Method for manufacturing coating layer and plasma-resistant member manufactured by same

Abstract

An embodiment of the present invention provides a method for manufacturing a coating layer, comprising the steps of: preparing an object to be coated; forming, on the object to be coated, an aluminum oxide-based, yttrium oxide-based or zirconium oxide-based first coating layer by means of aerosol deposition; and forming, on the first coating layer, an aluminum oxide-based, yttrium oxide-based or yttrium fluoride-based second coating layer by means of physical vapor deposition, wherein the second coating layer includes an array of columnar crystals that extend perpendicularly to the surface of the object to be coated.

Description

Method for manufacturing a coating layer and plasma-resistant member manufactured thereby

[0001] The present invention relates to a method for manufacturing a coating layer and a plasma-resistant member manufactured thereby, and more specifically, to a method for manufacturing a coating layer using a heterogeneous coating method and a plasma-resistant member manufactured thereby.

[0002] The manufacturing of integrated circuit devices, such as semiconductor devices and display devices, involves etching processes in a high-density plasma environment. These etching processes in a high-density plasma environment are performed using etching equipment equipped with plasma-resistant components.

[0003] However, recent integrated circuit devices with increasingly finer line widths are manufactured by performing etching processes in a very high-density plasma environment, so components within semiconductor devices require better plasma resistance characteristics.

[0004] Furthermore, with the increasing demand for high-density semiconductor devices, research is actively underway not only on vertically stacked semiconductor devices but also on stacked packaging technologies. To implement these technologies, via holes are formed using high-energy etching processes, placing increasing demands on plasma etching equipment components for plasma resistance.

[0005] Contaminants generated from components within semiconductor devices during high-energy etching are considered a major cause of device failure. Furthermore, semiconductor device failures are caused by a complex mix of factors, including the surface roughness of internal components, chemical changes on the surface during chamber process stabilization, and the grain size of surface components.

[0006] Contaminants generated during the semiconductor manufacturing process are directly related to semiconductor yield. The harsher the processing conditions, the more damage internal device components inflicted by etching gases and ions, leading to an increase in contaminants. The surface roughness of internal semiconductor device components during the process is further increased by etching gases, further increasing the number of fine contaminants, creating a vicious cycle of lowered product yields.

[0007] Therefore, when a high-power plasma (e.g., 10 kW or more) process is performed to manufacture ultra-fine line widths, minimizing contaminant particles generated from internal components of devices such as chambers is emerging as a very important topic.

[0008] One aspect of the present invention is to improve the plasma resistance characteristics of internal components of a semiconductor device such as an etching device.

[0009] An embodiment of the present invention provides a method for manufacturing a coating layer, comprising the steps of: preparing a coating object; forming a first coating layer of an aluminum oxide-based, yttrium oxide-based, or zirconium oxide-based on the coating object by aerosol deposition; and forming a second coating layer of an aluminum oxide-based, yttrium oxide-based, or yttrium fluoride-based on the first coating layer by physical vapor deposition; wherein the second coating layer includes an array of columnar crystals extending in a direction perpendicular to the surface of the coating object.

[0010] An embodiment of the present invention provides a method for manufacturing a coating layer, wherein the average width of the columnar structure is 50 to 350 μm.

[0011] An embodiment of the present invention provides a method for manufacturing a coating layer, wherein the first coating layer is formed of Al2O3, Y2O3, YSZ (Yttria Stabilized Zirconia), YAG (Yttrium Aluminum Garnet), YAM (Yttrium Aluminum Monoclinic), or YAP (Yttrium Aluminum Perovskite).

[0012] An embodiment of the present invention provides a method for manufacturing a coating layer, wherein the first coating layer has a thickness of 0.1 µm or more and 2 µm or less.

[0013] An embodiment of the present invention provides a method for manufacturing a coating layer, wherein the first coating layer has a surface roughness Ra of 0.04 µm or more and 0.08 µm or less.

[0014] An embodiment of the present invention provides a method for manufacturing a coating layer, wherein the second coating layer is formed of Al2O3, Y2O3, YOF (Yttrium Oxyfluoride), YF3 (Yttrium Fluoride), YAG (Yttrium Aluminum Garnet), YAM (Yttrium Aluminum Monoclinic), or YAP (Yttrium Aluminum Perovskite).

[0015] An embodiment of the present invention provides a method for manufacturing a coating layer, wherein the second coating layer is formed by EB-PVD (Electron-Beam Physical Vapor Deposition) or IBAD (Ion Beam Assisted Deposition).

