CN106449875A - Method for manufacturing CIGS thin film solar cell from MgZnO thin film - Google Patents
Method for manufacturing CIGS thin film solar cell from MgZnO thin film Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 238000000137 annealing Methods 0.000 claims abstract description 31
- 239000005361 soda-lime glass Substances 0.000 claims abstract description 29
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 6
- 239000010408 film Substances 0.000 claims description 92
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 42
- 238000004544 sputter deposition Methods 0.000 claims description 15
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000004044 response Effects 0.000 abstract description 3
- 230000003595 spectral effect Effects 0.000 abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract 4
- 239000011787 zinc oxide Substances 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 description 12
- 239000011701 zinc Substances 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 229910004613 CdTe Inorganic materials 0.000 description 1
- 229910017612 Cu(In,Ga)Se2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Disclosed is a method for manufacturing a CIGS thin film solar cell from an MgZnO thin film. The method comprises the steps of 1, preparing an Mo layer on soda-lime glass; 2, preparing a CIGS layer on the Mo layer; 3, preparing a CdS layer on the CIGS; 4, preparing an MgZnO thin film layer on the CdS layer; 5, performing annealing treatment on the prepared MgZnO thin film; and 6, preparing an aluminum-doped zinc oxide (AZO) layer on the MgZnO layer to constitute a CIGS thin film solar cell device. The MgZnO thin film material provided by the invention refers to the MgZnO thin film layer prepared by a magnetron sputtering method and the MgZnO thin film layer is used as a high-resistance layer of the CIGS cell; and compared with a conventional ZnO high-resistance layer, the absorption to the blue light can be improved, the spectral response range can be enlarged, the open-circuit voltage of the CIGS thin film solar cell is improved, and the efficiency of the cell is improved.
Description
Technical field
The invention belongs to technical field of thin-film solar, more particularly to a kind of CIGS (CIGS) thin film solar
The preparation method of battery resistive formation, and it is applied to the structure of CIGS thin film solaode based on the resistive formation.
Background technology
Energy crisis and environmental pollution are the two big basic problems faced by the current whole world.Cu(In,Ga)Se2(CIGS) thin
Film is to visible absorption coefficient height, and energy gap is suitable, the advantages of capability of resistance to radiation is strong, battery performance is stable, the low light level is good, quilt
It is considered one of most promising photoelectric material.
Traditional CIGS solar battery structure is mainly using soda lime glass/absorbed layer ClGS is thin for Mo electrode film/p-type
Film/cushion CdS film/ZnO resistive formation/AZO transparency conducting layer/Al gate electrode, for battery conversion efficiency, this comprehensively refers to
For mark, the performance of each layer membrane materials and mutual interface have vital impact and act on.Window layer ZnO film be by
High resistant ZnO (intrinsic ZnO or i ZnO) and low-resistance Zn0 (Zn0：Al or n ZnO) constitute, high resistant ZnO is used as CIGS solar cell
A part for PN junction has effect of crucial importance.First, the ZnO film for preparing under normal conditions all presents N pole, so
ZnO has the title of " one pole quasiconductor " again.Intrinsic ZnO film is generally highly resistant material, and resistivity reaches 1012Ω·cm.Due to ZnO
Lacking oxygen being formed easily in thin film and zinc fills out atom, forms defect level so that ZnO film in the band structure of ZnO crystal
N-type is presented, and therefore hetero-junctions can be constituted with other P-type materials.N-type ZnO film be widely used in Si solaode,
CIS solaode and CdTe solaode etc..Secondly, ZnO film is with higher absorbance in visible-range, same
When ZnO film to be subject to High energy particles Radiation to damage little, used in being particularly suitable for space, and ZnO material abundance, price
Cheaply, with very many advantages.
With people shorter wavelength region is explored increasingly deep, wide bandgap semiconductor has become World Focusing gradually
Focus, in order to lift the conversion efficiency of CIGS solar cell further, needs to prepare material and technique is upgraded to traditional,
The energy gap of wherein resistive formation ZnO film keeps 3.3eV immutable, limits lifting and the thin film solar of battery efficiency
The structure updating of battery, is badly in need of a kind of substitution material to further enhance the absorption to blue light, widens spectral response range, improve
Solaode open pressure, so as to lift battery efficiency.
