CN104505419B - 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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CN104505419B
CN104505419B CN201410699068.3A CN201410699068A CN104505419B CN 104505419 B CN104505419 B CN 104505419B CN 201410699068 A CN201410699068 A CN 201410699068A CN 104505419 B CN104505419 B CN 104505419B
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何湘衡
李廷凯
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HUNAN GONGCHUANG GROUP CO Ltd
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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

Crystal silicon and the carborundum films compound unijunction PIN solaode with transition zone and preparation method thereof
Technical field
The present invention relates to crystal silicon and film composite type solaode, particularly there is crystal silicon and the carbon of transition layer structure The structure design of SiClx film composite type unijunction PIN solaode and manufacture method thereof.
Background technology
Since French scientist AE.Becquerel found after opto-electronic conversion phenomenon in 1839,1883 years the One solaode with semiconductor selenium as substrate is born.Nineteen forty-six RuSSell obtains first solar energy The patent (US.2,402,662) of battery, its photoelectric transformation efficiency is only 1%.Until 1954, Bei Ershi The research testing room is just found that the silica-base material of doping has high photoelectric transformation efficiency.This research is for the modern times too Sun can be laid a good foundation by battery industry.In 1958, Haffman Utilities Electric Co. of the U.S. was the satellite dress of the U.S. Having gone up first piece of solar panel, its photoelectric transformation efficiency is about 6%.From this, monocrystal silicon and polycrystalline are silica-based The solaode research of sheet and production have had quick development, the yield of solaode in 2006 to reach 2000 megawatts, the photoelectric transformation efficiency of monocrystaline silicon solar cell reaches 24.7%, and commercial product reaches 22. 7%, 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 high efficiency III-V of first GaAs base Race's solaode.Owing to preparing key technology MOCVD (the Organometallic Chemistry gas of III-V race's thin-film material Deposition mutually) until about 1980 are just successfully researched and developed, the applied solar energy Battery Company of the U.S. was in 1988 It is successfully applied to this technology and prepares III-V race's solaode of the GaAs base that photoelectric transformation efficiency is 17%. Thereafter, the doping techniques of III-V race's material with GaAs substrate, the preparation skill of plural serial stage solaode Art has obtained research and development widely, and its photoelectric transformation efficiency reached 19% in 1993, within 2000, reaches 24%, within 2002, reach 26%, within 2005, reach 28%, within 2007, reach 30%.2007, the U.S. two Big III-V solaode company of race Emcore and SpectroLab produces high efficiency III-V race solar energy business Product, its photoelectric conversion rate reaches 38%, and this two company occupies the 9 of III-V race's solaode market, the whole world 5%, American National Energy Research Institute announces that they successfully have developed its photoelectric transformation efficiency and are up to more than 50% III-V race's solaode of level series connection.Owing to the substrate of this kind of solaode is expensive, equipment and process costs Height, is mainly used in the fields such as Aeronautics and Astronautics, national defence and military project.
External solaode research and production, substantially can be divided into three phases, i.e. have three generations's solar-electricity Pond.
First generation solaode, with the solaode of the silica-based single constituent element of monocrystal silicon and polycrystalline be substantially Represent.Only pay attention to improve photoelectric transformation efficiency and large-scale production, also exist high energy consumption, labour intensive, The problems such as and high cost unfriendly to environment, its price producing electricity is about 5～6 times of coal electricity；Until 2007 Year, the yield of first generation solaode still accounts for the 89% of global solar battery total amount, and expert is it is expected that first To progressively be eliminated after 10 years for solaode and become history.
Second filial generation solaode is thin-film solar cells, is the new technique grown up in recent years, its note Overweighting the energy consumption and process costs reduced in production process, brainstrust is called green photovoltaic industry.With monocrystal silicon Comparing with polysilicon solar cell, the consumption of its thin film HIGH-PURITY SILICON is its 1%, meanwhile, low-temperature plasma Enhanced chemical vapor deposition deposition technique, electroplating technology, printing technology is extensively studied and is applied to thin film The production of solaode.Owing to using the glass of low cost, rustless steel thin slice, macromolecule substrate is as substrate Material, greatly reduces production cost, and is conducive to large-scale production.The thin film that success has been researched and developed the most is too The material of sun energy battery is: CdTe, its photoelectric transformation efficiency is 16.5%, and commercial product is about 7%；Cul NSe, its photoelectric transformation efficiency is 19.5%, and commercial product is 11%；Non-crystalline silicon and microcrystal silicon, its photoelectricity turns Changing efficiency is 8.3～15%, and commercial product is 7～13.3%, in recent years, due to the film crystal of LCD TV The research and development of pipe, non-crystalline silicon and microcrystalline silicon film technology have had significant progress, and have been applied to the silica-base film sun Can battery.Brainstrust is it is expected that owing to thin-film solar cells has low cost, high efficiency, give birth on a large scale The ability produced, at following 5～10 years, the main flow becoming global solar battery was produced by thin-film solar cells Product.
Focus around thin-film solar cells research is, exploitation is efficient, low cost, long-life photovoltaic solar Can battery.They should have the feature that low cost, high efficiency, long-life, material source be abundant, nothing Poison, scientists relatively has an optimistic view of amorphous silicon thin-film solar cell.
The thin-film solar cells accounting for lion's share at present is non-crystal silicon solar cell, usually pin structure electricity Pond, Window layer is the P-type non-crystalline silicon of boron-doping, then one layer of unadulterated i layer of deposition, redeposited one layer of p-doped N-type non-crystalline silicon, and plated electrode.
