CN104505418B - Compound unijunction PIN solar cells of crystal silicon and silicon Germanium films with transition zone and preparation method thereof - Google Patents

Compound unijunction PIN solar cells of crystal silicon and silicon Germanium films with transition zone and preparation method thereof Download PDF

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CN104505418B
CN104505418B CN201410699067.9A CN201410699067A CN104505418B CN 104505418 B CN104505418 B CN 104505418B CN 201410699067 A CN201410699067 A CN 201410699067A CN 104505418 B CN104505418 B CN 104505418B
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hydrogen
transition zone
silicon
sio
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CN104505418A (en
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何湘衡
李廷凯
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HUNAN GONGCHUANG GROUP CO Ltd
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    • H—ELECTRICITY
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    • 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 at least one potential-jump barrier or surface barrier
    • H01L31/075—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 at least one potential-jump barrier or surface barrier the potential barriers being only of the PIN type
    • 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 at least one potential-jump barrier or surface barrier
    • H01L31/075—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 at least one potential-jump barrier or surface barrier the potential barriers being only of the PIN type
    • H01L31/077—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 at least one potential-jump barrier or surface barrier the potential barriers being only of the PIN type the devices comprising monocrystalline or polycrystalline materials
    • 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
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/547—Monocrystalline silicon PV cells
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/548—Amorphous silicon PV cells
    • 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

Abstract

The invention provides a kind of crystal silicon with transition zone and the compound unijunction PIN solar cells of silicon Germanium films and preparation method thereof.The solar cell is provided with transition zone simultaneously on the preceding surface of n-type silicon chip or in the back surface of n-type silicon chip or on the preceding surface of n-type silicon chip and back surface；The transition zone is one layer or multilayer, wherein any one layer is silicon rich silicon oxide layer.The preparation method is after silicon chip completes making herbs into wool, polishing and cleaning, hydrogenation drying process before adding, meanwhile, after the technique of this transition zone is completed, rear hydrogenation treatment mode is added, two methods are used to improve the stability of interface quality and structure.Using this transition zone and the preceding hydrogenation drying process and rear hydrotreated crystal silicon and silicon Germanium films composite battery with transition zone is employed, can be on the basis of original by battery conversion efficiency raising more than 10%.

Description

The compound unijunction PIN solar cells of crystal silicon and silicon Germanium films with transition zone And preparation method thereof
Technical field
The present invention relates to crystal silicon and film composite type solar cell, crystal silicon and germanium particularly with transition layer structure The structure design and its manufacture method of the compound unijunction PIN solar cells of silicon thin film.
Background technology
Since French scientist AE.Becquerel 1839 find opto-electronic conversion phenomenon after, 1883 first with Semiconductor selenium is born for the solar cell of substrate.Nineteen forty-six RuSSell obtains the patent of first solar cell (US.2,402,662), its photoelectric transformation efficiency is only 1%.Until 1954, the research of AT＆T Labs was just found that doping Silica-base material there is high photoelectric transformation efficiency.This research is laid a good foundation for modern sun energy battery industry.1958 Year, Haffman Utilities Electric Co.s of the U.S. have loaded onto first piece of solar panel for the satellite in the U.S., and its photoelectric transformation efficiency is about 6%.From this, the solar cell research and production of monocrystalline silicon and polycrystalline silicon substrate have quick development, solar energy in 2006 The yield of battery has reached 2000 megawatts, and the photoelectric transformation efficiency of monocrystaline silicon solar cell reaches 24.7%, commercial product 22.7% is reached, the photoelectric transformation efficiency of polysilicon solar cell reaches 20.3%, and commercial product reaches 15.3%.
On the other hand, the Zhores Alferov of the Soviet Union in 1970 have developed the race of high efficiency III-V of first GaAs base Solar cell.Due to prepare III-V race's thin-film material key technology MOCVD (metal organic chemical vapor deposition) until Just successfully researched and developed within 1980 or so, the applied solar energy Battery Company in the U.S. was successfully applied to the technology in 1988 and prepared Photoelectric transformation efficiency is III-V race's solar cell of 17% GaAs bases.Thereafter, III-V race's material by substrate of GaAs Doping techniques, the technology of preparing of plural serial stage solar cell obtained extensive research and development, its photoelectric transformation efficiency 19% was reached in 1993,24% is reached within 2000,26% is reached within 2002, reaches within 2005 28%, reach 30% within 2007. 2007, big III-V race solar cell company Emcore and SpectroLab in the U.S. two produced the race's sun of high efficiency III-V Energy commercial product, its photoelectric conversion rate is up to 38%, and this two company occupies the 95% of global III-V race's solar cell market, American National Energy Research Institute announces that they successfully have developed its photoelectric transformation efficiency is up to 50% plural serial stage III-V Race's solar cell.Because the substrate of this kind of solar cell is expensive, equipment and process costs are high, are mainly used in aviation, boat My god, the field such as national defence and military project.
External solar cell research and production, can substantially be divided into three phases, that is, have three generations's solar cell.
First generation solar cell, substantially using the solar cell of monocrystalline silicon and the single constituent element of polycrystalline silicon substrate as generation Table.Only pay attention to improve photoelectric transformation efficiency and large-scale production, there is high energy consumption, labour intensive, unfriendly to environment The problems such as with high cost, its price for producing electricity is about 5~6 times of coal electricity；Until, the production of first generation solar cell in 2007 Amount still accounts for the 89% of global solar battery total amount, expert, it is expected that first generation solar cell will progressively be eliminated after 10 years And as history.
Second generation solar cell is thin-film solar cells, is the new technology grown up in recent years, it pays attention to The energy consumption and process costs in production process are reduced, brainstrust is called green photovoltaic industry.With monocrystalline silicon and the polysilicon sun Energy battery is compared, and the consumption of its film HIGH-PURITY SILICON is its 1%, meanwhile, low-temperature plasma enhanced chemical vapor deposition deposition Technology, electroplating technology, printing technology is extensively studied and is applied to the production of thin-film solar cells.Due to using low cost Glass, stainless steel thin slice, macromolecule substrate greatly reduces production cost as baseplate material, and is conducive to large-scale Production.The material of the successful thin-film solar cells researched and developed is at present：CdTe, its photoelectric transformation efficiency is 16.5%, and business Industry product is about 7%；CulnSe, its photoelectric transformation efficiency is 19.5%, and commercial product is 11%；Non-crystalline silicon and microcrystal silicon, its Photoelectric transformation efficiency is 8.3~15%, and commercial product is 7~13.3%, in recent years, due to the thin film transistor (TFT) of LCD TV Research and development, non-crystalline silicon and microcrystalline silicon film technology have significant progress, and have been applied to silicon-based film solar cells.Brainstrust , it is expected that because thin-film solar cells has low cost, high efficiency, the ability of large-scale production, following 5~10 Year, thin-film solar cells is by the main product as global solar battery.
