# US 11,028,477 B2 · Bottom-up gap-fill by surface poisoning treatment

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- Number: US 11,028,477 B2
- Document ID: US11028477B2
- Status: Granted
- Kind: B2
- Application number: 15/297,270
- Filed: 2016-10-19
- Published: 2017-04-27
- Granted: 2021-06-08
- Earliest claimed: 2015-10-23
- Assignees: Applied Materials, Inc.
- Applicants: Applied Materials, Inc.
- Inventors: Mark Saly; Keiichi Tanaka; Eswaranand Venkatasubramanian; Mandyam Sriram; Bhaskar Jyoti Bhuyan; Pramit Manna; David Thompson; Andrew Short
- Web page: https://patentgrep.com/patent/US11028477B2

## CPC

- C23C 16/45527: {characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations}
- C23C 16/02: Pretreatment of the material to be coated (C23C16/04 takes precedence)
- C23C 16/04: Coating on selected surface areas, e.g. using masks
- C23C 16/045: {Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates}
- C23C 16/345: {Silicon nitride}
- C23C 16/402: {Silicon dioxide}
- C23C 16/45534: {Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers}
- H10P 14/6336: {in the presence of a plasma [PECVD]}
- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- 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: 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
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10

## Abstract

Methods for depositing film comprising exposing a substrate surface to an organic-based poisoning agent to preferentially inhibit film growth at the top of a feature relative to the bottom of the feature and depositing a film. The substrate can be exposed to the poisoning agent any number of times to promote bottom-up growth of the film in the feature.

## Claims

### Claim 1

A processing method comprising:
exposing a substrate surface having at least one feature thereon to a plasma comprising an organic-based poisoning agent to preferentially poison a top of the at least one feature relative to a bottom of the at least one feature, the organic-based poisoning agent selected from the group consisting of ethanolamine (ETA), hexane, and toluene, the plasma generated in an environment having a pressure in a range of from 0 Torr to 15 Torr via at least one source with a power in a range of from 50 W to 1000 W, the at least one feature having an aspect ratio greater than or equal to 10:1; and
depositing a film comprising silicon in the at least one feature in a bottom-up manner, such that growth on the top of the at least one feature is less than about 25% of the growth that occurs at the bottom of the feature after exposure to the organic-based poisoning agent and such that there are no voids or seams present in the at least one feature.

### Claim 2 (depends on 1)

The method of claim 1, wherein depositing the film in the at least one feature comprises sequentially exposing the substrate surface to a precursor and a reactant.

### Claim 3 (depends on 2)

The method of claim 2, wherein exposing the substrate surface to the poisoning agent occurs before each exposure to the precursor.

### Claim 4 (depends on 1)

The method of claim 1, wherein the substrate surface is exposed to the poisoning agent after depositing a film with a thickness in the range of about 10 Å to about 50 Å.

### Claim 5 (depends on 1)

The method of claim 1, wherein the plasma comprises one or more of NH3, N2, Ar, H2O, CO2, N2O, H2 and/or hydrazine.

### Claim 6 (depends on 1)

The method of claim 1, wherein the poisoning agent is present in the plasma in a sub-saturative amount.

### Claim 7 (depends on 1)

The method of claim 1, wherein the organic-based poisoning agent thermally reacts with the surface.

### Claim 8 (depends on 7)

The method of claim 7, wherein the organic-based poisoning agent is introduced in a small amount to react preferentially with the top of the at least one feature.

### Claim 9 (depends on 1)

The method of claim 1, further comprising repeating the exposure to the organic-based poisoning agent and the film deposition to fill the at least one feature.

### Claim 10 (depends on 9)

The method of claim 9, wherein the film deposited in the at least one feature has a wet etch rate ratio less than 2.

### Claim 11

A processing method comprising:
positioning a substrate surface in a processing chamber, the substrate surface having at least one feature thereon, the at least one feature creating a gap with a bottom, top and sidewalls, and having an aspect ratio greater than or equal to 10:1;
exposing the substrate surface to a plasma comprising an organic-based poisoning agent to preferentially inhibit film growth at the top of the at least one feature relative to a bottom of the at least one feature, the organic-based poisoning agent selected from the group consisting of ethanolamine (ETA), hexane, and toluene, the plasma generated in an environment having a pressure in a range of from 0 Torr to 15 Torr via at least one source with a power in a range of from 50 W to 1000 W;
sequentially exposing the substrate surface to a precursor and a reactant to deposit a layer in the gap; and
repeating exposure to the precursor and reactant to fill the gap of the at least one feature in a bottom-up manner, such that growth on the top of the at least one feature is less than about 25% of the growth that occurs at the bottom of the feature after exposure to the organic-based poisoning agent and such that there are no voids or seams present in the at least one feature.

### Claim 12 (depends on 11)

The processing method of claim 11, wherein the plasma is a directional plasma.

### Claim 13 (depends on 11)

The processing method of claim 11, wherein poisoning the substrate occurs after sequentially exposing the substrate to the precursor and the reactant in the range of two to about 10 times.

### Claim 14 (depends on 11)

The processing method of claim 11, wherein the substrate surface is exposed to the organic-based poisoning agent prior to each exposure to the precursor.

### Claim 15

A processing method comprising:
placing a substrate having a substrate surface into a processing chamber comprising a plurality of sections, each section separated from adjacent sections by a gas curtain, the substrate surface having at least one feature with a top, bottom and sides and an aspect ratio greater than or equal to 10:1;
exposing at least a portion of the substrate surface to a first process condition in a first section of the processing chamber, the first process condition comprising a plasma comprising an organic-based poisoning agent to preferentially inhibit film growth at the top of the at least one feature relative to the bottom of the at least one feature, such that growth on the top of the at least one feature is less than about 25% of the growth that occurs at the bottom of the feature after exposure to the organic-based poisoning agent and such that there are no voids or seams present in the at least one feature, the organic-based poisoning agent selected from the group consisting of ethanolamine (ETA), hexane, and toluene, the plasma generated in an environment having a pressure in a range of from 0 Torr to 15 Torr via at least one source with a power in a range of from 50 W to 1000 W;
laterally moving the substrate surface through a gas curtain to a second section of the processing chamber;
exposing the substrate surface to a second process condition in the second section of the processing chamber, the second process condition comprising silicon precursor;
laterally moving the substrate surface through a gas curtain to a third section of the processing chamber;
exposing the substrate surface to a third process condition in the third section of the processing chamber, the third process condition comprising an oxygen-containing reactant to form a SiO2 film; and
repeating exposure to the first section, second section and third section including lateral movement of the substrate surface to fill the at least one feature.