CN102916061A - Micro-crystalline germanium and non-crystalline germanium heterogeneous absorption layer material with narrow band gap and application thereof - Google Patents
Micro-crystalline germanium and non-crystalline germanium heterogeneous absorption layer material with narrow band gap and application thereof Download PDFInfo
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- CN102916061A CN102916061A CN2012104358149A CN201210435814A CN102916061A CN 102916061 A CN102916061 A CN 102916061A CN 2012104358149 A CN2012104358149 A CN 2012104358149A CN 201210435814 A CN201210435814 A CN 201210435814A CN 102916061 A CN102916061 A CN 102916061A
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Abstract
The invention relates to a micro-crystalline germanium and non-crystalline germanium heterogeneous absorption layer material with narrow band gap, wherein a multi-layer material for a micro-crystalline germanium film and a non-crystalline germanium film to alternatively grow is prepared by adopting a cascading cycle deposition method; the thickness of the micro-crystalline germanium film is 20-50 nm; the thickness of the non-crystalline germanium film is 1-10 nm; then, plasma processing or chemical annealing processing is carried out; the process cycles in such a manner to deposit the micro-crystalline germanium film and the non-crystalline germanium film till a micro-crystalline germanium and non-crystalline germanium heterogeneous film with the total thickness of 50-1500 nm is formed; and the micro-crystalline germanium and non-crystalline germanium heterogeneous absorption layer material with the narrow band gap can be used for a silicon-based thin-film solar cell with wide spectrum and laminated layers at four ends based on the group IV film material. The micro-crystalline germanium and non-crystalline germanium heterogeneous absorption layer material with the narrow band gap disclosed by the invention has the advantages that: the spectral response range of the thin-film solar cell can be expanded to 1800 nm; on the premise of not increasing the cost of equipment, the novel laminated solar cell with wide spectrum based on the group IV film material can be obtained; solar spectrum is utilized more sufficiently; and the photoelectric conversion efficiency of the cell is increased.
Description
[technical field]
The present invention relates to the silicon-based film solar cells technical field, particularly the heterogeneous absorbed layer material of a kind of narrow band gap microcrystalline germanium-amorphous germanium and application thereof.
[technical background]
In the solar cell field, silicon-based thin film solar cell is to be subject to the extensively low-cost technologies route of approval.Say on the traditional sense, silicon-based thin film solar cell refers to the solar cell take thin-film materials such as amorphous silicon, microcrystal silicon, sige alloy, silicon-carbon alloy, silica alloys as the Intrinsic Gettering layer, generally have the raw materials consumption amount low, be easy to large tracts of land preparation, manufacturing cost, energy consumption are low, and the advantages such as manufacture process is nontoxic, pollution-free are progressively moved towards industrialization at present.
Adopting the absorbed layer material of different band gap to make many knot laminated cells, is the effective way that improves the silicon-based thin film solar cell stabilization efficiency.At present, the most common laminated cell structure is amorphous silicon-microcrystal silicon binode lamination, amorphous silicon-amorphous silicon germanium-amorphous silicon germanium and amorphous silicon-amorphous silicon germanium-microcrystal silicon three knot laminated construction etc.In said structure, the first floor, the second layer and succeeding layer have the band gap of successively decreasing, and the solar spectrum wavelength that every one deck absorbs then constantly increases progressively.
But, which kind of battery structure no matter, the theoretical band gap of bottom battery all is not less than 1.1eV, thereby the long wave spectral absorption of solar cell is limited in 1100nm, only can utilize the about 80% of AM1.5 standard solar spectrum total radiation, causes certain light loss.Therefore, expand the spectral absorption scope, become the key of further raising silicon-based thin film solar cell efficient.
[summary of the invention]
The objective of the invention is for above-mentioned existing problems, the heterogeneous absorbed layer material of a kind of narrow band gap microcrystalline germanium-amorphous germanium and application thereof are provided, this material can absorb the wavelength greater than 1100nm, be applied to four endlap layer solar cell based on IV family thin-film material, novel structure, can expand the solar cell spectral response of near infrared region, maximally utilise solar spectrum.
