TWI781593B - Plasma resistant protective layer and formation method thereof - Google Patents

Abstract

A plasma resistant protective layer and a formation method thereof are provided in the present invention. The plasma resistant protective layer is formed on a metal substrate and includes a thermal barrier coating and a plasma corrosion resistant layer. The thermal barrier coating is disposed on the metal substrate, and the plasma corrosion resistant layer disposed on the thermal barrier coating. The thermal barrier coating can improve thermal expansion and contraction of plasma cavity during operation in order to avoid the peeling off of anti-plasma corrosion materials caused by stress generated between the plasma cavity and the anti-plasma corrosion material because of different coefficient of thermal expansion. Thus, the stability of plasma resistant protective layer can be increased; the plasma corrosion can be improved; and the frequency of device maintenance can be improved.

Description

Plasma corrosion-resistant protective layer and method for forming same

The present invention relates to photoelectric and semiconductor industries such as IC manufacturing, liquid crystal display panels, light-emitting diodes, micro-electromechanical and other industries that require the application of plasma processes, especially dry etching, physical vapor deposition (PVD) and plasma-enhanced chemical vapor deposition ( The technical field of PE-CVD) and other processes, especially a plasma-resistant film structure applied to any kind of photoelectric and semiconductor industry dry etching or plasma-assisted thin film process that may be exposed to plasma internal components, the protective film layer It is used to improve the yield rate of the above process and the service life of components.

In the current plasma process such as RIE (Reactive Ion Etch) or PECVD (Plasma enhanced chemical vapor deposition) environment, the vacuum chamber or parts are exposed to the reactive plasma environment, so they are very easy to be corroded.

Please refer to FIG. 1. FIG. 1 shows a common way to improve corrosion. On the anodic oxide layer 12 of the component 10, a plasma corrosion-resistant material layer 11 is coated by spraying, such as yttrium aluminum garnet (Y ₃ Al ₅ O ₁₂ ) yttrium oxide (Y ₂ O ₃ ), yttrium fluoride (YF ₃ ), yttrium oxyfluoride (YOF) and other plasma corrosion-resistant materials, because these oxides contain heavy metal atoms, they are resistant to plasma corrosion Better ability, especially when forming a certain lattice texture structure (Texture structure), such as by ion beam electron gun deposition (IAD) so that the <111> direction of the plasma erosion-resistant material lattice is arranged along the vertical direction of the substrate surface , which is covered by a small specific direction single crystal structure, which has better resistance to plasma erosion.

However, the plasma process is performed in a highly corrosive environment, even if the plasma corrosion-resistant material layer 11 is used to prevent the aluminum alloy substrate 13 from corroding. In fact, there are fine cracks caused by grain boundaries and defects on the plasma corrosion-resistant material layer 11 , and the plasma energy can still corrode the aluminum alloy substrate 13 through the cracks, resulting in the deterioration of the component 10 . In addition, the plasma process is still carried out in a high-temperature environment (200°C~300°C), and the thermal expansion coefficient of the aluminum alloy substrate is relatively large (23.2×10 ^-6 /K @ 20°C), and the expansion of the aluminum alloy substrate will expand after heating The cracks on the plasma corrosion resistant material layer 11 make the aluminum alloy substrate 13 more susceptible to plasma corrosion.

Therefore, how to solve the above problems is worthy of consideration by those skilled in the art.

In order to solve the problem that the thermal expansion of the metal substrate expands the gap of the plasma corrosion resistant material layer, the present invention adds a thermal barrier layer with low thermal conductivity between the plasma corrosion resistant layer and the anodic treatment layer. It can reduce the thermal expansion of the metal substrate, further improve the stability of the film structure and the corrosion resistance of the plasma corrosion resistance layer. The specific technical means are as follows: a plasma corrosion-resistant protective layer is formed on a metal substrate, and the plasma corrosion-resistant protective layer includes a thermal barrier layer and a plasma corrosion-resistant layer. The thermal barrier layer is disposed on the metal substrate. The plasma corrosion resistant layer is disposed on the thermal barrier layer.

In the above plasma corrosion resistant protective layer, the metal substrate further includes an anodic treatment layer, and the thermal barrier layer is disposed on the anodic treatment layer.

