CN102270699A - Preparation methods of CIGS (Cu (In, Ga) Se2)-free thin film solar cell and zinc sulfide buffer layer - Google Patents

Preparation methods of CIGS (Cu (In, Ga) Se2)-free thin film solar cell and zinc sulfide buffer layer Download PDF

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CN102270699A
CN102270699A CN2011102020788A CN201110202078A CN102270699A CN 102270699 A CN102270699 A CN 102270699A CN 2011102020788 A CN2011102020788 A CN 2011102020788A CN 201110202078 A CN201110202078 A CN 201110202078A CN 102270699 A CN102270699 A CN 102270699A
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zinc
preparation
film
buffer layer
print
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卢兰兰
刘壮
肖旭东
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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    • YGENERAL 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
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    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a preparation method of a CIGS (Cu (In, Ga) Se2)-free thin film solar cell. The method comprises the following steps: a step 1, forming a back electrode and a CIGS-free light absorption layer on the substrate in sequence so as to form a sample wafer; a step 2, dissolving zinc acetate dehydrate in absolute ethyl alcohol, adding a stabilizing agent and heating to form sol; a step 3, immersing the sample wafer in the sol for 5-10 seconds, and then lifting the sample wafer from the sol; a step 4, drying the sample wafer for 30 minutes at the temperature of 100-200 DEG C so as to form a zinc oxide thin film on the surface of the sample wafer; a step 5, placing the sample wafer into a selenylation room, carrying out annealing treatment in hydrogen sulfide atmosphere, and transforming the zinc oxide thin film into a zinc sulfide buffer layer film; and a step 6, forming a barrier layer and a window layer on the zinc sulfide buffer layer film in sequence. As a higher temperature can be realized in the annealing process by using the preparation method, so the crystallization quality of the film can be improved. The invention also provides a preparation method of the zinc sulfide buffer layer film.

Description

The preparation method of cadmium-free copper-indium-gallium-selenium thin-film solar cells and zinc sulphide buffer layer thin film thereof
[technical field]
The present invention relates to the preparation method of a kind of cadmium-free copper-indium-gallium-selenium thin-film solar cells and zinc sulphide resilient coating thereof.
[background technology]
Copper Indium Gallium Selenide (Cu (In, Ga) Se 2, being called for short CIGS) and thin-film solar cells is the novel solar battery that 20th century, the eighties, later development came out, its excellent performance has obtained paying close attention to widely.The typical structure of copper-indium-galliun-selenium film solar cell is a multi-layer film structure, comprising: metal gates (Al)/transparency electrode (AZO)/Window layer (ZnO)/resilient coating (CdS)/light absorbing zone (CIGS)/back electrode (Mo)/glass.
Although the thickness of resilient coating only has only 50nm, be vital for the CIGS battery.Thereby resilient coating can separate photo-generated carrier with CIGS absorbed layer formation heterojunction and protect absorbed layer not to be destroyed when being coated with upper electrode.
Resilient coating generally adopts cadmium sulfide (molecular formula CdS) material in the CIGS battery, and the CdS film adopts immersion method (CBD, chemical bath deposition) to prepare usually.Immersion method is a kind of technology of common preparation film, and substrate is immersed in cation and the anion pioneer solution, when the product of effects of ion concentration surpasses their solubility product, just can deposit the compound film that makes needs on substrate.
Though adopt CdS to obtain the battery of better performances, owing to contain heavy metal ion Cd as resilient coating 2+, the hull cell that this mode of production obtained in use may destroy biological environment because natural force and other factors tend to make cadmium to leak in the environment and go, and owing to the existence of cadmium, difficulty is also compared in the recovery reprocessing of this battery simultaneously.Therefore people are devoted to not have the exploitation of cadmium resilient coating always, in recent years a lot of reported in literature multiple nontoxic resilient coating, for example, indium sulfide In 2S 3, indium hydroxide In (OH) 3, tin oxide SnO 2, zinc selenide ZnSe, and Zinc compounds Zn (O, S, OH) x, indium thing Inx (OH, S) yDeng.