Focus around thin-film solar cells research is to develop efficient, inexpensive, long-life photovoltaic solar electricity Pond.They should have following feature：Low cost, high efficiency, long-life, material source are abundant, nontoxic, and scientists are relatively had an optimistic view of Amorphous silicon thin-film solar cell.
The thin-film solar cells for accounting for lion's share at present is non-crystal silicon solar cell, usually pin structure batteries, window Mouthful layer is the P-type non-crystalline silicon of boron-doping, then deposit one layer undoped with i layers, the N-type non-crystalline silicon of one layer of p-doped of redeposition, and plating Electrode.
Amorphous silicon battery typically uses PECVD (Plasma Enhanced Chemical Vapor Deposition --- plasma enhanced chemical vapor deposition) method make the gases such as high purity silane decompose deposition. Such a manufacture craft, continuous in production can be completed in multiple vacuum deposition chamber, to realize production in enormous quantities.Due to deposition point Solve temperature it is low, can on glass, stainless steel plate, ceramic wafer, flexible plastic sheet deposition film, it is easy to large area metaplasia produce, cost It is relatively low.The structure of the amorphous silica-based solar cell prepared on a glass substrate is：Glass/TCO/p-a-SiC：H/i-a-Si： H/n-a-Si：H/Al, the structure of the amorphous silica-based solar cell prepared on stainless steel lining bottom is：SS/ZnO/n-a-Si：H/ i-a-Si(Ge)：H/p-na-Si：H/ITO/Al.
Improve the efficiency of light absorption that the maximally effective approach of battery efficiency is to try to improve battery.For silica-base film, adopt It is inevitable approach with low bandgap material.The low bandgap material used such as Uni-Solar companies for a-SiGe (amorphous silicon germanium) alloy, Their a-Si/a-SiGe/a-SiGe three-knot laminated batteries, small area battery (0.25cm2) efficiency reaches 15.2%, stable effect Rate is up to 13%, 900cm2Component efficiency is up to 11.4%, and stabilization efficiency is up to 10.2%, and product efficiency reaches 7%-8%.
Internationally recognized amorphous silicon/microcrystalline silicon tandem solar cell is the next-generation technology of silicon-base thin-film battery, is to realize The important technology approach of high efficiency, low cost thin-film solar cells, is the new industrialization direction of hull cell.Japan three in 2005 Water chestnut heavy industry and the amorphous silicon/microcrystalline silicon tandem battery component sample efficiencies of Zhong Yuan chemical companies respectively reach 11.1% (40cm × 50cm) with 13.5% (91cm × 45cm).Japanese Sharp company in September, 2007 realizes amorphous silicon/microcrystalline silicon tandem solar-electricity Pond industrialization production (25MW, efficiency 8%-8.5%), European Oerlikon (Ao Likang) company, the U.S. AppliedMaterials (Applied Materials), it is also positive to research and develop Product-level non-crystalline silicon/micro-crystalline silicon cell key manufacture.
The country, Nankai University is carried out using national " 15 ", the project of Eleventh Five-Year Plan 973 and the project of Eleventh Five-Year Plan 863 to rely on Microcrystalline silicon materials and the research of amorphous silicon/microcrystalline silicon tandem battery.Small area micro-crystalline silicon cell efficiency is up to 9.36%, non-crystalline silicon/micro- Crystal silicon laminated cell efficiency is up to 11.8%, 10cm × 10cm component efficiencies up to 9.7%.Now just closed with Fujian Jun Shi energy companies Make, carry out the research and development of square meter level amorphous silicon/microcrystalline silicon tandem battery key equipment and cell manufacturing techniques.
Current silicon-base thin-film battery mainly has three kinds of structures：Using glass as the unijunction of substrate or double junction non-crystal silicon battery, with Glass is the non-crystalline silicon and microcrystal silicon binode battery of substrate, using stainless steel as the non-crystalline silicon of substrate and the knot of amorphous germanium-silicon alloy three electricity Pond.Because various products have its unique advantage, in following period of time from now on, these three battery structures can also synchronized development.Silicon The long term growth direction of base film battery is it will be apparent that except to make full use of its unique advantage, mainly overcoming product The problem of existing in terms of exploitation, production and selling.Silicon-base thin-film battery will further improve battery efficiency, utilize micro-crystalline silicon cell Battery efficiency, the photoinduction decline of reduction battery can be further improved as the bottom battery of multijunction cell.
The technological difficulties of current micro-crystalline silicon cell industrialization are to realize the high speed deposition technology of microcrystal silicon and realize large area The uniformity of microcrystalline silicon film material.If technical barrier in terms of microcrystal silicon large area high speed deposition can be when shorter Between in be resolved, it is contemplated that in the near future, the multijunction cell that non-crystalline silicon and microcrystal silicon are combined will turn into silica-base film electricity The major product in pond.Non-crystalline silicon and microcrystal silicon multijunction cell can be deposited on a glass substrate, can also be deposited on flexible substrate On, the silicon-base thin-film battery either still deposited with glass with flexible substrate can use amorphous and microcrystal silicon multijunction cell Structure.
The silicon-based film solar cells of commerciality are amorphous silicon thin-film solar cells at present.Due to the energy gap of non-crystalline silicon For 1.7, it is only capable of solar energy of the absorbing wavelength in 400-500nm.It is about left 6% because its solar energy conversion efficiency is low The right side, the conversion ratio of the silicon-based film solar cells is to be improved.
More than several aspects technology and background material, someone mention using the material of different energy gaps expanding to too The absorption spectrum of positive energy.But before patent No. ZL200910044772.4, not yet someone is using a series, with difference Six kinds of materials of energy gap constitute the thin-film solar cells of unijunction multilayer PIN structural, and also nobody develops and prepares this The manufacturing technology of the thin-film solar cells of unijunction multilayer PIN structural is planted, yet nobody develops and prepares this high conversion Silicon wafer and film composite type unijunction PIN solar cells and its manufacture method.
Patent No. ZL200910044772.4 is thin the solar cell and silicon substrate of monocrystalline silicon and the single constituent element of polycrystalline silicon substrate Film solar cell is combined, and proposes a kind of high conversion silicon wafer and film composite type unijunction PN, PIN solar cell and its system Make method, described high conversion silicon wafer and film composite type unijunction PIN solar cells have higher conversion efficiency and excellent Good stability.The present invention adds transition layer structure and proposes this mistake on the basis of patent No. ZL200910044772.4 Its preparation process of layer is crossed, the lifting of efficiency can be further obtained, and can be using the industrial production with large-scale.
