CN115838954B - Surface treatment process suitable for gas diffuser of CVD equipment - Google Patents
Surface treatment process suitable for gas diffuser of CVD equipment Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 54
- 230000008569 process Effects 0.000 title claims abstract description 35
- 238000004381 surface treatment Methods 0.000 title claims abstract description 33
- 230000003647 oxidation Effects 0.000 claims abstract description 115
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 111
- 239000007788 liquid Substances 0.000 claims abstract description 58
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003814 drug Substances 0.000 claims abstract description 45
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 18
- 230000009194 climbing Effects 0.000 claims abstract description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004327 boric acid Substances 0.000 claims abstract description 10
- 230000000903 blocking effect Effects 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- 239000000047 product Substances 0.000 claims description 49
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 48
- 238000005238 degreasing Methods 0.000 claims description 37
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- 238000001035 drying Methods 0.000 claims description 23
- 239000003513 alkali Substances 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
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- 238000011010 flushing procedure Methods 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- XLXCHZCQTCBUOX-UHFFFAOYSA-N 1-prop-2-enylimidazole Chemical compound C=CCN1C=CN=C1 XLXCHZCQTCBUOX-UHFFFAOYSA-N 0.000 claims description 5
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- 238000007789 sealing Methods 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
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- 229910001069 Ti alloy Inorganic materials 0.000 claims description 4
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 abstract description 5
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- 229910000365 copper sulfate Inorganic materials 0.000 description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 4
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- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 2
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- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 2
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- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Cleaning By Liquid Or Steam (AREA)
Abstract
The invention discloses a surface treatment process suitable for a gas diffuser of CVD equipment, and belongs to the technical field of electrolytic or electrophoretic production process methods of coating layers. The treatment process optimizes the oxidation liquid medicine in the anodic oxidation process, and proper amount of tartaric acid, boric acid and citric acid are added into oxalic acid solution as additives, so that the dissolution capacity of oxidation tank liquid to an oxidation film in the oxidation period is effectively reduced, the thickness of a blocking layer of the oxidation film is increased, and the corrosion resistance of the oxidation film is further improved. In the surface treatment process, the invention adopts a sectional climbing low-voltage oxidation mode, so that the pore diameter of the porous layer of the oxide film is reduced, the generated oxide film is thinner, more compact and uniform, the corrosion resistance of the oxide film is improved, and the content of impurity ions adsorbed in the film pores is reduced.
Description
Technical Field
The invention relates to the technical field of electrolytic or electrophoretic production process methods of coating layers, in particular to a surface treatment process suitable for a gas diffuser of CVD equipment.
Background
The CVD equipment component gas diffuser is of an aluminum flat plate structure, gas diffusion holes are uniformly distributed on the surface of the gas diffuser, and in the LTPS (low temperature polysilicon) and OLED (organic light emitting semiconductor) manufacturing industry, the anodic oxidation process of the CVD gas diffuser is to form a thin and compact oxide film on the surface of the gas diffuser in a specific solution by applying voltage.
Chinese patent CN113755925a discloses a method for surface modification of aluminum forgings by oxalic acid anodic oxidation, comprising the steps of: (1) surface pretreatment of aluminum forgings: ultrasonically cleaning and degreasing an aluminum forging by using an ethanol solution, then polishing by using sand paper, cleaning the surface of the aluminum forging by using acetone and deionized water, and finally cleaning and drying the aluminum forging by using the ethanol solution in an ultrasonic cleaner for later use; (2) anodic oxidation of aluminum forgings: placing the aluminum forging into an anodic oxidation liquid containing oxalic acid for anodic oxidation; washing the anodized aluminum forging by deionized water and drying by cold air to obtain an anodic oxide film; (3) blocking of anodic oxide film: and (3) sealing and anti-corrosion treatment is carried out on the aluminum forging with the surface provided with the anodic oxide film in a solution containing dichromate and 1, 4-butynediol. The invention adopts constant voltage to carry out anodic oxidation, and the voltage is higher, so that the technical problem that the pore diameter of a porous layer of an oxide film is larger and the generated oxide film is not compact and uniform may exist after treatment.
The aperture of the oxide film is reduced by adopting a step-up method, chinese patent CN113981500A provides an oxalic acid anodic oxidation process method for hard aluminum alloy shell parts, and the oxidation voltage, the oxidation time, the boost speed and the frequency of an electrolytic tank are adjusted and matched by introducing the step-up method, so that three technical indexes of the appearance, the film thickness and the insulation resistance of the oxalic acid anodic oxidation film layer formed on the surface of the shell parts meet standard acceptance requirements, the qualification rate is high, the problem that the oxalic acid anodic oxidation qualification rate of the hard aluminum material shell is low is thoroughly solved, the part rejection problem caused by film ablation and black spots is greatly reduced, the consistency of the insulation resistance of different parts of the shell parts is ensured, and the quality of the oxalic acid anodic oxidation film layer of the shell parts is greatly improved. The invention adopts oxalic acid solution to carry out anodic oxidation, and has the technical problems that the dissolution capacity of oxidation tank liquor to an oxidation film is higher and the thickness of an oxidation film blocking layer is lower during oxidation; in addition, although the invention adopts a step-up method, the anodic oxidation voltage is higher, and the reduction degree of the pore diameter of the porous layer of the oxide film is limited.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention is to provide a surface treatment process for a gas diffuser of a CVD apparatus, which improves the corrosion resistance of an oxide film and prolongs the service life.