Technical scheme of the present invention:
The heterogeneous absorbed layer material of a kind of narrow band gap microcrystalline germanium-amorphous germanium, it is the multilayer material by microcrystalline germanium film and amorphous germanium thin film alternating growth that adopts the preparation of layer-transferred cyclic deposition method, the thickness of microcrystalline germanium film is 20-50nm, the percent by volume that its internal crystallization composition accounts for all material is 40-80%, crystallite dimension is 15-40nm, the thickness of deposited amorphous germanium film is 1-10nm afterwards, then carry out plasma treatment or chemical annealing in process, cyclic deposition microcrystalline germanium film like this and amorphous germanium thin film, until form the microcrystalline germanium that gross thickness is 50-1500nm-amorphous germanium heterofilm, be the heterogeneous absorbed layer material of narrow band gap microcrystalline germanium-amorphous germanium.
The application of the heterogeneous absorbed layer material of a kind of described narrow band gap microcrystalline germanium-amorphous germanium, be used for the wide spectrum four endlap layer silicon-based thin film solar cell based on IV family thin-film material, this solar cell is by substrate, metal electrode, transparency conductive electrode, the N-shaped doped layer of bottom battery, the heterogeneous absorbed layer of microcrystalline germanium-amorphous germanium, the p-type doped layer of bottom battery, electrically conducting transparent and grid line combination electrode, the central, clear insulating barrier, electrically conducting transparent and grid line combination electrode, the microcrystal silicon battery, the amorphous silicon germanium battery, amorphous silicon battery and electrically conducting transparent and the stack of grid line combination electrode consist of, metal electrode wherein, transparency conductive electrode, the N-shaped doped layer of bottom battery, the heterogeneous absorbed layer of microcrystalline germanium-amorphous germanium, the p-type doped layer of bottom battery and electrically conducting transparent and grid line combination electrode consist of the bottom battery take microcrystalline germanium-amorphous germanium dissimilar materials as the thin film solar cell of absorbed layer, be used for absorbing the long wave solar spectrum of 1100-1800nm wave band, electrically conducting transparent and grid line combination electrode, the microcrystal silicon battery, the amorphous silicon germanium battery, amorphous silicon battery and electrically conducting transparent and grid line combination electrode consist of traditional silicon-based thin-film lamination top cell, be used for absorbing the solar spectrum of 300-1100nm wave band, bottom battery and top cell respectively have battery the two poles of the earth and are provided with four exits, link to each other with transparent insulating layer between bottom battery and the top cell, its resistivity is higher than 1010 Ω cm, 1100-1800nm wave band transmitance is higher than 60%, refractive index is 1.5-3.0.
Operation principle of the present invention:
Adopt the heterogeneous absorbed layer material of novel microcrystalline germanium-amorphous germanium of layer-transferred deposition process preparation, have excellent photoelectric conversion capacity.This be because, microcrystalline germanium material with single component, constantly accumulate grain boundary defects along with the increase of thickness in growth course, the significantly increase of defect state density makes the carrier transport characteristic variation, and then material is lost absorb photon and convert thereof into the ability of electronics.Adopt the layer-transferred deposition process, behind the certain thickness microcrystalline germanium material of deposition, deposition one deck amorphous germanium thin layer, and in conjunction with certain plasma treatment or chemical annealing in process technology, can effectively slow down because of grain growth, the crosslinked grain boundary defects that forms, reach the purpose of passivation grain boundary defects.In addition, it is periodic that microcrystalline germanium-the amorphous germanium heterostructure is a kind of mqw material, band gap is the potential barrier that the amorphous germanium material of 1.1eV consists of electronics and hole, by changing the thickness of amorphous germanium layer, can regulate the band gap of the heterogeneous absorbed layer material of microcrystalline germanium-amorphous germanium, make it between 0.70-1.10eV, to change, reach the purpose of expanding battery near infrared region spectral response.