The content of the invention
The present invention takes crystalline substance on the basis of high conversion silicon wafer and film composite type unijunction PIN solar battery technologies Silicon and the compound unijunction PIN structural of silicon Germanium films, there is provided tool for the design structure and its manufacture method of one transition zone of proposition There are compound unijunction PIN solar cells of crystal silicon and silicon Germanium films of transition zone and preparation method thereof, the preparation method exists Silicon chip is completed after making herbs into wool, polishing and cleaning, hydrogenation drying process before adding, meanwhile, after the technique of this transition zone is completed, plus Rear hydrogenation treatment mode is entered, two methods are used to improve the stability of interface quality and structure.Using this transition zone and adopt , can be with the preceding hydrogenation drying process and rear hydrotreated crystal silicon and silicon Germanium films composite battery with transition zone Battery conversion efficiency is improved more than 10% on the basis of original.
One of technical scheme：
The compound unijunction PIN solar cells of crystal silicon and silicon Germanium films with transition layer structure, selected from the following sun One of energy battery structure：
1) hearth electrode/n-layer/n-type silicon chip/transition zone/i-A-Si1-xGexLayer/p-A-Si1-xGexLayer/TCO/ antireflectives Film；
2) hearth electrode/n-layer/n-type silicon chip/transition zone/i- μ c-Si1-xGexLayer/i-A-Si1-xGexLayer/p-A-Si1-xGex Layer/TCO/ antireflective coatings；
3) hearth electrode/n-layer/n-type silicon chip/transition zone/p-A-Si1-xGexLayer/TCO/ antireflective coatings；
4) hearth electrode/n-layer/transition zone/n-type silicon chip/i-A-Si1-xGexLayer/p-A-Si1-xGexLayer/TCO/ antireflectives Film；
5) hearth electrode/n-layer/transition zone/n-type silicon chip/i- μ c-Si1-xGexLayer/i-A-Si1-xGexLayer/p-A-Si1-xGex Layer/TCO/ antireflective coatings；
6) hearth electrode/n-layer/transition zone/n-type silicon chip/p-A-Si1-xGexLayer/TCO/ antireflective coatings；
7) hearth electrode/n-layer/transition zone/n-type silicon chip/transition zone/i-A-Si1-xGexLayer/p-A-Si1-xGexLayer/TCO/ Antireflective coating；
8) hearth electrode/n-layer/transition zone/n-type silicon chip/transition zone/i- μ c-Si1-xGexLayer/i-A-Si1-xGexLayer/p-A- Si1-xGexLayer/TCO/ antireflective coatings；
9) hearth electrode/n-layer/transition zone/n-type silicon chip/transition zone/p-A-Si1-xGexLayer/TCO/ antireflective coatings；
Wherein Si1-xGexIn x values be 0≤x≤1；
The transition zone is one layer or multilayer, wherein any one layer is silicon rich silicon oxide layer；The silicon rich silicon oxide Layer choosing is from i-A-SiOx, i- μ c-SiOx, n-A-SiOx, n- μ c-SiOxAny one of, wherein 0≤x≤2；Or the richness Silica SiClx layer choosing is from n-type gradient μ c-SiOxWith n-type gradient A-SiOx, wherein 0≤x≤2, " gradient " refers to：By changing Becoming x values in silicon rich silicon oxide, progressively graded is to 0 from 2, and silica is then from silica --- change to silicon rich silicon oxide Layer --- silicon layer is changed to again；
Wherein, "/" represents the interface between two layers；N represents electron type (n-type) semiconductor, and i- represents intrinsic semiconductor, P- Represent cavity type (p-type) semiconductor；A- represents noncrystal, and μ c- represent crystallite.
Preferred scheme, the transition zone is two layers, respectively n-A-SiOxAnd i-A-SiOx, close to one layer of n-type silicon chip For n-A-SiOx。
Further preferably, the silicon atom density domination of the transition zone is in 2.2*1022/cm3~5.0*1022/cm3Between； Refractive index (n) is 1.46≤n≤3.88；Thicknesses of layers (h) is 0.5nm≤h≤10nm；Band gap (Eg) control 1.12~ 9.0eV between；Relative dielectric constant (ε) is 3.0≤ε≤11.7.
1), 2), 4), 5), 7), 8) the of wherein described solar battery structure plant the p-A-Si in structure1-xGexLayer material Material with p-A-SiC or can use p-A-Si1-xGexCombination with p-A-SiC is substituted, wherein Si1-xGexIn x values be 0 ≤x≤1。
3), 6), 9) the of the solar battery structure plant the p-A-Si in structure1-xGexLayer can use p-A-Si1-xGex Combination with p-A-SiC is substituted, wherein Si1-xGexIn x values be 0≤x≤1.
The i- μ c-Si of the solar battery structure1-xGexLayer or i-A-Si1-xGexLayer can use i- μ c-Si1-xGexWith i-A-Si1-xGexBoth replace according to the combination changed by Graded band-gap, and wherein graded refers to：By adjusting SiGe The value x of middle germanium is changed stepwise to 0 from 1, and SiGe is gradually changed to silicon layer from gradient SiGe.
Preferred scheme, the n-layer is selected from A-Si, μ c- or epi-Si1-xGexMaterial is a kind of or becomes according to by Graded band-gap Two kinds of the combination changed；epi-Si1-xGexIn 0≤x≤1, epi represent epitaxial growth monocrystalline；Wherein graded refers to：Pass through The value x of germanium is changed stepwise to 0 from 1 in regulation SiGe, and SiGe is gradually changed to silicon layer from gradient SiGe.
The hearth electrode preferably selects nesa coating or aluminium.
The two of technical scheme：
The preparation method of solar cell of the present invention, mainly includes the preparation of transition zone, the preparation of the transition zone Including：First after n-type silicon chip completes making herbs into wool, polishing and cleaning, then carry out preceding hydrogenation drying process；Then Silicon-rich oxidation is made Silicon thin film；Hydrotreating process after finally carrying out；Hydrogenation drying process is before described：Using hydrogen and nitrogen mixed gas or Person's hydrogen is as processing gas, and the wherein hydrogen/nitrogen volume ratio of mixed gas is between 0.1~100, preceding hydrogenation drying process Temperature control is between 30 DEG C~350 DEG C, and the preceding hydrogenation drying process time is 1~60 minute；The rear hydrotreating process is： Using the mixed gas or hydrogen of hydrogen and nitrogen as processing gas, the hydrogen/nitrogen volume ratio of wherein mixed gas exists Between 0.1~100；Afterwards hydrotreating temperatures 140 DEG C~~1200 DEG C between, the rear hydrogenation treatment time 1~3600 second it Between.