[0016] An embodiment of the present invention provides a method for manufacturing a coating layer, wherein the second coating layer has a thickness of 5 µm or more and 10 µm or less.

[0017] An embodiment of the present invention provides a plasma-resistant member including a coating object; and a coating layer formed on the coating object, wherein the coating layer includes a first coating layer formed on the coating object of an aluminum oxide system, a yttrium oxide system, or a zirconium oxide system; and a second coating layer formed on the first coating layer of an aluminum oxide system, a yttrium oxide system, or a yttrium fluoride system, wherein the second coating layer includes an array of columnar crystals extending in a direction perpendicular to a surface of the coating object.

[0018] An embodiment of the present invention provides a plasma-resistant member, wherein the second coating layer includes a columnar shape having a width of 50 nm or more and 350 nm or less.

[0019] An embodiment of the present invention provides a plasma-resistant member in which the first coating layer is formed by aerosol deposition.

[0020] An embodiment of the present invention provides a plasma-resistant member in which the second coating layer is formed by EB-PVD (Electron-Beam Physical Vapor Deposition) or IBAD (Ion Beam Assisted Deposition).

[0021] An embodiment of the present invention provides a plasma-resistant member, wherein the first coating layer is formed of Al2O3, Y2O3, YSZ (Yttria Stabilized Zirconia), YAG (Yttrium Aluminum Garnet), YAM (Yttrium Aluminum Monoclinic), or YAP (Yttrium Aluminum Perovskite).

[0022] An embodiment of the present invention provides a plasma-resistant member, wherein the first coating layer has a thickness of 0.1 µm or more and 2 µm or less.

[0023] An embodiment of the present invention provides a plasma-resistant member in which the first coating layer has a surface roughness Ra of 0.04 µm or more and 0.08 µm or less.

[0024] An embodiment of the present invention provides a plasma-resistant member, wherein the second coating layer is formed of Al2O3, Y2O3, YOF (Yttrium Oxyfluoride), YF3 (Yttrium Fluoride), YAG (Yttrium Aluminum Garnet), YAM (Yttrium Aluminum Monoclinic), or YAP (Yttrium Aluminum Perovskite).

[0025] An embodiment of the present invention provides a plasma-resistant member in which the second coating layer has a thickness of 5 µm or more and 10 µm or less.

[0026] According to an embodiment of the present invention, the plasma resistance characteristics of a semiconductor manufacturing device can be improved.

[0027] In addition, according to an embodiment of the present invention, the hardness of a coating layer formed in a semiconductor manufacturing device can be improved.

[0028] In addition, according to an embodiment of the present invention, the bonding strength of a coating layer formed in a semiconductor manufacturing device can be improved.

[0029] FIG. 1 is a schematic partial cross-sectional view of a plasma member having a coating layer applied thereto according to an embodiment of the present invention.

[0030] Figure 2 is a process diagram showing a method for manufacturing a coating layer according to an embodiment of the present invention.

[0031] Figure 3 is a graph showing the results of X-ray diffraction analysis of a coating layer manufactured according to an embodiment of the present invention and a coating layer of a comparative example.

[0032] Fig. 4 is a photograph showing the surface roughness of the first coating layer according to an embodiment of the present invention.

[0033] Figure 5 is a graph showing surface roughness according to the thickness of the first coating layer according to an embodiment of the present invention.

[0034] Figure 6 is a photograph showing the surface roughness of a second coating layer according to an embodiment of the present invention and a comparative example.

[0035] Figure 7 is a photograph showing the surface and cross-section of a coating layer according to an embodiment of the present invention and a comparative example.

[0036] Figure 8 is a graph showing the bonding strength of a coating layer according to an embodiment of the present invention and a coating layer of a comparative example.

[0037] Figure 9 is a graph showing the hardness of a coating layer according to an embodiment of the present invention and a coating layer of a comparative example.

[0038] Figure 10 is a graph showing the etching rate of a coating layer according to an embodiment of the present invention and a coating layer of a comparative example.

[0039] Figure 11 is a graph showing the F ion penetration depth of a coating layer according to an embodiment of the present invention and a coating layer of a comparative example.

[0040] Hereinafter, embodiments disclosed in the present specification will be described in detail with reference to the attached drawings. Regardless of the drawing numbers, identical or similar components will be given the same reference numerals and redundant descriptions thereof will be omitted. Hereinafter, in the description of embodiments according to the present invention, when each layer (film), region, pattern or structure is described as being formed "on" or "under" the substrate, each layer (film), region, pad or pattern, "on" and "under" include both "directly" and "indirectly" forming the structure. In addition, the reference for above / above or below / under each layer will be described based on the drawings. In the drawings, the thickness or size of each layer is exaggerated, omitted or schematically illustrated for convenience and clarity of description. In addition, the size of each component does not entirely reflect the actual size.

