CN103872166A - Light trapping structure of copper indium gallium selenium thin film solar cell and preparation method thereof - Google Patents
Light trapping structure of copper indium gallium selenium thin film solar cell and preparation method thereof Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 title abstract description 5
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 title abstract description 5
- 239000010408 film Substances 0.000 claims description 77
- 239000000758 substrate Substances 0.000 claims description 35
- 229910052711 selenium Inorganic materials 0.000 claims description 26
- 239000011669 selenium Substances 0.000 claims description 26
- 239000011805 ball Substances 0.000 claims description 19
- 239000011807 nanoball Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 230000007704 transition Effects 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000004642 Polyimide Substances 0.000 claims description 9
- 239000004793 Polystyrene Substances 0.000 claims description 9
- 239000002052 molecular layer Substances 0.000 claims description 9
- 229920001721 polyimide Polymers 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical group OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000004005 microsphere Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- ZWNQSJPQMSUVSE-UHFFFAOYSA-N [Cu].[Sn].[In] Chemical compound [Cu].[Sn].[In] ZWNQSJPQMSUVSE-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000005361 soda-lime glass Substances 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 230000007480 spreading Effects 0.000 claims description 3
- 238000003892 spreading Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 55
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 50
- 239000011787 zinc oxide Substances 0.000 description 28
- 238000011160 research Methods 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 4
- 239000002077 nanosphere Substances 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 230000003667 anti-reflective effect Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229960001296 zinc oxide Drugs 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013084 building-integrated photovoltaic technology Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02366—Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers
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- H01L31/0749—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 adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
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Abstract
The invention relates to a light trapping structure of a copper indium gallium selenium thin film solar cell and a preparation method thereof. The light trapping structure of the copper indium gallium selenium thin film solar cell comprises a cell base unit and a conductive thin film formed on the light incidence surface of the cell base unit, the light trapping structure with a texturing surface is formed on the conductive thin film, and incident light enters a cell absorbing layer of the cell base unit after being scattered by the light trapping structure. According to the light trapping structure of the copper indium gallium selenium thin film solar cell and the preparation method thereof, the light trapping structure is formed by further extending based on original cell base unit preparation flow, antireflection of incident light can be formed on the texturing surface, the incident light can also be scattered to enter the cell absorbing layer, the thickness of the cell absorbing layer can be lowered, the production cost of the cell/component is reduced, the absorbing rate of the thin film solar cell on the light can be improved greatly, and photoelectric conversion efficiency of the whole thin film solar cell can be further improved.
Description
Technical field
The present invention relates to photovoltaic technology development field, be specifically related to one and be suitable for light trapping structure improving Copper Indium Gallium Selenide (CIGS) thin-film solar cells efficiency and preparation method thereof.
Background technology
Low-carbon environment-friendly is the only way of human kind sustainable development, especially in the recent period " haze " becomes the highest word of the online frequency of occurrences, in the Executive Meeting of the State Council on February 12, directly saying without preamble of premier Li Keqiang: " will play assault of fortified positions and a protract war of administering haze." this is only a side portrayal, all aspects directly reflect that human needs develops new forms of energy and substitute existing fossil energy.From current energy source distribution, in a foreseeable future, solar energy power generating will occupy very important one seat in new energy field.In photovoltaic market product, be mainly divided into crystal silicon solar energy battery and thin-film solar cells at present, wherein crystal silicon solar energy battery is in occupation of 85% the market share nearly, although the content of element silicon in the earth's crust is fine, but need to expend a large amount of energy from the silicon purification technique of existing market feedback purifies, even bring the pollution of environment, from this view point, " environmental protection " of crystal silicon solar energy battery also need to give a discount.And thin-film solar cells is mainly to comprise silicon-based film solar cells, cadmium telluride diaphragm solar battery, copper-indium-galliun-selenium film solar cell three classes, wherein Copper Indium Gallium Selenide (CIGS) thin-film solar cells is to be developed by copper indium tin (CIS) the latter half eighties 20th century, gallium (Ga) is replaced to the part indium (In) in copper indium tin (CIS), form Copper Indium Gallium Selenide (hereinafter to be referred as CIGS) quaternary compound.