Amorphous silicon battery typically uses PECVD (Plasma Enhanced Chemical Vapor Deposition Plasma enhanced chemical vapor deposition) method makes the gas such as high purity silane decompose deposition.This kind of system Make technique, can complete in multiple vacuum deposition chamber continuously aborning, to realize producing in enormous quantities.Due to heavy Integral Solution temperature is low, can deposit thin film on glass, corrosion resistant plate, ceramic wafer, flexible plastic sheet, it is easy to big Area metaplasia is produced, and cost is relatively low.The structure of the non-crystalline silicon based solar battery prepared on a glass substrate is: Gl Ass/TCO/p-a-SiC:H/i-a-Si:H/n-a-Si:H/Al, at the bottom of stainless steel lining, the amorphous of preparation is silica-based too The structure of sun energy battery is: SS/ZnO/n-a-Si:H/i-a-Si (Ge): H/p-na-Si:H/ITO/Al.
Improve the maximally effective approach of battery efficiency and be to try to improve the efficiency of light absorption of battery.To silica-base film Speech, using low bandgap material is inevitable approach.The low bandgap material used such as Uni-Solar company is a-SiGe (amorphous silicon germanium) alloy, their a-Si/a-SiGe/a-SiGe three-knot laminated battery, little area cells (0.25cm2) Efficiency reaches 15.2%, and stabilization efficiency reaches 13%, 900cm2Component efficiency reaches 11.4%, and stabilization efficiency reaches 10. 2%, product efficiency reaches 7%-8%.
Internationally recognized amorphous silicon/microcrystalline silicon tandem solaode is the next-generation technology of silicon-base thin-film battery, is real The important technology approach of existing high efficiency, low cost thin-film solar cells, is the industrialization direction that hull cell is new.20 The amorphous silicon/microcrystalline silicon tandem battery component sample efficiencies of 05 year Mitsubishi heavy industry and Zhong Yuan chemical company is respectively Reach 11.1% (40cm × 50cm) and 13.5% (91cm × 45cm).Japanese Sharp company in JIUYUE, 2007 realizes Amorphous silicon/microcrystalline silicon tandem solar cell industry metaplasia produces (25MW, efficiency 8%-8.5%), Europe Oerliko N (Ao Likang) company, U.S. AppliedMaterials (Applied Materials), the most just researching and developing Product-level non-crystalline silicon/micro- Crystal silicon battery key manufacture.
Domestic, Nankai University is with country " 15 ", Eleventh Five-Year Plan 973 project and Eleventh Five-Year Plan 863 project for depending on Torr, carries out microcrystalline silicon materials and the research of amorphous silicon/microcrystalline silicon tandem battery.Little area micro-crystalline silicon cell efficiency reaches 9. 36%, amorphous silicon/microcrystalline silicon tandem battery efficiency reaches 11.8%, and 10cm × 10cm component efficiency reaches 9.7%.Existing Just cooperate with Fujian Jun Shi energy company, carry out square meter level amorphous silicon/microcrystalline silicon tandem battery key equipment and an electricity The research and development of pond manufacturing technology.
Silicon-base thin-film battery mainly has three kinds of structures at present: unijunction or double junction non-crystal silicon with glass as substrate are electric Pond, the non-crystalline silicon with glass as substrate and microcrystal silicon binode battery, the non-crystalline silicon with rustless steel as substrate and amorphous Germanium-silicon alloy three junction battery.Owing to various products have the advantage of its uniqueness, in following period of time these three from now on Battery structure also can synchronized development.The long term growth direction of silicon-base thin-film battery is it will be apparent that except wanting fully Utilize the advantage of its uniqueness, mainly overcome the problem that product development, production and selling aspect exist.Silica-based thin Film battery to improve battery efficiency further, utilizes micro-crystalline silicon cell can enter one as the end battery of multijunction cell Step improves battery efficiency, reduces the photoinduction decline of battery.
The technological difficulties of micro-crystalline silicon cell industrialization at present are to realize the high speed deposition technology of microcrystal silicon and realize big face The uniformity of long-pending microcrystalline silicon film material.If the technical barrier in terms of microcrystal silicon large area high speed deposition is permissible Have been resolved in relatively short period of time, it is contemplated that in the near future, many knot electricity that non-crystalline silicon and microcrystal silicon combine Pond will become the major product of silicon-base thin-film battery.Non-crystalline silicon and microcrystal silicon multijunction cell can be deposited on glass lined , it is also possible to deposit on flexible substrates, either with glass still with the silica-base film of flexible substrate deposition at the end Battery can use amorphous and microcrystal silicon multijunction cell structure.
Current gyp silicon-based film solar cells is amorphous silicon thin-film solar cell.Due to non-crystalline silicon Energy gap is 1.7, and it is only capable of the absorbing wavelength solar energy at 400 500nm.Because of its solar energy conversion efficiency Low, about about 6%, the conversion ratio of this silicon-based film solar cells is to be improved.
The technology of the most several aspects and background material, someone mentions and uses the material of different energy gap right to expand The absorption spectrum of solar energy.But before patent No. ZL200910044772.4, not yet someone uses one Series, has six kinds of materials of different energy gap to constitute the thin-film solar cells of unijunction multilamellar PIN structural, and And also nobody develops the manufacturing technology of the thin-film solar cells preparing this unijunction multilamellar PIN structural, also Also nobody develops and prepares this high conversion silicon wafer and film composite type unijunction PIN solaode and system thereof Make method.