Content of the invention
The purpose of the present invention is less for (1) resistive formation ZnO film energy gap in prior art, limits battery effect
The lifting of rate；(2) resistive formation ZnO film energy gap keeps 3.3eV immutable, limits the knot of CIGS thin film solaode
The problem of two aspects such as structure upgrading proposes a kind of preparation method of novel C IGS thin-film solar cells resistive formation.The method bag
Including a kind of MgZnO film material and CIGS thin film solar cell device being made using which, the resistive formation that the present invention is provided refers to
It is MgZnO structure, the position of the resistive formation ZnO in traditional handicraft can be replaced, compared with ZnO, MgZnO film energy gap is more
Greatly, spectral response range can be increased, so as to solar battery efficiency is improved, and due to MgZnO film more effectively using blue light
Material band gap is adjustable, and the overall structure of CIGS thin film solaode can be promoted to be upgraded.The present invention be by as follows
Technical scheme is realized：
A kind of method that utilization MgZnO film makes CIGS thin film solaode, it is characterised in that methods described includes
Following steps：
Step one, in soda-lime glass substrate deposit back electrode molybdenum Mo layer；
Step 2, on Mo layer prepare CIGS thin film layer as light absorbing zone；
Step 3, cadmium sulfide CdS layer is prepared on CIGS；
Step 4, Mg-doping ZnO layer i.e. MgZnO film is prepared on cadmium sulfide CdS layer；
Step 5, the MgZnO film to preparing in step 4 make annealing treatment；
Step 6, Al-Doped ZnO AZO layer being prepared on MgZnO film layer, constitutes such as SLG/Mo/CIGS/CdS/
The CIGS battery device structure of MgZnO/AZO.
Further, in step one, the back electrode molybdenum Mo layer, deposit thickness is 0.5 μm 1 μm, used as battery
Back electrode.
Further, in step 2, the CIGS thin film layer, deposit thickness is 1 μm 2 μm, and the light as battery is inhaled
Receive layer.
Further, in step 3, the cadmium sulfide CdS layer, deposit thickness is 30nm 80nm, used as the slow of battery
Rush layer.
The cadmium sulfide CdS layer is prepared using immersion method.
Further, in step 4, described MgZnO film, its using target be to be mixed by ZnO and MgO powder
The MgZnO target of sintering, in MgZnO film, the atomic ratio of Mg/ (Mg+Zn) is distributed in 8% 25%.
By adjusting the ratio of Mg and Zn, thin film energy gap is made to change between 3.5 3.9eV.
Further, described deposition MgZnO film layer, is deposited using the method for direct current or DC pulse magnetron sputtering
Thickness is 30nm 100nm.
Further, during MgZnO film layer is prepared, Sputtering power density is 1.65～3.73W/cm2, background is true
Empty is 3 × 10-3Below Pa, sputtering pressure is that 0.3 2Pa, during sputtering, matrix is not heated.
Further, in step 5, in air, vacuum or protective gas, MgZnO film is made annealing treatment
When, it is 10min～60min that annealing temperature is 100～300 DEG C, annealing time, and wherein described protective gas is argon or nitrogen
Gas.
Further, in step 6, the AZO thin film layer thickness is 300nm 1000nm, used as the saturating of battery
Bright conductive layer.
The growing method of the MgZnO film that the application is proposed, due to larger crystalline substance between CdS cushion and MgZnO film
Lattice mismatch and the difference of band gap, can often cause MgZnO film to become three-dimensional island growth, so as to affect the crystal mass of thin film, and
And lattice mismatch also often can introduce stress in the MgZnO film of deposition, this stress and stress relaxation all can be to quasiconductors
Performance generation strong influence, the crystal mass of deposition film in order to improve, need to make annealing treatment thin film.In sky
The MgZnO film for processing under different annealing temperature in gas, vacuum or protective gas, with the increase of annealing temperature, thin film table
Face is smoothened, and crystallite dimension becomes big, and annealing migrates surface atom, and the surface so as to reduce thin film is thick
Rugosity, improves film quality.
Description of the drawings
Fig. 1 is a kind of schematic flow sheet of utilization MgZnO film making CIGS thin film solaode method of the present invention；
Fig. 2 is transmitance figure of the MgZnO film of embodiment of the present invention 1- embodiment 4 in ultraviolet～visible-range；
Fig. 3 is the stereoscan photograph (without annealing) of the MgZnO film of the embodiment of the present invention 1；
Fig. 4 is stereoscan photograph of the MgZnO film of the embodiment of the present invention 1 after 150 DEG C of annealings of in the air；
Fig. 5 is the stereoscan photograph (without annealing) of the MgZnO film of the embodiment of the present invention 3；
Fig. 6 is stereoscan photograph of the MgZnO film of the embodiment of the present invention 3 after 250 DEG C of annealings in vacuum.
