CN109920865A - A method of preparing thin-film solar cells - Google Patents

A method of preparing thin-film solar cells Download PDF

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Publication number
CN109920865A
CN109920865A CN201711330314.8A CN201711330314A CN109920865A CN 109920865 A CN109920865 A CN 109920865A CN 201711330314 A CN201711330314 A CN 201711330314A CN 109920865 A CN109920865 A CN 109920865A
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China
Prior art keywords
solar panel
lamp
cigs
preparing
flashing light
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CN201711330314.8A
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Chinese (zh)
Inventor
祝海生
黄乐
陈立
凌云
黄夏
孙桂红
黄国兴
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XIANGTAN HONGDA VACUUM TECHNOLOGY Co Ltd
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XIANGTAN HONGDA VACUUM TECHNOLOGY Co Ltd
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Priority to CN201711330314.8A priority Critical patent/CN109920865A/en
Publication of CN109920865A publication Critical patent/CN109920865A/en
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    • 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
    • Y02BCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B10/00Integration of renewable energy sources in buildings
    • Y02B10/10Photovoltaic [PV]
    • 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
    • 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
    • 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
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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  • Photovoltaic Devices (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention discloses a kind of methods for preparing thin-film solar cells, it is described by Mo layers of vacuum magnetic-control sputtering on substrate after, vacuum evaporation CIGS absorbed layer, rear vacuum magnetic-control sputtering ZnO buffer, magnetic control sputtering plating AZO layers again after flashing light annealing, sintered CIGS solar panel is obtained.Compared with prior art, the evaporation coating method that the present invention is combined using vapor deposition with flashing light annealing process, the continuous coating process of CIGS solar battery not only may be implemented, the property retention of membrane system is in optimum state when simultaneously can also be by annealing in time, it is not influenced by the change of multiple temperature and the production method of membrane system, the solar panel prepared through the invention, its solar conversion efficiency can achieve 20%, remain domestically leading level for a long time with conversion ratio, plating film uniformity reaches 90%.

