Preparation method of anodic oxidation coating for semiconductor processing equipment component

Abstract

The invention belongs to the technical field of aluminum alloy material surface treatment, and particularly relates to a preparation method of an anodic oxidation coating for a semiconductor processing equipment part. Comprising the following steps that a solid solution layer or a cladding layer is formed on pretreated aluminum alloy through a vacuum laser treatment method, and the cladding layer is an aluminum layer; in the laser treatment process, the laser power ranges from 200 W to 400 W, and the scanning rate ranges from 800 mm / s to 2000 mm / s; and the aluminum alloy sample subjected to laser treatment is placed in an anodic oxidation electrolyte to be treated, an anodic oxidation coating is formed on the surface of the aluminum alloy, hole sealing treatment is conducted on the anodic oxidation coating, and the anodic oxidation coating for the semiconductor processing equipment component is obtained. According to the method, laser is adopted for conducting surface remelting or pure aluminum layer cladding on the aluminum alloy, a second phase cluster on the surface layer of the aluminum alloy sample is reduced or eliminated, the anodic oxidation thickness prepared after the aluminum alloy is subjected to laser pretreatment is uniform, large-size holes do not exist, and the compactness of a subsequent anodic oxidation coating is effectively improved.

Description

Technical Field

[0001] The invention belongs to the technical field of surface treatment of aluminum alloy materials, and in particular relates to a method for preparing an anodic oxidation coating for semiconductor process equipment components. Background Art

[0002] A typical semiconductor manufacturing process includes steps such as thin film deposition, spin coating of photoresist, exposure, development, plasma etching and removal of photoresist. The processing accuracy of photolithography, plasma etching and thin film deposition plays a decisive role in the performance and yield of the chip. However, in the etching and thin film deposition process of semiconductor manufacturing, a large amount of corrosive gases such as Cl2, HCl, HBr, NF3 are used, and wet chemical cleaning requires contact with strong acid solutions such as hydrochloric acid. These corrosive gases and acidic solutions will corrode the chamber components of the equipment, and the corrosion products on the surface will peel off and form particles. The particles will fall to the surface of the wafer, which will cause a short circuit in the circuit and reduce the yield of the chip. Therefore, special attention should be paid to the corrosion of the chamber components in the etching and thin film deposition equipment. Since the 1980s, 6061-T6 aluminum alloy has been often used to manufacture chamber components of etching and thin film deposition equipment because of its moderate strength, easy processing and good corrosion resistance. In the environment of corrosive gases and acidic solutions, aluminum alloys are still susceptible to corrosion, which will cause damage to parts. Therefore, it is necessary to prepare a protective coating on the surface of aluminum alloy to reduce the corrosion of chamber components, so as to extend the life of chamber components and the yield rate of chips. Anodized coating has excellent corrosion resistance, simple preparation and low cost, and is widely used for corrosion protection of aluminum alloy parts for semiconductor process equipment.

[0003] At present, the traditional anodizing treatment only involves alkaline degreasing and acid washing of 6061-T6 aluminum alloy, which cannot eliminate the large-sized second phase clusters on the surface of the aluminum alloy substrate, resulting in a large number of large-sized holes in the subsequently prepared anodized coating. The anodized coating consists of a thicker nanoporous layer on the outside and a dense layer on the inside. The sealing treatment can effectively seal the nanoporous layer and improve the corrosion resistance of the anodized coating. However, when there are large-sized holes in the coating formed by the dissolution of the second phase, the effect of the sealing treatment will be significantly reduced. As the main impurity element in aluminum alloys, Fe accumulates continuously during the production process of aluminum alloys and is difficult to purify and remove. The Fe-rich second phase composed of Fe, Al, Si and other elements is easy to form continuously distributed large-sized clusters in the matrix, which will lead to the formation of through-holes in the coating.

[0004] Existing anodizing coating pretreatment, such as patents CN104357840A and CN104046981A, uses pure aluminum powder as spray powder material, uses cold spraying or hot spraying to prepare a pure aluminum layer on the surface of the aluminum alloy, and then performs anodizing treatment to prepare anodizing coating, but there are the following problems: 1) Spraying is often carried out in an atmospheric environment, the pure aluminum layer is composed of micron-sized aluminum powder, and there is a naturally generated aluminum oxide film layer on the surface of the aluminum powder. The high-temperature carrier gas used in spraying will aggravate the oxidation of the aluminum powder, and oxidation in the subsequent anodizing process will accelerate the oxidation of the aluminum powder. 1) The pure aluminum layer prepared by cold spraying or thermal spraying has a large porosity, and the pores of the pure aluminum layer itself will become the source of pores and cracks in the coating; 2) The pure aluminum layer prepared by cold spraying or thermal spraying has poor bonding with the aluminum alloy substrate, while the anodized coating for semiconductor equipment parts needs to have corrosion resistance, high hardness, and wear resistance. The poor bonding of the pure aluminum bottom layer makes it difficult for the subsequently prepared anodized coating to meet the requirements. Summary of the invention

[0005] In order to solve the above problems, the present invention provides a method for preparing a high-performance anodized coating for semiconductor process equipment components. The laser is used to remelt the surface of the aluminum alloy or to clad the pure aluminum layer, thereby reducing or eliminating large-sized second phase clusters on the surface of the aluminum alloy sample, and then the sample after laser pre-treatment is anodized in an electrolyte to generate a uniform anodized coating without large-sized holes on the surface, and finally the anodized coating is sealed to greatly improve the service life of aluminum alloy components for semiconductor process equipment.

[0006] The present invention solves the above technical problems through the following technical solutions.

[0007] The object of the present invention is to provide a method for preparing an anodic oxidation coating for semiconductor process equipment components, comprising the following steps:

[0008] The pretreated aluminum alloy surface is subjected to vacuum laser treatment to form a solid solution layer or a cladding layer, wherein the cladding layer is an aluminum layer, so as to reduce or eliminate the second phase clusters on the surface of the aluminum alloy sample; during the laser treatment process, the laser spot diameter is 60 μm to 100 μm, the laser power is 200 W to 400 W, the scanning rate is 400 mm / s to 2000 mm / s, and the scanning spacing is 0.05 mm to 0.2 mm;

[0009] The aluminum alloy sample after laser treatment is placed in an anodizing electrolyte to form an anodizing coating on the surface of the aluminum alloy, and the anodizing coating is sealed to obtain an anodizing coating for semiconductor process equipment parts.

[0010] Preferably, when a solid solution layer is formed by laser treatment, the laser power is 200-400 W, the scanning rate is 800 mm / s-2000 mm / s, and the thickness of the solid solution layer is 20 μm-300 μm; when a pure aluminum cladding layer is formed by laser treatment, the laser power is 340 W-400 W, and the scanning rate is 1600 mm / s-2000 mm / s.

[0011] Preferably, when the solid solution layer is formed by laser processing, when the laser power is 200W, the corresponding scanning rate is 1800mm / s~2000mm / s; when the laser power is 300W, the corresponding scanning rate is 800mm / s~1600mm / s; when the laser power is 400W, the corresponding scanning rate is 800mm / s~1000mm / s.

[0012] Preferably, in the process of laser processing to form the cladding layer, N claddings are performed, where N≥1. Each time the pure aluminum layer is clad, the laser rotates 67°. After each cladding, the thickness of the pure aluminum layer is 20μm to 50μm; the total thickness of the cladding layer is 100μm to 1mm.

[0013] Preferably, during the laser treatment, the temperature of the aluminum alloy is 25°C to 180°C.

[0014] Preferably, the thickness of the cladding layer is 1.5 to 8 times the thickness of the anodized coating.

[0015] Preferably, before the laser treatment, vacuum is firstly performed, and then an inert gas is introduced as a protective gas to make the oxygen content lower than 0.01%.

[0016] Preferably, the anodizing electrolyte may be at least one of a sulfuric acid solution, a phosphoric acid solution, an oxalic acid solution, a tartaric acid solution, and an aluminum sulfate solution.

[0017] Preferably, the specific method of anodizing is: at the initial current density of 0.5A / dm 2 ~1A / dm 2 After anodizing for 15-20 minutes, the temperature was increased to 2A / dm 2 Then the current density was increased by 0.5A / dm at every 5min interval. 2 until the voltage reaches 60V.

[0018] Preferably, the sealing treatment method is selected from at least one of hot water sealing, steam sealing, metal salt sealing, polytetrafluoroethylene sealing, layered double hydroxide sealing, and metal ion impregnation-steam sealing.