Patent No. ZL200910044772.4 the solaode of silica-based to monocrystal silicon and polycrystalline single constituent element with silica-based Thin-film solar cells combines, and proposes a kind of high conversion silicon wafer and film composite type unijunction PN, the PIN sun Energy battery and manufacture method thereof, described high conversion silicon wafer and film composite type unijunction PIN solaode tool There are higher conversion efficiency and excellent stability.The present invention is on the basis of patent No. ZL200910044772.4 On, add transition layer structure and propose its preparation process of this transition zone, efficiency can be obtained further Promote, and the commercial production with large-scale can be applied.
Summary of the invention
The present invention, on the basis of high conversion silicon wafer and film composite type unijunction PIN solar battery technology, takes Crystal silicon and carborundum films compound unijunction PIN structural, propose design structure and the manufacturer thereof of a transition zone Method, it is provided that there is the crystal silicon of transition zone and carborundum films compound unijunction PIN solaode and preparation thereof Method, described preparation method completes making herbs into wool at silicon chip, polish and clean after, hydrogenation dried before adding, with Time, after completing the technique of this transition zone, adding rear hydrogenation treatment mode, two kinds of methods are used for improving interface matter Amount and the stability of structure.Use this transition zone and have employed front hydrogenation dried and rear hydrotreated tool There are crystal silicon and the carborundum films composite battery of transition zone, on the basis of original, battery conversion efficiency can be carried High by more than 10%.
One of technical scheme:
There is crystal silicon and the carborundum films compound unijunction PIN solaode of transition layer structure, selected from following One of solar battery structure:
1) hearth electrode/n-layer/n-type silicon wafer/transition zone/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating；
2) hearth electrode/n-layer/n-type silicon wafer/transition zone/i-μ c-SiC layer/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective Film；
3) hearth electrode/n-layer/n-type silicon wafer/transition zone/p-A-SiC layer/TCO/ antireflective coating；
4) hearth electrode/n-layer/transition zone/n-type silicon wafer/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating；
5) hearth electrode/n-layer/transition zone/n-type silicon wafer/i-μ c-SiC layer/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective Film；
6) hearth electrode/n-layer/transition zone/n-type silicon wafer/p-A-SiC layer/TCO/ antireflective coating；
7) hearth electrode/n-layer/transition zone/n-type 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-type silicon wafer/transition zone/i-μ c-SiC layer/i-A-SiC layer/p-A-SiC layer/p-A-Si C layer/TCO/ antireflective coating；
9) hearth electrode/n-layer/transition zone/n-type silicon wafer/transition zone/p-A-SiC layer/TCO/ antireflective coating；
Described transition zone is one layer or multilamellar, and the most any one layer is silicon rich silicon oxide layer；Described 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 described silicon rich silicon oxide layer is selected from N-shaped gradient μ c-SiOxWith N-shaped gradient A-SiOx, wherein 0≤x≤2, institute State " gradient " to refer to: by change in silicon rich silicon oxide x value from 2 progressively graded to 0, silicon oxide then from Silicon oxide changes to silicon rich silicon oxide layer and changes to silicon layer again；
Wherein, "/" represents the interface between two-layer；N represents electron type (N-shaped) quasiconductor, and i-represents that intrinsic is partly led Body, P-represents cavity type (p-type) quasiconductor；A-represents noncrystal, and μ c-represents crystallite.
Preferred version: described transition zone is two-layer, respectively n-A-SiOxAnd i-A-SiOx, brilliant near n-type silicon One layer of sheet is n-A-SiOx。
Further preferably, the silicon atom density domination of described transition zone is at 2.2*1022/cm3～5.0*1022/cm3It Between；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-Si1-xGexMaterial is a kind of or several Kind, epi-Si1-xGexIn 0≤x≤1, epi represents epitaxial growth monocrystalline.
Described hearth electrode preferably selects nesa coating or aluminum.
The two of technical scheme:
The preparation method of solaode of the present invention, mainly includes the preparation of transition zone, the preparation of described transition zone Including: after first completing making herbs into wool at n-type silicon wafer, polishing and clean, then hydrogenation dried before carrying out；Then make Make Si-rich silicon oxide film；Finally carry out rear hydrotreating process；Before described, hydrogenation dried is: use hydrogen With the mixed gas of nitrogen or hydrogen as process gas, wherein the hydrogen/nitrogen volume ratio of mixed gas is 0.1 ～between 100, front hydrogenation dried temperature controls between 30 DEG C～350 DEG C, the front hydrogenation dried time is 1～60 minute；Described rear hydrotreating process is: use hydrogen and the mixed gas of nitrogen or hydrogen as place Reason gas, wherein the hydrogen/nitrogen volume ratio of mixed gas is between 0.1～100；Rear hydrotreating temperatures is 14 0 DEG C～～1200 DEG C between, the rear hydrogenation treatment time is between 1～3600 second.