An oxidizing liquid medicine comprising the following concentration components: 20-60 g/L oxalic acid, 10-20 g/L tartaric acid, 10-30 g/L boric acid, 5-10 g/L citric acid and the balance of water.
In the oxidation liquid medicine, proper amounts of tartaric acid, boric acid and citric acid are added into the oxalic acid solution as additives, so that the dissolution capacity of the oxidation tank liquid to the oxidation film during oxidation can be effectively reduced, the thickness of the oxidation film blocking layer is increased, and the corrosion resistance of the oxidation film is further improved. In the surface treatment process, a sectional climbing low-voltage oxidation mode is adopted, the pore diameter of the porous layer of the oxide film is reduced, the generated oxide film is thinner, compact and uniform, the corrosion resistance of the oxide film is improved, and the content of impurity ions adsorbed in the film pores is reduced.
The invention discloses a preparation method of the oxidation liquid medicine in an anodic oxidation tank, which comprises the following steps:
step 1, cleaning an anodic oxidation tank at room temperature, adding 3/4 pure water, and measuring the pH to be 7+/-1, wherein the conductivity is less than or equal to 1uS/cm;
step 2, opening a temperature control system of the oxidation tank to control the temperature of the tank liquor at 5-10 ℃;
step 3, adding 20-60 g/L oxalic acid, 10-20 g/L tartaric acid, 10-30 g/L boric acid and 5-10 g/L citric acid, stirring while adding, detecting the temperature in real time, and always keeping the temperature between 5 and 10 ℃;
and 4, after the addition of the medicines is finished, supplementing the working liquid level by using pure water, continuously pumping and stirring until the medicines are completely dissolved in the tank liquor, and completing the preparation.
The invention provides a surface treatment process suitable for a gas diffuser of a CVD device, which comprises the following steps:
s1, blocking a non-hoisting threaded hole of a gas diffuser by an acid and alkali resistant rubber plug, installing a titanium alloy electrode screw in a hanging hole, then starting to hang by an angular titanium hanger, and hoisting the gas diffuser by a crane after the hanging is completed;
s2, transferring the gas diffuser to a water washing tank, degreasing the gas diffuser by degreasing liquid medicine, shaking the product back and forth during degreasing to enable the degreasing liquid medicine to fully enter holes of the gas diffuser, hanging the gas diffuser out of the water washing tank after degreasing, and flushing the surface of the product by high-pressure water with the pressure of more than or equal to 20MPa to ensure that no degreasing liquid medicine remains on the surface of the product;
s3, alkali liquor is adopted to carry out alkali washing on the gas diffuser, and the alkali liquor needs to shake back and forth during the alkali washing process to enable the alkali liquor to fully enter holes of the gas diffuser; transferring the gas diffuser after alkali washing and carrying out acid washing by adopting acid liquor, wherein the acid liquor needs to shake back and forth to fully enter holes of the gas diffuser, the gas diffuser is lifted out of a washing tank after acid washing, and the surface of a product is washed by high-pressure water with the pressure of more than or equal to 20MPa, so that no acid liquor residue is ensured on the surface of the product;
s4, re-fastening each shielding rubber plug and mounting the electrode screw, so that the electrode screw is tightly connected with a product during oxidation, and the hanging point ablation caused by poor conduction is prevented; confirming that the temperature and the concentration of the oxidation liquid medicine in the anodic oxidation tank are in a control range, hanging the fastened gas diffuser into the anodic oxidation tank, and stirring to ensure that the temperature and the concentration of the oxidation liquid medicine are uniform during oxidation;
s5, setting a constant-voltage anodic oxidation program, starting a power supply, and turning off the power supply after the oxidation is completed; after the gas diffuser is lifted out of the anodic oxidation tank, high-pressure water with the pressure of more than or equal to 20MPa is used for flushing the surface of the product, so that no residual oxidizing liquid medicine is ensured on the surface of the product;
s6, hanging the gas diffuser into a pure water tank at normal temperature in sequence for washing for 3-5 min, and washing the gas diffuser for 3-5 min at 40-50 ℃ in the pure water tank, wherein the gas diffuser needs to be rocked back and forth to ensure that the hole is completely washed;
s7, hanging the gas diffuser out, and drying the gas diffuser by using clean oil-free compressed air; dismantling an angular titanium hanger and an electrode screw for hanging a gas diffuser, wiping and cleaning the threaded hole used for hanging with a cotton swab once, and drying the threaded hole with compressed air; and after the clamping hanger is disassembled, putting the gas diffuser into an oven for drying, and finishing the surface treatment of the gas diffuser.
Preferably, the degreasing liquid in the step S2 is obtained by mixing an organic degreasing agent with water, and the concentration of the organic degreasing agent is 30-60 g/L.
Preferably, the degreasing treatment in the step S2 is performed at a temperature of 45-55 ℃ for 5-10 min.
Preferably, the lye in step S3 is an aqueous sodium hydroxide solution having a concentration of 20-40 g/L.
Preferably, the alkaline washing temperature in the step S3 is 28-32 ℃, and the alkaline washing time is 15-30S.
Preferably, the acid solution in the step S3 is an aqueous solution of nitric acid with a concentration of 150-250 g/L.
Preferably, the temperature of the acid washing in the step S3 is 25-35 ℃, and the acid washing time is 10-15 min.
