CN110459630A - Thin-film solar cells and preparation method thereof - Google Patents
Thin-film solar cells and preparation method thereof Download PDFInfo
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- CN110459630A CN110459630A CN201910526427.8A CN201910526427A CN110459630A CN 110459630 A CN110459630 A CN 110459630A CN 201910526427 A CN201910526427 A CN 201910526427A CN 110459630 A CN110459630 A CN 110459630A
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- zinc oxide
- oxide film
- zinc
- film layer
- oxygen atom
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- 239000010409 thin film Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 951
- 239000010408 film Substances 0.000 claims abstract description 823
- 239000011787 zinc oxide Substances 0.000 claims abstract description 475
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 366
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims abstract description 313
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 221
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 181
- 239000000758 substrate Substances 0.000 claims abstract description 129
- 230000008859 change Effects 0.000 claims abstract description 36
- 239000011701 zinc Substances 0.000 claims description 75
- 229910052725 zinc Inorganic materials 0.000 claims description 63
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 61
- 239000005864 Sulphur Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 239000001301 oxygen Substances 0.000 claims description 18
- 238000004073 vulcanization Methods 0.000 claims description 15
- 238000000231 atomic layer deposition Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 2
- 230000004044 response Effects 0.000 abstract description 3
- 230000003595 spectral effect Effects 0.000 abstract description 3
- 238000002310 reflectometry Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 480
- 229960001296 zinc oxide Drugs 0.000 description 335
- 239000002243 precursor Substances 0.000 description 17
- 238000004140 cleaning Methods 0.000 description 15
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 12
- 230000009467 reduction Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 238000001208 nuclear magnetic resonance pulse sequence Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 231100000701 toxic element Toxicity 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- -1 is greater than Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- PNHVEGMHOXTHMW-UHFFFAOYSA-N magnesium;zinc;oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Zn+2] PNHVEGMHOXTHMW-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 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
- H01L31/0352—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035272—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions characterised by at least one potential jump barrier or surface barrier
-
- 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
- H01L31/036—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 their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03923—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 their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIBIIICVI compound materials, e.g. CIS, CIGS
-
- 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 invention discloses a kind of thin-film solar cells and preparation method thereof, to provide a kind of band gap gradual change without vestalium thin-film solar cell buffer layer, to increase the band gap width of buffer layer, it help to obtain the spectral response of blue light region, it reduces the reflectivity of light, increase transmitance, improve the quantum efficiency and transfer efficiency of thin-film solar cells.The thin-film solar cells includes: substrate；Buffer layer on substrate is set, and buffer layer includes the zinc oxide film and zinc sulphide film layer of overlapping setting；Wherein, buffer layer includes at least: setting gradually the first zinc oxide film, the first zinc sulphide film layer, the second zinc oxide film and the second zinc sulphide film layer on substrate, and first oxygen atom in zinc oxide film account for the content of oxygen atom and sulphur atom total amount in the first zinc oxide film and the first zinc sulphide film layer, it is greater than, oxygen atom accounts for the content of oxygen atom and sulphur atom total amount in the second zinc oxide film and the second zinc sulphide film layer in the second zinc oxide film.
Description
Technical field
The present invention relates to technical field of thin-film solar more particularly to a kind of thin-film solar cells and its preparation sides
Method.
Background technique
In traditional copper indium gallium selenide (CIGS) thin-film solar cells, it is provided with buffer layer, the main function of buffer layer
It is to form pn-junction with absorbed layer to convert light energy into electric energy to the workspace as thin-film solar cells.
In order to form good pn-junction with absorbed layer, buffer layer must have good energy band to match with interlayer is absorbed,
To obtain maximum open-circuit voltage.In the prior art, use CdS as buffer layer, but Cd is toxic element, can be produced to environment
Raw harm.Moreover, the forbidden bandwidth of CdS can absorb the high-energy photon of 350-550nm in solar spectrum, cause in 2.4-2.5eV
The loss of photoelectric current reduces the transfer efficiency of thin-film solar cells, and CdS is mostly used wet process manufacture, other are true with producing line
Empty method is incompatible, while can also generate a large amount of waste liquids.Therefore, no Cd cushioning layer material becomes a big heat of CIGS battery research
Point is now concentrated mainly on Zn (O, S), (Zn, Mg) O and (Zn, Sn) OyAspect.And what existing Zn (O, S) optical material was formed
Buffer layer, thin-film solar cells transfer efficiency are low.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides a kind of thin-film solar cells and preparation method thereof, to
A kind of thin-film solar cells buffer layer of band gap gradual change is provided, the band gap width of buffer layer is increased, to help to obtain indigo plant
The spectral response in light area, while reducing the reflectivity of light, increasing transmitance, improve the quantum efficiency of thin-film solar cells and turning
Change efficiency.
The embodiment of the invention provides a kind of thin-film solar cells, comprising:
Substrate；
Buffer layer over the substrate is set, and the buffer layer includes the zinc oxide film and ZnS-film of overlapping setting
Layer；
Wherein, the buffer layer includes at least: setting gradually the first zinc oxide film over the substrate, the first vulcanization
Zinc film layer, the second zinc oxide film and the second zinc sulphide film layer, and oxygen atom accounts for described in first zinc oxide film
The content of oxygen atom and sulphur atom total amount, is greater than in one zinc oxide film and the first zinc sulphide film layer, second oxidation
Oxygen atom accounts for the content of oxygen atom and sulphur atom total amount in second zinc oxide film and the second zinc sulphide film layer in zinc film layer.
Second aspect, the embodiment of the invention also provides a kind of preparation methods of thin-film solar cells, this method comprises:
One substrate is provided；
Sequentially form over the substrate the first zinc oxide film, the first zinc sulphide film layer, the second zinc oxide film and
Second zinc sulphide film layer；Wherein,
It is former to account for oxygen in first zinc oxide film and the first zinc sulphide film layer for oxygen atom in first zinc oxide film
The content of son and sulphur atom total amount, is greater than, and oxygen atom accounts for second zinc oxide film and the in second zinc oxide film
The content of oxygen atom and sulphur atom total amount in curing zinc film layer.
Technical solution of the present invention has following beneficial technical effect:
Thin-film solar cells provided by the invention, by the zinc oxide film and sulphur that form overlapping setting in substrate surface
Change zinc film layer, to form buffer layer.Buffer layer includes at least: setting gradually the first zinc oxide film on substrate, first
Zinc sulphide film layer, the second zinc oxide film and the second zinc sulphide film layer, and oxygen atom accounts for the first oxygen in the first zinc oxide film
The content for changing oxygen atom and sulphur atom total amount in zinc film layer and the first zinc sulphide film layer, is greater than, and oxygen is former in the second zinc oxide film
Son accounts for the content of oxygen atom and sulphur atom total amount in the second zinc oxide film and the second zinc sulphide film layer.Wherein, at room temperature, it aoxidizes
The forbidden bandwidth of zinc (ZnO) is 3.37eV, and the forbidden bandwidth of zinc sulphide (ZnS) is 3.68eV, therefore, in the present invention buffer layer with
Be gradually distance from the direction of substrate, the content of oxygen atom is fewer and fewer, then band gap width is gradually increased since 3.37eV, maximum
To 3.68eV, so that the band gap width of buffer layer is gradually increased, the material of graded bandgap increases light incidence, the band gap of increase
The absorption of short-wavelength light will be reduced, so that more light enter in solar battery, to improve the amount of thin-film solar cells
Sub- efficiency and transfer efficiency.
Other features and advantages of the present invention will be illustrated in the following description, also, partly becomes from specification
It obtains it is clear that understand through the implementation of the invention.The objectives and other advantages of the invention can be by specification, right
Specifically noted structure is achieved and obtained in claim and attached drawing.
Detailed description of the invention
Attached drawing is used to provide to further understand technical solution of the present invention, and constitutes part of specification, with this
The embodiment of application technical solution for explaining the present invention together, does not constitute the limitation to technical solution of the present invention.
Fig. 1 is a kind of structural schematic diagram of thin-film solar cells provided in an embodiment of the present invention；
Fig. 2 is the structural schematic diagram of second of thin-film solar cells provided in an embodiment of the present invention；
Fig. 3 is the structural schematic diagram of the third thin-film solar cells provided in an embodiment of the present invention；
Fig. 4 is the structural schematic diagram of the 4th kind of thin-film solar cells provided in an embodiment of the present invention；
Fig. 5 is the structural schematic diagram of the 5th kind of thin-film solar cells provided in an embodiment of the present invention；
Fig. 6 is the structural schematic diagram of the 6th kind of thin-film solar cells provided in an embodiment of the present invention；
Fig. 7 is a kind of flow diagram of the preparation method of thin-film solar cells provided in an embodiment of the present invention.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
Attached drawing, the technical solution of the embodiment of the present invention is clearly and completely described.Obviously, described embodiment is this hair
Bright a part of the embodiment, instead of all the embodiments.Based on described the embodiment of the present invention, ordinary skill
Personnel's every other embodiment obtained under the premise of being not necessarily to creative work, shall fall within the protection scope of the present invention.
