CN103746033A - Acid etching texturing photoresist removing method for polycrystalline silicon solar cell - Google Patents
Acid etching texturing photoresist removing method for polycrystalline silicon solar cell Download PDFInfo
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- CN103746033A CN103746033A CN201310744395.1A CN201310744395A CN103746033A CN 103746033 A CN103746033 A CN 103746033A CN 201310744395 A CN201310744395 A CN 201310744395A CN 103746033 A CN103746033 A CN 103746033A
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 44
- 229910021420 polycrystalline silicon Inorganic materials 0.000 title claims abstract description 31
- 239000002253 acid Substances 0.000 title claims abstract description 10
- 238000005530 etching Methods 0.000 title abstract description 6
- 238000005245 sintering Methods 0.000 claims abstract description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 229920005591 polysilicon Polymers 0.000 claims description 29
- 235000008216 herbs Nutrition 0.000 claims description 17
- 210000002268 wool Anatomy 0.000 claims description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 238000005554 pickling Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 230000003628 erosive effect Effects 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 4
- 238000004380 ashing Methods 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003667 anti-reflective effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Electromagnetism (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
The invention discloses an acid etching texturing photoresist removing method for a polycrystalline silicon solar cell. The method comprises the following steps of sintering off an organic photoresist mask formed by etching a silicon wafer at high temperature by using a sinteringfurnace, and removing a surface oxide layer and remaining organic impurities in an acid washing way. The method for rapidly removing the organic photoresist mask is a purely-physical photoresist removing method, and compared with a conventional common organic photoresist removing method, the method has the advantages that pollution caused by an organic solvent and an acid-alkali solvent is avoided, wastewater discharge is avoided, the consumption of a chemical solvent and subsequent pollution disposal are greatly reduced, risks in a production process are reduced, the cost is also greatly lowered, and the production efficiency is improved.
Description
Technical field
The present invention relates to a kind of photoresist and remove fast method, be specifically related to a kind of polysilicon solar cell sour making herbs into wool quick removal method with photoresist.
Background technology
The making herbs into wool technology of at present traditional polysilicon solar cell is the wet etching technique of nitric acid and hydrofluoric acid solution.Utilize polysilicon surface fault of construction, form vermiform matte, although reflectivity is minimum, can arrive 22%, now blemish increases and causes battery efficiency to reduce on the contrary, mostly adopts more than 25% reflectivity in suitability for industrialized production.Adopt photoresist to form mask pattern and by the polysilicon making herbs into wool skill of acid solution isotropic etching, can when significantly reducing silicon face reflectivity, (be reduced to below 20%) again, improve battery efficiency.Yet the organic mask of photoresist must be removed clean otherwise can pollute cell piece after acid solution making herbs into wool.Traditional organic mask is removed technique has increased technological process greatly, causes the rising of battery production cost.In semiconductor technology, the removal of traditional organic photoresist mask mainly contains two methods, and organic mask is removed in concentrated sulfuric acid heating, and adopts specific organic striping additive to remove organic mask for photoresist molecular composition.These two kinds of conventional methods have not only been used a large amount of organic solvents, unfavorable to large-scale production in fail safe, and need a large amount of organic solvent or water to carry out rinsing, and cost is higher, seriously polluted on production line.Although plasma etchings etc. adopt to some extent the method that the ashing of photoresist mask is removed in semi-conductor industry, no matter be to introduce fluoro-gas or vacuum requirement, all strengthened cost, be not suitable for the high efficiency development model of the low-cost high yield of solar cell.
Summary of the invention
Technical problem to be solved by this invention is: a kind of removal method for organic photoresist after the polysilicon making herbs into wool of large-scale industrial production is provided, the method can reduce consumption and the follow-up pollution of chemical solvent and process, reduce the danger in production process, cost is low, and production efficiency is high.
For solving the problems of the technologies described above, technical scheme provided by the invention is: a kind of polysilicon solar cell sour making herbs into wool removal method with photoresist, the steps include: that the organic photoresist mask after silicon chip erosion at high temperature burns photoresist mask by sintering furnace, then adopt pickling to remove surface oxide layer and remaining organic impurities.
As preferably, described high temperature sintering furnace is chain-conveyer furnace or Muffle furnace; Industrial production line be take chain type multistage warm area sintering furnace as best.
The gas that described sintering furnace burning generates adopts suction type to collect.
As preferably, temperature during described high temperature sintering is 300 ℃~1000 ℃, 500 ℃~700 ℃ the bests.
As preferably, when high temperature sintering, pass into oxygen or cleaned air and guarantee sufficient combustion.
After described high temperature sintering, silicon chip is carried out to conventional pickling, acid used is hydrofluoric acid or hydrochloric acid, removes oxide layer and the remained on surface organic substance of silicon chip surface, then with deionized water, cleans.
Described photoresist is high-molecular organic material, is eurymeric photoresist or negative photoresist.