Preferred scheme：The preparation of the transition zone is chosen in particular from one of following three kinds of methods：
The is the step of 1. planting method：1) at hydrogenation is dried before being carried out using the mixed gas or hydrogen of hydrogen and nitrogen Reason：2) using plasma enhancing chemical vapor deposition (PECVD) or high density plasma CVD (HD- PECVD method), is process gas, deposition using the mixed gas of silane, phosphine, phosphine and hydrogen, hydrogen, carbon dioxide i-A-SiOx、n-ASiOx、i-μc-SiOx、n-μc-SiOxFour kinds of different types of Si-rich silicon oxide films；3) Silicon-rich oxygen is completed After SiClx film makes, hydrogenation treatment after being carried out using the mixed gas or hydrogen of hydrogen and nitrogen；
The is the step of 2. planting method：1) at hydrogenation is dried before being carried out using the mixed gas or hydrogen of hydrogen and nitrogen Reason；2) using plasma enhancing chemical vapor deposition (PECVD) or high density plasma CVD (HD- PECVD equipment), using hydrogen, oxygen, under plasma conditions, decomposes hydrogen, oxygen, allow silicon chip surface it is aqueous, Thermally grown Si-rich silicon oxide film is carried out under conditions of hydrogen ion, oxonium ion；3) complete after Si-rich silicon oxide film making, use Hydrogenation treatment after the mixed gas or hydrogen of hydrogen and nitrogen are carried out；
The is the step of 3. planting method：1) at hydrogenation is dried before being carried out using the mixed gas or hydrogen of hydrogen and nitrogen Reason；2) using the thermal oxide growth method under the conditions of wet oxygen, Si-rich silicon oxide film is made；3) Si-rich silicon oxide film system is completed After work, hydrogenation treatment after being carried out using the mixed gas or hydrogen of hydrogen and nitrogen.
Further preferably, the concretely comprising the following steps for method is 1. planted：
1) hydrogenation drying process before the n-type silicon chip after completing making herbs into wool, polishing, cleaning is done, uses hydrogen and nitrogen Mixed gas or hydrogen, mixed gas H2/N2Volume ratio dries silicon chip in the range of 0.1~100 under hydrogen atmosphere；Hydrogenation Drying temperature is between 30 DEG C~350 DEG C, and the time is 1~60 minute；
2) i-A-SiO is made using PECVD or HD-PECVD depositing operationsx、n-ASiOx、i-μc-SiOx、n-μc- SiOxFour kinds of different types of Si-rich silicon oxide films；Radio-frequency signal generator frequency range used in PECVD or HD-PECVD equipment For 13~67MHz；Wherein, i-A-SiO is madexDuring film, process gas, process warm are used as using silane, carbon dioxide, hydrogen Spend for 180~220 DEG C, radio frequency power density is in 5~50mW/cm2, operation pressure is 0.2~2.0mbar, oxidation ratio (CO2/ SiH4Flow-rate ratio)≤5, hydrogen dilution rate (H2/SiH4Flow-rate ratio) control in the range of 0.5~5；Make n-A-SiOxDuring film, make With the mixed gas of silane, phosphine or phosphine and hydrogen, carbon dioxide, hydrogen as process gas, technological temperature is 180~ 220 DEG C, radio frequency power density is in 5~50mW/cm2, operation pressure is 0.2~2.0mbar, doping ratio (PH3/SiH4Flow Than)≤10%, oxidation ratio (CO2/SiH4Flow-rate ratio)≤5, hydrogen dilution rate (H2/SiH4Flow-rate ratio) control in 0.5~5 scope It is interior；Make i- μ c-SiOxDuring film, using silane, carbon dioxide, hydrogen as process gas, technological temperature is 140~180 DEG C, radio frequency power density is in 50~300mW/cm2, operation pressure is 1.5~5mbar, oxidation ratio (CO2/SiH4Flow-rate ratio)≤ 5, hydrogen dilution rate (H2/SiH4Flow-rate ratio) control in the range of 5~150；Make n- μ c-SiOxDuring film, using silane, phosphine, The mixed gas of phosphine and hydrogen, carbon dioxide, hydrogen are as process gas, and technological temperature is 140~180 DEG C, radio-frequency power Density is in 50~300mW/cm2, operation pressure is 1.5~5.0mbar, doping ratio (PH3/SiH4Flow-rate ratio)≤10%, oxidation Ratio (CO2/SiH4Flow-rate ratio)≤5, hydrogen dilution rate (H2/SiH4Flow-rate ratio) control in the range of 5~150；
3) complete after Si-rich silicon oxide film makes, hydrogenation treatment after progress, rear hydrogenation treatment uses hydrogen and nitrogen Mixed gas or hydrogen, mixed gas H2/N2Volume ratio is controlled in the range of 0.1~100 times；Temperature control 140 DEG C~ 220 DEG C, processing time was controlled at 1~200 second.
Further preferably, the concretely comprising the following steps for method is 2. planted：
1) hydrogenation drying process before the n-type silicon chip after completing making herbs into wool, polishing, cleaning is done, uses hydrogen and nitrogen Mixed gas or hydrogen, mixed gas H2/N2Volume ratio dries silicon chip in the range of 0.1~100 under hydrogen atmosphere；Hydrogenation Drying temperature is between 30 DEG C~350 DEG C, and the time is 1~60 minute.
2) the thermally grown mode under the conditions of using plasma prepares intrinsic Si-rich silicon oxide film (i-A-SiOx), silicon wafer Piece underlayer temperature is 140~350 DEG C, and operation pressure is 0.2~5mbar, 0~300mW/cm of radio frequency power density2, the work used Skill gas is oxygen (O2), hydrogen (H2)；H2/O2Flow proportional is 0~2.
3) complete after rich and honour silicon oxide film growth, hydrogenation treatment after progress uses the gaseous mixture using hydrogen and nitrogen Body or hydrogen, mixed gas H2/N2Volume ratio is controlled in the range of 0.1~100 times；Hydrogenation temperature be 140~350 DEG C between, Processing time was controlled at 1~200 second.
Further preferably, the concretely comprising the following steps for method is 3. planted：
1) by complete making herbs into wool, polishing, cleaning after n-type silicon chip do before hydrogenation drying process, using using hydrogen with The mixed gas or hydrogen of nitrogen, mixed gas H2/N2Volume ratio is controlled in the range of 0.1~100 times, is done under hydrogen atmosphere Dry silicon chip；Drying temperature is hydrogenated between 30 DEG C~350 DEG C, the time is 1~60 minute.
2) intrinsic Si-rich silicon oxide film (i-A-SiO is prepared using the thermally grown mode under the conditions of wet oxygenx)；Technological temperature For 150~1200 DEG C, operation pressure is 0.1~100mbar；Use ultra-pure water and oxygen (O2) it is used as reactant, ultra-pure water rule Lattice are：At 25 DEG C, resistivity >=18M Ω * cm；H2O (water vapour)/O2Flow proportional is 0~1.
3) complete after rich and honour silicon oxide film growth, then hydrogenation treatment after carrying out, use hydrogen or hydrogen and nitrogen Mixed gas；Hydrogenation temperature is between 140~1200 DEG C, controlled at 1~60 minute processing time.
