# US 10,119,188 B2 · Plasma erosion resistant rare-earth oxide based thin film coatings

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 10,119,188 B2
- Document ID: US10119188B2
- Status: Granted
- Kind: B2
- Application number: 15/814,597
- Filed: 2017-11-16
- Published: 2018-03-15
- Granted: 2018-11-06
- Earliest claimed: 2013-06-20
- Assignees: Applied Materials, Inc.
- Applicants: Applied Materials, Inc.
- Inventors: Jennifer Y. Sun; Biraja P. Kanungo; Vahid Firouzdor; Tom Cho
- Web page: https://patentgrep.com/patent/US10119188B2

## CPC

- C23C 14/08: Oxides (C23C14/10 takes precedence)
- B32B 18/00: Layered products essentially comprising ceramics, e.g. refractory products
- C23C 14/083: {of refractory metals or yttrium}
- C23C 14/22: characterised by the process of coating
- C23C 14/228: {Gas flow assisted PVD deposition}
- C23C 14/34: Sputtering
- H01J 37/32477: {characterised by the means for protecting vessels or internal parts, e.g. coatings}
- H01J 37/32495: {Means for protecting the vessel against plasma}
- Y10T 428/24355: Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T 428/24967: Absolute thicknesses specified
- Y10T 428/24975: No layer or component greater than 5 mils thick
- Y10T 428/265: 1 mil or less
- 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)
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H)
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

An article comprises a body and at least one protective layer on at least one surface of the body. The at least one protective layer is a thin film having a thickness of less than approximately 20 microns that comprises a ceramic selected from a group consisting of Y3Al5O12, Y4Al2O9, Er2O3, Gd2O3, Er3Al5O12, Gd3Al5O12 and a ceramic compound comprising Y4Al2O9 and a solid-solution of Y2O3—ZrO2.

## Claims

### Claim 1

An article comprising:
a body; and
a first conformal protective layer on at least one surface of the body, wherein the first conformal protective layer is a thin film having a thickness of approximately 0.5-20 microns that comprises a first ceramic selected from a group consisting of
Y3Al5O12 having a hardness of approximately 8.5 GPa,
Er2O3 having a hardness of approximately 5 GPa,
Er3Al5O12 having a hardness of approximately 9 GPa, and
a ceramic compound comprising Y4Al2O9 and a solid-solution of Y2O3—ZrO2 having a hardness of approximately 7.825 GPa.

### Claim 2 (depends on 1)

The article of claim 1, wherein the first conformal protective layer comprises Er2O3, the first conformal protective layer having a crystalline structure with vertical cracks, a hardness of approximately 5 GPa, a surface roughness that matches an underlying surface roughness of the at least one surface, and a hermiticity of around 5.5E-9 cm3/s.

### Claim 3 (depends on 1)

The article of claim 1, wherein the first conformal protective layer comprises Er3Al5O12, the first conformal protective layer having an amorphous structure, a hardness of approximately 9 GPa, a surface roughness that matches an underlying surface roughness of the at least one surface, and a hermiticity of around 9.5E-10 cm3/s.

### Claim 4 (depends on 1)

The article of claim 1, wherein:
the article comprises a chamber component selected from a group consisting of a chamber lid, a nozzle, a showerhead base, a showerhead gas distribution plate (GDP), a chamber viewport, a process kit ring, a shield, a plasma screen, a flow equalizer, a chamber wall and a liner kit.

### Claim 5 (depends on 1)

The article of claim 1, further comprising:
a conformal protective layer stack on the at least one surface of the body, the conformal protective layer stack comprising at least the first conformal protective layer and a second conformal protective layer covering the first conformal protective layer, wherein the second conformal protective layer has a thickness of less than approximately 20 microns and comprises a second ceramic different from the first ceramic, the second ceramic selected from the group consisting of: Y3Al5O12, Y4Al2O9, Er2O3, Er3Al5O12, and a ceramic compound comprising Y4Al2O9 and a solid-solution of Y2O3—ZrO2.

