CN108231915A - A kind of CIGS thin film solar cell and preparation method thereof - Google Patents
A kind of CIGS thin film solar cell and preparation method thereof Download PDFInfo
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- CN108231915A CN108231915A CN201611145360.6A CN201611145360A CN108231915A CN 108231915 A CN108231915 A CN 108231915A CN 201611145360 A CN201611145360 A CN 201611145360A CN 108231915 A CN108231915 A CN 108231915A
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- 239000010409 thin film Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 34
- 239000002184 metal Substances 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000010408 film Substances 0.000 claims description 73
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 claims description 68
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 50
- 239000011787 zinc oxide Substances 0.000 claims description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 229910052733 gallium Inorganic materials 0.000 claims description 11
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 9
- 229910052711 selenium Inorganic materials 0.000 claims description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 239000005361 soda-lime glass Substances 0.000 claims description 4
- 238000002834 transmittance Methods 0.000 abstract description 6
- 231100000252 nontoxic Toxicity 0.000 abstract description 5
- 230000003000 nontoxic effect Effects 0.000 abstract description 5
- 239000010949 copper Substances 0.000 description 19
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 16
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 16
- 229910052802 copper Inorganic materials 0.000 description 13
- 239000011669 selenium Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 229910052738 indium Inorganic materials 0.000 description 8
- 238000010549 co-Evaporation Methods 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- 238000001755 magnetron sputter deposition Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 5
- UIFOTCALDQIDTI-UHFFFAOYSA-N arsanylidynenickel Chemical group [As]#[Ni] UIFOTCALDQIDTI-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 240000002329 Inga feuillei Species 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- 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
- H01L31/04—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
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
-
- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to CIGS thin film area of solar cell, disclose a kind of CIGS thin film preparation method of solar battery, the battery includes the substrate stacked gradually, metal back electrode, CIGS thin-film, buffer layer, Window layer, and the conduction band bottom of the CIGS thin-film is higher 0.001~0.1eV than the conduction band bottom of the cushioning layer material.The method for preparing CIGS thin film solar cell includes：It stacks gradually to form metal back electrode, CIGS thin-film, buffer layer, Window layer on substrate, wherein, the conduction band bottom of the CIGS thin-film is higher 0.001 0.1eV than the conduction band bottom of the buffer layer.CIGS thin film solar cell provided by the invention has the advantages that nontoxic and high transmittance.
Description
Technical field
The present invention relates to CIGS thin film area of solar cell, and in particular, to a kind of CIGS thin film solar cell, one
The CIGS thin film solar cell that kind prepares the method for CIGS thin film solar cell and is prepared by this method.
Background technology
In copper indium gallium selenide (CIGS) thin-film solar cells, generally by the use of cadmium sulfide (CdS) film as the buffering of battery
Layer requires CdS have that high transmitance, good energy band matches between CIGS thin film, good PN can be formed with CIGS
Knot.
In document 1, " efficiency with 81.2% fill factor is 19.9% ZnO/CdS/CuInGaSe2Solar-electricity
Pond (19.9%-efficient ZnO/CdS/CuInGaSe2Solar Cell with 81.2%Fill Factor, Ingrid
Repins,etc,Prog.Photovolt:Res.Appl.2008；16:In 235-239) ", pass through the fill factor of high-content
It realizes to ZnO/CdS/CuInGaSe2The modification of solar cell, specifically, the ZnO/CdS/CuInGaSe of the prior art2
The efficiency of solar cell reaches 19.9%.However, containing cadmium in the cadmium sulfide used in the prior art, have toxicity larger and
The disagreeableness shortcoming to environment.
" there is Zn (O, S, OH) in document 2xCu (InGa) Se of buffer layer2The development of base film PV modules
(Development of Cu(InGa)Se2-based thin-film PV modules with a Zn(O,S,OH)x
Buffer layer) " in, the prior art is with Zn (O, S, OH)xTraditional CdS, Zn (O, S, OH) are substituted as buffer layerx's
Energy gap higher, it is all to have better optical transmittance.And Zn (O, S, OH)xIt is environmentally friendly without cadmium.But Zn
(O,S,OH)xIn sulphur oxygen compare CIGS batteries each performance parameter have significant impact, and Zn (O, S, OH)xFilm
Preparation process be relatively difficult to control, the structure of this film of suitable copper indium gallium selenide cell can be manufactured in the prior art very
It is few.It is easy in fact, producing this film, but on battery, and reach a preferable efficiency and be but difficult.