Preferably, the anodic oxidation procedure in step S5 is as follows:
the oil stain remained on the surface of the matrix material can obstruct the infiltration of the oxidation liquid medicine, and influence the smoothness of the oxidation film and the combination degree with the surface of the matrix material. If the oil stain on the surface of the gas diffuser cannot be thoroughly removed before the surface treatment is performed, the oxide film cannot be uniformly adhered to the surface in the whole surface during the anodic oxidation. The greasy part of the surface appears to have formed oxide film, but the distribution of the oxide film inside is uneven, and the combination with the matrix material is weak, cracks or bubbles appear, and the quality of the oxide film is seriously reduced. Moreover, in the surface treatment process, the oil stains also pollute the oxidation liquid medicine, reduce the quality of the surface treatment and cause a series of chain reactions.
In order to sufficiently remove grease on the surface of the gas diffuser and avoid adverse effects of the grease on the anodizing process, the surface is degreased by adopting an organic degreasing agent. The organic degreasing agent takes glycidol, allyl glycidyl ether and potassium isopropoxide as raw materials, and is polymerized to form a polymer with branched side chains, wherein the polymer is subjected to click reaction with 1-pentanediol to introduce a hydrophobic group, then is subjected to addition reaction with methyl iodide after being subjected to subsequent reaction with 1-allyl imidazole, and hydrophilic quaternary ammonium groups are introduced. The organic degreasing agent has a three-dimensional structure, and branched side chains have rich functional groups and larger intramolecular cavities, and the organic degreasing agent has excellent solubility and low viscosity in an aqueous dispersion system. The degreasing liquid medicine prepared from the organic degreasing agent and water can reduce the oil-water interfacial tension of the greasy dirt of the substrate material, and the organic degreasing agent migrates to and is arranged on the interface, so that the process of separating the greasy dirt from the surface of the substrate material is accelerated.
Preferably, the preparation method of the organic degreasing agent comprises the following steps:
m1, uniformly mixing glycidol, allyl glycidyl ether, potassium isopropoxide and tetrahydrofuran, and carrying out ring-opening polymerization reaction in an oxygen-free closed environment; adding hydrochloric acid after the ring-opening polymerization reaction is finished to finish the reaction, stopping adding the hydrochloric acid after no sediment is generated, filtering and collecting filtrate, and removing tetrahydrofuran by rotary evaporation to obtain a ring-opening polymerization product for later use;
m2, taking the ring-opening polymerization product, 1-pentanethiol and tetrahydrofuran, uniformly mixing, then adding a photoinitiator, and carrying out click reaction under ultraviolet irradiation; removing tetrahydrofuran through rotary evaporation after the click reaction is finished to obtain a crude product, mixing the crude product with petroleum ether, filtering and collecting filtrate, and removing petroleum ether from the filtrate through rotary evaporation to obtain a click reaction product for later use;
m3, uniformly mixing the click reaction product, 1-allylimidazole, dibenzoyl peroxide and tetrahydrofuran, and carrying out polymerization reaction under the anaerobic condition; removing tetrahydrofuran and methanol by rotary evaporation after the polymerization reaction is finished, washing and drying to obtain a polymerization product for later use;
m4, mixing the polymerization product with methyl iodide uniformly, and then carrying out addition reaction under the condition of anaerobic sealing; and after the addition reaction is finished, washing and drying the product by diethyl ether to obtain the organic degreasing agent.
Specifically, the preparation method of the organic degreasing agent comprises the following steps of:
m1, uniformly mixing 2.95-3.85 parts of glycidol, 4.55-5.90 parts of allyl alcohol glycidyl ether, 0.95-1.30 parts of potassium isopropoxide and 50-75 parts of tetrahydrofuran, and carrying out ring-opening polymerization reaction in an anaerobic closed environment; adding hydrochloric acid after the ring-opening polymerization reaction is finished to finish the reaction, stopping adding the hydrochloric acid after no sediment is generated, filtering and collecting filtrate, and removing tetrahydrofuran by rotary evaporation to obtain a ring-opening polymerization product for later use;
m2, taking 2.75-4.70 parts of the ring-opening polymerization product, 0.60-1.05 parts of 1-pentanethiol and 40-60 parts of tetrahydrofuran, uniformly mixing, then adding 0.05-0.10 part of benzoin dimethyl ether, and carrying out click reaction under ultraviolet irradiation; removing tetrahydrofuran through rotary evaporation after the click reaction is finished to obtain a crude product, mixing the crude product with 35-50 parts of petroleum ether, filtering and collecting filtrate, and removing petroleum ether from the filtrate through rotary evaporation to obtain a click reaction product for later use;
m3, taking 2.20 to 2.90 parts of the click reaction product, 0.60 to 1.10 parts of 1-allylimidazole, 0.012 to 0.048 part of dibenzoyl peroxide and 40 to 60 parts of tetrahydrofuran, uniformly mixing, and carrying out polymerization reaction under the anaerobic condition; removing tetrahydrofuran by rotary evaporation after the polymerization reaction is finished, washing with methanol at 0-4 ℃ and drying to obtain a polymerization product for later use;
m4, taking 2.65-3.40 parts of the polymerization product and uniformly mixing with 30-60 parts of methyl iodide, and then carrying out addition reaction under the condition of anaerobic sealing; and after the addition reaction is finished, washing and drying the product by diethyl ether to obtain the organic degreasing agent.
Preferably, the temperature of the ring-opening polymerization reaction in the step M1 is 60-75 ℃, and the reaction time is 6-18 h.
Preferably, the concentration of the hydrochloric acid in the step M1 is 0.5-1.0 mol/L.
Preferably, the ultraviolet wavelength of the click reaction in the step M2 is 254-365 nm, and the reaction time is 0.5-2 h.
