CN101152652B - Method for cleaning surface of anodize parts - Google Patents

Method for cleaning surface of anodize parts Download PDF

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CN101152652B
CN101152652B CN200610113529XA CN200610113529A CN101152652B CN 101152652 B CN101152652 B CN 101152652B CN 200610113529X A CN200610113529X A CN 200610113529XA CN 200610113529 A CN200610113529 A CN 200610113529A CN 101152652 B CN101152652 B CN 101152652B
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cleaning
organic solvent
time
wiping
anodized
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CN101152652A (en
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童翔
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Beijing North Microelectronics Co Ltd
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Beijing North Microelectronics Co Ltd
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Abstract

The invention provides a cleaning method for the surface of an anode oxidized component. The core of the method is as follows: organic solution is firstly used for cleaning of the surface of the component; then alkaline solution and acid solution are used for cleaning of the surface of the component in turn but not in sequence; at last, ultrasonic wave is adopted to clean the component. Removing of settlings on the surface of the component can be realized. The method is an effective and simple method without destructiveness for cleaning of the anode oxidized surface and mainly comprises that the invention adopts organic solution, alkaline solution and diluted acid solution as well as an ultrasonic cleaning method for removing of anode oxidation and treatment of contamination on the surface. The method cannot lead to flaking of anode oxidation and newly anode oxidation treatment of the component even if micro-damage is produced.

Description

Method for cleaning surface of anodic oxidation part
Technical Field
The invention relates to a method for cleaning an object, in particular to a method for cleaning the surface of an anodic oxidation part.
Background
As technology nodes have evolved from 250nm to 65nm, and even below 45nm, as technology for semiconductor chips has advanced, the size of silicon wafers has increased from 200mm to 300mm, in which case the cost per wafer has become higher and higher. The process requirements for processing silicon wafers are becoming more and more strict. The processing of the semiconductor needs to go through a plurality of procedures including deposition, photoetching, etching and the like, the etching process is one of the more complicated procedures, and the state of plasma, various process parameters and the like in the plasma etching process are directly related to the etching result.
When the etching machine carries out a normal etching process, products in the etching process can be deposited on the surfaces of the parts in the etching reaction chamber of the etching machine. After the etching process is continuously performed for a certain RF hour, when the amount of the deposit in the etching reaction chamber reaches a certain degree, the process state of the etching reaction chamber may be greatly changed, thereby causing drift of the etching rate and reduction of the etching uniformity. At the moment, the process state of the etching reaction chamber can not meet the process standard of the product, and parts in the etching reaction chamber must be processed to remove pollutants on the surface of the parts and restore the normal process conditions of the etching reaction chamber, so that the production requirement of an equipment owner is met.
The common cleaning method is to use HNO3+ HF soaking and then to use carborundum paper to scrub for cleaning. In the cleaning process, because the surface of the anodic oxidation part has different characteristics from other metal parts, the method not only consumes time and labor in the cleaning process and is easy to damage the surface of the anodic oxidation part when removing the polymer, but also has an imperfect cleaning effect on the polymer and remains dark gray spots.
The etching reaction chamber is usually made of anodized aluminum, and the polycrystalline etching anodic oxidation piece is an anodic oxidation piece in a process chamber for plasma etching a polycrystalline silicon layer on a silicon wafer, and the anodic oxidation pieces are directly contacted with the process chamber, so that impurities in various process processes are easily deposited on the surface of the anodic oxidation piece and cannot be pumped out of the pumping chamber through a pump. However, the contaminants deposited on the surface of the anodized layer may continuously release various impurity particles during the process, thereby affecting the stability of the process and causing an increase in particles on the surface of the silicon wafer. The anodic oxidation usually forms a very thin aluminum oxide layer only on the surface of the aluminum material, and the aluminum oxide layer may be damaged or fall off by a little carelessness in the cleaning process, resulting in the rejection of parts.
Disclosure of Invention
The invention aims to provide a method for cleaning the surface of an anodized part, which can realize wet cleaning of the surface of the anodized part, has small damage to the surface of the part and completely meets the use requirement.