Beneficial effect: the quick removal method of organic photoresist mask of the present invention, it is a kind of photoresist removal method of pure physics, with respect to current conventional organic photoresist removal method, organic solvent-free and soda acid solvent contamination, without discharging of waste liquid, the consumption and the follow-up pollution that greatly reduce chemical solvent are processed, and have reduced the danger in production process, also greatly reduce cost, improved production efficiency.
Compare plasma ashing method, do not need vacuum environment, simple, cost is low, and speed is fast.
In addition, in polysilicon solar cell production process, electrode forms the same high temperature sintering technology that adopted.One of object of the high temperature sintering of electrode slurry is exactly to remove the organic substance containing in slurry, comprises organic solvent and high molecular organic thickening agent, and technical solution of the present invention is mated with existing polysilicon solar cell production technology very much.
After high temperature sintering, photoresist decomposes totally, and the impurity of polysilicon surface absorption is few, and follow-up cleaning is simple, to solar battery efficiency without negative effect.
Applied widely, be applicable to any organic photoresist, comprise eurymeric and negative photoresist.
Embodiment
Embodiment 1
Organic photoresist film is formed by following steps:
Organic photoresist adopts the BN308 negative photoresist of Beijing section China, and photoresist forms 2~3 micron films in the mode of spraying on polysilicon solar cell surface, after the exposure of developing, immerses etching making herbs into wool in hydrofluoric acid/nitric acid mixed solution, about 30s of time.Polysilicon chip takes out rear surface and remains photoresist film.
Polysilicon solar cell sour making herbs into wool quick removal method with photoresist, comprises the following steps:
Step 1 is cleaned the polysilicon chip of above-mentioned remained on surface organic photoresist film with pure water, remove remained on surface acid solution;
Step 2 is sent the polysilicon chip after above-mentioned cleaning into sintering in chain-type sintering furnace.The present embodiment adopts Despatch sintering furnace, and sintering furnace is divided into 7 warm areas, the about 6m of sintering zone length.
Sintered furnace temperature zone setting (℃): 420/550/580/580/630/815/895, belt speed 200cm/min; The about 3min of sintering time.
Step 3 is cleaned the silicon chip after sintering through alkali cleaning, pickling and pure water, remove porous surface silicon and metal impurities etc.;
Step 4 by silicon chip after above-mentioned cleaning spread, etching, plating antireflective film, print electrode and the conventional operation of the polysilicon solar cell such as sintering after the parameter such as testing photoelectronic efficiency.
Embodiment 2
Implementation step is identical with embodiment 1, only Despatch sintered furnace temperature zone is set (℃) be: 600/600/700/700/800/815/895, belt speed 300cm/min, the about 2min of sintering time.
Comparative example
Adopt stripper to remove the contrast of organic photoresist with routine:
Current existing photoresist is removed technology, has traditional stripper ejection technique and some physics degumming technologies, the plasma ashing technology that for example semi-conductor industry adopts, air phase boundary CO 2 technology etc.Physics degumming technology is to coordinate high-accuracy semiconductor device by using, very complicated, and complex steps is not suitable for the solar cell of low-cost demand.Therefore what with the present invention, compare is the ejection technique of traditional employing chemistry stripper, and the implementation step of this control methods comprises:
Step 1: the polysilicon of remained on surface organic photoresist film is cleaned in water, remove surperficial acid solution residual;
Step 2: the polysilicon chip of the remained on surface organic photoresist film after cleaning is immersed in stripper solution to soak time 15min, solution temperature 90 degree.What this comparative example adopted is the special-purpose stripper of BN-308.
Step 3: above-mentioned polysilicon chip is put into detergent solution, use Ultrasonic Cleaning 5min, remove film residual with the organic photoresist of peeling off.This comparative example adopts the scavenger specially of removing organic greasy dirt, can also select acetone, alcohol etc. to remove the solvent of organic impurities.
Step 4: above-mentioned polysilicon chip is cleaned with pure water
Step 5: with the step 3 in embodiment;
Step 6: with the step 4 in embodiment;
Attention: when comparative example is used, the photoresist and the remover that use in embodiment and contrast, when every liter of remover dissolving photoresist surpasses 6 grams, just need to change.
Comparing result:
From the implementation step of above-described embodiment and comparative example, can find out, embodiment provided by the invention compares ratio several advantages below:
1) technique is simple, save time: conventional striping need to be placed on silicon chip in remover and soak at a certain temperature, after striping, need the light carving rubber stripper of silicon chip surface to clean, required time is in 20min left and right, experiment shows, it is residual that organic photoresist soak time in stripper will produce intractable lower than 10min.If adopt fountain striping, although can save time, stripper consumption is very large.And sintering striping only needs technique one, do not need to adopt any additive, simple to operate, flow process is controlled easily, and required time is in 5min left and right.
2) cost is low: conventional striping, and the photoresist of current use and remover, when every liter of remover dissolves photoresist over 6 grams, just need to change, and cost is very high.After striping, the residual remover of silicon chip surface needs cleaning agent to clean, and has also increased cost.
