# US 12,112,940 B2 · Method of forming topology-controlled amorphous carbon polymer film

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- Number: US 12,112,940 B2
- Document ID: US12112940B2
- Status: Granted
- Kind: B2
- Application number: 16/930,305
- Filed: 2020-07-15
- Published: 2021-01-21
- Granted: 2024-10-08
- Earliest claimed: 2019-07-19
- Assignees: ASM IP Holding B.V.
- Applicants: ASM IP Holding B.V.
- Inventors: Timothee Julien Vincent Blanquart
- Web page: https://patentgrep.com/patent/US12112940B2

## CPC

- H10P 14/683: {carbon-based polymeric organic materials, e.g. polyimides, poly cyclobutene or PVC}
- H10P 14/6922: {the material containing Si, O and at least one of H, N, C, F or other non-metal elements, e.g. SiOC, SiOC:H or SiONC}
- C23C 14/0036: {Reactive sputtering}
- C23C 14/048: {using irradiation by energy or particles}
- C23C 14/0605: {Carbon}
- C23C 16/045: {Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates}
- C23C 16/26: Deposition of carbon only
- C23C 16/45536: {Use of plasma, radiation or electromagnetic fields}
- C23C 16/52: Controlling or regulating the coating process {(C23C16/45557, C23C16/279 take precedence)}
- C23C 16/56: After-treatment
- H10P 14/6336: {in the presence of a plasma [PECVD]}
- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- H10P 14/6532: {by exposure to a plasma}
- 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
- 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

In exemplary embodiment, a method of top-selective deposition using a flowable carbon-based film on a substrate having a recess defined by a top surface, sidewall, and a bottom, includes steps of: (i) depositing a flowable carbon-based film in the recess of the substrate in a reaction space until a thickness of the flowable carbon-based film in the recess reaches a predetermined thickness, and then stopping the deposition step; and (ii) exposing the carbon-based film to a nitrogen plasma in an atmosphere substantially devoid of hydrogen and oxygen so as to redeposit a carbon-based film selectively on the top surface.

## Claims

### Claim 1

A method of top-selective deposition using an initially flowable carbon-based film on a substrate having a recess defined by a top surface, sidewall, and a bottom, comprising steps of:
(i) depositing the initially flowable carbon-based film in the recess of the substrate in a reaction space, wherein the initially flowable carbon-based film accumulates within the recess, and then stopping the deposition step, wherein after deposition is stopped, the initially flowable carbon-based film forms a carbon-based film in the recess;
(ii) exposing the carbon-based film in the recess to a nitrogen plasma in an atmosphere substantially devoid of hydrogen and oxygen so as to redeposit a portion of the carbon-based film in the recess, wherein the carbon-based film is redeposited selectively on the top surface to form a redeposited carbon-based film on the top surface, wherein the nitrogen plasma is anisotropic; and
(iii) removing a portion of the carbon-based film remaining on the bottom of the recess by plasma ashing,
wherein the plasma ashing does not remove all of the redeposited carbon-based film on the top surface; and
repeating steps (i), (ii), and (iii) to form a top-selective deposited carbon-based film.

### Claim 2 (depends on 1)

The method according to claim 1, wherein steps (i) and (ii) are repeated multiple times until a thickness of the redeposited carbon-based film on the top surface reaches a desired final thickness.

### Claim 3 (depends on 1)

The method according to claim 1, wherein a thickness of the initially flowable carbon-based film accumulated within the recess in step (i) is more than a monolayer thickness but 15 nm or less.

### Claim 4 (depends on 1)

The method according to claim 1, wherein the atmosphere in step (ii) is in the reaction space used in step (i).

### Claim 5 (depends on 1)

The method according to claim 1, wherein the atmosphere in step (ii) is in another reaction space different from the reaction space used in step (i).

### Claim 6 (depends on 1)

The method according to claim 1, wherein step (ii) comprises:
feeding N2 to the atmosphere without feeding hydrogen and oxygen; and
applying RF power to the atmosphere in a manner generating the nitrogen plasma.

### Claim 7 (depends on 6)

The method according to claim 6, wherein RF power is in a range of 0.14 W/cm2 to 1.41 W/cm2 per unit area of the substrate, and a duration of step (ii) is in a range of 10 seconds to 300 seconds.

### Claim 8 (depends on 1)

The method according to claim 1, wherein step (i) is conducted by cyclic nitrogen plasma deposition.

### Claim 9 (depends on 1)

The method according to claim 1, wherein the top surface of the substrate on which the carbon-based film is redeposited is constituted by silicon.

### Claim 10 (depends on 1)

The method according to claim 1, comprising, after step (ii), removing the portion of carbon-based film remaining on the bottom of the recess by O2, H2, O2/Ar, or N2/H2 plasma ashing.

### Claim 11 (depends on 1)

The method according to claim 1, wherein the carbon-based film in the recess is an amorphous carbon film.

### Claim 12 (depends on 1)

The method according to claim 1, wherein the initially flowable carbon-based film is constituted by a hydrogenated amorphous carbon polymer, whereas the redeposited carbon-based film on the top surface is constituted by a nitrogen-doped hydrogenated amorphous carbon polymer.

### Claim 13 (depends on 1)

The method according to claim 1, wherein the plasma ashing comprises N2/H2 plasma ashing.

### Claim 14 (depends on 1)

The method according to claim 1, wherein the plasma ashing comprises using an ashing gas comprising a mixture of Ar and H2.

### Claim 15 (depends on 1)

The method according to claim 1, wherein the plasma ashing comprises using an ashing gas comprising a mixture of He and H2.

### Claim 16 (depends on 1)

The method according to claim 1, wherein the plasma ashing comprises using an ashing gas comprising a mixture of mixture of O2 and He.

### Claim 17 (depends on 1)

The method according to claim 1, wherein step (iii) is repeated a lesser number of times than a number of times steps (i) and (ii) are repeated.

### Claim 18 (depends on 1)

The method according to claim 1, wherein the pressure in step (i) is in a range of 100 to 1000 Pa.