Preferred version: the preparation of described transition zone is chosen in particular from one of following three kinds of methods:
The step 1. planting method is: before 1) using hydrogen and the mixed gas of nitrogen or hydrogen to carry out, hydrogenation is dry Dry process: 2) using plasma enhancing chemical gaseous phase deposition (PECVD) or high-density plasma chemical gas The method depositing (HD-PECVD) mutually, uses silane, phosphine, phosphine and the mixed gas of hydrogen, hydrogen Gas, carbon dioxide are process gas, deposit i-A-SiOx、n-ASiOx、i-μc-SiOx、n-μc-SiOxFour kinds are not Si-rich silicon oxide film with type；3) complete after Si-rich silicon oxide film makes, to use the mixed of hydrogen and nitrogen Close gas or hydrogen carries out rear hydrogenation treatment；
The step 2. planting method is: before 1) using hydrogen and the mixed gas of nitrogen or hydrogen to carry out, hydrogenation is dry Dry process；2) using plasma strengthens chemical gaseous phase deposition (PECVD) or high-density plasma chemical gas Deposit the equipment of (HD-PECVD) mutually, use hydrogen, oxygen, under plasma conditions, decompose hydrogen Gas, oxygen, allow the surface of silicon chip carry out thermally grown silicon rich silicon oxide under conditions of aqueous, hydrion, oxonium ion Thin film；3), after completing Si-rich silicon oxide film making, hydrogen and the mixed gas of nitrogen or hydrogen is used to carry out Rear hydrogenation treatment；
The step 3. planting method is: before 1) using hydrogen and the mixed gas of nitrogen or hydrogen to carry out, hydrogenation is dry Dry process；2) use the thermal oxide growth method under the conditions of wet oxygen, make Si-rich silicon oxide film；3) richness is completed After silicon silicon oxide film makes, hydrogen and the mixed gas of nitrogen or hydrogen is used to carry out rear hydrogenation treatment.
Further preferably, the concretely comprising the following steps of method is 1. planted:
1) by complete making herbs into wool, polishing, cleaned after n-type silicon wafer do before hydrogenation dried, use hydrogen and The mixed gas of nitrogen or hydrogen, mixed gas H2/N2Volume ratio is in the range of 0.1～100, under hydrogen atmosphere It is dried silicon chip；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 used to make i-A-SiOx、n-ASiOx、i-μc-SiOx、n-μc-SiOxFour kinds of different types of Si-rich silicon oxide film；Used by PECVD or HD-PECVD equipment Radio-frequency signal generator frequency range is 13～67MHz；Wherein, i-A-SiO is madexDuring thin film, use silane, two Carbonoxide, hydrogen are as process gas, and technological temperature is 180～220 DEG C, and radio frequency power density is 5～50mW/c m2, operation pressure is 0.2～2.0mbar, aoxidizes ratio (CO2/SiH4Flow-rate ratio)≤5, hydrogen dilution rate (H2/Si H4Flow-rate ratio) control in the range of 0.5～5；Make n-A-SiOxDuring thin film, use silane, phosphine or phosphorus Alkane and the mixed gas of hydrogen, carbon dioxide, hydrogen are 180～220 DEG C as process gas, technological temperature, penetrate Frequently power density is 5～50mW/cm2, operation pressure is 0.2～2.0mbar, doping ratio (PH3/SiH4Flow Than)≤10%, aoxidize ratio (CO2/SiH4Flow-rate ratio)≤5, hydrogen dilution rate (H2/SiH4Flow-rate ratio) control In the range of 0.5～5；Make i-μ c-SiOxDuring thin film, use silane, carbon dioxide, hydrogen as process gas, Technological temperature is 140～180 DEG C, and radio frequency power density is 50～300mW/cm2, operation pressure is 1.5～5mba R, aoxidizes ratio (CO2/SiH4Flow-rate ratio)≤5, hydrogen dilution rate (H2/SiH4Flow-rate ratio) control at 5～150 models In enclosing；Make n-μ c-SiOxDuring thin film, use silane, phosphine, phosphine and the mixed gas of hydrogen, titanium dioxide Carbon, hydrogen are as process gas, and technological temperature is 140～180 DEG C, and radio frequency power density is 50～300mW/cm2, operation pressure is 1.5～5.0mbar, doping ratio (PH3/SiH4Flow-rate ratio)≤10%, aoxidize ratio (CO2/ SiH4Flow-rate ratio)≤5, hydrogen dilution rate (H2/SiH4Flow-rate ratio) control in the range of 5～150；
3) after completing Si-rich silicon oxide film making, carrying out rear hydrogenation treatment, rear hydrogenation treatment uses hydrogen and nitrogen The mixed gas of gas or hydrogen, mixed gas H2/N2Volume ratio controls in the range of 0.1～100 times；Temperature control System is at 140 DEG C～220 DEG C, and the process time controlled at 1～200 second.
Further preferably, the concretely comprising the following steps of method is 2. planted:
1) by complete making herbs into wool, polishing, cleaned after n-type silicon wafer do before hydrogenation dried, use hydrogen With mixed gas or the hydrogen of nitrogen, mixed gas H2/N2Volume ratio is in the range of 0.1～100, at hydrogen atmosphere The driest silicon chip；Hydrogenation baking 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, radio frequency power density 0～300m W/cm2, the process gas of use is oxygen (O2), hydrogen (H2)；H2/O2Flow proportional is 0～2.
3), after completing rich and honour silicon oxide film growth, the mixed of rear hydrogenation treatment, use use hydrogen and nitrogen is carried out Close gas or hydrogen, mixed gas H2/N2Volume ratio controls in the range of 0.1～100 times；Hydrogenation temperature is 14 Between 0～350 DEG C, the process time controlled at 1～200 second.
Further preferably, the concretely comprising the following steps of method is 3. planted:
1) by complete making herbs into wool, polishing, cleaned after n-type silicon wafer do before hydrogenation dried, use use Hydrogen and the mixed gas of nitrogen or hydrogen, mixed gas H2/N2Volume ratio controls 0.1～100 times of scope In, under hydrogen atmosphere, it is dried silicon chip；Hydrogenation baking 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 wet oxygen is used to prepare intrinsic Si-rich silicon oxide film (i-A-SiOx)；Technique Temperature is 150～1200 DEG C, and operation pressure is 0.1～100mbar；Use ultra-pure water and oxygen (O2) as anti- The thing, ultra-pure water specification is answered to be: at 25 DEG C, resistivity >=18M Ω * cm；H2O (water vapour)/O2Flow proportional It is 0～1.
