CN110137278A - In-situ reducing prepares heterojunction solar battery of plating seed layer and preparation method thereof - Google Patents
In-situ reducing prepares heterojunction solar battery of plating seed layer and preparation method thereof Download PDFInfo
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- CN110137278A CN110137278A CN201910287335.9A CN201910287335A CN110137278A CN 110137278 A CN110137278 A CN 110137278A CN 201910287335 A CN201910287335 A CN 201910287335A CN 110137278 A CN110137278 A CN 110137278A
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- 238000007747 plating Methods 0.000 title claims abstract description 43
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 75
- 229910052751 metal Inorganic materials 0.000 claims abstract description 75
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000012528 membrane Substances 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 18
- 229910021419 crystalline silicon Inorganic materials 0.000 claims abstract description 14
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 14
- 239000010410 layer Substances 0.000 claims description 89
- 239000010408 film Substances 0.000 claims description 57
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 11
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- 229910052738 indium Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- -1 metallic bond coat Substances 0.000 claims description 3
- 239000012790 adhesive layer Substances 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims 1
- 230000005518 electrochemistry Effects 0.000 abstract description 3
- 239000010949 copper Substances 0.000 description 15
- 238000000151 deposition Methods 0.000 description 10
- 238000005240 physical vapour deposition Methods 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000008901 benefit Effects 0.000 description 6
- 229910003437 indium oxide Inorganic materials 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
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- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 238000000608 laser ablation Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
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- 238000001020 plasma etching Methods 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
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- 239000011241 protective layer Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
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- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/072—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E10/547—Monocrystalline silicon PV cells
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Abstract
The present invention discloses in-situ reducing and prepares heterojunction solar battery of plating seed layer and preparation method thereof, including n type single crystal silicon substrate layer；Intrinsic amorphous silicon film；P-type non-crystalline silicon film；The amorphous silicon membrane of N-type；Transparent conductive film；Plating metal electrode；The plating metal electrode includes metal seed layer, and the metal seed layer is formed on the transparent conductive film by electrochemical process in-situ reducing；Metal conductive layers, the metal conductive layers plating is on the surface of the metal seed layer.The present invention can significantly reduce process complexity compared to the preparation method with traditional electroplated electrode, forms seed layer by the method for electrochemistry, improves interface attachment characteristic, reduce interface contact resistance；The performance of heterojunction solar battery can be improved, realize purpose efficiently, inexpensive.
Description
Technical field
The present invention relates to the heterojunction solar batteries and preparation method thereof that in-situ reducing prepares plating seed layer, belong to heterogeneous
Connection solar cell field.
Background technique
Problem of energy crisis increasingly causes the worry of people, and environmental pollution also produces threat to people's lives,
Problem more eager at present is exactly to develop some new green energy resources, such as solar energy, wind energy, nuclear energy, biological energy source.It is modern
Society, with increasing rapidly for world population, each state all greatly develop science and technology with it is economical, and no matter the development in terms of which
The supply of the energy is required, therefore the mankind increasingly deepen its demand.Under such social background, economic development is pushed
Huge transformation has also had occurred in mode, improves manufacturing industry technical level, quality of improving the people's livelihood.Traditional energy reserves are increasingly
Sternness, environmental disruption increasingly sharpen, and finding the energy that is novel, reproducible, can substituting conventional fossil fuel is to maintain the mankind
The effective way of sustainable development, this also becomes the emphasis of this century numerous scientists research, and solar energy it is renewable with its,
Free of contamination good characteristic has been favored by people, and solar battery is exactly a kind of photovoltaic device that its energy is converted into electric energy
Part.
The principle of solar battery is that solar energy is converted directly into a kind of device of electric energy based on photovoltaic effect,
It is also the important component in solar energy practical application.Currently, crystal silicon solar energy battery has become the master of photovoltaic industry
Stream, 80% or more is all crystal-silicon solar cell in the market, and the cost for producing monocrystalline silicon is still relatively high at present, process flow
It is complicated, overall conversion efficiency is not high, high-temperature behavior is poor, photo attenuation etc. restricts its and further develops.