[0019] Compared with the prior art, the present invention has the following beneficial effects:

[0020] (1) The present invention performs vacuum laser treatment on the aluminum alloy sample after pretreatment, thereby reducing or eliminating large-sized second phase clusters on the surface of the aluminum alloy sample, which can effectively prevent the molten aluminum alloy and molten aluminum powder from contacting with oxygen during the treatment process, inhibit the generation of oxide impurity phases, and solve the problem that the traditional sprayed pure aluminum layer contains a large number of aluminum oxide grain boundaries, and the prepared anodized coating is relatively loose and easy to crack when heated; then the sample after laser pretreatment is anodized in an electrolyte to generate a uniform anodized coating without large-sized holes on the surface, and finally the anodized coating is sealed, which greatly improves the semiconductor process. The service life of aluminum alloy parts for equipment is extended; laser is used to remelt the surface of aluminum alloy or to clad a pure aluminum layer. The remelted aluminum alloy surface layer or the clad pure aluminum layer is metallurgically bonded to the substrate, and its bonding strength is much higher than that of the pure aluminum layer prepared by traditional spraying, which can ensure that the subsequent anodized coating is not easy to peel off, greatly improving the service life of aluminum alloy parts for semiconductor process equipment; compared with the traditional method of spraying pure aluminum and then anodizing, it can effectively improve the density of the subsequent anodized coating, and solve the problem that the traditional sprayed pure aluminum layer contains a large number of aluminum oxide grain boundaries, and the prepared anodized coating is relatively loose and easy to crack when heated.

[0021] (2) The present invention uses laser to perform surface remelting or pure aluminum layer cladding on aluminum alloy. By adjusting the laser power and scanning rate, the temperature and cooling rate of the aluminum alloy and pure aluminum powder at the molten point can be effectively controlled to obtain a dense aluminum alloy solid solution layer and a pure aluminum layer. Compared with the traditional method of spraying pure aluminum and then anodizing, the density of the subsequent anodized coating can be effectively improved; the failure time of the prepared anodized coating in a 5wt.% hydrochloric acid solution is greatly extended, which provides a guarantee for the long-term service of aluminum alloy parts for semiconductor process equipment in strong acid, highly corrosive gas and its plasma environment. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The following are scanning electron microscope photos of the cross-sections of the aluminum alloys prepared in Example 1, Example 2 and Comparative Example 1 of the present invention; wherein: Figure 2 (a) is Example 1, (b) is Example 2, and (c) is Comparative Example 1.

[0023] Figure 2 The following are scanning electron microscope photos of the cross-section of the anodized coating prepared in Example 1, Example 2 and Comparative Example 1 of the present invention; wherein: Figure 3 (a) is Example 1, (b) is Example 2, and (c) is Comparative Example 1.

[0024] Figure 3 This is a comparison chart of the failure time of the anodized coatings prepared in Example 1, Example 2 and Comparative Example 1 of the present invention in a hydrochloric acid bubble test.

[0025] Figure 4This is a comparison chart of the failure time of the hydrochloric acid bubble test of the anodic oxidation coatings prepared in Examples 3 to 10 of the present invention.

[0026] Figure 5 This is a comparison chart of the failure time of the anodized coatings prepared in Comparative Examples 2 to 9 of the present invention in a hydrochloric acid bubble test. DETAILED DESCRIPTION

[0027] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0028] It should be noted that the professional terms used in the present invention are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention. Unless otherwise specifically stated, the various raw materials, reagents, instruments and equipment used in the following embodiments of the present invention can be purchased from the market or prepared by existing methods.

[0029] During the preparation of conventional anodized coatings, the aluminum alloy is not subjected to laser pre-treatment. A large amount of second phase exists in the aluminum alloy matrix, which will be dissolved in the subsequent anodizing process to become large-sized holes in the anodized coating. Such defects cannot be effectively sealed by sealing treatment and become diffusion channels for hydrochloric acid solutions and corrosive gases such as Cl2, HCl, HBr, and NF3, reducing the protective performance of the coating on aluminum alloy parts.

[0030] The existing anodized coating pretreatment uses pure aluminum powder as the spray powder material, and uses cold spraying or hot spraying to prepare a pure aluminum layer on the aluminum alloy surface, and then performs anodizing treatment, such as patent numbers CN104357840A and CN104046981A. However, during the cold spraying or hot spraying process, because the aluminum layer contains a large number of aluminum oxide grain boundaries when the micron-grade aluminum powder is sprayed in an atmospheric environment, and the pure aluminum layer has a large porosity and poor bonding with the aluminum alloy matrix, the prepared anodized coating is relatively loose and easy to crack when heated. Therefore, the development of practical and effective aluminum alloy laser pretreatment technology can reduce or eliminate the second phase on the surface of the aluminum alloy sample, which can greatly improve the corrosion resistance of the aluminum alloy anodized coating used in semiconductor process equipment, extend the service life of chamber components and the yield rate of chip production.

[0031] Based on the above problems, on the one hand, the present invention provides a method for preparing an anodic oxidation coating for semiconductor process equipment components, comprising the following steps:

[0032] S1. The pretreated aluminum alloy surface is subjected to vacuum laser treatment to form a solid solution layer or a cladding layer, wherein the cladding layer is a pure aluminum layer, so as to reduce or eliminate the second phase clusters on the surface of the aluminum alloy sample. During the laser treatment process, the laser spot diameter is 60μm to 100μm, the laser power is 200W to 400W, the scanning rate is 400mm / s to 2000mm / s, and the scanning spacing is 0.05mm to 0.2mm.

[0033] S2. The aluminum alloy sample after laser treatment is placed in an anodizing electrolyte to form an anodizing coating on the surface of the aluminum alloy, and the anodizing coating is sealed to obtain an anodizing coating for semiconductor process equipment components.

[0034] The present invention adopts a vacuum laser treatment method to remelt the surface of the aluminum alloy to form an aluminum alloy solid solution layer or an aluminum layer, thereby reducing or eliminating large-sized second phase clusters on the surface of the aluminum alloy sample, and by adjusting the laser power and scanning rate, and effectively controlling the temperature and cooling rate of the aluminum alloy and the pure aluminum powder at the molten position, a dense aluminum alloy solid solution layer and a pure aluminum layer are obtained, and the molten aluminum alloy and the molten aluminum powder are prevented from contacting with oxygen during the treatment process, and the generation of oxide impurity phases is suppressed, thereby solving the problem that a large amount of aluminum oxide grain boundaries are contained in the traditional sprayed pure aluminum layer, and the prepared anodized coating is relatively loose and easily cracked when heated; the remelted aluminum alloy surface layer or the clad pure aluminum layer It is metallurgically bonded to the substrate, and its bonding strength is much higher than that of the pure aluminum layer prepared by traditional spraying, which can ensure that the subsequent anodized coating is not easy to peel off; the sample after laser pre-treatment is then anodized in an electrolyte to generate a uniform anodized coating without large-sized holes on the surface, and finally the anodized coating is sealed, which greatly improves the service life of aluminum alloy parts used in semiconductor process equipment. Compared with the traditional method of anodizing after spraying pure aluminum, it can effectively improve the density of the subsequent anodized coating, and solves the problem that the traditional sprayed pure aluminum layer contains a large number of aluminum oxide grain boundaries, and the prepared anodized coating is relatively loose and easy to crack when heated.

[0035] In some specific embodiments, when a solid solution layer is formed by a laser treatment method, the laser power is 200-400W, the scanning rate is 800mm / s-2000mm / s, the scanning spacing is 0.1mm, and the thickness of the solid solution layer is 20μm-300μm; when a pure aluminum cladding layer is formed by a laser treatment method, the laser power is 340W-400W, the scanning rate is 1600mm / s-2000mm / s, and the scanning spacing is 0.1mm. As a preferred solution of the present invention, when a solid solution layer is formed by a laser treatment method, when the laser power is 200W, the corresponding scanning rate is 1800mm / s-2000mm / s; when the laser power is 300W, the corresponding scanning rate is 800mm / s-1600mm / s; when the laser power is 400W, the corresponding scanning rate is 800mm / s-1000mm / s. The surface of aluminum alloy is remelted by laser treatment. The large-sized white precipitated phase clusters on the surface of aluminum alloy are dissolved into the aluminum alloy matrix, forming a solid solution layer on the surface of aluminum alloy. The solid solution layer is dense and pore-free. The solid solution layer on the surface of the remelted aluminum alloy is metallurgically bonded to the matrix, and the bonding strength is increased, which improves the density of the subsequent anodized coating. However, when the laser heat input is small, the large-sized precipitated phase clusters cannot be effectively dissolved, and the prepared anodized coating has poor protective performance. When the laser heat input is too large, the aluminum alloy melt vaporizes and large-sized keyholes appear in the solid solution layer, which will cause the corrosion resistance of the coating to drop sharply.