Description

A method of preparing thin-film solar cells
Technical field
The present invention relates to a kind of methods for preparing thin-film solar cells, belong to plated film field.
Background technique
CIGS solar battery is made of the Huang of optimal proportion four kinds of Cu (copper), In (indium), Ga (gallium), Se (selenium) elements Copper mine crystalline membrane solar battery, CIGS solar battery have layer structure, and absorbing material belongs to I-III-VI race chemical combination Object, substrate generally use stainless steel, glass or fexible film substrate, are the key technologies for forming solar panel.The product has Light absorpting ability is strong, and power generation stability is good, high conversion efficiency, daytime generating dutation it is long, generated energy is high, production cost is low and energy Source short equal many advantages return period.CIGS solar battery generally uses vacuum sputtering, evaporation or other antivacuum sides Method deposits plural layers respectively, forms P-N junction and constitutes electrooptical device.Since light incident layer, each layer is respectively as follows: metal Gate-shaped electrode, antireflective coating, Window layer (ZnO), transition zone (CdS), light absorbing layer (CIGS), metal back electrode (Mo), glass Or fexible film substrate.The method that the hearth electrode Mo and top electrode n-ZnO of CIGS solar battery generally use magnetron sputtering, work Skill route is more mature.The preparation of absorbed layer has many different methods, these deposition preparations include: evaporation, splash Penetrate rear selenizing method, electrochemical deposition method, spray pyrolysis method and silk screen print method etc..Wherein evaporation and sputtering and selenization technique it is owned by France in Vacuum method is widely used by industrial circle.
The existing mature technology of CIGS solar panel is to carry out film layer preparation on the glass substrate, is based on glass substrate The production equipment of CIGS solar panel be widely used in the whole world.But it is polynary with solar battery use environment Change, limits the use environment of solar battery, therefore CIGS thin film solar battery using the rigid substrate of such as glass substrate It comes into being.
Transparent conductive film currently on the market mainly has ITO (In2O3:Sn)、FTO(SnO2: F), AZO (ZnO:Al) three Kind.Each advantage and disadvantage for having oneself by oneself, if ITO resistivity ratio is lower, higher cost;Cost is relatively low by FTO, and film-forming temperature is high, hydrogen etc. Gas ions environmental stability is poor;AZO stability in hydrogen plasma environment is good, low in cost, and electric property is not so good as ITO.No Thin-film solar cells with absorbed layer need to select suitable transparent conductive film, to obtain best interfacial effect.Mix alumina Zinc (AZO) film is with its excellent electric conductivity, visible light-transmissive performance, good hydrogen plasma stability and valence The advantages that lattice are cheap, resourceful will likely become amorphous silicon/microcrystalline silicon film solar battery, CIGS thin film solar battery Transparent conductive film material.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the purpose of the present invention is obtain a kind of thin-film solar cells of preparing Method.
One of for achieving the above object, what the present invention used prepares the technical solution of the method for solar panel such as Under:
Preparation method in the present invention be using continuous steaming plating method, by Mo layers of vacuum magnetic-control sputtering on substrate after, very Sky vapor deposition CIGS absorbed layer, rear vacuum magnetic-control sputtering ZnO buffer are sintered magnetic control sputtering plating AZO layers again after flashing light annealing CIGS solar panel afterwards.
Preferably, the substrate of CIGS solar panel is flexible material.
Preferably, flashing light annealing uses inert gas lamp.
Preferably, inert gas lamp includes xenon lamp, argon lamp, helium lamp, krypton lamp.
Preferably, inert gas lamp is helical Xe flashlamp.
Preferably, inert gas lamp is indirect irradiation to the irradiation of film layer structure, and light irradiates after being reflected by reflecting mirror On film surface.
Preferably, 100~150J/ of flashing light energy density ㎡, the flashing light time in 0~4ms, pulse 1~2 time.
Preferably, Mo layers of magnetron sputtering temperature is at 80~120 DEG C, and by glow-discharge sputtering 60min, sputtering power is 60W。
Preferably, the vacuum evaporation temperature of cigs layer is at 600 DEG C or more, by four kinds of element powders with (atomic percent): Cu:21.65%, In:19.16%, Ga:6.12%, Se:53.08%, and Cu/ (In+Ga)=0.85, Ga/ (In+Ga)= The ratio of 0.24, Se/ (Cu+In+Ga)=1.13 is mixed, and is carried out vertical continuous vapor deposition, is cooled to vapor deposition after vapor deposition Preceding temperature.
Preferably, ZnO buffer carries out sputter using magnetron sputtering method, and 150 DEG C of underlayer temperature, sputtering time 30min splashes Penetrating power is 40W;ZnO buffer with a thickness of 0.05~0.09 μm.
Preferably, plated film is carried out by the way of magnetron sputtering for AZO layers, wherein the composition quality ratio of AZO target is ZnO: Al2O3=98%:2%, substrate heating temperature are 200 DEG C, and the flow by gas flow-control argon gas is 200sccm。
Part is not referred in the above method, the prior art is can refer to and carries out preparation production.
Compared with prior art, the present invention is using the evaporation coating method that combines with flashing light annealing process of vapor deposition, not only can be with Realize CIGS solar battery continuous coating process, while can also be by annealing in time when membrane system property retention best State is not influenced by the change of multiple temperature and the production method of membrane system, the solar panel prepared through the invention, Its solar conversion efficiency can achieve 20%, remain domestically leading level for a long time with conversion ratio, and plating film uniformity reaches 90%.
Specific embodiment
The method provided by the invention for preparing solar panel is made further in detail, completely below with reference to embodiment Explanation.The embodiments described below is exemplary, and for explaining only the invention, and is not considered as limiting the invention.
Experimental method in following embodiments is unless otherwise specified conventional method.Reality as used in the following examples It tests material unless otherwise specified, is that market is commercially available.
The film substrate used in the present embodiment is splashed Mo layers of vacuum magnetic control using continuous steaming plating method for flexibility PI substrate It penetrates after PI substrate, vacuum evaporation CIGS absorbed layer, rear vacuum magnetic-control sputtering ZnO buffer, magnetic control again after flashing light annealing AZO layers of sputter, obtain sintered CIGS solar panel.
Mo layers of sputtering uses vertical cathodic sputtering Mo layers, and plating initial vacuum is maintained at 10-5Pa, environment temperature is 80~120 DEG C, substrate heating temperature is 200 DEG C, and the flow by gas flow-control argon gas is 200sccm.Adjust substrate power supply Voltage be 600~800V, so that stainless steel base is generated electron emission around using field emission effect, collision argon molecules It is allowed to ionize, realizes glow discharge;The electric current that the voltage control for adjusting heating power supply passes through tungsten wire is 20~30A;Adjust coil The voltage of power supply, control are 60~90A by the electric current of electromagnetic coil, launching electronics around after tungsten wire fever, with workspace Between argon molecules constantly collide, ionize out argon ion;Under process above Parameter Conditions, sputtering time 60min, sputtering power For 60W, the Mo layer after sputtering is with a thickness of 0.8 μm.
CIGS absorbed layer is prepared using the method for vacuum evaporation, by four kinds of element powders with (atomic percent): Cu: 21.65%, In:19.16%, Ga:6.12%, Se:53.08%, and Cu/ (In+Ga)=0.85, Ga/ (In+Ga)=0.24, The ratio of Se/ (Cu+In+Ga)=1.13 is mixed, and 350mg is weighed after mixing and is deposited, and is voluntarily researched and developed using our company Evaporated device, carry out vertical continuous evaporating-plating, when vapor deposition keeps 10-5The high vacuum environment of Pa, 600 DEG C of room temperature when vapor deposition, Evaporation source internal temperature is 500~1300 DEG C;150 DEG C or so are gradually cooling to after vapor deposition;Cigs layer is with a thickness of 1.5 μm.
ZnO buffer is prepared by the way of magnetron sputtering, and 150 DEG C of underlayer temperature, sputtering time 30min, sputtering power For 40W;ZnO buffer with a thickness of 0.05~0.09 μm.
After ZnO buffer has been plated, the method annealed using indirect flashing light makes annealing treatment existing membrane system, anneals Carried out using spiral xenon lamp, flashing light energy density 100~150J/ ㎡, the flashing light time in 0~4ms, pulse 1~2 time, flashing light Light reflex to membrane system surface through reflecting mirror, and then made annealing treatment, the ZnO after vapor deposition annealing is with a thickness of 50nm.
AZO layers carry out plated film by the way of magnetron sputtering, and wherein the composition quality ratio of AZO target is ZnO:Al2O3= 98%:2%, substrate heating temperature are 200 DEG C, and the flow by gas flow-control argon gas is 200sccm.Adjust base The voltage of bottom power supply is 600~800V, and stainless steel base is made to generate electron emission around using field emission effect, collides argon Gas molecule is allowed to ionize, and realizes glow discharge;Ionize out argon ion;Under process above Parameter Conditions, sputtering time 30 minutes, AZO transparent conductive film is prepared, resistivity is 4.7~5.2 × 10-4Ohmcm, it is seen that average saturating in optical wavelength Crossing rate is 85%.
Be it is necessary to described herein finally: above embodiments are served only for making technical solution of the present invention further detailed Ground explanation, should not be understood as limiting the scope of the invention, those skilled in the art's above content according to the present invention The some nonessential modifications and adaptations made all belong to the scope of protection of the present invention.