Heterojunction solar battery is the successively double-sided deposition intrinsic amorphous silicon film conduct on N-shaped or p-type monocrystalline substrate
Passivation layer reduces Carrier recombination center to be saturated monocrystalline silicon surface due to the dangling bonds of the sharp cut-off generation of lattice.Again successively
Depositing n-type amorphous silicon membrane and p-type amorphous silicon membrane are as emitter and back surface field, in order to form built in field and generation
Separation of charge field, can effectively improve open-circuit voltage, fill factor and transfer efficiency, and hull cell is both utilized in this battery
Manufacturing process, has also given full play to the material property of crystalline silicon and amorphous silicon, and transfer efficiency with higher is (left for 27% at present
It is right), low temperature process, generating electricity on two sides, high conversion efficiency (industrialization) >=23% the advantages that, become the hot spot of solar cell development.
Screen printing technique has the advantages such as technical process is simple, printed pattern design space is big, suitable large-scale production
One preferred technique as amount of batteries electricity production pole preparation.But hetero-junction solar cell is limited to low temperature process processing procedure, selects low-temperature conductive silver
Slurry is to prepare electrode, therefore the electric conductivity of its electrode is poor, higher with the contact resistance of TCO, and the printing plasticity of electrode be difficult to it is simultaneous
It cares for, depth-width ratio is small, and electrode ohmic loss is larger.In addition, the price of low temperature silver paste is high, 30% or more battery manufacturing procedure is occupied
Cost ratio is badly in need of cost efficiency.In nature, the electric conductivity of copper is only second to silver, and physical property is similar with silver, and price is just
Preferably (silver-colored 1/100).Copper electrode is electroplated, and there is plasticity small, electrode optics damage is lost close to rectangle, good conductivity, electrode ohmic
Lose the advantages that small and low in cost, it is considered to be break through silk-screen technical bottleneck, improve effective trial of carrier collection, be the sun
The research hotspot of cell metallization.Metal electrode uses electro-coppering, and the electrode cost of solar cell is greatly lowered.It is different with N-shaped
For matter connection solar cell, basic structure is as shown in Figure 1, mainly non-including n type silicon substrate, intrinsic amorphous silicon layer, n (p) type
Doped polycrystal silicon layer, antireflection layer, metal electrode.Since the transverse conductance performance of doped amorphous silicon film is poor, in hetero-junctions
It needs to introduce layer of transparent conductive membrane layer between amorphous silicon and metal electrode in solar cell preparation process, as contact
Layer, antireflection layer and conducting shell.And it because its adhesion property of direct plating metal is poor on the oxide layer, is easy to fall off, therefore needs
One layer of metal seed layer is introduced, between transparent conductive film layer and metal electrode to improve contact performance.
Applicant devises a kind of process (patent: at wet process deposition and Low Temperature Thermal of two-sided heterojunction solar battery plating
Reason combines the method for preparing heterojunction solar battery, the patent No.: 201310080782.X), hetero-junction solar cell is transparent in deposition
After conductive film, need to deposit one layer of gold by physical vapour deposition (PVD) or magnetron sputtering whole face on two-side transparent conductive film
Belong to seed layer, adhesion layer and conductive layer as plating；Then plating mask is deposited on metal seed layer, is carried out figure and is turned
It moves, then the region for not needing plating is covered with exposure mask, realizes selective electroplating；After the completion of plating metal, by exposure mask chemistry
Solution removing；Finally by plating seed layer selective corrosion, and cleaning, drying, obtain having excellent moulding and good selectivity
Copper electrode.However, the method needs to carry out the deposition and subsequent selective corrosion of seed layer, process is complex, is unfavorable for
Industrial application.The present invention then uses the method for electrochemical reduction by In2O3: the metal In in Sn (ITO) is restored, because of gold
Belong to In to be easy to be corroded, therefore introduce a protective layer between metal seed layer (In) and copper electrode, is corroded to prevent In.
The most common method for preparing metal seed layer: physical vapour deposition (PVD) (including PVD, sputtering etc.), chemical gas
Mutually deposition, inkjet printing, printing, spraying, plating, chemical plating etc., but the method and process of above-mentioned traditional formation seed layer compares
Complicated and consumptive material is more, and for the present invention from improving the contact performance of transparent conductive film and metal electrode, simplifying technique, low cost etc. is square
To setting about, the technique that metal seed layer is prepared using electrochemical reduction method is realized, in current industrial-scale production trend
In have apparent advantage.