The present invention is further explained and illustrated below：
One kind of the compound unijunction PIN solar battery structures of crystal silicon and silicon Germanium films described above with transition zone Concrete composition is：
Hearth electrode/n-layer/n-type gradient μ c or A-SiOx/ n-type silicon chip/n-type gradient μ c or A-SiOx/μc-Si1-xGex/A– Si1-xGex/ p-A-SiC/TCO/ antireflective coatings；Wherein " gradient " refers to：By adjusting silica (SiOx) oxygen ratio x values (0≤x ≤ 2) from 2, progressively graded is to 0, and silica (SiOx) then change to graded oxidation silicon layer from silica and change to silicon again Layer.
Transition zone recited above can be one or more layers, you can be aoxidized from the intrinsic wealth and rank of amorphous state (amorphous) Doped amorphous (amorphous) silicon rich silicon oxide of the intrinsic rich and honour silica of silicon, crystallite state, n-type, the oxidation of n-type doped microcrystalline state Silicon-rich It is any in silicon to choose one or more；The position of transition zone can be the incident light side (front) of crystal silicon chip or be the back side, Or two sides is present simultaneously.
Described transition zone is silicon rich silicon oxide (silicon rich silicon dioxide SiOx) material, it is divided into The silicon rich silicon oxide material of intrinsic silicon rich silicon oxide material or the n-type doping undoped.Make n-type silicon rich silicon oxide material Impurity gas is phosphine.
Silicon wafer described in structure described above can be monocrystalline silicon piece or polysilicon chip.
Compared with prior art, advantage of the invention is that：
1st, solar cell of the present invention has transition zone, it is possible to achieve：
1) defect state at interface is reduced；Reach good passivation effect；
2) prevent epitaxial growth occur in the positive subsequent thin film depositing operation of silicon wafer；
3) nonmetallic, impurity metal ion diffusion between different film layers is stopped；Ensure the tunnelling effect to electronics simultaneously；
4) by the refractive index for the transition zone for adjusting front or the back side, strengthen falling into light effect lifting light utilization efficiency；
5) by adjusting the oxidation ratio of silicon rich silicon oxide, leakage current and parasitism electricity under silicon wafer boundary condition are reduced Hold.
2nd, preparation method of the invention carries out hydrogenation drying process after n-type silicon chip completes making herbs into wool, polishing and cleaning, with Further improve the quality and stability of silicon chip surface；Hydrogenation treatment is carried out after Si-rich silicon oxide film is made, to reduce The defect at the film layer interface and the stability for keeping film layer.
Brief description of the drawings
Fig. 1 is the structure of the compound unijunction PIN solar cells of crystal silicon and silicon thin film of use transition zone of the present invention Figure；
Fig. 2 is the technique of the compound unijunction PIN solar cells of crystal silicon and silicon thin film of use transition zone of the present invention Flow chart；
Fig. 3 is that the plasma-deposited silicon rich silicon oxide of one of the process of making transition zone of the present invention is thin Film schematic diagram；
Fig. 4 be one of the process of making transition zone of the present invention condition of plasma under thermal oxide growth Si-rich silicon oxide film schematic diagram；
Fig. 5 is that water vapour is raw to heat under the conditions of the wet oxygen of chamber by water vapour and oxygen simultaneous implantation by wet oxygen generator Long Si-rich silicon oxide film schematic diagram；
Fig. 6 is that water vapour is independently injected into thermally grown silicon rich silicon oxide under the conditions of the wet oxygen of chamber by steam generator Film schematic diagram；
Wherein：1 --- flowmeter；2a --- Top electrode；2b --- bottom electrode；3 --- air inlet head；4 --- vacuum chamber； 5 --- heating system；6 --- pressure gauge；7 --- radio-frequency power supply；8 --- n-type silicon chip；9 --- plasma；10 --- it is true Empty set is united；11 --- process gas air supply system；12 --- wet oxygen generator；13 --- steam generator；14 --- oxygen supply System.
Embodiment
With reference to specific embodiment, the present invention will be further explained
Embodiment 1
The compound unijunction PIN solar cells of crystal silicon and silicon Germanium films with transition layer structure, selected from the following sun One of energy battery structure：
10) hearth electrode/n-layer/n-type silicon chip/transition zone/i-A-Si1-xGexLayer/p-A-Si1-xGexLayer/TCO/ antireflectives Film；
11) hearth electrode/n-layer/n-type silicon chip/transition zone/i- μ c-Si1-xGexLayer/i-A-Si1-xGexLayer/p-A-Si1- xGexLayer/TCO/ antireflective coatings；
12) hearth electrode/n-layer/n-type silicon chip/transition zone/p-A-Si1-xGexLayer/TCO/ antireflective coatings；
13) hearth electrode/n-layer/transition zone/n-type silicon chip/i-A-Si1-xGexLayer/p-A-Si1-xGexLayer/TCO/ antireflectives Film；
14) hearth electrode/n-layer/transition zone/n-type silicon chip/i- μ c-Si1-xGexLayer/i-A-Si1-xGexLayer/p-A-Si1- xGexLayer/TCO/ antireflective coatings；
15) hearth electrode/n-layer/transition zone/n-type silicon chip/p-A-Si1-xGexLayer/TCO/ antireflective coatings；
16) hearth electrode/n-layer/transition zone/n-type silicon chip/transition zone/i-A-Si1-xGexLayer/p-A-Si1-xGexLayer/TCO/ Antireflective coating；
17) hearth electrode/n-layer/transition zone/n-type silicon chip/transition zone/i- μ c-Si1-xGexLayer/i-A-Si1-xGexLayer/p- A-Si1-xGexLayer/TCO/ antireflective coatings；
18) hearth electrode/n-layer/transition zone/n-type silicon chip/transition zone/p-A-Si1-xGexLayer/TCO/ antireflective coatings；
For Si1-xGexIn x values be 0≤x≤1；The transition zone is one layer or multilayer, wherein any one layer is equal For silicon rich silicon oxide layer；The silicon rich silicon oxide layer is selected from i-A-SiOx, i- μ c-SiOx, n-A-SiOx, n- μ c-SiOxIn appoint What is a kind of, wherein 0≤x≤2；Or the silicon rich silicon oxide layer is selected from n-type gradient μ c-SiOxWith n-type gradient A-SiOx, wherein 0 ≤ x≤2, " gradient " refers to：By change in silicon rich silicon oxide x values from 2 progressively graded to 0, and silica then from Silica --- changing to silicon rich silicon oxide layer --- changes to silicon layer again；
Wherein, "/" represents the interface between two layers；N represents electron type (n-type) semiconductor, and i- represents intrinsic semiconductor, P- Represent cavity type (p-type) semiconductor；A- represents noncrystal, and μ c- represent crystallite.