Specific embodiment
Below in conjunction with case study on implementation and accompanying drawing, technical scheme is further described.
Fig. 1 is the flow process of the method that a kind of utilization MgZnO film disclosed by the invention makes CIGS thin film solaode
Schematic diagram, as shown in figure 1, the battery includes soda-lime glass substrate, back electrode Mo layer, CIGS absorbed layer, CdS cushion, MgZnO
Resistive formation and top electrode AZO layer.The method for CIGS thin film solaode being made using MgZnO film is comprised the following steps：
Step one, in soda-lime glass substrate deposit back electrode molybdenum (Mo) layer；
The back electrode molybdenum Mo layer, deposit thickness is 0.5 μm 1 μm, used as the back electrode of battery.
Step 2, on Mo layer prepare CIGS thin film layer as light absorbing zone；
The CIGS thin film layer, deposit thickness is 1 μm 2 μm, used as the light absorbing zone of battery.
Step 3, on CIGS, CdS layer is prepared using water-bath (CBD) method；
The cadmium sulfide CdS layer, deposit thickness is 30nm 80nm, used as the cushion of battery.
Step 4, on CdS layer, resistive formation MgZnO is prepared using magnetically controlled sputter method；
Described MgZnO film, its using target be by the MgZnO target of ZnO and MgO powder technique,
In MgZnO film, the atomic ratio of Mg/ (Mg+Zn) is distributed in 8% 25%.By the ratio of Mg and Zn is adjusted, thin film forbidden band is made
Width changes between 3.5 3.9eV.MgZnO film layer, is the method deposition of thick using direct current or DC pulse magnetron sputtering
Spend for 30nm 100nm.During MgZnO film layer is prepared, Sputtering power density is 1.65～3.73W/cm2, background is true
Empty is 3 × 10-3Below Pa, sputtering pressure is that 0.3 2Pa, during sputtering, matrix is not heated.
Step 5, in step 4 prepare MgZnO film in air, made annealing treatment in vacuum or protective gas
To improve quality of forming film further；
When making annealing treatment to MgZnO film in air, vacuum or protective gas, annealing temperature is 100～300
DEG C, annealing time is 10min～60min.
Step 6, Al-Doped ZnO (AZO) layer being prepared on MgZnO film layer, constitutes such as SLG (soda-lime glass)/Mo/
The CIGS battery device structure of CIGS/CdS/MgZnO/AZO；
The AZO thin film layer thickness is 300nm 1000nm, used as the transparency conducting layer of battery.
Embodiment 1
According to the present invention, the manufacture method of battery step as described below：
Step one, prepares Mo layer in soda-lime glass substrate, and the thickness of film layer is 0.8 μm.
Step 2, prepares cigs layer on Mo layer, and the thickness of film layer is 2 μm.
Step 3, prepares CdS film layer in cigs layer, and the thickness of film layer is 50nm.
Step 4, using the method for magnetically controlled DC sputtering, prepares MgZnO layer, wherein Mg/ (Mg+Zn) atom on CdS layer
Than for 12%, power density be2, base vacuum is 3 × 10-3Below Pa, sputtering pressure is 1Pa, the thickness of film layer
For 50nm.
Step 5, the MgZnO film layer for preparing is annealed for 150 DEG C in atmosphere, and annealing time is 30min, by attached
Fig. 3 and accompanying drawing 4 carry out contrast discovery, and the film surface after annealing is smoothened, and mean diameter becomes big, and annealing makes surface original
Son is migrated, so as to improve the surface roughness of thin film.
Step 6, prepares AZO layer on SLG (soda-lime glass)/Mo/CIGS/CdS/MgZnO, and the thickness of film layer is
500nm.
By accompanying drawing 2 as can be seen that MgZnO film is higher than 90% in 400 1400nm scope internal transmission factors, its band gap is
3.6eV, used as SLG (the soda-lime glass)/Mo/CIGS/ for preparing under the resistive formation of CIGS thin film solaode, with equal conditions
CdS/ZnO/AZO structure is compared, and which is opened pressure energy and enough lifts 3% 7%, and battery efficiency can lift 0.5% 2%, in detail number
According to table 1 is referred to, table 1 is the parameters contrast of CIGS hull cell prepared by the embodiment of the present invention 1 and conventional method.
