CN107425087A - A kind of solar cell and its amorphous silicon hydride i film surface processing methods - Google Patents

A kind of solar cell and its amorphous silicon hydride i film surface processing methods Download PDF

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CN107425087A
CN107425087A CN201710641527.6A CN201710641527A CN107425087A CN 107425087 A CN107425087 A CN 107425087A CN 201710641527 A CN201710641527 A CN 201710641527A CN 107425087 A CN107425087 A CN 107425087A
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hydrogen
amorphous silicon
silicon hydride
film surfaces
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CN107425087B (en
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谷士斌
何延如
张�林
张娟
徐湛
杨荣
李立伟
孟原
郭铁
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ENN Solar Energy Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/02Details
    • H01L31/0236Special surface textures
    • H01L31/02363Special surface textures of the semiconductor body itself, e.g. textured active layers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/04Semiconductor 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 adapted as photovoltaic [PV] conversion devices
    • H01L31/06Semiconductor 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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
    • H01L31/072Semiconductor 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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
    • H01L31/0745Semiconductor 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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells
    • H01L31/0747Semiconductor 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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells comprising a heterojunction of crystalline and amorphous materials, e.g. heterojunction with intrinsic thin layer
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/186Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • H01L31/1868Passivation
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/547Monocrystalline silicon PV cells
    • YGENERAL 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
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    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract

The invention discloses a kind of silicon heterogenous solar cell and its amorphous silicon hydride i film surface processing methods, corona treatment is carried out to amorphous silicon hydride i film surfaces using the mixing of hydrogen argon or hydrogen helium mixture, both amorphous silicon hydride i film surfaces can preferably be cleaned for physically by argon or helium plasma, the increase of hydrogen plasma quantity can also be promoted, so as to strengthen passivation and the cleaning performance to amorphous silicon hydride i film surfaces;Meanwhile slight damage can be produced during argon or helium plasma physical bombardment to amorphous silicon hydride i film surfaces, hydrogen plasma not only plays passivation to amorphous silicon hydride i film surfaces, can also repair this slight damage.Hydrogen argon mixes or hydrogen helium hybrid plasma synergy, preferably passivation and cleaning action can be played to amorphous silicon hydride i film surfaces, so as to lift battery performance.

