CN104505419A - Crystal silicon and silicon carbide film compound unijunction PIN solar battery with transition layer, and preparation method thereof - Google Patents

Crystal silicon and silicon carbide film compound unijunction PIN solar battery with transition layer, and preparation method thereof Download PDF

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CN104505419A
CN104505419A CN201410699068.3A CN201410699068A CN104505419A CN 104505419 A CN104505419 A CN 104505419A CN 201410699068 A CN201410699068 A CN 201410699068A CN 104505419 A CN104505419 A CN 104505419A
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hydrogen
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mist
sio
silicon
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CN104505419B (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
    • 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
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • 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
    • H01L31/0248—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 characterised by their semiconductor bodies
    • H01L31/0352—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 characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
    • 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
    • H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
    • 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
    • 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 crystal silicon and silicon carbide film compound unijunction PIN solar battery with a transition layer, and a preparation method thereof. According to the solar battery, the front surface of an n-type silicon wafer or the back surface of the n-type silicon wafer or both the front surface and the back surface of the n-type silicon wafer are simultaneously provided with the transition layer, the transition layer has one layer or multiple layers, and one layer of the transition layer is a silicon-enriched oxygen ambient silica layer. The preparation method involves adding a pre-hydrogenation drying processing after the silicon wafer is textured, polished and cleaned and at the same time, adding a post-hydrogenation processing mode after the process of the transition layer is finished. The two methods are used for improving the interface quality and the structure stability. By using the transition layer and using the crystal silicon and silicon carbide film compound battery which is subjected to the pre-hydrogenation drying processing and post-hydrogenation processing and is provided with the transition layer, the battery conversion efficiency can be improved by more than 10% on the basis of the prior arts.

Description

There is the crystal silicon and carborundum films compound unijunction PIN solar cell and preparation method thereof of transition zone
Technical field
The present invention relates to crystal silicon and film composite type solar cell, particularly there is the crystal silicon of transition layer structure and the structural design of carborundum films compound unijunction PIN solar cell and manufacture method thereof.
Background technology
After French scientist AE.Becquerel found opto-electronic conversion phenomenon in 1839,1883 first be that the solar cell of substrate is born with semiconductor selenium.Nineteen forty-six RuSSell obtains the patent (US.2,402,662) of first solar cell, and its photoelectric conversion efficiency is only 1%.Until 1954, the research of Bell Laboratory has just found that the silica-base material adulterated has high photoelectric conversion efficiency.This research is laid a good foundation for modern sun energy battery industry.In 1958, Haffman Utilities Electric Co. of the U.S. was that the satellite of the U.S. has loaded onto first piece of solar panel, and its photoelectric conversion efficiency is about 6%.From then on, the solar cell research of monocrystalline silicon and polycrystalline silicon substrate and production have had and have developed fast, the output of solar cell in 2006 has reached 2000 megawatts, the photoelectric conversion efficiency of monocrystaline silicon solar cell reaches 24.7%, commercial product reaches 22.7%, the photoelectric conversion 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 high efficiency III-V race's solar cell of first GaAs base.Owing to preparing the key technology MOCVD (metal organic chemical vapor deposition) of III-V race's thin-film material until about 1980 are are just successfully researched and developed, the applied solar energy Battery Company of the U.S. was successfully applied this technology and is prepared III-V race's solar cell that photoelectric conversion efficiency is the GaAs base of 17% in 1988.Thereafter, take GaAs the doping techniques of III-V race's material of substrate, the technology of preparing of plural serial stage solar cell obtains research and development widely, its photoelectric conversion efficiency reached 19% in 1993, within 2000, reach 24%, within 2002, reach 26%, within 2005, reach 28%, within 2007, reach 30%.2007, large III-V solar cell company of race Emcore and SpectroLab of the U.S. two produces high efficiency III-V race solar energy commercial product, its photoelectric conversion rate reaches 38%, this two company occupies 95% of III-V race's solar cell market, the whole world, American National Energy Research Institute announce they successfully have developed its photoelectric conversion efficiency up to 50% III-V race's solar cell of plural serial stage.Because the substrate of this kind of solar cell is expensive, instrument and supplies cost is high, is mainly used in the fields such as Aeronautics and Astronautics, national defence and military project.
External solar cell research and production, roughly can be divided into three phases, namely have three generations's solar cell.
First generation solar cell is for representative substantially with the solar cell of monocrystalline silicon and the silica-based single constituent element of polycrystalline.Only pay attention to improve photoelectric conversion efficiency and large-scale production, there is high energy consumption, labour intensive, the problem such as unfriendly and high cost to environment, its price producing electricity is about 5 ~ 6 times of coal electricity; Until 2007, the output of first generation solar cell still accounts for 89% of global solar battery total amount, expert expects, and first generation solar cell will progressively be eliminated and become history after 10 years.
Second generation solar cell is thin-film solar cells, is the new technology grown up in recent years, and it pays attention to reduce the energy consumption in production process and process costs, and brainstrust is called green photovoltaic industry.Compare with polysilicon solar cell with monocrystalline silicon, the consumption of its film HIGH-PURITY SILICON is its 1%, meanwhile, and low-temperature plasma enhanced chemical vapor deposition deposition technique, electroplating technology, printing technology is extensively studied and is applied to the production of thin-film solar cells.Owing to adopting glass, the stainless steel thin slice of low cost, macromolecule substrate, as baseplate material, greatly reduces production cost, and is conducive to large-scale production.The material of the thin-film solar cells of success research and development is at present: CdTe, and its photoelectric conversion efficiency is 16.5%, and commercial product is about 7%; CulnSe, its photoelectric conversion efficiency is 19.5%, and commercial product is 11%; Amorphous silicon and microcrystal silicon, its photoelectric conversion efficiency is 8.3 ~ 15%, and commercial product is 7 ~ 13.3%, in recent years, due to the research and development of the thin-film transistor of LCD TV, amorphous silicon and microcrystalline silicon film technology have had significant progress, and are applied to silicon-based film solar cells.Brainstrust is estimated, because thin-film solar cells has low cost, high efficiency, the ability of large-scale production, at 5 ~ 10 years of future, thin-film solar cells will become the main product of global solar battery.