Invention content
The purpose of the present invention is overcome the method complex process of the prior art, toxicity high and the defects of transmitance is low, carry
For a kind of CIGS thin film solar cell and preparation method thereof, to obtain nontoxic and high transmittance CIGS thin film solar-electricity
Pond.
It was found by the inventors of the present invention that traditional cushioning layer material is CdS, its conduction band bottom is higher than the conduction band bottom of CIGS
About 0.3eV, the electronics that this potential barrier is unfavorable for generating flows to CdS directions from CIGS, so as to increase CIGS/CdS interfaces
It is compound, the electric current of battery is reduced, so as to reduce battery efficiency.It is formed according to the conduction band bottom material lower than the conduction band bottom of CIGS slow
When rushing layer, the transmission of electronics will not be hindered, is conducive to improve the electric current of battery, so as to obtain efficient battery.For example, using
TiO2When substituting traditional CdS film as cushioning layer material, due to TiO2Conduction band bottom it is lower 0.1eV than the conduction band bottom of CIGS, no
The transmission of electronics can be hindered, is conducive to improve the electric current of battery, so as to obtain efficient battery.Under preferable case, according to
Cushioning layer material energy gap it is high when, it is possible to produce the higher film of optical transmittance, so as to improve battery efficiency,
Such as TiO2Energy gap for 3.2eV, more than the energy gap of CdS film 2.4eV.
Based on above-mentioned discovery, the present inventor proposes following technical solution.
In a first aspect, the present invention provides a kind of CIGS thin film solar cell, which includes the substrate, the gold that stack gradually
Belong to back electrode, CIGS thin-film, buffer layer and Window layer, the conduction band bottom of the CIGS thin-film is than the cushioning layer material
The high 0.001~0.1eV in conduction band bottom.
Second aspect, the present invention provide a kind of method for preparing CIGS thin film solar cell, and this method includes：In substrate
On stack gradually to form metal back electrode, CIGS thin-film, buffer layer and Window layer, wherein, the CIGS thin-film
Conduction band bottom is higher 0.001~0.1eV than the conduction band bottom of the buffer layer.
The third aspect, the present invention provide the CIGS thin film solar cell being prepared by preceding method.
CIGS thin film solar cell provided by the invention has the advantages that nontoxic, high transmittance.
The method provided by the invention for preparing the battery containing titanium deoxid film has the advantages that simple for process.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It is it should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood to comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It between the endpoint value of a range and individual point value and can be individually combined with each other between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In a first aspect, the present invention provides a kind of CIGS thin film solar cell, the battery include the substrate stacked gradually,
Metal back electrode, CIGS thin-film, buffer layer and Window layer, the conduction band bottom of the CIGS thin-film is than the buffer layer material
High 0.001~the 0.1eV in conduction band bottom of material.
Preferably, the energy gap of the cushioning layer material is 3~3.2eV.
Preferably, the buffer layer is titanium deoxid film.By titanium deoxid film as CIGS thin film solar cell
Buffer layer there is nontoxic, high transmittance so that the CIGS for containing the titanium deoxid film as buffer layer is thin
Film solar cell with relative to the battery in the prior art for example using cadmium sulfide as buffer layer with more excellent
Performance.Also, for the relatively traditional cushioning layer material cadmium sulfide of titanium deoxid film provided by the invention, have more preferably with CIGS
Energy band matching, be conducive to the transmission of electronics.
Preferably, the thickness of the buffer layer is 1~100nm；Preferably 5~90nm；More preferably 10~80nm；Into one
Step is preferably 20~75nm.
Preferably, the thickness of the CIGS thin-film is 1.5~2.5 μm.
Preferably, in the CIGS thin-film, on the basis of the total atom number wherein contained, copper atom number accounting is
20~22%, phosphide atom number accounting is 17~22%, gallium atomicity accounting be 5~13% and selenium atom number accounting be 50~
51%.
Preferably, the substrate is soda-lime glass.
Preferably, the thickness of the substrate is 2.5~3.3mm.
Preferably, the metal back electrode is molybdenum back electrode.
Preferably, the thickness of the metal back electrode is 0.4~1 μm.
The Window layer includes intrinsic zinc oxide film and Al-Doped ZnO film.
Preferably, the thickness of the intrinsic zinc oxide film is 40~60nm.
Preferably, the thickness of the Al-Doped ZnO film is 100~800nm.Under preferable case, the Al-Doped ZnO
The weight content of alundum (Al2O3) in film is 1.5~2.5%.
Preferably, metal grid lines are also contained in the battery, the battery is nickeline film or nickel aluminium film.