[0036] In some specific embodiments, when a cladding layer is formed by a laser treatment method, the laser power is 340W to 400W, the scanning rate is 1600mm / s to 2000mm / s, the scanning spacing is 0.1mm, and during the laser treatment process, the laser spot diameter is 65μm. The laser treatment method is used to form a cladding layer on the surface of the aluminum alloy, that is, a pure aluminum layer, to eliminate the second phase clusters on the surface of the aluminum alloy sample, the pure aluminum layer and the aluminum alloy matrix are metallurgically bonded, the bonding strength is increased, the anodized coating grown on the pure aluminum surface is uniform and dense, and there are no visible large-sized holes, thereby improving the compactness of the subsequent anodized coating.

[0037] In some specific embodiments, during the process of laser processing to form a cladding layer, N claddings are performed, where N≥1. Each time a pure aluminum layer is clad, the laser rotates 67°. After each cladding, the thickness of the pure aluminum layer is 20μm to 50μm; the total thickness of the cladding layer is 200μm to 1mm.

[0038] In the present invention, during the pure aluminum layer cladding process, after the scraper evenly spreads the pure aluminum powder on the surface of the sample, the laser quickly heats the powder and the surface layer of the sample to a temperature above the melting point to form a molten pool, which is then cooled and solidified to form a pure aluminum layer firmly bonded to the sample. Since the thermal conductivity of the powder is poor, when the pure aluminum powder layer on the surface is thin, the laid powder can be evenly heated and melted to form a uniform and dense pure aluminum layer. If it is laid and clad at one time, there will be a large number of unmelted particles inside the pure aluminum layer, resulting in a large number of pores in the pure aluminum layer.

[0039] In the present invention, when each pure aluminum layer is completed and moved to the next pure aluminum layer, the laser scanning angle is rotated 67° to ensure that the laser scanning direction is completely repeated after continuous manufacturing of multiple layers, thereby avoiding stress concentration on the same plane and causing cracking of the cladding layer.

[0040] In some specific embodiments, during the process of laser processing to form a cladding layer, the cladding material used in the laser processing is aluminum powder or aluminum wire, the purity of the aluminum powder or aluminum wire is greater than 99.9%, and wire feeding, powder feeding or powder spreading are adopted. When the aluminum powder is supplied by upper powder feeding, the Hall flow rate of pure aluminum powder is less than 50s / 50g. In a preferred embodiment, during the process of laser processing to form a cladding layer, the cladding material used in the laser processing is aluminum powder, the purity of the aluminum powder is greater than 99.99%, and pure aluminum powder is supplied by powder spreading. When wire feeding is adopted, the wire feeding speed is 1600mm / s to 6000mm / s. As a preferred solution of the present invention, the powder spreading method is adopted, and the cladding material used in the laser processing is aluminum powder.

[0041] In some specific embodiments, during laser treatment, the temperature of the aluminum alloy is 25° C. to 180° C. In a preferred embodiment, when laser treatment is used for remelting to form a solid solution layer, the temperature of the aluminum alloy is room temperature, and when laser treatment is used for forming a cladding layer, the temperature of the aluminum alloy is 80° C.

[0042] When laser treatment is used to remelt and form a solid solution layer, the aluminum alloy melt needs to be quickly cooled to room temperature to form a solid solution. If the cooling rate is slow, the elements such as Fe and Si dissolved in the aluminum alloy melt will precipitate to form a second phase during the cooling process. Therefore, the temperature of the aluminum alloy substrate is set to room temperature to increase the cooling rate. When laser treatment is used to clad a pure aluminum layer to form a cladding layer, the pure aluminum cladding layer is obtained by multi-layer cladding, and the residual stress inside it gradually increases with the number of cladding layers. In addition, the high-purity aluminum melt will not form a large-sized precipitation phase during the slow solidification process. Increasing the initial temperature of the aluminum alloy substrate can effectively reduce the stress of the pure aluminum cladding layer and avoid cracking of the cladding layer. Since semiconductor equipment often uses 6061-T6 aluminum alloy, which is an aging-strengthened aluminum alloy, and the T6 state is the peak aging state, when the substrate temperature is too high, the aluminum alloy will change from the peak aging state to the over-aging state, resulting in a decrease in the mechanical properties of the aluminum alloy.

[0043] In some specific embodiments, the thickness of the cladding layer is 1.5 to 8 times the thickness of the anodized coating. In the process of industrial preparation of anodized coating, the thickness of the coating cannot be accurately controlled, and the anodized coating is formed by the re-deposition of aluminum oxide after the aluminum element is dissolved. Therefore, when the actual prepared coating thickness is greater than the preset thickness, if the thickness of the pure aluminum cladding layer is the same as the preset coating thickness, the pure aluminum layer is completely consumed, and part of the anodized coating is formed by the dissolution of the aluminum alloy. At this time, defects caused by the dissolution of the second phase will appear at the bottom of the coating, reducing the corrosion resistance of the coating; after the anodized coating fails due to corrosion, it is necessary to use chemical reagents to peel it off and re-prepare the coating. The preparation of a thick pure aluminum cladding layer can reduce the number of laser treatments of aluminum alloy parts, saving costs and time. The cladding of the pure aluminum layer can greatly increase the thickness of the pure aluminum layer through multiple powder-cladding cycles, but it is difficult to increase the thickness of the solid solution layer through multiple laser scanning by surface remelting, and the aluminum melt is prone to boiling after secondary heating, resulting in pores in the solid solution layer, reducing the density of the solid solution layer. Therefore, once the power and scanning speed of the laser processing are determined, the thickness of the solid solution layer is difficult to change.

[0044] In some specific embodiments, before laser treatment, vacuum is firstly performed, and then an inert gas is introduced as a protective gas to reduce the oxygen content to less than 0.01%. The present invention performs laser pretreatment on the aluminum alloy in a vacuum chamber, pre-vacuums and introduces high-purity argon as a protective gas before treatment, which can effectively avoid the contact of molten aluminum alloy and molten aluminum powder with oxygen during the treatment process, inhibit the generation of oxide impurity phases, and solve the problem of traditional spraying pure

[0045] In some specific embodiments, the anodizing electrolyte may be at least one of a sulfuric acid solution, a phosphoric acid solution, an oxalic acid solution, a tartaric acid solution, and an aluminum sulfate solution. In a preferred embodiment, the anodizing treatment is performed in a sulfuric acid solution, and the electrolyte includes components of the following concentrations: 220 g / L sulfuric acid and 12 g / L aluminum sulfate.

[0046] In some specific embodiments, the specific method of anodizing is: at the initial current density of 0.5A / dm 2 ~1A / dm 2 After anodizing for 15-20 minutes, the temperature was increased to 2A / dm 2 Then the current density was increased by 0.5A / dm at every 5min interval. 2 until the voltage reaches 60V.

[0047] In some specific embodiments, the sealing treatment method is selected from at least one of hot water sealing, steam sealing, metal salt sealing, polytetrafluoroethylene sealing, layered double hydroxide sealing, and metal ion impregnation-steam sealing. In a preferred embodiment, the aluminum alloy sample prepared with an anodic oxidation coating is vacuum impregnated in a 0.5mM Cr2(SO4)3 solution at a temperature of 25°C and a pressure of 1×10 4 Pa, time 1h; then at 150℃, 5×10 5 The holes were sealed at high temperature in water vapor of Pa for 18 h, then cooled to room temperature, taken out, rinsed with deionized water and blown dry.

[0048] In some specific embodiments, the pretreatment operation of the aluminum alloy sample is to grind the sample step by step with 80#, 320#, 600#, 1000# and 2000# SiC sandpaper after cutting. Each time the sandpaper with different mesh sizes is changed, the sample is rotated 90° so that the grinding direction is perpendicular to the existing scratch direction. After grinding, the sample is cleaned and dried; the cleaning reagent solvent is ethanol or acetone.

[0049] The invention is further described below through specific examples.

[0050] Example 1

[0051] A method for preparing an anodic oxidation coating for semiconductor process equipment components comprises the following steps:

[0052] S1. Processing the 6061-T6 aluminum alloy substrate: After cutting the 6061-T6 aluminum alloy substrate, polish it step by step with 80#, 320#, 600#, 1000# and 2000# SiC sandpaper. Each time when changing sandpaper with different mesh sizes, rotate the sample 90° so that the polishing direction is perpendicular to the existing scratch direction. After polishing, clean the surface of the 6061-T6 aluminum alloy substrate with ethanol and then dry it to obtain a pretreated aluminum alloy substrate.