[0041] In this description, expressions such as "including," "having," or "comprises" are intended to indicate certain features, numbers, steps, operations, elements, portions or combinations thereof, and should not be construed to exclude the presence or possibility of one or more other features, numbers, steps, operations, elements, portions or combinations thereof other than those described.

[0042] Additionally, although terms such as first, second, etc. may be used to describe various components, the components are not limited by the terms, and the terms are used only for the purpose of distinguishing one component from another.

[0043] In addition, when describing the embodiments disclosed in this specification, if it is determined that a detailed description of a related known technology may obscure the gist of the embodiments disclosed in this specification, the detailed description is omitted.

[0044] The attached drawings are only intended to facilitate understanding of the embodiments disclosed in this specification, and the technical ideas disclosed in this specification are not limited by the attached drawings, and should be understood to include all modifications, equivalents, or substitutes included in the spirit and technical scope of the present invention.

[0045] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

[0046] FIG. 1 is a schematic partial cross-sectional view of a plasma member having a coating layer applied thereto according to an embodiment of the present invention.

[0047] The plasma-resistant member (100) is a component or part (coating target) of a manufacturing device used in a high-density plasma environment, etc., and is a component or part that requires plasma-resistant characteristics. The member (100) requiring plasma-resistant characteristics may be, for example, an inner wall of a plasma chamber, a ceramic window, a focus ring, a source coil, a heating plate, an insert ring, a shield ring, a protection ring, an electrostatic chuck, etc.

[0048] The surface (110) of the member (100) exposed to a process such as plasma etching may be a surface of a substrate on which a plasma-resistant coating layer (200, 300) is applied. The material of the portion of the member (100) that becomes the substrate on which the coating layer (200, 300) is formed may be a metal such as iron, magnesium, aluminum, or an alloy thereof; a ceramic such as Al2O3, Y2O3, Al2O3+YAG (Yttrium Aluminum Garnet), SiO2, MgO, CaCO3, or quartz; or a polymer such as polyethylene terephthalate, polyethylene naphthalate, polypropylene adipate, or polyisocyanate.

[0049] Two or more coating layers (200, 300) may be applied to the member (100) using a heterogeneous coating method. The first coating layer (200) is a bond layer that joins the member (100) and the second coating layer (300). The second coating layer (300) is a coating layer that is applied over the first coating layer (200) to protect the member (100) from a process environment such as plasma etching.

[0050] Figure 2 is a process diagram showing a method for manufacturing a coating layer according to an embodiment of the present invention.

[0051] First, a member (100) that is a coating target on which a plasma coating layer (200, 300) is to be formed is prepared (S400). The member (100) may be, as described above, an inner wall of a plasma chamber, a ceramic window, a focus ring, a source coil, a heating plate, an insert ring, a shield ring, a protection ring, an electrostatic chuck, etc., but is not limited thereto.

[0052] A first coating layer (200), which is a bonding layer, is formed on the surface (110) of the member (100) (S410). The first coating layer can be formed by aerosol deposition (AD). In the present invention, aerosol deposition refers to a technology of forming a high-density coating film by colliding fine particles of nanometer to micrometer size with the surface of an object at a very high speed in a vacuum environment without a separate melting process. Specifically, it is a method of forming a ceramic coating layer on the substrate by spraying fine ceramic particles from a nozzle toward the substrate and colliding them, and using the impact force. In a vacuum environment, fine particles of nanometer to micrometer size can be collided with the surface of a product at a high speed without a separate melting process, thereby forming a high-density coating layer without pores. In the present invention, the particles supplied to the nozzle may be in an aerosol state, but are not limited thereto.

[0053] An example of the aerosol deposition process is as follows.

[0054] A carrier gas such as Ar or He is introduced into an aerosol chamber containing ceramic particle powder through a flow control device. The ceramic particles in the aerosol chamber are carried by the carrier gas and sprayed through a nozzle onto a coating target in a vacuum deposition chamber. The coating target is mounted on an XYZ stage, positioner, or robot, and moves in the X and Y axes by the movement of the stage, and coating is performed. The vacuum level inside the deposition chamber is controlled by a pump. The nozzle size for aerosol deposition can be 2 mm to 50 mm, and the flow rate can be 1 L / min to 60 L / min.

