CN102280588B - Silicon-based nuclear shell nanowire photovoltaic cell and preparation process thereof - Google Patents
Silicon-based nuclear shell nanowire photovoltaic cell and preparation process thereof Download PDFInfo
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 134
- 239000010703 silicon Substances 0.000 title claims abstract description 134
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 239000002070 nanowire Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 41
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 5
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims abstract description 5
- 238000001039 wet etching Methods 0.000 claims abstract description 4
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 36
- 239000011258 core-shell material Substances 0.000 claims description 24
- 230000005525 hole transport Effects 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 11
- 238000005516 engineering process Methods 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000003495 polar organic solvent Substances 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 2
- 239000010408 film Substances 0.000 claims 3
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- 238000006555 catalytic reaction Methods 0.000 claims 1
- 238000003486 chemical etching Methods 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 239000010409 thin film Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 abstract 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
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- 238000013459 approach Methods 0.000 description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 229920005591 polysilicon Polymers 0.000 description 3
- 150000003376 silicon Chemical class 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005247 gettering Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
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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
- Y02E10/549—Organic PV cells
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Abstract
The invention discloses a silicon-based nuclear shell nanowire photovoltaic cell and a preparation process thereof. The photovoltaic cell comprises an N-type silicon substrate, wherein an N-type silicon nanowire array serving as a photoactivity layer is formed on the front of the substrate, and a metal back electrode is arranged on the bottom of the substrate; and the silicon nanowire array and an organic conductive polymer in electron hole transmission form a nuclear shell Schottky heterojunction on which an ITO (indium tin oxide) top electrode is arranged. Furthermore, the organic conductive polymer comprises a PEDOT (polyethylenedioxythiophene):PSS (poly(sodium sulfonate)). The silicon nanowire array and the silicon substrate are formed by single crystal silicon or polycrystalline silicon with purity of 3-6N level, the nanowire height is 3-5 mu m, and the substrate thickness is 5-200 mu m. The preparation process is as follows: preparing the silicon nanowire array on the front of the N-type silicon substrate by using wet etching, then forming the nuclear shell nanowire heterojunction with the organic conductive polymer in electron hole transmission, and finally respectively assembling the metal back electrode and the ITO top electrode on the bottom of the silicon substrate and the heterojunction. The photovoltaic cell has the advantages of less raw material amount, low cost, high conversion efficiency and simple preparation process.
Description
Technical field
The present invention be more particularly directed to a kind of organic conductive polyalcohol nucleocapsid nano wire photovoltaic cell and preparation technology thereof of N-type silicon/hole transport, belong to solar energy switch technology field.
Background technology
Photovoltaic cell can constantly change in a steady stream electric energy with sunlight and solve lack of energy and the problem of environmental pollution that current people face.The photoelectric conversion efficiency of crystal silicon photovoltaic cell is high, has occupied 80% of whole photovoltaic market.But the crystal silicon photovoltaic cell high expensive, hindered the development of photovoltaic generation industry at present.Wherein, crystal silicon photovoltaic cell need to be used a greater number (200-300 μ m is thick) and high-purity (〉 6N level) crystalline silicon as raw material, cost of material accounts for more than 40% of whole photovoltaic module, is a principal element of crystal silicon photovoltaic cell high expensive.The usage quantity that how effectively to reduce raw material on the basis that keeps crystal silicon photovoltaic cell efficient is an effective way that reduces the photovoltaic module cost.The photovoltaic cell of silicon nanowire array can be realized this approach.The article of having reported (as, " Light trapping in silicon nanowire solar cells ", " Nano Letters ", 2010,10, p1082 – 1087) mention in that silicon nanowire array has remarkable photo-induction and catches performance, the silicon nanowire array that several μ m are high can absorb the spectral region of 300-1100nm(silicon Intrinsic Gettering fully) solar photon, can effectively reduce the usage quantity of crystalline silicon raw material.Simultaneously, photovoltaic junction in this photovoltaic cell can be made into the core-shell nano line structure, photo-generated carrier can effectively be separated by photovoltaic junction in the very short distance of silicon nanowires radial motion, thereby allows to use low-quality silicon raw material fabricate devices, further reduces the cost of silicon raw material.
