface of the substrate is then pretreated to enhance the surface of the substrate for the flowable deposition of amorphous silicon that follows. A flowable deposition process is then performed to deposit a flowable silicon layer over the surface of the substrate. Methods described herein generally improve overall etch selectivity by the conformal silicon deposition and the flowable silicon deposition process to realize seam-free gapfilling between features with high quality amorphous silicon film.

## Claims

### Claim 1

A method for manufacturing a semiconductor device, comprising:
positioning a substrate in a processing volume of a processing chamber, the substrate having at least one feature formed in a surface of the substrate, wherein the at least one feature is defined by sidewalls and a bottom surface;
pretreating the surface of the substrate, the pretreating comprising:
forming a plasma of a pretreatment gas mixture; and
exposing the surface of the substrate to radicalized species of the pretreatment gas mixture to form an oxynitride-terminated silicon layer or a nitride-terminated silicon layer on the surface of the substrate; and
depositing a flowable silicon film on the pretreated surface of the substrate to fill the at least one feature with flowable silicon film, wherein the flowable silicon film comprises amorphous silicon.

### Claim 2 (depends on 1)

The method of claim 1, wherein the pretreatment gas mixture comprises one or more of helium, ammonia, hydrogen, oxygen, nitrous oxide, and argon.

### Claim 3 (depends on 1)

The method of claim 1, the pretreatment gas mixture comprises one or more of hydrogen gas and ammonia.

### Claim 4 (depends on 1)

The method of claim 1, wherein the surface of the substrate prior to pretreating comprises hydroxy or hydrogen-terminated silicon.

### Claim 5 (depends on 4)

The method of claim 4, wherein the surface of the substrate after the pretreating comprises oxynitride-terminated silicon.

### Claim 6 (depends on 4)

The method of claim 4, wherein the surface of the substrate after the pretreating comprises nitrogen-terminated silicon.

### Claim 7 (depends on 1)

The method of claim 1, wherein the at least one feature has an aspect ratio of 5:1 or more.

### Claim 8 (depends on 1)

The method of claim 1, further comprising maintaining the processing volume at a pressure between about 1 Torr and about 50 Torr during the pretreating the surface of the substrate.

### Claim 9 (depends on 1)

The method of claim 1, wherein an RF power used to generate the plasma is between about 10 Watts and about 1000 Watts.

### Claim 10 (depends on 9)

The method of claim 9, wherein the RF power has a frequency of about 13.6 megahertz or about 2 megahertz.

### Claim 11

A method for manufacturing a semiconductor device, comprising:
positioning a substrate having at least one feature formed in a surface of the substrate, the at least one feature is defined by sidewalls and a bottom surface;
exposing the at least one feature formed in the surface of the substrate to a pretreatment process, the pretreatment process comprising:
exposing the surface of the substrate to one or more reactive radicals; and
depositing a flowable silicon film on the pretreated surface of the substrate to fill the at least one feature with flowable silicon film, wherein the flowable silicon film comprises amorphous silicon.

### Claim 12 (depends on 11)

The method of claim 11, wherein the one or more reactive radicals are formed from one or a combination of ammonia, hydrogen, oxygen, nitrous oxide, and nitrogen.

### Claim 13 (depends on 11)

The method of claim 11, wherein the surface of the substrate prior to the pretreatment process comprises hydroxy-terminated silicon or hydrogen-terminated silicon.

### Claim 14 (depends on 13)

The method of claim 13, wherein the surface of the substrate after pretreatment process comprises oxynitride-terminated silicon.

### Claim 15 (depends on 13)

The method of claim 13, wherein the surface of the substrate after pretreatment process comprises nitrogen-terminated silicon.

### Claim 16

A method for manufacturing a semiconductor device, comprising:
positioning a substrate in a processing volume of a processing chamber, the substrate having at least one feature formed in a surface of the substrate, the at least one feature defined by sidewalls and a bottom surface;
exposing the surface of the substrate to one or more of aminosilanes and chlorosilanes to form a nitrogen-containing-terminated silicon layer on the surface of the substrate, the sidewalls of the at least one feature, and the bottom surface of the at least one feature; and
depositing a flowable silicon film on the nitrogen-containing-terminated silicon layer on the surface of the substrate to fill the at least one feature with flowable silicon film, wherein the flowable silicon film comprises amorphous silicon.

### Claim 17 (depends on 16)

The method of claim 16, wherein the aminosilanes comprise silanamine and (3-Aminopropyl)triethoxysilane, and wherein the chlorosilanes comprises ClH3Si.

### Claim 18 (depends on 16)

The method of claim 16, wherein the nitrogen-containing-terminated silicon layer is an oxynitride-terminated silicon layer, a nitride-terminated-silicon layer, or a combination thereof.

### Claim 19 (depends on 16)

The method of claim 16, wherein filling the at least one feature with the flowable silicon film comprises:
forming a plasma of a second precursor using a radiofrequency power of between about 10 Watts and about 200 Watts; and
maintaining the substrate at a temperature between about −100 degrees Celsius and about 50 degrees Celsius and maintaining an internal volume of the processing chamber at a pressure between about 1 Torr and about 10 Torr.

### Claim 20 (depends on 1)

The method of claim 1, wherein filling the at least one feature with the flowable silicon film comprises:
forming a plasma of a second precursor using a radiofrequency power of between about 10 Watts and about 200 Watts; and
maintaining the substrate at a temperature between about −100 degrees Celsius and about 50 degrees Celsius and maintaining an internal volume of the processing chamber at a pressure between about 1 Torr and about 10 Torr.