Preferably, the temperature of the polymerization reaction in the step M3 is 65-85 ℃ and the reaction time is 1-4 h.
Preferably, the temperature of the addition reaction in the step M4 is 40-50 ℃ and the reaction time is 12-48 h.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the invention.
The invention has the following description and functions of partial raw materials in the formula:
oxalic acid: the organic matter has a chemical formula of H 2 C 2 O 4 Colorless transparent crystals or powder, the crystal structure of which has two forms, namely an alpha form (diamond shape) and a beta form (monoclinic form), is odorless, has no taste acid, is soluble in water and ethanol, and is insoluble in benzene and chloroform.
Tartaric acid: carboxylic acid with chemical formula of C 4 H 6 O 6 White crystalline powder, soluble in water and ethanol, slightly soluble in diethyl ether.
Boric acid: inorganic compound with chemical formula of H 3 BO 3 Is white crystalline powder, has a greasy feel and no smell.
Citric acid: also called citric acid, with molecular formula of C 6 H 8 O 7 Is an important organic acid, is colorless crystal, odorless, has strong sour taste and is easy to dissolve in water.
The invention has the beneficial effects that:
compared with the prior art, the oxidation liquid medicine disclosed by the invention has the advantages that a proper amount of tartaric acid, boric acid and citric acid are added into oxalic acid solution as additives, so that the dissolution capacity of oxidation tank liquid to an oxidation film during oxidation can be effectively reduced, the thickness of a blocking layer of the oxidation film is increased, and the corrosion resistance of the oxidation film is further improved.
Compared with the prior art, the method adopts a sectional climbing low-voltage oxidation mode, the pore diameter of the porous layer of the oxide film is reduced, the generated oxide film is thinner, compact and uniform, the corrosion resistance of the oxide film is improved, and the content of impurity ions adsorbed in the film pores is reduced.
The surface treatment process is adopted to treat the gas diffuser, so that the oxidation film has better corrosion resistance and the single use period is prolonged; by adopting the process, the thickness of the film layer can be reduced by coworkers meeting the corrosion resistance requirement, and the thinner oxide film ensures that the porous structure of the film contains fewer impurity ions and water vapor, so that the threshold voltage convergence is better.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Allyl alcohol glycidyl ether, CAS number: 106-92-3, shanghai Michlin Biochemical technologies Co., ltd.
Example 1
A surface treatment process suitable for a gas diffuser of a CVD apparatus, comprising the steps of:
s1, blocking a non-hoisting threaded hole of a gas diffuser by an acid and alkali resistant rubber plug, installing a titanium alloy electrode screw in a hanging hole, then starting to hang by an angular titanium hanger, and hoisting the gas diffuser by a crane after the hanging is completed;
s2, transferring the gas diffuser to a water washing tank, degreasing the gas diffuser by degreasing liquid, wherein the degreasing temperature is 50 ℃, the degreasing time is 7.5min, the degreasing liquid needs to shake back and forth to fully enter holes of the gas diffuser, and after the degreasing treatment is finished, the gas diffuser is lifted out of the water washing tank, and the surface of the product is rinsed by high-pressure water with the pressure of 20MPa, so that no degreasing liquid residue exists on the surface of the product;
s3, alkaline washing is carried out on the gas diffuser by adopting a 30g/L sodium hydroxide aqueous solution, the alkaline washing temperature is 30 ℃, the alkaline washing time is 15S, and the alkaline solution needs to shake back and forth to fully enter holes of the gas diffuser; transferring the gas diffuser after alkali washing, carrying out acid washing by adopting a nitric acid aqueous solution with the concentration of 200g/L, wherein the acid washing temperature is 30 ℃, the acid washing time is 10min, the acid liquid needs to shake back and forth to fully enter holes of the gas diffuser, the gas diffuser after acid washing is lifted out of a water washing tank, and the surface of a product is washed by high-pressure water with the pressure of 20MPa, so that no acid liquid residue is ensured on the surface of the product;
s4, re-fastening each shielding rubber plug and mounting the electrode screw, so that the electrode screw is tightly connected with a product during oxidation, and the hanging point ablation caused by poor conduction is prevented; confirming that the temperature and the concentration of the oxidation liquid medicine in the anodic oxidation tank are in a control range, hanging the fastened gas diffuser into the anodic oxidation tank, and stirring to ensure that the temperature and the concentration of the oxidation liquid medicine are uniform during oxidation;
s5, setting a constant-voltage anodic oxidation program, starting a power supply, wherein the anodic oxidation temperature is 15 ℃, and turning off the power supply after the oxidation is completed; hanging the gas diffuser out of the anodic oxidation tank, and flushing the surface of the product by using high-pressure water with the pressure of 20MPa to ensure that no oxidizing liquid medicine remains on the surface;
s6, hanging the gas diffuser into a pure water tank at normal temperature in sequence for washing for 4min, and washing a pure water tank at 45 ℃ for 4min, wherein the gas diffuser needs to be rocked back and forth during the washing process to ensure that the inside of the hole is completely washed;
s7, hanging the gas diffuser out, and drying the gas diffuser by using clean oil-free compressed air; dismantling an angular titanium hanger and an electrode screw for hanging a gas diffuser, wiping and cleaning the threaded hole used for hanging with a cotton swab once, and drying the threaded hole with compressed air; and after the clamping hanger is disassembled, putting the gas diffuser into an oven for drying, and finishing the surface treatment of the gas diffuser.