The purpose of the invention is realized by the following technical scheme:
a cleaning method for the surface of an anodic oxidation part comprises the following steps:
A. cleaning the surface of the part by using an organic solvent;
B. sequentially cleaning the surface of the part by using an alkaline solution and an acidic solution in no order;
C. the parts were cleaned with ultrasound.
The step A comprises the following steps:
a1, wiping the part with an organic solvent until no colored impurities fall off;
a2, spraying the organic solvent for a set spraying time, and repeating for multiple times, wherein the spraying time of each time can be the same as or different from that of the used organic solvent; and/or the presence of a gas in the gas,
and A3, soaking the parts in the organic solvent for a set soaking time, and repeating for multiple times, wherein the soaking time of each time can be the same as or different from that of the organic solvent.
The step A also comprises the following steps after the parts are wiped, sprayed and/or soaked for cleaning:
a4, drying the surface of the part by using clean high-pressure air; and/or the presence of a gas in the gas,
a5, wiping the part with a clean wipe until no colored foreign bodies are removed.
The organic solvent is as follows:
100% isopropyl alcohol, meeting the grade I standard of SEMI standard C41-1101A; or,
acetone, according to the electron purity level.
The step B comprises the following steps in no sequence:
b1, wiping the part with an acid solution for no more than a set wiping time;
b2, soaking the part in alkaline solution for a set cleaning time;
the step B also comprises the following steps after the parts are wiped and/or soaked for cleaning:
b3, spraying the cleaning time set by the parts with the organic solvent, and repeating for multiple times, wherein the cleaning time of each time can be the same as or different from that of the used organic solvent; and/or the presence of a gas in the gas,
and B4, drying the surface of the part by using clean high-pressure air.
The acid solution is as follows:
HF∶HNO3∶H2o is 0.1-2: 5: 50);
or,
the alkaline solution is as follows:
NH4OH∶H2O2∶H2o is 0.5-3: 2: 5.
The step C comprises the following steps:
and (3) putting the part into an ultrasonic groove containing an organic solvent, and cleaning for a set time.
The method comprises the following steps:
before cleaning, the method comprises the following steps:
a protective layer is arranged on the surface of the part which is not anodized,
before the step C, the method comprises the following steps:
and removing the surface of the part which is not subjected to anodic oxidation and arranging a protective layer.
According to the technical scheme provided by the invention, the method for cleaning the surface of the anodized part has the core that the surface of the part is cleaned by using an organic solvent; sequentially cleaning the surface of the part by using an alkaline solution and an acidic solution in a non-sequential manner; finally, the part is cleaned with ultrasonic waves. The purpose of removing the deposit on the surface of the part is achieved. The method is an effective method for cleaning the anodized surface without destructiveness and simply, and mainly comprises the steps of removing pollutants on the anodized surface by using an organic solvent, an alkaline solution, a diluted acidic solution and an ultrasonic cleaning method, wherein the method does not peel the anodized layer, and if the anodized layer is damaged, the damage is extremely slight, so that parts do not need to be anodized again.
Detailed Description
The core of the cleaning method for the surface of the anodic oxidation part is that the surface of the part is cleaned by an organic solvent; sequentially cleaning the surface of the part by using an alkaline solution and an acidic solution in a non-sequential manner; finally, the part is cleaned with ultrasonic waves. The purpose of removing the deposit on the surface of the part is achieved.
Before cleaning by this method, we analyzed the anodized surfaces to be cleaned using Scanning Electron Microscopy (SEM), energy spectrometer (EDS), and found that the deposits (contaminants) on the anodized surfaces of chamber parts over time were primarily comprised of: organic impurities, metal impurities, electrode impurities, silicon impurities, fluoride impurities, surface particles. Specifically, for example, fluoride impurities in the contamination include AlF, TiF, and the like; the metal impurities comprise Fe, Cr, Ni, Mo, V, Cu and the like; electrode impurities including W, P, etc.; the silicon-based particles include Si, SiO2, and the like.
The cleaning method specifically comprises the following steps:
cleaning the surface of a part with an organic solvent
The following methods or combinations thereof may be included:
1. wiping the part with an organic solvent until no colored impurities fall off; the parts are usually wiped by dipping the dust-free cloth with an organic solvent until the dust-free cloth is colorless.
