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CN101789466B - method for manufacturing solar battery - Google Patents

method for manufacturing solar battery Download PDF

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Publication number
CN101789466B
CN101789466B CN2010101081366A CN201010108136A CN101789466B CN 101789466 B CN101789466 B CN 101789466B CN 2010101081366 A CN2010101081366 A CN 2010101081366A CN 201010108136 A CN201010108136 A CN 201010108136A CN 101789466 B CN101789466 B CN 101789466B
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silicon
layer
ion
solar battery
annealing
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CN101789466A (en
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门传玲
安正华
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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Abstract

The invention relates to a method for manufacturing a solar battery. The method comprises the following steps: forming an injection layer in a silicon wafer by using an ion injection method and then taking the silicon wafer as a device piece; growing one or two films of SiO2,or SiC, Al2O3 and SI3N4 on substrates such as glass, plastics, ceramics, stainless steel and the like by using the methods of thin film deposition, electroplating, magnetron sputtering and the like, wherein the one or two films serve as a medium layer and an isolation layer; binding the medium layer and the isolation layer to the device piece after depositing an Al film; transferring a silicon layer by annealing; determining whether to corrode or polish according to the roughness degree of the surface of the transferred silicon layer; forming a thin silicon material; preparing a p-n knot on the thin silicon by doping boron, phosphorus and the like; and preparing an electrode through screen printing, photo-etching, electron beam evaporation, electron plating and the like to obtain the solar battery. The method not only has the advantages of high efficiency and high stability of a crystalline silicon solar battery, but also has the characteristics of reducing using amount of silicon due to the adoption of thin materials, reducing process steps and lowering cost.

