CN101719521A - Solar cell of sandwich structure consisting of Si/FeSi2/Si and manufacturing method thereof - Google Patents

Solar cell of sandwich structure consisting of Si/FeSi2/Si and manufacturing method thereof Download PDF

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CN101719521A
CN101719521A CN200910273050A CN200910273050A CN101719521A CN 101719521 A CN101719521 A CN 101719521A CN 200910273050 A CN200910273050 A CN 200910273050A CN 200910273050 A CN200910273050 A CN 200910273050A CN 101719521 A CN101719521 A CN 101719521A
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fesi
layer
solar cell
fesi2
sandwich structure
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高云
邵国胜
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Hubei University
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Hubei University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/548—Amorphous silicon PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a novel ultra-thin efficient solar cell of a sandwich structure consisting of Si/FeSi2/Si and a manufacturing method thereof. The method mainly substitutes a beta-FeSi2 material for the intrinsic silicon layer of a silicon solar cell of the conventional PIN structure. As a band gap of the beta-FeSi2 material is narrower than that of a Si material, the energy band structure of a heterojunction consisting of the beta-FeSi2 and the Si enables photon-generated carriers generated by illumination to be separated and moved directionally and reversely under the effect of the built-in field of the heterojunction so as to realize a function of photovoltaic conversion. The adopted beta-FeSi2 has a photoabsorption coefficient of 105/cm, which is two orders of magnitude greater than 103/cm of a monocrystalline silicon, and has higher electron and hole mobilities than those of the monocrystalline silicon. In the solar cell of a wide/narrow/wide band gap sandwich structure consisting of the beta-FeSi2 and the Si, an open-circuit voltage, which is determined by P-type and N-type silicon layers at both ends of the beta-FeSi2 layer, can reach over 0.7 V; and the solar cell can have the photovoltaic conversion efficiency equal to that of a crystal silicon solar cell within 5 microns of the total effective thickness. The ultra-thin efficient solar cell of the sandwich structure consisting of the Si/FeSi2/Si has the advantages of ultra thin, high efficiency, long service life and low cost equal to that of an amorphous silicon thin film solar cell, which can be directly applied to the commercialization production of solar cells.

Description

A kind of Si/FeSi 2The solar cell of/Si sandwich structure consisting and manufacture method thereof
Technical field
The present invention relates to a kind of new structure film photovoltaic cell, specifically a kind of Si/FeSi 2/ Si forms solar cell and the manufacture method thereof that the width band gap is mixed sandwich structure.
Background technology
The structural design of traditional solar cell adopts PN homojunction, PIN homojunction or PN heterojunction structure usually.The crystal silicon solar batteries of existing marketization mainly adopts PN homojunction structure.Its carrier mobility band structure figure as shown in Figure 1.Be that P type silicon contacts with N type silicon, produce self-built electromotive force, form built-in field between PN junction, the photo-generated carrier electronics separates under built-in field automatically with the hole, fixs mobilely respectively to P type and N type silicon direction, produces photoelectric current.Its open circuit voltage size mainly by the decision of self-built electromotive force size, can reach 0.7V usually, and electricity conversion can reach 20%.What adopt in the design of thin film amorphous silicon solar cell and preparation is PIN homojunction structure.Be that P type silicon, eigen I silicon and N type silicon combine.Its band structure figure as shown in Figure 2.The size that it is characterized in that self-built electromotive force is by P layer in the PIN structure and the decision of N layer silicon, and is irrelevant with the I layer.The I layer only provides the generation and the transmission channel of photo-generated carrier.Open circuit voltage can reach more than the 1.0V usually, and photoelectric conversion efficiency is 7%.PN heterojunction structure or band gap gradual change PN heterojunction structure are adopted in the application study exploitation usually in present commercialization multi-element compounds thin-film solar cells.Adopt N type CdS or metal oxide such as ZnO etc. to realize that by ion doping band gap width is adjustable, and by forming the PN heterojunction with materials such as P type CuInS, CdTe, its band structure figure is similar to the PN homojunction, and just P type and N type two ends can be with band gap width different.