3) after completing rich and honour silicon oxide film growth, then carry out rear hydrogenation treatment, use hydrogen or hydrogen and nitrogen The mixed gas of gas；Hydrogenation temperature is between 140～1200 DEG C, and the process time controlled at 1～60 minute.
Below the present invention it is further explained and illustrates:
The crystal silicon with transition zone described above and the one of carborundum films compound unijunction PIN solar battery structure Particular make-up is:
Hearth electrode/n-layer/N-shaped gradient μ c or A-SiOx/ n-type silicon wafer/N-shaped gradient μ c or A-SiOx/i-μc-SiC/i A SiC/p-A SiC/TCO/ antireflective coating；Wherein " gradient " refers to: by regulation silicon oxide (SiOx) oxygen ratio Example x value (0≤x≤2) from 2 progressively graded to 0, and silicon oxide (SiOx) then change to ladder from silicon oxide Degree silicon oxide layer changes to silicon layer again.
Transition zone recited above can be one or more layers, i.e. can be from amorphous state (amorphous) intrinsic wealth and rank oxygen SiClx, crystallite state intrinsic wealth and rank silicon oxide, N-shaped doped amorphous (amorphous) silicon rich silicon oxide, N-shaped adulterate Crystallite state silicon rich silicon oxide arbitrarily chooses one or more；The position of transition zone can be the incident illumination one of crystal silicon chip Side (front) or the back side or two sides exist simultaneously.
Described transition zone is silicon rich silicon oxide (silicon rich silicon dioxide SiOx) material, it is divided into and undoping Intrinsic silicon rich silicon oxide material or N-shaped doping silicon rich silicon oxide material.Make N-shaped silicon rich silicon oxide material Impurity gas be phosphine.
Silicon wafer described in structure described above can be monocrystalline silicon piece or polysilicon chip.
Compared with prior art, present invention have an advantage that
1, solaode 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, in the subsequent thin film depositing operation in silicon wafer front, epitaxial growth occurs；
3) nonmetal, the diffusion of impurity metal ion between different film layer is stopped；Ensure that the tunnelling to electronics is imitated simultaneously Really；
4) by regulation front or the refractive index of the transition zone at 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 parasitism electricity are reduced Hold.
2, the preparation method of the present invention complete making herbs into wool at n-type silicon wafer, polish and clean after carry out hydrogenating and be dried place Reason, to improve quality and the stability of silicon chip surface further；Hydrogenate after making Si-rich silicon oxide film Process, to reduce the defect of this film bed boundary and to keep the stability of film layer.
Accompanying drawing explanation
Fig. 1 is crystal silicon and the silicon thin film compound unijunction PIN solaode of employing transition zone of the present invention Structure chart；
Fig. 2 is crystal silicon and the silicon thin film compound unijunction PIN solaode of employing transition zone of the present invention Process chart；
Fig. 3 is the plasma-deposited silicon rich silicon oxide of one of the process of making transition zone of the present invention 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 raw Long Si-rich silicon oxide film schematic diagram；
Fig. 5 is that water vapour passes through wet oxygen generator by hot under the conditions of water vapour and oxygen simultaneous implantation to the wet oxygen of chamber Growth Si-rich silicon oxide film schematic diagram；
Fig. 6 is that water vapour passes through steam generator and is independently injected into thermally grown Silicon-rich oxidation under the conditions of the wet oxygen of chamber Silicon thin film schematic diagram；
Wherein: 1 effusion meter；The upper electrode of 2a；2b bottom electrode；3 air inlet heads；4 is true Plenum chamber；5 heating systems；6 piezometers；7 radio-frequency power supplies；8 n-type silicon wafers；9— Plasma；10 vacuum systems；11 process gas air supply systems；12 wet oxygen generators；1 3 steam generators；14 oxygen systems.
Detailed description of the invention
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 solaode of transition layer structure, selected from following One of solar battery structure:
1) hearth electrode/n-layer/n-type silicon wafer/transition zone/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating；
2) hearth electrode/n-layer/n-type silicon wafer/transition zone/i-μ c-SiC layer/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective Film；
3) hearth electrode/n-layer/n-type silicon wafer/transition zone/p-A-SiC layer/TCO/ antireflective coating；
4) hearth electrode/n-layer/transition zone/n-type silicon wafer/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating；
5) hearth electrode/n-layer/transition zone/n-type silicon wafer/i-μ c-SiC layer/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective Film；
6) hearth electrode/n-layer/transition zone/n-type silicon wafer/p-A-SiC layer/TCO/ antireflective coating；
7) hearth electrode/n-layer/transition zone/n-type 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-type silicon wafer/transition zone/i-μ c-SiC layer/i-A-SiC layer/p-A-SiC layer/p-A-Si C layer/TCO/ antireflective coating；
9) hearth electrode/n-layer/transition zone/n-type silicon wafer/transition zone/p-A-SiC layer/TCO/ antireflective coating；
Described transition zone is one layer or multilamellar, and the most any one layer is silicon rich silicon oxide layer；Described 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 described silicon rich silicon oxide layer is selected from N-shaped gradient μ c-SiOxWith N-shaped gradient A-SiOx, wherein 0≤x≤2, institute State " gradient " to refer to: by change in silicon rich silicon oxide x value from 2 progressively graded to 0, silicon oxide then from Silicon oxide changes to silicon rich silicon oxide layer and changes to silicon layer again；
Wherein, "/" represents the interface between two-layer；N represents electron type (N-shaped) quasiconductor, and i-represents that intrinsic is partly led Body, P-represents cavity type (p-type) quasiconductor；A-represents noncrystal, and μ c-represents crystallite.