The oxidation liquid medicine is prepared by the following method:
step 1, cleaning an anodic oxidation tank at room temperature, adding 3/4 pure water, measuring pH to 7, and measuring conductivity to be less than 1uS/cm;
step 2, opening a temperature control system of the oxidation tank to control the temperature of the tank liquor at 10 ℃;
step 3, adding 40g/L oxalic acid, 15g/L tartaric acid, 20g/L boric acid and 7.5g/L citric acid, stirring while adding, detecting the temperature in real time, and always keeping the temperature between 10 ℃;
and 4, after the addition of the medicines is finished, supplementing the working liquid level by using pure water, continuously pumping and stirring until the medicines are completely dissolved in the tank liquor, and completing the preparation.
The degreasing liquid medicine in the step S2 is obtained by mixing a commercial agent and water; the commercial agent is prepared by mixing sodium tetraborate, pentasodium triphosphate and water, wherein the mass fraction of the sodium tetraborate is 75%, and the mass fraction of the pentasodium triphosphate is 10%; the concentration of the commercial agent in the degreasing liquid medicine is 45g/L.
The anodic oxidation procedure in step S5 is as follows:
example 2
A surface treatment process suitable for a gas diffuser of a CVD apparatus, comprising the steps of:
s1, blocking a non-hoisting threaded hole of a gas diffuser by an acid and alkali resistant rubber plug, installing a titanium alloy electrode screw in a hanging hole, then starting to hang by an angular titanium hanger, and hoisting the gas diffuser by a crane after the hanging is completed;
s2, transferring the gas diffuser to a water washing tank, degreasing the gas diffuser by degreasing liquid, wherein the degreasing temperature is 50 ℃, the degreasing time is 7.5min, the degreasing liquid needs to shake back and forth to fully enter holes of the gas diffuser, and after the degreasing treatment is finished, the gas diffuser is lifted out of the water washing tank, and the surface of the product is rinsed by high-pressure water with the pressure of 20MPa, so that no degreasing liquid residue exists on the surface of the product;
s3, alkaline washing is carried out on the gas diffuser by adopting a 30g/L sodium hydroxide aqueous solution, the alkaline washing temperature is 30 ℃, the alkaline washing time is 15S, and the alkaline solution needs to shake back and forth to fully enter holes of the gas diffuser; transferring the gas diffuser after alkali washing, carrying out acid washing by adopting a nitric acid aqueous solution with the concentration of 200g/L, wherein the acid washing temperature is 30 ℃, the acid washing time is 10min, the acid liquid needs to shake back and forth to fully enter holes of the gas diffuser, the gas diffuser after acid washing is lifted out of a water washing tank, and the surface of a product is washed by high-pressure water with the pressure of 20MPa, so that no acid liquid residue is ensured on the surface of the product;
s4, re-fastening each shielding rubber plug and mounting the electrode screw, so that the electrode screw is tightly connected with a product during oxidation, and the hanging point ablation caused by poor conduction is prevented; confirming that the temperature and the concentration of the oxidation liquid medicine in the anodic oxidation tank are in a control range, hanging the fastened gas diffuser into the anodic oxidation tank, and stirring to ensure that the temperature and the concentration of the oxidation liquid medicine are uniform during oxidation;
s5, setting a constant-voltage anodic oxidation program, starting a power supply, wherein the anodic oxidation temperature is 15 ℃, and turning off the power supply after the oxidation is completed; hanging the gas diffuser out of the anodic oxidation tank, and flushing the surface of the product by using high-pressure water with the pressure of 20MPa to ensure that no oxidizing liquid medicine remains on the surface;
s6, hanging the gas diffuser into a pure water tank at normal temperature in sequence for washing for 4min, and washing a pure water tank at 45 ℃ for 4min, wherein the gas diffuser needs to be rocked back and forth during the washing process to ensure that the inside of the hole is completely washed;
s7, hanging the gas diffuser out, and drying the gas diffuser by using clean oil-free compressed air; dismantling an angular titanium hanger and an electrode screw for hanging a gas diffuser, wiping and cleaning the threaded hole used for hanging with a cotton swab once, and drying the threaded hole with compressed air; and after the clamping hanger is disassembled, putting the gas diffuser into an oven for drying, and finishing the surface treatment of the gas diffuser.
The oxidation liquid medicine is prepared by the following method:
step 1, cleaning an anodic oxidation tank at room temperature, adding 3/4 pure water, measuring pH to 7, and measuring conductivity to be less than 1uS/cm;
step 2, opening a temperature control system of the oxidation tank to control the temperature of the tank liquor at 10 ℃;
step 3, adding 40g/L oxalic acid, 15g/L tartaric acid, 20g/L boric acid and 7.5g/L citric acid, stirring while adding, detecting the temperature in real time, and always keeping the temperature between 10 ℃;
and 4, after the addition of the medicines is finished, supplementing the working liquid level by using pure water, continuously pumping and stirring until the medicines are completely dissolved in the tank liquor, and completing the preparation.
The degreasing liquid in the step S2 is obtained by mixing an organic degreasing agent with water, wherein the concentration of the organic degreasing agent is 45g/L.