Preferably, the nickel film and Ag films that the nickeline film expression is set gradually；And the nickel aluminium film represents
The nickel film and aluminium film set gradually.
Preferably, the thickness of the metal grid lines is 750~3100nm.In the case of more preferably, in the metal grid lines
Nickel film thickness be 40~60nm, preferably from about 50nm；And Ag films or the thickness of aluminium film in the metal grid lines
It spends for 700~3050nm.
Second aspect, the present invention provides a kind of method for preparing CIGS thin film solar cell, this method includes：It is serving as a contrast
It stacks gradually to form metal back electrode, CIGS thin-film, buffer layer and Window layer on bottom, wherein, the CIGS thin-film
Conduction band bottom it is higher 0.001~0.1eV than the conduction band bottom of the buffer layer.
Preferably, the energy gap of the cushioning layer material is 3~3.2eV.
Preferably, the buffer layer is titanium deoxid film.
Preferably, the process for forming the buffer layer includes：It will be laminated on substrate and be formed with metal back electrode and copper and indium
The battery intermediate of gallium selenium film carries out first with titanium tetrachloride solution and contacts.
Preferably, the condition of first contact includes：Temperature is 40~100 DEG C, and the time is 20~180min.
The titanium tetrachloride solution for example can be the aqueous solution of titanium tetrachloride.
To the concentration of the titanium tetrachloride solution, there is no particular limitation, as long as enabling to obtain after carrying out the first contact
Battery intermediate buffer layer thickness be 1~100nm；Preferably 5~90nm；More preferably 10~80nm；It is further excellent
It is selected as 20~75nm.
The various methods preparation that routine in the art may be used in those skilled in the art is provided with CIGS thin-film
Battery intermediate, there is no particular limitation to preparation method by the present invention.Under preferable case, this method further comprises：Pass through
Three stage Co-evaporation method deposits CIGS thin-film to obtain described being provided with copper on the battery intermediate for be provided with metallic film
The battery intermediate of indium gallium selenium film.
Preferably, the three stage Co-evaporation method includes：At 300~420 DEG C, it is being provided among the battery of metallic film
In, Ga and Se are steamed on body altogether to obtain IGS layers；In sources and Ga sources are then shut off, and Cu sources are opened to obtain at 450~550 DEG C
To copper-rich cigs layer；And then on the copper-rich cigs layer In, Ga, Se are steamed altogether described to be provided with copper indium gallium selenide thin to obtain
The battery intermediate of film.
Preferably, the condition of three stage Co-evaporation method is controlled so that be provided with CIGS thin-film described in thus obtained
In CIGS thin-film in battery intermediate, on the basis of the total atom number wherein contained (in CIGS thin-film), copper is former
Subnumber accounting is 20~22%, and phosphide atom number accounting is 17~22%, and gallium atomicity accounting is 5~13% and selenium atom number
Accounting is 50~51%.It was found by the inventors of the present invention that control the copper atom number in the CIGS thin-film in battery intermediate
Accounting is 20~22%, and phosphide atom number accounting is 17~22%, and gallium atomicity accounting is 5~13% and selenium atom number accounting
For 50~51% and setting thickness be the titanium dioxide layer of 20~75nm as buffer layer when, the transmitance of gained battery is more
Height, and it is more efficient.
Preferably, the condition of three stage Co-evaporation method is controlled so that be provided with CIGS thin-film described in thus obtained
The thickness of CIGS thin-film in battery intermediate is 1.5~2.5 μm.
Preferably, in the second aspect, the substrate is soda-lime glass and the preferably thickness of the substrate is
2.5~3.3mm.
Preferably, deposition is laminated to be formed with the depositing temperature of metal back electrode as 0~200 DEG C over the substrate.
Preferably, control deposits the condition of the metal back electrode over the substrate so that the gold being consequently formed
The thickness for belonging to back electrode is 0.4~1 μm.
Under preferable case, deposit over the substrate the metal back electrode may be used DC magnetron sputtering method or
It is carried out using radio frequency magnetron sputtering method.
Preferably, the Window layer includes the intrinsic zinc oxide film and Al-Doped ZnO film that respectively and sequentially form.
Preferably, the depositing temperature of the intrinsic zinc oxide film and the Al-Doped ZnO film is formed each independently
It is 0~200 DEG C.
Preferably, control forms the condition of the intrinsic zinc oxide film so that thus obtained intrinsic zinc oxide film
Thickness be 40~60nm.
