CN105655423A - Nano heterojunction solar cell based on chalcogenide cuprous compound and preparation method thereof - Google Patents
Nano heterojunction solar cell based on chalcogenide cuprous compound and preparation method thereof Download PDFInfo
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- CN105655423A CN105655423A CN201610035612.3A CN201610035612A CN105655423A CN 105655423 A CN105655423 A CN 105655423A CN 201610035612 A CN201610035612 A CN 201610035612A CN 105655423 A CN105655423 A CN 105655423A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 150000004770 chalcogenides Chemical class 0.000 title abstract 6
- 239000002184 metal Substances 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002086 nanomaterial Substances 0.000 claims abstract description 32
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000010703 silicon Substances 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 239000010408 film Substances 0.000 claims description 49
- 229910052798 chalcogen Inorganic materials 0.000 claims description 37
- 150000001787 chalcogens Chemical class 0.000 claims description 37
- 239000010409 thin film Substances 0.000 claims description 36
- 230000004888 barrier function Effects 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 238000000137 annealing Methods 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- 239000011669 selenium Substances 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 8
- 239000002070 nanowire Substances 0.000 claims description 8
- 238000001259 photo etching Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000005566 electron beam evaporation Methods 0.000 claims description 7
- 238000004549 pulsed laser deposition Methods 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 241000931526 Acer campestre Species 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- -1 nanometer rods Substances 0.000 claims description 3
- 229910052756 noble gas Inorganic materials 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 238000002207 thermal evaporation Methods 0.000 claims description 3
- 238000000427 thin-film deposition Methods 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 230000004323 axial length Effects 0.000 claims description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002127 nanobelt Substances 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 239000010931 gold Substances 0.000 description 18
- 230000009466 transformation Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035209—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
- H01L31/035227—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures the quantum structure being quantum wires, or nanorods
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- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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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
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- Y02E10/541—CuInSe2 material PV cells
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Abstract
The invention discloses a nano heterojunction solar cell based on a chalcogenide cuprous compound and a preparation method thereof. The nano heterojunction solar cell based on the chalcogenide cuprous compound is characterized in that a silicon substrate whose upper surface is covered with an insulating layer serves as a substrate, a chalcogenide cuprous compound quasi-one-dimensional nano-structure is dispersed on the insulating layer, a first metal film electrode and an In2S3 film are deposited respectively on two ends of the chalcogenide cuprous compound quasi-one-dimensional nano-structure, the chalcogenide cuprous compound quasi-one-dimensional nano-structure is in ohmic contact with the first metal film electrode and forms a heterojunction with the In2S3 film, a second metal film electrode is deposited above the In2S3 film, the In2S3 film is in ohmic contact with the second metal film electrode. According to the invention, the nano heterojunction solar cell completely uses environmental-friendly inorganic semiconductor materials, the preparation process is simple and easy, and the device performance is superior.
Description
One, technical field
The present invention relates to a kind of nano heterogeneous joint solar cell and preparation method thereof, be specifically based on nano solar battery of chalcogen cuprous compound hetero-junctions and preparation method thereof.
Two, background technology
From nineteen fifty-nine first piece based on since the integrated circuit invention of planar silicon, planar silicon technique dominates the development of IC industry always. Going through semicentennial development, integrated circuit is developed into super large-scale integration by the first piece of surface-mounted integrated circuit comprising five electronic components, and the integrated parts number of single circuit chip reaches several hundred million even tens, over ten billion. The process of integrated circuit development is actually the process that device feature size constantly reduces, integrated level improves constantly, the ratio of performance to price constantly reduces. Area of solar cell is also such.
At present, the silica-based solar cell market share is still up to more than 90%, but high crystal silicon price and its relatively low absorbance promote people in field of thin film solar cells, and especially inorganic matter field of thin film solar cells constantly seeks new breakthrough.