The anodic oxidation procedure in step S5 is as follows:
| sequence number | Set voltage/V | Climbing time/min | Hold time/min |
| 1 | 3 | 2 | 2 |
| 2 | 6 | 2 | 2 |
| 3 | 9 | 2 | 2 |
| 4 | 12 | 3 | 3 |
| 5 | 15 | 3 | 3 |
| 6 | 18 | 3 | 3 |
| 7 | 21 | 3 | 5 |
| 8 | 24 | 3 | 5 |
The preparation method of the organic degreasing agent comprises the following steps:
m1, uniformly mixing 2.95kg of glycidol, 4.55kg of allyl alcohol glycidyl ether, 0.95kg of potassium isopropoxide and 50kg of tetrahydrofuran, and carrying out ring-opening polymerization reaction in an oxygen-free closed environment, wherein the temperature of the ring-opening polymerization reaction is 65 ℃ and the reaction time is 12 hours; adding hydrochloric acid with the concentration of 1.0mol/L after the ring-opening polymerization reaction is finished to finish the reaction, stopping adding the hydrochloric acid after no sediment is generated, filtering and collecting filtrate, and removing tetrahydrofuran by rotary evaporation to obtain a ring-opening polymerization product for later use;
m2, taking 2.75kg of the ring-opening polymerization product, 0.60kg of 1-pentanethiol and 40kg of tetrahydrofuran, uniformly mixing, then adding 0.05kg of benzoin dimethyl ether, and carrying out click reaction under ultraviolet irradiation, wherein the ultraviolet wavelength of the click reaction is 365nm, and the reaction time is 1h; removing tetrahydrofuran through rotary evaporation after the click reaction is finished to obtain a crude product, mixing the crude product with 35kg of petroleum ether, filtering and collecting filtrate, and removing petroleum ether from the filtrate through rotary evaporation to obtain a click reaction product for later use;
m3, taking 2.20kg of the click reaction product, 0.60kg of 1-allylimidazole, 0.012kg of dibenzoyl peroxide and 40kg of tetrahydrofuran, uniformly mixing, and carrying out polymerization reaction under the anaerobic condition, wherein the temperature of the polymerization reaction is 75 ℃, and the reaction time is 2.5h; removing tetrahydrofuran by rotary evaporation after the polymerization reaction is finished, washing with methanol at 0 ℃, and drying to obtain a polymerization product for later use;
m4, mixing 2.65kg of the polymerization product with 30kg of methyl iodide uniformly, and then carrying out addition reaction under the condition of oxygen-free sealing, wherein the temperature of the addition reaction is 45 ℃, and the reaction time is 30 hours; and after the addition reaction is finished, washing and drying the product by diethyl ether to obtain the organic degreasing agent.
Comparative example 1
This control is substantially identical to the surface treatment process of example 1, except that the anodic oxidation procedure in this control is 50min with a constant voltage of 24V.
Comparative example 2
This comparative example was substantially identical to the surface treatment process of example 1, except that the formulation of the oxidizing chemical solution in this comparative example was an aqueous oxalic acid solution having a concentration of 82.5 g/L.
Test example 1
The corrosion resistance of the oxide film prepared by the surface treatment process is tested, and the test is referred to the national standard GB/T12967.3-2022, aluminium and aluminium alloy anodic oxide film and organic polymer film detection method part 3: the specific method and the steps in the salt spray test are carried out. The test method is a cyclic acceleration salt spray test (CCT test), in particular a CCT-AASS test. The test reagent is AASS test solution, the spray test temperature of CCT-AASS test is 35 ℃, and the spray test temperature is 80cm 2 The average sedimentation rate of the salt mist of the horizontal area is 1.5mL/h; in the drying test, the temperature in the box is 60 ℃ and the relative humidity is 20%; in the damp-heat test, the temperature in the box is 50 ℃ and the relative humidity is 95%; the cycle was set to 4h spray test +2h dry test +2h wet heat test. According to the regulations in annex B in the above standard, the corrosion condition of the anodic oxide film after the test is observed, the corresponding protection grade is determined, and when the protection grade is lower than 8 grades, the corrosion condition is evaluated according to the standard in the national standard GB T6461-2002, rating of test pieces and test specimens after corrosion test of metal and other inorganic coating layers on metal substrates. The corrosion resistance of the oxide film prepared by the surface treatment process of the invention is expressed in terms of protection grade, and the test results are shown in table 1.
Table 1:
after CCT-AASS test, the higher the protection level is, the stronger the corrosion resistance of the oxide film is.
Test example 2
The continuity of the oxide film prepared by the surface treatment process is tested, and the test is carried out by referring to the specific method and steps in the national standard GB/T8752-2006 copper sulfate method of the continuity test method of the anodic oxidation thin anodic oxide film of aluminum and aluminum alloy. The test reagent is a copper sulfate-hydrochloric acid solution: 20g of crystalline copper sulfate (analytically pure) and 20mL of hydrochloric acid (ρl.18 g/mL) were taken and diluted to 1000mL with distilled water in a volumetric flask. Four drops of copper sulfate solution were dropped into the selected test site and left at the test site for 5 minutes, after which the solution was quickly wiped off. Checking the surface of the sample, and counting the number of black dots and red dots; the test temperature was 20 ℃. The continuity of the oxide film is expressed in terms of the number of black dots and red dots, and the test results are shown in table 2.
Table 2:
| name of the name | Number of black and red dots in test area |
| Example 1 | 4 |
| Example 2 | 1 |
| Comparative example 3 | 9 |
| Comparative example 4 | 15 |
When the copper sulfate solution drops on the surface of the aluminum and aluminum alloy thin anodic oxide film with the exposed matrix metal or oxide film covering poorly, copper is chemically deposited on the aluminum surface, and at the same time, the naked eye or by means of a low-power magnifying glass is used for observation, and gas precipitation is observed at the exposed matrix metal part. After the test, black points or red points can be observed at the discontinuous parts of the oxide film, so that the continuity of the thin anodic oxide films of aluminum and aluminum alloy can be judged. The greater the number of black dots and red dots, the poorer the continuity of the oxide film.