The present invention provides a kind of thin-film solar cells and preparation method thereof, to provide a kind of film of band gap gradual change too
Positive energy battery buffer layer, increases the band gap width of buffer layer, to help to obtain the spectral response of blue light region, improves film too
The quantum efficiency and transfer efficiency of positive energy battery.
Referring to Fig. 1, a kind of thin-film solar cells provided in an embodiment of the present invention, comprising: substrate 01 is arranged in substrate 01
On buffer layer, buffer layer includes the zinc-oxide film and zinc sulfide film of overlapping setting, wherein as shown in Figure 1, buffer layer is extremely
It less include: the first zinc oxide film 02 being successively set on substrate 01, the first zinc sulphide film layer 03, the second zinc oxide film 04
And the second zinc sulphide film layer 05；Wherein, oxygen atom accounts for the first zinc oxide film 02 and the first sulphur in the first zinc oxide film 02
The content for changing oxygen atom and sulphur atom total amount in zinc film layer 03, is greater than, oxygen atom accounts for the second oxidation in the second zinc oxide film 04
The content of oxygen atom and sulphur atom total amount in zinc film layer 04 and the second zinc sulphide film layer 05.
It should be noted that the substrate in the embodiment of the present invention can be single layer structure, such as underlay substrate, or more
Layer structure, if substrate includes: glass substrate, sets gradually back electrode, light absorbing layer on the glass substrate, in light absorbing layer table
Face forms buffer layer.In addition, oxygen atom in the first zinc oxide film in the present invention, accounts for, the first zinc oxide film and the first vulcanization
The content of oxygen atom and sulphur atom total amount in zinc film layer, can indicate are as follows: the quantity of oxygen atom/(this in the first zinc oxide film
In first zinc oxide film in quantity the+the first zinc sulphide film layer of oxygen atom sulphur atom quantity)；Alternatively, also may indicate that are as follows:
The molecular amounts of zinc oxide/(vulcanization of molecular amounts+the first of zinc oxide in first zinc oxide film in first zinc oxide film
The molecular amounts of zinc sulphide in zinc film layer).That is, the ratio of O/ (O+S) is in reduction trend along the direction for being gradually distance from substrate.Buffering
Layer can also include the zinc oxide film and zinc sulphide film layer of multiple overlapping settings, however it is not limited to two layers of the oxidation illustrated in Fig. 1
Zinc film layer and two layers of zinc sulphide film layer.
Specifically, buffer layer provided in an embodiment of the present invention includes ZnO film layer and ZnS film layer, i.e. the material packet of buffer layer
Include Zn (O, S).Wherein, at room temperature, the forbidden bandwidth of ZnO is 3.37eV, and the forbidden bandwidth of ZnS is 3.68eV, therefore, the present invention
In the thin-film solar cells of middle offer, buffer layer is in reduction trend with the direction for being gradually distance from substrate, the content of oxygen atom,
Then band gap width is gradually increased since 3.37eV, and maximum can increase to 3.68eV, so that the band gap width of buffer layer
It is in increase tendency along the direction for being gradually distance from substrate, the material of graded bandgap increases light incidence, and the band gap of increase will reduce shortwave
The absorption of long light, so that more light enter in solar battery, to improve the quantum efficiency of thin-film solar cells and turn
Change efficiency.In addition, avoiding the harm to environment without the introducing of toxic element in buffer layer.
In some alternative embodiments, the zinc oxide film of setting is overlapped in buffer layer and zinc sulphide film layer includes but not
It is limited to meet following either conditions:
The quantity of oxygen atom is greater than the quantity of oxygen atom in the second zinc oxide film in condition one, the first zinc oxide film,
The quantity of sulphur atom is equal to the quantity of sulphur atom in the second zinc sulphide film layer in first zinc sulphide film layer；
The quantity of oxygen atom is equal to the quantity of oxygen atom in the second zinc oxide film in condition two, the first zinc oxide film,
Quantity of the quantity of sulphur atom less than sulphur atom in the second zinc sulphide film layer in first zinc sulphide film layer；
The quantity of oxygen atom is greater than the quantity of oxygen atom in the second zinc oxide film in condition three, the first zinc oxide film,
Quantity of the quantity of sulphur atom less than sulphur atom in the second zinc sulphide film layer in first zinc sulphide film layer；
The quantity of oxygen atom is greater than the quantity of oxygen atom in the second zinc oxide film in condition four, the first zinc oxide film,
The quantity of sulphur atom is greater than the quantity of sulphur atom in the second zinc sulphide film layer in first zinc sulphide film layer；
In condition five, the first zinc oxide film the quantity of oxygen atom less than oxygen atom in the second zinc oxide film quantity,
Quantity of the quantity of sulphur atom less than sulphur atom in the second zinc sulphide film layer in first zinc sulphide film layer.
Specifically, in order to enable the band gap width edge of buffer layer is gradually distance from the direction of substrate in the trend increased, this hair
Mainly by adjusting, " it is former to account for oxygen in the first zinc oxide film and the first zinc sulphide film layer for oxygen atom in the first zinc oxide film in bright
The content of son and sulphur atom total amount ".In order to further illustrate the process of adjusting, " oxygen atom accounts for first in the first zinc oxide film
The content of oxygen atom and sulphur atom total amount in zinc oxide film and the first zinc sulphide film layer " is indicated with formula, e.g., adjusts O/ (O
+ S) value so that the value is along being gradually distance from the direction of substrate in reduced trend.Then, the quantity of mode one: O becomes in reduction
The quantity of gesture, S remains unchanged.That is: it is to be understood that close to substrate the first zinc oxide film in oxygen atom quantity, be greater than,
The quantity of oxygen atom in the second zinc oxide film far from substrate, and the quantity of sulphur atom is equal to second in the first zinc sulphide film layer
The quantity of sulphur atom in zinc sulphide film layer.Or be also understood that and be, the zinc oxide in the first zinc oxide film of substrate
Quantity is greater than, far from substrate the second zinc oxide film in zinc oxide quantity, and in the first zinc sulphide film layer zinc sulphide number
Amount is equal to the quantity of zinc sulphide in the second zinc sulphide film layer.The quantity of mode two: O is constant, and the quantity of S is in increase tendency.That is: may be used
To be interpreted as, the quantity of sulphur atom, is less than in the first zinc sulphide film layer of substrate, the second zinc sulphide film layer far from substrate
The quantity of middle sulphur atom, and the quantity of oxygen atom is equal to the number of oxygen atom in the second zinc oxide film in the first zinc oxide film
Amount.Or be also understood that and be, the quantity of zinc sulphide, is less than in the first zinc sulphide film layer of substrate, the far from substrate
The quantity of zinc sulphide in curing zinc film layer, and the quantity of zinc oxide is equal in the second zinc oxide film in the first zinc oxide film
The quantity of zinc oxide.The quantity of mode three: O is in reduction trend, and the quantity of S is in increase tendency.That is: it is to be understood that close to lining
The quantity of oxygen atom, is greater than in first zinc oxide film at bottom, the quantity of oxygen atom in the second zinc oxide film far from substrate,
And in the first zinc sulphide film layer of substrate sulphur atom quantity, be less than, sulphur is former in the second zinc sulphide film layer far from substrate
The quantity of son.Or be also understood that and be, the quantity of zinc oxide, is greater than in the first zinc oxide film of substrate, far from lining
The quantity of zinc oxide in second zinc oxide film at bottom, and close to substrate the first zinc sulphide film layer in zinc sulphide quantity, it is small
In the quantity of zinc sulphide in the second zinc sulphide film layer far from substrate.Mode four, the quantity of O are in reduction trend, and the quantity of S is in
Reduction trend.That is: it is to be understood that in the first zinc oxide film of substrate oxygen atom quantity, greater than far from substrate
The quantity of oxygen atom in second zinc oxide film, and in the first zinc sulphide film layer of substrate sulphur atom quantity, be greater than remote
Quantity from sulphur atom in the second zinc sulphide film layer of substrate.Or be also understood that and be, close to the first Zinc oxide film of substrate
The quantity of zinc oxide in layer, greater than the quantity of zinc oxide in the second zinc oxide film far from substrate, and close to the first of substrate
The quantity of zinc sulphide in zinc sulphide film layer, greater than the quantity of zinc sulphide in the second zinc sulphide film layer far from substrate.Mode five, O
Quantity be in increase tendency, the quantity of S is in increase tendency.That is: it is to be understood that close to substrate the first zinc oxide film in oxygen
The quantity of atom, less than the quantity of oxygen atom in the second zinc oxide film far from substrate, and close to the first zinc sulphide of substrate
The quantity of sulphur atom in film layer, less than the quantity of sulphur atom in the second zinc sulphide film layer far from substrate.Or it is also understood that
For, close to substrate the first zinc oxide film in zinc oxide quantity, less than far from substrate the second zinc oxide film in aoxidize
The quantity of zinc, and close to substrate the first zinc sulphide film layer in zinc sulphide quantity, less than far from substrate the second ZnS-film
The quantity of zinc sulphide in layer.
