CN103367513A - Polycrystalline silicon thin film solar cell and preparation method thereof - Google Patents
Polycrystalline silicon thin film solar cell and preparation method thereof Download PDFInfo
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- CN103367513A CN103367513A CN2013102885823A CN201310288582A CN103367513A CN 103367513 A CN103367513 A CN 103367513A CN 2013102885823 A CN2013102885823 A CN 2013102885823A CN 201310288582 A CN201310288582 A CN 201310288582A CN 103367513 A CN103367513 A CN 103367513A
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Abstract
The invention provides an n-ZnO/p-Si heterojunction solar cell based on a ZnO nanoarray and a preparation method thereof. The structure of the cell is as follows: an FTO (fluorine-doped tin oxide) or AZO transparent conductive glass substrate/a ZnO seed crystal layer/an N-type ZnO nanoarray/a P-type polycrystalline silicon thin film/a metal electrode. The preparation method is as follows: the ZnO seed crystal layer is prepared on the FTO or AZO transparent conductive glass substrate by a sol-gel method or magnetron sputtering, the ZnO nanoarray is prepared on the ZnO seed crystal layer by a hydrothermal synthesis method, a metal inducing method is then adopted to deposit the P-type polycrystalline silicon thin film on the surface of the ZnO nanoarray, the metal electrode is plated finally, and thereby the n-ZnO/p-Si heterojunction solar cell is formed. The structure is characterized in that the ZnO nanorods are completely wrapped by the Si film, and the nanoarray is utilized to transfer carriers to increase the efficiency of photovoltaic conversion; a group of doping elements are shared by N-type ZnO and P-type Si, metal atoms also can be doped when the metal inducing method is utilized, and thereby an effective PN junction is formed.
Description
Technical field
The present invention relates to a kind of New Polycrystalline silicon solar battery structure and preparation method thereof, belong to new forms of energy, the technical fields such as Semiconductor Optic Electronics.
Background technology
Solar energy is resourceful regenerative resource, and preparation high conversion efficiency, high life, low production cost, low power consuming, the abundant solar cell of material safety non-toxic and source are the important directions of current solar cell development.
The ZnO/Si heterojunction solar battery is a kind of dual intensity band structure, not only can Effective Raise solar cell light-photoelectric transformation efficiency, can also effectively reduce the cost of solar cell.Aspect thin-film solar cells, adopt the whole bag of tricks making ZnO film on the Si substrate to come making ZnO/p-Si, ZnO/n-Si, n-ZnO/n-Si heterojunction solar battery both at home and abroad.Up to the present, the highest photovoltaic conversion efficiency of n-ZnO/n-Si heterojunction is that the highest photovoltaic conversion efficiency of 8.5%, n-ZnO/p-Si heterojunction is 6.8%, also has in theory the space that promotes.Aspect organic solar batteries, adopt TiO
2The solar cell photoelectric conversion efficiency of flatted membrane and polymer hybrid only is 0.09%, and adopts the TiO of same process preparation
2The solar cell of nano-array and ZnO nano array and polymer hybrid, peak efficiency reaches 0.29%, demonstrates fully the advantage of nano-array aspect raising photovoltaic conversion efficiency.
Nano-array is used for the ZnO/Si hetero-junction thin-film solar cell at present, structurally is to adopt making ZnO nano-array on the Si substrate, does not also appear at the structure of deposited polycrystalline silicon thin film on the ZnO nano array basis at present.On the Si substrate in the making ZnO nano array structure with the Si substrate contact be not real ZnO nanorod, but there is higher defect concentration in the ZnO inculating crystal layer between ZnO inculating crystal layer and the Si, be unfavorable for quick separation and the transfer of exciton.On the contrary, deposited polycrystalline silicon thin film on the ZnO nano array, directly forming core growth on ZnO nanorod of Si, the ZnO nano array can directly go deep into the inside to Si, realize the comprehensive clading ZnO nano rod of polysilicon membrane, not only reduce defect concentration between the two, and greatly increased both contacts area, be conducive to the quick separation of exciton, reduce compound probability.
The present invention has structurally overcome the deficiency of making ZnO nano array structure on the Si substrate, takes full advantage of the advantage that nanometer rods improves the photovoltaic conversion efficiency.First making ZnO inculating crystal layer on FTO or AZO transparent conducting glass is proposed, at inculating crystal layer growth ZnO nano array, again at nano-array basis deposition P type polysilicon membrane, form the ZnO/Si heterojunction solar of the comprehensive clading ZnO nano rod of polysilicon membrane, the complete clading ZnO nano array of polysilicon membrane is given full play to the effect of nano-array, transmits to a greater extent photo-generated carrier, reduce the interface recombination probability, improve delivery efficiency.