In thin-film solar cells market, CIGS is the most rising one as the thin-film solar cells of absorbed layer, and CIGS is the semi-conducting material of direct band gap, concrete excellent solar spectral response characteristic, and absorption coefficient can reach 10
-5cm
-1, theoretical light photoelectric transformation efficiency can reach 30%.In the laboratory research stage, in March, 2008, U.S.'s regenerative resource laboratory (NREL) adopts the technique of coevaporation CIGS at 0.5-1cm
2in cellar area, obtain the photoelectric conversion efficiency up to 19.9%; In August, 2010, the photoelectric conversion efficiency of the CIGS solar energy of German solar energy and Hydrogen Energy research center (ZSW) research reaches 20.3%, substantially approaches the peak efficiency of the polysilicon solar cell of existing acquisition.
Aspect study on the industrialization exploitation, in September, 2008, Japanese industries Technical Integration Studies place area is to have obtained 15.9% photoelectric conversion efficiency on the small-sized module of CIGS solar cell of 10cm x10cm; In December, 2010, (area reaches 1m to the large area assembly of the Miasol é of CIGS Thinfilm solar cell assembly manufacturer research and development
2) efficiency reach 15.7%, turned out to be the peak efficiency in current commercialization film assembly.
Structurally, the typical structure of CIGS thin-film solar cells is multi-layer film structure, total comprises base substrate, molybdenum (Mo) conductive layer, CIGS (or CZTS or CIS) absorbed layer, CdS transition zone, i-ZnO heterojunction N-shaped layer, AZO Window layer, MgF2 reflector and Ni-Al electrode layer, and wherein absorbed layer CIGS is the core of CIGS thin-film solar cells.
At present the technical research field of CIGS thin-film solar cells is main is embodied in following two aspects:
1. in improving photoelectric conversion efficiency, reduce battery/assembly cost, this art is mainly to rest in corresponding research institution and enterprise of several countries such as Germany, Japan and the U.S. at present.Because In, Ga material are very expensive, and annual yield and reserves all limited, world's year yield is 300 tons/year at present, especially, along with the fast development of LCDs industry since 2011, has caused the price of In sharply soaring.In order to reduce the cost of CIGS battery, American-European-Japanese correlative study mechanism and enterprise have started the research and development of slimline battery, reduce the thickness of absorbed layer CIGS.U.S. NREL corresponding cell photoelectric conversion efficiency while studying different CIGS absorber thickness, the small size battery efficiency of preparing on the basis of 1umCIGS absorbed layer is up to 17.16%, and is 0.75um at absorbed layer, and the Efficiency Decreasing of battery is 12.5%; When U.S. EPV obtains CIGS absorber thickness only for 0.47um, the photoelectric conversion efficiency of battery is 9.9%; When the CIGS absorber thickness of Japan Shell Solar research is 1um, battery efficiency is 12.8%;
2. in view of CIGS thin-film solar cells is most effective in current all thin-film solar cells, and the advantage of applying in architecture-integral and terminal consumption product market that thin-film solar cells itself possesses, therefore adopting flexible material to substitute hard soda-lime glass is also one of study hotspot in current CIGS field.Wherein, at the bottom of flexible substrates mainly comprises resistant to elevated temperatures polyimides (PI) material, stainless steel lining, the metal substrate such as titanium, molybdenum, copper.Adopt flexible substrates to combine with Roll-to-Roll technology in the market, U.S. NREL adopts coevaporation method, and the efficiency of having prepared small size CIGS battery in stainless steel flexible substrate is 17.5%; In May, 2011, the CIGS battery that conversion efficiency is 18.7% was prepared in Swiss Confederation's material science and technology experiment chamber on polyimides PI substrate.