In some alternative embodiments, the quantity of oxygen atom or the quantity of sulphur atom include doping concentration or place film
The thickness of layer.
Optionally, in order to enable the film layer forbidden bandwidth in buffer layer far from substrate is larger, close to the film layer forbidden band of substrate
Width reduces, and in the embodiment of the present invention, it is former to be greater than oxygen in the second zinc oxide film for the quantity of oxygen atom in the first zinc oxide film
The quantity of son, the quantity of sulphur atom is equal to the quantity of sulphur atom in the second zinc sulphide film layer in the first zinc sulphide film layer, comprising: the
The doping concentration of oxygen atom, is greater than in one zinc oxide film and the first zinc sulphide film layer, the second zinc oxide film and the second vulcanization
The doping concentration of sulphur atom in the doping concentration of oxygen atom in zinc film layer, the first zinc oxide film and the first zinc sulphide film layer, etc.
In the doping concentration of sulphur atom in the second zinc oxide film and the second zinc sulphide film layer；Alternatively, the thickness of the first zinc oxide film
Greater than the thickness of second zinc oxide film, the thickness of the first zinc sulphide film layer is equal to the second zinc sulphide film layer
Thickness.
Specifically, referring to fig. 2, the buffer layer of thin-film solar cells includes substrate 01, is successively set on substrate 01
First zinc oxide film 02, the first zinc sulphide film layer 03, the second zinc oxide film 04, the second zinc sulphide film layer 05.Wherein, first
Zinc sulphide film layer 03 is identical with 05 thickness of the second zinc sulphide film layer, and 02 thickness of the first zinc oxide film is greater than the second zinc oxide film
04 thickness, so that the quantity of the oxygen atom in the first zinc oxide film 02 accounts for the first zinc oxide film 02 and the first vulcanization
The content of 03 total amount of zinc film layer, is greater than, and the quantity of the oxygen atom in the second zinc oxide film 04 accounts for 04 He of the second zinc oxide film
The content of second zinc sulphide film layer, 05 total amount；So that the band gap width of buffer layer becomes along the direction far from substrate in increase
Gesture.
Alternatively, changing the quantity of oxygen atom by the doping concentration for adjusting oxygen atom, so that the quantity for reaching oxygen atom becomes
Change trend.The doping concentration of oxygen atom, is greater than in first zinc oxide film and the first zinc sulphide film layer, the second zinc oxide film and
The doping concentration of oxygen atom in second zinc sulphide film layer, and sulphur atom is mixed in the first zinc oxide film and the first zinc sulphide film layer
Miscellaneous concentration, is equal to, the doping concentration of sulphur atom in the second zinc oxide film and the second zinc sulphide film layer, so that oxygen atom
Quantity is in reduction trend along the direction for being gradually distance from substrate.
It should be noted that the material used when forming buffer layer is zinc oxide and zinc sulphide, therefore, the present invention is implemented
The doping concentration of oxygen atom can be understood as the doping concentration of zinc oxide in example, and the doping concentration of sulphur atom can be understood as vulcanizing
The doping concentration of zinc.
Optionally, in order to enable the film layer forbidden bandwidth in buffer layer far from substrate is larger, close to the film layer forbidden band of substrate
Width reduces, and in the embodiment of the present invention, it is former to be equal to oxygen in the second zinc oxide film for the quantity of oxygen atom in the first zinc oxide film
The quantity of son, quantity of the quantity of sulphur atom less than sulphur atom in the second zinc sulphide film layer in the first zinc sulphide film layer, comprising: the
The doping concentration of oxygen atom, is equal in one zinc oxide film and the first zinc sulphide film layer, the second zinc oxide film and the second vulcanization
The doping concentration of sulphur atom, small in the doping concentration of oxygen atom in zinc film layer, the first zinc oxide film and the first zinc sulphide film layer
In the doping concentration of sulphur atom in the second zinc oxide film and the second zinc sulphide film layer；Alternatively, the thickness of the first zinc oxide film
Equal to the thickness of the second zinc oxide film, the thickness of the thickness of the first zinc sulphide film layer less than the second zinc sulphide film layer.
Specifically, referring to Fig. 3, thin-film solar cells buffer layer includes substrate 01, be successively set on substrate 01
One zinc oxide film 02, the first zinc sulphide film layer 03, the second zinc oxide film 04, the second zinc sulphide film layer 05.Wherein, the first sulphur
Change the thickness of zinc film layer 03 less than the second zinc sulphide film layer 05, the thickness of the first zinc oxide film 02 is equal to the second zinc oxide film
04 thickness, so that the quantity of the oxygen atom in the first zinc oxide film 02 accounts for the first zinc oxide film 02 and the first vulcanization
The content of 03 total amount of zinc film layer, is greater than, and the quantity of the oxygen atom in the second zinc oxide film 04 accounts for 04 He of the second zinc oxide film
The content of second zinc sulphide film layer, 04 total amount；So that the band gap width of buffer layer is in become larger along the direction far from substrate
Gesture.
Alternatively, changing the quantity of oxygen atom by the doping concentration for adjusting oxygen atom, so that the quantity for reaching oxygen atom becomes
Change trend.The doping concentration of oxygen atom, is equal in first zinc oxide film and the first zinc sulphide film layer, the second zinc oxide film and
The doping concentration of oxygen atom in second zinc sulphide film layer, and sulphur atom is mixed in the first zinc oxide film and the first zinc sulphide film layer
Miscellaneous concentration, is less than, the doping concentration of sulphur atom in the second zinc oxide film and the second zinc sulphide film layer, so that oxygen atom
Quantity is in reduction trend along the direction for being gradually distance from substrate.
It should be noted that the material used when forming buffer layer is zinc oxide and zinc sulphide, therefore, the present invention is implemented
The doping concentration of oxygen atom can be understood as the doping concentration of zinc oxide in example, and the doping concentration of sulphur atom can be understood as vulcanizing
The doping concentration of zinc.
Optionally, in order to enable the film layer forbidden bandwidth in buffer layer far from substrate is larger, close to the film layer forbidden band of substrate
Width reduces, and in the embodiment of the present invention, it is former to be greater than oxygen in the second zinc oxide film for the quantity of oxygen atom in the first zinc oxide film
The quantity of son, quantity of the quantity of sulphur atom less than sulphur atom in the second zinc sulphide film layer in the first zinc sulphide film layer, comprising: the
The doping concentration of oxygen atom, is greater than in one zinc oxide film and the first zinc sulphide film layer, the second zinc oxide film and the second vulcanization
The doping concentration of sulphur atom, small in the doping concentration of oxygen atom in zinc film layer, the first zinc oxide film and the first zinc sulphide film layer
In the doping concentration of sulphur atom in the second zinc oxide film and the second zinc sulphide film layer；Alternatively, the thickness of the first zinc oxide film
Greater than the thickness of the second zinc oxide film, the thickness of the thickness of the first zinc sulphide film layer less than the second zinc sulphide film layer.
Specifically, referring to fig. 4, buffer layer includes substrate 01, be successively set on the first zinc oxide film 02 on substrate 01,
First zinc sulphide film layer 03, the second zinc oxide film 04, the second zinc sulphide film layer 05.Wherein, the thickness of the first zinc sulphide film layer 03
The thickness less than the second zinc sulphide film layer 05 is spent, the thickness of the first zinc oxide film 02 is greater than the thickness of the second zinc oxide film 04
Degree, therefore, the quantity of the oxygen atom in the first zinc oxide film 02 accounts for the first zinc oxide film 02 and the first zinc sulphide film layer 03
The content of total amount, is greater than, and the quantity of the oxygen atom in the second zinc oxide film 04 accounts for the second zinc oxide film 04 and the second vulcanization
The content of 04 total amount of zinc film layer；So that the band gap width of buffer layer is in increase tendency along the direction far from substrate.
Alternatively, changing the quantity of oxygen atom by the doping concentration for adjusting oxygen atom, so that the quantity for reaching oxygen atom becomes
Change trend.The doping concentration of oxygen atom, is greater than in first zinc oxide film and the first zinc sulphide film layer, the second zinc oxide film and
The doping concentration of oxygen atom in second zinc sulphide film layer, and sulphur atom is mixed in the first zinc oxide film and the first zinc sulphide film layer
Miscellaneous concentration, is less than, the doping concentration of sulphur atom in the second zinc oxide film and the second zinc sulphide film layer, so that oxygen atom
Quantity is in reduction trend along the direction for being gradually distance from substrate.
It should be noted that the material used when forming buffer layer is zinc oxide and zinc sulphide, therefore, the present invention is implemented
The doping concentration of oxygen atom can be understood as the doping concentration of zinc oxide in example, and the doping concentration of sulphur atom can be understood as vulcanizing
The doping concentration of zinc.