Chalcogen cuprous compound be a class environmental friendliness and in the earth's crust transient metal chalcogenide compound of rich content, due to cation defect, in p-type semiconductor characteristic, in addition, it has higher absorptance and excellent photoelectric characteristic, thus has relatively broad applied research in field of thin film solar cells. By Cu prepared by tradition high-vacuum technology2S/CdS(IEEETrans.Electron.,1977,24,381)��Cu2-xSe/CdS (Appl.Phys.lett., 1985,46,1095) system, is study one of thin film solar system the earliest. Along with the development of nanotechnology, based on Cu2The research of the thin-film solar cells that S is nanocrystalline also achieves significant progress (NanoLett., 2008,8,2551). Although its photoelectric transformation efficiency only 1.6%, but liquid phase synthesis significantly reduces its production cost, remains current study hotspot based on nanocrystalline thin-film solar cells. Comparing thin-film material, quasi-one dimensional nanostructure, owing to can more effectively reduce the photo-generated carrier compound in defect, interface etc., improves photo-generated carrier and separates and collection efficiency, perform meritorious deeds never to be obliterated in nano solar battery performance lifting. University of California Berkeley professor Yang Peidong passes through liquid phase cation replacement method, is prepared for based on single CdS-Cu2The nano solar battery of S nucleocapsid structure, and obtain the transformation efficiency (Naturenanotechnology, 2011,6,568) of 5.4%.But, the use of toxic element Cd hampers this material system paces in the area of solar cell marketization all the time, people just make great efforts to seek can eco-friendly n-type semiconductor, to replace the CdS window layer material as such photovoltaic system.
N-type semiconductor In2S3Being considered as the ideal chose replacing CdS, its body energy gap is 2.0-2.2eV, close with CdS. Research shows with In2S3For the CIGS thin film solaode of cushion, transformation efficiency has reached 16.4%, and traditional with the CdS thin-film solar cells performance being cushion quite (Prog.Photovolt:Res.Appl., 2003,11,437). The present inventor place seminar achieves the n-type In being expected to be applied to field of thin film solar cells also by pulsed laser technique2S3The deposition of thin film (Mater.Res.Express, 2015,2,056401; Application for a patent for invention number: ZL201410500670.X).
Three, summary of the invention
On the basis that prior art exists, it is contemplated that build based on the nano heterogeneous joint solar cell of chalcogen cuprous compound, have great significance at nano solar battery development field, to be solved technical problem is that with n-type semiconductor In2S3As window layer material so that it is form hetero-junctions with chalcogen cuprous compound.
This invention address that technical problem, adopt the following technical scheme that
The present invention is based on the nano heterogeneous joint solar cell of chalcogen cuprous compound, it is characterized in that: be covered with the silicon-based substrate of insulating barrier for substrate with upper surface, described insulating barrier is dispersed with chalcogen cuprous compound quasi-one dimensional nanostructure, has respectively deposited the first metal film electrode and In at the two ends of described chalcogen cuprous compound quasi-one dimensional nanostructure2S3Thin film, described chalcogen cuprous compound quasi-one dimensional nanostructure and described first metal film electrode are Ohmic contact, with described In2S3Thin film forms hetero-junctions; At described In2S3Thin film disposed thereon has the second metal film electrode, described In2S3Thin film and described second metal film electrode are Ohmic contact.
The nano heterogeneous joint solar cell of the present invention, its feature lies also in: the chemical structural formula of described chalcogen cuprous compound quasi-one dimensional nanostructure is Cu2-xA, wherein A is element sulphur or selenium element, 0��x��0.25; Described chalcogen cuprous compound quasi-one dimensional nanostructure is nano wire, nanometer rods, nanotube or nano belt; The axial length of described chalcogen cuprous compound quasi-one dimensional nanostructure is not less than 10 ��m, and radical length is 100-1000nm.
Described insulating barrier is SiO2��Si3N4Or HfO2; The resistivity of described insulating barrier is more than 1 �� 103�� cm, thickness are 100-500nm. Silicon-based substrate is p-type silicon chip, n-type silicon chip or intrinsic silicon chip.