Preferably, control forms the condition of the Al-Doped ZnO film so that thus obtained Al-Doped ZnO film
Thickness be 100~800nm.
Preferably, metal grid lines are also contained in the battery, control forms the condition of the metal grid lines so that thus
The thickness of the metal grid lines arrived is 750~3100nm.Particularly, when the metal grid lines are nickeline film or nickel aluminium film,
Control forms the condition of the metal grid lines so that the thickness of the nickel film in the metal grid lines is 40~60nm, preferably
About 50nm；And so that the thickness of the Ag films or aluminium film in the metal grid lines is 700~3050nm.
Preferably, the intrinsic zinc oxide film is formed to carry out using radio frequency magnetron sputtering method.
Preferably, formed the Al-Doped ZnO film using radio frequency magnetron sputtering method or DC magnetron sputtering method into
Row.
Preferably, the metal grid lines are prepared by electron beam evaporation or the method for thermal evaporation.
According to a kind of preferred embodiment, the method for preparing CIGS thin film solar cell includes：
(1) metal back electrode is prepared on substrate, forms the battery intermediate for being provided with metal back electrode, and control prepares item
Part so that the thickness of metal back electrode is 0.4~1 μm；
(2) CIGS thin-film is formed on the battery intermediate for being provided with metal back electrode after step (1), obtained
To the battery intermediate for being provided with CIGS thin-film, control preparation condition so that the thickness of CIGS thin-film for 1.5~
2.5μm；
(3) the battery intermediate for being provided with CIGS thin-film after step (2) is carried out with titanium tetrachloride solution
First contact, obtains containing battery intermediate of the titanium dioxide as buffer layer；It is preferred that the condition of first contact includes：Temperature
It is 40~100 DEG C to spend, and the time is 20~180min；
(4) described after step (3) contains titanium dioxide as setting native oxide on the battery intermediate of buffer layer
Zinc film, control condition so that the thickness of the intrinsic zinc oxide film is 40~60nm；
(5) Al-Doped ZnO film is set on the battery intermediate after step (4), and control condition described to mix alumina
The thickness for changing zinc film is 100~800nm；
(6) metal grid lines are set on the battery intermediate after step (5), control condition causes the thickness of the metal grid lines
It spends for 750~3100nm.
In aforementioned preferred embodiment, in step (2), it is preferred to use three stage Co-evaporation method carries out.
The third aspect, the present invention provides the CIGS thin film solar cells being prepared by preceding method.
The present invention will be described in detail by way of examples below.
Thickness used below is a kind of lining of the soda-lime glass (float glass) of 3mm as CIGS thin film solar cell
Bottom.
Embodiment 1
(1) molybdenum back electrode is prepared, prepares molybdenum (Mo) film with DC magnetron sputtering method on substrate, thickness is
1000nm, depositing temperature are 200 DEG C；
(2) copper indium gallium selenide (CIGS) film that deposition thickness is 2 microns on Mo films, is prepared with three stage Co-evaporation method,
Underlayer temperature is risen to after 300 DEG C and steams In-Ga-Se altogether so that (In, Ga) is made2Se3(IGS) layer；Then, In sources, Ga sources are closed,
550 DEG C are raised the temperature to, opens Cu sources, copper-rich cigs layer is made；Finally, then on the surface of copper-rich cigs layer In-Ga- is prepared
Se makes the poor copper of CIGS, is respectively 21.1%, 9.7%, 19.2% and 50% with the atomicity accounting for obtaining Cu, In, Ga and Se
CIGS thin-film；
(3) prepare thickness be 50nm titanium deoxid film as buffer layer, the sample that step (2) obtains is put into
In the titanium tetrachloride aqueous solution of 300mM, titanium deoxid film is prepared as the cushioning layer material of battery, water temperature by the use of chemical bath method
It it is 70 DEG C, the time is 60 minutes；
(4) the intrinsic zinc oxide film (i-ZnO) that thickness is 50nm is prepared, is prepared, is not added with radio frequency magnetron sputtering method
Heat deposition；
(5) Al-Doped ZnO film (AZO) that thickness is 200nm is prepared, is prepared, is not added with heat sink with radio-frequency magnetron sputter method
Product；
(6) prepare metal grid lines, material be nickeline (Ni/Ag) film, thickness 50/1000nm, deposited by electron beam evaporation side
It is prepared by method.
Obtain CIGS thin film solar cell C1.
