CN115223835A - Plasma corrosion resistant protective layer and method for forming the same - Google Patents
Plasma corrosion resistant protective layer and method for forming the same Download PDFInfo
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- CN115223835A CN115223835A CN202110442122.6A CN202110442122A CN115223835A CN 115223835 A CN115223835 A CN 115223835A CN 202110442122 A CN202110442122 A CN 202110442122A CN 115223835 A CN115223835 A CN 115223835A
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- layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/32798—Further details of plasma apparatus not provided for in groups H01J37/3244 - H01J37/32788; special provisions for cleaning or maintenance of the apparatus
- H01J37/32807—Construction (includes replacing parts of the apparatus)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
- B05C5/02—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work
- B05C5/0208—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work for applying liquid or other fluent material to separate articles
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/32458—Vessel
- H01J37/32467—Material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/32458—Vessel
- H01J37/32477—Vessel characterised by the means for protecting vessels or internal parts, e.g. coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/32458—Vessel
- H01J37/32477—Vessel characterised by the means for protecting vessels or internal parts, e.g. coatings
- H01J37/32495—Means for protecting the vessel against plasma
Abstract
The invention provides a protective layer capable of resisting plasma corrosion and a forming method thereof, which are formed on a metal substrate. The thermal barrier layer is arranged on the metal substrate. The plasma corrosion resistant layer is arranged on the thermal barrier layer. The thermal barrier layer can reduce the phenomena of expansion with heat and contraction with cold of the plasma cavity body during operation, and has the advantages of avoiding the phenomenon that the anti-plasma corrosion material is peeled off due to the stress generated between the plasma cavity body and the anti-plasma corrosion material because of different thermal expansion coefficients, increasing the stability of the anti-plasma protection film layer, reducing the phenomena that the plasma cavity body is corroded by the plasma, and reducing the frequency of machine maintenance.
Description
Technical Field
The present invention relates to the technical field of plasma-resistant film layer structures for internal parts possibly exposed to plasma in the industries of photoelectric and semiconductor, such as IC manufacturing, liquid crystal display panels, light emitting diodes, micro electro mechanical systems, etc., particularly dry etching, physical Vapor Deposition (PVD), plasma-enhanced chemical vapor deposition (PE-CVD), etc., and the present invention particularly relates to a plasma-resistant film layer structure for internal parts possibly exposed to plasma in the dry etching or plasma-assisted film process of any kind of photoelectric and semiconductor industries, wherein the protective film layer is used for improving the yield of the above processes and prolonging the service life of the parts.
Background
Currently, in the Plasma process such as RIE (Reactive Ion Etch) or PECVD (Plasma enhanced chemical vapor deposition), the vacuum chamber or the components are exposed to the Reactive Plasma environment and thus are very vulnerable to erosion.
Referring to fig. 1, fig. 1 shows a conventional way of improving corrosion, a layer 11 of plasma erosion resistant material, such as yttrium aluminum garnet (Y3 Al5O 12) yttria (Y2O 3), yttrium fluoride (YF 3), yttrium Oxyfluoride (YOF), etc., is coated on an anodized layer 12 of a component 10 by spraying, and since these oxides contain heavier metal atoms, the plasma erosion resistance is better, and particularly when forming a certain lattice directional structure (Texture structure), the <111> direction of the lattice of the plasma erosion resistant material is arranged to extend perpendicular to the surface of the substrate by ion beam electron gun evaporation (IAD), which is covered by a fine single crystal structure with a specific direction, the plasma erosion resistance is better.
However, the plasma process is performed in a highly corrosive environment even though the plasma corrosion resistant material layer 11 is used to prevent the aluminum alloy substrate 13 from being corroded. In fact, the plasma etching resistant material layer 11 has Grain boundaries (Grain Boundary) and defects causing fine cracks, through which the plasma energy can still etch the aluminum alloy substrate 13, resulting in deterioration of the component 10. In addition, the plasma process is still performed in a high temperature environment (200-300 ℃), and the aluminum alloy substrate has a larger thermal expansion coefficient (23.2 × 10-6/K @20 ℃), so that the aluminum alloy substrate expands after being heated to expand the cracks on the plasma corrosion resistant material layer 11, and the aluminum alloy substrate 13 is more easily corroded by the plasma.