Optionally, in order to enable the film layer forbidden bandwidth in buffer layer far from substrate is larger, close to the film layer forbidden band of substrate
Width reduces, and guarantees that the ratio edge of O/ (O+S) is gradually distance from the direction of substrate in reduction trend.In the embodiment of the present invention, first
The quantity of oxygen atom is greater than the quantity of oxygen atom in the second zinc oxide film in zinc oxide film, and sulphur is former in the first zinc sulphide film layer
The quantity of son is greater than the quantity of sulphur atom in the second zinc sulphide film layer, comprising: the first zinc oxide film and the first zinc sulphide film layer
The doping concentration of middle oxygen atom, is greater than, the doping concentration of oxygen atom in the second zinc oxide film and the second zinc sulphide film layer, and first
The doping concentration of sulphur atom, is greater than in zinc oxide film and the first zinc sulphide film layer, the second zinc oxide film and the second zinc sulphide
The doping concentration of sulphur atom in film layer；Alternatively, thickness of the thickness of the first zinc oxide film greater than the second zinc oxide film, first
The thickness of zinc sulphide film layer is greater than the thickness of the second zinc sulphide film layer.
Optionally, in order to enable the film layer forbidden bandwidth in buffer layer far from substrate is larger, close to the film layer forbidden band of substrate
Width reduces, and guarantees that the ratio edge of O/ (O+S) is gradually distance from the direction of substrate in reduction trend.In the embodiment of the present invention, first
The quantity of oxygen atom is less than the quantity of oxygen atom in the second zinc oxide film in zinc oxide film, and sulphur is former in the first zinc sulphide film layer
Quantity of the quantity of son less than sulphur atom in the second zinc sulphide film layer, comprising: the first zinc oxide film and the first zinc sulphide film layer
The doping concentration of middle oxygen atom, is less than, the doping concentration of oxygen atom in the second zinc oxide film and the second zinc sulphide film layer, and first
The doping concentration of sulphur atom, is less than in zinc oxide film and the first zinc sulphide film layer, the second zinc oxide film and the second zinc sulphide
The doping concentration of sulphur atom in film layer；Alternatively, thickness of the thickness of the first zinc oxide film less than the second zinc oxide film, first
Thickness of the thickness of zinc sulphide film layer less than the second zinc sulphide film layer.
In some alternative embodiments, above-mentioned thin-film solar cells buffer layer provided in an embodiment of the present invention, first
Zinc oxide film and substrate contact.I.e. when forming the zinc oxide film and zinc sulphide film layer of overlapping setting, the first Zinc oxide film
Layer is directly and substrate contact.Meanwhile using the first zinc sulphide film layer as the surface of buffer layer.Close to the surface of substrate in the present invention
ZnO film layer is formed, so that ZnO film layer is contacted with CIGS light absorbing layer, ensure that good Lattice Matching and energy band matching；Remote
Surface from substrate deposits ZnS film layer, so that the forbidden bandwidth of buffer-layer surface is larger, effectively reduces photon reflection, from
And the absorption of short-wavelength light is reduced, luminous energy loss is reduced, to improve the quantum efficiency and transfer efficiency of thin-film solar cells.
In some alternative embodiments, referring to Fig. 5, the buffer layer of thin-film solar cells further include: third zinc oxide
Film layer 06 and third zinc sulphide film layer 07, wherein third zinc oxide film 06 and third zinc sulphide film layer 07 are successively set on
Between one zinc sulphide film layer 03 and the second zinc oxide film 04, third zinc oxide film 06 is contacted with the first zinc sulphide film layer 03,
Third zinc sulphide film layer 07 is located between third zinc oxide film 06 and the second zinc oxide film 04.
It should be noted that more can also be arranged between the first zinc sulphide film layer 03 and the second zinc oxide film 04
The zinc oxide film and zinc sulphide film layer of lamination setting, so that the band gap width of buffer layer is in along the direction for being gradually distance from substrate
Increase tendency.Zinc oxide film and zinc sulphide film layer group between the first zinc sulphide film layer 03 and the second zinc oxide film 04
At band gap width the trend that is gradually increased is presented, can also part film layer the trend increased is presented or band gap width is constant.
Specifically, oxygen atom accounts for oxygen atom in third zinc oxide film and third zinc sulphide film layer in third zinc oxide film
With the content of sulphur atom total amount, it is greater than, oxygen atom accounts for the second zinc oxide film and the second ZnS-film in the second zinc oxide film
The content of oxygen atom and sulphur atom total amount in layer, and oxygen atom accounts for third zinc oxide film and third sulphur in third zinc oxide film
The content for changing oxygen atom and sulphur atom total amount in zinc film layer, is less than, oxygen atom accounts for the first Zinc oxide film in the first zinc oxide film
The content of oxygen atom and sulphur atom total amount in layer and the first zinc sulphide film layer.So that buffer layer includes being sequentially deposited at substrate
On the first zinc oxide film, the first zinc sulphide film layer, third zinc oxide film, third zinc sulphide film layer, the second zinc oxide
When film layer, the second zinc sulphide film layer, buffer layer is gradually increased along the direction forbidden bandwidth for being gradually distance from substrate.
Specifically, as shown in figure 5, the first zinc oxide film 02, third zinc oxide film 06 and the second zinc oxide film
04 thickness is gradually reduced, the first zinc sulphide film layer 03, third zinc sulphide film layer 07, the second zinc sulphide film layer 05 thickness gradually
Increase.Therefore the band gap width of buffer layer shown in fig. 5 is gradually increased along the direction for being gradually distance from substrate.
Alternatively, in third zinc oxide film oxygen atom account in third zinc oxide film and third zinc sulphide film layer oxygen atom and
The content of sulphur atom total amount, is equal to, and oxygen atom accounts for the second zinc oxide film and the second zinc sulphide film layer in the second zinc oxide film
The content of middle oxygen atom and sulphur atom total amount.So that buffer layer includes the first Zinc oxide film for being sequentially deposited at substrate
Layer, the first zinc sulphide film layer, third zinc oxide film, third zinc sulphide film layer, the second zinc oxide film, the second zinc sulphide film layer
When, buffer layer is in increase tendency along the direction forbidden bandwidth for being gradually distance from substrate, and the forbidden band of the film layer among buffer layer is wide
Degree is equal far from the forbidden bandwidth of film layer of substrate with buffer layer.
Alternatively, in third zinc oxide film oxygen atom account in third zinc oxide film and third zinc sulphide film layer oxygen atom and
The content of sulphur atom total amount, is equal to, and oxygen atom accounts for the first zinc oxide film and the first zinc sulphide film layer in the first zinc oxide film
The content of middle oxygen atom and sulphur atom total amount.So that buffer layer includes the first Zinc oxide film for being sequentially deposited at substrate
Layer, the first zinc sulphide film layer, third zinc oxide film, third zinc sulphide film layer, the second zinc oxide film, the second zinc sulphide film layer
When, buffer layer is in increase tendency along the direction forbidden bandwidth for being gradually distance from substrate, and the forbidden band of the film layer among buffer layer is wide
Degree is equal close to the forbidden bandwidth of film layer of substrate with buffer layer.
It should be noted that for " oxygen atom accounts for third zinc oxide film and third zinc sulphide in third zinc oxide film
The adjusting of the content of oxygen atom and sulphur atom total amount in film layer ", can according in above-described embodiment to " in the first zinc oxide film
Oxygen atom accounts for the content of oxygen atom and sulphur atom total amount in the first zinc oxide film and the first zinc sulphide film layer " regulative mode into
Row is adjusted, and something in common repeats no more.
In some alternative embodiments, in above-mentioned thin-film solar cells provided in an embodiment of the present invention, referring to Fig. 6,
Further include: the 4th zinc oxide film 08 between substrate 01 and the first zinc oxide film 02 is set, is arranged in the second zinc sulphide
The 4th zinc sulphide film layer 09 on film layer 05.Wherein, the thickness of the 4th zinc oxide film 08 is greater than the first zinc oxide film 02
Thickness, the thickness of the 4th zinc sulphide film layer 09 is greater than the thickness of the second zinc sulphide film layer 05.In the embodiment of the present invention, by into
One step increases by the 4th zinc oxide film, contacts, ensure that good with CIGS light absorbing layer to further increase ZnO film layer
Lattice Matching and energy band matching, and by increasing by the 4th zinc sulphide film layer 09, further such that the forbidden bandwidth of buffer-layer surface
It is larger.
In some alternative embodiments, the thickness of buffer layer provided in an embodiment of the present invention can be 30nm-50nm.Into
One step adjusts the content of oxygen atom by any of the above-described mode, so as to adjust the band gap width of buffer layer to 3.37eV-
3.68eV, so that the band gap width of buffer layer is gradually increased, the material of graded bandgap increases light incidence, and the band gap of increase will be reduced
The absorption of short-wavelength light improves the transfer efficiency of thin-film solar cells so that more light enter in solar battery.