Described In2S3The thickness of thin film is 200-1000nm.
Described first metal film electrode is Au electrode, Ti/Au combination electrode, Cr/Au combination electrode or Ni/Au combination electrode; The thickness of described Au electrode is 30-100nm; Described Ti/Au combination electrode, Cr/Au combination electrode, Ni/Au combination electrode are that deposition has Au thick for 30-100nm on Ti, Cr, Ni of thickness 3-10nm respectively.
Described second metal film electrode is In electrode, In/Au combination electrode, Ag electrode or Al electrode; The thickness of described In electrode, Ag electrode or Al electrode is 30-100nm; Described In/Au combination electrode is that deposition has Au thick for 3-10nm on the In that thickness is 30-100nm.
Described In2S3Minimum range between thin film and described first metal film electrode is 2-5 ��m, and the distance between described second metal film electrode and described first metal film electrode is more than 8 ��m.
The preparation method of above-mentioned nano heterogeneous joint solar cell, comprises the steps:
(1) take upper surface and be covered with the silicon-based substrate of insulating barrier as substrate, chalcogen cuprous compound quasi-one dimensional nanostructure is dispersed on described insulating barrier;
(2) by a uv-exposure photoetching and film deposition techniques, in one end of chalcogen cuprous compound quasi-one dimensional nanostructure, deposition has the first metal film electrode;
(3) by second positioning uv-exposure photoetching and pulsed laser deposition technique, the other end at chalcogen cuprous compound quasi-one dimensional nanostructure deposits In2S3Thin film;
In will be completed2S3The device of thin film deposition is put in quick anneal oven, rinses furnace chamber with noble gas, then device is annealed, and annealing atmosphere is N2Or Ar, annealing gas pressure is 0.02-0.04MPa, and annealing temperature is 300-350 DEG C, and annealing time is 5-30min;
(4) uv-exposure photoetching and film deposition techniques are positioned by three times, at In2S3Thin film disposed thereon the second metal film electrode, namely obtains the nano heterogeneous joint solar cell based on chalcogen cuprous compound.
Concrete, step (3) deposits In by pulsed laser deposition technique2S3During thin film, the air pressure of vacuum chamber is not higher than 5 �� 10-3Pa, the running parameter of pulse laser is: optical maser wavelength 248nm, pulse width 25ns, and laser energy is 174mJ, and laser frequency is 5Hz, and the plated film time is 15-60min; The target used is high-purity In2S3The intrinsic target of powder compacting.
Concrete, the depositional mode of step (2) first metal film electrode is electron beam evaporation, and gas pressure in vacuum is not higher than 6 �� 10-3Pa, evaporation rate is 0.01-0.05nm/s;
Concrete, if the second metal film electrode in step (4) is In electrode or In/Au combination electrode, then: the depositional mode of In is thermal evaporation, and gas pressure in vacuum is not higher than 6 �� 10-3Pa, evaporation rate is 0.1-0.5nm/s; The depositional mode of Au is electron beam evaporation, and gas pressure in vacuum is not higher than 6 �� 10-3Pa, evaporation rate is 0.01-0.05nm/s;
If the second metal film electrode in step (4) is Ag electrode or Al electrode, then depositional mode is electron beam evaporation, and gas pressure in vacuum is not higher than 6 �� 10-3Pa, evaporation rate is 0.05-0.3nm/s.
Compared with the prior art, beneficial effects of the present invention is embodied in:
1, the present invention is based on the chalcogen cuprous compound quasi-one dimensional nanostructure of liquid phase synthesis, by microelectronic techniques such as uv-exposure photoetching, vacuum evaporation depositions, has constructed Cu2-xA/In2S3Nano heterogeneous joint solar cell. (Nanotechnology2013,24,045402 compared with the CuS/ITO schottky junction nano solar battery reported before this; Chinese patent: ZL201210053645.2), p-n heterojunction built in field is more beneficial for separation and the collection of photo-generated carrier, can effective boost device performance.