[0053] S2. Place the pretreated aluminum alloy substrate into the vacuum chamber of the laser processing equipment, start the vacuum pump to evacuate the chamber to a background vacuum, and then introduce argon gas as a protective gas to reduce the oxygen content in the vacuum chamber to less than 0.01%.

[0054] S3. Use vacuum laser treatment method for surface remelting process: the laser spot diameter is 65μm, the laser power is 300W, the scanning rate is 1400mm / s, the scanning spacing is 0.1mm, and the temperature of the aluminum alloy substrate is 25℃.

[0055] S4. After the remelting process, anodizing treatment is performed: the aluminum alloy substrate sample is placed in an anodizing electrolyte, the electrolyte has the following concentration components: sulfuric acid 220g / L, aluminum sulfate 12g / L; at a current density of 1A / dm 2 Anodize for 20 min at 400 °C and then increase to 2 A / dm 2 Then the current density was increased by 0.5A / dm at every 5min interval. 2 , until the voltage rises to 60V, the anodic oxidation coating is obtained, and then the aluminum alloy substrate sample is taken out, cleaned with ethanol and blown dry.

[0056] S5. Sealing treatment: The aluminum alloy substrate prepared with anodized coating was vacuum impregnated in a 0.5 mM Cr2(SO4)3 solution at a temperature of 25°C and a pressure of 1×10 4 Pa, time 1h; then at 150℃, 5×10 5 The holes were sealed at high temperature in water vapor of Pa for 18 hours, then cooled to room temperature, taken out, rinsed with deionized water and dried, to obtain an anodic oxidation coating for semiconductor process equipment parts.

[0057] Example 2

[0058] A method for preparing an anodic oxidation coating for semiconductor process equipment components comprises the following steps:

[0059] S1. Process the 6061-T6 aluminum alloy substrate in the same manner as in Example 1.

[0060] S2. Place the pretreated aluminum alloy substrate into the vacuum chamber of the laser processing equipment, start the vacuum pump to evacuate the chamber to a background vacuum, and then introduce argon gas as a protective gas to reduce the oxygen content in the vacuum chamber to less than 0.01%.

[0061] S3. Use vacuum laser treatment method to carry out surface remelting process: the laser spot diameter is 65μm, the laser power is 300W, the scanning rate is 800mm / s, the scanning spacing is 0.1mm, and the temperature of the aluminum alloy substrate is 25℃.

[0062] S4. After the remelting process, anodizing treatment is performed: the aluminum alloy substrate sample is placed in an anodizing electrolyte, the electrolyte has the following concentration components: sulfuric acid 220g / L, aluminum sulfate 12g / L; at a current density of 1A / dm 2 Anodize for 20 min at 400 °C and then increase to 2 A / dm 2 Then the current density was increased by 0.5A / dm at every 5min interval. 2 , until the voltage rises to 60V, the anodic oxidation coating is obtained, and then the aluminum alloy substrate sample is taken out, cleaned with ethanol and blown dry.

[0063] S5. Sealing treatment: The aluminum alloy substrate prepared with anodized coating was vacuum impregnated in a 0.5 mM Cr2(SO4)3 solution at a temperature of 25°C and a pressure of 1×10 4 Pa, time 1h; then at 150℃, 5×10 5 The holes were sealed at high temperature in water vapor of Pa for 18 hours, then cooled to room temperature, taken out, rinsed with deionized water and dried, to obtain an anodic oxidation coating for semiconductor process equipment parts.

[0064] Example 3

[0065] A method for preparing an anodic oxidation coating for semiconductor process equipment components comprises the following steps:

[0066] S1. Process the 6061-T6 aluminum alloy substrate in the same manner as in Example 1.

[0067] S2. Place the pretreated aluminum alloy substrate into the vacuum chamber of the laser processing equipment, start the vacuum pump to evacuate the chamber to a background vacuum, and then introduce argon gas as a protective gas to reduce the oxygen content in the vacuum chamber to less than 0.01%.

[0068] S3. Use vacuum laser treatment method to carry out surface remelting process: the laser spot diameter is 65μm, the laser power is 400W, the scanning rate is 800mm / s, the scanning spacing is 0.1mm, and the temperature of the aluminum alloy substrate is 25℃.

[0069] S4. After the remelting process, anodizing treatment is performed: the aluminum alloy substrate sample is placed in an anodizing electrolyte, the electrolyte has the following concentration components: sulfuric acid 220g / L, aluminum sulfate 12g / L; at a current density of 1A / dm 2 Anodize for 20 min at 400 °C and then increase to 2 A / dm 2 Then the current density was increased by 0.5A / dm at every 5min interval. 2 , until the voltage rises to 60V, the anodic oxidation coating is obtained, and then the aluminum alloy substrate sample is taken out, cleaned with ethanol and blown dry.

[0070] S5. Sealing treatment: The aluminum alloy substrate prepared with anodized coating was vacuum impregnated in a 0.5 mM Cr2(SO4)3 solution at a temperature of 25°C and a pressure of 1×10 4 Pa, time 1h; then at 150℃, 5×10 5 The holes were sealed at high temperature in water vapor of Pa for 18 hours, then cooled to room temperature, taken out, rinsed with deionized water and dried, to obtain an anodic oxidation coating for semiconductor process equipment parts.

[0071] Example 4

[0072] A method for preparing an anodic oxidation coating for semiconductor process equipment components comprises the following steps:

[0073] S1. Process the 6061-T6 aluminum alloy substrate in the same manner as in Example 1.

[0074] S2. Place the pretreated aluminum alloy substrate into the vacuum chamber of the laser processing equipment, start the vacuum pump to evacuate the chamber to a background vacuum, and then introduce argon gas as a protective gas to reduce the oxygen content in the vacuum chamber to less than 0.01%.

[0075] S3. Use vacuum laser treatment method to carry out surface remelting process: the laser spot diameter is 65μm, the laser power is 200W, the scanning rate is 2000mm / s, the scanning spacing is 0.1mm, and the temperature of the aluminum alloy substrate is 25℃.

[0076] S4. After the remelting process, anodizing treatment is performed: the aluminum alloy substrate sample is placed in an anodizing electrolyte, the electrolyte has the following concentration components: sulfuric acid 220g / L, aluminum sulfate 12g / L; at a current density of 1A / dm 2 Anodize for 20 min at 400 °C and then increase to 2 A / dm 2 Then the current density was increased by 0.5A / dm at every 5min interval. 2 , until the voltage rises to 60V, the anodic oxidation coating is obtained, and then the aluminum alloy substrate sample is taken out, cleaned with ethanol and blown dry.

[0077] S5. Sealing treatment: The aluminum alloy substrate prepared with anodized coating was vacuum impregnated in a 0.5 mM Cr2(SO4)3 solution at a temperature of 25°C and a pressure of 1×10 4 Pa, time 1h; then at 150℃, 5×10 5 The holes were sealed at high temperature in water vapor of Pa for 18 hours, then cooled to room temperature, taken out, rinsed with deionized water and dried, to obtain an anodic oxidation coating for semiconductor process equipment parts.

[0078] Example 5

[0079] A method for preparing an anodic oxidation coating for semiconductor process equipment components comprises the following steps:

[0080] S1. Process the 6061-T6 aluminum alloy substrate in the same manner as in Example 1.

[0081] S2. Place the pretreated aluminum alloy substrate into the vacuum chamber of the laser processing equipment, start the vacuum pump to evacuate the chamber to a background vacuum, and then introduce argon gas as a protective gas to reduce the oxygen content in the vacuum chamber to less than 0.01%.

[0082] S3. An aluminum layer is formed on the surface of the aluminum alloy substrate by using a vacuum laser treatment method: a pure aluminum cladding layer is formed by using a vacuum laser treatment method: when the pure aluminum layer is clad, the purity of the aluminum is 99.99%, and the pure aluminum powder is supplied in a powder spreading manner. The laser spot diameter is 65μm, the laser power is 400W, the scanning rate is 1600mm / s, the scanning spacing is 0.1mm, and cladding is performed 10 times. After each cladding, the thickness of the pure aluminum layer is 30μm. After each pure aluminum layer cladding is completed, the laser rotates 67°.

[0083] S4. After the laser treatment process, anodizing treatment is performed: the aluminum alloy substrate sample is placed in an anodizing electrolyte, the electrolyte has the following concentration components: sulfuric acid 220g / L, aluminum sulfate 12g / L; at a current density of 1A / dm 2 Anodize for 20 min at 400 °C and then increase to 2 A / dm 2 Then the current density was increased by 0.5A / dm at every 5min interval. 2 , until the voltage rises to 60V, the anodic oxidation coating is obtained, and then the aluminum alloy substrate sample is taken out, cleaned with ethanol and blown dry.