From current technical research development progress and present situation, at least also there is following shortcoming about the technical research of CIGS thin-film solar cells:
(1). in order to reduce the cost of CIGS battery, the mode of taking is at present substantially all to improve in battery aspect, reduce the thickness of absorbed layer CIGS, but from result of study, CIGS absorbed layer is the most key core of CIGS thin-film solar cells, the attenuate of its thickness can make the efficiency of battery/assembly reduce by a relatively large margin, also mean, keep or promote and reduce costs obtaining compromise in efficiency, therefore cannot reduce from reducing the angle of thickness the manufacturing cost of battery/assembly from the technical merit of present stage;
(2). from the angle of CZTS battery, CZTS is a kind of semi-conducting material of direct band gap, optical band gap is in 1.45eV left and right, approach very much the ideal bandgap 1.4eV of photovoltaic cell, mate very much with the response spectrum of sunlight, than In, Ga, Zn, the Sn reserves in the earth's crust are all very abundant, but this structure battery at present temporarily still in laboratory to the pilot scale stage, still have many technical problems to be studied;
(3). from flexible angle, than the CIGS battery of hard soda-lime glass substrate, the CIGS battery of flexible substrate has a lot of advantages, and quality is light, flexible, be easy to carry, and in space, BIPV, has broad application prospects.But at present its efficiency still still lower, cost compare is high.
(4). in order to reduce the reflection of incident light in the Window layer AZO of top, in existing structure, be mainly to plate one deck magnesium fluoride anti-reflection layer at AZO, but magnesium fluoride film is very expensive.
Summary of the invention
The object of the present invention is to provide a kind of light trapping structure that improves copper-indium-galliun-selenium film solar cell efficiency and preparation method thereof.
A kind of light trapping structure that improves copper-indium-galliun-selenium film solar cell efficiency, it comprises thin-film solar cells elementary cell, it comprises base substrate from the bottom to top, front electrodes conduct layer, battery obsorbing layer, transition zone, native oxide zinc heterojunction N-shaped layer and Window layer, described battery obsorbing layer is CIGS thin-film, described Window layer is as the incidence surface of solar cell, described light trapping structure comprises that uniform spreading is located at the micro-nano layer of described Window layer upper surface, described micro-nano layer is the uniform micro-nano ball composition of particle diameter, in the upper surface plating layer of conductive film of described micro-nano layer, remove micro-nano ball by Ultrasonic Cleaning, be described light trapping structure, incident light enters into the described battery obsorbing layer of below after described light trapping structure scattering.
In a preferred embodiment, described battery obsorbing layer can be selected from any in following: CIGS thin-film, copper-zinc-tin-sulfur film, copper indium tin thin film.
In a preferred embodiment, described conductive film is Al-Doped ZnO conducting film, and described Window layer is Al-Doped ZnO Window layer.
In a preferred embodiment, the particle diameter of described micro-nano ball is 200 ~ 3000nm.
In a preferred embodiment, described base substrate comprises hard substrate and flexible substrate, and described hard substrate is common soda-lime glass, and described flexible substrate is stainless steel, titanium, molybdenum, copper sheet metal substrate and polyimides PI substrate.
In a preferred embodiment, described front electrodes conduct layer is molybdenum (Mo) conductive layer, and described transition zone is cadmium sulfide (CdS) transition zone.
A preparation method who improves the light trapping structure of copper-indium-galliun-selenium film solar cell efficiency, the method comprises:
The formation of step S10, described battery elementary cell, is specially, and starts from base substrate sequentially superpose from lower to upper conductive layer, battery obsorbing layer, transition zone, heterojunction type layer and Window layer, obtains battery elementary cell;
The formation of step S20, micro-nano ball layer, be specially, getting concentration is the Nano/micron ball solution of 0.5wt.%, it is mixed in the ratio of 1:1～1:10 with deionized water, then the pH value of this mixed solution is adjusted to 2～6, then described thin-film solar cells elementary cell is put in this solution, place after 10s～2min, take out, water is rinsed well, now in Window layer, form micro-nano ball layer, and obtain battery structure A;
Step S30, prepare Al-Doped ZnO conducting film, be specially, on the basis of step S20, on battery structure A, utilize magnetron sputtering mode to plate one deck Al-Doped ZnO conducting film, so that the upper surface of described thin-film solar cells elementary cell forms U-shaped suede structure, and obtain battery structure B;
The removal of step S40, micro-nano ball, is specially, and on the basis of step S30, adopts ultrasonic equipment to clean the Nano/micron ball of removing battery structure B upper surface, now on the surface of conductive film, just forms the light trapping structure of the U-shaped matte of nanoscale.