Description

A kind of solar cell and its amorphous silicon hydride i film surface processing methods
The present patent application is the applying date on November 26th, 2015, Application No. 201510842967.9, entitled " A kind of divisional application of the patent application of solar cell and its amorphous silicon hydride i film surfaces processing method ".
Technical field
The present invention relates to manufacture of solar cells technical field, more particularly to silicon heterogenous solar cell and its hydrogenation Non-crystalline silicon i film surface processing methods.
Background technology
Silicon heterogenous solar cell is a kind of electric using mixed type made of crystalline silicon substrates and amorphous silicon membrane technique Pond, there is high conversion efficiency, the advantage such as technological process is simple, temperature coefficient is low, get more and more people's extensive concerning.Existing silicon is heterogeneous The production technology of joint solar cell includes:Cleaning, making herbs into wool, to amorphous silicon hydride i (ia-Si:H) film layer and amorphous silicon hydride p (pa-Si:H) film layer and amorphous silicon hydride n (na-Si:H) film layer is deposited, transparent conductive oxide film is sunk Product, gate electrode silk-screen printing, annealing etc..
Plasma treatment technique is one of important preparation technology of silicon heterogenous solar cell, is usually used in hydrogenated amorphous Silicon i (ia-Si:H) the processing of film surface, it is possible to reduce state the defects of the unsaturated silicon dangling bonds in surface, reduce answering for interface Close, improve the passivation effect at interface, lift the performance of battery.
Corona treatment can be divided into two kinds of physical treatment and chemical treatment.The reaction mechanism of physical treatment be utilize etc. from Particle in daughter makees the bombardment of pure physics, the atom of material surface or the atom on attachment material surface is destroyed, conventional gas Body is the inactive gas such as argon gas, helium.Chemically treated reaction mechanism be utilize height reaction particle living in plasma with Chemical reaction effect occurs for material surface, and so as to realize that the contamination of molecular level removes purpose, conventional gas has hydrogen, oxygen The gases such as gas, carbon tetrafluoride, Nitrogen trifluoride.
Existing silicon heterogenous solar cell mainly carries out plasma using hydrogen to the amorphous silicon hydride i film layers of deposition Body processing, the processing method is a kind of handling process based on chemical reaction, and wherein hydrogen plasma saturable is hydrogenated amorphous The defects of silicon i film surfaces unsaturated silicon dangling bonds state, the compound of interface is reduced, to reach the mesh of passivation interface defect state , but hydrogen plasma energy is relatively low, and it is weaker to the cleansing power at interface, effective cleaning action can not be played so that dirty Dye thing can not be cleaned completely, so as to influence battery performance.
Therefore, how to improve the cleaning performance of silicon heterogenous solar cell interface and passivation effect seems particularly significant.
The content of the invention
It is an object of the invention to provide a kind of amorphous silicon hydride i film surfaces processing side of silicon heterogenous solar cell Method, amorphous silicon hydride i film layers can be carried out effectively to clean and be passivated, so as to remove its surface contaminant and its surface of saturation not The defects of silicon dangling bonds of saturation state, reduce surface state, reduce Interface composites, improve interface performance, it is cell performance so as to improve Energy.
The embodiments of the invention provide a kind of amorphous silicon hydride i film surface methods of silicon heterogenous solar cell, bag Include:
S1, deposition of hydrogenated amorphous silicon i film layers;
S2, corona treatment, mixing are carried out to amorphous silicon hydride i film surfaces using mixed gas in the deposition chamber Gas is hydrogen and argon gas mixing or hydrogen and helium mix.
Preferably, before performing step S2, in the deposition chamber using hydrogen amorphous silicon hydride i film surfaces are carried out etc. from Daughter is handled.
Preferably, corona treatment is carried out to amorphous silicon hydride i film surfaces using hydrogen, processing time is 1 to 200 Second, more excellent, processing time is 10 to 150 seconds.
Preferably, corona treatment is carried out to amorphous silicon hydride i film surfaces using the mixed gas of hydrogen and argon gas, Hydrogen and argon flow amount volume ratio are 1:0.01 to 1:10, processing time is 10 to 1000 seconds;More excellent, hydrogen and argon flow amount Volume ratio is 1:0.1 to 1:5, processing time is 50~500 seconds.
Preferably, corona treatment is carried out to amorphous silicon hydride i film surfaces using the mixed gas of hydrogen and helium, Hydrogen and helium gas flow volume ratio are 1:0.01 to 1:40, processing time is 10 to 3000 seconds;More excellent, hydrogen and helium gas flow Volume ratio is 1:0.1 to 1:20;, processing time is 50 to 2000 seconds.
The embodiment of the present invention additionally provides a kind of silicon heterogenous solar cell, and the hydrogenation of silicon heterogenous solar cell is non- Crystal silicon i film surfaces carry out corona treatment using above-mentioned arbitrary method.
In the technical scheme of the embodiment of the present invention, the amorphous silicon hydride i film layer tables of heterojunction solar battery are improved Surface plasma processing method, using hydrogen and argon gas mixing or the mixed gas of hydrogen and helium mix to amorphous silicon hydride I film layers carry out corona treatment, amorphous silicon hydride i film layers can be carried out effectively to clean and be passivated, so as to remove its surface The defects of pollutant and the unsaturated silicon dangling bonds in its surface of saturation state, reduce surface state, reduce Interface composites, improve interface Performance, so as to improve battery performance.
Brief description of the drawings
Fig. 1 is the amorphous silicon hydride i film surface processing methods of the silicon heterogenous solar cell of one embodiment of the invention.
Embodiment
Hydrogen is used to carry out in plasma treatment procedure amorphous silicon hydride i film layers in order to improve, because hydrogen plasma Physical efficiency amount is relatively low, weaker to the cleansing power of film surface, can not play effective cleaning action, it is different that the present invention provides a kind of silicon The amorphous silicon hydride i film surface processing methods of matter joint solar cell.To make the object, technical solutions and advantages of the present invention more Add clear, the present invention is described in further detail by the following examples.
As shown in figure 1, one embodiment of the invention provides a kind of amorphous silicon hydride i film layers of silicon heterogenous solar cell Surface treatment method, including:
S1, deposition of hydrogenated amorphous silicon i film layers;
S2, corona treatment, mixing are carried out to amorphous silicon hydride i film surfaces using mixed gas in the deposition chamber Gas is hydrogen and argon gas mixing or hydrogen and helium mix.
Preferably, before performing step S2, in the deposition chamber using hydrogen amorphous silicon hydride i film surfaces are carried out etc. from Daughter is handled.
Preferably, corona treatment is carried out to amorphous silicon hydride i film surfaces using hydrogen, processing time is 1 to 200 Second, more excellent, processing time is 10 to 150 seconds.
Preferably, corona treatment is carried out to amorphous silicon hydride i film surfaces using the mixed gas of hydrogen and argon gas, Hydrogen and argon flow amount volume ratio are 1:0.01 to 1:10, processing time is 10 to 1000 seconds;More excellent, hydrogen and argon flow amount Volume ratio is 1:0.1 to 1:5, processing time is 50~500 seconds.
