CN103022173A - Transparent conductive layer structure of copper indium gallium selenide thin-film battery and manufacturing method thereof - Google Patents
Transparent conductive layer structure of copper indium gallium selenide thin-film battery and manufacturing method thereof Download PDFInfo
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- CN103022173A CN103022173A CN2012105315687A CN201210531568A CN103022173A CN 103022173 A CN103022173 A CN 103022173A CN 2012105315687 A CN2012105315687 A CN 2012105315687A CN 201210531568 A CN201210531568 A CN 201210531568A CN 103022173 A CN103022173 A CN 103022173A
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Abstract
The invention provides a transparent conductive layer structure of a copper indium gallium selenide thin-film battery and a manufacturing method thereof and belongs to the technical field of photoelectric material new energy. The copper indium gallium selenide thin-film battery comprises an upper electrode (Ni/Al), a transparent conductive layer (ZnO: Al), a window layer (ZnO), a buffer layer (CdS), an absorbing layer (P type CuInGaSe2), a back electrode (Mo) and a substrate (glass/stainless steel and the like). The transparent conductive layer is provided with a surface light trapping structure like a pyramid and is a thin film containing Al, wherein ZnO is mixed in the thin film. The surface light trapping structure like the pyramid can enlarge light absorbing surface area and effectively reduce reflection rate, thereby reducing optical loss and improving battery conversion efficiency.
Description
Technical field
The invention belongs to the photoelectric material technical field of new energies, relate to a kind of structure of transparent conductive layer and manufacture method thereof with copper-indium-galliun-selenium film solar cell of " pyramid-like " surperficial light trapping structure.
Background technology
At present, thin-film solar cells has larger advantage than the most ripe crystal-silicon solar cell of development being lowered into this aspect: the one, realize filming after, can greatly save expensive semi-conducting material; The 2nd, material preparation and the battery of hull cell form simultaneously, have therefore saved many operations; The 3rd, thin film solar cell adopts the low temperature process technology, not only is conducive to save energy and reduce the cost, and is convenient to adopt inexpensive substrate (glass, stainless steel, polymer etc.).Therefore, development low cost new thin-film solar cells is the inexorable trend of following international photovoltaic industry.As the direct gap compound semiconductor material, the absorption coefficient of CIGS thin-film (CIGS) solar cell is up to 105cm
-1, electricity conversion is the highest in all thin-film solar cells; And good stability, without the photo attenuation effect; Allow simultaneously with cheap, flexible substrate serialization deposition, its material cost and production cost have larger reduction space.The CIGS hull cell is the most competitive commercialization thin-film solar cells of a new generation, has become one of global photovoltaic area research focus, thereby research CIGS hull cell optoelectronic transformation efficiency is significant.
The surface light trapping structure can increase the surface area of light absorption, can effectively reduce the reflection of light rate, thereby reduce optical loss and improve cell conversion efficiency.Therefore, can improve the single present situation of CIGS thin-film solar cells structure of transparent conductive layer by making surperficial light trapping structure, thereby improve absorbed layer Optical Absorption rate, strengthen the optoelectronic transformation efficiency of CIGS hull cell.
The main method Direct precipitation of MOCVD or thermal spraying that adopts goes out " pyramid-like " surperficial light trapping structure in the prior art, but easily produces harmful substance, can pollute environment.And another kind of with the method that erodes away again " pyramid-like " surperficial light trapping structure behind the magnetron sputtering deposition flat film with rare HCL, working (machining) efficiency is low, and environment is had pollution, and " pyramid-like " surperficial light trapping structure is uncontrollable.
Summary of the invention
One of purpose of the present invention is for the structure of transparent conductive layer of current C IGS thin-film solar cells single, the deficiency that the absorptivity of absorbed layer is limited proposes a kind of copper indium gallium selenide film battery structure of transparent conductive layer with pyramid-like shape surface light trapping structure that can Effective Raise Optical Absorption efficient.
Two of purpose of the present invention is to propose a kind of manufacture method with copper indium gallium selenide film battery structure of transparent conductive layer of pyramid-like shape surface light trapping structure.This manufacture method is simply efficient, and is controlled accurate, adapts to suitability for industrialized production.