2. Spraying the organic solvent for a set spraying time of the part, and repeating for many times, wherein the spraying time of each time can be the same as or different from that of the used organic solvent; the surface of an oxide layer of a part is directly sprayed by an organic solvent at least for a set spraying time, and then the surface of the part is dried by clean high-pressure gas or the part is wiped by clean dust-free cloth until the dust-free cloth is colorless.
3. The soaking time set by the parts in the organic solvent can be repeated for a plurality of times, and the soaking time of each time can be the same as or different from that of the used organic solvent. The parts are usually directly soaked in an organic solvent for at least a set soaking time, and then cleaned by clean dust-free cloth until no color is formed on the dust-free cloth or the parts are dried by clean high-pressure air.
The dust-free cloth is the wiping material, and the dust-free cloth needs to meet the use standard of an ultraclean room. The requirements of CL4 (class 100 clean room) are met, and a wiping pad can also be used as a wiping object, which needs to meet the semiconductor industry standard. Meets the CL4 (100-grade clean room) requirement.
The organic solvents here are:
100% isopropyl alcohol, meeting the grade I standard of SEMI standard C41-1101A; of course, other organic solvents may be used.
Or the following steps are adopted:
and the acetone meets the requirement of electronic purity level.
The electronic purity is a grade of chemical reagents in national standards, called MOS grade for short, and the electronic purity is extremely low in electrical impurity content.
Secondly, sequentially cleaning the surface of the part by using an alkaline solution and an acidic solution in no order
It should be noted here that the cleaning may be performed by an alkaline solution and then by an acidic solution, or may be performed by an acidic solution and then by an alkaline solution.
1. The cleaning method of the acid solution is to dip the acid solution by a dust-free cloth (or a wiping pad) to wipe the parts for not exceeding the set wiping time;
after the process is finished, in order to enter the next process, organic solvent is generally needed to directly spray the surface of the oxide layer of the part, the set spraying time is not less than, and then the surface of the part is dried by clean high-pressure gas.
2. Soaking the part in alkaline solution for a set cleaning time; the parts are usually soaked directly in alkaline solution for at least a set soaking time, and then wiped by clean dust-free cloth until no color is formed on the dust-free cloth.
After the process is finished, in order to enter the next process, organic solvent is generally needed to directly spray the surface of the oxide layer of the part, the set spraying time is not less than, and then the surface of the part is dried by clean high-pressure gas.
The formulation of the acidic solution here is:
HF∶HNO3∶H2o is 0.1-2: 5: 50;
the preferable formula is as follows:
HF∶HNO3∶H2o is 1: 5: 50;
or,
the formulation of the alkaline solution here is:
NH4OH∶H2O2∶H2o is 0.5-3: 2: 50;
the preferable formula is as follows:
NH4OH∶H2O2∶H2o is 1: 2.
Thirdly, parts are cleaned by ultrasonic waves
And (3) putting the part into an ultrasonic groove containing an organic solvent, and cleaning for a set time.
In addition, in order to protect the non-oxidized surface of the part, a protective layer, namely an adhesive tape for resisting chemical corrosion, needs to be arranged on the surface of the part which is not subjected to anodic oxidation before cleaning; after cleaning, a protective layer is arranged on the surface of the part which is not subjected to anodic oxidation, namely the adhesive tape resisting chemical corrosion is removed.
It can be seen that the basic cleaning method of the present invention is:
step 1, isopropanol (IPA: 100%, conforming to SEMI Standard C41-1101A, grade 1 or better) is used to remove organic impurities from the anodized surface, and other organic solvents may be used if desired, but provided that they do not cause recontamination of the anodized part.
Step 2, using alkaline solution NH4OH (Ammonia, 29%, meeting SEMI Standard C21-0301, grade 1 or better) + H2O2(hydrogen peroxide, 29%, meeting SEMI standard C31-1101, grade 1 or better) to clean anodized surfaces. The alkaline solution can remove organic impurities, metal impurities and fluoride. H2O2 is a strong oxidant, which can oxidize metal impurities into high-valence metal ions, and the metal ions can form stable complex ions with ammonia water, so that the complex ions can be removed. E.g. Cu by H2O2Oxidation to Cu +, followed by Cu + and Ammonia formation of Cu + (NH)3)4 2+. The alkaline solution has good effect at the temperature of more than 50 ℃.