Preferably, corona treatment is carried out to amorphous silicon hydride i film surfaces using the mixed gas of hydrogen and helium, Hydrogen and helium gas flow volume ratio are 1:0.01 to 1:40, processing time is 10 to 3000 seconds;More excellent, hydrogen and helium gas flow Volume ratio is 1:0.1 to 1:20;, processing time is 50 to 2000 seconds.
To amorphous silicon hydride i film surfaces carry out corona treatment when, using hydrogen and argon gas mixing or hydrogen and The mixed gas of helium mix, both interface can preferably be cleaned for physically by argon or helium plasma, The increase of hydrogen plasma quantity can also be promoted, so as to strengthen passivation and the cleaning performance to amorphous silicon hydride i film surfaces; Meanwhile slight damage, hydrogen etc. can be produced during argon or helium plasma physical bombardment to amorphous silicon hydride i film surfaces Gas ions not only play passivation to amorphous silicon hydride i film surfaces, can also repair this slight damage.Hydrogen argon mixes or hydrogen Helium hybrid plasma is acted synergistically, and preferably passivation and cleaning action can be played to interface.
Table one is listed using hydrogen-argon-mixed body to battery after amorphous silicon hydride i film surfaces progress corona treatment The data of performance.Battery performance is mainly represented with two data:1.Eff:Efficiency, the conversion efficiency of battery;2.FF: Fill factor, the fill factor, curve factor of battery.Battery performance has been normalized, and normalized refers to by certain Kind algorithm process will need data to be processed to be limited in the certain limit of needs, be easy to follow-up data to handle.In following tables Normalize and refer to based on the battery performance prepared after former amorphous silicon hydride i film surface corona treatments (unit 1), The battery performance prepared after amorphous silicon hydride i film surface corona treatments after improvement is contrasted with it, obtains one Individual ratio, for example it is 20% that former treatment technology, which prepares the conversion efficiency of battery, improves processing technology of interface and prepares the conversion of battery Efficiency is 20.2%, then battery conversion efficiency improves ((20.2-20)/20) * 100%=1%, i.e. galvanic cell conversion efficiency For 1, battery conversion efficiency is 1.01 after improvement.
Table one carries out the battery performance of corona treatment using hydrogen-argon-mixed body
It is larger that the difficulty of lifting conversion efficiency of solar cell is limited by factors, lifting one thousandth unit is Through being extraordinary improvement.As shown in Table 1, the battery conversion efficiency before improvement is 1 and fill factor, curve factor is 1, after improvement After film surface treatment technology, the battery performance of solar cell has good lifting, and wherein conversion efficiency highest can improve To 1.011, fill factor, curve factor highest can bring up to 1.0095.
Corona treatment is carried out to amorphous silicon hydride i film surfaces using hydrogen helium mixture, because helium atom amount is small In argon, it is smaller to being damaged caused by amorphous silicon hydride i film surfaces, and corresponding cleaning performance is also slightly poor.Therefore, compared to hydrogen For gas mixes with argon gas, amount of helium will be more than argon gas amount, hydrogen and helium gas flow volume ratio in hydrogen and helium mix gas For 1:0.01 to 1:40, more excellent, hydrogen and helium gas flow volume ratio are 1:0.1 to 1:20;Hydrogen helium mixture processing time Also longer than hydrogen-argon-mixed body processing time, its processing time is 10 to 3000 seconds, more excellent, and processing time is 50 to 2000 Second.
Corona treatment is carried out using the hydrogen helium mixture under above-mentioned condition, can be reached and hydrogen argon mixed processing phase The conversion efficiency of near experimental result, wherein solar cell can bring up to 1.009, and fill factor, curve factor can bring up to 1.008 so that Solar cell properties have obtained good lifting.
The embodiment of the present invention two:A kind of amorphous silicon hydride i film surface processing methods of silicon heterogenous solar cell, bag Include:
Deposition of hydrogenated amorphous silicon i film layers;
Corona treatment is carried out to amorphous silicon hydride i film surfaces using hydrogen in the deposition chamber;
Corona treatment is carried out to amorphous silicon hydride i film surfaces using hydrogen and argon gas mixed gas again.
Table two lists the data of the battery performance using the solar cell obtained after the processing of the present embodiment method.Battery Performance is mainly represented with two data:1.Eff:Efficiency, the conversion efficiency of battery;2.FF:Fill factor, battery Fill factor, curve factor, battery performance has been normalized.
The battery performance of hydrogen-argon-mixed bulk plasmon processing after two first hydrogen plasma process of table
Due to first individually being handled using hydrogen plasma, first amorphous silicon hydride i film surfaces can be carried out necessarily Passivation, damaged with reducing caused by argon plasma bombardment;Handled again using hydrogen-argon-mixed bulk plasmon, on the one hand Argon plasma plays preferably cleaning performance and increases the quantity of hydrogen plasma, and another aspect hydrogen plasma plays more excellent Passivation effect and repair slight damage caused by argon plasma bombardment, it is comprehensive to play more excellent cleaning action and passivation is made With.
From upper table two, compared to the conversion efficiency 1 and fill factor, curve factor 1 of solar cell before improvement, using first hydrogen etc. The conversion efficiency highest of solar cell can bring up to 1.015 after hydrogen-argon-mixed bulk plasmon processing after gas ions processing, Fill factor, curve factor highest can bring up to 1.01 so that solar cell properties have obtained good lifting.
The embodiment of the present invention additionally provides a kind of silicon heterogenous solar cell, and the hydrogenation of silicon heterogenous solar cell is non- Crystal silicon i film surfaces carry out corona treatment using above-mentioned arbitrary method.
In the technical scheme of the embodiment of the present invention, the amorphous silicon hydride i film layer tables of heterojunction solar battery are improved Face processing method, corona treatment is carried out to amorphous silicon hydride i film surfaces using the mixing of hydrogen argon or hydrogen helium mixture, Both amorphous silicon hydride i film surfaces can preferably be cleaned for physically by argon or helium plasma, moreover it is possible to Enough promote the increase of hydrogen plasma quantity, so as to strengthen passivation and the cleaning performance to amorphous silicon hydride i film surfaces;Together When, amorphous silicon hydride i film surfaces can be produced during argon or helium plasma physical bombardment slight damage, hydrogen etc. from Daughter not only plays passivation to amorphous silicon hydride i film surfaces, can also repair this slight damage.Hydrogen argon mixes or hydrogen helium Hybrid plasma is acted synergistically, and preferably passivation and cleaning action can be played to amorphous silicon hydride i film surfaces.
Obviously, those skilled in the art can carry out the essence of various changes and modification without departing from the present invention to the present invention God and scope.So, if these modifications and variations of the present invention belong to the scope of the claims in the present invention and its equivalent technologies Within, then the present invention is also intended to comprising including these changes and modification.

