# US 10,319,583 B2 · Selective deposition of silicon nitride films for spacer applications

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- Number: US 10,319,583 B2
- Document ID: US10319583B2
- Status: Granted
- Kind: B2
- Application number: 15/455,744
- Filed: 2017-03-10
- Published: 2017-09-14
- Granted: 2019-06-11
- Earliest claimed: 2016-03-13
- Assignees: Applied Materials, Inc.
- Applicants: Applied Materials, Inc.
- Inventors: Ning Li; Mihaela Balseanu; Li-Qun Xia
- Web page: https://patentgrep.com/patent/US10319583B2

## CPC

- H10P 14/69433: {the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz}
- C23C 16/045: {Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates}
- C23C 16/345: {Silicon nitride}
- C23C 16/45519: {Inert gas curtains}
- C23C 16/45536: {Use of plasma, radiation or electromagnetic fields}
- C23C 16/45551: {for relative movement of the substrate and the gas injectors or half-reaction reactor compartments}
- 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}
- H10P 14/6682: {the compound being a silane, e.g. disilane, methylsilane or chlorosilane}
- H10P 14/6687: {the compound comprising silicon and nitrogen}
- H10P 50/283: {by chemical means}
- H10P 95/00: Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass
- 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)

## Abstract

Methods for forming a spacer comprising depositing a film on the top, bottom and sidewalls of a feature and treating the film to change a property of the film on the top and bottom of the feature so that the film can be selectively etched from the top and bottom of the feature relative to the film on the sidewalls of the feature.

## Claims

### Claim 1

A processing method comprising:
providing a substrate surface having at least one feature thereon, the at least one feature comprising a top, a bottom and a sidewall;
forming a film on the at least one feature so that the film is formed on the top, bottom and sidewall; and
treating the film with a plasma to change a property of the film on the top and bottom of the feature so that the top and bottom of the feature have a wet etch rate that is more than 10 times greater than the film on the sidewall, wherein treating the film comprises exposing the film to a directional plasma having an ion concentration greater than or equal to about 1010/cm3.

### Claim 2 (depends on 1)

The method of claim 1, further comprising repeatedly forming the film and treating the film sequentially to deposit a film of a total thickness.

### Claim 3 (depends on 1)

The method of claim 1, wherein the film comprises SiN.

### Claim 4 (depends on 1)

The method of claim 1, wherein the plasma comprises one or more of hydrogen, argon, nitrogen, ammonia, oxygen or helium.

### Claim 5 (depends on 1)

The method of claim 1, wherein the directional plasma is a remote plasma formed in a plasma assembly having a slot with edges through which the plasma flows.

### Claim 6 (depends on 1)

The method of claim 1, wherein forming the film comprises sequentially exposing the substrate surface to a silicon precursor and a nitrogen reactant to form a silicon nitride film.

### Claim 7 (depends on 6)

The method of claim 6, wherein the substrate surface is exposed to a nitrogen precursor between exposure to the silicon precursor and the nitrogen reactant, the nitrogen precursor comprising a species that does not react with silicon precursor molecules on the substrate surface.

### Claim 8 (depends on 7)

The method of claim 7, wherein forming the film comprises sequentially exposing the substrate surface to a silicon precursor comprising dichlorosilane, a nitrogen precursor comprising ammonia and a nitrogen reactant comprising a N2/Ar plasma or a H2/Ar plasma.

### Claim 9 (depends on 7)

The method of claim 7, wherein the plasma comprises ammonia and helium.

### Claim 10 (depends on 9)

The method of claim 9, wherein the wet etch rate of the top and bottom of the feature is greater than or equal to about 20 Å/min.

### Claim 11 (depends on 1)

The method of claim 1, wherein treating the film occurs after a film having a thickness in the range of about 1 Å to about 50 Å is deposited.

### Claim 12 (depends on 1)

The method of claim 1, further comprising etching the film with dilute HF to selectively remove the film from the top and bottom of the feature.

### Claim 13

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 having a top, bottom and sidewalls;
exposing the substrate surface to a deposition environment comprising at least one deposition cycle, the deposition cycle comprising sequential exposure to a silicon precursor and a nitrogen containing reactant to form a silicon nitride film on the top, bottom and sidewalls of the at least one feature; and
exposing the silicon nitride film to a treatment environment to modify the silicon nitride film deposited on the top and bottom of the at least one feature so that the film on the top and bottom have a wet etch rate that is more than 10 times greater than the film on the sidewalls, the treatment environment comprising a plasma having an ion concentration greater than or equal to about 1010/cm3.

### Claim 14 (depends on 13)

The method of claim 13, wherein the deposition cycle further comprises exposing the substrate surface to a nitrogen precursor between the silicon precursor and the nitrogen reactant.

### Claim 15 (depends on 14)

The method of claim 14, wherein the silicon precursor comprises dichlorosilane, the nitrogen precursor comprises ammonia and the nitrogen reactant comprises an N2/Ar plasma or a H2/Ar plasma.

### Claim 16 (depends on 15)

The method of claim 15, wherein the treatment environment comprises an ammonia/helium plasma.

### Claim 17 (depends on 13)

The method of claim 13, further comprising selectively etching the silicon nitride film from the top and bottom of the at least one feature.

### Claim 18

A processing method comprising:
placing a substrate having a substrate surface with a feature into a processing chamber comprising a plurality of process regions, each process region separated from adjacent process regions by a gas curtain, the feature comprising a top, a bottom and a sidewall;
exposing at least a portion of the substrate surface to a first process condition in a first process region of the processing chamber, the first process condition comprising a silicon precursor;
laterally moving the substrate surface through a gas curtain to a second process region of the processing chamber;
exposing the substrate surface to a second process condition in the second process region of the processing chamber, the second process condition comprising a nitrogen precursor;
laterally moving the substrate surface through a gas curtain to a third process region of the processing chamber;
exposing the substrate surface to a third process condition in the third process region of the processing chamber, the third process condition comprising a nitrogen reactant to form a silicon nitride film on the top, bottom and sidewalls of the feature;
repeating exposure to the first process condition, the second process condition and the third process condition to form a silicon nitride film with a predetermined thickness; and
moving the substrate surface to a fourth process region of the processing chamber, the fourth process region comprising a treatment environment comprising a plasma having an ion concentration greater than or equal to about 1010/cm3 that selectively decreases the wet etch rate of the silicon nitride film on the top and bottom of the feature.