2, the Cu prepared by the present invention2-xA/In2S3Nano heterogeneous joint solar cell, uses eco-friendly inorganic semiconductor material completely, and preparation process is simple;
3, the present invention is based on the quasi-one dimensional nanostructure of liquid phase synthesis, builds nano heterogeneous joint solar cell, and compared with tradition high vacuum evaporation technology, cost significantly reduces;
4, the device preparation of the present invention is realized by conventional microelectronic technical process, has good compatibility with existing silicon technology, it is easy to accomplish integrated on existing IC chip of device;
5, the present invention is prepared based on the nano heterogeneous joint solar cell of chalcogen cuprous compound, employs the structure of one-dimensional nano structure and film combinations first, in that context it may be convenient to realize the connection in series-parallel of multiple nano solar battery.
Four, accompanying drawing explanation
Fig. 1 is the present invention device architecture schematic diagram based on the nano heterogeneous joint solar cell of chalcogen cuprous compound; Wherein 1 is silicon-based substrate, and 2 is insulating barrier, and 3 is chalcogen cuprous compound quasi-one dimensional nanostructure, and 4 is the first metal film electrode, and 5 is In2S3Thin film, 6 second is metal film electrode.
Fig. 2 is the device SEM photograph of nano heterogeneous joint solar cell in the embodiment of the present invention 1.
Fig. 3 is Cu in the embodiment of the present invention 12-xSe/In2S3The photovoltaic property curve of film heterojunction, can be seen that in figure that device open-circuit voltage is 0.2V, and short circuit current is 1.15nA, and fill factor, curve factor is 25%, and transformation efficiency reaches��3.2%.
Fig. 4 is Cu in the embodiment of the present invention 22S/In2S3The photovoltaic property curve of film heterojunction, can be seen that in figure that device open-circuit voltage is 0.07V, and short circuit current is 2.67nA, and fill factor, curve factor is 21.5%, and transformation efficiency reaches��1.61%.
Five, detailed description of the invention
The present invention is described in detail based on chalcogen cuprous compound quasi-one dimensional nanostructure and In below in conjunction with accompanying drawing2S3The preparation method of film heterojunction nano solar battery, non-limiting examples is as follows.
Embodiment 1
Referring to Fig. 1, the nano heterogeneous joint solar cell of the present invention is to be covered with the silicon-based substrate 1 of insulating barrier 2 for substrate with upper surface, insulating barrier 2 is dispersed with chalcogen cuprous compound quasi-one dimensional nanostructure 3, has respectively deposited the first metal film electrode 4 and In at the two ends of chalcogen cuprous compound quasi-one dimensional nanostructure 32S3Thin film 5, chalcogen cuprous compound quasi-one dimensional nanostructure 3 and the first metal film electrode 4 are in Ohmic contact, with In2S3Thin film 5 forms hetero-junctions; At In2S3Thin film 5 disposed thereon has the second metal film electrode 6, In2S3Thin film 5 and the second metal film electrode 6 are in Ohmic contact.
Concrete, chalcogen cuprous compound quasi-one dimensional nanostructure used by the present embodiment is the Cu of solwution method synthesis2-xSe nano wire; Substrate used is with 300nmSiO2The P type Si sheet of insulating barrier, In2S3Film thickness is 200nm, and the first metal film electrode is thickness is the Au electrode of 50nm, and the second metal film electrode is thickness is the In electrode of 50nm.
The preparation method of the nano heterogeneous joint solar cell of the present embodiment is as follows:
The Cu that solwution method is synthesized2-xSe nano wire ultrasonic disperse in alcoholic solution, with dropper take a small amount of solution drop in cleaning with 300nmSiO2On the P type Si sheet of insulating barrier, make Cu2-xSe nano wire is evenly distributed on SiO2On insulating barrier.