Described n-layer is selected from A-SiC, A-Si, crystallite or epi-Si1-xGexMaterial one or more, epi-Si1- xGexIn 0≤x≤1, epi represents epitaxial growth monocrystalline.
Described hearth electrode preferably selects nesa coating or aluminum.
As it is shown in figure 1, transition zone described in the present embodiment is two-layer, respectively n-A-SiOxAnd i-A-SiOx, close One layer of n-type silicon wafer is n-A-SiOx。
Embodiment 2
The manufacture method of described transition zone, as in figure 2 it is shown, include following methods:
The first: n-type silicon wafer is tentatively cleaned, chemistry making herbs into wool, chemically or mechanically twin polishing after, to n Type silicon wafer cleans again, and the silicon chip after cleaned is done front hydrogenation dried, and the mode of process is: by silicon Sheet is delivered to have in the equipment of airtight chamber, emptying air to chamber pressure less than or equal to (≤) 1Pascal；Chamber Temperature controls, between 30 DEG C～350 DEG C, to be passed through the mixed gas of hydrogen or hydrogen and nitrogen；Under hydrogen atmosphere It is dried silicon chip.The purity of hydrogen and nitrogen more than or equal to (>=) 99.99%；According to mixed gas, hydrogen and nitrogen The volume ratio of gas is 0.1～100 times；Hydrogenation drying time be 1～60 minute.By after over hydrogenation dried Silicon chip sends into PECVD (Plasma Enhanced Chemical Vapor Deposition) or HD-PECVD (High Density-Plasma Enhanced Chemical Vapor Deposition) equipment, uses PECVD, H D-PECVD depositing operation makes Si-rich silicon oxide film；Radio frequency range is 13～67MHz.To i-A-Si Ox, n-ASiOx, i-μ c-SiOx, tetra-kinds of different types of Si-rich silicon oxide film of n-μ c-SiOx, it makes work Skill condition such as following table:
After completing rich and honour silicon oxide film deposition, carry out rear hydrogenation treatment with PECVD or HD-PECVD equipment: Being passed through hydrogen or hydrogen and the mixed gas of nitrogen volume ratio 0.1～100, temperature controls at 140 DEG C～220 DEG C, The process time controlled at 1～200 second.
The second: n-type silicon wafer is tentatively cleaned, chemistry making herbs into wool, chemically or mechanically twin polishing after, right N-type silicon wafer cleans again, and the silicon chip after cleaned is done front hydrogenation dried, and the mode of process is: will Silicon chip is delivered to have in the equipment of airtight chamber, emptying air to chamber pressure less than or equal to (≤) 1Pascal；Chamber Room temperature controls, between 30 DEG C～350 DEG C, to be passed through the mixed gas of hydrogen or hydrogen and nitrogen；At hydrogen atmosphere The driest silicon chip.The purity of hydrogen and nitrogen more than or equal to (>=) 99.99%；According to mixed gas, hydrogen with The volume ratio of nitrogen is 0.1～100 times；Hydrogenation drying time be 1～60 minute.Under the conditions of using plasma Thermally grown mode prepares intrinsic Si-rich silicon oxide film (i-A-SiOx).Its preparation condition is: silicon wafer substrate temperature Degree is 150～350 DEG C, and operation pressure is 0.2～5mbar, radio frequency power density 0～300mW/cm2, uses Process gas be oxygen (O2), hydrogen (H2)；H2/O2 flow proportional is 0～2；
After completing rich and honour silicon oxide film growth, then carry out rear hydrogenation treatment with PECVD.It is passed through hydrogen or hydrogen Gas and the mixed gas of nitrogen, mixed gas H2/N2Volume ratio controls in the range of 0.1～100 times, and temperature controls At 140 DEG C～220 DEG C, the process time controlled at 1～200 second.
The third: n-type silicon wafer is tentatively cleaned, chemistry making herbs into wool, chemically or mechanically twin polishing after, right N-type silicon wafer cleans again, and the silicon chip after cleaned is done front hydrogenation dried, and the mode of process is: will Silicon chip is delivered to have in the equipment of airtight chamber, emptying air to chamber pressure less than or equal to (≤) 1Pascal；Chamber Room temperature controls, between 30 DEG C～350 DEG C, to be passed through the mixed gas of hydrogen or hydrogen and nitrogen；At hydrogen atmosphere The driest silicon chip.The purity of hydrogen and nitrogen more than or equal to (>=) 99.99%；According to mixed gas, hydrogen with The volume ratio of nitrogen is 0.1～100 times；Hydrogenation drying time be 1～60 minute.Use the heat under the conditions of wet oxygen raw Long mode prepares intrinsic Si-rich silicon oxide film (i-A-SiOx).Its preparation condition is: silicon wafer substrate temperature is 150～1200 DEG C, operation pressure is 0.1～100mbar, the ultra-pure water (Deionized water) of use and oxygen Gas (O2)；Ultra-pure water specification is: at 25 DEG C, resistivity >=18M Ω * cm, injects in the form of water vapour In reaction chamber, injecting water temperature is 50～110 DEG C；H2O (water vapour)/O2Flow proportional is 0～1.Water vapour Loading mode can be by wet oxygen generator by water vapour and oxygen simultaneous implantation to chamber, it is also possible to be to pass through water Steam generator is independently injected into chamber, as accompanying drawing illustrates shown in middle Fig. 5-6.
