IP Library Granted Patent US 10,443,126
Granted Patent B1
US 10,443,126 · App. 15/947,402 · Granted Oct 15, 2019

Zone-controlled rare-earth oxide ALD and CVD coatings

Inventors: Xiaowei Wu (San Jose, CA); Jennifer Y. Sun (Mountain View, CA); Michael R. Rice (Pleasanton, CA)
Assignee: Applied Materials, Inc.
C23C16/405C23C14/083C23C16/45542H01L21/0228H01L21/67161
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Quick Facts
Patent No.
US 10,443,126
App. No.
15/947,402
Granted
Oct 15, 2019
Kind
B1
Abstract

Disclosed herein is a rare-earth oxide coating on a surface of an article with one or more interruption layers to control crystal growth and methods of its formation. The coating may be deposited by atomic layer deposition and/or by chemical vapor deposition. The rare-earth oxides in the coatings disclosed herein may have an atomic crystalline phase that is different from the atomic crystalline phase or the amorphous phase of the one or more interruption layers.

Claims (53)

1. A method comprising:

depositing a plasma resistant protective coating comprising a plurality of crystalline rare-earth oxide layers and a plurality of crystalline or amorphous metal oxide layers onto a surface of an article using an atomic layer deposition (ALD) process or a chemical vapor deposition (CVD) process, wherein depositing the plasma resistant protective coating comprises alternately depositing:

a crystalline rare-earth oxide layer of the plurality of crystalline rare-earth oxide layers using ALD or CVD; and

a crystalline or amorphous metal oxide layer of the plurality of crystalline or amorphous metal oxide layers using ALD or CVD;

wherein when the plurality of metal oxide layers are crystalline, the plurality of metal oxide layers have an atomic crystalline phase different from an atomic crystalline phase of the plurality of crystalline rare-earth oxide layers;

wherein the plurality of crystalline or amorphous metal oxide layers are interrupt layers that inhibit grain growth of the plurality of crystalline rare-earth oxide layers such that all grains in the plurality of crystalline rare-earth oxide layers have a grain size that is below 100 nm in length and that is below 200 nm in width; and

wherein a thickness ratio of thickness of the crystalline rare-earth oxide layer to thickness of the crystalline or amorphous metal oxide layer is about 10:1 to about 500:1 such that the thickness of the crystalline or amorphous metal oxide layer is lower than the thickness of the crystalline rare-earth oxide layer.

2. The method of claim 1 , wherein the crystalline rare-earth oxide layer comprises yttrium oxide in a cubic phase, wherein depositing the crystalline rare-earth oxide layer using ALD comprises preforming a deposition cycle comprising:

injecting a yttrium-containing precursor into a deposition chamber containing the article to cause the yttrium-containing precursor to adsorb onto the surface of the article to form a first half reaction; and

injecting an oxygen-containing reactant into the deposition chamber to form a second half reaction; and

repeating the deposition cycle one or more times until a target thickness is achieved for the crystalline rare-earth oxide layer.

3. The method of claim 2 , wherein depositing the crystalline or amorphous metal oxide layer using ALD comprises preforming a deposition cycle comprising:

injecting a metal-containing precursor into a deposition chamber containing the article to cause the metal-containing precursor to adsorb onto the crystalline rare-earth oxide layer to form a first half reaction; and

injecting an oxygen-containing reactant into the deposition chamber to form a second half reaction; and

repeating the deposition cycle one or more times until a target thickness is achieved for the crystalline or amorphous metal oxide layer.

4. The method of claim 1 , wherein the atomic crystalline phase different from the atomic crystalline phase of the crystalline rare-earth oxide is selected from the group consisting of hexagonal phase, monoclinic phase, cubic phase, hexagonal phase, tetragonal phase, and combinations thereof.

5. The method of claim 1 , wherein the metal oxide layer is crystalline and is selected from the group consisting of:

a composition ranging from a pure crystalline single phase zirconia in at least one of a tetragonal phase or a monoclinic phase to a crystalline multiphase or a crystalline single phase yttrium zirconium oxide with an atomic percentage of zirconium of about 5%, based on total atoms in the composition;

a mixture of about 65 wt % of zirconium oxide in a tetragonal phase and about 35 wt % of zirconium oxide in a monoclinic phase;

about 100 wt % multi-elemental oxide of zirconium yttrium oxide in a tetragonal phase;

a mixture of about 70 wt % of a multi-elemental oxide of zirconium yttrium oxide in a first cubic phase and about 30 wt % of yttrium oxide in a second cubic phase, wherein the first cubic phase and the second cubic phase have a lattice structure that is different from the lattice structure of the crystalline rare-earth oxide layer; and

a mixture of about 30 wt % of a multi-elemental oxide of zirconium yttrium oxide in the first cubic phase and about 70 wt % of yttrium oxide in the second cubic phase.

6. The method of claim 1 , wherein the crystalline or amorphous metal oxide layer is selected from the group consisting of one or more rare earth metal-containing oxides, zirconium oxide, aluminum oxide, and mixtures thereof.