β-FeSi 2It is a kind of novel direct gap semiconductor material that can be used for photovoltaic cell.Its energy of absorption edge is positioned at about 0.86eV, has the absorption coefficient of light than high two orders of magnitude of crystal silicon material, and its electron mobility and hole mobility can reach 100cm 2More than/the Vs, have advantages such as radiation resistance, high-temperature stability.Adopt FeSi 2Just can realize abundant absorption to the solar energy near infrared spectrum being applicable to the making of thin-film solar cells with the thickness of hundreds of nanometer only as photovoltaic material, have great application prospect.Yet at present FeSi 2The technology of photovoltaic device mainly adopts FeSi 2Form the PN heterojunction structure with wide band gap semiconducter, as with P type FXeSi 2With N type Si or N type FeSi 2Si forms simple PN junction with the P type, and its device architecture as shown in Figure 4.Fig. 5 is with N type FeSi 2Forming simple PN junction with P type Si is that example has provided the carrier mobility band structure schematic diagram under this design.The open circuit voltage of this simple PN junction structure is by FeSi 2The self-built electromotive force decision of layer and Si layer.Because the affinity of Si is 4.01eV, band gap width is 1.11eV, FeSi 2Affinity be 4.33eV, band gap width is approximately 0.86eV.Can draw by the energy band diagram analysis, no matter select by P type FeSi 2With the heterojunction of N type Si composition, or by N type FeSi 2With the heterojunction that P type Si forms, its self-built electromotive force V BiWith corresponding open circuit voltage only be the part of the self-built electromotive force of PN junction of Si, can not reach the numerical value of silicon PN junction open circuit voltage.Especially with N type FeSi 2Form PN junction with P type silicon, at FeSi 2Its open circuit voltage scope is only at 0.3-0.5V under the non-heavily doped assorted situation, and therefore, power output and electricity conversion are difficult to reach the level of crystal silicon solar batteries.In addition, because FeSi 2Effective controllable dopedly also do not realize, therefore, experimentally adopt solar cell properties that the PN junction structure obtains than theoretical estimate low.This theory analysis is with experimentally resulting by N type FeSi at present 2The PN junction solar cell open circuit voltage of forming with P type Si is 0.22V only, and conversion efficiency is 0.56% to be consistent.
In sum, utilize FeSi 2Semiconductor adopts simple FeSi as photovoltaic material 2The PN heterostructure that/Si forms is to be difficult to realize big power output and high conversion efficiency, to FeSi 2The effective controllable method shortage of doping content has also restricted FeSi 2The development of the PN heterojunction solar battery that/Si forms.The present invention is according to PIN homojunction structure photovoltaic property principle in the solar cell, in conjunction with β-FeSi 2The material self-characteristic has designed the Si/FeSi that a kind of wide and narrow strip is mixed 2/ Si sandwich structure in order to improve open circuit voltage, increases photoelectric conversion efficiency.In addition, the design uses intrinsic FeSi 2Layer is a light absorbing zone, has avoided FeSi 2In the doping problem.
Summary of the invention
The objective of the invention is at present FeSi 2The open circuit voltage that exists in the photovoltaic technology is low, the problem that electricity conversion is little and propose the Si/FeSi that a kind of wide and narrow strip is mixed 2Solar cell new device structure of/Si sandwich structure and preparation method thereof.
The objective of the invention is to reach by following measure.Design a kind of Si/FeSi 2The sandwich structure film photovoltaic cell that/Si forms.Its basic structure comprises: transparent substrates (1) or opaque substrate (7), transparent conductive film (2), P type silicon doping layer (3), intrinsic FeSi 2Layer (4), N type silicon doping layer (5), back electrode (6), in sandwich structure, be provided with can realize ultra-thin, have a β-FeSi of high absorption coefficient and higher carrier mobility efficiently 2Layer.