[0055] The first coating layer (200) may be coated with ceramic particles of an aluminum oxide-based material, a yttrium oxide-based material, or a zirconium oxide-based material, such as Al2O3, Y2O3, YSZ (Yttria Stabilized Zirconia), YAG (Yttrium Aluminum Garnet), YAM (Yttrium Aluminum Monoclinic), or YAP (Yttrium Aluminum Perovskite). The first coating layer (200) may include a crystalline, amorphous, or a mixed crystalline and amorphous material.

[0056] The thickness of the first coating layer (200) can be controlled by adjusting the moving speed of the coating object or the number of coatings. In an embodiment of the present invention, the thickness of the first coating layer (200) may be 0.1 μm or more and 2 μm or less. When the thickness of the first coating layer (200) is less than 0.1 μm, it is impossible to prevent defects (pitting) existing on the surface (110) of the member from affecting the formation of the second coating layer (300), and the bonding strength of the coating layer may be reduced. When the thickness of the first coating layer (200) exceeds 2 μm, the columnar structure of the second coating layer (300) may grow excessively, causing cracks to occur in the second coating layer (300). Preferably, the thickness of the first coating layer (200) may be 0.2 μm or more and 1.0 μm or less.

[0057] When an aerosol deposition coating layer (200) is formed on a member (100) having a large surface roughness, the surface roughness of the first coating layer (200) also increases, so the member surface (110) can be mirror-finished before forming the first coating layer (200). Mirror-finishing is used to make the member surface (110) smooth, and methods include lapping, polishing, chemical mechanical polishing (CMP), grinding, polishing, cutting, and machining.

[0058] It is preferable that the surface roughness Ra of the member surface (110) is 0.1 ㎛ or less. If the surface roughness Ra of the member surface (110) exceeds 0.1 ㎛, defects (pitting) on ​​the surface (110) of the member may increase, which may deteriorate the quality of the coating layer. The surface roughness Ra of the member surface (110) may be 0.03 ㎛ or more and 0.1 ㎛ or less.

[0059] Since the surface roughness of the first coating layer (200) affects the surface roughness of the second coating layer (300) described below, the surface roughness of the first coating layer (200) may be 0.1 ㎛ or less. The surface roughness Ra of the first coating layer (200) may be 0.03 ㎛ or more and 0.1 ㎛ or less, and preferably 0.04 ㎛ or more and 0.08 ㎛ or less.

[0060] Aerosol deposition allows for high-speed coating because the powder to be coated is directly sprayed, and since the thickness of the coating layer is proportional to the number of coatings, it is easy to control the thickness of the coating layer.

[0061] A second coating layer (300) is formed on the first coating layer (200) (S420). The second coating layer (300) is preferably formed using a different coating process from the first coating layer (200). The second coating layer (300) has strong resistance to plasma exposed during a semiconductor process, thereby enabling components of semiconductor devices, such as semiconductor etching devices, to secure corrosion resistance against plasma.

[0062] The second coating layer (300) can be formed by a process that can satisfy requirements such as strong bonding force and corrosion resistance. In an embodiment of the present invention, the second coating layer (300) can be formed by physical vapor deposition (PVD). Preferably, the second coating layer (300) can be formed by electron-beam physical vapor deposition (EB-PVD) or ion beam assisted deposition (IBAD). EB-PVD coating using electron beam equipment is a deposition method that melts and vaporizes a raw material and then deposits it on a substrate, and is a type of physical coating method that utilizes the phase change (solid phase → liquid phase → vapor phase → solid phase) of the material in the process, while IBAD is a deposition method that combines electron beam evaporation and ion beam deposition technology.

[0063] Below, the process of forming a second coating layer (300) using the IBAD method is described.

[0064] In an embodiment of the present invention, a second coating layer (300) was deposited on the surface of the first coating layer (200) by applying an electron beam of 20 to 30 kW at a deposition chamber temperature of 250 to 400°C. The formation of the second coating layer (300) was about 2 × 10 -4 It was carried out in a vacuum of 10 torr.

[0065] The second coating layer (300) can be coated with a ceramic material such as an aluminum oxide, a yttrium oxide, or a yttrium fluoride, such as Al2O3, Y2O3, YOF (Yttrium Oxyfluoride), YF3 (Yttrium Fluoride), YAG (Yttrium Aluminum Garnet), YAM (Yttrium Aluminum Monoclinic), or YAP (Yttrium Aluminum Perovskite).

[0066] When the second coating layer (300) is formed by EB-PVD, which is a different process from the process of forming the first coating layer (200), an array of columnar grains, i.e., a columnar structure, in which columnar grains grown on the surface of the first coating layer (200) are gathered is formed on the second coating layer (300). The columnar grains grow in a vertical direction (in the thickness direction of the second coating layer (300)) on the surface of the first coating layer (200).