[0084] S5. Sealing treatment: The aluminum alloy substrate prepared with anodized coating was vacuum impregnated in a 0.5 mM Cr2(SO4)3 solution at a temperature of 25°C and a pressure of 1×10 4 Pa, time 1h; then at 150℃, 5×10 5 The holes were sealed at high temperature in water vapor of Pa for 18 hours, then cooled to room temperature, taken out, rinsed with deionized water and dried, to obtain an anodic oxidation coating for semiconductor process equipment parts.

[0085] Example 6

[0086] A method for preparing an anodic oxidation coating for semiconductor process equipment components comprises the following steps:

[0087] S1. Process the 6061-T6 aluminum alloy substrate in the same manner as in Example 1.

[0088] S2. Place the pretreated aluminum alloy substrate into the vacuum chamber of the laser processing equipment, start the vacuum pump to evacuate the chamber to a background vacuum, and then introduce argon gas as a protective gas to reduce the oxygen content in the vacuum chamber to less than 0.01%.

[0089] S3. An aluminum layer is formed on the surface of the aluminum alloy substrate by using a vacuum laser treatment method: an aluminum layer is formed by using a vacuum laser treatment method: when the pure aluminum layer is clad, the temperature of the aluminum alloy substrate is 80°C, the purity of the aluminum is 99.99%, and the pure aluminum powder is supplied by a powder spreading method. The spot diameter of the laser is 65μm, the laser power is 340W, the scanning rate is 2000mm / s, the scanning spacing is 0.1mm, and cladding is performed 10 times. After each cladding, the thickness of the pure aluminum layer is 30μm. After each pure aluminum layer cladding is completed, the laser rotates 67°.

[0090] S4. After the laser treatment process, anodizing treatment is performed: the aluminum alloy substrate sample is placed in an anodizing electrolyte, the electrolyte has the following concentration components: sulfuric acid 220g / L, aluminum sulfate 12g / L; at a current density of 1A / dm 2 Anodize for 20 min at 400 °C and then increase to 2 A / dm 2 Then the current density was increased by 0.5A / dm at every 5min interval. 2 , until the voltage rises to 60V, the anodic oxidation coating is obtained, and then the aluminum alloy substrate sample is taken out, cleaned with ethanol and blown dry.

[0091] S5. Sealing treatment: The aluminum alloy substrate prepared with anodized coating was vacuum impregnated in a 0.5 mM Cr2(SO4)3 solution at a temperature of 25°C and a pressure of 1×10 4 Pa, time 1h; then at 150℃, 5×10 5 The holes were sealed at high temperature in water vapor of Pa for 18 hours, then cooled to room temperature, taken out, rinsed with deionized water and dried, to obtain an anodic oxidation coating for semiconductor process equipment parts.

[0092] Example 7

[0093] A method for preparing an anodic oxidation coating for semiconductor process equipment components comprises the following steps:

[0094] S1. Process the 6061-T6 aluminum alloy substrate in the same manner as in Example 1.

[0095] S2. Place the pretreated aluminum alloy substrate into the vacuum chamber of the laser processing equipment, start the vacuum pump to evacuate the chamber to a background vacuum, and then introduce argon gas as a protective gas to reduce the oxygen content in the vacuum chamber to less than 0.01%.

[0096] S3. An aluminum layer is formed on the surface of the aluminum alloy substrate by using a vacuum laser treatment method: When the pure aluminum layer is clad, the temperature of the aluminum alloy substrate is 80°C, the purity of the aluminum is 99.99%, and the pure aluminum powder is supplied by a powder spreading method. The spot diameter of the laser is 65μm, the laser power is 370W, the scanning rate is 2000mm / s, the scanning spacing is 0.1mm, and cladding is performed 10 times. After each cladding, the thickness of the pure aluminum layer is 30μm. After each pure aluminum layer cladding is completed, the laser rotates 67°.

[0097] S4. After the laser treatment process, anodizing treatment is performed: the aluminum alloy substrate sample is placed in an anodizing electrolyte, the electrolyte has the following concentration components: sulfuric acid 220g / L, aluminum sulfate 12g / L; at a current density of 1A / dm 2 Anodize for 20 min at 400 °C and then increase to 2 A / dm 2 Then the current density was increased by 0.5A / dm at every 5min interval. 2 , until the voltage rises to 60V, the anodic oxidation coating is obtained, and then the aluminum alloy substrate sample is taken out, cleaned with ethanol and blown dry.

[0098] S5. Sealing treatment: The aluminum alloy substrate prepared with anodized coating was vacuum impregnated in a 0.5 mM Cr2(SO4)3 solution at a temperature of 25°C and a pressure of 1×10 4 Pa, time 1h; then at 150℃, 5×10 5 The holes were sealed at high temperature in water vapor of Pa for 18 hours, then cooled to room temperature, taken out, rinsed with deionized water and dried, to obtain an anodic oxidation coating for semiconductor process equipment parts.

[0099] Example 8

[0100] A method for preparing an anodic oxidation coating for semiconductor process equipment components comprises the following steps:

[0101] S1. Process the 6061-T6 aluminum alloy substrate in the same manner as in Example 1.

[0102] S2. Place the pretreated aluminum alloy substrate into the vacuum chamber of the laser processing equipment, start the vacuum pump to evacuate the chamber to a background vacuum, and then introduce argon gas as a protective gas to reduce the oxygen content in the vacuum chamber to less than 0.01%.

[0103] S3. An aluminum layer is formed on the surface of the aluminum alloy substrate by using a vacuum laser treatment method: When the pure aluminum layer is clad, the temperature of the aluminum alloy substrate is 80°C, the purity of the aluminum is 99.99%, and the pure aluminum powder is supplied by a powder spreading method. The spot diameter of the laser is 65μm, the laser power is 340W, the scanning rate is 1800mm / s, the scanning spacing is 0.1mm, and cladding is performed 10 times. After each cladding, the thickness of the pure aluminum layer is 30μm. After each pure aluminum layer cladding is completed, the laser rotates 67°.

[0104] S4. After the laser treatment process, anodizing treatment is performed: the aluminum alloy substrate sample is placed in an anodizing electrolyte, the electrolyte has the following concentration components: sulfuric acid 220g / L, aluminum sulfate 12g / L; at a current density of 1A / dm 2 Anodize for 20 min at 400 °C and then increase to 2 A / dm 2 Then the current density was increased by 0.5A / dm at every 5min interval. 2 , until the voltage rises to 60V, the anodic oxidation coating is obtained, and then the aluminum alloy substrate sample is taken out, cleaned with ethanol and blown dry.

[0105] S5. Sealing treatment: The aluminum alloy substrate prepared with anodized coating was vacuum impregnated in a 0.5 mM Cr2(SO4)3 solution at a temperature of 25°C and a pressure of 1×10 4 Pa, time 1h; then at 150℃, 5×10 5 The holes were sealed at high temperature in water vapor of Pa for 18 hours, then cooled to room temperature, taken out, rinsed with deionized water and dried, to obtain an anodic oxidation coating for semiconductor process equipment parts.

[0106] Example 9

[0107] A method for preparing an anodic oxidation coating for semiconductor process equipment components comprises the following steps:

[0108] S1. Process the 6061-T6 aluminum alloy substrate in the same manner as in Example 1.

[0109] S2. Place the pretreated aluminum alloy substrate into the vacuum chamber of the laser processing equipment, start the vacuum pump to evacuate the chamber to a background vacuum, and then introduce argon gas as a protective gas to reduce the oxygen content in the vacuum chamber to less than 0.01%.

[0110] S3. An aluminum layer is formed on the surface of the aluminum alloy substrate by using a vacuum laser treatment method: When the pure aluminum layer is clad, the temperature of the aluminum alloy substrate is 80°C, the purity of the aluminum is 99.99%, and the pure aluminum powder is supplied in a powder spreading manner. The laser spot diameter is 65μm, the laser power is 400W, the scanning rate is 2000mm / s, the scanning spacing is 0.1mm, and cladding is performed 10 times. After each cladding, the thickness of the pure aluminum layer is 30μm. After each pure aluminum layer cladding is completed, the laser rotates 67°.

[0111] S4. After the laser treatment process, anodizing treatment is performed: the aluminum alloy substrate sample is placed in an anodizing electrolyte, the electrolyte has the following concentration components: sulfuric acid 220g / L, aluminum sulfate 12g / L; at a current density of 1A / dm 2 Anodize for 20 min at 400 °C and then increase to 2 A / dm 2 Then the current density was increased by 0.5A / dm at every 5min interval. 2 , until the voltage rises to 60 V, then the aluminum alloy substrate sample is taken out, cleaned with ethanol and blown dry.