ZnS replaces the research of CdS as the solar cell resilient coating, be have or not the highest a kind of of battery efficiency in the Cd resilient coating.This is because wide than CdS (2.4eV) of the energy gap of ZnS (3.6-3.8eV), not only can improve the short circuit current of battery, also helps the spectral response that hull cell obtains blue light region, and its lattice parameter and CIGS absorbed layer mate more.
In the preparation of CIGS solar cell, the method that obtains the ZnS film is very important, adopts the CBD method mostly as the preparation of the ZnS resilient coating of solar cell at present, and there is following problem in this method: 1) have precipitation from homogeneous solution during thin film deposition, when generating ZnS, also generated Zn (OH) 2, Zn (OH) 2Sneak into the ZnS film, cause the non-ZnS pure phase of film that obtains.ZnS adhesive force with impurity is poor, easy to crack; 2) in the preparation process of ZnS film, if the instability of the skewness of solution temperature concentration and stir speed (S.S.) also can cause reappearance bad, uniformity of film is difficult to control more when large-area preparation.
[summary of the invention]
Based on this, be necessary to provide a kind of film-formation result preparation method of cadmium-free copper-indium-gallium-selenium thin-film solar cells preferably.
A kind of preparation method of cadmium-free copper-indium-gallium-selenium thin-film solar cells comprises the steps:
Step 1, on substrate, form back electrode and Copper Indium Gallium Selenide light absorbing zone successively, form print;
Step 2, Zinc diacetate dihydrate is dissolved in the absolute ethyl alcohol, adds stabilizer again, add thermosetting colloidal sol;
Step 3, described print is immersed in the described colloidal sol, dip time is 5~10 seconds, then described print is mentioned from described colloidal sol;
Step 4, with described print 100~200 ℃ dry 30 minutes down, make described print surface form zinc-oxide film;
Step 5, described print is put into the indoor annealing in process of carrying out of selenizing under the atmosphere of hydrogen sulfide, described zinc-oxide film is converted into the zinc sulphide buffer layer thin film; And
Step 6, on described zinc sulphide buffer layer thin film, form barrier layer and Window layer successively, obtain described cadmium-free copper-indium-gallium-selenium thin-film solar cells.
In a preferred embodiment, in the step 2, described stabilizer is a monoethanolamine.
In a preferred embodiment, in the step 2, the temperature of described heating is 60~70 ℃.
In a preferred embodiment, in the step 2, the concentration of described Zinc diacetate dihydrate in described colloidal sol is 0.1~0.8mol/L.
In a preferred embodiment, in the step 4, the thickness of described zinc-oxide film is 30~200nm.
In a preferred embodiment, in the step 5, the temperature of annealing in process is 400~500 ℃, and the time is 10~60 minutes.
In addition, also be necessary to provide a kind of film-formation result preparation method of zinc sulphide buffer layer thin film preferably.
A kind of preparation method of zinc sulphide buffer layer thin film comprises the steps:
Zinc diacetate dihydrate is dissolved in the absolute ethyl alcohol, adds stabilizer again, add thermosetting colloidal sol;
Print is immersed in the described colloidal sol, and dip time is 5~10 seconds, then described print is mentioned from described colloidal sol;
Described print was descended dry 30 minutes at 100~200 ℃, make described print surface form zinc-oxide film; And
Described print is carried out annealing in process under the atmosphere of hydrogen sulfide, described zinc-oxide film is converted into the zinc sulphide buffer layer thin film.
The ZnS film of traditional C BD method preparation because temperature is higher, therefore can improve the crystalline quality of film because bath temperature is lower, and what generally obtain is the film of amorphous, and adopts above-mentioned preparation method in annealing process.In addition, take the uniformity of film of dip-coating method preparation better, technology is relatively easy to control.
[embodiment]
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, the present invention is described in detail below in conjunction with embodiment.A lot of details have been set forth in the following description so that fully understand the present invention.