[0067] According to an embodiment of the present invention, the width a of the columnar grains grown vertically on the second coating layer (300) increases, thereby improving the hardness of the coating layer. It is preferable that the average width of the columnar grains be 50 nm or more and 350 nm or less. If the average width of the columnar grains is less than 50 nm, the effect of improving the hardness of the coating layer due to the columnar structure does not appear. If the average width of the columnar grains exceeds 350 nm, cracks may occur in the longitudinal direction of the columnar grains (the direction perpendicular to the width), that is, in the thickness direction of the second coating layer (300). The average width of the columnar grains can be calculated by measuring the widths of the main grains located at 10 points at regular intervals in an arbitrary region. The width of the columnar grains can be measured by selecting the middle part in the longitudinal direction of the columnar grains, but is not limited thereto, and a person having ordinary skill in the art to which the present invention pertains can appropriately select and measure it.

[0068] The thickness of the second coating layer (300) is preferably 5 μm or more and 10 μm or less. If the thickness of the second coating layer (300) is less than 5 μm, the plasma resistance characteristics for harsh environments such as etching processes may be reduced. If the thickness of the second coating layer (300) exceeds 10 μm, cracks may occur due to stress applied to the second coating layer (300), causing the second coating layer (300) to break.

[0069] Below, the experimental results for a heterogeneous coating layer (200, 300) manufactured according to an embodiment of the present invention and a comparative example (single coating layer) are described.

[0070] In a comparative example, a Y2O3 single coating layer was deposited on a coating target using the IBAD process. In an embodiment of the present invention, a Y2O3 coating layer was deposited on the first coating layer (200) using the aerosol deposition process, and a Y2O3 coating layer was deposited on the second coating layer (300) using the IBAD process.

[0071] Figure 3 is a graph showing the results of X-ray diffraction analysis of a coating layer manufactured according to an embodiment of the present invention and a coating layer of a comparative example.

[0072] Figure 3a shows the results of X-ray diffraction analysis of a comparative example in which a single coating layer is formed, and Figure 3b shows the results of X-ray diffraction analysis of a coating layer of an example of the present invention in which a heterogeneous coating layer is formed.

[0073] The X-ray source used was Cu, and 2θ was measured in the range of 25.1 to 33.1. In the comparative example, a full width at half maximum (FWHM) of 1.331° and a columnar width of 61.0 angstroms (Å) were measured. In the embodiment of the present invention, a full width at half maximum (FWHM) of 1.207° and a columnar width of 67.2 angstroms were measured.

[0074] Fig. 4 is a photograph showing the surface roughness of the first coating layer according to an embodiment of the present invention.

[0075] Fig. 4 is an optical microscope photograph measured at a magnification of 400 times, showing the surface of the first coating layer that was subjected to the aerosol deposition process once (1 pass) (Fig. 4a), twice (2 passes) (Fig. 4b), and three times (3 passes) (Fig. 4c), respectively. In the first coating layer (200) that was subjected to the aerosol deposition process once, it was observed that a defect (dotted circle area) was generated in the first coating layer (200) due to a defect (pitting) in the substrate, which is the surface (110) of the member, and the surface roughness Ra of the first coating layer (200) was measured to be 0.078 ㎛. When the aerosol deposition process was performed twice and three times, the defects generated in the first coating layer (200) were reduced, and the surface roughness Ra was also reduced to 0.068 ㎛ and 0.067 ㎛, respectively.

[0076] FIG. 5 is a graph showing surface roughness according to the thickness of the first coating layer according to an embodiment of the present invention, and Table 1 shows the thickness and surface roughness Ra of the first coating layer (200) according to the number of coatings of the first coating layer (200).

[0077] Number of coatings (times) Thickness (㎛) Ra (㎛) 10.100.07820.180.06830.200.06750.330.049100.650.120150.980.128281.810.150