Description

Method for manufacturing solar battery
Technical field
The present invention relates to a kind of solar cell and preparation method thereof, relate to a kind of ion injection, porous epitaxial silicon monocrystalline silicon or rather in conjunction with the adjustable thin layer monocrystalline silicon of bonding prepared thickness, finish solar cell according to the production process of solar cell then and make, belong to a kind of manufacturing process of microelectronics and solid electronics, silica-based solar cell.
Background technology
In this technical field, studying maximum solar cells at present has silicon solar cell, compound semiconductor solar cell and DSSC.In silicon solar cell with monocrystaline silicon solar cell research the earliest and technology the most ripe, photoelectric conversion efficiency is the highest, the high conversion efficiency in laboratory is 24.7% at present, the monocrystaline silicon solar cell efficient of industrial-scale production is 15%.But because monocrystalline silicon to the purity requirement height of silicon raw material and use amount is big, preparation technology is loaded down with trivial details, so production cost is high, is difficult to apply.Be Siemens Method as the main production technology of the polysilicon of monocrystalline silicon raw material at present, promptly earlier silica sand (SiO2) is reduced to purity and is 97%~98% silicon and hydrochloric acid reaction generation hydrogen chloride silicon, again with its reduction, thermal decomposition, can obtain purity and be the polysilicon (bar-shaped or granular) more than 99.99999%.The polysilicon that obtains dissolved make the monocrystalline silicon mold, row cutting and etching are corroded again, finally obtain thickness and are about the thick silicon chip of 300 μ m.Not only energy consumption height and environmental pollution are serious in this process.Compare with monocrystaline silicon solar cell, the raw material sources channel of polysilicon solar cell is more wide, and is low and cost of material is cheaper to the purity requirement of raw material.The high conversion efficiency in laboratory is 20.3%, and the conversion efficiency of industrial-scale production reaches 13%~16%.Be fit to large-scale commercial applications production.
With respect to silicon solar cell, CIS/CIGS, GaAs and CdTe thin-film solar cells become people with its low cost, high efficiency, high stability and study maximum compound semiconductor solar cells, but because its manufacture craft poor repeatability, reasons such as the rate of finished products of high-efficiency battery is low have limited the commercialization process.DSSC (DSSC) is the solar cell of new generation that develops after the nineties in 20th century, won extensive attention with advantages such as its potential low cost, simple relatively manufacture craft and technology, but also there are a series of problems in electrode material, dye sensitizing agent and electrolytical selection and preparation etc., restricted the further raising of dye sensitive solar battery conversion efficiency and stability.
In the cost of silicon solar cell, about 50%~60% cost comes from the silicon raw material, if adopt thin-film solar cells, the depositing silicon film is as absorbed layer on inexpensive substrate, the silicon thin film thick as 40 μ m can absorb 80% sunlight, thereby reduce the consumption of expensive silicon, reach the purpose that reduces cost.What research was maximum at present is polysilicon membrane and amorphous silicon thin-film solar cell.At present, MIT is at SiO 2The multi-crystal silicon film solar battery efficient of making on the substrate reaches 16.5%.Multi-crystal silicon film solar battery preparation technology mainly contains chemical vapour deposition technique (CVD) and liquid phase epitaxial method (L PE), apparatus expensive, complex process.The amorphous silicon thin-film solar cell cost is low, it is the hull cell of present industry size maximum, high conversion efficiency has reached 16.6%, but because of the optical band gap of amorphous silicon is 1.7eV, its material itself is insensitive to the Long wavelength region of solar radiation spectrum, thereby has limited the conversion efficiency of non-crystal silicon solar cell; In addition, its photoelectric efficiency decays along with the prolongation of light application time, promptly so-called photic decline S-W effect.In recent years, the research to amorphous silicon thin-film solar cell mostly is the stability that improves battery conversion efficiency and improve battery.
In recent years, the novel silicon solar cell of development has silicon ribbon solar cell, microcrystalline silicon film solar cell and HIT solar cell etc.Banded polysilicon technology can be avoided cutting process, greatly reduces the silicon solar cell production cost, and main technique has granular silicon belt technology and EFG technology etc.When the solar cell cost is reduced to 1$/W, just have the advantage of competing, but serious cutting loss problem is difficult to the cost of monocrystalline silicon and polycrystal silicon cell is reduced to below the 2$/W with conventional energy resource.In the laboratory research stage, the solar battery efficiency of granular silicon belt preparation is the highest to have reached 8.25%, and cost has been reduced to 0.8$/W.Because the silicon ribbon defective is many, surface smoothness is not high, all bring negative effect for subsequent technique and battery efficiency, therefore improving the silicon ribbon quality is the ultimate challenge that silicon ribbon technology faces.But microcrystal silicon is owing to have the high stable of