[0112] S5. Sealing treatment: The aluminum alloy substrate prepared with anodized coating was vacuum impregnated in a 0.5 mM Cr2(SO4)3 solution at a temperature of 25°C and a pressure of 1×10 4 Pa, time 1h; then at 150℃, 5×10 5 The holes were sealed at high temperature in water vapor of Pa for 18 hours, then cooled to room temperature, taken out, rinsed with deionized water and dried, to obtain an anodic oxidation coating for semiconductor process equipment parts.

[0113] Example 10

[0114] A method for preparing an anodic oxidation coating for semiconductor process equipment components comprises the following steps:

[0115] S1. Process the 6061-T6 aluminum alloy substrate in the same manner as in Example 1.

[0116] S2. Place the pretreated aluminum alloy substrate into the vacuum chamber of the laser processing equipment, start the vacuum pump to evacuate the chamber to a background vacuum, and then introduce argon gas as a protective gas to reduce the oxygen content in the vacuum chamber to less than 0.01%.

[0117] S3. An aluminum layer is formed on the surface of the aluminum alloy substrate by using a vacuum laser treatment method: When the pure aluminum layer is clad, the temperature of the aluminum alloy substrate is 80°C, the purity of the aluminum is 99.99%, and the pure aluminum powder is supplied by a powder spreading method. The spot diameter of the laser is 65μm, the laser power is 370W, the scanning rate is 1800mm / s, the scanning spacing is 0.1mm, and cladding is performed 10 times. After each cladding, the thickness of the pure aluminum layer is 30μm. After each pure aluminum layer cladding is completed, the laser rotates 67°.

[0118] S4. After the laser treatment process, anodizing treatment is performed: the aluminum alloy substrate sample is placed in an anodizing electrolyte, the electrolyte has the following concentration components: sulfuric acid 220g / L, aluminum sulfate 12g / L; at a current density of 1A / dm 2 Anodize for 20 min at 400 °C and then increase to 2 A / dm 2 Then the current density was increased by 0.5A / dm at every 5min interval. 2 , until the voltage rises to 60 V, then the aluminum alloy substrate sample is taken out, cleaned with ethanol and blown dry.

[0119] S5. Sealing treatment: The aluminum alloy substrate prepared with anodized coating was vacuum impregnated in a 0.5 mM Cr2(SO4)3 solution at a temperature of 25°C and a pressure of 1×10 4 Pa, time 1h; then at 150℃, 5×10 5 The holes were sealed at high temperature in water vapor of Pa for 18 hours, then cooled to room temperature, taken out, rinsed with deionized water and dried, to obtain an anodic oxidation coating for semiconductor process equipment parts.

[0120] Embodiment 11

[0121] A method for preparing an anodic oxidation coating for semiconductor process equipment components comprises the following steps:

[0122] S1. Process the 6061-T6 aluminum alloy substrate in the same manner as in Example 1.

[0123] S2. Place the pretreated aluminum alloy substrate into the vacuum chamber of the laser processing equipment, start the vacuum pump to evacuate the chamber to a background vacuum, and then introduce argon gas as a protective gas to reduce the oxygen content in the vacuum chamber to less than 0.01%.

[0124] S3. An aluminum layer is formed on the surface of the aluminum alloy substrate by using a vacuum laser treatment method: An aluminum layer is formed by using a vacuum laser treatment method: When the pure aluminum layer is clad, the temperature of the aluminum alloy substrate is 80°C, the purity of the aluminum is 99.99%, and the pure aluminum powder is supplied by a powder spreading method. The spot diameter of the laser is 65μm, the laser power is 340W, the scanning rate is 1600mm / s, the scanning spacing is 0.1mm, and cladding is performed 10 times. After each cladding, the thickness of the pure aluminum layer is 30μm. After each pure aluminum layer cladding is completed, the laser rotates 67°.

[0125] S4. After the laser treatment process, anodizing treatment is performed: the aluminum alloy substrate sample is placed in an anodizing electrolyte, the electrolyte has the following concentration components: sulfuric acid 220g / L, aluminum sulfate 12g / L; at a current density of 1A / dm 2 Anodize for 20 min at 400 °C and then increase to 2 A / dm 2 Then the current density was increased by 0.5A / dm at every 5min interval. 2 , until the voltage rises to 60V, the anodic oxidation coating is obtained, and then the aluminum alloy substrate sample is taken out, cleaned with ethanol and blown dry.

[0126] S5. Sealing treatment: The aluminum alloy substrate prepared with anodized coating was vacuum impregnated in a 0.5 mM Cr2(SO4)3 solution at a temperature of 25°C and a pressure of 1×10 4 Pa, time 1h; then at 150℃, 5×10 5 The holes were sealed at high temperature in water vapor of Pa for 18 hours, then cooled to room temperature, taken out, rinsed with deionized water and dried, to obtain an anodic oxidation coating for semiconductor process equipment parts.

[0127] Example 12

[0128] A method for preparing an anodic oxidation coating for semiconductor process equipment components comprises the following steps:

[0129] S1. Process the 6061-T6 aluminum alloy substrate in the same manner as in Example 1.

[0130] S2. Place the pretreated aluminum alloy substrate into the vacuum chamber of the laser processing equipment, start the vacuum pump to evacuate the chamber to a background vacuum, and then introduce argon gas as a protective gas to reduce the oxygen content in the vacuum chamber to less than 0.01%.

[0131] S3. An aluminum layer is formed on the surface of the aluminum alloy substrate by using a vacuum laser treatment method: When the pure aluminum layer is clad, the temperature of the aluminum alloy substrate is 80°C, the purity of the aluminum is 99.99%, and the pure aluminum powder is supplied by a powder spreading method. The spot diameter of the laser is 65μm, the laser power is 400W, the scanning rate is 1800mm / s, the scanning spacing is 0.1mm, and cladding is performed 10 times. After each cladding, the thickness of the pure aluminum layer is 30μm. After each pure aluminum layer cladding is completed, the laser rotates 67°.

[0132] S4. After the laser treatment process, anodizing treatment is performed: the aluminum alloy substrate sample is placed in an anodizing electrolyte, the electrolyte has the following concentration components: sulfuric acid 220g / L, aluminum sulfate 12g / L; at a current density of 1A / dm 2 Anodize for 20 min at 400 °C and then increase to 2 A / dm 2 Then the current density was increased by 0.5A / dm at every 5min interval. 2 , until the voltage rises to 60V, the anodic oxidation coating is obtained, and then the aluminum alloy substrate sample is taken out, cleaned with ethanol and blown dry.

[0133] S5. Sealing treatment: The aluminum alloy substrate prepared with anodized coating was vacuum impregnated in a 0.5 mM Cr2(SO4)3 solution at a temperature of 25°C and a pressure of 1×10 4 Pa, time 1h; then at 150℃, 5×10 5 The holes were sealed at high temperature in water vapor of Pa for 18 hours, then cooled to room temperature, taken out, rinsed with deionized water and dried, to obtain an anodic oxidation coating for semiconductor process equipment parts.

[0134] Example 13

[0135] A method for preparing an anodic oxidation coating for semiconductor process equipment components comprises the following steps:

[0136] S1. Process the 6061-T6 aluminum alloy substrate in the same manner as in Example 1.

[0137] S2. Place the pretreated aluminum alloy substrate into the vacuum chamber of the laser processing equipment, start the vacuum pump to evacuate the chamber to a background vacuum, and then introduce argon gas as a protective gas to reduce the oxygen content in the vacuum chamber to less than 0.01%.

[0138] S3. An aluminum layer is formed on the surface of the aluminum alloy substrate by using a vacuum laser treatment method: When the pure aluminum layer is clad, the temperature of the aluminum alloy substrate is 80°C, the purity of the aluminum is 99.99%, and the pure aluminum powder is supplied by a powder spreading method. The spot diameter of the laser is 65μm, the laser power is 370W, the scanning rate is 1600mm / s, the scanning spacing is 0.1mm, and cladding is performed 10 times. After each cladding, the thickness of the pure aluminum layer is 30μm. After each pure aluminum layer cladding is completed, the laser rotates 67°.

[0139] S4. After the laser treatment process, anodizing treatment is performed: the aluminum alloy substrate sample is placed in an anodizing electrolyte, the electrolyte has the following concentration components: sulfuric acid 220g / L, aluminum sulfate 12g / L; at a current density of 1A / dm 2 Anodize for 20 min at 400 °C and then increase to 2 A / dm 2 Then the current density was increased by 0.5A / dm at every 5min interval. 2 , until the voltage rises to 60 V, then the aluminum alloy substrate sample is taken out, cleaned with ethanol and blown dry.