The preparation method of the cadmium-free copper-indium-gallium-selenium thin-film solar cells of one execution mode comprises the steps:
Step 1, on substrate, form back electrode and Copper Indium Gallium Selenide light absorbing zone successively, form print.
Concrete, glass substrate can being cleaned finish puts into vacuum chamber and carries out after aura handles, sputtering sedimentation Mo forms back electrode, transfer to another chamber then and carry out magnetron sputtering or heating in vacuum evaporation copper indium gallium metal, copper indium gallium is deposited on the glass Mo substrate step by step, prepare the copper indium gallium metal preformed layer of CIGS hull cell, and then the indoor Solid State Source light selenizing of carrying out of the vacuum heat that changes Solid State Source light selenizing device over to handles, and copper indium gallium metal preformed layer is transformed into the optical absorbing layer of CIGS hull cell.
In addition, also glass substrate can being cleaned finish puts into vacuum chamber and carries out after aura handles, and sputtering sedimentation Mo forms back electrode, adopts coevaporation method to prepare the optical absorbing layer of CIGS hull cell then.
Step 2, Zinc diacetate dihydrate is dissolved in the absolute ethyl alcohol, adds stabilizer again, add thermosetting colloidal sol.
Concrete, can adopt analytically pure Zinc diacetate dihydrate Zn (CH 3COO) 22H 2O is as presoma, and absolute ethyl alcohol (EtOH) is dissolved in Zinc diacetate dihydrate in the absolute ethyl alcohol as solvent, adds a spot of monoethanolamine again as stabilizer, treat that solution is clarified fully after, add thermosetting transparent and uniform colloidal sol under 60~70 ℃.This colloidal sol can exist long-term and stably, and cost of material has been saved in not waste fully in the use.
Wherein, the concentration of Zinc diacetate dihydrate in described colloidal sol is preferably 0.1~0.8mol/L.
Following chemical reaction has taken place in step 2:
In whole process, zinc acetate is the key reaction thing in the source of end product ZnO as presoma; And monoethanolamine makes colloidal sol be alkalescent as stabilizer, makes Zn 2+With Zn (OH) 2Form exist to keep the colloidal sol clarification; Ethanol does not participate in reaction as solvent.
Step 3, described print is immersed in the described colloidal sol, dip time is 5~10 seconds, then described print is mentioned from described colloidal sol.
Concrete, the colloidal sol for preparing can be placed on the table top, print is fixed with anchor clamps, allows print immerse fully in the colloidal sol, and dip time is 5~10s, slowly evenly print is put forward, and stops the several seconds.Can repeat said process according to the needed film thickness of experiment.Take the uniformity of film of dip-coating method preparation better, technology is relatively easy to control.
Step 4, with described print 100~200 ℃ dry 30 minutes down, make described print surface form zinc-oxide film.
Concrete, the print after film forming can being finished is put into insulating box, dry 30min under 100~200 ℃.In this step, ethanol, Ammoniom-Acetate all volatilize; And Zn (OH) 2Stay on the substrate as intermediate product, and when drying, be decomposed to form ZnO film.Following chemical reaction takes place during this time:
The thickness of the zinc-oxide film that obtains is preferably 30~200nm.
Step 5, described print is put into the indoor annealing in process of carrying out of selenizing under the atmosphere of hydrogen sulfide, described zinc-oxide film is converted into the zinc sulphide buffer layer thin film.
Concrete, use the light irradiated heat in that the print that is coated with zinc-oxide film is positive, heat with contact thermal source or light radiation mode at the print back side, the two sides adds heat request carries out simultaneously, make print can be fast, intensification equably.When its temperature is controlled at 400~500 ℃ when interval, feed volume ratio this moment is hydrogen sulfide-argon gas mist of 1: 5, obtain the active sulfur atom by the light radiation activation, promote the reaction of the zinc atom in sulphur atom and the zinc oxide, impel the Zinc oxide film generation fundamental change of print, become ZnS compound semiconductor film material gradually, become the buffer layer thin film of cadmium-free copper-indium-gallium-selenium thin-film solar cells.Reaction time is preferably 10~60 minutes.Following chemical reaction takes place during this time:
ZnO+H 2S→ZnS+H 2O (4)
Step 6, on described zinc sulphide buffer layer thin film, form Window layer, transparency electrode and metal gates successively.