After completing rich and honour silicon oxide film growth, reusable heat growth furnace/equipment carries out rear hydrogenation treatment.Be passed through hydrogen or Person's hydrogen and the mixed gas of nitrogen, mixed gas H2/N2Volume ratio controls in the range of 0.1～100 times, temperature Controlling at 140 DEG C～1200 DEG C, the process time controlled at 1～60 minute.
Use any one method in three of the above method to obtain silicon rich silicon oxide transition zone, and do with front hydrogenation Hydrogenation process dry, rear reduces the defect of oxide interface and keeps the stability of this layer material.

Claims (10)

1. there is crystal silicon and carborundum films compound unijunction PIN solaode, its feature of transition layer structure It is, selected from one of following solar battery structure:
1) hearth electrode/n-layer/n-type silicon wafer/transition zone/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating；
2) hearth electrode/n-layer/n-type silicon wafer/transition zone/i-μ c-SiC layer/i-A-SiC layer/p-A-SiC layer/TCO/ anti-reflection Penetrate film；
3) hearth electrode/n-layer/n-type silicon wafer/transition zone/p-A-SiC layer/TCO/ antireflective coating；
4) hearth electrode/n-layer/transition zone/n-type silicon wafer/i-A-SiC layer/p-A-SiC layer/TCO/ antireflective coating；
5) hearth electrode/n-layer/transition zone/n-type silicon wafer/i-μ c-SiC layer/i-A-SiC layer/p-A-SiC layer/TCO/ anti-reflection Penetrate film；
6) hearth electrode/n-layer/transition zone/n-type silicon wafer/p-A-SiC layer/TCO/ antireflective coating；
7) hearth electrode/n-layer/transition zone/n-type silicon wafer/transition zone/i-A-SiC layer/p-A-SiC layer/p-A-SiC layer/TC O/ antireflective coating；
8) hearth electrode/n-layer/transition zone/n-type 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-type silicon wafer/transition zone/p-A-SiC layer/TCO/ antireflective coating；
Described transition zone is one layer or multilamellar, and the most any one layer is silicon rich silicon oxide layer；Described Silicon-rich oxygen SiClx 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 described silicon rich silicon oxide layer is selected from N-shaped gradient μ c-SiOxWith N-shaped gradient A-SiOx, 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 silicon oxide is then Change to silicon rich silicon oxide layer from silicon oxide and change to silicon layer again；
Wherein, "/" represents the interface between two-layer；N represents electron type (N-shaped) quasiconductor, and i-represents intrinsic half Conductor, P-represents cavity type (p-type) quasiconductor；A-represents noncrystal, and μ c-represents crystallite.
The most according to claim 1, solaode, is characterized in that, described transition zone is two-layer, respectively n-A- SiOxAnd i-A-SiOx, one layer of close n-type silicon wafer is n-A-SiOx。
The most according to claim 1, solaode, is characterized in that, the silicon atom density domination of described 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 controls between 1.12～9.0eV；Relative dielectric constant ε is 3.0≤ε≤11.7.
The most according to claim 1, solaode, is characterized in that, described n-layer selected from A-SiC, A-Si, Crystallite Si1-xGexAnd epi-Si1-xGexIn material any one or appoint several, epi-Si1-xGexIn 0≤x≤1, epi Represent epitaxial growth monocrystalline.
The most according to claim 1, solaode, is characterized in that, described hearth electrode selects nesa coating Or aluminum.
6. according to a preparation method for solaode described in any one of claim 1-5, it is characterized in that, bag Including the preparation of transition zone, the preparation of described transition zone includes: first complete making herbs into wool, polishing and clear at n-type silicon wafer After washing, then carry out front hydrogenation dried；Then Si-rich silicon oxide film is made；Finally carry out rear hydrogenation treatment Process；
Before described, hydrogenation dried is: use hydrogen and the mixed gas of nitrogen or hydrogen as process gas, Wherein the hydrogen/nitrogen volume ratio of mixed gas is between 0.1～100, and front hydrogenation dried temperature controls 3 Between 0 DEG C～350 DEG C, the front hydrogenation dried time is 1～60 minute；
Described rear hydrotreating process is: use hydrogen and the mixed gas of nitrogen or hydrogen as process gas, Wherein the hydrogen/nitrogen volume ratio of mixed gas is between 0.1～100；Rear hydrotreating temperatures is at 140 DEG C～12 Between 00 DEG C, the rear hydrogenation treatment time is between 1～3600 second.
