# US 12,002,657 B2 · Multi-layer plasma resistant coating by atomic layer deposition

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- Number: US 12,002,657 B2
- Document ID: US12002657B2
- Status: Granted
- Kind: B2
- Application number: 17/534,013
- Filed: 2021-11-23
- Published: 2022-05-19
- Granted: 2024-06-04
- Earliest claimed: 2017-01-20
- Assignees: Applied Materials, Inc.
- Applicants: Applied Materials, Inc.
- Inventors: Xiaowei Wu; David Fenwick; Jennifer Y. Sun; Guodong Zhan
- Web page: https://patentgrep.com/patent/US12002657B2

## CPC

- H01J 37/32495: {Means for protecting the vessel against plasma}
- C23C 16/045: {Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates}
- C23C 16/06: characterised by the deposition of metallic material
- C23C 16/403: {of aluminium, magnesium or beryllium}
- C23C 16/405: {of refractory metals or yttrium}
- C23C 16/4404: {Coatings or surface treatment on the inside of the reaction chamber or on parts thereof}
- 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 16/45529: {specially adapted for making a layer stack of alternating different compositions or gradient compositions}
- C23C 16/45531: {specially adapted for making ternary or higher compositions}
- C23C 16/45544: {characterized by the apparatus}
- C23C 16/45565: {Shower nozzles}
- C23C 16/50: using electric discharges {(generation and control of plasma in discharge tubes for surface treatment H01J37/32, H01J37/34)}
- H01J 37/3244: {Gas supply means}
- H01J 2237/3321: CVD [Chemical Vapor Deposition]
- H01J 2237/334: Etching
- H01J 2237/335: Cleaning
- H10P 72/0406: {for cleaning followed by drying, rinsing, stripping, blasting or the like}
- H10P 72/0421: {for drying etching}
- H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H)
- 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

## Abstract

Described herein are articles, systems and methods where a plasma resistant coating is deposited onto a surface of an article using an atomic layer deposition (ALD) process. The plasma resistant coating has a first layer and a second layer including a solid solution of Y2O3—ZrO2 and uniformly covers features, such as those having an aspect ratio of length to width of about 3:1 to about 300:1.

## Claims

### Claim 1

An article comprising:
a body; and
a plasma resistant coating on a surface of at least a portion of the body, wherein the plasma resistant coating comprises:
a stress relief layer having a thickness of about 10 nm to about 1.5 μm; and
a stack of alternating layers of a rare earth metal-containing oxide and a second oxide, the stack of alternating layers comprising:
a plurality of layers of the rare earth metal-containing oxide each having a thickness of about 1 angstrom to about 100 angstroms and having a polycrystalline or amorphous structure; and
a plurality of layers of the second oxide each having a thickness of about 0.5 angstroms to about 4 angstroms,
wherein the rare earth metal-containing oxide naturally occurs in a crystalline structure, wherein the plurality of layers of the second oxide cause the plurality of layers of the rare earth metal-containing oxide to have the polycrystalline or amorphous structure rather than the crystalline structure, and wherein a thickness ratio of the plurality of layers of the rare earth metal-containing oxide to the plurality of layers of the second oxide is 2:1 to 25:1.

### Claim 2 (depends on 1)

The article of claim 1, wherein the plasma resistant coating uniformly covers the surface, is resistant to cracking and delamination at a temperature of up to 350° C., and is porosity-free.

### Claim 3 (depends on 1)

The article of claim 1, wherein the stack of alternating layers comprises about 10-90 mol % Y2O3 and about 10-90 mol % ZrO2.

### Claim 4 (depends on 1)

The article of claim 1, wherein the stack of alternating layers comprises about 40-80 mol % Y2O3 and about 20-60 mol % ZrO2.

### Claim 5 (depends on 1)

The article of claim 1, wherein the stack of alternating layers comprises a mixture of about 60-70 mol % Y2O3 and about 30-40 mol % ZrO2.

### Claim 6 (depends on 1)

The article of claim 1, wherein the surface of the body on which the plasma resistant coating is deposited has an aspect ratio of length to width of about 10:1 to about 300:1, and wherein the plasma resistant coating uniformly covers the surface.

### Claim 7 (depends on 1)

The article of claim 1, wherein the article is a chamber component for a semiconductor processing chamber selected from a group consisting of a chamber wall, a shower head, a plasma generation unit, a diffuser, a nozzle, and a gas line.

### Claim 8 (depends on 1)

The article of claim 1, wherein the stack of alternating layers comprises Y4Al2O9 and a solid solution of Y2O3—ZrO2.

### Claim 9 (depends on 1)

The article of claim 1, wherein the stress relief layer comprises amorphous Al2O3.

### Claim 10 (depends on 1)

The article of claim 1, wherein the plasma resistant coating is resistant to cracking and delamination at a temperature of up to 350° C. and is porosity-free.