[0078] When the number of coatings of the first coating layer (200) was up to 5 and the thickness of the first coating layer (200) became 0.33㎛, the surface roughness Ra decreased the most to 0.049㎛. When the number of coatings exceeded 5, the surface roughness Ra increased again. Fig. 6 is a photograph showing the surface roughness of the second coating layer according to an embodiment of the present invention and a comparative example. Fig. 6 is an optical microscope photograph measured at a magnification of 400x. FIG. 6a is a photograph of a surface of a member (110) before performing a coating process, FIG. 6b is a photograph of a surface of a member (110) in which aerosol deposition is performed once to form a first coating layer (200) with a thickness of 150 nm, FIG. 6c is a photograph of a surface of a member (110) in which aerosol deposition is performed twice to form a first coating layer (200) with a thickness of 300 nm, and FIG. 6d is a photograph of a surface of a member (110) in which aerosol deposition is performed three times to form a first coating layer (200) with a thickness of 500 nm. FIG. 6e is a photograph of a surface of a comparative example in which a single coating layer (30) with a thickness of 10 μm is formed on a surface of a member (110) by an IBAD process, and FIG. 6f is a photograph of a surface in which a second coating layer (300) with a thickness of 10 μm is formed on the first coating layer (200) of FIG. 6b, FIG. 6g is a surface photograph of a second coating layer (300) formed with a thickness of 10 μm on the first coating layer (200) of FIG. 6c, and FIG. 6h is a surface photograph of a second coating layer (300) formed with a thickness of 10 μm on the first coating layer (200) of FIG. 6d.

[0079] In Fig. 6a, the black portion is a defect (pitting) that the substrate, which is the surface (110) of the member, has, and in Figs. 6b to 6g, the black portion is a defect in the coating film that occurs due to the defect (pitting) of the substrate.

[0080] Tables 2 (a), (b), (c), (d), (e), (f), (g), and (h) represent the surface roughness Ra (linear roughness) and Sa (area roughness) corresponding to the photographs in Figs. 6a to 6h, respectively. The units of the surface roughness Ra (linear roughness) and Sa (area roughness) are μm.

[0081] Classification (a) (b) (c) (d) (e) (f) (g) (h) Ra 0.036 0.078 0.068 0.067 0.059 0.069 0.068 0.067 Sa 0.078 0.087 0.081 0.075 0.098 0.080 0.074 0.070

[0082] Referring to FIG. 6 and Table 2, the surface roughness of the first coating film (200) increases compared to the surface roughness of the member surface (110). This is due to the impact of the aerosol when forming the first coating film (200). However, referring to FIGS. 6f to 6h, it can be seen that the defects occurring in the second coating film (200) are reduced compared to the comparative example (FIG. 6e). This is because the first coating layer (200) acting as a buffer layer has the effect of reducing the defects occurring in the second coating layer (300). FIG. 7 is a photograph showing the surface and cross-section of a coating layer according to an embodiment of the present invention and a comparative example. FIG. 7 is a SEM photograph (magnification 5,000 times) measuring the surface and cross-section of the coating layer at an acceleration voltage of 10.0 kV. FIG. 7a is a surface photograph of a comparative example in which a single coating layer is formed, and 7b is a cross-sectional photograph of the comparative example. The thickness of the single coating layer (30) of the comparative example is 10 μm.

[0083] Figures 7c to 7h are photographs of coating layers according to embodiments of the present invention. Figure 7c is a surface photograph of a first coating layer (200) having a thickness of 150 nm and a second coating layer (300) having a thickness of 10 μm, and Figure 7d is a cross-sectional photograph. Figure 7e is a surface photograph of a first coating layer (200) having a thickness of 300 nm and a second coating layer (300) having a thickness of 10 μm, and Figure 7f is a cross-sectional photograph. Figure 7g is a surface photograph of a first coating layer (200) having a thickness of 500 μm and a second coating layer (300) having a thickness of 10 μm, and Figure 7h is a cross-sectional photograph.

[0084] Referring to Fig. 7, it can be seen that the width of the columnar structure of the second coating layer (300) according to the embodiment of the present invention is larger than the width of the columnar structure of the comparative example. In the embodiment of the present invention, the first coating layer (200) formed by aerosol deposition acts as a seed or buffer layer for IBAD deposition of the second coating layer (300). Therefore, due to the first coating layer (200), the width of the columnar structure formed in the second coating layer (300) increases compared to the prior art.

[0085] Table 3 shows the widths of the main phases of the coating layers of the examples and comparative examples of the present invention. (a), (c), (e), and (g) of Table 3 correspond to Figs. 7a, 7c, 7e, and 7g, respectively.

[0086] (a) (c) (e) (g) Width of the column (Angstrom) 61.0145.1150.3181.3

[0087] It can be seen that the width of the columnar shape of the coating layer according to the embodiment of the present invention has increased compared to the comparative example. Fig. 8 is a graph showing the bonding strength of the coating layer according to the embodiment of the present invention and the coating layer of the comparative example. The bonding strength of the coating layer represents the sum of the bonding strengths between the member (100), the first coating layer (200), and the second coating layer (300). In Fig. 8, the y-axis represents the bonding strength, and the unit of the bonding strength is N.