Concrete, the print that will be formed with resilient coating changes the vacuum magnetic-control sputtering chamber again over to, high barrier of deposition intrinsic i-ZnO and low-resistance conducting ZnO: Al (or Ga, B) Window layer; In the middle of above-mentioned operation, carry out the cutting and the line of film, just prepare the cadmium-free copper-indium-gallium-selenium Thinfilm solar cell assembly.
The ZnS film of traditional C BD method preparation owing to temperature higher (400~500 ℃), can improve the crystalline quality of film because bath temperature is lower, and what generally obtain is the film of amorphous, and adopts above-mentioned preparation method in annealing process.In addition, produce the CIGS battery for large-scale industrialization, adopting this legal system to be equipped with resilient coating does not need to develop new main equipment, can directly utilize the industrial equipment of existing maturation, greatly reduces new equipment cost of developing and risk.Further, it is simple that above-mentioned preparation method also has operating process, is easy to control; The raw material availability height is saved cost; Do not produce a large amount of poisonous waste liquids to environment advantage such as close friend very.
Based on above-mentioned principle, the present invention also provides the preparation method of the zinc sulphide buffer layer thin film of an execution mode, comprises the steps:
Zinc diacetate dihydrate is dissolved in the absolute ethyl alcohol, adds stabilizer again, add thermosetting colloidal sol;
Print is immersed in the described colloidal sol, and dip time is 5~10 seconds, then described print is mentioned from described colloidal sol;
Described print was descended dry 30 minutes at 100~200 ℃, make described print surface form zinc-oxide film; And
Described print is carried out annealing in process under the atmosphere of hydrogen sulfide, described zinc-oxide film is converted into the zinc sulphide buffer layer thin film.
Preferably, described stabilizer is a monoethanolamine.
Preferably, the temperature of described heating is 60~70 ℃.
Preferably, the concentration of described Zinc diacetate dihydrate in described colloidal sol is 0.1~0.8mol/L.
Preferably, the thickness of described zinc-oxide film is 30~200nm.
Preferably, the temperature of annealing in process is 400~500 ℃, and the time is 10~60 minutes.
Above-mentioned preparation method owing to temperature higher (400~500 ℃), can improve the crystalline quality of zinc sulphide buffer layer thin film in annealing process.
Below illustrate with specific embodiment.
Embodiment 1
With 4.39 gram Zn (CH 3COO) 22H 2O joins in the 50ml absolute ethyl alcohol, stirs to be emulsus, drips the monoethanolamine of 1.22ml again in solution, and solution is clarified the back fully and leave standstill 10min under 65 ℃, can obtain the zinc hydroxide sol of transparent and stable.The print that is formed with back electrode and Copper Indium Gallium Selenide light absorbing zone is immersed in 10s in the above-mentioned colloidal sol, slowly evenly print is put forward.The print of filming after finishing is put into 120 ℃ of following dryings of insulating box 30 minutes, can obtain to have adhered to the print of ZnO film.Then at the indoor H of selenizing 2Anneal under the S atmosphere, annealing temperature is 400 ℃, and the time is 60 minutes; Obtained the ZnS buffer layer thin film.
The print that will be formed with resilient coating at last changes the vacuum magnetic-control sputtering chamber again over to, high barrier of deposition intrinsic i-ZnO and low-resistance conducting ZnO: Al Window layer; In the middle of above-mentioned operation, carry out the cutting and the line of film simultaneously, just prepare the cadmium-free copper-indium-gallium-selenium Thinfilm solar cell assembly.