3) without organic volatile and organic liquid waste discharge: conventional striping, in striping process, stripper is volatilization in a large number at high temperature, and these organic volatiles can serious environment pollution.And sintering striping waste gas is carbon dioxide, to process simply, environmental pollution is low.Conventional striping, can produce the discarded stripper that is dissolved with in a large number photoresist, also has a large amount of discarded cleaning agents.These liquid entered environments can form pollution, need complicated procedures of forming to process.
Battery efficiency is residual very responsive to photoresist, experimental result is as shown in table 1, can find out, battery efficiency is normal, (in table, data difference belongs to normal deviate to adopt photoresist removal method of the present invention can reach the same effect of traditional conventional striping method, do not represent performance difference), photoresist is removed very clean.
The electrical performance of cell data of table 1 embodiment and contrast (50 mean values, 156 * 156 polysilicon chips)
Performance | U oc(V) | I sc(A) | R sh(Ω) | FF | R s(Ω) | η Cell |
Embodiment 1 | 0.614923 | 8.81989 | 163.8109 | 77.61357 | 77.61357 | 17.29705 |
Embodiment 2 | 0.615175 | 8.803929 | 196.7772 | 77.72823 | 77.72823 | 17.29836 |
Comparative example | 0.613598 | 8.832831 | 300.924 | 77.66743 | 77.66743 | 17.29712 |
In table:
U
oc(V): open circuit voltage; I
sc(A): short circuit current; FF: fill factor, curve factor; R
sh(Ω): series resistance;
R
s(Ω): parallel resistance; η
cell: the photoelectric conversion efficiency of battery.
Claims (8)
1. a polysilicon solar cell sour making herbs into wool removal method with photoresist, the steps include: that the organic photoresist mask after silicon chip erosion is burnt photoresist mask by sintering furnace, then adopts pickling to remove surface oxide layer and remaining organic impurities.
2. a kind of polysilicon solar cell sour making herbs into wool removal method with photoresist according to claim 1, is characterized in that: described sintering furnace is chain-conveyer furnace or Muffle furnace.
3. a kind of polysilicon solar cell sour making herbs into wool removal method with photoresist according to claim 1, is characterized in that: the gas that described sintering furnace burning generates adopts suction type to collect.
4. a kind of polysilicon solar cell sour making herbs into wool removal method with photoresist according to claim 1, is characterized in that: temperature during described sintering furnace sintering is 300 ℃~1000 ℃.
5. a kind of polysilicon solar cell sour making herbs into wool removal method with photoresist according to claim 4, is characterized in that: temperature during described sintering furnace sintering is 500 ℃~700 ℃.
6. a kind of polysilicon solar cell sour making herbs into wool removal method with photoresist according to claim 1, is characterized in that: when sintering, pass into oxygen or air.
7. a kind of polysilicon solar cell sour making herbs into wool removal method with photoresist according to claim 1, is characterized in that: the acid that described pickling adopts is hydrofluoric acid or hydrochloric acid.
8. a kind of polysilicon solar cell sour making herbs into wool removal method with photoresist according to claim 1, is characterized in that: described photoresist is eurymeric photoresist or negative photoresist.
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CN201310744395.1A CN103746033A (en) | 2013-12-30 | 2013-12-30 | Acid etching texturing photoresist removing method for polycrystalline silicon solar cell |
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CN201310744395.1A CN103746033A (en) | 2013-12-30 | 2013-12-30 | Acid etching texturing photoresist removing method for polycrystalline silicon solar cell |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109152222A (en) * | 2018-09-19 | 2019-01-04 | 中山市瑞宝电子科技有限公司 | One kind is novel to take off film method |
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CN102689870A (en) * | 2012-05-15 | 2012-09-26 | 清华大学 | Nano porous material capable of being perfomed direct photoetching imaging and preparation method thereof |
CN202770195U (en) * | 2012-09-27 | 2013-03-06 | 淄博晨启电子有限公司 | Photoresist removal furnace for nickel-plated chips |
CN103094371A (en) * | 2013-01-21 | 2013-05-08 | 西安交通大学苏州研究院 | Polycrystalline silicon suede structure and suede manufacturing method thereof |
-
2013
- 2013-12-30 CN CN201310744395.1A patent/CN103746033A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1614076A (en) * | 2004-09-24 | 2005-05-11 | 李建康 | Electrode template for DC sputtering and microfigure method |
CN102689870A (en) * | 2012-05-15 | 2012-09-26 | 清华大学 | Nano porous material capable of being perfomed direct photoetching imaging and preparation method thereof |
CN202770195U (en) * | 2012-09-27 | 2013-03-06 | 淄博晨启电子有限公司 | Photoresist removal furnace for nickel-plated chips |
CN103094371A (en) * | 2013-01-21 | 2013-05-08 | 西安交通大学苏州研究院 | Polycrystalline silicon suede structure and suede manufacturing method thereof |
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CN109152222A (en) * | 2018-09-19 | 2019-01-04 | 中山市瑞宝电子科技有限公司 | One kind is novel to take off film method |
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Application publication date: 20140423 |