It is emphasized that in above-described embodiment only with buffer layer include overlapping setting the first zinc oxide film, first
For zinc sulphide film layer, third zinc oxide film, third zinc sulphide film layer, the second zinc oxide film, the second zinc sulphide film layer into
Row explanation, but above-mentioned six film layers are not limited to, it can also include more circulations.Certainly, buffer layer includes multiple overlapping settings
Zinc oxide film and when zinc sulphide film layer, the forbidden bandwidth of composition can be gradually increased along the direction for being gradually distance from substrate,
Or the trend increased is presented.
Based on same invention thought, referring to Fig. 7, the embodiment of the invention also provides a kind of preparations of thin-film solar cells
Method, this method comprises:
S101, a substrate is provided；
The substrate of the embodiment of the present invention includes: glass substrate, the back electrode of setting on the glass substrate, is arranged in back electrode
On light absorbing layer.
Specifically, back electrode layer is formed on the glass substrate；Light absorbing layer is formed on back electrode layer.For example, by glass
Base-plate cleaning is clean, such as successively using cleaning solution Mucasol (universal cleaning liquid, German BRAND manufacturer production), ethyl alcohol, ultrapure
The sequence of water is cleaned by ultrasonic glass substrate, and glass substrate can use soda-lime glass.Then on the glass substrate cleaned up
Deposit molybdenum back electrode layer.Copper indium gallium selenide layer is formed on back electrode layer using techniques such as coevaporation or magnetron sputterings, thus shape
At light absorbing layer, the technique for forming light absorbing layer is same as the prior art.
S102, the first zinc oxide film, the first zinc sulphide film layer, the second zinc oxide film and second is formed on the substrate
Zinc sulphide film layer；Wherein, oxygen atom accounts for oxygen original in the first zinc oxide film and the first zinc sulphide film layer in the first zinc oxide film
The content of son and sulphur atom total amount, is greater than, oxygen atom accounts for the second zinc oxide film and the second zinc sulphide in the second zinc oxide film
The content of oxygen atom and sulphur atom total amount in film layer.
It should be noted that can also include: to form window on the buffer layer in the production method of thin-film solar cells
Layer.Wherein, Window layer (can be abbreviated as the zinc oxide of zinc-magnesium oxide (being abbreviated as ZMO) or zinc oxide (ZnO), boron-doping
BZO), the zinc oxide (being abbreviated as AZO) of aluminium is mixed.The method for forming Window layer is same as the prior art.
Specifically, buffer layer provided in an embodiment of the present invention includes ZnO film layer and ZnS film layer, i.e. the material packet of buffer layer
Include Zn (O, S).Wherein, at room temperature, the forbidden bandwidth of ZnO is 3.37eV, and the forbidden bandwidth of ZnS is 3.68eV, therefore, the present invention
The buffer layer of the thin-film solar cells of middle offer is in reduction trend with the direction for being gradually distance from substrate, the content of oxygen atom,
Then band gap width increases since 3.37eV, and maximum can increase to 3.68eV so that buffer layer band gap width along by
Gradually for the direction far from substrate in increasing, the material of graded bandgap increases light incidence, and the band gap of increase will reduce the suction of short-wavelength light
It receives, so that more light enter in solar battery, to improve the quantum efficiency and transfer efficiency of thin-film solar cells.Separately
Outside, it is not introduced into such as cadmium toxic element in buffer layer, therefore avoids the harm to environment.
In some alternative embodiments, the first zinc oxide film, the first zinc sulphide film layer, the second zinc oxide film and
Second zinc sulphide film layer includes but is not limited to meet following either condition:
The quantity of oxygen atom is greater than the quantity of oxygen atom in the second zinc oxide film, the first vulcanization in first zinc oxide film
The quantity of sulphur atom is equal to the quantity of sulphur atom in the second zinc sulphide film layer in zinc film layer；
The quantity of oxygen atom is equal to the quantity of oxygen atom in the second zinc oxide film, the first vulcanization in first zinc oxide film
Quantity of the quantity of sulphur atom less than sulphur atom in the second zinc sulphide film layer in zinc film layer；
The quantity of oxygen atom is greater than the quantity of oxygen atom in the second zinc oxide film, the first vulcanization in first zinc oxide film
Quantity of the quantity of sulphur atom less than sulphur atom in the second zinc sulphide film layer in zinc film layer；
The quantity of oxygen atom is greater than the quantity of oxygen atom in the second zinc oxide film, the first vulcanization in first zinc oxide film
The quantity of sulphur atom is greater than the quantity of sulphur atom in the second zinc sulphide film layer in zinc film layer；
Quantity of the quantity of oxygen atom less than oxygen atom in the second zinc oxide film, the first vulcanization in first zinc oxide film
Quantity of the quantity of sulphur atom less than sulphur atom in the second zinc sulphide film layer in zinc film layer.
In some alternative embodiments, the quantity of oxygen atom or the quantity of sulphur atom are doping concentration or place film layer
Thickness.
In some alternative embodiments, the quantity of oxygen atom is greater than in the second zinc oxide film in the first zinc oxide film
The quantity of oxygen atom, the quantity of sulphur atom is equal to the quantity of sulphur atom in the second zinc sulphide film layer, packet in the first zinc sulphide film layer
Include: the doping concentration of oxygen atom in the first zinc oxide film and the first zinc sulphide film layer is greater than, the second zinc oxide film and second
The doping of sulphur atom is dense in the doping concentration of oxygen atom in zinc sulphide film layer, the first zinc oxide film and the first zinc sulphide film layer
Degree, is equal to, the doping concentration of sulphur atom in the second zinc oxide film and the second zinc sulphide film layer；Alternatively, the first zinc oxide film
Thickness be greater than the thickness of the second zinc oxide film, the thickness of the first zinc sulphide film layer is equal to the thickness of the second zinc sulphide film layer.
In some alternative embodiments, the quantity of oxygen atom is equal in the second zinc oxide film in the first zinc oxide film
The quantity of oxygen atom, quantity of the quantity of sulphur atom less than sulphur atom in the second zinc sulphide film layer, packet in the first zinc sulphide film layer
Include: the doping concentration of oxygen atom in the first zinc oxide film and the first zinc sulphide film layer is equal to, the second zinc oxide film and second
The doping of sulphur atom is dense in the doping concentration of oxygen atom in zinc sulphide film layer, the first zinc oxide film and the first zinc sulphide film layer
Degree, is less than, the doping concentration of sulphur atom in the second zinc oxide film and the second zinc sulphide film layer；Alternatively, the first zinc oxide film
Thickness be equal to the thickness of the second zinc oxide film, the thickness of the thickness of the first zinc sulphide film layer less than the second zinc sulphide film layer.
In some alternative embodiments, the quantity of oxygen atom is greater than in the second zinc oxide film in the first zinc oxide film
The quantity of oxygen atom, quantity of the quantity of sulphur atom less than sulphur atom in the second zinc sulphide film layer, packet in the first zinc sulphide film layer
Include: the doping concentration of oxygen atom in the first zinc oxide film and the first zinc sulphide film layer is greater than, the second zinc oxide film and second
The doping of sulphur atom is dense in the doping concentration of oxygen atom in zinc sulphide film layer, the first zinc oxide film and the first zinc sulphide film layer
Degree, is less than, the doping concentration of sulphur atom in the second zinc oxide film and the second zinc sulphide film layer；Alternatively, the first zinc oxide film
Thickness be greater than the thickness of the second zinc oxide film, the thickness of the thickness of the first zinc sulphide film layer less than the second zinc sulphide film layer.
Optionally, in the first zinc oxide film oxygen atom quantity be greater than the second zinc oxide film in oxygen atom quantity,
The quantity of sulphur atom is greater than the quantity of sulphur atom in the second zinc sulphide film layer in first zinc sulphide film layer, comprising: the first zinc oxide
The doping concentration of oxygen atom, is greater than in film layer and the first zinc sulphide film layer, in the second zinc oxide film and the second zinc sulphide film layer
The doping concentration of sulphur atom, is greater than, the second oxygen in the doping concentration of oxygen atom, the first zinc oxide film and the first zinc sulphide film layer
Change the doping concentration of sulphur atom in zinc film layer and the second zinc sulphide film layer；Alternatively, the thickness of the first zinc oxide film is greater than second
The thickness of zinc oxide film, the thickness of the first zinc sulphide film layer are greater than the thickness of the second zinc sulphide film layer.
Optionally, in the first zinc oxide film oxygen atom quantity less than oxygen atom in the second zinc oxide film quantity,
Quantity of the quantity of sulphur atom less than sulphur atom in the second zinc sulphide film layer in first zinc sulphide film layer, comprising: the first zinc oxide
The doping concentration of oxygen atom, is less than in film layer and the first zinc sulphide film layer, in the second zinc oxide film and the second zinc sulphide film layer
The doping concentration of sulphur atom, is less than, the second oxygen in the doping concentration of oxygen atom, the first zinc oxide film and the first zinc sulphide film layer
Change the doping concentration of sulphur atom in zinc film layer and the second zinc sulphide film layer；Alternatively, the thickness of the first zinc oxide film is less than second
The thickness of zinc oxide film, the thickness of the thickness of the first zinc sulphide film layer less than the second zinc sulphide film layer.