monocrystalline silicon, the advantages such as saving material low temperature large tracts of land deposition of amorphous silicon, and spectral response can be expanded to infrared light (λ>800nm), the potentiality of further raising the efficiency are very big, are acknowledged as silicon-based film solar cells material of new generation.At present, the research of microcrystalline silicon film solar cell is concentrated on Nankai University's optoelectronic thin-film device and technical research institute, the United Solar company of the U.S., the Kaneka company of Japan, the J ulich photovoltaic research institute of Germany, the Utrecht university of Holland and the IMT research institute of Switzerland of China, microcrystalline silicon solar cell efficient all reaches more than 9%, but deposition rate not high (0.5nm/s).Therefore, improving deposition rate is the most important thing of microcrystalline silicon film solar cell industryization.
At semiconductor applications, the silicon materials on the insulator are that SOI (Silicon-on-insulator) material receives much attention in the application prospect in power device field in recent years, and development is very fast.The preparation technology of SOI material mainly contains and annotates the oxygen isolation is the SIMOX technology, and bonding and wafer thinning is the Smart-Cut technology.The former is by injecting the high dose oxonium ion in monocrystalline silicon piece, forming buried insulation SiO behind the high annealing 2Layer, thus soi structure formed.The latter is the wafer bonding of elder generation with the silicon chip after a slice thermal oxidation and a slice light, and thinning back side forms soi structure to needed thickness again.
Summary of the invention
The present invention proposes a kind of method for manufacturing solar battery, and the high efficiency of the existing crystal silicon solar energy battery of this method, the advantage of high stable have been brought into play the characteristics of layer material save silicon consumption again, reduce processing step, reduce cost.
For achieving the above object, technical scheme of the present invention is: a kind of method for manufacturing solar battery specifically may further comprise the steps:
A) the device sheet is made
Adopt ion implantation technique in monocrystalline silicon piece, to inject hydrogen ion or helium ion or hydrogen, two kinds of ions of helium, perhaps in monocrystalline silicon piece, introduce porous silicon, and on porous silicon epitaxial monocrystalline silicon;
B) support substrates is made
Adopt sputter or vacuum evaporation method on glass or pottery or stainless steel or plastic, to deposit SiC, SiO 2, Al 2O 3Or Si 3N 4In one or both films as dielectric layer and separator, and then plate the layer of aluminum thin layer as support substrates;
C) form bonding pad
Device sheet and support substrates through clean, dry back bonding under the room temperature that normal temperature and pressure or vacuum or plasma are assisted;
D) annealing in process
With bonding pad in annealing in process under 300~1500 ℃ of temperature and under nitrogen or the helium protective atmosphere, split in bubble layer or epitaxial monocrystalline silicon place that bonding pad forms behind the ion implantation annealing of device sheet, the device silicon chip that ruptures a) uses behind etch polishing set by step repeatedly;
E) form " black silicon "
Adopt corrosion or polishing to remove ion implanted layer, the residue top layer silicon on the para-linkage sheet adopts the chemical-mechanical polishing mathing polishing, keeps the surperficial rough of top layer silicon, forms " black silicon ", and at SF 6Carry out surface treatment in the reaction atmosphere;
F) in top layer silicon, mix boron and phosphorus and form p-n junction;
G) obtain solar cell
As back electrode, adopt methods such as silk screen printing, photoetching, electron beam evaporation, electronics plating to make preceding electrode the aluminium lamination in the step b), obtain solar cell.
In step a), adopt two kinds of methods to make the device sheet: a kind of method is to introduce the monocrystalline silicon piece of injection sheath as the device sheet by ion implantation technique; Another is to introduce porous silicon in monocrystalline silicon piece, and behind epitaxial monocrystalline silicon on the porous silicon, as the device sheet.
Inject ion and be hydrogen ion or helium ion or hydrogen, two kinds of ions of helium, ion implantation dosage is 1 * 10 14H +/ cm 2To 1 * 10 19H +/ cm 2Between, ion implantation energy at 10KeV between 500KeV.
In step b), directly behind first depositing Al film on the above-mentioned substrate, be bonded together with the device sheet again.
Bonding adopts dual mode to carry out: a kind of mode is that the monocrystalline silicon piece after surface in the step b) has been deposited the support substrates of Al film and ion and injects carries out bonding; Another kind be surface in the step b) has been deposited the support substrates of Al film and on porous silicon extension the silicon chip of monocrystalline silicon carry out bonding.
The annealing in process temperature is at 300~1500 ℃, and the time is 2 hours to 6 hours, and carries out under protective atmospheres such as nitrogen or helium.
The top layer silicon thickness that forms behind the bonding is 1~100 μ m.
At normal temperature and pressure or vacuum or the auxiliary room temperature bonding of plasma, bonding EVG bonding machine.
The top layer silicon that obtains in step e) is natural " black silicon ", carries out etch polishing according to the surperficial rough degree of top layer " black silicon ", and at SF 6Carry out surface treatment in the reaction atmosphere or directly make solar cell.
