# US 10,501,843 B2 · Plasma erosion resistant rare-earth oxide based thin film coatings

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- Number: US 10,501,843 B2
- Document ID: US10501843B2
- Status: Granted
- Kind: B2
- Application number: 15/814,601
- Filed: 2017-11-16
- Published: 2018-03-29
- Granted: 2019-12-10
- 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/US10501843B2

## 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

A method of manufacturing an article comprising:
performing at least one of ion assisted deposition (IAD) or physical vapor deposition (PVD) to deposit a first protective layer on at least one surface of an article, wherein the first protective layer is a thin film that comprises a first ceramic selected from a group consisting of:
Y3Al5O12 having at least two of a volume resistivity of 11.3E16 Ω·cm +/−up to 30%, a dielectric constant of 9.76 +/− up to 30%, a thermal conductivity of 20.1 W/m·K +/− up to 30%, a hardness of 8.5 Gpa +/− up to 30%, or a hermiticity of 4.4E-10 cm3/s +/− up to 30%,
Er2O3 having a hardness of 5 Gpa +/− up to 30%,
Er3Al5O12 having a hardness of 9 Gpa +/− up to 30%, and
a ceramic compound comprising Y4Al2O9 and a solid-solution of Y2O3—ZrO2, the ceramic compound having at least one of a dielectric constant of 9.83 +/− up to 30%, a thermal conductivity of 19.9 W/m·K +/− up to 30%, or a hermiticity of 1.2E-9 cm3/s +/− up to 30%.

### Claim 2 (depends on 1)

The method of claim 1, wherein the first protective layer comprises Er2O3, the first protective layer further having at least one of a dielectric constant of 9.67 +/− up to 30%, a thermal conductivity of 19.4 W/m·K +/− up to 30%, or a hermiticity of 5.5E-9 cm3/s +/− up to 30%.

### Claim 3 (depends on 1)

The method of claim 1, wherein the first protective layer comprises Er3Al5O12, the first protective layer further having at least one of a dielectric constant of 9.54 +/− up to 30%, a thermal conductivity of 19.2 W/m·K +/− up to 30%, or a hermiticity of 9.5E-10 cm3/s +/− up to 30%.

### Claim 4 (depends on 1)

The method 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; and
the article comprises at least one of Al2O3, AlN, Al, anodized Al, Titanium, stainless steel, quartz, sapphire, Si, or SiC.

### Claim 5 (depends on 1)

The method of claim 1, further comprising:
performing at least one of IAD or PVD to deposit a second protective layer on at least a portion of the first protective layer, wherein the second protective layer is a thin film that comprises a second ceramic different from the first ceramic, the second ceramic selected from a group consisting of: Y3Al5O12, Y4Al2O9, Er2O3, Gd2O3, Er3Al5O12, Gd3Al5O12, and the ceramic compound comprising Y4Al2O9 and a solid-solution of Y2O3—ZrO2.

### Claim 6 (depends on 5)

The method of claim 5, wherein:
the first protective layer has an amorphous structure and comprises Y3Al5O12 or Er3Al5O12; and
the second protective layer has a crystalline or nano-crystalline structure and comprises Er2O3, Gd2O3, or the ceramic compound comprising Y4Al2O9 and a solid-solution of Y2O3—ZrO2.

### Claim 7 (depends on 5)

The method of claim 5, wherein the article has a first coefficient of thermal expansion value, the first protective layer has a second coefficient of thermal expansion value, and the second 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 5)

The method of claim 5, further comprising:
prior to depositing the first protective layer on the article, performing a thermal spraying process to deposit an additional protective layer on the at least one surface of the article, wherein the additional protective layer is a thick film that comprises a second ceramic selected from a group consisting of Y3Al5O12, Y4Al2O9, Y2O3, and the ceramic compound comprising Y4Al2O9 and a solid-solution of Y2O3—ZrO2, wherein the first protective layer covers at least a portion of the additional protective layer.

### Claim 9 (depends on 1)

The method of claim 1, further comprising:
forming features in the first protective layer by masking the article and performing at least one of thin-film deposition or etching of specific areas that are not masked after performing at least one of the IAD or the PVD.

### Claim 10 (depends on 1)

The method of claim 1, wherein a first roughness of the first protective layer is approximately the same as a second roughness of the article, and wherein the first protective layer has a thickness of less than approximately 20 microns.

### Claim 11 (depends on 1)

The method of claim 1, wherein the first ceramic is the Y3Al5O12, and wherein the Y3Al5O12 has an amorphous structure and an erosion rate of about 1 nm/hr +/− up to 30% when exposed to a CH4/Cl2 plasma chemistry.

### Claim 12 (depends on 1)

The method of claim 1, wherein the first ceramic is the Er3Al5O12, and wherein the Er3Al5O12 has an amorphous structure and an erosion rate of about 70 nm/hr +/− up to 30% when exposed to a H2/NF3 plasma chemistry.