Summary of the invention
The present invention mainly overcomes shortcoming in the prior art, proposes that a kind of in-situ reducing prepares plating seed layer
Heterojunction solar battery and preparation method thereof.
The present invention solves technical solution provided by above-mentioned technical problem: in-situ reducing prepares the heterogeneous of plating seed layer
Connection solar cell, including
N type single crystal silicon substrate layer；
Intrinsic amorphous silicon film, the intrinsic amorphous silicon film are formed in the two sides up and down of the n type single crystal silicon substrate layer
On surface；
P-type non-crystalline silicon film, the p-type amorphous silicon membrane are formed on the surface of intrinsic amorphous silicon film described in side；
The amorphous silicon membrane of N-type, the amorphous silicon membrane of the N-type are formed in the table of intrinsic amorphous silicon film described in the other side
On face；
Transparent conductive film, the transparent conductive film are formed in the amorphous silicon of the P-type non-crystalline silicon film and the N-type
On the surface of film；
Metal electrode, the metal electrode are formed on the surface of the transparent conductive film；
The metal electrode includes
Metal seed layer, the metal seed layer are formed on the transparent conductive film by electrochemical process reduction；
Metal conductive layers, the metal conductive layers plating is on the surface of the metal seed layer.
Further technical solution is that the metal electrode is formed on the surface of two transparent conductive films.
Further technical solution is that metal bonding is also electroplate between the metal seed layer and the metal conductive layers
Layer.
Further technical solution is, the metal seed layer, metallic bond coat, metal conductive layers thickness be followed successively by 1-
80nm、0.1-10μm、0.1-100μm。
Further technical solution is that the metal seed layer is indium layer.
Further technical solution is that the metallic bond coat includes at least one in Ni, Cu, Ag, Cr, Pb, Sn or In
Kind metal.
Further technical solution is, the metal conductive layers include in Ni, Cu, Ag, Cr, In, Sn, Al or Au extremely
A kind of few metal.
In-situ reducing prepares the preparation method of the heterojunction solar battery of plating seed layer, comprising the following steps:
Step S10, hetero-junction solar cell substrate is prepared, and it is thin on hetero-junction solar cell substrate two sides to deposit electrically conducting transparent
Film；
Step S20, again on the surface of transparent conductive film exposure mask at figure；
Step S30, the transparent conductive film being covered by the mask in hetero-junction solar cell substrate using electrochemical reducing
Middle In2O3: the metal In of Sn is restored, and forms metal seed layer；
Step S40, by way of plating formed metal seed layer mask open at successively plating metal adhesive layer,
Metal conductive layers；
Step S50, exposure mask is removed；
Step S60, it finally anneals, forms the interfacial contact layer of low melting point.
Further technical solution is that the annealing atmosphere of the step S60 is in the gases such as hydrogen, air, nitrogen, argon gas
One or more of combinations, annealing temperature is 150 DEG C -200 DEG C.
Further technical solution is the detailed process of the step S10 are as follows:
Step S101, damage removal and surface-texturing are carried out to n type single crystal silicon substrate layer；
Step S102, in the equal deposition intrinsic amorphous silicon membrane in two side surfaces of n type single crystal silicon substrate layer；
Step S103, P-type non-crystalline silicon film, N-type are deposited respectively on the surface of two deposition intrinsic amorphous silicon membranes
Amorphous silicon membrane；
Step S104, transparent conductive film is deposited on the surface of P-type non-crystalline silicon film；
Step S105, transparent conductive film is deposited on the surface of the amorphous silicon membrane of N-type.
The invention has the following advantages that the present invention achieves that the preparation of metal electrode using electrochemistry, plating mode, no
By high-temperature technology, can use less, even without silver；Compared to the method with tradition preparation seed layer, complex process can significantly reduce
Property, seed layer is formed by the method for electrochemistry, avoids interfacial contact, reduces interface contact resistance；Cu and Ag has close
Conductivity and density, be the metal for the conductivity second that nature is only second to Ag and price is the 1/100 of Ag, with silk-screen printing
Ag electrode is lower compared to its cost, uniformity is more preferable, because silk-screen printing may cause grid line interruption；Hetero-junctions electricity can be improved
The performance in pond realizes purpose efficiently, inexpensive.