The key that obtains above-mentioned silicon nanowires photovoltaic cell is design and the photovoltaic junction of constructing the core-shell nano linear array structure.Mention a kind of employing P type heterojunction photovoltaic cell that silicon nanowire array/the N-type organic semiconductor mixes in the application for a patent for invention of publication number CN101257094.Mention that in this photovoltaic cell silicon nanowire array serves as the sunlight anti-reflection layer, the photoactive layer of device (base) is still body phase crystalline silicon, still needs to make device with high quantity, high-quality silicon raw material.
Summary of the invention
The object of the invention is to propose a kind of nuclear shell nanowire photovoltaic cell and preparation technology thereof, it is with low cost, and photoelectric conversion efficiency is high, and is easy to preparation, thereby has overcome deficiency of the prior art.
For achieving the above object, the present invention has adopted following technical scheme:
A kind of silicon-based nuclear shell nanowire photovoltaic cell, it is characterized in that: it comprises the N-type silicon substrate, described N-type silicon substrate front is formed with silicon nanowire array as photoactive layer, its bottom surface is provided with metal back electrode, the nanowire heterojunction that on described silicon nanowire array, the organic conductive polymer of conformal covering hole transport forms nucleocapsid structure is as photovoltaic junction, and described heterojunction is provided with the ITO top electrode.
Preferably, the organic conductive polymer of described hole transport comprises PEDOT:PSS.
Monocrystalline or polysilicon that described N-type silicon nanowire array and silicon substrate are the 3-6N level by purity form, and wherein, the silicon nanowires height is 3-5 μ m, and Si-Substrate Thickness is 5-200 μ m.
Described metal back electrode comprises the Al electrode layer that covers on N-type silicon substrate bottom surface, and described ITO top electrode comprises the ito glass that covers on heterojunction.
A kind of preparation technology of silicon-based nuclear shell nanowire photovoltaic cell, it is characterized in that, this technique is: adopt wet etching to prepare silicon nanowire array in N-type silicon substrate front, then cover on silicon nanowire array so that the organic conductive polymer of hole transport is conformal, form core-shell nano line heterojunction, difference assembling metal back electrode and ITO top electrode on N-type silicon substrate bottom surface and heterojunction, obtain target product at last.
Further, this technique specifically comprises the steps:
ⅰ, prepare silicon nanowire array in the positive metal assistance chemistry of silicones etching with catalytic activity that adopts of N-type silicon substrate;
After ⅱ, the solution of getting the organic conductive polymer of hole transport were filled silicon nanowire array, the solvent in this organic conductive polymer solution was removed in evaporation, forms the conformal organic conductive thin polymer film that covers on silicon nanowire array;
ⅲ, on N-type silicon substrate bottom surface and heterojunction respectively assembling metal back electrode and ITO top electrode, obtain target product.
Step I is specially: at first form discontinuous silver-colored film in the positive deposited electroless of N-type silicon substrate, then by the catalytic action of silver-colored film, at N-type silicon substrate front wet etching formation silicon nanowire array, remove at last silver-colored film.
The organic conductive polymer of described hole transport comprises PEDOT:PSS, and described metal back electrode comprises the Al electrode layer that is deposited on N-type silicon substrate bottom surface.
The process of assembling ITO top electrode is on heterojunction array:
Get the organic conductive polymer solution that applies hole transport on the conducting surface of ito glass, and be placed on the heterojunction surface, the solvent in this organic conductive polymer solution is removed in then evaporation, and the conducting surface of ito glass is fixedly connected with heterojunction.
The organic conductive polymer solution of described hole transport comprises that volume ratio is polar organic solvent and the commercial PEDOT:PSS aqueous solution of 1:3-1:1, and described polar organic solvent is selected from any one in ethanol, acetone and isopropyl alcohol at least.
The principal character of silicon of the present invention/PEDOT:PSS nuclear shell nanowire photovoltaic cell is: photoactive layer is the silicon nanowire array that is positioned on silicon substrate, photovoltaic is become the N-type silicon of core-shell nano line structure and the organic conductive polymer of hole transport, PEDOT:PSS heterojunction particularly, PEDOT:PSS conduction, transparent wherein, and the conduction band of Fermi level and silicon approaches can be effectively and silicon formation Window layer/absorption build Schottky photovoltaic junction, is conducive to opto-electronic conversion.In addition, silicon nanowires and silicon substrate are to be formed by monocrystalline or polysilicon that purity is the 3-6N level, and nanowire height is 3-5 μ m, and substrate thickness is 5-200 μ m, is conducive to reduce device cost.In addition, this photovoltaic cell also can comprise the assemblies such as top electrode ito glass, Al hearth electrode.