Claims (8)

  1. A kind of 1. amorphous silicon hydride i film surface processing methods of silicon heterogenous solar cell, it is characterised in that:
    S1, deposition of hydrogenated amorphous silicon i film layers;
    S2, corona treatment is carried out to the amorphous silicon hydride i film surfaces using mixed gas in the deposition chamber, it is described Mixed gas is hydrogen and argon gas mixing or hydrogen and helium mix;
    Wherein, before performing step S2, plasma is carried out to the amorphous silicon hydride i film surfaces using hydrogen in the deposition chamber Body processing.
  2. 2. processing method as claimed in claim 1, it is characterised in that:Using the hydrogen to the amorphous silicon hydride i film layers Surface carries out corona treatment, and processing time is 1 to 200 second.
  3. 3. processing method as claimed in claim 2, it is characterised in that:Using the hydrogen to the amorphous silicon hydride i film layers Surface carries out corona treatment, and processing time is 10 to 150 seconds.
  4. 4. the processing method as described in claims 1 to 3 is any, it is characterised in that:Using the mixed gas pair of hydrogen and argon gas The amorphous silicon hydride i film surfaces carry out corona treatment, and hydrogen and argon flow amount volume ratio are 1:0.01 to 1:10, place It is 10 to 1000 seconds to manage the time.
  5. 5. processing method as claimed in claim 4, it is characterised in that:Using the mixed gas of hydrogen and argon gas to the hydrogenation Non-crystalline silicon i film surfaces carry out corona treatment, and hydrogen and argon flow amount volume ratio are 1:0.1 to 1:5, processing time 50 ~500 seconds.
  6. 6. the processing method as described in claims 1 to 3 is any, it is characterised in that:Using the mixed gas pair of hydrogen and helium The amorphous silicon hydride i film surfaces carry out corona treatment, and hydrogen and helium gas flow volume ratio are 1:0.01 to 1:40, place It is 10 to 3000 seconds to manage the time.
  7. 7. processing method as claimed in claim 6, it is characterised in that:Using the mixed gas of hydrogen and helium to the hydrogenation Non-crystalline silicon i film surfaces carry out corona treatment, and hydrogen and helium gas flow volume ratio are 1:0.1 to 1:20;Processing time is 50 to 2000 seconds.
  8. A kind of 8. silicon heterogenous solar cell, it is characterised in that:The amorphous silicon hydride i film layer tables of silicon heterogenous solar cell Face uses the method as described in claim 1 to 7 is any to carry out corona treatment.
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