In the above plasma corrosion resistant protective layer, the thermal conductivity of the thermal barrier layer is less than half of the thermal conductivity of the anodized layer.

In the above plasma corrosion resistant protective layer, the thermal conductivity of the thermal barrier layer is less than half of the thermal conductivity of the plasma corrosion resistant layer.

In the above-mentioned protective layer resistant to plasma corrosion, the thermal barrier layer has an amorphous structure.

The above plasma corrosion resistant protective layer, 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) oxide group.

The above plasma corrosion resistant protective layer, wherein the plasma corrosion resistant layer is selected from oxides of aluminum (Al), yttrium (Y), erbium (Er), rhodium (Rh) and oxides and nitrides of lanthanides , the group consisting of borides and fluorides.

In the above-mentioned protective layer resistant to plasma corrosion, the thermal barrier layer is deposited and formed by ion beam assisted electron gun evaporation (Ion Assisted Deposition, IAD) technology.

In the above plasma corrosion resistant protective layer, the plasma corrosion resistant layer is deposited and formed by plasma spraying.

The invention also provides a method for forming a plasma corrosion resistant protective layer, including: 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 protective layer resistant to plasma corrosion, in step S10, the metal substrate further includes an anodic treatment layer, and the thermal barrier layer is formed on the anodic treatment layer.

In the method for forming a protective layer resistant to plasma corrosion, the thermal conductivity of the thermal barrier layer is less than half of the thermal conductivity of 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 half of the thermal conductivity of the plasma corrosion-resistant layer.

In the above method for forming the plasma corrosion resistant protective layer, the thermal barrier layer has an amorphous structure.

The above-mentioned method for forming a protective layer resistant to plasma corrosion, 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), and hafnium (Hf) oxides.

The method for forming the above-mentioned plasma corrosion-resistant protective layer, wherein the plasma corrosion-resistant layer is selected from oxides of aluminum (Al), yttrium (Y), erbium (Er), rhodium (Rh) and oxides of lanthanides , nitride, boride and fluoride group.

In the method for forming the plasma corrosion-resistant protective layer, the thermal barrier layer is formed by ion beam assisted electron gun evaporation (Ion Assisted Deposition, IAD) technology.

In the method for forming the plasma corrosion-resistant protective layer, the plasma corrosion-resistant layer is formed by depositing by plasma spraying.

10: Parts

11: Use plasma corrosion resistant material layer

12: Anodized layer

13: Metal substrate

100: protective layer resistant to plasma corrosion

110: Plasma corrosion resistant layer

120: thermal barrier layer

200: metal substrate

210: Substrate

220: Anodized layer

S10~S20: Flow chart steps

Figure 1 shows common ways to improve corrosion.

FIG. 2 is a schematic diagram of the plasma corrosion-resistant protective layer of the present invention.

Figure 3 shows a side view of the thermal barrier layer.

FIG. 4 illustrates a method for forming a protective layer resistant to plasma corrosion.

Please refer to FIG. 2 . FIG. 2 is a schematic diagram of the plasma corrosion-resistant protective layer of the present invention. The plasma corrosion resistant protection layer 100 is formed on a metal substrate 200 . The plasma corrosion resistant protective layer 100 includes a thermal barrier layer 120 and a plasma corrosion resistant layer 110 . Wherein, 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 (Thermal Barrier Coating, TBC) is laminated and formed on the metal substrate by e-gun evaporation (e-gun evaporation), physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma spraying, etc. 200, the deposition thickness is 5um~50um. The material of the thermal barrier layer 120 is selected from the group consisting of yttrium (Y), gadolinium (Gd), ytterbium (Yb) oxides and niobium (Nb), zirconium (Zr), A group consisting of aluminum (Al) and hafnium (Hf) oxides. In this way, a thermal barrier layer 120 with low thermal conductivity can be formed, and the thermal conductivity of the thermal barrier layer 120 is less than half of the thermal conductivity of the anodized layer 220, and the thermal conductivity of the thermal barrier layer 120 is less than that of the plasma corrosion resistant layer. Less than half of the thermal conductivity of 110. Further, by controlling the deposition conditions, the thermal barrier layer 120 can form an amorphous structure, which can reduce the porosity of the thermal barrier layer 120, thereby reducing the chance of plasma ions passing through the thermal barrier layer 120 to corrode the metal substrate 200 . In a preferred embodiment, the material of the thermal barrier layer 120 is yttrium stabilized zirconia (8YSZ), which has extremely low thermal conductivity (less than 4W/mk, and alumina is about 25W/mk). In another embodiment, the thermal barrier layer 120 can be deposited by ion beam assisted electron gun evaporation (Ion Assisted Deposition, IAD) technology, and the thickness of the stack is 10um˜20um.