Focus around thin-film solar cells research is, exploitation is efficient, low cost, long-life photovoltaic solar cell.They should have following feature: low cost, high efficiency, long-life, material source are abundant, nontoxic, the relatively more good amorphous silicon thin-film solar cell of scientists.
The thin-film solar cells accounting for lion's share is at present non-crystal silicon solar cell, is generally pin structure battery, and Window layer is the P-type non-crystalline silicon of boron-doping, then deposits the unadulterated i layer of one deck, then deposits the N-type amorphous silicon that one deck mixes phosphorus, and plated electrode.
Amorphous silicon battery generally adopts PECVD (Plasma Enhanced Chemical Vapor Deposition---plasma enhanced chemical vapor deposition) method that the gases such as high purity silane are decomposed and deposits.This kind of manufacture craft, can complete in multiple vacuum deposition chamber continuously aborning, to realize producing in enormous quantities.Due to deposition decomposition temperature low, can on glass, corrosion resistant plate, ceramic wafer, flexible plastic sheet deposit film, be easy to large areaization produce, cost is lower.The structure of the amorphous silicon based solar battery prepared on a glass substrate is: Glass/TCO/p-a-SiC:H/i-a-Si:H/n-a-Si:H/Al, and the structure of the amorphous silicon based solar battery prepared at the bottom of stainless steel lining is: SS/ZnO/n-a-Si:H/i-a-Si (Ge): H/p-na-Si:H/ITO/Al.
Improve the most effective approach of battery efficiency is improve the efficiency of light absorption of battery as far as possible.For silica-base film, low bandgap material is adopted to be inevitable approach.The low bandgap material adopted as Uni-Solar company is a-SiGe (amorphous silicon germanium) alloy, and their a-Si/a-SiGe/a-SiGe tri-ties laminated cell, small size battery (0.25cm 2) efficiency reaches 15.2%, stabilization efficiency reaches 13%, 900cm 2component efficiency reaches 11.4%, and stabilization efficiency reaches 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 the important technology approach realizing high efficiency, low cost thin-film solar cells, is the industrialization direction that hull cell is new.The amorphous silicon/microcrystalline silicon tandem battery component sample efficiencies of Mitsubishi heavy industrys in 2005 and Zhong Yuan chemical company reaches 11.1% (40cm × 50cm) and 13.5% (91cm × 45cm) respectively.Japanese Sharp company realizes amorphous silicon/microcrystalline silicon tandem solar cell industryization in September, 2007 and produces (25MW, efficiency 8%-8.5%), Europe Oerlikon (Ao Likang) company, U.S. AppliedMaterials (Applied Materials), also just researching and developing Product-level amorphous silicon/micro-crystalline silicon cell key manufacture.
Domestic, Nankai University for relying on, carries out microcrystalline silicon materials and the research of amorphous silicon/microcrystalline silicon tandem battery with country " 15 ", Eleventh Five-Year Plan 973 project and Eleventh Five-Year Plan 863 project.Small size micro-crystalline silicon cell efficiency reaches 9.36%, and amorphous silicon/microcrystalline silicon tandem battery efficiency reaches 11.8%, 10cm × 10cm component efficiency and reaches 9.7%.Now just cooperate with Fujian Jun Shi energy company, 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 contains three kinds of structures: the unijunction or the double junction non-crystal silicon battery that take glass as substrate, take glass as amorphous silicon and the microcrystal silicon binode battery of substrate, take stainless steel as amorphous silicon and amorphous germanium silicon alloy three junction battery of substrate.Because various product has the advantage of its uniqueness, these three kinds of battery structures of following period of time also can synchronized development from now on.The long term growth direction of silicon-base thin-film battery is clearly, except making full use of the advantage of its uniqueness, mainly overcomes product development, production and selling aspect Problems existing.Silicon-base thin-film battery will improve battery efficiency further, utilizes micro-crystalline silicon cell can improve battery efficiency further as the end battery of multijunction cell, reduces the photoinduction decline of battery.
The technological difficulties of current micro-crystalline silicon cell industrialization realize the high speed deposition technology of microcrystal silicon and realize the uniformity of large area microcrystalline silicon film material.If the technical barrier of microcrystal silicon large area high speed deposition aspect can be resolved in the shorter time, estimate in the near future, the multijunction cell that amorphous silicon and microcrystal silicon combine will become the major product of silicon-base thin-film battery.Amorphous silicon and microcrystal silicon multijunction cell can deposit on a glass substrate, also can deposit on flexible substrates, no matter are can adopt amorphous and microcrystal silicon multijunction cell structure with glass or with the silicon-base thin-film battery of flexible substrate deposition.
Current gyp silicon-based film solar cells is amorphous silicon thin-film solar cell.Energy gap due to amorphous silicon is 1.7, it only can absorbing wavelength at the solar energy of 400-500nm.Because its solar energy conversion efficiency is low, greatly about about 6%, the transfer ratio of this silicon-based film solar cells is to be improved.
The technology of several aspect and background material above, someone mentions and adopts the material of different energy gap to expand absorption spectrum to solar energy.But before patent No. ZL200910044772.4, not yet someone adopts a series, there are six kinds of materials of different energy gap to form the thin-film solar cells of unijunction multilayer PIN structural, and nobody develops the manufacturing technology of the thin-film solar cells preparing this unijunction multilayer PIN structural, yet nobody develops this high conversion silicon wafer of preparation and film composite type unijunction PIN solar cell and manufacture method thereof.
Patent No. ZL200910044772.4 combines the solar cell of monocrystalline silicon and the silica-based single constituent element of polycrystalline with silicon-based film solar cells, a kind of high conversion silicon wafer and film composite type unijunction PN are proposed, PIN solar cell and manufacture method thereof, described high conversion silicon wafer and film composite type unijunction PIN solar cell have higher conversion efficiency and excellent stability.The present invention, on the basis of patent No. ZL200910044772.4, adds transition layer structure and proposes its preparation process of this transition zone, can obtain the lifting of efficiency further, and can apply the industrial production with large-scale.