Therefore, it is worth the thinking of those skilled in the art to solve the above problems.
Disclosure of Invention
In order to solve the problem that the gap of the plasma corrosion resistant material layer is expanded due to the thermal expansion of the metal substrate, the invention is to add a thermal barrier layer with low thermal conductivity between the plasma corrosion resistant layer and the anodic treatment layer. The metal substrate has the beneficial effects that the thermal expansion phenomenon of the metal substrate can be reduced, and the stable structure of the film layer and the corrosion resistance of the anti-plasma corrosion layer are further improved. The specific technical means is as follows:
a protective layer for resisting plasma corrosion is formed on a metal substrate and comprises a thermal barrier layer and a plasma corrosion resistant layer. The thermal barrier layer is arranged on the metal substrate. The plasma corrosion resistant layer is arranged on the thermal barrier layer.
The above-mentioned plasma corrosion resistant protective layer is characterized in that the metal substrate further comprises an anodic treatment layer, and the thermal barrier layer is disposed on the anodic treatment layer.
The above-mentioned protective layer resistant to plasma etching is characterized in that the thermal conductivity of the thermal barrier layer is not more than one-half of the thermal conductivity of the anodized layer.
The above-mentioned protective layer resistant to plasma etching is characterized in that the thermal conductivity coefficient of the thermal barrier layer is less than half of the thermal conductivity coefficient of the plasma etching resistant layer.
The above-mentioned protective layer resistant to plasma etching is characterized in that the thermal barrier layer has an Amorphous (amophorus) structure.
The above-mentioned plasma-erosion resistant protective layer is characterized in that the thermal barrier layer is selected from the group consisting of yttrium (Y), gadolinium (Gd), ytterbium (Yb) oxide, and niobium (Nb), zirconium (Zr), aluminum (Al), hafnium (Hf) oxide.
The above-mentioned plasma-erosion resistant protective layer is characterized in that the plasma-erosion resistant layer is selected from the group consisting of oxides of aluminum (Al), yttrium (Y), erbium (Er), rhodium (Rh), and oxides, nitrides, borides, and fluorides of lanthanides.
The above-mentioned protective layer resistant to plasma erosion is characterized in that the thermal barrier layer is formed by Deposition using Ion Assisted electron gun evaporation (IAD) technique.
The above-mentioned protective layer is characterized in that the plasma-corrosion-resistant layer is formed by deposition in a plasma spraying manner.
The invention also provides a forming method of the protective layer resisting the plasma corrosion, which comprises the following steps:
s10: forming a thermal barrier layer on a metal substrate; and
s20: forming a plasma corrosion resistant layer on the thermal barrier layer.
In the above method for forming a protection layer resistant to plasma etching, in step S10, the metal substrate further includes an anodized layer, and the thermal barrier layer is formed on the anodized layer.
In the method for forming the plasma corrosion resistant protective layer, the thermal conductivity of the thermal barrier layer is less than one half of the thermal conductivity of the anodized layer.
The method for forming the above-described resist against plasma corrosion is characterized in that the thermal conductivity of the thermal barrier layer is less than one-half of the thermal conductivity of the resist against plasma corrosion.
The method for forming the plasma corrosion resistant protective layer is characterized in that the thermal barrier layer is of an Amorphous (amophorus) structure.
The method for forming the plasma-erosion resistant protective layer is characterized in that the thermal barrier layer is selected from the group consisting of yttrium (Y), gadolinium (Gd) and ytterbium (Yb) oxides and the group consisting of niobium (Nb), zirconium (Zr), aluminum (Al) and hafnium (Hf) oxides.