Embodiment 2
The present embodiment is carried out using method similar to Example 1, the difference is that the step of the present embodiment (3) is：
Prepare thickness be 55nm titanium deoxid film as buffer layer, the sample that step (2) obtains is put into 450mM's
In titanium tetrachloride solution, titanium deoxid film is prepared as the cushioning layer material of battery by the use of chemical bath method, water temperature is 80 DEG C, when
Between be 65 minutes.
Obtain CIGS thin film solar cell C2.
Embodiment 3
The present embodiment is carried out using method similar to Example 1, the difference is that the step of the present embodiment (3) is：
Prepare thickness be 60nm titanium deoxid film as buffer layer, the sample that step (2) obtains is put into 200mM's
In titanium tetrachloride solution, titanium deoxid film is prepared as the cushioning layer material of battery by the use of chemical bath method, water temperature is 60 DEG C, when
Between be 70 minutes.
Obtain CIGS thin film solar cell C3.
Embodiment 4
The present embodiment is carried out using method similar to Example 2, the difference is that the step of the present embodiment (2) is：
Deposition thickness is 2 microns copper indium gallium selenide (CIGS) film on Mo films, is prepared, will served as a contrast with three stage Co-evaporation method
Bottom temperature is risen to after 300 DEG C steams In-Ga-Se so that (In, Ga) is made altogether2Se3(IGS) layer；Then, In sources, Ga sources are closed, it will be warm
Degree is increased to 550 DEG C, opens Cu sources, and copper-rich cigs layer is made；Finally, then on the surface of copper-rich cigs layer In-Ga-Se is prepared,
Make the poor copper of CIGS, control Cu sources, In sources, Ga sources and Se sources flow cause Cu, In, Ga in copper indium gallium selenide (CIGS) film and
The atomicity accounting of Se is respectively 19.5%, 20.8%, 9.7% and 50% CIGS thin-film.
Obtain CIGS thin film solar cell C4.
Test case
This test case is used to test the performance for the battery that previous embodiment and comparative example are prepared.Specifically：
Battery performance test uses the 3A grade solar simulators of Newport, model 94023A, and current and voltage data is adopted
It is measured with 2420 current voltmeters of Keithley.
As a result as shown in table 1.
Table 1
By the result of above-mentioned test case can be seen that CIGS thin film solar cell provided by the invention have it is nontoxic,
The advantages of transmitance is high.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail, within the scope of the technical concept of the present invention, a variety of simple variants can be carried out to technical scheme of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of CIGS thin film solar cell, the substrate, metal back electrode, copper indium gallium selenide which includes stacking gradually are thin
Film, buffer layer and Window layer, which is characterized in that the conduction band bottom of the CIGS thin-film is than the conduction band bottom of the cushioning layer material
High 0.001~0.1eV.
2. battery according to claim 1, wherein, the energy gap of the cushioning layer material is 3~3.2eV.
3. battery according to claim 1 or 2, wherein, the buffer layer is titanium deoxid film.
4. according to the battery described in any one in claim 1-3, wherein, the thickness of the buffer layer is 1~100nm；It is excellent
It is selected as 5~90nm；More preferably 10~80nm；Further preferably 20~75nm.
5. according to the battery described in any one in claim 1-4, wherein, in the CIGS thin-film, wherein to contain
On the basis of some total atom numbers, copper atom number accounting is 20~22%, and phosphide atom number accounting is 17~22%, gallium atomicity accounting
It is 50~51% for 5~13% and selenium atom number accounting.
6. according to the electrode described in any one in claim 1-5, wherein, the substrate is soda-lime glass；Preferably,
The metal back electrode is molybdenum back electrode；Preferably,
The Window layer includes intrinsic zinc oxide film and Al-Doped ZnO film.
7. a kind of method for preparing CIGS thin film solar cell, this method include：It stacks gradually to form the metal back of the body on substrate
Electrode, CIGS thin-film, buffer layer and Window layer, wherein, the conduction band bottom of the CIGS thin-film is than the buffer layer
The high 0.001-0.1eV in conduction band bottom.
8. according to the method described in claim 7, wherein, the energy gap of the cushioning layer material is 3~3.2eV；Preferably,
The buffer layer is titanium deoxid film.
9. according to the method described in claim 8, wherein, the process for forming the buffer layer includes：Shape will be laminated on substrate
First is carried out into the battery intermediate for having metal back electrode and CIGS thin-film with titanium tetrachloride solution to contact；Preferably,
The condition of first contact includes：Temperature is 40~100 DEG C, and the time is 20~180min.
10. the CIGS thin film solar cell that the method in claim 7-9 described in any one is prepared.
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