3,4,5 layers is effective light absorbing zone, and wherein the 3rd layer thickness is 0.01～0.5 μ m, the material doped P-type silicon of attaching most importance to, and doping content is 10 19～10 20Cm -2The 4th layer thickness is 0.2～4 μ m, and material is intrinsic β-FeSi 2Layer or involuntary doping β-FeSi 2Layer, carrier concentration is 10 15～10 17Cm -2The 5th layer thickness is 0.01～2 μ m, and material is heavily doped N type Si, and dosed carrier concentration is 10 19～10 21
Being positioned at what adopt in the middle of the PN junction of Si is β-FeSi 2Layer material can order about the tilting table stepwise band structure that electronics or holoe carrier separation and oriented opposite move by wide/narrow/broad-band gap in conjunction with forming.
The three-decker that is adopted can be PIN, NIP, PPN, PNN, NPP, NNP structure.The intermediate layer is that weak P type of intrinsic-OR or weak N type mix, and PN type Si order in two ends is interchangeable.
Silicon doping layer and β-FeSi 2Layer can be monocrystalline, polycrystalline, amorphous or microstructure.
Transparent conductive film (2) can be the SnO2:F of suede structure or ITO or other transparent conductive films of ZnO or planar structure.
Back electrode (6) can be Al or Ag or Al/Ag metal material layer electrode, or ZAO and Al or Al/Ag metallic multilayer combination electrode, and wherein ZAO is ZnO:Al, or other can constitute the electrode of ohmic contact with N type silicon.
Elaborate the New Si/FeSi that the present invention relates to below 2The operation principle of/Si sandwich structure consisting solar cell.
Fig. 6 has provided by Si/FeSi 2The carrier mobility of/Si sandwich structure consisting photovoltaic cell can be with schematic diagram.In this structural design, open circuit voltage is that therefore, the open circuit voltage in this design is consistent with silicon solar cell, can reach 0.7V by the self-built electromotive force decision between the N layer silicon of the 3rd layer P layer and layer 5.Because β-FeSi 2Can be with band gap width only for about 0.86eV, less than the 1.11eV of Si, weak p type of the involuntary doping of intrinsic-OR or weak N type FeSi 2Be clipped in and just in time form an angled step shape between the silicon PN junction and can be with step.As seen from Figure 7, at intrinsic FeSi 2And between the N type Si owing to being with the discontinuous additional potential barrier that produces.But because N layer Si adopts heavy doping in the design, barrier width is very narrow, and electronics can pass potential barrier by the tunnelling mode and arrive the N district.Therefore, this sandwich structure is FeSi 2Provide the passage of carrier separation and directional drift with the photo-generated carrier (electronics and hole) in the Si layer, electronics is to the drift of N type layer, and photovoltaic effect has been realized to the drift of P type layer in the hole.
Good effect of the present invention and advantage are as follows:
1, New Si/FeSi 2/ Si forms PIN film photovoltaic cell material requested iron and silicon is environmentally friendly material, and nontoxic pollution-free, raw material memory space on earth are big, and be cheap, really realizes sustainable development reproducibility green energy resource.
2, because main light-absorption layer adopts FeSi 2Layer has the absorption coefficient of light than high two orders of magnitude of crystal silicon, and required light-absorption layer thickness only needs 1% of crystal silicon solar batteries, promptly about 1 μ m.Therefore, the upstream silicon materials of required consumption are few, have ultra-thin, advantage cheaply;
3, the intermediate layer is adopted and is intrinsic FeSi 2Layer need not FeSi 2Layer painstakingly mixes, and can reduce because the high defect concentration of mixing and causing improves electricity conversion.In addition, manufacture craft is simpler, and feasibility is stronger.
4, because the open circuit voltage of this sandwich structure design is that two ends P type and N type silicon doping decision are arranged, open circuit voltage can reach the level consistent with crystal silicon solar batteries, i.e. 0.7V.The intermediate layer is an intrinsic layer, and defect concentration is low, absorption coefficient of light height, and the theoretical modeling structure shows that its electricity conversion can meet or exceed crystal silicon solar batteries, has the high efficiency characteristics.