In some alternative embodiments, this method further include: the first zinc sulphide film layer and the second zinc oxide film it
Between form third zinc oxide film and third zinc sulphide film layer；In third zinc oxide film oxygen atom account for third zinc oxide film and
The content of oxygen atom and sulphur atom total amount, is greater than in third zinc sulphide film layer, and oxygen atom accounts for the second oxygen in the second zinc oxide film
Change the content of oxygen atom and sulphur atom total amount in zinc film layer and the second zinc sulphide film layer, and oxygen atom accounts in third zinc oxide film
The content of oxygen atom and sulphur atom total amount, is less than, the first zinc oxide film in third zinc oxide film and third zinc sulphide film layer
Middle oxygen atom accounts for the content of oxygen atom and sulphur atom total amount in the first zinc oxide film and the first zinc sulphide film layer；Alternatively, third
Oxygen atom accounts for the content of oxygen atom and sulphur atom total amount in third zinc oxide film and third zinc sulphide film layer in zinc oxide film,
It is equal to, it is total to account for oxygen atom and sulphur atom in the second zinc oxide film and the second zinc sulphide film layer for oxygen atom in the second zinc oxide film
The content of amount；Alternatively, oxygen atom accounts for oxygen atom in third zinc oxide film and third zinc sulphide film layer in third zinc oxide film
With the content of sulphur atom total amount, it is equal to, oxygen atom accounts for the first zinc oxide film and the first ZnS-film in the first zinc oxide film
The content of oxygen atom and sulphur atom total amount in layer.
It is formed on the substrate before the first zinc oxide film and the first zinc sulphide film layer of overlapping setting, this method is also wrapped
It includes: forming the 4th zinc oxide film between substrate and the first zinc oxide film, the thickness of the 4th zinc oxide film is greater than first
The thickness of zinc oxide film；This method further include: the 4th zinc sulphide film layer, the 4th zinc sulphide are formed in the second zinc sulphide film layer
The thickness of film layer is greater than the thickness of the second zinc sulphide film layer.
It should be noted that in the embodiment of the present invention in the preparation method of thin-film solar cells, with the above-mentioned film sun
The embodiment something in common of energy battery buffer layer, details are not described herein again, and its advantages and explanation refer to above-mentioned film
The embodiment of solar battery.
In some alternative embodiments, the first zinc oxide film, the first zinc sulphide film layer, are sequentially formed on substrate
Zinc oxide film layer and the second zinc sulphide film layer, comprising: sequentially form the first oxygen on substrate by Atomic layer deposition method
Change zinc film layer, the first zinc sulphide film layer, the second zinc oxide film and the second zinc sulphide film layer.
In a particular embodiment, Atomic layer deposition method is mainly prepared by vacuum method, with the light in CIGS producing line
Other vacuum technologies such as absorbed layer are preferably compatible, and generate without waste liquid；It is buffered in addition, being formed by Atomic layer deposition method
Layer forms buffer layer compared to using sputtering technology, and film formation compactness is preferable, can also inhibit due to the undesirable production of film compactness
Caused by raw micropore the phenomenon that thin-film solar cells internal short-circuit, improve battery performance；Using Atomic layer deposition method
Buffer layer is made, is further implemented in the uniformity that Nano grade accurately controls film thickness, guarantees large area film forming, and can be real
Film is grown under existing low temperature, is suitable for substrate of various shapes.
In some alternative embodiments, the preparation method of above-mentioned thin-film solar cells provided in an embodiment of the present invention
In, the first zinc oxide film, the first zinc sulphide film layer, the second zinc oxide film are formed on the substrate by Atomic layer deposition method
And the second zinc sulphide film layer, comprising: friendship is formed on the substrate by Atomic layer deposition method in the precursor source of zinc, oxygen, sulphur
The zinc oxide film and zinc sulphide film layer of folded setting.Wherein, the precursor source of oxygen is water (H2O)；The precursor source of zinc is diethyl
Base zinc (ZnEt2)；The precursor source of sulphur is hydrogen sulfide (H2) or sulphur S.
In some alternative embodiments, the preparation method of above-mentioned thin-film solar cells provided in an embodiment of the present invention
In, the zinc oxide film and zinc sulphide film layer of overlapping setting are formed on the substrate by Atomic layer deposition method, comprising:
The ZnO film layer and ZnS film layer that overlapping setting is formed by a ZnO pulse cycle and b ZnS pulse cycle, repeat
A ZnO pulse cycle and b ZnS pulse cycle are c times total, and with the increase of cycle-index c, the value for adjusting a, b makes a/a+b
Value be gradually reduced；Wherein, a >=1, b >=1, c >=1.
Specifically, form ZnO film layer close to the surface of substrate ensure that so that ZnO film layer is contacted with CIGS light absorbing layer
Preferable Lattice Matching and energy band matching；ZnS film layer is deposited on the surface far from substrate, so that the forbidden bandwidth of buffer-layer surface
It is larger, to reduce the absorption of short-wavelength light, luminous energy loss is reduced, to improve the quantum efficiency of thin-film solar cells and turn
Change efficiency.Multiple ZnO film layers are formed between ZnO film layer and ZnS film layer and film layer that ZnS film layer is arranged alternately, so that
Trend from small to large is presented along the direction for being gradually distance from substrate in the forbidden bandwidth of buffer layer.Further, mainly pass through tune
The circulation ratio of pulse further adjusts buffer layer to adjust the ratio of O/ (S+O) in section production ZnO film layer and ZnS film layer
Forbidden bandwidth.
Wherein, when recycling c times, the number for adjusting the value of a, b is not specifically limited herein, e.g., can be gradually reduced a's
Value；Or gradually increase the value of b；Alternatively, being gradually reduced the value of a, while increasing the value of b.
In the present invention when making the buffer layer of thin-film solar cells, it is arranged alternately by ZnO film layer and ZnS film layer
Mode avoids individually adopting to ensure that thin-film solar cells has preferable open-circuit voltage (Voc), short circuit current (Isc)
The smaller Voc of the Isc higher phenomenon caused by the first ZnO film layer.
It should be noted that forming the circulation number of the ZnO film layer being arranged alternately and ZnS film layer, specific limit is not done herein
It is fixed.I.e., it is possible to by repeatedly adjusting the value of a and the value of b, so that forming multiple circulations adjusts forbidden bandwidth, so that slow
The forbidden bandwidth for rushing layer meets needs, as forbidden bandwidth is adjusted to 3.37eV-3.68eV.
In some alternative embodiments, the preparation of above-mentioned thin-film solar cells buffer layer provided in an embodiment of the present invention
In method, the pulse parameter of zinc-oxide film is formed are as follows: the precursor source of 0.1-0.5s Zn, 5-15s N2Cleaning, 0.1-0.5s
The precursor source of O, 5-15s N2Cleaning；Form the pulse parameter of zinc sulphide film layer are as follows: the precursor source of 0.1-0.5s Zn, 5-
15s N2Cleaning, the precursor source of 0.1-0.5s S, 5-15sN2Cleaning.
Specifically, when forming zinc oxide film by ZnO pulse cycle, the parameter of each pulse cycle are as follows: successively lead to
The precursor source for entering 0.1-0.5s Zn is deposited；It is passed through 5-15s N2It is cleaned；It is passed through the precursor source of 0.1-0.5s O
It is deposited；It is passed through 5-15s N2It is cleaned.Oxidation is formed by the chemical reaction of the precursor source of the precursor source and O of Zn
Zinc film layer.When forming zinc sulphide film layer by ZnS pulse cycle, the parameter of each pulse cycle are as follows: be successively passed through 0.1-
The precursor source of 0.5s Zn is deposited；It is passed through 5-15s N2It is cleaned；The precursor source for being passed through 0.1-0.5s S is sunk
Product；It is passed through 5-15s N2It is cleaned.Wherein, by N2As carrying and purge gas.
It should be noted that when forming zinc oxide film or zinc sulphide film layer, it can be by the deposition temperature in vacuum chamber
Degree is between 100 ° -300 °.Preferably, depositing temperature can be 150 °.
In some alternative embodiments, the preparation method of above-mentioned thin-film solar cells provided in an embodiment of the present invention
In, form the pulse parameter of zinc oxide film are as follows: the precursor source of 0.4s Zn, 10s N2Cleaning, 0.4s O precursor source,
10s N2Cleaning；Form the pulse parameter of zinc sulphide film layer are as follows: the precursor source of 0.4s Zn, 10s N2Before cleaning, 0.4s S
Drive body source, 10s N2Cleaning.
Below by the preparation method for the thin-film solar cells that specific embodiment the present invention is described in detail embodiment provides.