In a preferred embodiment, described Nano/micron ball is polystyrene or silicon dioxide microsphere, and its particle diameter is 200nm～3000nm.
In a preferred embodiment, in step S30, the deposit thickness of described conductive film depends on the particle diameter of described Nano/micron ball and the absorptivity of solar cell maximum, and the thickness of described conductive film is 50 ~ 3000nm.
In a preferred embodiment, in step S20, the process conditions of described magnetron sputtering are as follows: base vacuum degree is better than 3.0 x10-4Pa, operating air pressure 0.4～0.8Pa, working gas Ar+O2, shielding power supply is radio frequency (13.56MHz), power 150～1000W, underlayer temperature is RT～100 DEG C, and deposition rate is 10～100nm/min..
The light trapping structure of copper-indium-galliun-selenium film solar cell of the present invention, by conductive film being set on the incidence surface in battery elementary cell, and on conductive film, being formed with the light trapping structure of matte, incident light enters into the battery obsorbing layer of battery elementary cell after light trapping structure scattering.Copper-indium-galliun-selenium film solar cell of the present invention, make incident light can on matte, form antireflective, can carry out again scattering and enter into battery obsorbing layer, not only can reduce the thickness of battery obsorbing layer, reduce the production cost of battery/assembly, can also make thin-film solar cells be greatly improved to the absorptivity of incident light, further improve the photoelectric conversion efficiency of thin-film solar cells entirety.
The present invention relates to light trapping structure of copper-indium-galliun-selenium film solar cell and preparation method thereof, can on the preparation flow of original copper indium gallium selenide film battery elementary cell, further continue the technique that forms light trapping structure, it also has the following advantages:
1), technique is simple, avoid the process optimization in the battery aspect of thin-film solar cells elementary cell own, but in existing Al-Doped ZnO Window layer, form the light trapping structure of U-shaped matte, reduce incident reflection of light, make more light can scatter to battery obsorbing layer, increase the light path of incident light in battery obsorbing layer, improve battery efficiency 5-10%;
2), the introducing of this light trapping structure can substitute the anti-reflection layers such as original magnesium fluoride, the manufacturing cost of reduction assembly;
3), the Preparation equipment of whole technique and existing CIGS battery fits like a glove, can large area suitability for industrialized production.
Brief description of the drawings
Fig. 1 is the structural representation of the light trapping structure of copper-indium-galliun-selenium film solar cell in an embodiment.
Fig. 2 is the preparation technology figure of the light trapping structure of copper-indium-galliun-selenium film solar cell in an embodiment.
Fig. 3 is the distribution map of nanosphere on Al-Doped ZnO conducting film surface.
Fig. 4 is the distribution map of micron ball on Al-Doped ZnO conducting film surface.
Embodiment
Below in conjunction with specific embodiment and accompanying drawing, light trapping structure to copper-indium-galliun-selenium film solar cell of the present invention and preparation method thereof is described in further detail.
The problem existing for current copper indium gallium selenium solar hull cell technical research exploitation: photoelectric conversion efficiency promotes with the contradiction of contradiction, battery obsorbing layer thickness and battery/assembly cost of battery obsorbing layer thickness, in the face of the demand that the market competitive pressure and the terminal par of crystal silicon solar energy battery are surfed the Net, the invention provides a kind of be arranged on copper-indium-galliun-selenium film solar cell elementary cell 10 upper surfaces light trapping structure.
Refer to Fig. 1, a kind of light trapping structure that improves copper-indium-galliun-selenium film solar cell efficiency, it at least comprises battery elementary cell 10, battery elementary cell 10 sequentially comprises base substrate 11 from the bottom to top, front electrodes conduct layer 12, battery obsorbing layer 13, transition zone 14, native oxide zinc heterojunction N-shaped layer 15 and Window layer 16, wherein, battery obsorbing layer 13 can be selected from any in following: CIGS thin-film (CIGS), copper-zinc-tin-sulfur film (CZTS), copper indium tin thin film (CIG), corresponding formation CIGS thin-film (CIGS) solar cell elementary cell respectively, copper-zinc-tin-sulfur film (CZTS) solar cell elementary cell and copper indium tin thin film (CIG) solar cell elementary cell, following execution mode describes as an example of CIGS thin-film (CIGS) solar cell elementary cell example.