The n-layer is selected from A-Si, crystallite or epi-Si1-xGexMaterial is one or more of, epi-Si1-xGexIn 0≤x≤1, Epi represents epitaxial growth monocrystalline.
The hearth electrode preferably selects nesa coating or aluminium.
As shown in figure 1, transition zone described in the present embodiment is two layers, respectively n-A-SiOxAnd i-A-SiOx, close to n-type silicon One layer of chip is n-A-SiOx。
Embodiment 2
The manufacture method of the transition zone, as shown in Fig. 2 including following methods：
The first：Tentatively cleaning, chemical making herbs into wool are carried out to n-type silicon chip, chemically or mechanically after twin polishing, to n-type silicon Chip is cleaned again, hydrogenation drying process before the silicon chip after cleaning is done, and the mode of processing is：Silicon chip is delivered to close In the equipment of closed chamber room, emptying air to chamber pressure is less than or equal to (≤) 1Pascal；Chamber temp is controlled 30 DEG C~350 Between DEG C, the mixed gas of hydrogen or hydrogen and nitrogen is passed through；Silicon chip is dried under hydrogen atmosphere.The purity of hydrogen and nitrogen is big In equal to (>=) 99.99%；According to mixed gas, the volume ratio of hydrogen and nitrogen is 0.1~100 times；Hydrogenate drying time For 1~60 minute.By silicon chip feeding PECVD (the Plasma Enhanced Chemical after over hydrogenation drying process Vapor Deposition) or HD-P ECVD (High Density-Plasma Enhanced Chemical Vapor Deposition) in equipment, Si-rich silicon oxide film is made using PECVD or HD-PECVD depositing operations；Rf frequency model Enclose for 13~67MHz.To i-A-SiOx、n-ASiOx、i-μc-SiOx、n-μc-SiOxFour kinds of different types of silicon rich silicon oxides are thin Film, its technological process such as following table：
Complete after rich and honour silicon oxide film deposition, hydrogenation treatment after being carried out with PECVD or HD-PECVD equipment：It is passed through hydrogen Or the mixed gas of hydrogen and nitrogen volume ratio 0.1~100, temperature control is at 140 DEG C~220 DEG C, and processing time is controlled 1 ~200 seconds.
Second：Tentatively cleaning, chemical making herbs into wool are carried out to n-type silicon chip, chemically or mechanically after twin polishing, to n-type silicon Chip is cleaned again, hydrogenation drying process before the silicon chip after cleaning is done, and the mode of processing is：Silicon chip is delivered to close In the equipment of closed chamber room, emptying air to chamber pressure is less than or equal to (≤) 1Pascal；Chamber temp is controlled 30 DEG C~350 Between DEG C, the mixed gas of hydrogen or hydrogen and nitrogen is passed through；Silicon chip is dried under hydrogen atmosphere.The purity of hydrogen and nitrogen is big In equal to (>=) 99.99%；According to mixed gas, the volume ratio of hydrogen and nitrogen is 0.1~100 times；Hydrogenate drying time For 1~60 minute.Thermally grown mode under the conditions of using plasma prepares intrinsic Si-rich silicon oxide film (i-A-SiOx).Its Preparation condition is：Silicon wafer substrate temperature be 150~350 DEG C, operation pressure be 0.2~5mbar, radio frequency power density 0~ 300mW/cm2, the process gas used is oxygen (O2), hydrogen (H2)；H2/O2 flow proportionals are 0~2；
Complete after rich and honour silicon oxide film growth, then hydrogenation treatment after being carried out with PECVD.It is passed through hydrogen or hydrogen and nitrogen The mixed gas of gas, mixed gas H2/N2Volume ratio control in the range of 0.1~100 times, temperature control at 140 DEG C~220 DEG C, Processing time was controlled at 1~200 second.
The third：Tentatively cleaning, chemical making herbs into wool are carried out to n-type silicon chip, chemically or mechanically after twin polishing, to n-type silicon Chip is cleaned again, hydrogenation drying process before the silicon chip after cleaning is done, and the mode of processing is：Silicon chip is delivered to close In the equipment of closed chamber room, emptying air to chamber pressure is less than or equal to (≤) 1Pascal；Chamber temp is controlled 30 DEG C~350 Between DEG C, the mixed gas of hydrogen or hydrogen and nitrogen is passed through；Silicon chip is dried under hydrogen atmosphere.The purity of hydrogen and nitrogen is big In equal to (>=) 99.99%；According to mixed gas, the volume ratio of hydrogen and nitrogen is 0.1~100 times；Hydrogenate drying time For 1~60 minute.Intrinsic Si-rich silicon oxide film (i-A-SiO is prepared using the thermally grown mode under the conditions of wet oxygenx).It is prepared Condition is：Silicon wafer substrate temperature is 150~1200 DEG C, and operation pressure is 0.1~100mbar, the ultra-pure water used (Deionized water) and oxygen (O2)；Ultra-pure water specification is：At 25 DEG C, resistivity >=18M Ω * cm, with water vapour In form injection reaction chamber, injection water temperature is 50~110 DEG C；H2O (water vapour)/O2Flow proportional is 0~1.The load of water vapour Entering mode is occurred with oxygen simultaneous implantation to chamber or by water vapour by wet oxygen generator by water vapour Device is independently injected into chamber, as shown in Fig. 5-6 in brief description of the drawings.
Complete after rich and honour silicon oxide film growth, hydrogenation treatment after reusable heat growth furnace/equipment is carried out.Be passed through hydrogen or The mixed gas of hydrogen and nitrogen, mixed gas H2/N2Volume ratio is controlled in the range of 0.1~100 times, and temperature control is at 140 DEG C ~1200 DEG C, processing time was controlled at 1~60 minute.
Silicon rich silicon oxide transition zone is obtained using any one method in three of the above method, and dried with preceding hydrogenation, Hydrogenation process reduces the defect of oxide interface and keeps the stability of the layer material afterwards.