Detailed description of the invention
Fig. 1 is the basic block diagram of existing hetero-junction solar cell；
Fig. 2 is the feasible SEM spectrum of the present invention；
Fig. 3 is basic block diagram of the invention；
Fig. 4 is the partial enlarged view in Fig. 3；
Fig. 5 is the process flow chart of the hetero-junction solar cell (single side) based on the technology of the present invention route:
Fig. 6 is the process flow chart of the hetero-junction solar cell (two-sided) based on the technology of the present invention route.
Specific embodiment
Further description is done to the present invention below with reference to embodiment and attached drawing.
As shown in Figures 3 and 4, a kind of in-situ reducing of the invention prepares the heterojunction solar battery of plating seed layer, has
Such as flowering structure:
Cu/Ni/In/ITO/p-a-Si/i-a-Si/n-c-Si/i-a-Si/n-a-Si/ITO/In/N i/Cu, wherein Cu be
Metallic copper, Ni are metallic nickel, and In is indium metal, and ITO is the indium oxide transparent conductive film for mixing tin, and p-a-Si is P type amorphous silicon
Film, i-a-Si are intrinsic amorphous silicon film, and n-c-Si is n type single crystal silicon substrate, and n-a-Si is N-type amorphous silicon membrane.
The preparation flow of the embodiment is as shown in Figure 6:
(1) damage removal and surface-texturing are carried out to n type single crystal silicon substrate layer；
(2) in the equal deposition intrinsic amorphous silicon membrane in two side surfaces of n type single crystal silicon substrate layer；
(3) amorphous silicon of P-type non-crystalline silicon film, N-type is deposited respectively on the surface of two deposition intrinsic amorphous silicon membranes
Film；
(4) the indium oxide transparent conductive film for mixing tin is deposited on the surface of P-type non-crystalline silicon film；
(5) the indium oxide transparent conductive film for mixing tin is deposited on the surface of the amorphous silicon membrane of N-type；
The indium oxide transparent conductive film for mixing tin in above-mentioned steps (4) and (5) can be (anti-by PECVD, PVD, RPD
Answer plasma-deposited) etc. modes prepare, thickness is between 1nm-1000nm；
(6) again on the surface for the indium oxide transparent conductive film for mixing tin exposure mask at figure；
Above-mentioned membrane material includes photoresist, ink, polymer, dry film etc., the mask material that the present invention uses for photoresist,
Mask pattern can be formed by the methods of photoetching, plasma etching, laser ablation；
(7) using electrochemical reducing by In in transparent conductive film in hetero-junction solar cell substrate2O3: the metal In of Sn is also
Original comes out, and forms metal seed layer；
The wherein experimental provision that the electrochemical reducing is related to can be direct current electrode position, pulsed plating etc.；Electricity
The solution of chemical reduction method can be citrate, sulfamate, bicarbonate, the weak acid and mild base salts such as acetate, weak acid
Highly basic salt system；
(8) by way of plating formed metal seed layer mask open at two-sided successively electroplated Ni, Cu, wherein
Ni is the metallic bond coat of electro-coppering, and copper is metal conductive layers, ultimately forms the figure of metal electrode；The wherein plating of copper electrode
Liquid is alkaline system, and the electroplate liquid of metallic bond coat Ni is acid system.
(9) remove exposure mask, by the dissolution of solution, wet etching, photoetching lift off, heating or laser mode remove
The exposure mask of covering；
(10) it finally anneals, forms the interfacial contact layer of low melting point, there is good interface contact and adhere to.
Above-described embodiment is restored the metal In in the transparent conductive film of indium oxide base using electrochemical reducing,
As the seed layer of plating copper electrode, preparation method with traditional seed layer: physical vapour deposition (PVD) (including PVD, sputtering
Deng), chemical vapor deposition, inkjet printing, printing, spraying, plating, the methods of chemical plating compare, there is simple process, adhesion
The advantages that good, at low cost, and the contact performance of metal electrode and transparent conductive film can be improved, with existing hetero-junctions sun electricity
The characteristics of pond preparation process matches.
The above is not intended to limit the present invention in any form, although the present invention takes off through the foregoing embodiment
Show, however, it is not intended to limit the invention, any person skilled in the art, is not departing from technical solution of the present invention range
It is interior, made when the technology contents using the disclosure above and change or be modified to the equivalent embodiments of equivalent variations a bit, but it is all not
Be detached from technical solution of the present invention content, according to the technical essence of the invention it is to the above embodiments it is any it is simple modification,
Equivalent variations and modification, all of which are still within the scope of the technical scheme of the invention.