For realizing that the technical scheme that one of purpose of the present invention adopts is: a kind of copper indium gallium selenide film battery structure of transparent conductive layer, comprise the Copper Indium Gallium Selenide transparency conducting layer, described conductive layer has surperficial light trapping structure, and this surface light trapping structure is pyramid-like shape.
Preferably, described surperficial light trapping structure has a plurality of pyramid-like shape projections, in the same size or the difference of described a plurality of pyramid-like shape projections.
Preferably, the size of described pyramid-like shape projection, pyramid-like shape projection is divided into some parts, big or small identical with a part, the varying in size of different piece.
Preferably, the projection of described pyramid-like shape is the bulge-structure of cone, oblique pyramid or terrace with edge.
Preferably, this Copper Indium Gallium Selenide transparency conducting layer is the conducting film that contains the Al doping ZnO.
Preferably, the thickness of this Copper Indium Gallium Selenide transparency conducting layer is 0.1um～0.6um.
For realizing that the technical scheme that two of purpose of the present invention adopts is: a kind of according to claim 1 manufacture method of described copper indium gallium selenide film battery structure of transparent conductive layer comprises following manufacturing step:
(1) based on the digital modeling method of the surperficial light trapping structure microscopic appearance feature of Fractal Geometry Theory, makes up on computers the mathematical model of pyramid-like shape surface light trapping structure;
(2) be enclosed in a certain proportion of Zn and Al in the quartz ampoule and connect vacuum system, with the quartz ampoule sealed-off, or with the high purity inert gas protection, then add hot smelting after vacuumizing, finally make the Zn-Al alloy target;
(3) will be superimposed with successively substrate Ultrasonic Cleaning in acetone of back electrode, absorbed layer, resilient coating and Window layer, dries up with nitrogen after in deionized water and absolute ethyl alcohol, cleaning successively again, simultaneously the ZnAl alloys target is placed under the straight argon atmosphere pre-sputter with the cleaning target surface;
(4) substrate is placed direct current reaction magnetron sputtering equipment, use computer according to the data of the surperficial light trapping structure model of designed pyramid-like shape, control the three-dimensional run trace of sputtering target, finally form the surperficial light trapping structure of pyramid-like shape on the Window layer surface.
Above-mentioned sealed-off refers to end in the device exhaust process, and gas pressure intensity reaches the 10-5 handkerchief when following in the pipe, the process that device and gas extraction system are separated and kept sealing.
Preferably, Al be entrained in the content in the alloys target be 2～3%(wt), 2～3%(wt) expression weight ratios be 2～3%.
Preferably, substrate Ultrasonic Cleaning time in acetone is 25～35min.
Preferably, to place under the straight argon atmosphere pre-sputtering time be 7～9min to the Zn-Al alloy target.
Compared with prior art, beneficial effect of the present invention is:
(1) the copper indium gallium selenide film battery transparency conducting layer with " pyramid-like " surperficial light trapping structure provided by the invention, its " pyramid-like " structure can increase the surface area of light absorption with respect to planar structure; Its " pyramid-like " structure is a kind of surperficial light trapping structure, falls into light effect good, in the mean transmissivity of visible light and near infrared range 〉=95%, resistivity＜1.5 * 10
-3Ω cm.This copper indium gallium selenide film battery transparency conducting layer with " pyramid-like " surperficial light trapping structure can improve battery conversion efficiency effectively, has great application prospect and value in the world today of energy shortage.
(2) " pyramid-like " surperficial light trapping structure of copper indium gallium selenide film battery transparency conducting layer provided by the present invention adopts the initiatively mode of design: the rough morphology that adopts first the methods analyst layer at transparent layer light trapping structures such as fractal Brownian function simulation, Fractal Interpolation Simulation method of Fractal Geometry Theory; The methods such as recycling Fourier filtering method, Method of Random Mid-point Displacement, successive random additions are studied the stack of the Fractal Simulation of various rough surfaces and curve thereof, curved surface; Utilize at last the OpenGL image display technology, under Object ARX secondary development environment, carry out the digitlization 2D/3D modelling of surperficial light trapping structure, thereby can realize controlled, the accurate manufacturing of surperficial light trapping structure.