Claims (11)

1. with transition layer structure crystal silicon and the compound unijunction PIN solar cells of silicon Germanium films, it is characterized in that, selected from One of lower solar battery structure：
1) hearth electrode/n-layer/n-type silicon chip/transition zone/composition layer/p-A-Si1-xGexLayer/TCO/ antireflective coatings；
2) hearth electrode/n-layer/n-type silicon chip/transition zone/composition layer/i-A-Si1-xGexLayer/p-A-Si1-xGexLayer/TCO/ subtracts Reflectance coating；Or hearth electrode/n-layer/n-type silicon chip/transition zone/i- μ c-Si1-xGexLayer/composition layer/p-A-Si1-xGexLayer/ TCO/ antireflective coatings；
3) hearth electrode/n-layer/n-type silicon chip/transition zone/p-A-Si1-xGexWith p-A-SiC combination layers/TCO/ antireflective coatings；
4) hearth electrode/n-layer/transition zone/n-type silicon chip/composition layer/p-A-Si1-xGexLayer/TCO/ antireflective coatings；Or bottom electricity Pole/n-layer/transition zone/n-type silicon chip/i-A-Si1-xGexLayer/composition layer/TCO/ antireflective coatings；
5) hearth electrode/n-layer/transition zone/n-type silicon chip/composition layer/i-A-Si1-xGexLayer/p-A-Si1-xGexLayer/TCO/ subtracts Reflectance coating；Or hearth electrode/n-layer/transition zone/n-type silicon chip/i- μ c-Si1-xGexLayer/composition layer/p-A-Si1-xGexLayer/ TCO/ antireflective coatings；
6) hearth electrode/n-layer/transition zone/n-type silicon chip/p-A-Si1-xGexWith p-A-SiC combination layers/TCO/ antireflective coatings；
7) hearth electrode/n-layer/transition zone/n-type silicon chip/transition zone/composition layer/p-A-Si1-xGexLayer/TCO/ antireflective coatings；
8) hearth electrode/n-layer/transition zone/n-type silicon chip/transition zone/composition layer/i-A-Si1-xGexLayer/p-A-Si1-xGexLayer/ TCO/ antireflective coatings；Or hearth electrode/n-layer/transition zone/n-type silicon chip/transition zone/i- μ c-Si1-xGexLayer/composition layer/p- A-Si1-xGexLayer/TCO/ antireflective coatings；
9) hearth electrode/n-layer/transition zone/n-type silicon chip/transition zone/p-A-Si1-xGexWith p-A-SiC combination layers/TCO/ antireflectives Film；Si1-xGexIn x values be 0≤x≤1；The transition zone is one layer or multilayer, wherein any one layer is Silicon-rich oxygen SiClx layer；The silicon rich silicon oxide layer is selected from i-A-SiOx, i- μ c-SiOx, n-A-SiOx, n- μ c-SiOxAny one of, Wherein 0≤x≤2；Or the silicon rich silicon oxide layer is selected from n-type gradient μ c-SiOxWith n-type gradient A-SiOx, wherein 0≤x≤2, The gradient refers to：By changing in silicon rich silicon oxide x values, from 2, progressively graded is to 0, and silica is then from silica --- Change to silicon rich silicon oxide layer --- silicon layer is changed to again；Wherein, "/" represents the interface between two layers；N represents electron type (n Type) semiconductor, i- represents intrinsic semiconductor, and P- represents cavity type (p-type) semiconductor；A- represents noncrystal, and μ c- represent crystallite； Composition layer is to use i- μ c-Si1-xGexWith i-A-Si1-xGexBoth are according to the combination changed by Graded band-gap, wherein graded Refer to：It is changed stepwise by the value x for adjusting germanium in SiGe from 1 to 0, and SiGe is gradually changed to silicon from gradient SiGe Layer.
2. solar cell according to claim 1, it is characterized in that, the transition zone is two layers, respectively n-A-SiOxAnd i- A-SiOx, one layer of close n-type silicon chip is n-A-SiOx。
3. solar cell according to claim 1, it is characterized in that, the silicon atom density domination of the transition zone 2.2 × 1022/cm3~5.0 × 1022/cm3Between；Refractive index n is 1.46≤n≤3.88；Thicknesses of layers h is 0.5nm≤h≤10nm；Band Gap Eg is controlled between 1.12~9.0eV；Relative dielectric constant ε is 3.0≤ε≤11.7.
4. solar cell according to claim 1, it is characterized in that, the solar battery structure 1), 2), 4), 5), 7), p-A-Si 8) in kind structure1-xGexLayer material is with p-A-SiC or uses p-A-Si1-xGexCombination with p-A-SiC is replaced Generation, Si1-xGexIn x values be 0≤x≤1.
5. solar cell according to claim 1, it is characterized in that, the n-layer is selected from A-Si, μ c-Si1-xGexAnd epi- Si1-xGexAny of material or according to two kinds of the combination changed by Graded band-gap；epi-Si1-xGexIn 0≤x≤1, Epi represents epitaxial growth monocrystalline；Wherein graded refers to：It is changed stepwise by the value x for adjusting germanium in SiGe from 1 to 0, and SiGe is gradually changed to silicon layer from gradient SiGe.
6. solar cell according to claim 1, it is characterized in that, the hearth electrode selects nesa coating or aluminium.
7. a kind of preparation method according to any one of the claim 1-6 solar cells, it is characterized in that, including transition zone Prepare, the preparation of the transition zone includes：First after n-type silicon chip completes making herbs into wool, polishing and cleaning, then carry out preceding hydrogenation drying Processing；Then Si-rich silicon oxide film is made；Hydrotreating process after finally carrying out；Hydrogenation drying process is before described：Use The mixed gas or hydrogen of hydrogen and nitrogen as processing gas, wherein the hydrogen/nitrogen volume ratio of mixed gas 0.1~ Between 100, preceding hydrogenation drying process temperature control is between 30 DEG C~350 DEG C, and the preceding hydrogenation drying process time is 1~60 point Clock；The rear hydrotreating process is：Mixed gas or hydrogen using hydrogen and nitrogen is as processing gas, wherein mixing The hydrogen/nitrogen volume ratio of gas is between 0.1~100；Hydrotreating temperatures are between 140 DEG C~1200 DEG C afterwards, rear hydrogenation Processing time is between 1~3600 second.
8. the preparation method of solar cell according to claim 7, it is characterized in that, the preparation of the transition zone is chosen in particular from One of three kinds of methods below：The is the step of 1. planting method：1) before being carried out using the mixed gas or hydrogen of hydrogen and nitrogen Hydrogenate drying process：2) using plasma enhancing chemical vapor deposition (PECVD) or high-density plasma chemical gas phase are heavy The method of product (HD-PECVD), is process gas using the mixed gas of silane, phosphine, phosphine and hydrogen, hydrogen and carbon dioxide Body, deposits i-A-SiOx、n-ASiOx、i-μc-SiOx、n-μc-SiOxAny of four kinds of different types appoint several Silicon-rich Silicon oxide film；3) complete after Si-rich silicon oxide film making, after being carried out using the mixed gas or hydrogen of hydrogen and nitrogen Hydrogenation treatment；The is the step of 2. planting method：1) hydrogenation drying before being carried out using the mixed gas or hydrogen of hydrogen and nitrogen Processing；2) using plasma enhancing chemical vapor deposition (PECVD) or high density plasma CVD (HD- PECVD equipment), using hydrogen and oxygen, under plasma conditions, decomposes hydrogen and oxygen, allow silicon chip surface containing Thermally grown Si-rich silicon oxide film is carried out under conditions of water, hydrogen ion and oxonium ion；3) complete after Si-rich silicon oxide film making, Hydrogenation treatment after being carried out using the mixed gas or hydrogen of hydrogen and nitrogen；The is the step of 3. planting method：1) hydrogen is used Hydrogenation drying process before being carried out with the mixed gas or hydrogen of nitrogen；2) using the thermal oxide growth method under the conditions of wet oxygen, Make Si-rich silicon oxide film；3) complete after Si-rich silicon oxide film making, use the mixed gas or hydrogen of hydrogen and nitrogen Hydrogenation treatment after gas is carried out.