Claims (10)

1. a kind of method for preparing thin-film solar cells, which is characterized in that it is described by Mo layers of vacuum magnetic-control sputtering on substrate Later, vacuum evaporation CIGS absorbed layer, rear vacuum magnetic-control sputtering ZnO buffer, magnetic control sputtering plating AZO layers again after flashing light annealing, Obtain sintered CIGS solar panel.
2. the method according to claim 1 for preparing solar panel, it is characterised in that: CIGS solar panel Substrate is flexible material.
3. the method according to claim 1 for preparing solar panel, it is characterised in that: flashing light annealing uses indifferent gas Body lamp.
4. the method according to claim 1 for preparing solar panel, it is characterised in that: inert gas lamp includes xenon Lamp, argon lamp, helium lamp, krypton lamp.
5. the method according to claim 1 for preparing solar panel, it is characterised in that: inert gas lamp is spiral xenon Lamp.
6. the method according to claim 1 for preparing solar panel, it is characterised in that: inert gas lamp is to film layer knot The irradiation of structure is indirect irradiation, and light is radiated on film surface after being reflected by reflecting mirror.
7. the method according to claim 1 for preparing solar panel, it is characterised in that: flashing light energy density 100~ 150J/ ㎡, the flashing light time in 0~4ms, pulse 1~2 time.
8. the method according to claim 1 for preparing solar panel, it is characterised in that: Mo layers of magnetron sputtering temperature At 80~120 DEG C, pass through glow-discharge sputtering 60min, sputtering power 60W.
9. the method according to claim 1 for preparing solar panel, it is characterised in that: four kinds of element powder of cigs layer End is with atomic percent: the ratio of Cu:21.65%, In:19.16%, Ga:6.12%, Se:53.08% are mixed.
10. the method according to claim 1 for preparing solar panel, it is characterised in that: the composition quality of AZO target Than for ZnO:Al2O3=98%:2%.
CN201711330314.8A 2017-12-13 2017-12-13 A method of preparing thin-film solar cells Pending CN109920865A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114256380A (en) * 2020-09-21 2022-03-29 比亚迪股份有限公司 Preparation method of solar cell and solar cell

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CN104835869A (en) * 2015-05-13 2015-08-12 清华大学 Copper indium gallium selenide film solar battery and preparation method thereof
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CN101728461A (en) * 2009-11-06 2010-06-09 清华大学 Method for preparing absorbing layer of thin film solar cell
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114256380A (en) * 2020-09-21 2022-03-29 比亚迪股份有限公司 Preparation method of solar cell and solar cell

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Application publication date: 20190621