After ethanol volatilizees, use a photoetching technique and electron beam evaporation technique at Cu2-xIt is 50nm gold electrode that thickness is prepared in one end of Se nano wire, and during evaporation, gas pressure in vacuum is 6 �� 10-3Pa, evaporation rate is 0.02nm/s;
Then, use second positioning uv-exposure technology and pulsed laser deposition technique at Cu2-xIt is the In of 200nm that the other end of Se nano wire prepares a thickness2S3Thin film, during plated film, the air pressure of PLD vacuum chamber is 1 �� 10-3Pa, the running parameter of pulse laser is: optical maser wavelength 248nm, pulse width 25ns, and laser energy is 174mJ, and laser frequency is 5HZ, and the plated film time is 40min; In2S3The spacing at film edge distance gold electrode edge is 4 ��m.
In will be completed2S3The device of thin film deposition is put into and is annealed in quick anneal oven processing 30min, needs quick anneal oven noble gas N before annealing2Pre-flush 2 times, annealing atmosphere is N2, annealing gas pressure is 0.02MPa, and annealing temperature is 300 DEG C;
Ultraviolet photolithographic technology and thermal evaporation is positioned at In finally by three times2S3Preparing the In electrode that thickness is 50nm on thin film, during evaporation, the air pressure of vacuum chamber is 6 �� 10-3Pa, the speed of evaporation is 0.2nm/s. The spacing at In electrode edge distance gold electrode edge is 10 ��m.
The SEM of the nano solar battery prepared by the present embodiment schemes as shown in Figure 2.
Nano solar battery prepared by the present embodiment is 30mW/cm in light intensity2, under wavelength 532nm monochromatic light exposure, present significant photovoltaic property, as it is shown on figure 3, its short circuit current is 1.15nA, open-circuit voltage is 0.2V, and fill factor, curve factor is 25%, and transformation efficiency is��3.2%.
Embodiment 2
The preparation method of the nano heterogeneous joint solar cell of the present embodiment is identical with embodiment 1, and differing only in chalcogen cuprous compound quasi-one dimensional nanostructure used by the present embodiment is the Cu that chemical vapour deposition technique (CVD) grows2S nano wire. Nano solar battery prepared by the present embodiment is 50mW/cm in light intensity2, under wavelength 405nm monochromatic light exposure, present significant photovoltaic property, as shown in Figure 4, its open-circuit voltage is 0.07V, and short circuit current is 2.67nA, and fill factor, curve factor is 21.5%, and transformation efficiency is��1.61%.
Claims (10)
1. the nano heterogeneous joint solar cell based on chalcogen cuprous compound, it is characterized in that: be covered with the silicon-based substrate (1) of insulating barrier (2) for substrate with upper surface, described insulating barrier (2) is dispersed with chalcogen cuprous compound quasi-one dimensional nanostructure (3), has respectively deposited the first metal film electrode (4) and In at the two ends of described chalcogen cuprous compound quasi-one dimensional nanostructure (3)2S3Thin film (5), described chalcogen cuprous compound quasi-one dimensional nanostructure (3) and described first metal film electrode (4) are in Ohmic contact, with described In2S3Thin film (5) forms hetero-junctions; At described In2S3Thin film (5) disposed thereon has the second metal film electrode (6), described In2S3Thin film (5) and described second metal film electrode (6) are in Ohmic contact.
2. nano heterogeneous joint solar cell according to claim 1, it is characterised in that: the chemical structural formula of described chalcogen cuprous compound quasi-one dimensional nanostructure (3) is Cu2-xA, wherein A is element sulphur or selenium element, 0��x��0.25;
Described chalcogen cuprous compound quasi-one dimensional nanostructure (3) is nano wire, nanometer rods, nanotube or nano belt;
The axial length of described chalcogen cuprous compound quasi-one dimensional nanostructure (3) is not less than 10 ��m, and radical length is 100-1000nm.
3. nano heterogeneous joint solar cell according to claim 1, it is characterised in that: described insulating barrier (2) is SiO2��Si3N4Or HfO2; The resistivity of described insulating barrier (2) is more than 1 �� 103�� cm, thickness are 100-500nm.