Table 1
Embodiment 2
Step one, prepares Mo layer in soda-lime glass substrate, and the thickness of film layer is 0.9 μm.
Step 2, prepares cigs layer on Mo layer, and the thickness of film layer is 1.5 μm.
Step 3, prepares CdS film layer in cigs layer, and the thickness of film layer is 70nm.
Step 4, using the method for DC pulse magnetron sputtering, prepares MgZnO layer, wherein Mg/ (Mg+Zn) on CdS layer
Atomic ratio be 19%, power density be 2.56W/cm2, base vacuum is 3 × 10-3Below Pa, sputtering pressure is 1Pa, film layer
Thickness be 70nm.
Step 5, the MgZnO film layer for preparing is annealed for 150 DEG C in high-purity argon gas, and annealing time is 30min.
Step 6, prepares AZO layer on SLG (soda-lime glass)/Mo/CIGS/CdS/MgZnO, and the thickness of film layer is
500nm.By accompanying drawing 2 as can be seen that MgZnO film is higher than 90% in 400 1400nm scope internal transmission factors, its band gap is
3.73eV, compared with Example 1, band gap is significantly improved, and illustrates that, with the rising of Mg content, the band gap of the film layer is higher.With with
Deng under the conditions of prepare SLG (soda-lime glass)/Mo/CIGS/CdS/ZnO/AZO structure compare, which is opened pressure energy and enough lifts 5%
8%, battery efficiency can lift 1% 2%.
Embodiment 3
Step one, prepares Mo layer in soda-lime glass substrate, and the thickness of film layer is 0.6 μm.
Step 2, prepares cigs layer on Mo layer, and the thickness of film layer is 1.2 μm.
Step 3, prepares CdS film layer in cigs layer, and the thickness of film layer is 45nm.
Step 4, using the method for magnetically controlled DC sputtering, prepares MgZnO layer, the original of wherein Mg/ (Mg+Zn) on CdS layer
Son is than being 12%, and power density is 2.56W/cm2, base vacuum is 3 × 10-3Below Pa, sputtering pressure is 1Pa, the thickness of film layer
Spend for 40nm.
Step 5, the MgZnO film layer for preparing is annealed for 250 DEG C in a vacuum, and annealing time is 30min, by attached
Fig. 5 and accompanying drawing 6 carry out contrast discovery, and the film surface after annealing is smoothened, and mean diameter becomes big, and annealing makes surface original
Son is migrated, and so as to improve the surface roughness of thin film, improves the quality of PN junction.
Step 6, prepares AZO layer on SLG (soda-lime glass)/Mo/CIGS/CdS/MgZnO, and the thickness of film layer is
450nm.
By accompanying drawing 2 as can be seen that Zn (O, S) thin film is higher than 90% in 400 1800nm scope internal transmission factors, its band gap is
3.65eV, compared with SLG (the soda-lime glass)/Mo/CIGS/CdS/ZnO/AZO structure for preparing under equal conditions, 6% 10%,
Battery efficiency can lift 1.5% 3%, compared with the embodiment 1 under square one, open pressure and efficiency slightly rises, this and
Band gap increase has relation, illustrates that the rising of annealing temperature is conducive to lifting thin film band gap.
Embodiment 4
Step one, prepares Mo layer in soda-lime glass substrate, and the thickness of film layer is 0.8 μm.
Step 2, prepares cigs layer on Mo layer, and the thickness of film layer is 2 μm.
Step 3, prepares CdS film layer in cigs layer, and the thickness of film layer is 50nm.
Step 4, using the method for DC pulse magnetron sputtering, prepares MgZnO layer, wherein Mg/ (Mg+Zn) on CdS layer
Atomic ratio be 19%, power density be 2.56W/cm2, base vacuum is 3 × 10-3Below Pa, sputtering pressure is 1Pa, film layer
Thickness be 50nm.
Step 5, the MgZnO film layer for preparing is annealed for 250 DEG C in high pure nitrogen, and annealing time is 30min.
Step 6, prepares AZO layer on SLG (soda-lime glass)/Mo/CIGS/CdS/MgZnO, and the thickness of film layer is
500nm.