### Claim 6 (depends on 5)

The article of claim 5, wherein:
the first conformal protective layer in the conformal protective layer stack has an amorphous structure and comprises Y3Al5O12 or Er3Al5O12; and
the second conformal protective layer in the conformal protective layer stack has a crystalline or nano-crystalline structure and comprises Er2O3 or the ceramic compound comprising Y4Al2O9 and a solid-solution of Y2O3—ZrO2.

### Claim 7 (depends on 5)

The article of claim 5, wherein the body has a first coefficient of thermal expansion value, the first conformal protective layer has a second coefficient of thermal expansion value, and the second conformal protective layer has a third coefficient of thermal expansion value, wherein the second coefficient of thermal expansion value is between the first coefficient of thermal expansion value and the third coefficient of thermal expansion value.

### Claim 8 (depends on 1)

The article of claim 1, wherein the first conformal protective layer comprises a plurality of surface features that are not on the at least one surface, the plurality of surface features comprising at least one of a mesa, a channel, or a seal ring.

### Claim 9 (depends on 1)

The article of claim 1, wherein the first conformal protective layer comprises the ceramic compound comprising Y4Al2O9 and a solid-solution of Y2O3—ZrO2, and wherein the first conformal protective layer has an erosion rate of about 3 nm per hour of exposure to a CH4/C12 plasma chemistry and an erosion rate of about 35 nm per hour of exposure to an H2/NF3 plasma chemistry.

### Claim 10 (depends on 1)

The article of claim 1, wherein the article comprises a viewport of quartz or sapphire, and wherein the viewport and the first conformal protective layer are transparent to optical signals transmitted through the viewport.

### Claim 11 (depends on 1)

The article of claim 1, wherein the first conformal protective layer has a thickness of 0.5-7.0 microns.

### Claim 12 (depends on 1)

The article of claim 1, wherein the body has a diameter of at least 12 inches, and wherein the at least one surface of the body has a curvature of less than about 50 microns over the body due to film stress associated with the first conformal protective layer.

### Claim 13 (depends on 1)

The article of claim 1, wherein the at least one surface comprises one or more first surface features that are also in the first conformal protective layer, and wherein the first conformal protective layer comprises one or more additional surface features that are not on the at least one surface.

### Claim 14 (depends on 1)

The article of claim 1, wherein the body comprises one or more holes, and wherein the first conformal protective layer does not plug the one or more holes.

### Claim 15 (depends on 1)

The article of claim 1, wherein the first conformal protective layer comprises Er2O3 and the body comprises Al2O3, the article further comprising:
a transition layer between the conformal protective layer and the body, wherein the transition layer comprises Er3Al5O12.

### Claim 16 (depends on 1)

The article of claim 1, wherein the body comprises at least one of Al2O3, AlN, Al, anodized Al, Titanium, stainless steel, quartz, sapphire, Si or SiC.

### Claim 17 (depends on 1)

The article of claim 1, further comprising:
a second protective layer on the at least one surface of the body, wherein the second protective layer is a thick film having a thickness of greater than approximately 100 microns that comprises a second ceramic selected from a group consisting of Y3Al5O12, Y Al2O9, Y2O3, and the ceramic compound comprising Y4Al2O9 and a solid-solution of Y2O3—ZrO2, wherein the first conformal protective layer covers the second protective layer.

### Claim 18 (depends on 1)

The article of claim 1, wherein a first roughness of the first conformal protective layer is approximately the same as a second roughness of the body.

### Claim 19 (depends on 1)

The article of claim 1, wherein the first conformal protective layer has an erosion resistance property that will cause it to change in average surface roughness (Ra) by not more than approximately 8 μin after 100 hours of exposure to CH4/C12 plasma chemistry.

### Claim 20 (depends on 1)

The article of claim 1, wherein the term “approximately” with respect to the hardness of the first conformal protective layer means±less than 30%.