5, the Si/FeSi of the present invention's design 2/ Si sandwich structure is contained FeSi 2With crystal silicon or two kinds of materials of amorphous silicon.Because FeSi 2Have than silicon low can band gap, its absorption spectrum ranges mainly comprises near infrared band.Therefore top silicon layer is to FeSi 2Absorption bands be fully transparent.Therefore this designs is less demanding to illumination condition, even if not overabundant indoor at sunlight, its optoelectronic transformation efficiency can not be subjected to too big influence yet, has than crystal silicon solar battery application space more widely.
6, battery adopts the full-inorganic structure, annealed processing, and anti-900 ℃ of high temperature do not exist owing to illumination causes the defective generation and shine into the product problem of unstable with free.Predicted life can be complementary with crystal silicon solar batteries, reaches 30 years.Has long-life advantage.
7, in the manufacture craft of device, effectively layer (sandwich structure layer) can wait and realize by conventional films manufacture method such as plasma reaction sputter, magnetron sputtering, other electrode making are consistent with the thin-film solar cells technology of packaging technology and existing use, are easy to realize industrialization production.
Description of drawings
Fig. 1 is the interior charge carrier migration energy band schematic diagram of crystal silicon solar batteries that conventional P N homojunction constitutes.
Fig. 2 is the interior charge carrier migration energy band schematic diagram of non-crystal silicon solar cell that traditional PI N homojunction constitutes.
Fig. 3 is that prior art adopts simple FeSi 2/ Si forms PN junction FeSi 2The device architecture figure of solar cell.
Fig. 4 is that prior art adopts simple FeSi 2/ Si forms PN junction FeSi 2Carrier mobility can be with schematic diagram in the solar cell.
Fig. 5 is that the present invention is the Si/FeSi of substrate design with transparent or non-transparent material 2/ Si forms sandwich
The device architecture schematic diagram of 4 structure solar cells.
Fig. 6 is Si/FeSi of the present invention 2Carrier mobility can be with schematic diagram in the/Si sandwich structure consisting solar cell.
Fig. 7 is the crystal Si/FeSi that the present invention adopts 2/ Si sandwich structure solar cell and corresponding employing FeSi 2The photovoltaic property analog result comparison diagram of the PN junction solar cell that/Si forms.
Fig. 8 is the crystal Si/FeSi that the present invention adopts gross thickness to form less than 5 μ m thickness 2/ Si sandwich structure solar cell and thickness are the photovoltaic property analog result comparison diagram of the PN junction crystal silicon solar energy battery of 180 μ m.
Fig. 9 is that the present invention adopts the only amorphous Si/FeSi of 500nm composition of optimized thickness 2/ Si sandwich structure solar cell and optimized thickness are the photovoltaic property analog result comparison diagram of the amorphous silicon PIN solar cell of 300nm.
1----transparent substrates wherein, 2----transparent conductive film, 3----P type silicon doping layer, the non-doped F eSi2 layer of 4----intrinsic, 5----N type silicon doping layer, 6----dorsum electrode layer, the opaque substrate of 7----
Embodiment
Below in conjunction with accompanying drawing specific design of the present invention and execution mode are elaborated:
Consult Fig. 5 (a), the Si/FeSi that designs for the present invention 2The device architecture figure of/Si film photovoltaic cell.For the manufacturing process with present amorphous silicon thin-film solar production line is complementary, it is substrate that the design adopts transparent material, as glass etc.When adopting the P-i-N structure, with transparent conducting glass TCO the SnO with suede structure of transparent substrates 1 2: on the F transparent conductive film 2, deposit the thick boron doped P type silicon doping layer 3 of one deck 400nm earlier, doping content is 5 * 10 19/ cm 2Then depositing second layer thickness is the non-doping intrinsic FeSi of 2000nm 2Layer, continuing deposit thickness is the n type silicon doping layer of the thick phosphorus doping of 2000nm, doping content is 1 * 10 19/ cm 2The back electrode of the effective layer of Al/Ag electrode connection that the dorsum electrode layer employing is consistent with non-crystal silicon solar cell is drawn carving technology with laser at last and cover glass sealing EVA (ethylene-vinyl acetate) paper tinsel technology is carried out follow-up stacked wafer module production.