By accompanying drawing 2 as can be seen that MgZnO film is higher than 90% in 400 1400nm scope internal transmission factors, its band gap is
3.9eV, compared with SLG (the soda-lime glass)/Mo/CIGS/CdS/ZnO/AZO structure for preparing under equal conditions, 10% 15%,
Battery efficiency can lift 2% 5%, compared with the embodiment 2 under square one, open pressure and efficiency slightly rises, this and band
Gap increase has relation, illustrates that the rising of annealing temperature is conducive to lifting thin film band gap, and detailed data refers to table 2, and table 2 is this
The parameters contrast of CIGS hull cell prepared by bright embodiment 4 and conventional method.
Table 2
Applicant describes in detail to embodiments of the invention with reference to Figure of description and describes, but this area skill
Art personnel are it should be understood that above example is only the preferred embodiments of the invention, and explanation in detail is intended merely to help reader
More fully understand that the present invention is spiritual, and not limiting the scope of the invention, conversely, any invention essence based on the present invention
Any improvement that god is made or modification should all fall within the scope and spirit of the invention.
Main advantage of the present invention opens pressure so as to raising efficiency in raising, and this has embodied in an embodiment, other tables
Lattice content belongs to the content that those skilled in the art can fully understand, so without the need for repeating again.
Claims (11)
1. a kind of method that utilization MgZnO film makes CIGS thin film solaode, it is characterised in that methods described include with
Lower step：
Step one, in soda-lime glass substrate deposit back electrode molybdenum Mo layer；
Step 2, on Mo layer prepare CIGS thin film layer as light absorbing zone；
Step 3, cadmium sulfide CdS layer is prepared on CIGS；
Step 4, Mg-doping ZnO layer i.e. MgZnO film is prepared on cadmium sulfide CdS layer；
Step 5, the MgZnO film to preparing in step 4 make annealing treatment.
Step 6, Al-Doped ZnO AZO layer being prepared on MgZnO film layer, constitutes such as SLG/Mo/CIGS/CdS/MgZnO/AZO
CIGS battery device structure.
2. according to claim 1 make CIGS thin film solaode method, it is characterised in that：
In step one, the back electrode molybdenum Mo layer, deposit thickness is 0.5 μm 1 μm, used as the back electrode of battery.
3. according to claim 1 make CIGS thin film solaode method, it is characterised in that：
In step 2, the CIGS thin film layer, deposit thickness is 1 μm 2 μm, used as the light absorbing zone of battery.
4. according to claim 1 make CIGS thin film solaode method, it is characterised in that：
In step 3, the cadmium sulfide CdS layer, deposit thickness is 30nm 80nm, used as the cushion of battery.
5. according to claim 4 make CIGS thin film solaode method, it is characterised in that：
The cadmium sulfide CdS layer is prepared using immersion method.
6. according to claim 1 make CIGS thin film solaode method, it is characterised in that：
In step 4, described MgZnO film, its using target formed by ZnO and MgO powder technique
MgZnO target, in MgZnO film, the atomic ratio of Mg/ (Mg+Zn) is distributed in 8% 25%.
7. according to claim 6 make CIGS thin film solaode method, it is characterised in that：
By adjusting the ratio of Mg and Zn, thin film energy gap is made to change between 3.5 3.9eV.
8. the method for the making CIGS thin film solaode according to claim 6 or 7, it is characterised in that：
Described deposition MgZnO film layer, be using direct current or DC pulse magnetron sputtering method deposit thickness be 30nm
100nm.
9. according to claim 8 make CIGS thin film solaode method, it is characterised in that：
During MgZnO film layer is prepared, Sputtering power density is 1.65～3.73W/cm2, base vacuum is 3 × 10-3Pa
Hereinafter, sputtering pressure is that 0.3 2Pa, during sputtering, matrix is not heated.
10. according to claim 1 make CIGS thin film solaode method, it is characterised in that：
In step 5, when making annealing treatment to MgZnO film in air, vacuum or protective gas, annealing temperature is
100～300 DEG C, it is argon or nitrogen that annealing time is 10min～60min, wherein described protective gas.
11. methods for making CIGS thin film solaode according to claim 1, it is characterised in that：
In step 6, the AZO thin film layer thickness is 300nm 1000nm, used as the transparency conducting layer of battery.
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