[0088] The single coating layer (30) of the comparative example has a thickness of 10 μm. The total thickness of the coating layers (200, 300) of the embodiment of the present invention is 10.5 μm, with the first coating layer (200) having a thickness of 500 nm and the second coating layer (300) having a thickness of 10 μm. For each of the embodiment and comparative example of the present invention, three samples were produced and the bonding strength was measured.

[0089] Table 4 shows the bonding strength measured for the samples, and Fig. 8 is a graph showing the average of the bonding strength measured for the samples. As shown in Table 4, the bonding strength of the coating layer according to the embodiment of the present invention was improved by approximately 21% compared to the comparative example.

[0090] Sample 1 Sample 2 Sample 3 Average comparison Example 13.77 15.44 16.24 15.15 Example 20.02 18.62 16.31 18.32

[0091] FIG. 9 is a graph showing the hardness of a coating layer according to an embodiment of the present invention and a coating layer of a comparative example. In an embodiment of the present invention, indentation hardness (HIT) was measured. In FIG. 9, the y-axis represents the plastic hardness, and the unit of the plastic hardness is GPa. The single coating layer (30) of the comparative example has a thickness of 10 μm. The total thickness of the coating layers (200, 300) of the embodiment of the present invention is 10.5 μm, where the first coating layer (200) has a thickness of 500 nm, and the second coating layer (300) has a thickness of 10 μm. For each of the embodiment of the present invention and the comparative example, four samples were produced and the plastic hardness was measured. Table 5 shows the plastic hardness measured for the samples, and FIG. 9 is a graph showing the average of the plastic hardness measured for the samples. As shown in Table 5, the plastic hardness of the coating layer according to the embodiment of the present invention was improved by about 22% compared to the comparative example.

[0092] Sample 1 Sample 2 Sample 3 Sample 4 Average comparison Example 12.63412.59112.11211.57112.227 Example 14.28215.16515.73514.39614.895

[0093] Fig. 10 is a graph showing the etching rate of a coating layer according to an embodiment of the present invention and a coating layer of a comparative example. In Fig. 10, the y-axis is the etching rate, and the unit of the etching rate is nm / min. In Fig. 10, (a) is a comparative example in which a coating layer with a thickness of 10 μm is formed on the surface (110) of a member by the IBAD process, (b) is an example in which aerosol deposition is performed once on the surface (110) of a member to form a first coating layer (200) with a thickness of 150 nm and a second coating layer with a thickness of 10 μm, (c) is an example in which aerosol deposition is performed twice on the surface (110) of a member to form a first coating layer (200) with a thickness of 300 nm and a second coating layer with a thickness of 10 μm, and (d) is an example in which aerosol deposition is performed three times on the surface (110) of a member to form a first coating layer (200) with a thickness of 500 nm and a second coating layer with a thickness of 10 μm. The etching test was performed at an RF power of 600 W, a bias power of 400 W, and an etching gas of CF4:O2:Ar = It was performed under the conditions of 30:5:10 (sccm), pressure 10 mTorr, and time 240 minutes.

[0094] As shown in Fig. 10, the etching rate of the comparative example was 3.50 nm / min, while the etching rates of the examples of the present invention were measured as 3.05 nm / min, 2.86 nm / min, and 2.34 nm / min, respectively.

[0095] Figure 11 is a graph showing the F ion penetration depth of a coating layer according to an embodiment of the present invention and a coating layer of a comparative example.

[0096] Fig. 11 shows the results of measuring the F ion penetration depth for the same comparative example and embodiment as Fig. 10. Figs. 11a, 11b, 11c, and 11d correspond to (a), (b), (c), and (d) of Fig. 10, respectively. In Fig. 11, F1s is a graph for F ions. As shown in Fig. 11, it can be seen that the penetration depth and amount of F ions increase during the etching process in the coating layer according to the embodiment of the present invention as the thickness of the first coating layer (200) increases. In the comparative example (Fig. 11a), the F ions penetrated to a depth of about 120 nm, but in the embodiments of the present invention (Figs. 11b, 11c, and 11d), the F ions penetrated to a depth of 1,000 nm or more. That is, the width of the columns increases, so that the F ions can easily penetrate into the gaps between the columns. For example, if the second coating layer (300) is Y2O3 with a cubic structure, the volume expands by approximately 5% as F ions penetrate and change into YOF with a trigonal structure. As a result, the second coating layer (300) becomes a more dense equiaxed material, and thus the plasma resistance characteristics can be improved.