The plasma corrosion resistant layer 110 is deposited on the thermal barrier layer 120 through e-gun evaporation, physical vapor deposition (PVD), chemical vapor deposition (CVD), and plasma spraying. The material of the plasma corrosion resistant layer 110 is selected from oxides of aluminum (Al), yttrium (Y), erbium (Er), rhodium (Rh) and oxides, nitrides, borides and fluorides of lanthanides. group. In a preferred embodiment, the material of the plasma corrosion-resistant layer 110 is yttrium oxide (Y ₂ O ₃ ), which is deposited by plasma spraying.

Please refer to FIG. 3, which is a side view of the thermal barrier layer. In FIG. 3, the thermal barrier layer 120 is formed by depositing yttrium stabilized zirconia (8YSZ). It is confirmed that the porosity of the thermal barrier layer 120 is less than 0.5% when observed by a Thermal Field Emission Scanning Electron Microscope (FE-SEM) at a magnification of 35,000.

Please refer to FIG. 4 . FIG. 4 illustrates a method for forming a protective layer resistant to plasma corrosion. First, a thermal barrier layer 120 is formed on a metal substrate 200 (step S10 ). Wherein, in one embodiment, the metal substrate 200 includes a substrate 210 and an anodized layer 220, and in step S10, the thermal barrier layer 120 is formed on the anodized layer 220 of the metal substrate 200, and the thermal barrier layer The thermal conductivity of the anodized layer is less than half of that of the anodized layer.

Further, in step S10, the thermal barrier layer 120 (Thermal Barrier Coating, TBC) is deposited via electron gun evaporation (e-gun evaporation), physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma spraying Or the ion beam assisted electron gun evaporation (Ion Assisted Deposition, IAD) method is laminated and formed on the metal substrate 200 . And the material of the thermal barrier layer 120 is selected from the group consisting of yttrium (Y), gadolinium (Gd), ytterbium (Yb) oxides and niobium (Nb), zirconium (Zr), aluminum (Al), hafnium (Hf ) group of oxides.

In a preferred embodiment, step S10 is to use yttrium stabilized zirconia (8YSZ) as the material, and form the thermal barrier layer 120 by lamination by ion beam assisted electron gun deposition (IAD). During the ion beam-assisted electron gun evaporation, the average evaporation rate of the material is 3A/s, and the temperature is kept at room temperature during the process to prevent thermal stress. Argon (Ar) and oxygen (O2) are introduced into the ion source process as the source of plasma ions, and ion beam evaporation is performed with an ion beam intensity of at least 600V/600mA to form a thickness of 10um~20um and an amorphous structure The thermal barrier layer 120.

After the thermal barrier layer 120 is formed, a plasma corrosion resistant layer 110 is formed on the thermal barrier layer 120 (step S20 ). Wherein, the plasma corrosion resistant layer 110 is formed by means of e-gun evaporation, physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma spraying and the like. And the material of the plasma corrosion resistant layer 110 is selected from the oxides of aluminum (Al), yttrium (Y), erbium (Er), rhodium (Rh) and the oxides, nitrides, borides and fluorides of lanthanide elements. group. In a preferred embodiment, step S20 is to select yttrium oxide (Y ₂ O ₃ ) material and deposit it by plasma spraying to form the plasma corrosion resistant layer 110 . In addition, the thermal conductivity of the thermal barrier layer 120 is less than half of the thermal conductivity of the plasma corrosion resistant layer 110 .

The plasma corrosion-resistant protective layer and its formation method provided by the present invention form a thermal barrier layer 120 between the metal substrate 200 and the plasma corrosion-resistant layer 110, and utilize the characteristics of the low thermal conductivity of the thermal barrier layer 120 to reduce the heat loss of the metal substrate. The thermal expansion of the metal substrate 200 reduces the chance of the metal substrate 200 being corroded. In addition, the thermal barrier layer 120 also has the characteristics of low porosity, which can further reduce the penetration of plasma through the thermal barrier layer 120. chance of corroding the metal substrate 200, and can increase the stability of the protection layer. Therefore, the plasma corrosion-resistant protective layer of the present invention can improve the corrosion resistance of the plasma corrosion-resistant layer of parts in the plasma process, and reduce the frequency of machine maintenance.