In order to give full play to the narrow band gap advantage of the heterogeneous absorbed layer material of microcrystalline germanium-amorphous germanium, improve battery conversion efficiency, we propose a kind of four endlap layer battery structure design of novelty.The traditional structure of silicon-based thin-film lamination solar cell is that band gap is absorbed respectively by the solar spectrum of shortwave to long wave to narrow different sub-battery by wide, with the form series combination of tunnel junctions, realizes transporting of electric current between each sub-battery.Yet, if the heterogeneous absorbed layer material of narrow band gap microcrystalline germanium-amorphous germanium is directly used in the silicon-based thin-film lamination solar cell of traditional structure, owing to be subject to the restriction of laminated cell currents match principle, under the relatively low prerequisite of open circuit voltage, can't really improve the conversion efficiency of laminated cell.Adopt four novel endlap layer battery structure, replace traditional n/p tunnel junctions with insulating properties transparent intermediate layer material, realize physical connection and the electricity separation of top cell and bottom battery, make top cell and bottom battery can absorb respectively the solar spectrum of 300-1100nm and 1100-1800nm wave band, be independent of each other in electricity, broken away from the restriction of laminated cell currents match principle; On the other hand, the transparent oxide insulating barrier of low-refraction, function with light regime, the effect in reflector in the middle of playing, incident light is carried out the selectivity reallocation, the short-wavelength light that is fit to is reflected back into top cell, guarantee simultaneously to be fit to the effectively transmission of light that the bottom battery utilizes, the narrow band gap advantage of the heterogeneous absorbed layer material of microcrystalline germanium-amorphous germanium is not fully exerted.
Advantage of the present invention and beneficial effect are: a kind of novel absorbing layer material for thin film solar cell is prepared in research and development, namely based on the heterogeneous absorbed layer material of periodic narrow crack microcrystalline germanium-amorphous germanium of crystal boundary passivating technique, this material has the feature of low defect state density, and band gap can be adjustable continuously between 0.70-1.10eV, the spectral response range of thin film solar cell can be expanded to 1800nm, realize wide spectral absorption, can effectively utilize 95% of AM1.5 solar spectrum total radiation; This material is used for the wide spectrum four endlap layer battery based on IV family thin-film material, can give full play to the advantage of the heterogeneous absorbed layer material of narrow band gap microcrystalline germanium-amorphous germanium aspect the expansion spectral response range, and compatible mutually with traditional silicon-based thin-film lamination battery technology, both are organically combined, under the prerequisite that does not increase equipment cost, just can obtain the new molded breadth spectrum solar cell based on IV family thin-film material, utilize more fully solar spectrum, improved the photoelectric conversion efficiency of battery.
[description of drawings]
Fig. 1 is the heterogeneous absorbed layer material structure of narrow band gap microcrystalline germanium-amorphous germanium schematic diagram.
Among the figure: 1. microcrystalline germanium material i1 2. amorphous germanium material i2
3. microcrystalline germanium material i1 4. amorphous germanium material i2
5. microcrystalline germanium material i1 6. amorphous germanium material i2
7. microcrystalline germanium material i1 8. amorphous germanium material i2
9. microcrystalline germanium material i1 10. amorphous germanium material i2
11. microcrystalline germanium material i1 12. amorphous germanium material i2
13. microcrystalline germanium material i1 14. amorphous germanium material i2
15. microcrystalline germanium material i1 16. amorphous germanium material i2
17. microcrystalline germanium material i1 18. amorphous germanium material i2
19. microcrystalline germanium material i1 20. amorphous germanium material i2
21. microcrystalline germanium material i1 22. amorphous germanium material i2
23. microcrystalline germanium material i1 24. amorphous germanium material i2
25. microcrystalline germanium material i1 26. amorphous germanium material i2
Fig. 2 is based on the wide spectrum four endlap layer battery structure schematic diagrames of IV family thin-film material.