Preferably, light trapping structure comprises the micro-nano layer 30 with sunken optical property that is arranged on Al-Doped ZnO Window layer 16 upper surfaces, at upper surface plating one deck Al-Doped ZnO film 20 of micro-nano layer 30, the micro-nano ball that micro-nano layer 21 is located at Al-Doped ZnO Window layer 16 upper surfaces by uniform spreading forms, the particle diameter of micro-nano ball is 200～3000nm, remove micro-nano ball by Ultrasonic Cleaning, thereby form nano level U-shaped matte pattern on Al-Doped ZnO Window layer 16 surfaces, incident light enters into the battery obsorbing layer 13 of below after U-shaped matte scattering.
Front electrodes conduct layer is molybdenum (Mo) conductive layer, and transition zone is cadmium sulfide (CdS) transition zone.
Please be simultaneously referring to Fig. 2, the present invention also provides a kind of preparation method of light trapping structure of copper-indium-galliun-selenium film solar cell, and the method comprises:
The formation of step S10, described battery elementary cell, is specially, and starts from base substrate sequentially superpose from lower to upper conductive layer, battery obsorbing layer, transition zone, heterojunction type layer and Window layer, obtains battery elementary cell;
The formation of step S20, micro-nano ball layer, be specially, getting concentration is the Nano/micron ball solution of 0.5wt.%, it is mixed in the ratio of 1:1～1:10 with deionized water, then the pH value of this mixed solution is adjusted to 2～6, then described thin-film solar cells elementary cell is put in this solution, place after 10s～2min, take out, water is rinsed well, now in Window layer, form micro-nano ball layer 30, and obtain battery structure A;
Step S30, prepare Al-Doped ZnO conducting film, be specially, on the basis of step S20, on battery structure A, utilize magnetron sputtering mode to plate one deck Al-Doped ZnO conducting film, so that the upper surface of described thin-film solar cells elementary cell forms U-shaped suede structure, and obtain battery structure B;
The removal of step S40, micro-nano ball, is specially, and on the basis of step S30, adopts ultrasonic equipment to clean the Nano/micron ball of removing battery structure B upper surface, now on the surface of conductive film, just forms the light trapping structure of the U-shaped matte of nanoscale.
In step S20, Nano/micron ball is polystyrene or silicon dioxide microsphere, and its particle diameter is 200nm～3000nm; Because the isoelectric point (Isoelectric Point) of Al-Doped ZnO conducting film film is larger, probably in 6 ~ 10 left and right, and polystyrene microsphere (PS) or the isoelectric point of silicon dioxide (SiO2) microballoon are smaller, be generally 2 ~ 4 left and right.Therefore in the time battery structure A being put in faintly acid polystyrene that PH is 2 ~ 6 left and right or silicon dioxide microsphere solution, negative electricity can be brought in Al-Doped ZnO Window layer surface in battery structure A, and polystyrene or the surface of silica nanometer/micron ball will become positively charged causes the mutual electrostatic attraction of this bi-material.After 10s～2min., (as shown in Figure 3, Figure 4) almost will be adsorbed by one deck nanosphere in the surface of Al-Doped ZnO conducting film.The coverage rate of Nano/micron ball on Al-Doped ZnO conducting film film surface can change along with the time of microspheres solution concentration, pH value, dipping plated film.
In step S30, the deposit thickness of conductive film depends on that the particle diameter of described Nano/micron ball and the absorptivity of solar cell maximum decide, must make incident light enter into battery obsorbing layer by zinc-oxide film scattering completely, the thickness of conductive film can be preferably 50 ~ 3000nm.
In addition, in step S30, the process conditions of described magnetron sputtering are as follows: base vacuum degree is better than 3.0 x10-4Pa, operating air pressure 0.4～0.8Pa, working gas Ar+O2, shielding power supply is radio frequency (13.56MHz), power 150～1000W, underlayer temperature is RT～100 DEG C, and deposition rate is 10～100nm/min.