[0097] As described above, according to an embodiment of the present invention, the generation of contaminant particles and surface damage can be suppressed, thereby extending the lifespan of semiconductor device components and improving the production yield and operating rate.

[0098] As described above, the present invention has been described with specific details such as specific components and limited embodiments and drawings, but these are provided only to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and those with ordinary skill in the art to which the present invention pertains may make various modifications and variations without departing from the essential characteristics of the present invention. Therefore, the spirit of the present invention should not be limited to the described embodiments, and all technical ideas that are equivalent or equivalent to the following claims as well as the claims should be interpreted as being included in the scope of the rights of the present invention. In addition, each of the above embodiments can be combined and operated as needed.

Claims

1. Step of preparing the coating target; A step of forming a first coating layer of aluminum oxide, yttrium oxide or zirconium oxide on the coating target object by aerosol deposition; and A method for manufacturing a coating layer, comprising: forming a second coating layer of aluminum oxide, yttrium oxide or yttrium fluoride on the first coating layer by physical vapor deposition; A method for manufacturing a coating layer, wherein the second coating layer comprises an array of columnar crystals extending in a vertical direction on the surface of the first coating layer.

2. In paragraph 1, A method for manufacturing a coating layer, wherein the average width of the above-mentioned columnar structures is 50 to 350 ㎛.

3. In paragraph 1, A method for manufacturing a coating layer, wherein the first coating layer is formed of Al2O3, Y2O3, YSZ (Yttria Stabilized Zirconia), YAG (Yttrium Aluminum Garnet), YAM (Yttrium Aluminum Monoclinic), or YAP (Yttrium Aluminum Perovskite).

4. In paragraph 1, A method for manufacturing a coating layer, wherein the first coating layer has a thickness of 0.1 ㎛ or more and 2 ㎛ or less.

5. In paragraph 1, A method for manufacturing a coating layer, wherein the first coating layer has a surface roughness Ra of 0.04 ㎛ or more and 0.08 ㎛ or less.

6. In paragraph 1, A method for manufacturing a coating layer, wherein the second coating layer is formed of Al2O3, Y2O3, YOF (Yttrium Oxyfluoride), YF3 (Yttrium Fluoride), YAG (Yttrium Aluminum Garnet), YAM (Yttrium Aluminum Monoclinic), or YAP (Yttrium Aluminum Perovskite).

7. In paragraph 6, A method for manufacturing a coating layer, wherein the second coating layer is formed by EB-PVD (Electron-Beam Physical Vapor Deposition) or IBAD (Ion Beam Assisted Deposition).

8. In paragraph 1, A method for manufacturing a coating layer, wherein the second coating layer has a thickness of 5 ㎛ or more and 10 ㎛ or less.

9. Coating target; and In the plasma member including a coating layer formed on the coating target object, The above coating layer is, A first coating layer of aluminum oxide, yttrium oxide or zirconium oxide formed on the coating target; and A second coating layer of aluminum oxide, yttrium oxide or yttrium fluoride formed on the first coating layer; A plasma-resistant member, wherein the second coating layer comprises an array of columnar elements extending in a vertical direction on the surface of the first coating layer.

10. In paragraph 9, A plasma-resistant member having an average width of the above-mentioned main body of 50 to 350 μm.

11. In paragraph 9, The first coating layer is a plasma-resistant member formed by aerosol deposition.

12. In paragraph 11, The second coating layer is a plasma-resistant member formed by EB-PVD (Electron-Beam Physical Vapor Deposition) or IBAD (Ion Beam Assisted Deposition).

13. In paragraph 9, A plasma-resistant member, wherein the first coating layer is formed of Al2O3, Y2O3, YSZ (Yttria Stabilized Zirconia), YAG (Yttrium Aluminum Garnet), YAM (Yttrium Aluminum Monoclinic), or YAP (Yttrium Aluminum Perovskite).

14. In paragraph 9, The first coating layer is a plasma-resistant member having a thickness of 0.1 ㎛ or more and 2 ㎛ or less.

15. In paragraph 9, The first coating layer is a plasma-resistant member having a surface roughness Ra of 0.04 ㎛ or more and 0.08 ㎛ or less.

16. In paragraph 9, The second coating layer is a plasma-resistant member formed of Al2O3, Y2O3, YOF (Yttrium Oxyfluoride), YF3 (Yttrium Fluoride), YAG (Yttrium Aluminum Garnet), YAM (Yttrium Aluminum Monoclinic), or YAP (Yttrium Aluminum Perovskite).

17. In paragraph 9, The second coating layer is a plasma-resistant member having a thickness of 5 ㎛ or more and 10 ㎛ or less.

Images