Step 3, using an acidic solution HF (hydrofluoric acid, 49%, conforming to SEMI Standard C28-0301, grade 1 or better) + HNO3(nitric acid, 67%, meeting SEMI Standard C35-0301, grade 1 or better) for cleaning anodized surfaces from HF (49%, adhering to SEMI Standard C28-0301, Gradel or better) + HNO3(67%, adherence to SEMI Standard C41-1101A, Gradel or better). HNO in this acidic solution3Capable of removing metal particles and electrode impurities, HF capable of removing silicon particles, e.g. SiO2The reaction is as follows:
4HF+SiO2=SiF4+2H2O
6HF+SiO2=H2SiF6+2H2O
in this acidic solution, the concentrations of H + and F-are low, so he has a low reaction constant (K1 ═ 1.3X 10-3mol/l), HNO3H + can be decomposed, so HNO3May result in even lower F-concentrations. Since HF can attack ceramic grain boundaries, great care must be taken in using HF to treat the surface of ceramic materials (anodized alumina is a ceramic material). Considered HNO during cleaning3The increased concentration can enhance the removal of metals and metal ions. HNO3The strongly oxidizing acid may be reacted with an active metal such as Fe, Ni, Al, Zn, or with an inactive metal such as Cu.
The use of a wiping pad (e.g., 3m CE2200) can help dislodge contaminants from the anodized surface while also wiping localized stains off the ceramic surface of the ESC with the above-mentioned solution.
It has been mentioned above that step 2 and step 3 can be interchanged.
And 4, ultrasonic cleaning, wherein the Particle on the anodized surface can be removed, and the Particle in some holes of the anodized part can be removed. Such as suction holes in the liner. It is desirable that the density of particles of Particle 0.3 μm on the parts after ultrasonic cleaning be less than 5Particle/cm 2.
Several solutions for cleaning the surface of the anodized part by this method are shown below as two examples of cleaning by this method, but the method is not limited to the following examples:
the first embodiment is as follows:
and 11, firstly, protecting the surface, which is not subjected to anodic oxidation treatment and can react with chemical liquid adopted in the cleaning process, of the anodic oxidation part by using a chemical corrosion resistant adhesive tape.
And step 12, spraying the surface of the anodic oxide layer with ultra-pure water UPW (impedance resistance is more than or equal to 18 omega/cm, 25 ℃) for at least 5mins, and then blowing the surface of the part with an N2 gun with a filter (0.05-0.1 mu m).
And step 13, wiping the surface of the dried anodized layer by using dust-free cloth dipped with isopropanol until no color exists on the dust-free cloth.
And step 14, soaking the anodized surface in UPW at the temperature of 80 ℃ for 1 hour, and wiping the anodized surface by using a dust-free cloth.
Step 15, soaking the parts in 6% H2O2Middle 30mins, then wiping the ESC surface with a dust-free cloth. If necessary, a wiping pad (3MTM CE2200) was used to wipe local stains on the anodized surface.
Step 16, spraying the parts for at least 5mins by using UPW (resistance is more than or equal to 18 omega/cm, 25 ℃), and then using nitrogen N with a filter (0.05-0.1 mu m)2And (5) drying the surfaces of the parts by using a gun.
Step 17, dipping with HF and HNO3∶H2A dust free cloth of O (1: 5: 50) was used to wipe the anodized part surface for a maximum wiping time of no more than 30seconds, and a wiping pad (3MTM CE2200) was also used to wipe the part surface.
Step 18, spraying the parts for at least 10mins by using UPW (resistance is more than or equal to 18 omega/cm, 25 ℃), during spraying, cleaning holes and grooves, and then using N with a filter (0.05-0.1 mu m)2And (5) drying the surfaces of the parts by using a gun.
Step 19, soaking the parts in NH4OH∶H2O2∶H220mins in O (1: 2), wiped with a dust-free cloth or wiping pad (3MTM CE 2200).
110, spraying the surface of the part for at least 5mins by using UPW (resistance is more than or equal to 18 omega/cm, 25 ℃), paying attention to the cleaning of He pores and some grooves during spraying, and then using N with a filter (0.05-0.1 mu m)2And (5) drying the surfaces of the parts by using a gun.