The description of the present invention is as above, but it is not intended to limit the scope of patent rights claimed by the present invention. The scope of its patent protection shall depend on the scope of the appended patent application and its equivalent fields. All changes or modifications made by those with common knowledge in the field without departing from the spirit or scope of this patent belong to equivalent changes or designs completed under the spirit disclosed in this creation, and should be included in the scope of the following patent application Inside.

100: protective layer resistant to plasma corrosion

110: Plasma corrosion resistant layer

120: thermal barrier layer

200: metal substrate

210: Substrate

220: Anodized layer

Claims (16)

A protective layer resistant to plasma corrosion is formed on a metal substrate, and the protective layer resistant to plasma corrosion includes: a thermal barrier layer disposed on the metal substrate; and a plasma corrosion resistant layer disposed on the thermal barrier layer; wherein, the thermal conductivity of the thermal barrier layer is less than half of the thermal conductivity of the plasma corrosion resistant layer. The plasma corrosion-resistant protective layer as claimed in claim 1, wherein the metal substrate further includes an anodized layer, and the thermal barrier layer is disposed on the anodized layer. The plasma corrosion-resistant protective layer according to claim 2, wherein the thermal conductivity of the thermal barrier layer is less than half of the thermal conductivity of the anodized layer. The plasma corrosion-resistant protective layer as claimed in claim 1, wherein the thermal barrier layer has an amorphous structure. The plasma corrosion-resistant protective layer as claimed in 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) oxide group. The plasma corrosion-resistant protective layer as claimed in claim 1, wherein the plasma corrosion-resistant layer is selected from oxides of aluminum (Al), yttrium (Y) rhodium (Rh) and oxides, nitrides, and lanthanides. A group consisting of borides and fluorides. The plasma corrosion-resistant protective layer as claimed in claim 1, wherein the thermal barrier layer is formed by ion beam assisted electron gun evaporation (Ion Assisted Deposition, IAD) technology. The plasma corrosion-resistant protective layer as claimed in claim 1, wherein the plasma corrosion-resistant layer is deposited and formed by plasma spraying. A method for forming a protective layer resistant to plasma corrosion, comprising: S10: forming a thermal barrier layer on a metal substrate; and S20: forming a plasma corrosion resistant layer on the thermal barrier layer; wherein, the thermal conductivity of the thermal barrier layer is the thermal conductivity of the plasma corrosion resistant layer less than half of that. The method for forming a plasma corrosion-resistant protective layer as claimed in claim 9, wherein, in step S10, the metal substrate further includes an anodized layer, and the thermal barrier layer is formed on the anodized layer. The method for forming a plasma corrosion-resistant protective layer according to claim 10, wherein the thermal conductivity of the thermal barrier layer is less than half of the thermal conductivity of the anodized layer. The method for forming a plasma corrosion-resistant protective layer as claimed in claim 9, wherein the thermal barrier layer has an amorphous structure. The method for forming a plasma corrosion-resistant protective layer as claimed in Claim 9, wherein the thermal barrier layer is selected from the group consisting of yttrium (Y), gadolinium (Gd), ytterbium (Yb) oxides and niobium ( A group consisting of Nb), zirconium (Zr), aluminum (Al), and hafnium (Hf) oxides. The method for forming a plasma corrosion-resistant protective layer as claimed in claim 9, wherein the plasma corrosion-resistant layer is selected from oxides of aluminum (Al), yttrium (Y), rhodium (Rh) and oxides of lanthanides, The group consisting of nitrides, borides and fluorides. The method for forming a plasma corrosion-resistant protective layer according to claim 9, wherein the thermal barrier layer is formed by ion beam assisted electron gun evaporation (Ion Assisted Deposition, IAD) technology. The method for forming a plasma corrosion-resistant protective layer as claimed in claim 9, wherein the plasma corrosion-resistant layer is deposited and formed by plasma spraying.

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