Embodiment 2
With 2.195g Zn (CH 3COO) 22H 2O joins in the 50ml absolute ethyl alcohol, stirs to be emulsus, drips the monoethanolamine of 0.61ml again in solution, and solution is clarified the back fully and leave standstill 10min under 65 ℃, can obtain the zinc hydroxide sol of transparent and stable.The print that is formed with back electrode and Copper Indium Gallium Selenide light absorbing zone is immersed in 10s in the above-mentioned colloidal sol, slowly evenly print is put forward.Print after finishing filming was put into 100 ℃ of insulating boxs dry 30 minutes down, print was immersed in the colloidal sol again, and the process above repeating obtains the suitable print that has adhered to ZnO film of thickness several times.Then at the indoor H of selenizing 2Anneal under the S atmosphere, annealing temperature is 500 ℃, and the time is 10 minutes; Obtained the ZnS buffer layer thin film.The print that will be formed with resilient coating at last changes the vacuum magnetic-control sputtering chamber again over to, high barrier of deposition intrinsic i-ZnO and low-resistance conducting ZnO: Al Window layer; In the middle of above-mentioned operation, carry out the cutting and the line of film simultaneously, just prepare the cadmium-free copper-indium-gallium-selenium Thinfilm solar cell assembly.
Embodiment 3
With 6.57g Zn (CH 3COO) 22H 2O joins in the 50ml absolute ethyl alcohol, stirs to be emulsus, drips the monoethanolamine of 1.83ml again in solution, and solution is clarified the back fully and leave standstill 10min under 65 ℃, can obtain the zinc hydroxide sol of transparent and stable.The print that is formed with back electrode and Copper Indium Gallium Selenide light absorbing zone is immersed in 10s in the above-mentioned colloidal sol, slowly evenly print is put forward.The print of filming after finishing is put into 100 ℃ of following dryings of insulating box 30 minutes, obtained adhering to the print of ZnO film.Then at the indoor H of selenizing 2Anneal under the S atmosphere, annealing temperature is 450 ℃, and the time is 30 minutes; Obtained the ZnS buffer layer thin film.The print that will be formed with resilient coating at last changes the vacuum magnetic-control sputtering chamber again over to, high barrier of deposition intrinsic i-ZnO and low-resistance conducting ZnO: A1 Window layer; In the middle of above-mentioned operation, carry out the cutting and the line of film simultaneously, just prepare the cadmium-free copper-indium-gallium-selenium Thinfilm solar cell assembly.
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 claim of the present invention.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 preparation method of a cadmium-free copper-indium-gallium-selenium thin-film solar cells is characterized in that, comprises the steps:
Step 1, on substrate, form back electrode and Copper Indium Gallium Selenide light absorbing zone successively, form print;
Step 2, Zinc diacetate dihydrate is dissolved in the absolute ethyl alcohol, adds stabilizer again, add thermosetting colloidal sol;
Step 3, described print is immersed in the described colloidal sol, dip time is 5~10 seconds, then described print is mentioned from described colloidal sol;
Step 4, with described print 100~200 ℃ dry 30 minutes down, make described print surface form zinc-oxide film;
Step 5, described print is put into the indoor annealing in process of carrying out of selenizing under the atmosphere of hydrogen sulfide, described zinc-oxide film is converted into the zinc sulphide buffer layer thin film; And
Step 6, on described zinc sulphide buffer layer thin film, form barrier layer and Window layer successively, obtain described cadmium-free copper-indium-gallium-selenium thin-film solar cells.
2. the preparation method of cadmium-free copper-indium-gallium-selenium thin-film solar cells according to claim 1 is characterized in that: in the step 2, described stabilizer is a monoethanolamine.
3. the preparation method of cadmium-free copper-indium-gallium-selenium thin-film solar cells according to claim 1 is characterized in that: in the step 2, the temperature of described heating is 60~70 ℃.