Step 111, the ESC is then moved to a class 1000 clean room and the ceramic surface roughness of the ESC is measured (e.g., pocket-sized EMD-1500-
Step 112, place ESC in ultrasonic tank with UPW to ultrasonic clean for 60mins (room temperature). The anodic oxidation surface is absolutely not contacted with the bottom of the ultrasonic tank in the ultrasonic cleaning process
Step 113, removing the chemical-resistant adhesive tape on the surface of the part, wiping the chemical-resistant adhesive tape-protected surface with IPA, and then rinsing with IPA
The component surface, including the holes and grooves on the component surface, is blow dried 114 using an N2 supply apparatus.
The part is taken to a class 100 clean room, and then baked in a heat lamp or oven at 120 ℃ for 2hours, after which the part is allowed to cool slowly (with oven cooling) to 50-60 ℃. The ESC Surface is then tested for Particle size (e.g., using a QIII + Surface Particle Detector:. QIII type Surface Particle tester).
Example two:
and step 21, firstly, protecting the surface, which is not subjected to anodic oxidation treatment and can react with chemical liquid adopted in the cleaning process, of the anodic oxidation part by using a chemical corrosion resistant adhesive tape.
Step 22, spraying the surface of the anodic oxide layer for at least 5mins by using UPW (resistance is more than or equal to 18 omega/cm, 25 ℃), and then using N with a filter (0.05-0.1 mu m)2And (5) drying the surfaces of the parts by using a gun.
Step 23, soaking the parts in 6% H2O2Middle 30mins, then wiping the ESC surface with a dust-free cloth. If necessary, a wiping pad (3MTM CE2200) was used to wipe local stains on the anodized surface.
24, spraying the parts for at least 5mins by using UPW (resistance is more than or equal to 18 omega/cm, 25 ℃), and then using N with a filter (0.05-0.1 mu m)2And (5) drying the surfaces of the parts by using a gun.
And 25, soaking the part in IPA for 30mins, and wiping the surface of the part with a dust-free cloth. Spraying ESC with UPW (resistance > 18 Ω/cm, 25 deg.C) for at least 5mins, and filtering with N (0.05-0.1 μm)2And (5) drying the surfaces of the parts by using a gun.
Step 26, soaking the parts in NH4 OH: H2O2∶H220mins in O (1: 2), wiped with a dust-free cloth or wiping pad (3MTM CE 2200).
And 27, spraying the surface of the part for at least 5mins by using UPW (resistance is more than or equal to 18 omega/cm, 25 ℃), paying attention to the cleaning of He pores and grooves during spraying, and then blowing the surface of the part by using an N2 gun with a filter (0.05-0.1 mu m).
Step 28, dipping with HF and HNO3∶H2A dust free cloth of O (1: 5: 50) was used to wipe the anodized part surface for a maximum wiping time of no more than 30seconds, and a wiping pad (3MTM CE2200) was also used to wipe the part surface.
Spraying the parts with UPW (resistance > 18 omega/cm, 25 ℃) for at least 10mins, wherein the holes and grooves are cleaned, and then using N with a filter (0.05-0.1 mu m)2Gun blowerAnd drying the surface of the part.
Step 210, the ESC is then moved to a class 1000 clean room and the ceramic surface roughness of the ESC is measured (e.g., Fowler Pocket Surf: Fred V.Fowler Co., Inc., Newton, Mass.)
Step 211, place the ESC in an ultrasonic tank with UPW to ultrasonically clean for 60mins (room temperature). The anodic oxidation surface is absolutely not contacted with the bottom of the ultrasonic tank in the ultrasonic cleaning process
Step 212, remove the chemical resistant tape from the surface of the component, wipe the chemical resistant tape protected surface with IPA, and rinse with IPA
The component surface, including the holes and grooves on the component surface, is blow dried using an N2 supply apparatus, step 213.
Step 214, the part is taken to a class 100 clean room, then baked in a heat lamp or oven at 120 ℃ for 2hours, after which the part is allowed to cool slowly (with oven cooling) to 50-60 ℃. The ESC Surface is then tested for Particle size (e.g., using a QIII + Surface Particle Detector: Pentagon Technologies, Livermore, Calif.).