For ease of understanding design of the present invention, now provide following several and not only comprise following several execution mode:
Execution mode 1
A kind of preparation method who improves Copper Indium Gallium Selenide (CIGS) thin-film solar cells efficiency light trapping structure, comprises the following steps:
S10, get background copper-indium-galliun-selenium film solar cell, be prepared into the solar cell of Al-Doped ZnO Window layer;
S20, get the nanosphere solution that concentration is 0.5wt.%, mix in the ratio of 1:4 with deionized water, the material of Nano/micron ball is polystyrene (PS) microballoon, particle diameter is 400nm, and the pH value of this mixed solution is adjusted to 4, and the battery in S10 is put in this solution, place 10s, take out, water is rinsed well, obtains battery structure A;
S30, on battery structure A, utilize magnetron sputtering mode to plate one deck Al-Doped ZnO conducting film, deposit thickness is 300nm, obtains battery structure B.
S40, employing ultrasonic equipment clean the Nano/micron ball of removing battery structure B upper surface, can form on the AZO surface of CIGS battery top Window layer the light trapping structure of U-shaped matte.
Execution mode 2
A kind of preparation method who improves Copper Indium Gallium Selenide (CIGS) thin-film solar cells efficiency light trapping structure, comprises the following steps:
S10, get background copper-indium-galliun-selenium film solar cell, be prepared into the solar cell of Al-Doped ZnO Window layer;
S20, get the nanosphere solution that concentration is 0.5wt.%, mix in the ratio of 1:6 with deionized water, the material of Nano/micron ball is polystyrene (PS) microballoon, particle diameter is 500nm, and the pH value of this mixed solution is adjusted to 4, and the battery in S10 is put in this solution, place 30s, take out, water is rinsed well, obtains battery structure A;
S30, on battery structure A, utilize magnetron sputtering mode to plate one deck Al-Doped ZnO conducting film, deposit thickness is 400nm, obtains battery structure B.
S40, employing ultrasonic equipment clean the Nano/micron ball of removing battery structure B upper surface, can form on the AZO surface of CIGS battery top Window layer the light trapping structure of U-shaped matte.
It should be noted that, purport of the present invention is not change copper-indium-galliun-selenium film solar cell architecture basics, adds light trapping structure at the upper surface of its Al-Doped ZnO Window layer, can improve the efficiency 5-10% left and right of hull cell; And, utilize the also anti-reflection layer such as magnesium fluoride of alternative costliness of this light trapping structure, thereby further reduce the cost of CIGS thin-film solar cells/assembly, to adapt to the demand in par access terminals market.
To sum up, the light trapping structure of raising copper-indium-galliun-selenium film solar cell efficiency of the present invention, by conductive film being set on the incidence surface in battery elementary cell, and on conductive film, being formed with the light trapping structure with matte, incident light enters into the battery obsorbing layer of battery elementary cell after light trapping structure scattering.The light trapping structure of copper-indium-galliun-selenium film solar cell of the present invention, can make incident light can on matte, form antireflective, can carry out again scattering and enter into battery obsorbing layer, not only can reduce the thickness of battery obsorbing layer, reduce the production cost of battery/assembly, can also make thin-film solar cells be greatly improved to the absorptivity of incident light, further improve the photoelectric conversion efficiency of thin-film solar cells entirety.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. the light trapping structure of a copper-indium-galliun-selenium film solar cell, it comprises thin-film solar cells elementary cell, it comprises base substrate from the bottom to top, front electrodes conduct layer, battery obsorbing layer, transition zone, native oxide zinc heterojunction N-shaped layer and Window layer, described battery obsorbing layer is CIGS thin-film, described Window layer is as the incidence surface of solar cell, it is characterized in that, described light trapping structure comprises that uniform spreading is located at the micro-nano layer of described Window layer upper surface, described micro-nano layer is the uniform micro-nano ball composition of particle diameter, in the upper surface plating layer of conductive film of described micro-nano layer, remove micro-nano ball by Ultrasonic Cleaning, be described light trapping structure, incident light enters into the described battery obsorbing layer of below after described light trapping structure scattering.