Summary of the invention
The present invention is on the basis of high conversion silicon wafer and film composite type unijunction PIN solar battery technology, take crystal silicon and the compound unijunction PIN structural of carborundum films, project organization and the manufacture method thereof of a transition zone are proposed, provide the crystal silicon and carborundum films compound unijunction PIN solar cell and preparation method thereof with transition zone, described preparation method completes making herbs into wool at silicon chip, polishing and cleaning after, add front hydrogenation drying process, simultaneously, after completing the technique of this transition zone, add rear hydrogenation treatment mode, two kinds of methods are for improving the stability of interface quality and structure.Adopt this transition zone and have employed front hydrogenation drying process and the rear hydrotreated crystal silicon with transition zone and carborundum films composite battery, can by battery conversion efficiency raising more than 10% on original basis.
One of technical scheme of the present invention:
There is crystal silicon and the carborundum films compound unijunction PIN solar cell of transition layer structure, be selected from one of following solar battery structure:
1) hearth electrode/n layer/N-shaped silicon wafer/transition zone/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating;
2) hearth electrode/n layer/N-shaped silicon wafer/transition zone/i-μ c-SiC layer/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating;
3) hearth electrode/n layer/N-shaped silicon wafer/transition zone/p-A-SiC layer/TCO/ antireflective coating;
4) hearth electrode/n layer/transition zone/N-shaped silicon wafer/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating;
5) hearth electrode/n layer/transition zone/N-shaped silicon wafer/i-μ c-SiC layer/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating;
6) hearth electrode/n layer/transition zone/N-shaped silicon wafer/p-A-SiC layer/TCO/ antireflective coating;
7) hearth electrode/n layer/transition zone/N-shaped silicon wafer/transition zone/i-A-SiC layer/p-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating;
8) hearth electrode/n layer/transition zone/N-shaped silicon wafer/transition zone/i-μ c-SiC layer/i-A-SiC layer/p-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating;
9) hearth electrode/n layer/transition zone/N-shaped silicon wafer/transition zone/p-A-SiC layer/TCO/ antireflective coating;
Described transition zone is one deck or multilayer, and wherein one deck is silicon rich silicon oxide layer arbitrarily; Described silicon rich silicon oxide layer is selected from i-A-SiO x, i-μ c-SiO x, n-A-SiO x, n-μ c-SiO xin any one, wherein 0≤x≤2; Or described silicon rich silicon oxide layer is selected from N-shaped gradient μ c-SiO xwith N-shaped gradient A-SiO x, wherein 0≤x≤2, described " gradient " refers to: by changing x value in silicon rich silicon oxide, from 2, progressively graded is to 0, and silica then---changes to silicon rich silicon oxide layer---from silica and changes to silicon layer again;
Wherein, "/" represent two-layer between interface; N represents electron type (N-shaped) semiconductor, and i-represents intrinsic semiconductor, and P-represents cavity type (P type) semiconductor; A-represents noncrystal, and μ c-represents crystallite.
Preferred version: described transition zone is two-layer, is respectively n-A-SiO xand i-A-SiO x, be n-A-SiO near one deck of N-shaped silicon wafer x.
Further preferably, the silicon atom density domination of described transition zone is at 2.2*10 22/ cm 3~ 5.0*10 22/ cm 3between; Refractive index (n) is 1.46≤n≤3.88; Thicknesses of layers (h) is 0.5nm≤h≤10nm; Band gap (Eg) controls between 1.12 ~ 9.0eV; Relative dielectric constant (ε) is 3.0≤ε≤11.7.
Preferred version, described n layer is selected from A-SiC, A-Si, crystallite or epi-Si 1-xge xmaterial one or more, epi-Si 1-xge xin 0≤x≤1, epi represents epitaxial growth monocrystalline.
Described hearth electrode preferably selects nesa coating or aluminium.
Technical scheme two of the present invention:
The preparation method of solar cell of the present invention, mainly comprises the preparation of transition zone, and the preparation of described transition zone comprises: first after N-shaped silicon wafer completes making herbs into wool, polishing and cleaning, then carries out front hydrogenation drying process; Then Si-rich silicon oxide film is made; Finally carry out rear hydrotreating process; Described front hydrogenation drying is treated to: the mist of use hydrogen and nitrogen or hydrogen are as process gas, wherein the hydrogen/nitrogen volume ratio of mist is between 0.1 ~ 100, the dry treatment temperature of front hydrogenation controls between 30 DEG C ~ 350 DEG C, and the front hydrogenation dry processing time is 1 ~ 60 minute; Described rear hydrotreating process is: the mist of use hydrogen and nitrogen or hydrogen are as process gas, and wherein the hydrogen/nitrogen volume ratio of mist is between 0.1 ~ 100; Rear hydrotreating temperatures is between 140 DEG C ~ ~ 1200 DEG C, and the rear hydrogenation treatment time is between 1 ~ 3600 second.
Preferred version: the preparation of described transition zone is specifically selected from one of following three kinds of methods:
The step of 1. planting method is: 1) use the mist of hydrogen and nitrogen or hydrogen to carry out front hydrogenation drying process: 2) using plasma strengthens the method for chemical vapour deposition (CVD) (PECVD) or high density plasma CVD (HD-PECVD), the mist of silane, phosphine, phosphine and hydrogen, hydrogen, carbon dioxide is used to be process gas, deposition i-A-SiO x, n-ASiO x, i-μ c-SiO x, n-μ c-SiO xfour kinds of dissimilar Si-rich silicon oxide film; 3), after completing Si-rich silicon oxide film making, the mist of hydrogen and nitrogen or hydrogen is used to carry out rear hydrogenation treatment;
The step of 2. planting method is: 1) use the mist of hydrogen and nitrogen or hydrogen to carry out front hydrogenation drying process; 2) using plasma strengthens the equipment of chemical vapour deposition (CVD) (PECVD) or high density plasma CVD (HD-PECVD), use hydrogen, oxygen, under plasma conditions, decompose hydrogen, oxygen, allow the surface of silicon chip under the condition of moisture, hydrogen ion, oxonium ion, carry out heat growth Si-rich silicon oxide film; 3), after completing Si-rich silicon oxide film making, the mist of hydrogen and nitrogen or hydrogen is used to carry out rear hydrogenation treatment;
The step of 3. planting method is: 1) use the mist of hydrogen and nitrogen or hydrogen to carry out front hydrogenation drying process; 2) adopt the thermal oxide growth method under wet oxygen condition, make Si-rich silicon oxide film; 3), after completing Si-rich silicon oxide film making, the mist of hydrogen and nitrogen or hydrogen is used to carry out rear hydrogenation treatment.