At step C) before the bonding just on substrate first depositing Al film as back electrode.
The device silicon chip that strips down after bonding, annealing continues to use repeatedly by claim 2 and 3 described methods, up to exhausting behind etch polishing.
The invention has the beneficial effects as follows: on the basis of traditional bonding technology, wherein one of key technology path is exactly to utilize a slice hydrogen ion/helium ion or hydrogen, the silicon chip of two kinds of ions injections of helium back formation bubble layer and the inexpensive substrate bondings such as glass that the surface has deposited the Al film, annealing then, bubble layer can split automatically in annealing process, and monocrystalline silicon has been transferred to the raw material that becomes follow-up making solar cell on the substrate.Another key technology path be exactly be used in extension on the porous silicon epitaxial wafer of monocrystalline silicon replace above-mentioned injection sheet, equally with inexpensive substrate bonding, annealing that the Al film is arranged, the monocrystalline silicon of extension can be transferred to substrate in annealing process, as the silicon materials of solar cell.The high efficiency of existing like this crystal silicon solar energy battery, the advantage of high stable have been brought into play the characteristics of layer material save silicon consumption again, and the thickness of silicon layer can be as thin as tens nanometers.Because the fusing point of Al film is low, can increase bond strength in annealing in addition, improve the bonding rate of finished products, the Al film can be used as the back electrode of solar cell again simultaneously, reduces processing step, reduces cost.
Description of drawings
Fig. 1,2 is respectively the making schematic flow sheet of two kinds of embodiment of the present invention.
Wherein: 1 is monocrystalline silicon piece, and 101 is the implanted layer that monocrystalline silicon piece forms after ion injects, and 102 is top monocrystalline silicon, and 103 is the epitaxy single-crystal silicon layer on the porous silicon; 2 is substrates such as glass, special plastic, pottery, stainless steel; 3 is the Al film; 4 is porous silicon layer.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and embodiment, but the present invention never only is limited to embodiment.
Embodiment 1: as shown in Figure 1, method for manufacturing solar battery according to the requirement to top layer silicon thickness, adopts earlier ion injection method to form an implanted layer 101 in monocrystalline silicon piece 1, then with this silicon chip as the device sheet.By methods such as the vacuum electronic beam evaporation SiO that on glass substrate 2, grows 2Film is as dielectric layer and separator, depositing Al film 3 backs and device sheet are bonded together then, again by annealing, the realization top layer silicon 102 of splitting at the bubble place of implanted layer 101 shifts, suitably corrosion and polishing, form the top monocrystalline silicon material that there is the rough degree of certain microcosmic on the surface at last, i.e. " black silicon ".On top layer silicon, make p-n junction by boron-doping, phosphorus etc., make electrode, obtain solar cell at last by methods such as silk screen printing, photoetching, electron beam evaporation, electronics platings.Inject ion and be hydrogen ion or helium ion or hydrogen, two kinds of ions of helium, ion implantation dosage is 1 * 10 14H +/ cm 2To 1 * 10 19H +/ cm 2Between, ion implantation energy at 10KeV between 500KeV.
Can adopt glass or pottery or stainless steel or plastics as substrate, and on substrate, deposit SiO 2Or SiC, Al 2O 3, Si 3N 4In one or both films as dielectric layer and separator, then behind the depositing Al film as support substrates, perhaps, be bonded together with above-mentioned device sheet more directly on the above-mentioned substrate directly behind the depositing Al film.
Can be at normal temperature and pressure or vacuum or the auxiliary room temperature bonding of plasma.The EVG bonding machine that bonding can adopt EVG company to produce.
The annealing in process temperature is at 300~1500 ℃, and the time is 2 hours to 6 hours, and carries out under protective atmospheres such as nitrogen or helium.
The top layer silicon thickness that forms behind the bonding is 1~100 μ m.The device silicon chip that strips down after bonding, annealing continues to use repeatedly behind etch polishing, up to exhausting.
The top layer silicon surface has certain rough degree, is natural " black silicon ", can also carry out suitable etch polishing according to the surperficial rough degree of top layer silicon, and as SF 6Deng carrying out surface treatment in the reaction atmosphere, also can not carry out the reacting gas surface treatment, directly make solar cell.
Embodiment 2: as shown in Figure 2, method for manufacturing solar battery at first can prepare porous silicon layer 4 by electrochemical erosion method on monocrystalline silicon piece 1, then in 4 surperficial epitaxy single-crystal silicon thin layers, 103 backs as the device sheet; Substrate 2 surface deposition Al films 3 back and device sheet bondings, quick high-temp annealing, bonding pad splits at the porous silicon layer place, and epitaxy single-crystal silicon thin layer 103 is transferred on the substrate 2 smoothly.On thin-layer silicon, make p-n junction by boron-doping, phosphorus etc. then, make electrode, obtain solar cell at last by silk screen printing, photoetching, electron beam evaporation, electronics plating etc.