From the test results shown in tables 1 and 2, it can be seen that example 2 has the best corrosion resistance and continuity. The reason for this result may be that, in the oxidation liquid medicine, proper amounts of tartaric acid, boric acid and citric acid are added as additives into the oxalic acid solution, so that the dissolution capacity of the oxidation tank liquid to the oxidation film during oxidation can be effectively reduced, the thickness of the oxidation film barrier layer is increased, and the corrosion resistance of the oxidation film is improved. In the surface treatment process, a sectional climbing low-voltage oxidation mode is adopted, the pore diameter of the porous layer of the oxide film is reduced, the generated oxide film is thinner, compact and uniform, the corrosion resistance of the oxide film is improved, and the content of impurity ions adsorbed in the film pores is reduced.
In addition, example 2 uses an organic degreasing agent for degreasing the substrate, the organic degreasing agent has a three-dimensional structure, branched side chains have rich functional groups and large intramolecular cavities, and the organic degreasing agent has excellent solubility and low viscosity in an aqueous dispersion system. The degreasing liquid medicine prepared from the organic degreasing agent and water can reduce the oil-water interfacial tension of the greasy dirt of the substrate material, the organic degreasing agent migrates to the interface and is arranged on the interface, the process that the greasy dirt is separated from the surface of the substrate material is accelerated, the problems that the greasy dirt hinders infiltration with the oxidation liquid medicine, the smoothness of an oxidation film is affected and the bonding degree with the surface of the substrate material is affected are solved, and the pollution of the greasy dirt to the oxidation liquid medicine and the reduction of the surface treatment quality caused by the greasy dirt are prevented. So that the finished product has better corrosion resistance and continuity.
Claims (8)
1. The surface treatment process suitable for the gas diffuser of the CVD equipment is characterized in that the oxidation liquid medicine is subjected to anodic oxidation treatment, and the specific process steps are as follows:
s1, blocking a non-hoisting threaded hole of a gas diffuser by an acid and alkali resistant rubber plug, installing a titanium alloy electrode screw in a hanging hole, then starting to hang by an angular titanium hanger, and hoisting the gas diffuser by a crane after the hanging is completed;
s2, transferring the gas diffuser to a water washing tank, degreasing the gas diffuser by degreasing liquid medicine, shaking the product back and forth during degreasing to enable the degreasing liquid medicine to fully enter holes of the gas diffuser, hanging the gas diffuser out of the water washing tank after degreasing, and flushing the surface of the product by high-pressure water with the pressure of more than or equal to 20MPa to ensure that no degreasing liquid medicine remains on the surface of the product;
s3, alkali liquor is adopted to carry out alkali washing on the gas diffuser, and the alkali liquor needs to shake back and forth during the alkali washing process to enable the alkali liquor to fully enter holes of the gas diffuser; transferring the gas diffuser after alkali washing and carrying out acid washing by adopting acid liquor, wherein the acid liquor needs to shake back and forth to fully enter holes of the gas diffuser, the gas diffuser is lifted out of a washing tank after acid washing, and the surface of a product is washed by high-pressure water with the pressure of more than or equal to 20MPa, so that no acid liquor residue is ensured on the surface of the product;
s4, re-fastening each shielding rubber plug and mounting the electrode screw, so that the electrode screw is tightly connected with a product during oxidation, and the hanging point ablation caused by poor conduction is prevented; confirming that the temperature and the concentration of the oxidation liquid medicine in the anodic oxidation tank are in a control range, hanging the fastened gas diffuser into the anodic oxidation tank, and stirring to ensure that the temperature and the concentration of the oxidation liquid medicine are uniform during oxidation;
s5, setting an anodic oxidation program, starting a power supply, and turning off the power supply after the oxidation is completed; after the gas diffuser is lifted out of the anodic oxidation tank, high-pressure water with the pressure of more than or equal to 20MPa is used for flushing the surface of the product, so that no residual oxidizing liquid medicine is ensured on the surface of the product;
s6, sequentially hanging the gas diffuser into a pure water tank at normal temperature for water washing for 3-5 min and a pure water tank at 40-50 ℃ for water washing for 3-5 min, and shaking the gas diffuser back and forth during the water washing to ensure that the water washing in the holes is complete;
s7, hanging the gas diffuser out, and drying the gas diffuser by using clean oil-free compressed air; dismantling an angular titanium hanger and an electrode screw for hanging a gas diffuser, wiping and cleaning the threaded hole used for hanging with a cotton swab once, and drying the threaded hole with compressed air; after the clamping hanger is disassembled, the gas diffuser is put into an oven for drying, and the surface treatment of the gas diffuser is finished;
the preparation method of the oxidation liquid medicine in the anodic oxidation tank comprises the following steps:
step 1, cleaning an anodic oxidation tank at room temperature, adding 3/4 pure water, and measuring the pH to be 7+/-1, wherein the conductivity is less than or equal to 1uS/cm;
step 2, opening a temperature control system of the oxidation tank to control the temperature of the tank liquor to be 5-10 ℃;
step 3, adding 20-60 g/L oxalic acid, 10-20 g/L tartaric acid, 10-30 g/L boric acid and 5-10 g/L citric acid, stirring while adding, detecting the temperature in real time, and always keeping the temperature between 5 ℃ and 10 ℃;
after the addition of the medicines is finished, the working liquid level is supplemented by pure water, and the medicines are continuously inflated and stirred until the medicines are completely dissolved in the tank liquor, so that the preparation is finished;
in step S5, specific parameters of the anodic oxidation process are as follows:
stage 1: setting a voltage of 3V, a climbing time of 2min and a holding time of 2min;
2, stage: setting voltage 6V, climbing time 2min and keeping time 2min;
3, stage: setting voltage 9V, climbing time 2min and keeping time 2min;
stage 4: setting voltage 12V, climbing for 3min and keeping for 3min;
stage 5: setting voltage to 15V, climbing for 3min, and keeping for 3min;
stage 6: setting voltage 18V, climbing for 3min and keeping for 3min;
7, stage: setting voltage 21V, climbing for 3min and keeping for 5min;
8, stage: setting voltage 24V, climbing for 3min and maintaining for 5min.