Further preferably, the concrete steps of 1. planting method are:
1) by complete making herbs into wool, polishing, cleaned after N-shaped silicon wafer do front hydrogenation drying process, use mist or the hydrogen of hydrogen and nitrogen, mist H 2/ N 2volume ratio in 0.1 ~ 100 scope, dry silicon chip under hydrogen atmosphere; Hydrogenation baking temperature is between 30 DEG C ~ 350 DEG C, and the time is 1 ~ 60 minute;
2) PECVD or HD-PECVD depositing operation is adopted to make i-A-SiO x, n-ASiO x, i-μ c-SiO x, n-μ c-SiO xfour kinds of dissimilar Si-rich silicon oxide film; PECVD or HD-PECVD equipment radio freqnency generator frequency range used is 13 ~ 67MHz; Wherein, i-A-SiO is made xduring film, use silane, carbon dioxide, hydrogen as process gas, technological temperature is 180 ~ 220 DEG C, and radio frequency power density is at 5 ~ 50mW/cm 2, operation pressure is 0.2 ~ 2.0mbar, oxidation ratio (CO 2/ SiH 4flow-rate ratio)≤5, hydrogen dilution rate (H 2/ SiH 4flow-rate ratio) control in 0.5 ~ 5 scope; Make n-A-SiO xduring film, use the mist of silane, phosphine or phosphine and hydrogen, carbon dioxide, hydrogen as process gas, technological temperature is 180 ~ 220 DEG C, and radio frequency power density is at 5 ~ 50mW/cm 2, operation pressure is 0.2 ~ 2.0mbar, doping ratio (PH 3/ SiH 4flow-rate ratio)≤10%, oxidation ratio (CO 2/ SiH 4flow-rate ratio)≤5, hydrogen dilution rate (H 2/ SiH 4flow-rate ratio) control in 0.5 ~ 5 scope; Make i-μ c-SiO xduring film, use silane, carbon dioxide, hydrogen as process gas, technological temperature is 140 ~ 180 DEG C, and radio frequency power density is at 50 ~ 300mW/cm 2, operation pressure is 1.5 ~ 5mbar, oxidation ratio (CO 2/ SiH 4flow-rate ratio)≤5, hydrogen dilution rate (H 2/ SiH 4flow-rate ratio) control in 5 ~ 150 scopes; Make n-μ c-SiO xduring film, use the mist of silane, phosphine, phosphine and hydrogen, carbon dioxide, hydrogen as process gas, technological temperature is 140 ~ 180 DEG C, and radio frequency power density is at 50 ~ 300mW/cm 2, operation pressure is 1.5 ~ 5.0mbar, doping ratio (PH 3/ SiH 4flow-rate ratio)≤10%, oxidation ratio (CO 2/ SiH 4flow-rate ratio)≤5, hydrogen dilution rate (H 2/ SiH 4flow-rate ratio) control in 5 ~ 150 scopes;
3) after completing Si-rich silicon oxide film making, carry out rear hydrogenation treatment, rear hydrogenation treatment uses mist or the hydrogen of hydrogen and nitrogen, mist H 2/ N 2volume ratio controls within the scope of 0.1 ~ 100 times; Temperature controls at 140 DEG C ~ 220 DEG C, and the processing time controlled at 1 ~ 200 second.
Further preferably, the concrete steps of 2. planting method are:
1) by complete making herbs into wool, polishing, cleaned after N-shaped silicon wafer do front hydrogenation drying process, use mist or the hydrogen of hydrogen and nitrogen, mist H 2/ N 2volume ratio in 0.1 ~ 100 scope, dry silicon chip under hydrogen atmosphere; Hydrogenation baking temperature is between 30 DEG C ~ 350 DEG C, and the time is 1 ~ 60 minute.
2) the hot growth pattern under using plasma condition prepares intrinsic Si-rich silicon oxide film (i-A-SiO x), silicon wafer substrate temperature is 140 ~ 350 DEG C, and operation pressure is 0.2 ~ 5mbar, radio frequency power density 0 ~ 300mW/cm 2, the process gas of use is oxygen (O 2), hydrogen (H 2); H 2/ O 2flow proportional is 0 ~ 2.
3) after completing the growth of rich and honour silicon oxide film, carry out rear hydrogenation treatment, use mist or the hydrogen of hydrogen and nitrogen, mist H 2/ N 2volume ratio controls within the scope of 0.1 ~ 100 times; Hydrogenation temperature is between 140 ~ 350 DEG C, and the processing time controlled at 1 ~ 200 second.
Further preferably, the concrete steps of 3. planting method are:
1) by complete making herbs into wool, polishing, cleaned after N-shaped silicon wafer do front hydrogenation drying process, use mist or the hydrogen of hydrogen and nitrogen, mist H 2/ N 2volume ratio controls within the scope of 0.1 ~ 100 times, dry silicon chip under hydrogen atmosphere; Hydrogenation baking temperature is between 30 DEG C ~ 350 DEG C, and the time is 1 ~ 60 minute.