The method for forming the above-described slurry corrosion resistant protective layer is characterized in that the slurry corrosion resistant layer is selected from the group consisting of oxides of aluminum (Al), yttrium (Y), erbium (Er), rhodium (Rh), and oxides, nitrides, borides, and fluorides of lanthanoids.
The method for forming the plasma corrosion resistant protective layer is characterized in that the thermal barrier layer is formed by Deposition through Ion Assisted electron gun evaporation (IAD) technology.
The method for forming the plasma corrosion resistant protective layer is characterized in that the plasma corrosion resistant layer is formed by deposition in a plasma spraying manner.
Drawings
FIG. 1 illustrates a common way to improve corrosion.
FIG. 2 is a schematic diagram of the protection layer for resisting plasma etching according to the present invention.
FIG. 3 is a side view of a thermal barrier layer.
Fig. 4 illustrates a method for forming a passivation layer resistant to plasma etching.
Detailed Description
Referring to fig. 2, fig. 2 is a schematic diagram illustrating a protection layer for resisting plasma corrosion according to the present invention. The protection layer 100 resistant to plasma corrosion is formed on a metal substrate 200. The plasma-erosion resistant protective layer 100 includes a thermal barrier layer 120 and a plasma-erosion resistant layer 110. The thermal barrier layer 120 is disposed on the metal substrate 200, and the plasma corrosion resistant layer 110 is disposed on the thermal barrier layer 120. In another embodiment, the metal substrate 200 includes a substrate 210 and an anodized layer 220, and the thermal barrier layer 120 is disposed on the anodized layer 220.
The Thermal Barrier layer 120 (TBC) is formed by deposition on the metal substrate 200 by electron gun evaporation (e-gun evaporation), physical Vapor Deposition (PVD), chemical Vapor Deposition (CVD), plasma spraying, etc., and has a deposition thickness of 5 to 50um. The thermal barrier layer 120 is made of an oxide selected from the group consisting of yttrium (Y), gadolinium (Gd), and ytterbium (Yb) and an oxide selected from the group consisting of niobium (Nb), zirconium (Zr), aluminum (Al), and hafnium (Hf). Thus, the thermal barrier layer 120 with a low thermal conductivity is formed, and the thermal conductivity of the thermal barrier layer 120 is less than one half of the thermal conductivity of the anodized layer 220, and the thermal conductivity of the thermal barrier layer 120 is less than one half of the thermal conductivity of the plasma-erosion resistant layer 110. Further, by controlling the deposition conditions, the thermal barrier layer 120 can form an Amorphous (Amorphous) structure, which can reduce the porosity of the thermal barrier layer 120, thereby reducing the chance of plasma ions penetrating through the thermal barrier layer 120 to corrode the metal substrate 200. In a preferred embodiment, the thermal barrier layer 120 is made of yttrium stabilized zirconia (8 YSZ), which has a very low thermal conductivity (less than 4W/mk, about 25W/mk for alumina). In another embodiment, the thermal barrier layer 120 may be deposited by Ion Assisted electron gun evaporation (IAD) technique, and the thickness of the stack is 10 um-20 um.
The plasma erosion resistant layer 110 is deposited on the thermal barrier layer 120 by electron gun evaporation (e-gun evaporation), physical Vapor Deposition (PVD), chemical Vapor Deposition (CVD), and plasma spraying. The material of the plasma erosion resistant layer 110 is selected from the group consisting of oxides of aluminum (Al), yttrium (Y), erbium (Er), rhodium (Rh), and oxides, nitrides, borides, and fluorides of lanthanides. In a preferred embodiment, the material of the plasma erosion resistant layer 110 is yttrium oxide (Y2O 3) and is deposited by plasma spraying.
Referring to fig. 3, fig. 3 is a side view of a thermal barrier layer. In FIG. 3, the thermal barrier layer 120 is formed by deposition of yttrium stabilized zirconia (8 YSZ). The Thermal barrier layer 120 was observed with a Thermal Field Emission Scanning Electron Microscope (FE-SEM) at 35000 magnifications, and the porosity was confirmed to be 0.5% or less.