The required doped chemical of N-type ZnO nano array and P type Si film is same or with gang's element among the present invention, can form effective PN junction, improve the open circuit voltage of battery, can avoid again the battery performance that the doped chemical counterdiffusion causes in preparation or use procedure to change.
The preparation method of polysilicon membrane is a lot, can be divided into direct preparation and indirectly preparation.Directly preparation refers to directly prepare polysilicon membrane by PECVD, LPCVD or HWCVD on substrate, but the speed of growth is slow.The HWCVD growth rate is higher than common PE CVD, but has the problem of the pollution of high-temperature metal wire material.What preparation method was commonly used indirectly is the metal-induced crystallization technology, the method is less demanding to substrate, the polysilicon membrane of metal-induced crystallization preparation depends primarily on metal species and crystallization temperature, irrelevant with factors such as the structure of amorphous silicon, metal layer thickness, can simplify preparation technology to the initial condition of amorphous silicon is less demanding, reduce production costs, but this technology can be introduced metal impurities, the electric property of polysilicon membrane is exerted an influence.The general method of pickling or directional solidification that adopts is removed metal impurities, but causes the waste of metallic pollution and metal material.
The metal A l pollution that the present invention prepares metal inducement in the polysilicon membrane has dexterously become favorable factor.During metal-induced crystallization, Al and Si on the ZnO spread, and Al is diffused into outer surface, and Si is diffused into ZnO nano array surface nucleating growth and forms polysilicon membrane.Polysilicon membrane contacts with the ZnO nano array is more large-area, better transmits charge carrier, improves the photovoltaic conversion efficiency.It is that the P type mixes that Al mixes among the Si, mixes among the ZnO and mixes for N-type, utilizes the doping of Al atom, forms effective PN heterojunction, not only improves the open circuit voltage of solar cell, and the metal A l of remnants effectively utilizes, and avoids pollution and the waste of metal material.
Each stage technique of compositions, process of the present invention is ripe, and the feasibility degree is high, but and the large tracts of land preparation, without high temperature highly energy-consuming step, material source is abundant, safety non-toxic.
Summary of the invention
The present invention proposes a kind of n-ZnO/p-Si heterojunction solar battery based on the ZnO nano array, and technical scheme may further comprise the steps:
(1) employing is based on the new type solar energy structure of ZnO nano array, and structure comprises successively: FTO or AZO transparent conducting glass substrate, ZnO inculating crystal layer, N-type ZnO nano array, P type polysilicon membrane, metal electrode.
(2) adopt sol-gel process or magnetron sputtering method making ZnO inculating crystal layer on FTO transparent conducting glass substrate, recycling hydrothermal synthesis method making ZnO nano-array.
(3) prepare polysilicon membrane at the ZnO nano array.Method by the metal-induced crystallization amorphous silicon membrane prepares polysilicon membrane.In ZnO nano array surface vacuum evaporation layer of metal, with PECVD deposition one deck amorphous silicon membrane, obtain polysilicon membrane through heat-treatment of annealing again, P type polysilicon doping comprises B, Al.The effect of the full clading ZnO nano rod of polysilicon membrane is formed on can go directly nano-array bottom of the polysilicon membrane after the crystallization.
(4) in polysilicon membrane surface vacuum evaporation layer of metal as electrode, prepare above-mentioned n-ZnO/p-Si heterojunction solar battery based on the ZnO nano array.
The invention has the advantages that:
(1) each stage technique of compositions, process of the present invention is ripe, and the feasibility degree is high, but and the large tracts of land preparation, without high temperature highly energy-consuming step, can adopt cheap simple glass substrate, material source is abundant, safety non-toxic.
(2) the present invention structurally utilizes the advantage of nano-array, and overcome the deficiency of making ZnO on the Si substrate, employing is at ZnO nano array basis growth preparation polysilicon membrane, the ZnO nano array can directly go deep into the inside to the Si film, realize the comprehensive clading ZnO nano rod of polysilicon membrane, take full advantage of nano array structure to the distinctive photoelectricity transmission separation effect of photo-generated carrier, increase the contact area of ZnO nanorod and polysilicon membrane, the effective communication photo-generated carrier, reduce the interface recombination probability, improve delivery efficiency.
(3) the required doped chemical of N-type ZnO nano array and P type Si film is same or with gang's element among the present invention, can form effective PN junction, improve the open circuit voltage of battery, can avoid again the battery performance that the doped chemical counterdiffusion causes in preparation or use procedure to change.
(4) the present invention has become the metal A l pollution that metal inducement prepares in the polysilicon membrane into favorable factor.When adopting metal A l revulsion to prepare polysilicon membrane, utilize the doping of Al atom, Al mixes and is the doping of P type among the Si, mixes among the ZnO and mixes for N-type, is conducive to form effective PN heterojunction, is conducive to improve the open circuit voltage of solar cell.Remaining metal A l effectively utilizes, and avoids the pollution of metal material.