(3) adopt method by the sputtering target Direct precipitation of PC control direct current reaction magnetron sputtering equipment in the manufacture method of the present invention, the high and Environmental Safety of working (machining) efficiency.Make " pyramid-like " surperficial light trapping structure in the prior art and mainly adopt MOCVD or thermal spraying Direct precipitation, can produce harmful substance, contaminated environment; And with using rare HCL caustic solution behind the magnetron sputtering deposition flat film, working (machining) efficiency is low again, and environment is had pollution, and structure is uncontrollable.And processing method provided by the invention is magnetron sputtering Direct precipitation mode, only needs just can process required structure in conjunction with PC, has the advantages such as working (machining) efficiency is high, operation is simple and reliable, environmental protection.
Description of drawings
Fig. 1 is the design vertical view of copper indium gallium selenide film battery structure of transparent conductive layer of the present invention.
Fig. 2 is the side sectional view of copper indium gallium selenide film battery structure of transparent conductive layer of the present invention.
Fig. 3 is the scanning electron microscope (SEM) photograph of copper indium gallium selenide film battery structure of transparent conductive layer of the present invention.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited to this.
Embodiment
As shown in Figure 1 to Figure 3, processing thickness as 0.5um, it is that 3% the copper indium gallium selenide film battery transparency conducting layer with " pyramid-like " surperficial light trapping structure is example that Al is entrained in content in the target.
(1) adopts first the rough morphology of the methods analyst layer at transparent layer light trapping structure such as fractal Brownian function simulation, Fractal Interpolation Simulation method of Fractal Geometry Theory; The methods such as recycling Fourier filtering method, Method of Random Mid-point Displacement, successive random additions are studied the stack of the Fractal Simulation of various rough surfaces and curve thereof, curved surface; Utilize at last the OpenGL image display technology, under Object ARX secondary development environment, carry out the digitlization 2D/3D modelling of surperficial light trapping structure, and generate the three-dimensional data of " pyramid-like " surperficial light trapping structure;
(2) be that the Zn of 24.88:1 and Al are enclosed in and connect vacuum system in the quartz ampoule with mass ratio, with the quartz ampoule sealed-off, or with the high purity inert gas protection, then add hot smelting after finding time, finally make the Zn-Al alloy target;
(3) will be superimposed with successively substrate Ultrasonic Cleaning 30min in acetone of back electrode, absorbed layer, resilient coating and Window layer before the sputter, dries up with nitrogen after in deionized water and absolute ethyl alcohol, cleaning successively again, simultaneously the Zn-Al alloy target is placed under the straight argon atmosphere pre-sputter 8min with the cleaning target surface;
(4) many targets of the JGP450 type head magnetron sputtering apparatus that adopts Shen Keyi to develop: substrate is placed this equipment, use PC according to the three-dimensional data of " pyramid-like " the surperficial light trapping structure that generates, control the three-dimensional run trace of a plurality of target heads of this magnetic control sputtering system, finally forming thickness on the Window layer surface is " pyramid-like " surperficial light trapping structure of 0.5um.In the sputter procedure oxygen outlet is placed near the substrate, argon gas places near the target, to reduce the toxic effect of target as far as possible; Sputter gas is high-purity argon (99.99%), and reacting gas is high-purity 02 (99.99%); Sputtering pressure is regulated between 1.2～2.5mTorr, adopts DC power supply constant current mode of operation; With S4933M/MT type flowmeter control sputter gas flow, control sputtering power, sputtering time, underlayer temperature with PC, realize that the optimization of " pyramid-like " surperficial light trapping structure is initiatively made.
" pyramid-like " provided by the present invention surperficial light trapping structure can increase the surface area of light absorption, can effectively reduce reflectivity, thereby reduces optical loss and improve cell conversion efficiency; This manufacture method adopts direct current reaction magnetron sputtering, and it is simply efficient, and is controlled accurate, is adapted to trend and commercially produces.