### Claim 13 (depends on 1)

The method of claim 1, wherein the first ceramic is the ceramic compound comprising the Y4Al2O9 and the solid-solution of Y2O3—ZrO2, and wherein the ceramic compound comprising the Y4Al2O9 and the solid-solution of Y2O3—ZrO2 further has an amorphous structure and an erosion rate of about 3 nm/hr +/− up to 30% when exposed to a CH4/Cl2 plasma chemistry.

### Claim 14 (depends on 1)

The method of claim 1, wherein the first ceramic is Y3Al5O12, and wherein the first ceramic has a hardness of 8.5 GPa +/− up to 30%, a dielectric constant of 9.76 +/− up to 30%, a volume resistivity of 11.3E16 Ω·cm +/−up to 30%, and a thermal conductivity of 20.1 W/m·K +/− up to 30% 10%.

### Claim 15 (depends on 1)

The method of claim 1, wherein the first ceramic is the Er2O3, and wherein the first ceramic has a hardness of 5 GPa +/− up to 30%, a dielectric constant of 9.67 +/− up to 30%, and a thermal conductivity of 19.4 W/m·K +/− up to 30%.

### Claim 16 (depends on 1)

The method of claim 1, wherein the first ceramic is the Er3Al5O12, and wherein the first ceramic has a hardness of 9 GPa +/− up to 30%, a dielectric constant of 9.54 +/− up to 30%, and a thermal conductivity of 19.2 W/m·K +/− up to 30%.

### Claim 17 (depends on 1)

The method of claim 1, wherein the first ceramic is the ceramic compound comprising Y4Al2O9 and a solid-solution of Y2O3—ZrO2, and wherein the first ceramic has a hardness of 7.8 GPa +/− up to 30%, a dielectric constant of 9.83 +/− up to 30%, a volume resistivity of 4.1E16 Ω·cm +/− up to 30%, and a thermal conductivity of 19.9 W/m·K +/− up to 30%.

### Claim 18

A method of manufacturing an article comprising:
performing at least one of ion assisted deposition (IAD) or physical vapor deposition (PVD) to deposit a first protective layer on at least one surface of an article, wherein the first protective layer is a thin film that comprises a first ceramic selected from a group consisting of:
Y3Al5O12 having at least two of a volume resistivity of 11.3E16 Ω·cm +/−up to 30%, a dielectric constant of 9.76 +/− up to 30%, a thermal conductivity of 20.1 W/m·K +/− up to 30%, a hardness of 8.5 Gpa +/− up to 30%, or a hermiticity of 4.4E-10 cm3/s +/− up to 30%,
Er2O3 having a hardness of 5 Gpa +/− up to 30%,
Er3Al5O12 having a hardness of 9 Gpa +/− up to 30%, and
a ceramic compound comprising Y4Al2O9and a solid-solution of Y2O3—ZrO2, the ceramic compound having at least two of a volume resistivity of 4.1E16 Ω·cm +/− up to 30%, a dielectric constant of 9.83 +/− up to 30%, a thermal conductivity of 19.9 W/m·K +/− up to 30%, a hardness of 7.8 Gpa +/− up to 30%, or a hermiticity of 1.2E-9 cm3/s +/− up to 30%; and
forming a plurality of surface features on a surface of the first protective layer, wherein the plurality of surface features are not in the at least one surface of the article, and wherein a thickness of the first protective layer at first locations that include the plurality of surface features is greater than a thickness of the first protective layer at second locations that do not include the plurality of surface features.

### Claim 19

A method of manufacturing an article comprising:
performing at least one of ion assisted deposition (IAD) or physical vapor deposition (PVD) to deposit a first protective layer on at least one surface of an article, wherein the article comprises Al2O3, and wherein the first protective layer is a thin film that comprises a first ceramic selected from a group consisting of:
Er2O3 having a hardness of 5 Gpa +/− up to 30%, and
a ceramic compound comprising Y4Al2O9 and a solid-solution of Y2O3—ZrO2, the ceramic compound having at least two of a volume resistivity of 4.1E16 Ω·cm +/− up to 30%, a dielectric constant of 9.83 +/− up to 30%, a thermal conductivity of 19.9 W/m·K +/− up to 30%, a hardness of 7.8 Gpa +/− up to 30%, or a hermiticity of 1.2E-9 cm3/s +/− up to 30%; and
forming a transition layer between the at least one surface of the article and the first protective layer, wherein the transition layer provides a diffusion bond between the first protective layer and the at least one surface of the article, and wherein:
the transition layer is Y3Al5O12 if the first protective layer is the ceramic compound comprising Y4Al2O9 and a solid-solution of Y2O3—ZrO2, and
the transition layer is Er3Al5O12 if the first protective layer is the Er2O3.

### Claim 20 (depends on 19)

The method of claim 19, wherein: the first protective layer is the Er2O3 and the transition layer is Er3Al5O12.