Claims (3)

1. a method for manufacturing solar battery is characterized in that, specifically may further comprise the steps:
A) the device sheet is made
Adopt ion implantation technique in monocrystalline silicon piece, to inject hydrogen ion or helium ion or hydrogen, two kinds of ions of helium, perhaps in monocrystalline silicon piece by electrochemical erosion method introducing porous silicon, and on porous silicon epitaxial monocrystalline silicon;
B) support substrates is made
Adopt sputter or vacuum evaporation method on glass or pottery or stainless steel or plastic, to deposit SiC, SiO 2, Al 2O 3Or Si 3N 4In one or both films as dielectric layer and separator, and then plate the layer of aluminum thin layer as support substrates;
C) form bonding pad
Device sheet and support substrates through clean, dry back bonding under the room temperature that normal temperature and pressure or vacuum or plasma are assisted;
D) annealing in process
With bonding pad in annealing in process under 300~1500 ℃ of temperature and under nitrogen or the helium protective atmosphere, on bubble layer that bonding pad forms behind the ion implantation annealing of device sheet or the porous silicon split in the epitaxial monocrystalline silicon place, and the device silicon chip that ruptures a) uses behind etch polishing set by step repeatedly;
E) form " black silicon "
The place's rough surface that splits of ion implanted layer or porous silicon correspondence after above-mentioned annealing in process forms natural " black silicon "; Perhaps adopt corrosion or polishing to remove ion implanted layer or remaining porous silicon layer, the residue top layer silicon on the para-linkage sheet adopts the chemical-mechanical polishing mathing polishing, and at SF 6Carry out surface treatment in the reaction atmosphere and form " black silicon ";
F) in top layer silicon, mix boron and phosphorus and form p-n junction;
G) obtain solar cell
As back electrode, adopt silk screen printing, photoetching, electron beam evaporation, electronics electroplating method to make preceding electrode the aluminium lamination in the step b), obtain solar cell.
2. method for manufacturing solar battery according to claim 1 is characterized in that: injecting ion is hydrogen ion, and ion implantation dosage is 1 * 10 14H +/ cm 2To 1 * 10 19H +/ cm 2Between, ion implantation energy at 10KeV between 500KeV.
3. method for manufacturing solar battery according to claim 1 is characterized in that: the top layer silicon thickness that forms behind the bonding is 1~100 μ m.
CN2010101081366A 2010-02-10 2010-02-10 method for manufacturing solar battery Expired - Fee Related CN101789466B (en)

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CN101950779B (en) 2010-09-07 2012-07-04 中国科学院微电子研究所 Method for preparing solar cell in situ
CN102117850B (en) * 2010-11-12 2012-09-19 北京大学 Solar battery with micro-nano composite structure and production method thereof
CN102074654B (en) * 2010-11-23 2012-06-27 中国科学院半导体研究所 Preparation method for improving efficiency of polymer solar battery
CN102259829A (en) * 2011-07-04 2011-11-30 上海先进半导体制造股份有限公司 Isolation cavity and manufacturing method thereof
CN102275867B (en) * 2011-07-12 2014-08-06 上海先进半导体制造股份有限公司 Semiconductor device with partially sealed shell and manufacturing method of semiconductor device
CN102361039B (en) * 2011-10-31 2013-08-28 上海理工大学 Transparent conducting layer-based black silicon solar cell and preparation method thereof
CN102605353B (en) * 2012-03-16 2014-01-22 江苏辉伦太阳能科技有限公司 Method for increasing structural strength of black silicon by silica liquid-phase deposition
CN103117235A (en) * 2013-01-31 2013-05-22 上海新傲科技股份有限公司 Plasma-assisted bonding method
CN105742374B (en) * 2014-12-09 2017-12-05 中国科学院苏州纳米技术与纳米仿生研究所 photovoltaic device and preparation method thereof
CN107680901B (en) * 2017-09-27 2020-07-07 闽南师范大学 Flexible composite substrate for semiconductor epitaxy and manufacturing method
CN109979809B (en) * 2019-03-13 2021-10-26 电子科技大学 Preparation method of single crystal film, single crystal film and resonator device
CN110098145B (en) * 2019-04-03 2021-08-17 京东方科技集团股份有限公司 Monocrystalline silicon thin film and manufacturing method thereof

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SG54593A1 (en) * 1996-11-15 1998-11-16 Canon Kk Method of manufacturing semiconductor article
CA2233096C (en) * 1997-03-26 2003-01-07 Canon Kabushiki Kaisha Substrate and production method thereof
US6664169B1 (en) * 1999-06-08 2003-12-16 Canon Kabushiki Kaisha Process for producing semiconductor member, process for producing solar cell, and anodizing apparatus
JP2008112847A (en) * 2006-10-30 2008-05-15 Shin Etsu Chem Co Ltd Process for manufacturing single crystal silicon solar cell and single crystal silicon solar cell
JP5090716B2 (en) * 2006-11-24 2012-12-05 信越化学工業株式会社 Method for producing single crystal silicon solar cell

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