The method for preparing thin-film solar cells buffer layer, comprising:
Step 1: placing the substrate into the sample tray of atomic layer deposition apparatus, and it is sent into atomic layer deposition apparatus, closes
Closed chamber room, and vacuumize.
Step 2: setting forms the temperature of the growth procedure and deposition of zinc oxide film or zinc sulphide film layer in buffer layer
Degree；
Wherein, depositing temperature can be 150 DEG C；Use H2O is as the source O, ZnEt2As the source Zn, H2S is high-purity as the source S
N2As carrying and purge gas, and carry ZnEt2Gas flow be 150sccm, H2S and H2The carrier gas flux of O is
200sccm.Wherein, setting forms the ZnO pulse sequence of ZnO film layer successively are as follows: 0.4s ZnEt2、10s N2Cleaning, 0.4s
H2O、10s N2Cleaning；It is arranged and forms the ZnS pulse sequence of ZnS film layer successively are as follows: 0.4s ZnEt2、10s N2Cleaning, 0.4s
H2S、10s N2Cleaning.
The specific embodiment to form thin-film solar cells buffer layer is set forth below.
Embodiment 1
Pulse sequence in buffer layer preparation method are as follows:
Step 1 forms zinc oxide film by 60 ZnO pulse cycles；
Step 2, the zinc oxide film and sulphur that overlapping setting is formed by 4 ZnO pulse cycles and 1 ZnS pulse cycle
Change zinc film layer, and repeat 4 ZnO pulse cycles and 1 ZnS pulse cycle totally 12 times, to pass through 60 pulse cycle shapes
At zinc oxide film and zinc sulphide film layer；
Step 3, the zinc oxide film and sulphur that overlapping setting is formed by 1 ZnO pulse cycle and 1 ZnS pulse cycle
Change zinc film layer, and repeat 1 ZnO pulse cycle and 1 ZnS pulse cycle totally 30 times, to pass through 60 pulse cycle shapes
At zinc oxide film and zinc sulphide film layer；
Step 4, the zinc oxide film and sulphur that overlapping setting is formed by 1 ZnO pulse cycle and 4 ZnS pulse cycles
Change zinc film layer, and repeat 1 ZnO pulse cycle and 4 ZnS pulse cycles totally 12 times, to pass through 60 pulse cycle shapes
At zinc oxide film and zinc sulphide film layer；
Step 5 forms zinc sulphide film layer by 60 ZnS pulse cycles.
Embodiment 2
Pulse sequence in buffer layer preparation method are as follows:
Step 1 forms zinc oxide film by 60 ZnO pulse cycles；
Step 2, the zinc oxide film and sulphur that overlapping setting is formed by 9 ZnO pulse cycles and 1 ZnS pulse cycle
Change zinc film layer, and repeat 9 ZnO pulse cycles and 1 ZnS pulse cycle totally 6 times, to be formed by 60 pulse cycles
Zinc oxide film and zinc sulphide film layer；
Step 3, the zinc oxide film and sulphur that overlapping setting is formed by 1 ZnO pulse cycle and 1 ZnS pulse cycle
Change zinc film layer, and repeat 1 ZnO pulse cycle and 1 ZnS pulse cycle totally 30 times, to pass through 60 pulse cycle shapes
At zinc oxide film and zinc sulphide film layer；
Step 4, the zinc oxide film and sulphur that overlapping setting is formed by 1 ZnO pulse cycle and 9 ZnS pulse cycles
Change zinc film layer, and repeat 1 ZnO pulse cycle and 9 ZnS pulse cycles totally 6 times, to be formed by 60 pulse cycles
Zinc oxide film and zinc sulphide film layer；
Step 5 forms zinc sulphide film layer by 60 ZnS pulse cycles.
Embodiment 3
Pulse sequence in buffer layer preparation method are as follows:
Step 1 forms zinc oxide film by 60 ZnO pulse cycles；
Step 2, the zinc oxide film and sulphur that overlapping setting is formed by 7 ZnO pulse cycles and 3 ZnS pulse cycles
Change zinc film layer, and repeat 7 ZnO pulse cycles and 3 ZnS pulse cycles totally 6 times, to be formed by 60 pulse cycles
Zinc oxide film and zinc sulphide film layer；
Step 3, the zinc oxide film and sulphur that overlapping setting is formed by 1 ZnO pulse cycle and 1 ZnS pulse cycle
Change zinc film layer, and repeat 1 ZnO pulse cycle and 1 ZnS pulse cycle totally 30 times, to pass through 60 pulse cycle shapes
At zinc oxide film and zinc sulphide film layer；
Step 4, the zinc oxide film and sulphur that overlapping setting is formed by 3 ZnO pulse cycles and 7 ZnS pulse cycles
Change zinc film layer, and repeat 3 ZnO pulse cycles and 7 ZnS pulse cycles totally 6 times, to be formed by 60 pulse cycles
Zinc oxide film and zinc sulphide film layer；
Step 5 forms zinc sulphide film layer by 60 ZnS pulse cycles.
Embodiment 4
Pulse sequence in buffer layer preparation method are as follows:
Step 1 forms zinc oxide film by 60 ZnO pulse cycles；
Step 2, the zinc oxide film and sulphur that overlapping setting is formed by 4 ZnO pulse cycles and 1 ZnS pulse cycle
Change zinc film layer, and repeat 4 ZnO pulse cycles and 1 ZnS pulse cycle totally 12 times, to pass through 60 pulse cycle shapes
At zinc oxide film and zinc sulphide film layer；
Step 3, the zinc oxide film and sulphur that overlapping setting is formed by 3 ZnO pulse cycles and 2 ZnS pulse cycles
Change zinc film layer, and repeat 3 ZnO pulse cycles and 2 ZnS pulse cycles totally 12 times, to pass through 60 pulse cycle shapes
At zinc oxide film and zinc sulphide film layer；
Step 4, the zinc oxide film and sulphur that overlapping setting is formed by 2 ZnO pulse cycles and 3 ZnS pulse cycles
Change zinc film layer, and repeat 2 ZnO pulse cycles and 3 ZnS pulse cycles totally 12 times, to pass through 60 pulse cycle shapes
At zinc oxide film and zinc sulphide film layer；
Step 5, the zinc oxide film and sulphur that overlapping setting is formed by 1 ZnO pulse cycle and 4 ZnS pulse cycles
Change zinc film layer, and repeat 1 ZnO pulse cycle and 4 ZnS pulse cycles totally 12 times, to pass through 60 pulse cycle shapes
At zinc oxide film and zinc sulphide film layer；
Step 6 forms zinc sulphide film layer by 60 ZnS pulse cycles.
Embodiment 1-4 only illustrates 4 kinds of embodiments, how is demonstrated by by ZnO in control pulse ratio adjusting buffer layer
The thickness of film layer or ZnS film layer, so that the forbidden bandwidth presentation of buffer layer is gradually increased with substrate is gradually distance from
Trend.Certainly various ways can be used when adjusting pulse ratio, and the data of above embodiments offer are provided.
The film of band gap gradual change can be effectively prepared in the preparation method of the thin-film solar cells of the embodiment of the present invention
The incident direction (along the direction for moving closer to substrate) along photon, the light of each tunic may be implemented in solar battery buffer layer
Band gap Eg is learned to successively decrease.Along photon incident direction, the ratio of O/ (O+S) is increasing, and forbidden bandwidth is smaller and smaller；It is optional
Ground, by adjust prepare ZnO and ZnS pulse cycle number ratio realization band gap width adjustment, along the surface CIGS into
When row growth, after ZnO film layer is completed in preparation, according to gradually decreasing ZnO pulse cycle number, increase ZnS pulse cycle number, thus
Realization is gradually reduced along photon incident direction forbidden bandwidth, is conducive to the wave-length coverage (E > Eg (CIGS)) for absorbing entire sunlight
Photon energy；In addition, the forbidden bandwidth of film is smaller, and what corresponding refractive index was incremented by instead, light can be efficiently reduced
Son reflection, improves absorption efficiency.
In conclusion thin-film solar cells provided in an embodiment of the present invention has the beneficial effect that
1, by adjusting the ratio of O/ (S+O) in buffer layer in the embodiment of the present invention, so that the ratio is along being gradually distance from
The direction of substrate is gradually reduced, so that the forbidden bandwidth of buffer layer is gradually increased along the direction for being gradually distance from substrate, it may be assumed that
The forbidden bandwidth of the buffer layer contacted with thin-film solar cells light absorbing layer is smaller, thus preferably with light absorbing layer in CIGS
The forbidden bandwidth of matching, the buffer layer far from thin-film solar cells light absorbing layer is larger, so that the absorption of short-wavelength light is reduced,
Luminous energy loss is reduced, to improve the quantum efficiency and transfer efficiency of thin-film solar cells.Preferably, in the embodiment of the present invention
The forbidden bandwidth of the buffer layer of thin-film solar cells is within the scope of 3.37eV-3.68eV.
2, in the structure of the buffer layer of thin-film solar cells of the present invention, due to using nontoxic ZnO film layer and ZnS film
Layer, avoids the harm to environment, while improving the forbidden bandwidth of buffer layer, increases absorptivity.