In summary, the cleaning method according to the technical scheme of the invention is a nondestructive and simple effective method for cleaning the anodized surface, and mainly comprises the steps of removing pollutants on the anodized surface by using an organic solvent, an alkaline solution, a diluted acidic solution and an ultrasonic cleaning method, wherein the method does not peel off the anodized layer, and if the pollutants are damaged, the pollutants are extremely trace, so that parts do not need to be anodized again.
The method can not only meet the cleaning requirement of the anodic oxidation piece in the process chamber with low process, but also meet the requirement of the anodic oxidation piece in the process chamber with high process (0.25 mu m).
The damage of the traditional wet cleaning method to the parts is large, the damage of the cleaning method to the parts is almost zero, the service life of the parts is prolonged, and the cost of the parts and the consumables of an equipment owner is saved.
Compared with the traditional cleaning method for the polycrystalline etching anodic oxidation piece, the wet cleaning method saves about 1 hour, and saves the labor cost of a cleaner.
Compared with the traditional cleaning method of the polycrystalline etching anodic oxidation piece, the wet cleaning method saves about 30 of liquid medicine and saves the cost of chemical liquid medicine of a cleaner.
The technical key points of the invention and what the points to be protected are
The cleaning method can completely meet the requirement of an anodic oxidation piece of a high-process (0.25 mu m) process chamber, and is the key for ensuring the production of the high-process.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims (8)

1. A method for cleaning the surface of an anodized part is characterized by comprising the following steps:
A. cleaning the surface of the part by using an organic solvent;
B. sequentially cleaning the surface of the part by using an alkaline solution and an acidic solution in no order;
C. cleaning the part by using ultrasonic waves;
the acid solution is as follows: HF: HNO3∶H2O is 0.1-2: 5: 50;
the alkaline solution is as follows: NH (NH)4OH∶H2O2∶H2O is 0.5-3: 2: 5.
2. The method for cleaning the surface of an anodized part according to claim 1, wherein the step a comprises:
a1, wiping the part with an organic solvent until no colored impurities fall off; and/or the presence of a gas in the gas,
a2, spraying the organic solvent for a set spraying time, and repeating for multiple times, wherein the spraying time of each time can be the same as or different from that of the used organic solvent; and/or the presence of a gas in the gas,
and A3, soaking the parts in the organic solvent for a set soaking time, and repeating for multiple times, wherein the soaking time of each time can be the same as or different from that of the organic solvent.
3. The method of claim 2, wherein step a further comprises, after the wiping, spraying and/or soaking the part for cleaning:
a4, drying the surface of the part by using clean high-pressure air; and/or the presence of a gas in the gas,
a5, wiping the part with a clean wipe until no colored foreign bodies are removed.
4. The method for cleaning the surface of an anodized part according to claim 1 or 2, wherein the organic solvent is:
100% isopropyl alcohol, meeting the grade I standard of SEMI standard C41-1101A; or,
acetone, according to the electron purity level.
5. The method for cleaning the surface of an anodized part according to claim 1, wherein the step B comprises, in no order:
b1, wiping the part with an acid solution for no more than a set wiping time;
b2, soaking the parts in alkaline solution for a set cleaning time.
6. The method of claim 5, wherein step B further comprises, after the wiping and/or soaking the part for cleaning:
b3, spraying the cleaning time set by the parts with the organic solvent, and repeating for multiple times, wherein the cleaning time of each time can be the same as or different from that of the used organic solvent; and/or the presence of a gas in the gas,
and B4, drying the surface of the part by using clean high-pressure air.
7. The method of claim 1, wherein step C comprises:
and (3) putting the part into an ultrasonic groove containing an organic solvent, and cleaning for a set time.
8. The method for cleaning the surface of an anodized part according to claim 1, wherein:
before cleaning, the method comprises the following steps:
arranging a protective layer on the surface of the part which is not subjected to anodic oxidation;
after step C, comprising:
and removing the surface of the part which is not subjected to anodic oxidation and arranging a protective layer.
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CN102825028B (en) * 2012-09-11 2015-07-08 同济大学 Cleaning method of glazed surface of YCOB crystal

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