7. The method of claim 6 , wherein the one or more rare earth metal-containing oxides are selected from the group consisting of lanthanum oxide, praseodymium oxide, neodymium oxide, samarium oxide, europium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, and mixtures thereof.

8. The method of claim 6 , wherein the crystalline or amorphous metal oxide layer comprises a multi-elemental oxide or a mixture of a first metal oxide and a second metal oxide, and wherein depositing the crystalline or amorphous metal oxide layer comprises performing a super deposition cycle comprising:

a first deposition cycle comprising:

injecting a first metal-containing precursor into a deposition chamber containing the article coated with the crystalline rare-earth oxide layer to cause the first metal-containing precursor to adsorb onto the crystalline rare-earth oxide layer to form a first half reaction;

injecting an oxygen-containing reactant into the deposition chamber to form a second half reaction;

repeating the first deposition cycle one or more times until a first target thickness is achieved and a first layer is formed; and

a second deposition cycle comprising:

injecting a second metal-containing precursor into a deposition chamber containing an article coated with the first layer to cause the second metal-containing precursor to adsorb onto the first layer to form a third half reaction;

injecting an oxygen-containing reactant into the deposition chamber to form a fourth half reaction;

repeating the second deposition cycle one or more times until a second target thickness is achieved and a second layer is formed; and

repeating the super deposition cycle one or more times until a final target thickness if achieved.

9. The method of claim 8 , wherein the crystalline or amorphous metal oxide layer further comprises a third metal oxide, and wherein the super deposition cycle further comprises a third deposition cycle comprising:

injecting a third metal-containing precursor into a deposition chamber containing an article coated with the second layer to cause the third metal-containing precursor to adsorb onto the second layer to form a fifth half reaction;

injecting an oxygen-containing reactant into the deposition chamber to form a sixth half reaction; and

repeating the third deposition cycle one or more times until a third target thickness is achieved and a third layer is formed.

10. The method of claim 8 , wherein the final target thickness of the plasma resistant protective coating is about 500 nm to about 10 μm, and wherein the plasma resistant protective coating is uniform, conformal, and porosity-free.

11. The method of claim 6 , wherein the crystalline or amorphous metal oxide layer comprises a multi-elemental oxide or a mixture of a first metal oxide and a second metal oxide, and wherein depositing the crystalline or amorphous metal oxide layer comprises performing a deposition cycle comprising:

co-injecting a mixture of a first metal-containing precursor and a second metal-containing precursor or sequentially injecting a first metal-containing precursor and a second metal-containing precursor into a deposition chamber containing the article coated with the crystalline rare-earth oxide layer to cause the first metal-containing precursor and the second metal-containing precursor to adsorb onto the crystalline rare-earth oxide layer to form a first half reaction;

injecting an oxygen-containing reactant into the deposition chamber to form a second half reaction; and

repeating the deposition cycle one or more times until a target thickness is achieved.

12. A method comprising depositing a plasma resistant protective coating onto a surface of an article using an atomic layer deposition (ALD) process or a chemical vapor deposition (CVD) process, comprising:

depositing a stack of alternating layers of crystalline yttrium oxide layers and crystalline or amorphous metal oxide layers using the ALD process or the CVD process,

wherein the crystalline yttrium oxide layers have a cubic phase,

wherein when the metal oxide layers are crystalline, the metal oxide layers have an atomic crystalline phase different from the cubic phase of the crystalline yttrium oxide layers,

wherein a first layer in the stack of alternating layers is a crystalline yttrium oxide layer,

wherein the crystalline or amorphous metal oxide layers are interrupt layers that inhibit grain growth in the crystalline yttrium oxide layers such that all grains in the crystalline yttrium oxide layers have a grain size that is below 100 nm in length and that is below 200 nm in width, and

wherein a thickness ratio of the thickness of the crystalline yttrium oxide layers to the thickness of the crystalline or amorphous metal oxide layers is about 10:1 to about 500:1 such that the thickness of the crystalline or amorphous metal oxide layers is lower than the thickness of the crystalline yttrium oxide layers.

13. The method of claim 1 , wherein the plurality of crystalline or amorphous metal oxide layers are a plurality of crystalline metal oxide layers.

14. The method of claim 1 , wherein the plurality of crystalline or amorphous metal oxide layers are a plurality of amorphous layers comprising aluminum oxide.

15. The method of claim 1 , wherein the plurality of crystalline rare-earth oxide layers comprise a first rare earth oxide, and wherein the plurality of crystalline or amorphous metal oxide layers comprise a second rare earth oxide that is different from the first rare earth oxide.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 19, 2018
From: WU, XIAOWEI; SUN, JENNIFER Y.; RICE, MICHAEL R.
To: APPLIED MATERIALS, INC.
Reel/Frame 045584/0734 →
Cited By (2)
US 12,404,584 US 12,486,571