Among the figure: p-type doped layer 33. electrically conducting transparents of the heterogeneous absorbed layer 32. bottom batteries of N-shaped doped layer 31. narrow band gap microcrystalline germanium-amorphous germaniums of 27. substrates, 28. metal electrodes, 29. transparency conductive electrodes, 30. bottom batteries and grid line combination electrode 34. transparent insulating layers, 35. electrically conducting transparents and grid line combination electrode 36. microcrystal silicon batteries 37. amorphous silicon germanium battery 38. amorphous silicon batteries, 39. electrically conducting transparents and grid line combination electrodes
[embodiment]
Embodiment:
The heterogeneous absorbed layer material of a kind of narrow band gap microcrystalline germanium-amorphous germanium, as shown in Figure 1, it is the multilayer material by microcrystalline germanium film and amorphous germanium thin film alternating growth that adopts the preparation of layer-transferred cyclic deposition method, wherein the microcrystalline germanium film 1,3,5,7,9,11,13,15,17,19,21,23,25 adopt the preparation of plasma assisted reaction heat CVD technology, namely the chemical reaction by germane and hydrogen is 250-350 ℃ of lower preparation at depositing temperature, volumetric flow of gas percentage is: germane accounts for 0.1-2%, hydrogen is surplus, the thickness of microcrystalline germanium film is 45nm, the percent by volume that its internal crystallization composition accounts for all material is 60%, crystallite dimension is 30nm, and band gap is 0.7-0.8eV; Amorphous germanium thin film 2,4,6,8,10,12,14,16,18,20,22,24,26 using plasmas strengthen the chemical vapour deposition technique preparation, and reacting gas is pure germanium alkane, and reaction temperature is 250-300 ℃, and film thickness is 5nm; The gross thickness of microcrystalline germanium-amorphous germanium heterofilm is 650nm.
The heterogeneous absorbed layer material of this narrow band gap microcrystalline germanium-amorphous germanium is used for wide spectrum four endlap layer silicon-based thin film solar cell based on IV family thin-film material, this solar cell is by substrate 27, metal electrode 28, transparency conductive electrode 29, the N-shaped doped layer 30 of bottom battery, the heterogeneous absorbed layer 31 of microcrystalline germanium-amorphous germanium, the p-type doped layer 32 of bottom battery, electrically conducting transparent and grid line combination electrode 33, transparent insulating layer 34, electrically conducting transparent and grid line combination electrode 35, microcrystal silicon battery 36, amorphous silicon germanium battery 37, amorphous silicon battery 38 and electrically conducting transparent and 39 stacks of grid line combination electrode consist of, wherein metal electrode 28, transparency conductive electrode 29, the N-shaped doped layer 30 of bottom battery, the heterogeneous absorbed layer 31 of microcrystalline germanium-amorphous germanium, the bottom battery that the p-type doped layer 32 of bottom battery and electrically conducting transparent and grid line combination electrode 33 consist of take microcrystalline germanium-amorphous germanium dissimilar materials as the thin film solar cell of absorbed layer, be used for absorbing the long wave solar spectrum of 1100-1800nm wave band, electrically conducting transparent and grid line combination electrode 35, microcrystal silicon battery 36, amorphous silicon germanium battery 37, amorphous silicon battery 38 and electrically conducting transparent and grid line combination electrode 39 consist of traditional silicon-based thin-film lamination top cell, be used for absorbing the solar spectrum of 300-1100nm wave band, bottom battery and top cell respectively have battery the two poles of the earth and are provided with four exits 28,33,35,39, link to each other with transparent insulating layer 34 between bottom battery and the top cell, its resistivity is higher than 10
10Ω cm, 1100-1800nm wave band transmitance are higher than 60%, refractive index is 1.5-3.0.
The central, clear insulating layer material that relates among this embodiment is hydrogenated amorphous silica material, using plasma strengthens the chemical vapour deposition technique preparation, namely the chemical reaction by silane, carbon dioxide and hydrogen is 200 ℃ of lower preparations at depositing temperature, and thickness is 500nm, and refractive index is 2.0-2.5.Microcrystal silicon battery 37, amorphous silicon germanium battery 38 and amorphous silicon battery 39 using plasmas strengthen the chemical vapour deposition technique preparation, traditional laminated silicon-base film solar cell that its series connection obtains can reach the conversion efficiency of 12-13%, combine with the bottom battery, can make four endlap layer battery conversion efficiency based on IV family thin-film material reach 13-14%.