The above-mentioned parameter that provides is optimized device simulation result, and effective layer concrete thickness of indication of the present invention can be done an amount of adjustment according to concrete effect in the actual production R﹠D process.FeSi 2The thickness of layer can change in the 200nm-4000nm scope, and gross thickness can guarantee that below 5 μ m, electricity conversion can reach more than 19% in this varied in thickness scope.
It is substrate that the present invention also can adopt flexible opaque substrates such as stainless steel.Its concrete structure is shown in Fig. 5 (b).The manufacture method of concrete effectively layer is consistent with the method for manufacturing solar battery that with the transparent conducting glass is substrate.
Above-mentioned Si/FeSi 2The design of/Si film photovoltaic cell goes for effective layer material of monocrystalline, polycrystalline, amorphous and crystallite.
Fig. 7 provides New Si/FeSi that thickness is respectively 400/2000/2000nm 2/ Si battery and thickness are the FeSi of 2000/2000nm 2The photovoltaic property simulation comparison diagram of the PN junction solar cell that/Si forms.The transformation efficiency that can obtain the PN junction structure only is 12.1%, and fill factor, curve factor is 0.79, and open circuit voltage is 0.47V, and novel PIN structural design transformation efficiency can reach 19.7%, and fill factor, curve factor reaches 0.83, and open circuit voltage reaches 0.7V.Therefore this new design will improve open circuit voltage greatly, improve electricity conversion, than simple FeSi 2The PN junction structure that/Si forms has higher applicability.
Fig. 8 has provided the New Si/FeSi that thickness is respectively 400/2000/2000nm 2/ Si battery and thickness are the photovoltaic property simulation comparison diagram of the PN junction crystal silicon solar batteries of 100/180000nm.Can obtain novel FeSi 2Battery adopts only 4.4 microns gross thickness, just can realize transformation efficiency 19.7%, and fill factor, curve factor 0.83, open circuit voltage are 0.69V.The transformation efficiency of the brilliant solar cell of the PN junction of corresponding 180 micron thickness only is 17.1%, and fill factor, curve factor is 0.84, and open circuit voltage is 0.68V.Therefore, as can be seen, adopt this device architecture design gross thickness only to be 2.5% of crystal silicon battery, open circuit voltage is consistent with crystal silicon battery, and transformation efficiency is then greater than crystal silicon battery.Once enter effective layer owing in this simulation, only considered light, take zigzag front and rear surfaces layer to realize the repeatedly reflection of light in effective layer if consider actual conditions, hull cell effective layer thickness degree can also further reduce, and efficient can further improve.
Fig. 9 has provided amorphous silicon and the amorphous FeSi that thickness is respectively 20/500/20nm 2The Si/FeSi that forms 2/ Si battery and thickness are the photovoltaic property simulation comparison diagram of the PIN amorphous silicon battery of 8/300/15nm.Can obtain because amorphous silicon has the band gap width bigger than silicon, the open circuit voltage of novel amorphous FeSi2 battery can be brought up to 0.8V, and transformation efficiency reaches 21.2%, and fill factor, curve factor is 0.77, the transformation efficiency of the PIN amorphous silicon battery that corresponding 300nm is thick only is 11%, and fill factor, curve factor is 0.65.Therefore this new structure also can adopt non-crystalline material, can obtain the photoelectric conversion efficiency higher than amorphous silicon thin-film solar cell under the suitable situation of film thickness.