Referring to fig. 4, fig. 4 illustrates a method for forming a passivation layer resistant to plasma etching. First, a thermal barrier layer 120 is formed on a metal substrate 200 (step S10). In one embodiment, the metal substrate 200 includes a substrate 210 and an anodized layer 220, and the thermal barrier layer 120 is formed on the anodized layer 220 of the metal substrate 200 in step S10, and the thermal conductivity of the thermal barrier layer is less than one-half of the thermal conductivity of the anodized layer.
Further, in step S10, a Thermal Barrier layer 120 (TBC) is formed on the metal substrate 200 by electron gun evaporation (e-gun evaporation), physical Vapor Deposition (PVD), chemical Vapor Deposition (CVD), plasma spray Coating, or Ion Assisted electron gun evaporation (IAD) by lamination. The thermal barrier layer 120 is made of an oxide selected from the group consisting of yttrium (Y), gadolinium (Gd), and ytterbium (Yb) and an oxide selected from the group consisting of niobium (Nb), zirconium (Zr), aluminum (Al), and hafnium (Hf).
In a preferred embodiment, step S10 is to select yttrium-stabilized zirconia (8 YSZ) as the material, and form the thermal barrier layer 120 by Ion-Assisted electron-gun Deposition (IAD) lamination. When the ion beam assisted electron gun evaporation is carried out, the average evaporation rate of the material is 3A/s, and the temperature is kept at room temperature in the process so as to prevent the generation of thermal stress. The ion source process is conducted by introducing argon (Ar) and oxygen (O2) as plasma ion source, and performing ion beam evaporation with an ion beam intensity of at least 600V/600mA to form a thermal barrier layer 120 with a thickness of 10-20 um and an amorphous structure.
After the formation of the thermal barrier layer 120, a plasma-erosion resistant layer 110 is formed on the thermal barrier layer 120 (step S20). The plasma-erosion resistant layer 110 is formed by electron gun evaporation (e-gun evaporation), physical Vapor Deposition (PVD), chemical Vapor Deposition (CVD), plasma spraying, etc. And the material of the plasma erosion resistant layer 110 is selected from the group consisting of oxides of aluminum (Al), yttrium (Y), erbium (Er), rhodium (Rh), and oxides, nitrides, borides, and fluorides of lanthanides. In a preferred embodiment, step S20 is performed by selecting a yttrium oxide (Y2O 3) material and depositing the material by plasma spraying to form the plasma-erosion resistant layer 110. In addition, the thermal conductivity of the thermal barrier layer 120 is less than one-half of the thermal conductivity of the plasma corrosion resistant layer 110.
The protection layer for resisting plasma corrosion and the forming method thereof provided by the invention form a thermal barrier layer 120 between the metal substrate 200 and the plasma corrosion resisting layer 110, and reduce the phenomenon of thermal expansion of the metal substrate 200 by utilizing the characteristic of low thermal conductivity of the thermal barrier layer 120, thereby reducing the chance of corrosion of the metal substrate 200. In addition, the thermal barrier layer 120 also has a low porosity, which further reduces the chance of plasma penetrating the thermal barrier layer 120 to corrode the metal substrate 200 and increases the stability of the passivation layer. Therefore, the plasma corrosion resistant protective layer of the invention can improve the corrosion resistance of the plasma corrosion resistant layer of the parts in the plasma process and reduce the frequency of machine maintenance.
The above-described embodiments are merely exemplary for convenience of description, and various modifications may be made by those skilled in the art without departing from the scope of the invention as claimed in the claims.
Claims (18)
1. A protection layer for resisting plasma corrosion, formed on a metal substrate, comprising:
a thermal barrier layer disposed on the metal substrate; and
and the plasma corrosion resistant layer is arranged on the thermal barrier layer.