Description of drawings
Accompanying drawing is structural representation of the present invention, further specifies the present invention below in conjunction with accompanying drawing and implementation case.
Fig. 1 is a kind of structural representation of the multi-crystal silicon film solar battery based on the ZnO nano array;
Reference numeral: 1.FTO transparent conducting glass substrate; 2.ZnO inculating crystal layer; 3.N type ZnO nano array; 4.P type polysilicon membrane; 5. metal electrode.
Fig. 2 is case study on implementation 1 aluminum-induced crystallized technique annealing pre-structure schematic diagram;
Reference numeral: 1.FTO transparent conducting glass substrate; 2.ZnO inculating crystal layer; 3.N type ZnO nano array; 6. induce metallic aluminium; 7. amorphous silicon membrane.
Fig. 3 is structural representation after the case study on implementation 1 aluminum-induced crystallized technique annealing;
Reference numeral: 1.FTO transparent conducting glass substrate; 2.ZnO inculating crystal layer; 3.N type ZnO nano array; 4.P type polysilicon membrane; 8. aluminium film after annealing.
Embodiment
The present invention will be further described below by embodiment, and the present invention is confined to absolutely not the embodiment that states:
Embodiment 1:
Such as Fig. 2, as substrate, adopt sol-gel process making ZnO inculating crystal layer with FTO glass, then adopt hydrothermal synthesis method at inculating crystal layer growth N-type ZnO nano array; Evaporation layer of metal Al on nano-array adopts PECVD to mix the Al amorphous silicon membrane in Al film deposition; Adopt vacuum evaporation one deck Al at annealed film again, form the n-ZnO/p-Si heterojunction solar battery based on the ZnO nano array.Zinc ion concentration is 0.005mol/L, and bath temperature is 60 ℃, and water-bath time 8h, PECVD reaction chamber temperature are 300 ℃, and the annealing heat treatment temperature is 650 ℃.
Such as Fig. 3, after Overheating Treatment, Al and Si on the ZnO spread, and Al is diffused into outer surface, Si diffusion ZnO surface, and polysilicon membrane contacts with the ZnO nano array is more large-area, better transmits charge carrier, improves the photovoltaic conversion efficiency.
Embodiment 2:
Select FTO glass as substrate, adopt magnetron sputtering method making ZnO inculating crystal layer.Then adopt hydrothermal synthesis method at inculating crystal layer growth N-type ZnO nano array; Evaporation layer of metal Ni on nano-array adopts PECVD to mix the B amorphous silicon membrane in Ni film deposition; Adopt vacuum coating plating one deck Al at annealed film again, form the n-ZnO/p-Si heterojunction solar battery based on the ZnO nano array.Zinc ion concentration is 0.015mol/L, and bath temperature is 70 ℃, and water-bath time 7h, PECVD reaction chamber temperature are 350 ℃, and the annealing heat treatment temperature is 550 ℃.
Embodiment 3:
Select FTO glass as substrate, adopt magnetron sputtering method making ZnO inculating crystal layer.Then adopt hydrothermal synthesis method at inculating crystal layer growth N-type ZnO nano array; Evaporation layer of metal Ag on nano-array adopts PECVD to mix the B amorphous silicon membrane in Ag film deposition; Adopt vacuum coating plating one deck Cu at annealed film again, form the n-ZnO/p-Si heterojunction solar battery based on the ZnO nano array.Zinc ion concentration is 0.025mol/L, and bath temperature is 80 ℃, and water-bath time 5.5h, PECVD reaction chamber temperature are 400 ℃, and the annealing heat treatment temperature is 500 ℃.
Embodiment 4:
Select FTO glass as substrate, adopt magnetron sputtering method making ZnO inculating crystal layer.Then adopt hydrothermal synthesis method at inculating crystal layer growth N-type ZnO nano array; Evaporation layer of metal Cu on nano-array adopts PECVD to mix the B amorphous silicon membrane in Cu film deposition; Adopt vacuum coating plating one deck Pt at annealed film again, form the n-ZnO/p-Si heterojunction solar battery based on the ZnO nano array.Zinc ion concentration is 0.035mol/L, and bath temperature is 85 ℃, and water-bath time 4.5h, PECVD reaction chamber temperature are 450 ℃, and the annealing heat treatment temperature is 450 ℃.
Embodiment 5:
Select AZO glass as substrate, adopt magnetron sputtering method making ZnO inculating crystal layer.Then adopt hydrothermal synthesis method at inculating crystal layer growth N-type ZnO nano array; Evaporation layer of metal Au on nano-array adopts PECVD to mix the B amorphous silicon membrane in Au film deposition; Adopt vacuum coating plating one deck Ag at annealed film again, form the n-ZnO/p-Si heterojunction solar battery based on the ZnO nano array.Zinc ion concentration is 0.04mol/L, and bath temperature is 90 ℃, and water-bath time 3h, PECVD reaction chamber temperature are 500 ℃, and the annealing heat treatment temperature is 400 ℃.