The most according to claim 6, the preparation method of solaode, is characterized in that, the system of described transition zone Standby any one method being chosen in particular from following three kinds of methods:
The step 1. planting method is: 1) use hydrogen and the mixed gas of nitrogen or hydrogen to carry out front hydrogenation Dried: 2) using plasma enhancing chemical gaseous phase deposition (PECVD) or high-density plasma The method learning vapour deposition (HD-PECVD), use silane, phosphine, phosphine and the mixed gas of hydrogen, Hydrogen and carbon dioxide are process gas, deposit i-A-SiOx、n-A-SiOx、i-μc-SiOx、n-μc-SiOxFour Kind different types of any one or appoint several Si-rich silicon oxide film；3) after completing Si-rich silicon oxide film making, Hydrogen and the mixed gas of nitrogen or hydrogen is used to carry out rear hydrogenation treatment；
The step 2. planting method is: 1) use hydrogen and the mixed gas of nitrogen or hydrogen to carry out front hydrogenation Dried；2) using plasma strengthens chemical gaseous phase deposition (PECVD) or high-density plasma Learn the equipment of vapour deposition (HD-PECVD), use hydrogen and oxygen, under plasma conditions, decompose Hydrogen and oxygen, allow the surface of silicon chip carry out thermally grown Silicon-rich oxygen under conditions of aqueous, hydrion and oxonium ion SiClx thin film；3), after completing Si-rich silicon oxide film making, hydrogen and the mixed gas of nitrogen or hydrogen are used Gas carries out rear hydrogenation treatment；
The step 3. planting method is: 1) use hydrogen and the mixed gas of nitrogen or hydrogen to carry out front hydrogenation Dried；2) use the thermal oxide growth method under the conditions of wet oxygen, make Si-rich silicon oxide film；3) complete After becoming Si-rich silicon oxide film to make, hydrogen and the mixed gas of nitrogen or hydrogen is used to carry out rear hydrogenation treatment.
The most according to claim 7, the preparation method of solaode, is characterized in that, 1. plant the tool of method Body step is:
1) by complete making herbs into wool, polishing, cleaned after n-type silicon wafer do before hydrogenation dried, use hydrogen With mixed gas or the hydrogen of nitrogen, mixed gas H2/N2Volume ratio is in the range of 0.1～100, at hydrogen atmosphere Enclose lower dry silicon chip；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 used to make i-A-SiOx、n-A-SiOx、i-μc-S iOx、n-μc-SiOxFour kinds different types of any one or appoint several Si-rich silicon oxide film；PECVD or HD Radio-frequency signal generator frequency range used by-PECVD device is 13～67MHz；Wherein, i-A-SiO is madex During thin film, using silane, carbon dioxide and hydrogen is 180～220 DEG C as process gas, technological temperature, penetrates Frequently power density is 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 thin film, use silane, phosphine or Phosphine and the mixed gas of hydrogen, carbon dioxide and hydrogen are as process gas, and technological temperature is 180～220 DEG C, Radio frequency power density is 5～50mW/cm2, operation pressure is 0.2～2.0mbar, PH3/SiH4Flow-rate ratio≤10%, CO2/SiH4Flow-rate ratio≤5, H2/SiH4Flow-ratio control is in the range of 0.5～5；Make i-μ c-SiOxThin film Time, use silane, carbon dioxide, hydrogen as process gas, technological temperature is 140～180 DEG C, radio frequency merit Rate density is 50～300mW/cm2, operation pressure is 1.5～5mbar, CO2/SiH4Flow-rate ratio≤5, H2/Si H4Flow-ratio control is in the range of 5～150；Make n-μ c-SiOxDuring thin film, use silane, phosphine, phosphine It is 140～180 DEG C with the mixed gas of hydrogen, carbon dioxide, hydrogen as process gas, technological temperature, penetrates Frequently power density is 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 makes, to carry out rear hydrogenation treatment, rear hydrogenation treatment use hydrogen and The mixed gas of nitrogen or hydrogen, mixed gas H2/N2Volume ratio controls in the range of 0.1～100 times；Temperature Degree controls at 140 DEG C～220 DEG C, and the process time controlled at 1～200 second.
The most according to claim 7, the preparation method of solaode, is characterized in that, 2. the plant method Concretely comprise the following steps:
1) by complete making herbs into wool, polishing, cleaned after n-type silicon wafer do before hydrogenation dried, use hydrogen Gas and the mixed gas of nitrogen or hydrogen, mixed gas H2/N2Volume ratio is in the range of 0.1～100, at hydrogen Silicon chip it is dried under atmosphere；Hydrogenation baking 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, radio frequency power density 0～300m W/cm2, the process gas of use is oxygen and hydrogen；H2/O2Flow proportional is 0～2；
3) after completing Si-rich silicon oxide film growth, carry out rear hydrogenation treatment, use hydrogen and the mixing of nitrogen Gas or hydrogen, mixed gas H2/N2Volume ratio controls in the range of 0.1～100 times；Hydrogenation temperature is 14 Between 0～350 DEG C, the process time controlled at 1～200 second.
The most according to claim 7, the preparation method of solaode, is characterized in that, 3. the plant method Concretely comprise the following steps:
1) by complete making herbs into wool, polishing, cleaned after n-type silicon wafer do before hydrogenation dried, use hydrogen Gas and the mixed gas of nitrogen or hydrogen, mixed gas H2/N2Volume ratio controls in the range of 0.1～100 times, Silicon chip it is dried under hydrogen atmosphere；Hydrogenation baking 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 wet oxygen is used to prepare intrinsic Si-rich silicon oxide film i-A-SiOx；Process warm Degree is 150～1200 DEG C, and operation pressure is 0.1～100mbar；Use ultra-pure water and oxygen as reactant, Ultra-pure water specification is: at 25 DEG C, resistivity >=18M Ω cm；H2O (water vapour)/O2Flow proportional be 0～ 1；
3), after completing Si-rich silicon oxide film growth, then carry out rear hydrogenation treatment, use hydrogen or hydrogen and The mixed gas of nitrogen；Hydrogenation temperature is between 140～1200 DEG C, and the process time controlled at 1～60 minute.
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