2. The protective layer of claim 1, wherein the metal substrate further comprises an anodized layer, and the thermal barrier layer is disposed on the anodized layer.
3. The protective layer of claim 2, wherein the thermal barrier layer has a thermal conductivity less than one-half of the thermal conductivity of the anodized layer.
4. The protective layer of claim 1, wherein the thermal barrier layer has a thermal conductivity less than one-half of the thermal conductivity of the plasma etch resistant layer.
5. The protective layer of claim 1, wherein the thermal barrier layer is an Amorphous (amophorus) structure.
6. The plasma corrosion resistant protective layer of claim 1, wherein the thermal barrier layer is selected from the group consisting of yttrium (Y), gadolinium (Gd), ytterbium (Yb) oxides and niobium (Nb), zirconium (Zr), aluminum (Al), hafnium (Hf) oxides.
7. The protective layer of claim 1, wherein the plasma corrosion resistant layer is selected from the group consisting of oxides of aluminum (Al), yttrium (Y), erbium (Er), rhodium (Rh), and oxides, nitrides, borides, and fluorides of lanthanides.
8. The protective layer of claim 1, wherein the thermal barrier layer is deposited by Ion Assisted electron gun evaporation (IAD) techniques.
9. The plasma corrosion resistant protective layer of claim 1 wherein the plasma corrosion resistant layer is deposited by plasma spraying.
10. A method of forming a protective layer resistant to plasma etching, comprising:
s10: forming a thermal barrier layer on a metal substrate; and
s20: forming a plasma corrosion resistant layer on the thermal barrier layer.
11. The method as claimed in claim 10, wherein the metal substrate further includes an anodized layer, and the thermal barrier layer is formed on the anodized layer in step S10.
12. The method of claim 11, wherein the thermal barrier layer has a thermal conductivity less than one-half of a thermal conductivity of the anodized layer.
13. The method of claim 10, wherein the thermal barrier layer has a thermal conductivity less than one-half of a thermal conductivity of the plasma etch resistant layer.
14. The method of claim 10, wherein the thermal barrier layer is of Amorphous (amophorus) structure.
15. The method of claim 10, wherein the thermal barrier layer is selected from the group consisting of yttrium (Y), gadolinium (Gd), ytterbium (Yb) oxide, and niobium (Nb), zirconium (Zr), aluminum (Al), hafnium (Hf) oxide.
16. The method according to claim 10, wherein the plasma corrosion resistant layer is selected from the group consisting of oxides of aluminum (Al), yttrium (Y), erbium (Er), rhodium (Rh), and oxides, nitrides, borides, and fluorides of lanthanides.
17. The method as claimed in claim 10, wherein the thermal barrier layer is deposited by Ion Assisted electron gun Deposition (IAD) technique.
18. The method as claimed in claim 10, wherein the plasma etching resistant layer is deposited by plasma spraying.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW110114391 | 2021-04-21 | ||
| TW110114391A TWI781593B (en) | 2021-04-21 | 2021-04-21 | Plasma resistant protective layer and formation method thereof |
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| Publication Number | Publication Date |
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| CN115223835A true CN115223835A (en) | 2022-10-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202110442122.6A Pending CN115223835A (en) | 2021-04-21 | 2021-04-23 | Plasma corrosion resistant protective layer and method for forming the same |
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| TW (1) | TWI781593B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9850568B2 (en) * | 2013-06-20 | 2017-12-26 | Applied Materials, Inc. | Plasma erosion resistant rare-earth oxide based thin film coatings |
| TWM615992U (en) * | 2021-04-21 | 2021-08-21 | 翔名科技股份有限公司 | Passivation layer capable of preventing plasma corrosion |
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- 2021-04-21 TW TW110114391A patent/TWI781593B/en active
- 2021-04-23 CN CN202110442122.6A patent/CN115223835A/en active Pending
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| TW202242197A (en) | 2022-11-01 |
| TWI781593B (en) | 2022-10-21 |
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