2) the hot growth pattern under wet oxygen condition is adopted to prepare intrinsic Si-rich silicon oxide film (i-A-SiO x); Technological temperature is 150 ~ 1200 DEG C, and operation pressure is 0.1 ~ 100mbar; Use ultra-pure water and oxygen (O 2) as reactant, ultra-pure water specification is: at 25 DEG C, resistivity>=18M Ω * cm; H 2o (water vapour)/O 2flow proportional is 0 ~ 1.
3) after completing the growth of rich and honour silicon oxide film, then carry out rear hydrogenation treatment, use the mist of hydrogen or hydrogen and nitrogen; Hydrogenation temperature is between 140 ~ 1200 DEG C, and the processing time controlled at 1 ~ 60 minute.
Below the present invention be further explained and illustrate:
The one of the crystal silicon and carborundum films compound unijunction PIN solar battery structure above with transition zone specifically forms:
Hearth electrode/n layer/N-shaped gradient μ c or A-SiO x/ N-shaped silicon wafer/N-shaped gradient μ c or A-SiO x/ i-μ c-SiC/i – A – SiC/p-A – SiC/TCO/ antireflective coating; Wherein " gradient " refers to: by regulating silica (SiO x) oxygen ratio x value (0≤x≤2) from 2 progressively graded to 0, and silica (SiO x) then change to graded oxidation silicon layer from silica and change to silicon layer again.
Transition zone recited above can be one or more layers, namely from the rich and honour silica of amorphous state (amorphous) intrinsic, the rich and honour silica of crystallite state intrinsic, N-shaped doped amorphous (amorphous) silicon rich silicon oxide, N-shaped doped microcrystalline state silicon rich silicon oxide, can choose one or more arbitrarily; The position of transition zone can be that the incident light side (front) of crystal silicon chip or the back side or two sides exist simultaneously.
Described transition zone is silicon rich silicon oxide (silicon rich silicon dioxide SiO x) material, be divided into the silicon rich silicon oxide material of plain intrinsic silicon rich silicon oxide material or N-shaped doping.The impurity gas making N-shaped silicon rich silicon oxide material is phosphine.
Silicon wafer described in described structure can be monocrystalline silicon piece or polysilicon chip above.
Compared with prior art, advantage of the present invention is:
1, solar cell of the present invention has transition zone, can realize:
1) defect state at interface is reduced; Reach good passivation effect;
2) prevent from occurring epitaxial growth in the subsequent thin film depositing operation in silicon wafer front;
3) diffusion that is nonmetal between different rete, impurity metal ion is stopped; Ensure the tunnelling effect to electronics simultaneously;
4) by regulating the refractive index of the transition zone in front or the back side, strengthen falling into light effect to promote light utilization efficiency;
5) by regulating the oxidation ratio of silicon rich silicon oxide, the leakage current under silicon wafer boundary condition and parasitic capacitance is reduced.
2, preparation method of the present invention carries out hydrogenation drying process after N-shaped silicon wafer completes making herbs into wool, polishing and cleaning, to improve quality and the stability of silicon chip surface further; Hydrogenation treatment is carried out, to reduce the defect at this rete interface and to keep the stability of rete after making Si-rich silicon oxide film.
Accompanying drawing explanation
Fig. 1 is the crystal silicon of employing transition zone of the present invention and the structure chart of silicon thin film compound unijunction PIN solar cell;
Fig. 2 is the crystal silicon of employing transition zone of the present invention and the process chart of silicon thin film compound unijunction PIN solar cell;
Fig. 3 is the plasma-deposited Si-rich silicon oxide film schematic diagram of one of the process of making transition zone of the present invention;
Fig. 4 is thermal oxide growth Si-rich silicon oxide film schematic diagram under the condition of plasma of one of the process of making transition zone of the present invention;
Fig. 5 is that heat under water vapour and oxygen simultaneous implantation to the wet oxygen condition of chamber is grown Si-rich silicon oxide film schematic diagram by wet oxygen generator by water vapour;
Fig. 6 is that under water vapour is independently injected into the wet oxygen condition of chamber by steam generator, heat grows Si-rich silicon oxide 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-shaped silicon wafer; 9---plasma; 10---vacuum system; 11---process gas air supply system; 12---wet oxygen generator; 13---steam generator; 14---oxygen system.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further explained
Embodiment 1
There is crystal silicon and the carborundum films compound unijunction PIN solar cell of transition layer structure, be selected from one of following solar battery structure:
1) hearth electrode/n layer/N-shaped silicon wafer/transition zone/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating;
2) hearth electrode/n layer/N-shaped silicon wafer/transition zone/i-μ c-SiC layer/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating;
3) hearth electrode/n layer/N-shaped silicon wafer/transition zone/p-A-SiC layer/TCO/ antireflective coating;
4) hearth electrode/n layer/transition zone/N-shaped silicon wafer/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating;
5) hearth electrode/n layer/transition zone/N-shaped silicon wafer/i-μ c-SiC layer/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating;
6) hearth electrode/n layer/transition zone/N-shaped silicon wafer/p-A-SiC layer/TCO/ antireflective coating;
7) hearth electrode/n layer/transition zone/N-shaped silicon wafer/transition zone/i-A-SiC layer/p-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating;
8) hearth electrode/n layer/transition zone/N-shaped silicon wafer/transition zone/i-μ c-SiC layer/i-A-SiC layer/p-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating;
9) hearth electrode/n layer/transition zone/N-shaped silicon wafer/transition zone/p-A-SiC layer/TCO/ antireflective coating;
Described transition zone is one deck or multilayer, and wherein one deck is silicon rich silicon oxide layer arbitrarily; Described silicon rich silicon oxide layer is selected from i-A-SiO x, i-μ c-SiO x, n-A-SiO x, n-μ c-SiO xin any one, wherein 0≤x≤2; Or described silicon rich silicon oxide layer is selected from N-shaped gradient μ c-SiO xwith N-shaped gradient A-SiO x, wherein 0≤x≤2, described " gradient " refers to: by changing x value in silicon rich silicon oxide, from 2, progressively graded is to 0, and silica then---changes to silicon rich silicon oxide layer---from silica and changes to silicon layer again;
Wherein, "/" represent two-layer between interface; N represents electron type (N-shaped) semiconductor, and i-represents intrinsic semiconductor, and P-represents cavity type (P type) semiconductor; A-represents noncrystal, and μ c-represents crystallite.