Claims (10)
1. the heterojunction solar battery that in-situ reducing prepares plating seed layer, which is characterized in that including
N type single crystal silicon substrate layer；
Intrinsic amorphous silicon film, the intrinsic amorphous silicon film are formed in the both side surface up and down of the n type single crystal silicon substrate layer
On；
P-type non-crystalline silicon film, the p-type amorphous silicon membrane are formed on the surface of intrinsic amorphous silicon film described in side；
The amorphous silicon membrane of N-type, the amorphous silicon membrane of the N-type are formed in the surface of intrinsic amorphous silicon film described in the other side
On；
Transparent conductive film, the transparent conductive film are formed in the amorphous silicon membrane of the P-type non-crystalline silicon film and the N-type
Surface on；
Metal electrode, the metal electrode are formed on the surface of the transparent conductive film；
The metal electrode includes
Metal seed layer, the metal seed layer are formed on the transparent conductive film by electrochemical process in-situ reducing；
Metal conductive layers, the metal conductive layers plating is on the surface of the metal seed layer.
2. the heterojunction solar battery that in-situ reducing according to claim 1 prepares plating seed layer, which is characterized in that institute
Metal electrode is stated to be formed on the surface of two transparent conductive films.
3. in-situ reducing according to claim 1 or 2 prepares the heterojunction solar battery of plating seed layer, feature exists
In being also electroplate with metallic bond coat between the metal seed layer and the metal conductive layers.
4. the heterojunction solar battery that in-situ reducing according to claim 3 prepares plating seed layer, which is characterized in that institute
State metal seed layer, metallic bond coat, metal conductive layers thickness be followed successively by 1-80nm, 0.1-10 μm, 0.1-100 μm.
5. a kind of in-situ reducing according to claim 1 prepares the heterojunction solar battery of plating seed layer, feature exists
In the metal seed layer is indium layer.
6. a kind of in-situ reducing according to claim 3 prepares the heterojunction solar battery of plating seed layer, feature exists
In the metallic bond coat includes at least one of Ni, Cu, Ag, Cr, Pb, Sn or In metal.
7. a kind of in-situ reducing according to claim 6 prepares the heterojunction solar battery of plating seed layer, feature exists
In the metal conductive layers include at least one of Ni, Cu, Ag, Cr, In, Sn, Al or Au metal.
8. the preparation method that in-situ reducing prepares the heterojunction solar battery of plating seed layer, which is characterized in that including following step
It is rapid:
Step S10, hetero-junction solar cell substrate is prepared, and deposits transparent conductive film on hetero-junction solar cell substrate two sides；
Step S20, again on the surface of transparent conductive film exposure mask at figure；
It step S30, will be in the transparent conductive film that be not covered by the mask in hetero-junction solar cell substrate using electrochemical reducing
In2O3: the metal In of Sn is restored, and forms metal seed layer；
Step S40, by way of plating at the mask open for forming metal seed layer successively plating metal adhesive layer, metal
Conducting shell；
Step S50, exposure mask is removed；
Step S60, it finally anneals, forms the interfacial contact layer of low melting point.
9. in-situ reducing according to claim 8 prepares the preparation method of the heterojunction solar battery of plating seed layer,
It is characterized in that, the annealing atmosphere of the step S60 is the group of one or more of gases such as hydrogen, air, nitrogen, argon gas
It closes, annealing temperature is 150 DEG C -200 DEG C.
10. in-situ reducing according to claim 8 prepares the preparation method of the heterojunction solar battery of plating seed layer,
It is characterized in that, the detailed process of the step S10 are as follows:
Step S101, damage removal and surface-texturing are carried out to n type single crystal silicon substrate layer；
Step S102, in the equal deposition intrinsic amorphous silicon membrane in two side surfaces of n type single crystal silicon substrate layer；
Step S103, the amorphous of P-type non-crystalline silicon film, N-type is deposited respectively on the surface of two deposition intrinsic amorphous silicon membranes
Silicon thin film；
Step S104, transparent conductive film is deposited on the surface of P-type non-crystalline silicon film；
Step S105, transparent conductive film is deposited on the surface of the amorphous silicon membrane of N-type.
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