3, it when making the buffer layer of thin-film solar cells, is contacted, be ensure that with CIGS light absorbing layer by ZnO film layer
Good Lattice Matching and energy band matching, in such a way that ZnO film layer and ZnS film layer are arranged alternately, to ensure that film too
Positive energy battery has preferable open-circuit voltage (Voc), short circuit current (Isc), avoids individually using Isc caused by OS film smaller
Voc higher phenomenon.
Although disclosed herein embodiment it is as above, the content only for ease of understanding the present invention and use
Embodiment is not intended to limit the invention.Technical staff in any fields of the present invention is taken off not departing from the present invention
Under the premise of the spirit and scope of dew, any modification and variation, but the present invention can be carried out in the form and details of implementation
Scope of patent protection, still should be subject to the scope of the claims as defined in the appended claims.
Claims (10)
1. a kind of thin-film solar cells, which is characterized in that the thin-film solar cells includes:
Substrate；
Buffer layer over the substrate is set, and the buffer layer includes the zinc oxide film and zinc sulphide film layer of overlapping setting；
Wherein, the buffer layer includes at least: setting gradually the first zinc oxide film, the first ZnS-film over the substrate
Layer, the second zinc oxide film and the second zinc sulphide film layer, and oxygen atom accounts for first oxygen in first zinc oxide film
The content for changing oxygen atom and sulphur atom total amount in zinc film layer and the first zinc sulphide film layer, is greater than, second Zinc oxide film
Oxygen atom accounts for the content of oxygen atom and sulphur atom total amount in second zinc oxide film and the second zinc sulphide film layer in layer.
2. thin-film solar cells according to claim 1, which is characterized in that overlap the oxidation of setting in the buffer layer
Zinc film layer and zinc sulphide film layer meet following either condition:
The quantity of oxygen atom is greater than the quantity of oxygen atom in second zinc oxide film in first zinc oxide film, described
The quantity of sulphur atom is equal to the quantity of sulphur atom in the second zinc sulphide film layer in first zinc sulphide film layer；
The quantity of oxygen atom is equal to the quantity of oxygen atom in second zinc oxide film in first zinc oxide film, described
The quantity of sulphur atom is less than the quantity of sulphur atom in the second zinc sulphide film layer in first zinc sulphide film layer；
The quantity of oxygen atom is greater than the quantity of oxygen atom in second zinc oxide film in first zinc oxide film, described
The quantity of sulphur atom is less than the quantity of sulphur atom in the second zinc sulphide film layer in first zinc sulphide film layer；
The quantity of oxygen atom is greater than the quantity of oxygen atom in second zinc oxide film in first zinc oxide film, described
The quantity of sulphur atom is greater than the quantity of sulphur atom in the second zinc sulphide film layer in first zinc sulphide film layer；
The quantity of oxygen atom is less than the quantity of oxygen atom in second zinc oxide film in first zinc oxide film, described
The quantity of sulphur atom is less than the quantity of sulphur atom in the second zinc sulphide film layer in first zinc sulphide film layer.
3. thin-film solar cells according to claim 2, which is characterized in that the quantity of the oxygen atom or the sulphur are former
The quantity of son includes the thickness of doping concentration or place film layer.
4. thin-film solar cells described in -3 any claims according to claim 1, which is characterized in that first Zinc oxide film
Layer and the substrate contact.
5. thin-film solar cells according to claim 4, which is characterized in that the buffer layer further include:
Third zinc oxide film and third zinc sulphide between the first zinc sulphide film layer and the second zinc oxide film are set
Film layer, the third zinc oxide film are contacted with the first zinc sulphide film layer, and the third zinc sulphide film layer is located in described
Between third zinc oxide film and second zinc oxide film；
In the third zinc oxide film oxygen atom account in the third zinc oxide film and third zinc sulphide film layer oxygen atom and
The content of sulphur atom total amount accounts for second zinc oxide film and the second vulcanization greater than oxygen atom in second zinc oxide film
The content of oxygen atom and sulphur atom total amount in zinc film layer, and be less than oxygen atom in first zinc oxide film and account for first oxygen
Change the content of oxygen atom and sulphur atom total amount in zinc film layer and the first zinc sulphide film layer；Or
In the third zinc oxide film oxygen atom account in the third zinc oxide film and third zinc sulphide film layer oxygen atom and
The content of sulphur atom total amount, is equal to, and oxygen atom accounts for second zinc oxide film and the second sulphur in second zinc oxide film
Change the content of oxygen atom and sulphur atom total amount in zinc film layer；Or
In the third zinc oxide film oxygen atom account in the third zinc oxide film and third zinc sulphide film layer oxygen atom and
The content of sulphur atom total amount, is equal to, and oxygen atom accounts for first zinc oxide film and the first sulphur in first zinc oxide film
Change the content of oxygen atom and sulphur atom total amount in zinc film layer.
6. a kind of preparation method of thin-film solar cells, which is characterized in that this method comprises:
One substrate is provided；
The first zinc oxide film, the first zinc sulphide film layer, the second zinc oxide film and second are sequentially formed over the substrate
Zinc sulphide film layer；Wherein,
In first zinc oxide film oxygen atom account in first zinc oxide film and the first zinc sulphide film layer oxygen atom and
The content of sulphur atom total amount, is greater than, and oxygen atom accounts for second zinc oxide film and the second sulphur in second zinc oxide film
Change the content of oxygen atom and sulphur atom total amount in zinc film layer.
7. preparation method according to claim 6, which is characterized in that first zinc oxide film, the first ZnS-film
Layer, the second zinc oxide film and the second zinc sulphide film layer meet following either condition:
The quantity of oxygen atom is greater than the quantity of oxygen atom in second zinc oxide film in first zinc oxide film, described
The quantity of sulphur atom is equal to the quantity of sulphur atom in the second zinc sulphide film layer in first zinc sulphide film layer；
The quantity of oxygen atom is equal to the quantity of oxygen atom in second zinc oxide film in first zinc oxide film, described
The quantity of sulphur atom is less than the quantity of sulphur atom in the second zinc sulphide film layer in first zinc sulphide film layer；
The quantity of oxygen atom is greater than the quantity of oxygen atom in second zinc oxide film in first zinc oxide film, described
The quantity of sulphur atom is less than the quantity of sulphur atom in the second zinc sulphide film layer in first zinc sulphide film layer；
The quantity of oxygen atom is greater than the quantity of oxygen atom in second zinc oxide film in first zinc oxide film, described
The quantity of sulphur atom is greater than the quantity of sulphur atom in the second zinc sulphide film layer in first zinc sulphide film layer；
The quantity of oxygen atom is less than the quantity of oxygen atom in second zinc oxide film in first zinc oxide film, described
The quantity of sulphur atom is less than the quantity of sulphur atom in the second zinc sulphide film layer in first zinc sulphide film layer.
8. preparation method according to claim 7, which is characterized in that the number of the quantity of the oxygen atom or the sulphur atom
Amount is the thickness of doping concentration or place film layer.
9. preparation method according to claim 8, which is characterized in that this method further include:
Third zinc oxide film and third ZnS-film are formed between the first zinc sulphide film layer and the second zinc oxide film
Layer；
In the third zinc oxide film oxygen atom account in the third zinc oxide film and third zinc sulphide film layer oxygen atom and
The content of sulphur atom total amount, is greater than, and oxygen atom accounts for second zinc oxide film and the second sulphur in second zinc oxide film
Change the content of oxygen atom and sulphur atom total amount in zinc film layer, and oxygen atom accounts for the third oxidation in the third zinc oxide film
The content of oxygen atom and sulphur atom total amount, is less than in zinc film layer and third zinc sulphide film layer, oxygen in first zinc oxide film
Atom accounts for the content of oxygen atom and sulphur atom total amount in first zinc oxide film and the first zinc sulphide film layer；Or
In the third zinc oxide film oxygen atom account in the third zinc oxide film and third zinc sulphide film layer oxygen atom and
The content of sulphur atom total amount, is equal to, and oxygen atom accounts for second zinc oxide film and the second sulphur in second zinc oxide film
Change the content of oxygen atom and sulphur atom total amount in zinc film layer；Or
In the third zinc oxide film oxygen atom account in the third zinc oxide film and third zinc sulphide film layer oxygen atom and
The content of sulphur atom total amount, is equal to, and oxygen atom accounts for first zinc oxide film and the first sulphur in first zinc oxide film
Change the content of oxygen atom and sulphur atom total amount in zinc film layer.
10. according to preparation method described in any claim of claim 6-9, which is characterized in that sequentially form over the substrate
First zinc oxide film, the first zinc sulphide film layer, the second zinc oxide film and the second zinc sulphide film layer, comprising:
Sequentially form the first zinc oxide film, the first zinc sulphide film layer, second over the substrate by Atomic layer deposition method
Zinc oxide film and the second zinc sulphide film layer.
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