Described n layer is selected from A-SiC, A-Si, crystallite or epi-Si 1-xge xmaterial one or more, epi-Si 1- xge xin 0≤x≤1, epi represents epitaxial growth monocrystalline.
Described hearth electrode preferably selects nesa coating or aluminium.
As shown in Figure 1, transition zone described in the present embodiment is two-layer, is respectively n-A-SiO xand i-A-SiO x, be n-A-SiO near one deck of N-shaped silicon wafer x.
Embodiment 2
The manufacture method of described transition zone, as shown in Figure 2, comprises following methods:
The first: N-shaped silicon wafer is tentatively cleaned, chemical making herbs into wool, after chemistry or mechanical twin polishing, N-shaped silicon wafer is cleaned again, silicon chip after cleaned is done front hydrogenation drying process, the mode of process is: delivered to by silicon chip and have in the equipment of airtight chamber, emptying air to chamber pressure is less than or equal to (≤) 1Pascal; Chamber temp controls, between 30 DEG C ~ 350 DEG C, to pass into the mist of hydrogen or hydrogen and nitrogen; Dry silicon chip under hydrogen atmosphere.The purity of hydrogen and nitrogen is more than or equal to (>=) 99.99%; According to mist, the volume ratio of hydrogen and nitrogen is 0.1 ~ 100 times; Hydrogenation drying time is 1 ~ 60 minute.Silicon chip after over hydrogenation drying process is sent into PECVD (Plasma Enhanced Chemical Vapor Deposition) or HD-PECVD (High Density-Plasma Enhanced Chemical Vapor Deposition) equipment, adopts PECVD, HD-PECVD depositing operation to make Si-rich silicon oxide film; Radio frequency range is 13 ~ 67MHz.The Si-rich silicon oxide film dissimilar to i-A-SiOx, n-ASiOx, i-μ c-SiOx, n-μ c-SiOx tetra-kinds, its technological process is as following table:
After completing rich and honour silicon oxide film deposition, carry out rear hydrogenation treatment with PECVD or HD-PECVD equipment: the mist passing into hydrogen or hydrogen and nitrogen volume ratio 0.1 ~ 100, temperature controls at 140 DEG C ~ 220 DEG C, and the processing time controlled at 1 ~ 200 second.
The second: N-shaped silicon wafer is tentatively cleaned, chemical making herbs into wool, after chemistry or mechanical twin polishing, N-shaped silicon wafer is cleaned again, silicon chip after cleaned is done front hydrogenation drying process, the mode of process is: delivered to by silicon chip and have in the equipment of airtight chamber, emptying air to chamber pressure is less than or equal to (≤) 1Pascal; Chamber temp controls, between 30 DEG C ~ 350 DEG C, to pass into the mist of hydrogen or hydrogen and nitrogen; Dry silicon chip under hydrogen atmosphere.The purity of hydrogen and nitrogen is more than or equal to (>=) 99.99%; According to mist, the volume ratio of hydrogen and nitrogen is 0.1 ~ 100 times; Hydrogenation drying time is 1 ~ 60 minute.Hot growth pattern under using plasma condition prepares intrinsic Si-rich silicon oxide film (i-A-SiO x).Its preparation condition is: silicon wafer substrate temperature is 150 ~ 350 DEG C, and operation pressure is 0.2 ~ 5mbar, radio frequency power density 0 ~ 300mW/cm2, and the process gas of use is oxygen (O2), hydrogen (H2); H2/O2 flow proportional is 0 ~ 2;
After completing the growth of rich and honour silicon oxide film, then carry out rear hydrogenation treatment with PECVD.Pass into the mist of hydrogen or hydrogen and nitrogen, mist H 2/ N 2volume ratio controls within the scope of 0.1 ~ 100 times, and temperature controls at 140 DEG C ~ 220 DEG C, and the processing time controlled at 1 ~ 200 second.
The third: N-shaped silicon wafer is tentatively cleaned, chemical making herbs into wool, after chemistry or mechanical twin polishing, N-shaped silicon wafer is cleaned again, silicon chip after cleaned is done front hydrogenation drying process, the mode of process is: delivered to by silicon chip and have in the equipment of airtight chamber, emptying air to chamber pressure is less than or equal to (≤) 1Pascal; Chamber temp controls, between 30 DEG C ~ 350 DEG C, to pass into the mist of hydrogen or hydrogen and nitrogen; Dry silicon chip under hydrogen atmosphere.The purity of hydrogen and nitrogen is more than or equal to (>=) 99.99%; According to mist, the volume ratio of hydrogen and nitrogen is 0.1 ~ 100 times; Hydrogenation drying time is 1 ~ 60 minute.The hot growth pattern under wet oxygen condition is adopted to prepare intrinsic Si-rich silicon oxide film (i-A-SiO x).Its preparation condition is: silicon wafer substrate temperature is 150 ~ 1200 DEG C, and operation pressure is 0.1 ~ 100mbar, the ultra-pure water (Deionized water) of use and oxygen (O 2); Ultra-pure water specification is: at 25 DEG C, resistivity>=18M Ω * cm, injects reaction chamber in the form of water vapour, and injecting water temperature is 50 ~ 110 DEG C; H 2o (water vapour)/O 2flow proportional is 0 ~ 1.The loading mode of water vapour can be by wet oxygen generator by water vapour and oxygen simultaneous implantation to chamber, also can be independently be injected into chamber by steam generator, as accompanying drawing illustrates shown in middle Fig. 5-6.
After completing the growth of rich and honour silicon oxide film, reusable heat growth furnace/equipment carries out rear hydrogenation treatment.Pass into the mist of hydrogen or hydrogen and nitrogen, mist H 2/ N 2volume ratio controls within the scope of 0.1 ~ 100 times, and temperature controls at 140 DEG C ~ 1200 DEG C, and the processing time controlled at 1 ~ 60 minute.