9. the preparation method of solar cell according to claim 8, it is characterized in that, 1. the plant concretely comprising the following steps for method：
1) hydrogenation drying process before the n-type silicon chip completed after making herbs into wool, polishing, cleaning is done, uses mixing for hydrogen and nitrogen Close gas or hydrogen, mixed gas H2/N2Volume ratio dries silicon chip in the range of 0.1~100 under hydrogen atmosphere；Hydrogenate drying Temperature is between 30 DEG C~350 DEG C, and the time is 1~60 minute；
2) i-A-SiO is made using PECVD or HD-PECVD depositing operationsx、n-ASiOx、i-μc-SiOx、n-μc-SiOxFour kinds Any of different type appoints several Si-rich silicon oxide films；Radio-frequency signal generator used in PECVD or HD-PECVD equipment Frequency range is 13~67MHz；Wherein, i-A-SiO is madexDuring film, process gas is used as using silane, carbon dioxide and hydrogen Body, technological temperature is 180~220 DEG C, and radio frequency power density is in 5~50mW/cm2, operation pressure is 0.2~2.0mbar, CO2/ SiH4Flow-rate ratio≤5, H2/SiH4Flow-ratio control is in the range of 0.5~5；Make n-A-SiOxDuring film, silane, phosphine are used Or mixed gas, carbon dioxide and the hydrogen of phosphine and hydrogen, as process gas, technological temperature is 180~220 DEG C, radio frequency Power density is in 5~50mW/cm2, operation pressure is 0.2~2.0mbar, PH3/SiH4Flow-rate ratio≤10%, CO2/SiH4Flow Than≤5, H2/SiH4Flow-ratio control is in the range of 0.5~5；Make i- μ c-SiOxDuring film, using silane, carbon dioxide and Hydrogen is 140~180 DEG C as process gas, technological temperature, and radio frequency power density is in 50~300mW/cm2, operation pressure is 1.5~5mbar, CO2/SiH4Measure ratio≤5, H2/SiH4Flow-ratio control is in the range of 5~150；Make n- μ c-SiOxDuring film, Using the mixed gas of silane, phosphine, phosphine and hydrogen, carbon dioxide and hydrogen as process gas, technological temperature be 140~ 180 DEG C, radio frequency power density is in 50~300mW/cm2, operation pressure is 1.5~5.0mbar, PH3/SiH4Flow-rate ratio≤10%, CO2/SiH4Flow-rate ratio≤5, H2/SiH4Flow-ratio control is in the range of 5~150；3) complete after Si-rich silicon oxide film making, Hydrogenation treatment after progress, rear hydrogenation treatment uses the mixed gas or hydrogen of hydrogen and nitrogen, mixed gas H2/N2Volume ratio Control is in the range of 0.1~100 times；Temperature control is at 140 DEG C~220 DEG C, and processing time was controlled at 1~200 second.
10. the preparation method of solar cell according to claim 8, it is characterized in that, 2. the plant concretely comprising the following steps for method：
1) hydrogenation drying process before the n-type silicon chip completed after making herbs into wool, polishing, cleaning is done, uses mixing for hydrogen and nitrogen Close gas or hydrogen, mixed gas H2/N2Volume ratio dries silicon chip in the range of 0.1~100 under hydrogen atmosphere；Hydrogenate drying Temperature is between 30 DEG C~350 DEG C, and the time is 1~60 minute；
2) the thermally grown mode under the conditions of using plasma prepares intrinsic Si-rich silicon oxide film i-A-SiOx, silicon wafer substrate Temperature is 140~350 DEG C, and operation pressure is 0.2~5mbar, 0~300mW/cm of radio frequency power density2, the process gas used Body is oxygen (O2) and hydrogen (H2)；H2/O2Flow proportional is 0~2；
3) complete after rich and honour silicon oxide film growth, hydrogenation treatment after progress uses the mixed gas or hydrogen of hydrogen and nitrogen Gas, mixed gas H2/N2Volume ratio is controlled in the range of 0.1~100 times；Hydrogenation temperature be 140~350 DEG C between, processing time Control was at 1~200 second.
11. the preparation method of solar cell according to claim 8, it is characterized in that, 3. the plant concretely comprising the following steps for method：
1) hydrogenation drying process before the n-type silicon chip completed after making herbs into wool, polishing, cleaning is done, uses mixing for hydrogen and nitrogen Close gas or hydrogen, mixed gas H2/N2Volume ratio is controlled in the range of 0.1~100 times, and silicon chip is dried under hydrogen atmosphere；Hydrogen Change drying temperature between 30 DEG C~350 DEG C, the time is 1~60 minute；
2) intrinsic Si-rich silicon oxide film (i-A-SiO is prepared using the thermally grown mode under the conditions of wet oxygenx)；Technological temperature is 150 ~1200 DEG C, operation pressure is 0.1~100mbar；Using ultra-pure water and oxygen as reactant, ultra-pure water specification is：25 At DEG C, resistivity >=18M Ω * cm；H2O (water vapour)/O2Flow proportional is 0~1；
3) complete after rich and honour silicon oxide film growth, then hydrogenation treatment after carrying out, use the mixing of hydrogen or hydrogen and nitrogen Gas；Hydrogenation temperature is between 140~1200 DEG C, controlled at 1~60 minute processing time.
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KR20090076035A (en) * 2008-01-07 2009-07-13 엘지전자 주식회사 Solar cell having passivated porous surface and fabrication method thereof
CN101894871A (en) * 2009-11-18 2010-11-24 湖南共创光伏科技有限公司 High-conversion rate silicon crystal and thin film compound type unijunction PIN (Positive Intrinsic-Negative) solar battery and manufacturing method thereof
CN103594541A (en) * 2013-10-12 2014-02-19 南昌大学 Polycrystalline silicon/monocrystalline silicon heterojunction structure applied to solar cell and preparation method thereof

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KR20090076035A (en) * 2008-01-07 2009-07-13 엘지전자 주식회사 Solar cell having passivated porous surface and fabrication method thereof
CN101894871A (en) * 2009-11-18 2010-11-24 湖南共创光伏科技有限公司 High-conversion rate silicon crystal and thin film compound type unijunction PIN (Positive Intrinsic-Negative) solar battery and manufacturing method thereof
CN103594541A (en) * 2013-10-12 2014-02-19 南昌大学 Polycrystalline silicon/monocrystalline silicon heterojunction structure applied to solar cell and preparation method thereof

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