4. the preparation method of cadmium-free copper-indium-gallium-selenium thin-film solar cells according to claim 1 is characterized in that: in the step 2, the concentration of described Zinc diacetate dihydrate in described colloidal sol is 0.1~0.8mol/L.
5. the preparation method of cadmium-free copper-indium-gallium-selenium thin-film solar cells according to claim 1 is characterized in that: in the step 4, the thickness of described zinc-oxide film is 30~200nm.
6. the preparation method of cadmium-free copper-indium-gallium-selenium thin-film solar cells according to claim 1 is characterized in that: in the step 5, the temperature of annealing in process is 400~500 ℃, and the time is 10~60 minutes.
7. the preparation method of a zinc sulphide buffer layer thin film is characterized in that, comprises the steps:
Zinc diacetate dihydrate is dissolved in the absolute ethyl alcohol, adds stabilizer again, add thermosetting colloidal sol;
Print is immersed in the described colloidal sol, and dip time is 5~10 seconds, then described print is mentioned from described colloidal sol;
Described print was descended dry 30 minutes at 100~200 ℃, make described print surface form zinc-oxide film; And
Described print is carried out annealing in process under the atmosphere of hydrogen sulfide, described zinc-oxide film is converted into the zinc sulphide buffer layer thin film.
8. the preparation method of zinc sulphide buffer layer thin film according to claim 7 is characterized in that: described stabilizer is a monoethanolamine.
9. the preparation method of zinc sulphide buffer layer thin film according to claim 7 is characterized in that: the temperature of described heating is 60~70 ℃.
10. the preparation method of zinc sulphide buffer layer thin film according to claim 7 is characterized in that: the concentration of described Zinc diacetate dihydrate in described colloidal sol is 0.1~0.8mol/L.
CN2011102020788A 2011-07-18 2011-07-18 Preparation methods of CIGS (Cu (In, Ga) Se2)-free thin film solar cell and zinc sulfide buffer layer Pending CN102270699A (en)

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CN102544237A (en) * 2012-02-29 2012-07-04 广东工业大学 Preparation method for buffering layer material of copper indium gallium selenide film solar battery
CN102651432A (en) * 2012-05-17 2012-08-29 上海大学 Method for preparing thin film type LED
CN103151429A (en) * 2013-03-27 2013-06-12 上海空间电源研究所 Chemical treatment method for improving quality of surface layer of copper-indium-gallium-selenium thin film material
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CN103972329A (en) * 2014-05-07 2014-08-06 杭州电子科技大学 Preparation method of cadmium-free buffer layer of copper indium gallium selenium thin-film solar cell
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Cited By (9)

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CN103255396A (en) * 2012-02-17 2013-08-21 任丘市永基光电太阳能有限公司 Preparation method of cadmium-free buffer layer in flexible CIGS thin film solar cell
CN102544237A (en) * 2012-02-29 2012-07-04 广东工业大学 Preparation method for buffering layer material of copper indium gallium selenide film solar battery
CN102651432A (en) * 2012-05-17 2012-08-29 上海大学 Method for preparing thin film type LED
US20140273333A1 (en) * 2013-03-13 2014-09-18 Intermolecular Inc. Methods for fabricating ZnOSe alloys
US8980682B2 (en) * 2013-03-13 2015-03-17 Intermolecular, Inc. Methods for fabricating ZnOSe alloys
CN103151429A (en) * 2013-03-27 2013-06-12 上海空间电源研究所 Chemical treatment method for improving quality of surface layer of copper-indium-gallium-selenium thin film material
CN103151429B (en) * 2013-03-27 2015-10-28 上海空间电源研究所 A kind of chemical treatment method for improving CIGS thin-film material surface quality
CN103972329A (en) * 2014-05-07 2014-08-06 杭州电子科技大学 Preparation method of cadmium-free buffer layer of copper indium gallium selenium thin-film solar cell
CN103972329B (en) * 2014-05-07 2016-04-27 杭州电子科技大学 A kind of copper-indium-galliun-selenium film solar cell is without the preparation method of cadmium resilient coating

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