Adopt any one method in above three kinds of methods to obtain silicon rich silicon oxide transition zone, and keep the stability of this layer material by the defect that front hydrogenation is dry, rear hydrogenation process reduces oxide interface.

Claims (10)

1. there is crystal silicon and the carborundum films compound unijunction PIN solar cell of transition layer structure, it is characterized in that, be selected from one of following solar battery structure:
1) hearth electrode/n layer/N-shaped silicon wafer/transition zone/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating;
2) hearth electrode/n layer/N-shaped silicon wafer/transition zone/i-μ c-SiC layer/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating;
3) hearth electrode/n layer/N-shaped silicon wafer/transition zone/p-A-SiC layer/TCO/ antireflective coating;
4) hearth electrode/n layer/transition zone/N-shaped silicon wafer/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating;
5) hearth electrode/n layer/transition zone/N-shaped silicon wafer/i-μ c-SiC layer/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating;
6) hearth electrode/n layer/transition zone/N-shaped silicon wafer/p-A-SiC layer/TCO/ antireflective coating;
7) hearth electrode/n layer/transition zone/N-shaped silicon wafer/transition zone/i-A-SiC layer/p-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating;
8) hearth electrode/n layer/transition zone/N-shaped silicon wafer/transition zone/i-μ c-SiC layer/i-A-SiC layer/p-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating;
9) hearth electrode/n layer/transition zone/N-shaped silicon wafer/transition zone/p-A-SiC layer/TCO/ antireflective coating;
Described transition zone is one deck or multilayer, and wherein one deck is silicon rich silicon oxide layer arbitrarily; Described silicon rich silicon oxide layer is selected from i-A-SiO x, i-μ c-SiO x, n-A-SiO x, n-μ c-SiO xin any one, wherein 0≤x≤2; Or described silicon rich silicon oxide layer is selected from N-shaped gradient μ c-SiO xwith N-shaped gradient A-SiO x, wherein 0≤x≤2, described " gradient " refers to: by changing x value in silicon rich silicon oxide, from 2, progressively graded is to 0, and silica then---changes to silicon rich silicon oxide layer---from silica and changes to silicon layer again;
Wherein, "/" represent two-layer between interface; N represents electron type (N-shaped) semiconductor, and i-represents intrinsic semiconductor, and P-represents cavity type (P type) semiconductor; A-represents noncrystal, and μ c-represents crystallite.
2. solar cell according to claim 1, it is characterized in that, described transition zone is two-layer, is respectively n-A-SiO xand i-A-SiO x, be n-A-SiO near one deck of N-shaped silicon wafer x.
3. solar cell according to claim 1, it is characterized in that, the silicon atom density domination of described transition zone is at 2.2*10 22/ cm 3~ 5.0*10 22/ cm 3between; Refractive index (n) is 1.46≤n≤3.88; Thicknesses of layers (h) is 0.5nm≤h≤10nm; Band gap (Eg) controls 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, described n layer is selected from A-SiC, A-Si, crystallite or epi-Si 1-xge xmaterial one or more, epi-Si 1-xge xin 0≤x≤1, epi represents epitaxial growth monocrystalline.
5. solar cell according to claim 1, it is characterized in that, described hearth electrode selects nesa coating or aluminium.
6. the preparation method of the described solar cell of one of claim 1-5, is characterized in that, mainly comprises the preparation of transition zone, and the preparation of described transition zone comprises: first after N-shaped silicon wafer completes making herbs into wool, polishing and cleaning, then carries out front hydrogenation drying process; Then Si-rich silicon oxide film is made; Finally carry out rear hydrotreating process;
Described front hydrogenation drying is treated to: the mist of use hydrogen and nitrogen or hydrogen are as process gas, wherein the hydrogen/nitrogen volume ratio of mist is between 0.1 ~ 100, the dry treatment temperature of front hydrogenation controls between 30 DEG C ~ 350 DEG C, and the front hydrogenation dry processing time is 1 ~ 60 minute;
Described rear hydrotreating process is: the mist of use hydrogen and nitrogen or hydrogen are as process gas, and wherein the hydrogen/nitrogen volume ratio of mist is between 0.1 ~ 100; Rear hydrotreating temperatures is between 140 DEG C ~ ~ 1200 DEG C, and the rear hydrogenation treatment time is between 1 ~ 3600 second.
7. the preparation method of solar cell according to claim 6, it is characterized in that, the preparation of described transition zone is specifically selected from one of following three kinds of methods:
The step of 1. planting method is: 1) use the mist of hydrogen and nitrogen or hydrogen to carry out front hydrogenation drying process: 2) using plasma strengthens the method for chemical vapour deposition (CVD) (PECVD) or high density plasma CVD (HD-PECVD), the mist of silane, phosphine, phosphine and hydrogen, hydrogen, carbon dioxide is used to be process gas, deposition i-A-SiO x, n-ASiO x, i-μ c-SiO x, n-μ c-SiO xfour kinds of dissimilar Si-rich silicon oxide film; 3), after completing Si-rich silicon oxide film making, the mist of hydrogen and nitrogen or hydrogen is used to carry out rear hydrogenation treatment;
The step of 2. planting method is: 1) use the mist of hydrogen and nitrogen or hydrogen to carry out front hydrogenation drying process; 2) using plasma strengthens the equipment of chemical vapour deposition (CVD) (PECVD) or high density plasma CVD (HD-PECVD), use hydrogen, oxygen, under plasma conditions, decompose hydrogen, oxygen, allow the surface of silicon chip under the condition of moisture, hydrogen ion, oxonium ion, carry out heat growth Si-rich silicon oxide film; 3), after completing Si-rich silicon oxide film making, the mist of hydrogen and nitrogen or hydrogen is used to carry out rear hydrogenation treatment;
The step of 3. planting method is: 1) use the mist of hydrogen and nitrogen or hydrogen to carry out front hydrogenation drying process; 2) adopt the thermal oxide growth method under wet oxygen condition, make Si-rich silicon oxide film; 3), after completing Si-rich silicon oxide film making, the mist of hydrogen and nitrogen or hydrogen is used to carry out rear hydrogenation treatment.