Embodiment 6:
Select AZO glass as substrate, adopt magnetron sputtering method making ZnO inculating crystal layer.Then adopt hydrothermal synthesis method at inculating crystal layer growth N-type ZnO nano array; Evaporation layer of metal Pd on nano-array adopts PECVD to mix the B amorphous silicon membrane in Pd film deposition; Adopt vacuum coating plating one deck Ag at annealed film again, form the n-ZnO/p-Si heterojunction solar battery based on the ZnO nano array.Zinc ion concentration is 0.05mol/L, and bath temperature is 100 ℃, and water-bath time 2h, PECVD reaction chamber temperature are 600 ℃, and the annealing heat treatment temperature is 350 ℃.
Claims (10)
1. the multi-crystal silicon film solar battery based on the ZnO nano array is characterized in that, its structure comprises successively: FTO or AZO transparent conducting glass substrate, ZnO inculating crystal layer, N-type ZnO nano array, P type polysilicon membrane, metal electrode.
2. according to right 1 described structure, it is characterized in that, N-type ZnO nano array is directly deeply inner to the Si film, realizes the comprehensive clading ZnO nano rod of polysilicon membrane.
3. according to right 1 described structure, it is characterized in that, the required doped chemical of N-type ZnO nano array and P type Si film is same or with gang's element, can form effective PN junction, improve the open circuit voltage of battery, can avoid again the battery performance that the doped chemical counterdiffusion causes in preparation or use procedure to change.
4. according to right 1 described structure, it is characterized in that, adopt first sol-gel process or magnetron sputtering method making ZnO inculating crystal layer on FTO or AZO transparent conducting glass substrate in the preparation N-type ZnO nano array process, then adopt hydrothermal synthesis method at inculating crystal layer preparation N-type ZnO nano array, the N-type doped chemical comprises B, Al.
5. according to right 1 described structure, it is characterized in that, in the step of the above-mentioned P type polysilicon membrane of preparation, form P type polysilicon membrane by metal-induced crystallization amorphous silicon membrane, thermal anneal process, the P type mixes and comprises B, Al.
6. according to right 5 described preparation methods, it is characterized in that, in the step of the above-mentioned P type polysilicon membrane of preparation, the described metal of inducing comprises Al, Ni, Cu, Au, Ag, Pd.
7. according to right 6 described preparation methods, it is characterized in that, in the step of the above-mentioned P type polysilicon membrane of preparation, if it is that the P type mixes that employing induces metal A l, Al to mix among the Si, mixing among the ZnO is that N-type is mixed, effectively form the PN heterojunction, improve the open circuit voltage of battery.
8. according to right 1 described structure, it is characterized in that, adopt the vacuum evaporation metal electrode, metal electrode comprises Al, Ag, Cu, Pt.
9. according to right 3 described preparation methods, it is characterized in that, zinc ion concentration is between 0.005-0.5mol/L, and bath temperature is between 60-100 ℃, and the water-bath time is between 2-8h.
10. according to right 4 described preparation methods, it is characterized in that, in the step of the above-mentioned P type polysilicon membrane of preparation, the PECVD reaction chamber temperature arranges between 300-600 ℃; Heat treatment temperature is between 350-650 ℃.
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| CN103632754A (en) * | 2013-11-21 | 2014-03-12 | 中国科学院宁波材料技术与工程研究所 | Ultrathin aluminum-doped ZnO transparent conductive film and preparing method thereof |
| CN106206779A (en) * | 2016-08-01 | 2016-12-07 | 中国科学院高能物理研究所 | Heterojunction solar battery with silicon nano column array as substrate and preparation method thereof |
| WO2016206050A1 (en) * | 2015-06-25 | 2016-12-29 | 华为技术有限公司 | Photoelectric detector |
| CN106711251A (en) * | 2015-11-16 | 2017-05-24 | 中国科学院福建物质结构研究所 | SIS/MIS structure flexible crystalline silicon battery |
| CN108573851A (en) * | 2017-03-08 | 2018-09-25 | 上海新昇半导体科技有限公司 | The preparation method of autoregistration seed layer and autoregistration film |
| CN108793766A (en) * | 2018-06-12 | 2018-11-13 | 西安理工大学 | The electrochomeric films and preparation method thereof of ir transmissivity in a kind of effective modulation |
| CN109930121A (en) * | 2019-02-26 | 2019-06-25 | 宜春学院 | A kind of preparation method of zinc oxide conductive thin film |
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Application publication date: 20131023 |