Above-described embodiment is the better execution mode of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. a copper indium gallium selenide film battery structure of transparent conductive layer comprises the Copper Indium Gallium Selenide transparency conducting layer, it is characterized in that: described conductive layer has surperficial light trapping structure, and this surface light trapping structure is pyramid-like shape.
2. structure of transparent conductive layer according to claim 1 is characterized in that: described surperficial light trapping structure has a plurality of pyramid-like shapes projections, in the same size or the difference of described a plurality of pyramid-like shape projections.
3. structure of transparent conductive layer according to claim 2, it is characterized in that: the projection of described pyramid-like shape is the bulge-structure of cone, oblique pyramid or terrace with edge.
4. structure of transparent conductive layer according to claim 1, it is characterized in that: this Copper Indium Gallium Selenide transparency conducting layer is the conducting film that contains the Al doping ZnO.
5. structure of transparent conductive layer according to claim 1, it is characterized in that: the thickness of this Copper Indium Gallium Selenide transparency conducting layer is 0.1um～0.6um.
6. the manufacture method of described copper indium gallium selenide film battery structure of transparent conductive layer according to claim 1 is characterized in that, comprises following manufacturing step:
(1) based on the digital modeling method of the surperficial light trapping structure microscopic appearance feature of Fractal Geometry Theory, makes up on computers the mathematical model of pyramid-like shape surface light trapping structure;
(2) be enclosed in a certain proportion of Zn and Al in the quartz ampoule and connect vacuum system, with the quartz ampoule sealed-off, or with the high purity inert gas protection, then add hot smelting after vacuumizing, finally make the Zn-Al alloy target;
(3) will be superimposed with successively substrate Ultrasonic Cleaning in acetone of back electrode, absorbed layer, resilient coating and Window layer, dries up with nitrogen after in deionized water and absolute ethyl alcohol, cleaning successively again, simultaneously the Zn-Al alloy target is placed under the straight argon atmosphere pre-sputter with the cleaning target surface;
(4) substrate is placed direct current reaction magnetron sputtering equipment, use computer according to the data of the surperficial light trapping structure model of designed pyramid-like shape, control the three-dimensional run trace of sputtering target, finally form the surperficial light trapping structure of pyramid-like shape on the Window layer surface.
7. the manufacture method of structure of transparent conductive layer according to claim 6, it is characterized in that: the content that Al is entrained in the alloys target is 2～3%wt.
8. the manufacture method of structure of transparent conductive layer according to claim 6, it is characterized in that: substrate Ultrasonic Cleaning time in acetone is 25～35min.
9. the manufacture method of structure of transparent conductive layer according to claim 6 is characterized in that: the ZnAl alloys target places that pre-sputtering time is 7～9min under the straight argon atmosphere.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104282781A (en) * | 2013-07-01 | 2015-01-14 | 台积太阳能股份有限公司 | Solar cell absorber thin film and method of fabricating same |
| CN109962122A (en) * | 2017-12-22 | 2019-07-02 | 北京铂阳顶荣光伏科技有限公司 | Thin-film solar cells and preparation method thereof |
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| CN102242345A (en) * | 2011-06-29 | 2011-11-16 | 南开大学 | Direct preparation method of textured zinc oxide transparent electroconductive film |
| CN102637751A (en) * | 2012-05-15 | 2012-08-15 | 南开大学 | Broad-spectrum light trapping transparent electroconductive film for solar battery and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101944541A (en) * | 2009-07-08 | 2011-01-12 | 深圳先进技术研究院 | Thin-film photovoltaic cell and manufacturing method thereof |
| CN102242345A (en) * | 2011-06-29 | 2011-11-16 | 南开大学 | Direct preparation method of textured zinc oxide transparent electroconductive film |
| CN102637751A (en) * | 2012-05-15 | 2012-08-15 | 南开大学 | Broad-spectrum light trapping transparent electroconductive film for solar battery and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104282781A (en) * | 2013-07-01 | 2015-01-14 | 台积太阳能股份有限公司 | Solar cell absorber thin film and method of fabricating same |
| CN109962122A (en) * | 2017-12-22 | 2019-07-02 | 北京铂阳顶荣光伏科技有限公司 | Thin-film solar cells and preparation method thereof |
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Application publication date: 20130403 |