8. the preparation method of solar cell according to claim 7, it is characterized in that, the concrete steps of 1. planting method are:
1) by complete making herbs into wool, polishing, cleaned after N-shaped silicon wafer do front hydrogenation drying process, use mist or the hydrogen of hydrogen and nitrogen, mist H 2/ N 2volume ratio in 0.1 ~ 100 scope, dry silicon chip under hydrogen atmosphere; Hydrogenation baking temperature is between 30 DEG C ~ 350 DEG C, and the time is 1 ~ 60 minute;
2) PECVD or HD-PECVD depositing operation is adopted to make i-A-SiO x, n-ASiO x, i-μ c-SiO x, n-μ c-SiO xfour kinds of dissimilar Si-rich silicon oxide film; PECVD or HD-PECVD equipment radio freqnency generator frequency range used is 13 ~ 67MHz; Wherein, i-A-SiO is made xduring film, use silane, carbon dioxide, hydrogen as process gas, technological temperature is 180 ~ 220 DEG C, and radio frequency power density is at 5 ~ 50mW/cm 2, operation pressure is 0.2 ~ 2.0mbar, oxidation ratio (CO 2/ SiH 4flow-rate ratio)≤5, hydrogen dilution rate (H 2/ SiH 4flow-rate ratio) control in 0.5 ~ 5 scope; Make n-A-SiO xduring film, use the mist of silane, phosphine or phosphine and hydrogen, carbon dioxide, hydrogen as process gas, technological temperature is 180 ~ 220 DEG C, and radio frequency power density is at 5 ~ 50mW/cm 2, operation pressure is 0.2 ~ 2.0mbar, doping ratio (PH 3/ SiH 4flow-rate ratio)≤10%, oxidation ratio (CO 2/ SiH 4flow-rate ratio)≤5, hydrogen dilution rate (H 2/ SiH 4flow-rate ratio) control in 0.5 ~ 5 scope; Make i-μ c-SiO xduring film, use silane, carbon dioxide, hydrogen as process gas, technological temperature is 140 ~ 180 DEG C, and radio frequency power density is at 50 ~ 300mW/cm 2, operation pressure is 1.5 ~ 5mbar, oxidation ratio (CO 2/ SiH 4flow-rate ratio)≤5, hydrogen dilution rate (H 2/ SiH 4flow-rate ratio) control in 5 ~ 150 scopes; Make n-μ c-SiO xduring film, use the mist of silane, phosphine, phosphine and hydrogen, carbon dioxide, hydrogen as process gas, technological temperature is 140 ~ 180 DEG C, and radio frequency power density is at 50 ~ 300mW/cm 2, operation pressure is 1.5 ~ 5.0mbar, doping ratio (PH 3/ SiH 4flow-rate ratio)≤10%, oxidation ratio (CO 2/ SiH 4flow-rate ratio)≤5, hydrogen dilution rate (H 2/ SiH 4flow-rate ratio) control in 5 ~ 150 scopes;
3) after completing Si-rich silicon oxide film making, carry out rear hydrogenation treatment, rear hydrogenation treatment uses mist or the hydrogen of hydrogen and nitrogen, mist H 2/ N 2volume ratio controls within the scope of 0.1 ~ 100 times; Temperature controls at 140 DEG C ~ 220 DEG C, and the processing time controlled at 1 ~ 200 second.
9. the preparation method of solar cell according to claim 7, it is characterized in that, the concrete steps of 2. planting method are:
1) by complete making herbs into wool, polishing, cleaned after N-shaped silicon wafer do front hydrogenation drying process, use mist or the hydrogen of hydrogen and nitrogen, mist H 2/ N 2volume ratio in 0.1 ~ 100 scope, dry silicon chip under hydrogen atmosphere; Hydrogenation baking temperature is between 30 DEG C ~ 350 DEG C, and the time is 1 ~ 60 minute.
2) the hot growth pattern under using plasma condition prepares intrinsic Si-rich silicon oxide film (i-A-SiO x), silicon wafer substrate temperature is 140 ~ 350 DEG C, and operation pressure is 0.2 ~ 5mbar, radio frequency power density 0 ~ 300mW/cm 2, the process gas of use is oxygen (O 2), hydrogen (H 2); H 2/ O 2flow proportional is 0 ~ 2.
3) after completing the growth of rich and honour silicon oxide film, carry out rear hydrogenation treatment, use mist or the hydrogen of hydrogen and nitrogen, mist H 2/ N 2volume ratio controls within the scope of 0.1 ~ 100 times; Hydrogenation temperature is between 140 ~ 350 DEG C, and the processing time controlled at 1 ~ 200 second.
10. the preparation method of solar cell according to claim 7, it is characterized in that, the concrete steps of 3. planting method are:
1) by complete making herbs into wool, polishing, cleaned after N-shaped silicon wafer do front hydrogenation drying process, use mist or the hydrogen of hydrogen and nitrogen, mist H 2/ N 2volume ratio controls within the scope of 0.1 ~ 100 times, dry silicon chip under hydrogen atmosphere; Hydrogenation baking temperature is between 30 DEG C ~ 350 DEG C, and the time is 1 ~ 60 minute.
2) the hot growth pattern under wet oxygen condition is adopted to prepare intrinsic Si-rich silicon oxide film (i-A-SiO x); Technological temperature is 150 ~ 1200 DEG C, and operation pressure is 0.1 ~ 100mbar; Use ultra-pure water and oxygen (O 2) as reactant, ultra-pure water specification is: at 25 DEG C, resistivity>=18M Ω * cm; H 2o (water vapour)/O 2flow proportional is 0 ~ 1.
3) after completing the growth of rich and honour silicon oxide film, then carry out rear hydrogenation treatment, use the mist of hydrogen or hydrogen and nitrogen; Hydrogenation temperature is between 140 ~ 1200 DEG C, and the processing time controlled at 1 ~ 60 minute.
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