The main process of the manufacturing process of photovoltaic cell of the present invention is: at first metal assistance chemistry of silicones is etched in and prepares silicon nanowire array on silicon substrate; Adopt subsequently the organic conductive polymer solution of the hole transport as an example of the PEDOT:PSS aqueous solution example of adding polar organic solvent to fill in the silicon nanowire array of metal assistance chemistry of silicones etching, form silicon/PEDOT:PSS core-shell nano linear array after solvent evaporated; At last by preparing metal back electrode at silicon substrate back of the body surface heat evaporation and at the front surface assembling ITO of silicon/PEDOT:PSS core-shell nano linear array top electrode, forming photovoltaic device.Wherein, have super-hydrophobicity because metal assistance chemistry of silicones etching prepares the silicon nanowire array surface, the PEDOT:PSS aqueous solution is difficult to fill silicon nanowire array, is difficult to form the core-shell nano line.So, in the present invention, alcohol, acetone or isopropyl alcohol isopolarity organic solvent are added in the PEDOT:PSS aqueous solution, thereby make PEDOT:PSS solution effectively fill silicon nanowire array, to form the core-shell nano line.
The operation principle of photovoltaic cell of the present invention is: sunlight sees through the ito glass top electrode and the PEDOT:PSS layer is absorbed by silicon nanowires, produce hole-duplet, separated by silicon/PEDOT:PSS photovoltaic junction with back cavitation-duplet, the hole is collected by the ITO top electrode after being transferred to the PEDOT:PSS layer, electronics is collected by the AL hearth electrode, realizes whole opto-electronic conversion.
Compared with prior art, the invention has the advantages that: this silicon-based nuclear shell nanowire photovoltaic cell raw material consumption is few, with low cost, and photoelectric conversion efficiency is high, and its preparation technology is succinct, easy to operate, can realize the large-scale production of photovoltaic cell.
Description of drawings
Fig. 1 is the structural representation of silicon in the present invention/PEDOT:PSS nuclear shell nanowire photovoltaic cell, and in figure: 1 is the AL hearth electrode, and 2 is silicon substrate, 3 is silicon/PEDOT:PSS core-shell nano linear array, 31 is silicon nanowire array, and 32 is the PEDOT:PSS layer, and 4 is the top electrode ito glass;
Fig. 2 a is the electron scanning micrograph of silicon shown in Fig. 1/PEDOT:PSS core-shell nano linear array;
Fig. 2 b is the transmission electron microscope photo of a single silicon/PEDOT:PSS core-shell nano line;
Fig. 2 c is the transmission electron microscope photo at silicon/PEDOT:PSS core-shell nano line interface;
Fig. 3 is that a typical silicon/PEDOT:PSS nuclear shell nanowire photovoltaic cell of the present invention is at the current-voltage characteristic curve figure of AM 1.5G simulated solar illumination.
Specific embodiments
Below in conjunction with accompanying drawing and a preferred embodiment, technical scheme of the present invention is elaborated.
Consult Fig. 1, this silicon/PEDOT:PSS nuclear shell nanowire photovoltaic cell is made of ito glass, silicon/PEDOT:PSS core-shell nano linear array, N-type silicon substrate and Al electrode.
The principal character of this photovoltaic cell is, photoactive layer is silicon nanowire array, and photovoltaic is become N-type silicon and the PEDOT:PSS heterojunction of core-shell nano line structure.Wherein PEDOT:PSS conduction, transparent, and the conduction band of Fermi level and silicon approaches, can be effectively and silicon formation Window layer/absorption build Schottky photovoltaic junction, be conducive to opto-electronic conversion.Aforementioned silicon nanowires and silicon substrate are to be formed by monocrystalline or polysilicon that purity is the 3-6N level, and nanowire height is 3-5 μ m, and substrate thickness is 5-200 μ m, is conducive to reduce the cost of material of device.