[0140] S5. Sealing treatment: The aluminum alloy substrate prepared with anodized coating was vacuum impregnated in a 0.5 mM Cr2(SO4)3 solution at a temperature of 25°C and a pressure of 1×10 4 Pa, time 1h; then at 150℃, 5×10 5 The holes were sealed at high temperature in water vapor of Pa for 18 hours, then cooled to room temperature, taken out, rinsed with deionized water and dried, to obtain an anodic oxidation coating for semiconductor process equipment parts.

[0141] Comparative Example 1

[0142] A method for preparing an anodic oxidation coating for semiconductor process equipment components comprises the following steps:

[0143] S1. Process the 6061-T6 aluminum alloy substrate in the same manner as in Example 1.

[0144] S2. Anodizing treatment: The aluminum alloy substrate sample is placed in an anodizing electrolyte, the electrolyte has the following components: sulfuric acid 220g / L, aluminum sulfate 12g / L; at a current density of 1A / dm 2 Anodize for 20 min at 400 °C and then increase to 2 A / dm 2 Then the current density was increased by 0.5A / dm at every 5min interval. 2 , until the voltage rises to 60 V, then the aluminum alloy substrate sample is taken out, cleaned with ethanol and blown dry.

[0145] S3, sealing treatment: the aluminum alloy substrate prepared with anodized coating was vacuum impregnated in a 0.5 mM Cr2(SO4)3 solution at a temperature of 25 °C and a pressure of 1×10 4 Pa, time 1h; then at 150℃, 5×10 5 The holes were sealed at high temperature in water vapor of Pa for 18 hours, then cooled to room temperature, taken out, rinsed with deionized water and dried, to obtain an anodic oxidation coating for semiconductor process equipment parts.

[0146] Comparative Example 2

[0147] A method for preparing an anodized coating for semiconductor process equipment components is basically the same as Example 1, and the difference from Example 1 is: S3, a surface remelting process is performed using a vacuum laser treatment method: the laser spot diameter is 65μm, the laser power is 200W, the scanning rate is 800mm / s, the scanning spacing is 0.1mm, and the temperature of the aluminum alloy substrate is room temperature.

[0148] Comparative Example 3

[0149] A method for preparing an anodized coating for semiconductor process equipment components is basically the same as Example 1, and the difference from Example 1 is: S3, a surface remelting process is performed using a vacuum laser treatment method: the laser spot diameter is 65μm, the laser power is 200W, the scanning rate is 1400mm / s, the scanning spacing is 0.1mm, and the temperature of the aluminum alloy substrate is room temperature.

[0150] Comparative Example 4

[0151] A method for preparing an anodized coating for semiconductor process equipment components is basically the same as Example 1, and the difference from Example 1 is: S3, a surface remelting process is performed using a vacuum laser treatment method: the laser spot diameter is 65μm, the laser power is 400W, the scanning rate is 1400mm / s, the scanning spacing is 0.1mm, and the temperature of the aluminum alloy substrate is room temperature.

[0152] Comparative Example 5

[0153] A method for preparing an anodized coating for semiconductor process equipment components is basically the same as Example 1, and the difference from Example 1 is: S3, a surface remelting process is performed using a vacuum laser treatment method: the laser spot diameter is 65μm, the laser power is 300W, the scanning rate is 2000mm / s, the scanning spacing is 0.1mm, and the temperature of the aluminum alloy substrate is room temperature.

[0154] Comparative Example 6

[0155] A method for preparing an anodized coating for semiconductor process equipment components is basically the same as Example 1, and the difference from Example 1 is: S3, a surface remelting process is performed using a vacuum laser treatment method: the laser spot diameter is 65μm, the laser power is 400W, the scanning rate is 2000mm / s, the scanning spacing is 0.1mm, and the temperature of the aluminum alloy substrate is room temperature.

[0156] Comparative Example 7

[0157] A method for preparing an anodic oxidation coating for semiconductor process equipment components is basically the same as Example 2, and the difference from Example 5 is: S3, forming an aluminum layer on the surface of an aluminum alloy substrate by a vacuum laser processing method: forming a pure aluminum cladding layer by a vacuum laser processing method: when cladding the pure aluminum layer, the purity of the aluminum is 99.99%, and pure aluminum powder is supplied in a powder spreading manner. The spot diameter of the laser is 65μm, the laser power is 200W, the scanning rate is 800mm / s, the scanning spacing is 0.1mm, and cladding is performed 10 times. After each cladding, the thickness of the pure aluminum layer is 30μm. After each pure aluminum layer cladding is completed, the laser rotates 67°.

[0158] Comparative Example 8

[0159] A method for preparing an anodic oxidation coating for semiconductor process equipment components is basically the same as Example 2, and the difference from Example 5 is: S3, forming an aluminum layer on the surface of an aluminum alloy substrate by a vacuum laser processing method: forming a pure aluminum cladding layer by a vacuum laser processing method: when cladding the pure aluminum layer, the purity of the aluminum is 99.99%, and pure aluminum powder is supplied in a powder spreading manner. The spot diameter of the laser is 65μm, the laser power is 200W, the scanning rate is 1600mm / s, the scanning spacing is 0.1mm, and cladding is performed 10 times. After each cladding, the thickness of the pure aluminum layer is 30μm. After each pure aluminum layer cladding is completed, the laser rotates 67°.

[0160] Comparative Example 9

[0161] A method for preparing an anodic oxidation coating for semiconductor process equipment components is basically the same as Example 2, and the difference from Example 5 is: S3, forming an aluminum layer on the surface of an aluminum alloy substrate by a vacuum laser processing method: forming a pure aluminum cladding layer by a vacuum laser processing method: when cladding the pure aluminum layer, the purity of the aluminum is 99.99%, and pure aluminum powder is supplied in a powder spreading manner. The spot diameter of the laser is 65μm, the laser power is 200W, the scanning rate is 1800mm / s, the scanning spacing is 0.1mm, and cladding is performed 10 times. After each cladding, the thickness of the pure aluminum layer is 30μm. After each pure aluminum layer cladding is completed, the laser rotates 67°.

[0162] Comparative Example 10

[0163] A method for preparing an anodic oxidation coating for semiconductor process equipment components is basically the same as Example 2, and the difference from Example 5 is: S3, forming an aluminum layer on the surface of an aluminum alloy substrate by a vacuum laser processing method: forming a pure aluminum cladding layer by a vacuum laser processing method: when cladding the pure aluminum layer, the purity of the aluminum is 99.99%, and pure aluminum powder is supplied in a powder spreading manner. The spot diameter of the laser is 65μm, the laser power is 200W, the scanning rate is 2000mm / s, the scanning spacing is 0.1mm, and cladding is performed 10 times. The thickness of the pure aluminum layer after each cladding is 30μm. After each pure aluminum layer cladding is completed, the laser rotates 67°.

[0164] The morphology of the cross-section of the aluminum alloy and the anodized coating prepared in Example 1, Example 5 and Comparative Example 1 was tested, and the results are as follows:

[0165] Figure 1 The following are scanning electron microscope photos of the cross-sections of the aluminum alloys prepared in Example 1, Example 5 and Comparative Example 1 of the present invention; wherein: Figure 1 (a) is Example 1, (b) is Example 5, and (c) is Comparative Example 1; Figure 1 As shown in the figure, after surface remelting treatment, the white large-sized precipitate phase clusters on the surface of the aluminum alloy are dissolved into the aluminum alloy matrix, the thickness of the solid solution layer is about 60μm, and the solid solution layer is dense and has no pores; after pure aluminum layer cladding, a pure aluminum layer about 300μm thick is formed on the surface of the aluminum alloy; and uniformly distributed large-sized precipitate phase clusters can be observed in the cross-section of the aluminum alloy without pre-treatment.

[0166] Figure 2 The following are scanning electron microscope photos of the cross-section of the anodized coating prepared in Example 1, Example 5 and Comparative Example 1 of the present invention; wherein: Figure 2 (a) is Example 1, (b) is Example 5, and (c) is Comparative Example 1; Figure 2 As shown in the figure, an anodized coating with a thickness of about 60 μm was prepared on the surface of the aluminum alloy by the same anodizing process; after surface remelting treatment, the anodized coating grown on the surface of the aluminum alloy had no through holes, and only holes were generated by the dissolution of the precipitated phase at the interface between the coating and the substrate; after cladding of the pure aluminum layer, the anodized coating grown on the pure aluminum surface was uniform and dense, without visible large-sized holes; in the anodized coating prepared on the surface of the aluminum alloy without pre-treatment, a large number of through holes can be observed, all of which are caused by the dissolution of strip-like precipitate phase clusters in the aluminum alloy.