Claims (7)

1. Si/FeSi 2/ Si sandwich structure consisting solar cell, its basic structure comprises: transparent substrates (1) or opaque substrate (7), transparent conductive film (2), P type silicon doping layer (3), intrinsic FeSi2 layer (4), N type silicon doping layer (5), back electrode (6), it is characterized in that in sandwich structure, being provided with can realize ultra-thin, have a β-FeSi of high absorption coefficient and higher carrier mobility efficiently 2Layer.
2. Si/FeSi according to claim 1 2/ Si sandwich structure consisting solar cell is characterized in that 3,4,5 layers for effective light absorbing zone, and wherein the 3rd layer thickness is 0.01～0.5 μ m, the material doped P-type silicon of attaching most importance to, and doping content is 10 19～10 20Cm -2The 4th layer thickness is 0.2～4 μ m, and material is intrinsic β-FeSi 2Layer or involuntary doping β-FeSi 2Layer, carrier concentration is 10 15～10 17Cm -2The 5th layer thickness is 0.01～2 μ m, and material is heavily doped N type Si, and dosed carrier concentration is 10 19～10 21
3. Si/FeSi according to claim 1 2/ Si sandwich structure consisting solar cell, it is characterized in that being positioned at what adopt in the middle of the PN junction of Si is β-FeSi 2Layer material can order about the tilting table stepwise band structure that electronics or holoe carrier separation and oriented opposite move by wide/narrow/broad-band gap in conjunction with forming.
4. Si/FeSi according to claim 1 2/ Si sandwich structure consisting solar cell is characterized in that the three-decker that is adopted can be PIN, NIP, PPN, PNN, NPP, NNP structure, and the intermediate layer is that weak P type of intrinsic-OR or weak N type mix, and PN type Si order in two ends is interchangeable.
5. Si/FeSi according to claim 1 2/ Si sandwich structure consisting solar cell is characterized in that its silicon doping layer and FeSi 2Layer can be monocrystalline, polycrystalline, amorphous or microstructure.
6. Si/FeSi according to claim 1 2/ Si sandwich structure consisting solar cell is characterized in that described transparent conductive film (2) can be the SnO2:F of suede structure or ITO or other transparent conductive films of ZnO or planar structure.
7. Si/FeSi according to claim 1 2/ Si sandwich structure consisting solar cell, it is characterized in that described back electrode (6) can be Al or Ag or Al/Ag metal material layer electrode, or ZAO and Al or Al/Ag metallic multilayer combination electrode, wherein ZAO is ZnO:Al, or other can constitute the electrode of ohmic contact with N type silicon.
CN200910273050A 2009-12-01 2009-12-01 Solar cell of sandwich structure consisting of Si/FeSi2/Si and manufacturing method thereof Pending CN101719521A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103606584A (en) * 2011-11-02 2014-02-26 常州合特光电有限公司 Heterojunction solar battery composed of amorphous silicon/crystalline silicon/beta-FeSi2
CN103646973A (en) * 2013-01-09 2014-03-19 郑州大学 Efficient thin-film photovoltaic cell
GB2484455B (en) * 2010-09-30 2015-04-01 Univ Bolton Photovoltaic cells
CN114156371A (en) * 2021-10-20 2022-03-08 广东爱旭科技有限公司 Silicon-based FeSi2Thin film quantum well solar cell and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2484455B (en) * 2010-09-30 2015-04-01 Univ Bolton Photovoltaic cells
CN103606584A (en) * 2011-11-02 2014-02-26 常州合特光电有限公司 Heterojunction solar battery composed of amorphous silicon/crystalline silicon/beta-FeSi2
CN103646973A (en) * 2013-01-09 2014-03-19 郑州大学 Efficient thin-film photovoltaic cell
CN103646973B (en) * 2013-01-09 2017-02-15 郑州大学 Efficient thin-film photovoltaic cell
CN114156371A (en) * 2021-10-20 2022-03-08 广东爱旭科技有限公司 Silicon-based FeSi2Thin film quantum well solar cell and preparation method thereof

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Application publication date: 20100602