Claims (2)
1. heterogeneous absorbed layer material of narrow band gap microcrystalline germanium-amorphous germanium, it is characterized in that: be the multilayer material by microcrystalline germanium film and amorphous germanium thin film alternating growth that adopts the preparation of layer-transferred cyclic deposition method, the thickness of microcrystalline germanium film is 20-50nm, the percent by volume that its internal crystallization composition accounts for all material is 40-80%, crystallite dimension is 15-40nm, the thickness of deposited amorphous germanium film is 1-10nm afterwards, then carry out plasma treatment or chemical annealing in process, cyclic deposition microcrystalline germanium film like this and amorphous germanium thin film, until form the microcrystalline germanium that gross thickness is 50-1500nm-amorphous germanium heterofilm, be the heterogeneous absorbed layer material of narrow band gap microcrystalline germanium-amorphous germanium.
2. as claimed in claim 1 application of the heterogeneous absorbed layer material of narrow band gap microcrystalline germanium-amorphous germanium, it is characterized in that: be used for the wide spectrum four endlap layer silicon-based thin film solar cell based on IV family thin-film material, this solar cell is by substrate, metal electrode, transparency conductive electrode, the N-shaped doped layer of bottom battery, the heterogeneous absorbed layer of microcrystalline germanium-amorphous germanium, the p-type doped layer of bottom battery, electrically conducting transparent and grid line combination electrode, the central, clear insulating barrier, electrically conducting transparent and grid line combination electrode, the microcrystal silicon battery, the amorphous silicon germanium battery, amorphous silicon battery and electrically conducting transparent and the stack of grid line combination electrode consist of, metal electrode wherein, transparency conductive electrode, the N-shaped doped layer of bottom battery, the heterogeneous absorbed layer of microcrystalline germanium-amorphous germanium, the p-type doped layer of bottom battery and electrically conducting transparent and grid line combination electrode consist of the bottom battery take microcrystalline germanium-amorphous germanium dissimilar materials as the thin film solar cell of absorbed layer, be used for absorbing the long wave solar spectrum of 1100-1800nm wave band, electrically conducting transparent and grid line combination electrode, the microcrystal silicon battery, the amorphous silicon germanium battery, amorphous silicon battery and electrically conducting transparent and grid line combination electrode consist of traditional silicon-based thin-film lamination top cell, be used for absorbing the solar spectrum of 300-1100nm wave band, bottom battery and top cell respectively have battery the two poles of the earth and are provided with four exits, link to each other with transparent insulating layer between bottom battery and the top cell, its resistivity is higher than 10
10Ω cm, 1100-1800nm wave band transmitance are higher than 60%, refractive index is 1.5-3.0.
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| CN105304751A (en) * | 2015-09-18 | 2016-02-03 | 新奥光伏能源有限公司 | Heterogeneous junction solar cell, preparation method thereof and surface passivation method |
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| JPH11261102A (en) * | 1998-03-10 | 1999-09-24 | Canon Inc | Photovoltaic device |
| JP2004335733A (en) * | 2003-05-07 | 2004-11-25 | National Institute Of Advanced Industrial & Technology | Thin film solar cell |
| CN101931017A (en) * | 2010-08-24 | 2010-12-29 | 江苏绿洲新能源有限公司 | Solar battery with intermediate band and method for generating quantum dot structure absorbing layer |
| WO2011105160A1 (en) * | 2010-02-24 | 2011-09-01 | 株式会社カネカ | Thin film photoelectric conversion device and process for production thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11261102A (en) * | 1998-03-10 | 1999-09-24 | Canon Inc | Photovoltaic device |
| JP2004335733A (en) * | 2003-05-07 | 2004-11-25 | National Institute Of Advanced Industrial & Technology | Thin film solar cell |
| WO2011105160A1 (en) * | 2010-02-24 | 2011-09-01 | 株式会社カネカ | Thin film photoelectric conversion device and process for production thereof |
| CN101931017A (en) * | 2010-08-24 | 2010-12-29 | 江苏绿洲新能源有限公司 | Solar battery with intermediate band and method for generating quantum dot structure absorbing layer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105304751A (en) * | 2015-09-18 | 2016-02-03 | 新奥光伏能源有限公司 | Heterogeneous junction solar cell, preparation method thereof and surface passivation method |
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