4. nano heterogeneous joint solar cell according to claim 1, it is characterised in that: described In2S3The thickness of thin film (5) is 200-1000nm.
5. nano heterogeneous joint solar cell according to claim 1, it is characterised in that: described first metal film electrode (4) is Au electrode, Ti/Au combination electrode, Cr/Au combination electrode or Ni/Au combination electrode;
The thickness of described Au electrode is 30-100nm;
Described Ti/Au combination electrode, Cr/Au combination electrode, Ni/Au combination electrode are that deposition has Au thick for 30-100nm on Ti, Cr, Ni of thickness 3-10nm respectively.
6. nano heterogeneous joint solar cell according to claim 1, it is characterised in that: described second metal film electrode (6) is In electrode, In/Au combination electrode, Ag electrode or Al electrode;The thickness of described In electrode, Ag electrode or Al electrode is 30-100nm; Described In/Au combination electrode is that deposition has Au thick for 3-10nm on the In that thickness is 30-100nm.
7. nano heterogeneous joint solar cell according to claim 1, it is characterised in that: described In2S3Minimum range between thin film (5) and described first metal film electrode (4) is 2-5 ��m, and the distance between described second metal film electrode (6) and described first metal film electrode (4) is more than 8 ��m.
8. the preparation method of nano heterogeneous joint solar cell described in any one in a claim 1��7, it is characterised in that comprise the steps:
(1) take upper surface and be covered with the silicon-based substrate of insulating barrier as substrate, chalcogen cuprous compound quasi-one dimensional nanostructure is dispersed on described insulating barrier;
(2) by a uv-exposure photoetching and film deposition techniques, in one end of chalcogen cuprous compound quasi-one dimensional nanostructure, deposition has the first metal film electrode;
(3) by second positioning uv-exposure photoetching and pulsed laser deposition technique, the other end at chalcogen cuprous compound quasi-one dimensional nanostructure deposits In2S3Thin film;
In will be completed2S3The device of thin film deposition is put in quick anneal oven, rinses furnace chamber with noble gas, then device is annealed, and annealing atmosphere is N2Or Ar, annealing gas pressure is 0.02-0.04MPa, and annealing temperature is 300-350 DEG C, and annealing time is 5-30min;
(4) uv-exposure photoetching and film deposition techniques are positioned by three times, at In2S3Thin film disposed thereon the second metal film electrode, namely obtains the nano heterogeneous joint solar cell based on chalcogen cuprous compound.
9. preparation method according to claim 8, it is characterised in that: step (3) deposits In by pulsed laser deposition technique2S3During thin film, the air pressure of vacuum chamber is not higher than 5 �� 10-3Pa, the running parameter of pulse laser is: optical maser wavelength 248nm, pulse width 25ns, and laser energy is 174mJ, and laser frequency is 5Hz, and the plated film time is 15-60min; The target used is high-purity In2S3The intrinsic target of powder compacting.
10. preparation method according to claim 8, it is characterised in that: the depositional mode of step (2) first metal film electrode is electron beam evaporation, and gas pressure in vacuum is not higher than 6 �� 10-3Pa, evaporation rate is 0.01-0.05nm/s;
If the second metal film electrode in step (4) is In electrode or In/Au combination electrode, then: the depositional mode of In is thermal evaporation, and gas pressure in vacuum is not higher than 6 �� 10-3Pa, evaporation rate is 0.1-0.5nm/s; The depositional mode of Au is electron beam evaporation, and gas pressure in vacuum is not higher than 6 �� 10-3Pa, evaporation rate is 0.01-0.05nm/s;
If the second metal film electrode in step (4) is Ag electrode or Al electrode, then depositional mode is electron beam evaporation, and gas pressure in vacuum is not higher than 6 �� 10-3Pa, evaporation rate is 0.05-0.3nm/s.
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