[0167] The hydrochloric acid bubble test was performed on the anodized coatings prepared in Examples 1 to 13 and Comparative Examples 1 to 10, wherein the "hydrochloric acid bubble test" was proposed by Lam Research in 1992 and became a standard test method for studying anodized coatings in the integrated circuit industry in 1994. The basic principle of using the hydrochloric acid bubble test to test the failure of anodized coatings is as follows: When the hydrochloric acid solution penetrates into the pores, cracks and other defects of the anodized coating and passes through the coating to contact the aluminum alloy substrate, the hydrochloric acid reacts with the aluminum alloy to continuously generate hydrogen bubbles. At this time, continuous bulging bubbles can be observed on the surface of the sample. The time from the start of the experiment to the generation of continuous hydrogen bubbles is recorded and recorded as the failure time of the anodized coating. Use epoxy resin to fix the quartz tube on the surface of the coating, and drip 5wt.% hydrochloric acid to start the experiment.

[0168] Figure 3 The following is a comparison chart of the failure time of the hydrochloric acid bubble test of the anodic oxidation coatings prepared in Example 1, Example 5 and Comparative Example 1 of the present invention; wherein (a) is Example 1, (b) is Example 5, and (c) is Comparative Example 1; Figure 3 As shown in the figure, in 5wt.% HCl solution, the failure time of the anodized coating on the aluminum alloy after surface remelting and pure aluminum layer cladding pre-treatment is 1433 minutes and 2644 minutes respectively; the failure time of the anodized coating prepared from the aluminum alloy without pre-treatment is 342 minutes; after surface remelting and pure aluminum layer cladding pre-treatment, the protective performance of the anodized coating is significantly improved, and the failure time is much longer than the prior art such as the anodized coating prepared by patent number CN104046981A (the longest failure time is 300min).

[0169] Figure 4 The following is a comparison of the failure time of the hydrochloric acid bubble test of the anodic oxidation coatings prepared in Examples 1 to 4 of the present invention and Comparative Examples 1 to 6; Table 1 is a comparison of the failure time of Examples 1 to 4 and Comparative Examples 1 to 6. Figure 4 and as shown in Table 1. After surface remelting by different processes, the corrosion resistance of the anodic oxidation coatings varies greatly. When the laser heat input is small, the large-sized precipitated phase clusters cannot be effectively dissolved, and the protective performance of the prepared anodic oxidation coating is similar to that of the anodic oxidation coating without pretreatment. When the laser heat input is too large, the aluminum alloy melt vaporizes to form large-sized keyholes in the solid solution layer, which will cause a sharp drop in the protective performance of the coating.

[0170] Figure 5 The following is a comparison of the failure time of the hydrochloric acid bubble test of the anodic oxidation coatings prepared in Examples 5 to 13, Comparative Example 1, and Comparative Examples 7 to 10 of the present invention. Table 2 Comparison of the failure time of Examples 5 to 13, Comparative Example 1, and Comparative Examples 7 to 10. Figure 5As shown in Table 2, after the pure aluminum layer is clad by different processes, the failure time of the prepared anodized coating varies with the density of the pure aluminum layer. However, when the laser power is high, the density of the pure aluminum cladding layer is high, and the protective performance of the prepared anodized coating is still significantly improved compared with the coating prepared without pretreatment. The pure aluminum layer prepared under low laser power conditions is loose and porous, and the protective performance of the subsequently prepared anodized coating is similar to that of the coating without laser treatment.

[0171] Table 1 Comparison of failure time of Examples 1 to 4 and Comparative Examples 1 to 6

[0172]

[0173] Table 2 Comparison of failure time of Examples 5 to 13 and Comparative Example 1, and Comparative Example 7 to Comparative Example 10

[0174]

[0175]

[0176] In summary, the present invention performs laser pre-treatment on the pretreated aluminum alloy sample to reduce or eliminate large-sized second phase clusters on the surface of the aluminum alloy sample, and then performs anodizing treatment on the sample after laser pre-treatment in an electrolyte to generate a uniform anodized coating without large-sized holes on the surface, and finally performs a pore sealing treatment on the anodized coating, thereby greatly improving the service life of aluminum alloy parts for semiconductor process equipment; laser is used to remelt the surface of the aluminum alloy or to clad a pure aluminum layer, and the remelted aluminum alloy surface layer or the clad pure aluminum layer is metallurgically bonded to the substrate, and the bonding strength is much higher than that of the pure aluminum layer prepared by traditional spraying, which can ensure that the subsequent anodized coating is not easy to peel off, and the failure time in a 5wt.% hydrochloric acid solution is greatly extended, which provides a guarantee for the long-term service of aluminum alloy parts for semiconductor process equipment in strong acid, strong corrosive gas and plasma environment.

[0177] It should be noted that when the present invention involves a numerical range, it should be understood that the two endpoints of each numerical range and any value between the two endpoints can be selected. Since the steps and methods used are the same as those in the embodiments, in order to avoid redundancy, the present invention describes a preferred embodiment. Although the preferred embodiments of the present invention have been described, those skilled in the art may make additional changes and modifications to these embodiments once they know the basic creative concept. Therefore, the attached claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present invention.

[0178] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.

Claims

1. A method for preparing an anodic oxidation coating for semiconductor process equipment components, characterized in that: The following steps are involved: The pretreated aluminum alloy surface is subjected to vacuum laser treatment to form a solid solution layer or a cladding layer, and the cladding layer is a pure aluminum layer, which reduces or eliminates the second phase clusters on the surface of the aluminum alloy sample; during the laser treatment process, the laser spot diameter is 60μm to 100μm, the laser power is 200W to 400W, the scanning rate is 400mm / s to 2000mm / s, and the scanning spacing is 0.05mm to 0.2mm; The aluminum alloy sample after laser treatment is placed in an anodizing electrolyte to form an anodizing coating on the surface of the aluminum alloy, and the anodizing coating is sealed to obtain an anodizing coating for semiconductor process equipment parts.

2. The method for preparing an anodic oxidation coating for semiconductor process equipment parts according to claim 1, characterized in that: When the solid solution layer is formed by laser treatment, the laser power is 200-400W, the scanning rate is 800mm / s-2000mm / s, and the thickness of the solid solution layer is 20μm-300μm; when the pure aluminum cladding layer is formed by laser treatment, the laser power is 340W-400W, and the scanning rate is 1600mm / s-2000mm / s.

3. The method for preparing an anodic oxidation coating for semiconductor process equipment parts according to claim 1, characterized in that: When the solid solution layer is formed by laser treatment, when the laser power is 200W, the corresponding scanning rate is 1800mm / s~2000mm / s; when the laser power is 300W, the corresponding scanning rate is 800mm / s~1600mm / s; when the laser power is 400W, the corresponding scanning rate is 800mm / s~1000mm / s.

4. The method for preparing an anodic oxidation coating for semiconductor process equipment parts according to claim 1, characterized in that: In the process of laser processing to form the cladding layer, N claddings are performed, where N≥1. Each time the pure aluminum layer is clad, the laser rotates 67°. After each cladding, the thickness of the pure aluminum layer is 20μm to 50μm; the total thickness of the cladding layer is 100μm to 1mm.

5. The method for preparing an anodic oxidation coating for semiconductor process equipment parts according to claim 1, characterized in that: During the laser treatment process, the temperature of the aluminum alloy is 25°C to 180°C.

6. The method for preparing an anodic oxidation coating for semiconductor process equipment parts according to claim 1, characterized in that: The thickness of the cladding layer is 1.5 to 8 times the thickness of the anodized coating.

7. The method for preparing an anodic oxidation coating for semiconductor process equipment parts according to claim 1, characterized in that: Before laser treatment, vacuum is first performed, and then inert gas is introduced as a protective gas to reduce the oxygen content to less than 0.01%.

8. The method for preparing an anodic oxidation coating for semiconductor process equipment parts according to claim 1, characterized in that: The anodizing electrolyte is at least one of a sulfuric acid solution, a phosphoric acid solution, an oxalic acid solution, a tartaric acid solution, and an aluminum sulfate solution.

9. The method for preparing an anodic oxidation coating for semiconductor process equipment parts according to claim 1, characterized in that: The specific method of anodizing is: the initial current density is 0.5A / dm 2 ~1A / dm 2 After anodizing for 15-20 minutes, the temperature was increased to 2A / dm 2 Then the current density was increased by 0.5A / dm at every 5min interval. 2 until the voltage reaches 60V.

10. The method for preparing an anodic oxidation coating for semiconductor process equipment parts according to claim 1, characterized in that: The sealing treatment method is selected from at least one of hot water sealing, steam sealing, metal salt sealing, polytetrafluoroethylene sealing, layered double hydroxide sealing, and metal ion impregnation-steam sealing.

Images