2. The surface treatment process for a gas diffuser of a CVD apparatus according to claim 1, wherein: the degreasing liquid in the step S2 is obtained by mixing an organic degreasing agent with water, and the concentration of the organic degreasing agent is 30-60 g/L; the degreasing treatment temperature is 45-55 ℃, and the treatment time is 5-10 min.
3. The surface treatment process for a gas diffuser of a CVD apparatus according to claim 1, wherein: in the step S3, the alkali liquor is sodium hydroxide aqueous solution with the concentration of 20-40 g/L, the temperature of alkali washing is 28-32 ℃, and the time of alkali washing is 15-30S; the acid liquor is a nitric acid aqueous solution with the concentration of 150-250 g/L, the pickling temperature is 25-35 ℃, and the pickling time is 10-15 min.
4. The surface treatment process for a gas diffuser of a CVD apparatus according to claim 2, wherein the organic degreasing agent is prepared by the following method in parts by weight:
m1, uniformly mixing 2.95-3.85 parts of glycidol, 4.55-5.90 parts of allyl alcohol glycidyl ether, 0.95-1.30 parts of potassium isopropoxide and 50-75 parts of tetrahydrofuran, and carrying out ring-opening polymerization reaction in an oxygen-free closed environment; adding hydrochloric acid after the ring-opening polymerization reaction is finished to finish the reaction, stopping adding the hydrochloric acid after no sediment is generated, filtering and collecting filtrate, and removing tetrahydrofuran by rotary evaporation to obtain a ring-opening polymerization product for later use;
m2, taking 2.75-4.70 parts of the ring-opening polymerization product, 0.60-1.05 parts of 1-pentanethiol and 40-60 parts of tetrahydrofuran, uniformly mixing, adding 0.05-0.10 part of benzoin dimethyl ether, and carrying out click reaction under ultraviolet irradiation; removing tetrahydrofuran through rotary evaporation after the click reaction is finished to obtain a crude product, mixing the crude product with 35-50 parts of petroleum ether, filtering and collecting filtrate, and removing petroleum ether from the filtrate through rotary evaporation to obtain a click reaction product for later use;
m3, taking 2.20-2.90 parts of the click reaction product, 0.60-1.10 parts of 1-allylimidazole, 0.012-0.048 parts of dibenzoyl peroxide and 40-60 parts of tetrahydrofuran, uniformly mixing, and carrying out polymerization reaction under an anaerobic condition; removing tetrahydrofuran by rotary evaporation after the polymerization reaction is finished, washing with methanol at 0-4 ℃, and drying to obtain a polymerization product for later use;
m4, taking 2.65-3.40 parts of the polymerization product and 30-60 parts of methyl iodide, uniformly mixing, and then carrying out addition reaction under the condition of anaerobic sealing; and after the addition reaction is finished, washing and drying the product by diethyl ether to obtain the organic degreasing agent.
5. The surface treatment process for a gas diffuser of a CVD apparatus according to claim 4, wherein: the temperature of the ring-opening polymerization reaction in the step M1 is 60-75 ℃, and the reaction time is 6-18 h.
6. The surface treatment process for a gas diffuser of a CVD apparatus according to claim 4, wherein: and (3) the ultraviolet wavelength of the click reaction in the step (M2) is 254-365 nm, and the reaction time is 0.5-2 h.
7. The surface treatment process for a gas diffuser of a CVD apparatus according to claim 4, wherein: and (3) the temperature of the polymerization reaction in the step (M3) is 65-85 ℃, and the reaction time is 1-4 hours.
8. The surface treatment process for a gas diffuser of a CVD apparatus according to claim 4, wherein: and (3) the temperature of the addition reaction in the step M4 is 40-50 ℃, and the reaction time is 12-48 h.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2390588C1 (en) * | 2008-12-25 | 2010-05-27 | Открытое акционерное общество "Всероссийский институт легких сплавов" (ОАО "ВИЛС") | Procedure for hard anodising items out of aluminium alloys |
| CN107604342A (en) * | 2016-07-12 | 2018-01-19 | Abm股份有限公司 | Its manufacture method of hardware and the process chamber with hardware |
-
2022
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2390588C1 (en) * | 2008-12-25 | 2010-05-27 | Открытое акционерное общество "Всероссийский институт легких сплавов" (ОАО "ВИЛС") | Procedure for hard anodising items out of aluminium alloys |
| CN107604342A (en) * | 2016-07-12 | 2018-01-19 | Abm股份有限公司 | Its manufacture method of hardware and the process chamber with hardware |
Non-Patent Citations (2)
| Title |
|---|
| 四酸体系铝合金瓷质氧化工艺研究;何潘亮;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;第B022-37页 * |
| 钱苗根.材料表面技术及其应用手册.机械工业出版社,1998,第230页. * |
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