2. the light trapping structure of copper-indium-galliun-selenium film solar cell according to claim 1, is characterized in that, described battery obsorbing layer can be selected from any in following: CIGS thin-film, copper-zinc-tin-sulfur film, copper indium tin thin film.
3. the light trapping structure of copper-indium-galliun-selenium film solar cell according to claim 1, is characterized in that, described conductive film is Al-Doped ZnO conducting film, and described Window layer is Al-Doped ZnO Window layer.
4. the light trapping structure of copper-indium-galliun-selenium film solar cell according to claim 1, is characterized in that, the particle diameter of described micro-nano ball is 200 ~ 3000nm.
5. the light trapping structure of copper-indium-galliun-selenium film solar cell according to claim 1, it is characterized in that, described base substrate comprises hard substrate and flexible substrate, described hard substrate is common soda-lime glass, and described flexible substrate is stainless steel, titanium, molybdenum, copper sheet metal substrate and polyimides PI substrate.
6. according to the light trapping structure of the copper-indium-galliun-selenium film solar cell described in claim 1 to 5 any one, it is characterized in that, described front electrodes conduct layer is molybdenum (Mo) conductive layer, and described transition zone is cadmium sulfide (CdS) transition zone.
7. a preparation method for the light trapping structure of copper-indium-galliun-selenium film solar cell, is characterized in that, the method comprises:
The formation of step S10, described battery elementary cell, is specially, and starts from base substrate sequentially superpose from lower to upper conductive layer, battery obsorbing layer, transition zone, heterojunction type layer and Window layer, obtains battery elementary cell;
The formation of step S20, micro-nano ball layer, be specially, getting concentration is the Nano/micron ball solution of 0.5wt.%, it is mixed in the ratio of 1:1～1:10 with deionized water, then the pH value of this mixed solution is adjusted to 2～6, then described thin-film solar cells elementary cell is put in this solution, place after 10s～2min, take out, water is rinsed well, now in Window layer, form micro-nano ball layer, and obtain battery structure A;
Step S30, prepare Al-Doped ZnO conducting film, be specially, on the basis of step S20, on battery structure A, utilize magnetron sputtering mode to plate one deck Al-Doped ZnO conducting film, so that the upper surface of described thin-film solar cells elementary cell forms U-shaped suede structure, and obtain battery structure B;
The removal of step S40, micro-nano ball, is specially, and on the basis of step S30, adopts ultrasonic equipment to clean the Nano/micron ball of removing battery structure B upper surface, now on the surface of conductive film, just forms the light trapping structure of the U-shaped matte of nanoscale.
8. preparation method according to claim 7, is characterized in that, described Nano/micron ball is polystyrene or silicon dioxide microsphere, and its particle diameter is 200nm～3000nm.
9. preparation method according to claim 7, it is characterized in that, in step S30, the deposit thickness of described conductive film depends on the particle diameter of described Nano/micron ball and the absorptivity of solar cell maximum, and the thickness of described conductive film is 50 ~ 3000nm.
10. preparation method according to claim 7, it is characterized in that, in step S20, the process conditions of described magnetron sputtering are as follows: base vacuum degree is better than 3.0 x10-4Pa, operating air pressure 0.4～0.8Pa, working gas Ar+O2, shielding power supply is radio frequency (13.56MHz), power 150～1000W, underlayer temperature is RT～100 DEG C, deposition rate is 10～100nm/min..
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| CN108512486A (en) * | 2018-02-13 | 2018-09-07 | 全球能源互联网研究院有限公司 | A kind of flexible light electric heating composite battery |
| CN110880460A (en) * | 2018-09-05 | 2020-03-13 | 北京铂阳顶荣光伏科技有限公司 | Preparation method and preparation device of solar cell |
| CN110890431A (en) * | 2018-08-17 | 2020-03-17 | 北京铂阳顶荣光伏科技有限公司 | Thin film solar cell and preparation method thereof |
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| CN112599644A (en) * | 2020-11-26 | 2021-04-02 | 佛山汉狮建材科技有限公司 | Light energy plate for electric curtain and preparation method thereof |
| CN112599644B (en) * | 2020-11-26 | 2022-09-30 | 佛山汉狮建材科技有限公司 | Light energy plate for electric curtain and preparation method thereof |
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