The preparation technology of this silicon/PEDOT:PSS nuclear shell nanowire photovoltaic cell comprises the steps:
(1) prepare silicon nanowire array on silicon substrate.At first cleaned N-type silicon chip is placed in 0.02M silver nitrate and 5M hydrofluoric acid mixed aqueous solution under room temperature, at the discontinuous silver-colored film of surface of silicon nanowires deposited electroless one deck, sample is placed in the mixed aqueous solution of 4.6M hydrofluoric acid and 0.8M hydrogen peroxide subsequently, and metal assistance chemistry of silicones etching prepares silicon nanowire array.At last, the silicon chip that etching is good is placed in 40% nitric acid and removes silver catalyst, then uses successively 5% hydrofluoric acid, washed with de-ionized water, obtains silicon nanowire array 31 on silicon substrate;
(2) preparation silicon/PEDOT:PSS core-shell nano linear array: alcohol and the commercial PEDOT:PSS aqueous solution are mixed take volume ratio as 1:3, subsequently the mixed solution spin coating is filled in silicon nanowire array, at last sample is placed on solvent evaporated in the baking oven of 120 ℃, obtains silicon/PEDOT:PSS core-shell nano linear array 3(and consult Fig. 2 a-2c);
(3) preparation silicon/PEDOT:PSS nuclear shell nanowire photovoltaic cell: at first adopt hot evaporation at silicon substrate back of the body surface deposition Al electrode, the PEDOT:PSS that spin coating one deck is wet on ito glass subsequently also is placed on silicon/PEDOT:PSS core-shell nano line surface, at last sample is placed on solvent evaporated in the baking oven of 120 ℃, has namely obtained silicon/PEDOT:PSS nuclear shell nanowire photovoltaic cell.Test obtains the photovoltaic performance (see figure 3) of device, and its photoelectric conversion efficiency can reach more than 6%.
In the present invention, photoactive layer is N-type silicon nanowire array (3-5 μ m), can fully absorb the 300-1100nm sunlight, can reduce the usage quantity of silicon raw material.Simultaneously, the present invention adopts Schottky heterojunction that the organic conductive polymer of the N-type silicon/hole transport of core-shell nano line structure forms as photovoltaic junction, photo-generated carrier disjoint paths in photoactive layer is short, can adopt low-purity, low-quality cheap silicon raw material to make device.And the way that the present invention adopts the organic conductive polymer solution to fill is constructed photovoltaic junction, and technique is simple, can construct large-area device.To sum up, the organic conductive polyalcohol nucleocapsid nano wire photovoltaic cell of the N-type silicon/hole transport in the present invention can be realized low cost, high efficiency.
Be only below the introduction of inner characteristic of the present invention being carried out by concrete exemplary applications, the protection range of inventing is not constituted any limitation.All employing equivalents or equivalence are replaced and the technical scheme of formation, all drop in rights protection scope of the present invention.
Claims (5)
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| CN103030100B (en) * | 2013-01-09 | 2015-10-21 | 华北电力大学 | A kind of preparation method with the sub-wavelength silicon nanowire array of antireflection characteristic |
| CN103647016B (en) * | 2013-12-12 | 2016-04-20 | 中国科学院半导体研究所 | Based on the thermoelectric device preparation method of nucleocapsid structure |
| WO2015096028A1 (en) * | 2013-12-24 | 2015-07-02 | 香港城市大学 | Solar cell and manufacturing method therefor |
| CN104600196B (en) * | 2015-01-09 | 2017-08-01 | 浙江大学 | A kind of preparation method and product of conductive organic matter/silicon nanowire solar cell |
| CN105720197B (en) * | 2016-02-19 | 2018-10-09 | 暨南大学 | It is a kind of to respond silicon-based hybrid heterojunction photovoltaic sensor and preparation method thereof from driving wide spectrum |
| CN108831955B (en) * | 2018-06-08 | 2020-08-11 | 海门名驰工业设计有限公司 | A kind of silicon solar cell and preparation method thereof |
| CN109467159B (en) * | 2018-11-29 | 2021-10-01 | 长春理工大学 | Self-powered semiconductor photocatalytic device with WSA position-sensitive structure |
| CN118064899B (en) * | 2024-02-02 | 2025-01-10 | 西安电子科技大学 | Full spectrum silicon-based composite photo-anode array and preparation method and application thereof |
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