CN104157734B - A kind of preparation method of copper zinc germanium sulfur/copper zinc germanium selenium absorbing layer of thin film solar cell - Google Patents
A kind of preparation method of copper zinc germanium sulfur/copper zinc germanium selenium absorbing layer of thin film solar cell Download PDFInfo
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- CN104157734B CN104157734B CN201410392589.4A CN201410392589A CN104157734B CN 104157734 B CN104157734 B CN 104157734B CN 201410392589 A CN201410392589 A CN 201410392589A CN 104157734 B CN104157734 B CN 104157734B
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- copper zinc
- zinc germanium
- sulfur
- thin film
- film solar
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- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 34
- 239000010409 thin film Substances 0.000 title claims abstract description 31
- 239000011669 selenium Substances 0.000 title claims abstract description 29
- -1 copper zinc germanium sulfur Chemical compound 0.000 title claims abstract description 28
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- LBSAHBJMEHMJTN-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Zn].[Zn] LBSAHBJMEHMJTN-UHFFFAOYSA-N 0.000 title claims abstract 13
- 239000002184 metal Substances 0.000 claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- 239000010408 film Substances 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 19
- 239000011701 zinc Substances 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 238000004544 sputter deposition Methods 0.000 claims abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010439 graphite Substances 0.000 claims abstract description 4
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 4
- 239000011521 glass Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 238000005987 sulfurization reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052802 copper Inorganic materials 0.000 abstract description 7
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052725 zinc Inorganic materials 0.000 abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000004223 radioprotective effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000005361 soda-lime glass Substances 0.000 abstract description 2
- 238000004073 vulcanization Methods 0.000 abstract 1
- MIUMTDPSDBCACC-UHFFFAOYSA-N copper zinc Chemical compound [Cu][Zn][Cu] MIUMTDPSDBCACC-UHFFFAOYSA-N 0.000 description 13
- QLMUUIHSNUYEAS-UHFFFAOYSA-N [Ge].[Cu].[Zn] Chemical compound [Ge].[Cu].[Zn] QLMUUIHSNUYEAS-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 235000007926 Craterellus fallax Nutrition 0.000 description 1
- 240000007175 Datura inoxia Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- AXXSTBHPDOVPLV-UHFFFAOYSA-N [Ge][Zn][Se] Chemical compound [Ge][Zn][Se] AXXSTBHPDOVPLV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000002233 thin-film X-ray diffraction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02614—Transformation of metal, e.g. oxidation, nitridation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses the preparation method of a kind of copper zinc germanium sulfur/copper zinc germanium selenium absorbing layer of thin film solar cell, on soda-lime glass substrate, first prepare CuZnGe metal initialization layer with radio-frequency magnetron sputter method, then carry out vulcanizing/selenization.In the present invention, magnetron sputtering uses simple substance copper target, simple substance zinc target and elemental Germanium target；Vulcanization reaction/selenylation reaction is carried out in vacuum chamber, layered metal film presoma and the sulfur powder/selenium powder of sputtering gained is positioned in graphite, carries out the process of after cure/rear selenizing, obtain copper zinc germanium sulfur/copper zinc germanium selenium absorbing layer of thin film solar cell.Absorbing layer of thin film solar cell prepared by the present invention has abundant raw material source, environmentally friendly, and radioprotective antidamping ability is strong, and good stability, preparation technology is simple, it is adaptable to the advantage of industrialized production.
Description
Technical field
The present invention relates to photoelectric functional material technology field, specifically refer to a kind of copper zinc germanium sulfur/copper zinc germanium selenium thin-film solar cells and inhale
Receive the preparation method of layer.
Background technology
Along with constantly deepening and environmental pollution day by day serious of energy crisis, solaode is reproducible as one, cleaning
, the free of contamination energy is increasingly by concern and the attention of whole world various countries.Copper-indium-galliun-selenium film solar cell is as thin film
The Typical Representative of solaode has obtained good development in the past twenty years, and its laboratory conversion efficiency has reached
20.8%, Industrial Efficiency is also stabilized in 14%～about 15%, but rare element In and Ga becomes its following large-scale production
One important bottleneck, the searching earth's crust is rich in element and replaces In and Ga to become the focus of research recently.And derived institute by CIGS
The Cu base quaternary compound Cu obtained2-II-IV-VI4(II=Zn, Cd；IV=Ge, Sn；VI=Se, S) quasiconductor receives extensively
Concern, also will be the most potential replacer becoming CIGS thin film solaode.Wherein, copper zinc germanium sulfur/copper zinc germanium selenium
Thin film is as the absorbed layer material of solaode, because it is direct band-gap semicondictor material, has higher absorptance, institute
Containing element relatively horn of plenty in the earth's crust, stability of material is good and of great interest.
At present, existing multiple method prepares copper zinc germanium sulfur/copper zinc germanium selenium thin film, mainly includes chemical spray pyrolysis method, coevaporation
Method, vacuum vapor deposition method and chemical vapor transportation method.Compared with these methods, magnetically controlled sputter method is advantageously in the big face of thin film
Amass preparation, and deposition process is stably more prone to control.Can be by the regulation sputtering sedimentation time, it is achieved regulation and control copper zinc germanium sulfur/copper
The component ratio of zinc germanium selenium thin film.
Summary of the invention
Present invention aim at providing the preparation method of a kind of copper zinc germanium sulfur/copper zinc germanium Se solar cell absorption layer material, it has
Contained element mineral resources is abundant and does not contains toxic component, and environmentally friendly, preparation technology is simple, it is adaptable to the advantage of industrialized production.
The present invention proposes the preparation method of a kind of copper zinc germanium sulfur/copper zinc germanium selenium absorbing layer of thin film solar cell, and its concrete technology walks
Rapid as follows:
1) magnetically controlled sputter method is used to deposit the first metal layer, the second metal level, the 3rd metal level the most on a glass substrate,
Metallic film presoma to stratiform；Wherein, described the first metal layer, the second metal level, the 3rd metal level are respectively Cu gold
Belong to layer, Zn metal level or Ge metal level any one；
Wherein, clean glass substrate: use acetone, ethanol and deionized water to carry out ultrasonic cleaning successively, clean be placed on from
Sub-water preserves, uses front nitrogen gun to dry up；
2) layered metallic film presoma and sulfur powder/selenium powder are placed in graphite, carry out vulcanizing/selenization, obtain
Described copper zinc germanium sulfur/copper zinc germanium selenium absorbing layer of thin film solar cell.
Wherein, described copper zinc germanium metallic film presoma uses Cu simple substance target, prepared by Zn simple substance target and Ge simple substance target.
Wherein, described step 1) in, deposit on a glass substrate the first metal layer, the second metal level, the 3rd metal level suitable
Sequence is variable.
Wherein, described step 1) in, the air pressure of sputtering is 0.2-2Pa, and power density is 1-6w/cm2。
Wherein, the preparation of the metallic film presoma of described stratiform is carried out under vacuum.Preferably, magnetron sputtering
Vacuum be 1 × 10-4Below Pa.
Wherein, the heat treatment of described sulfuration/selenizing is carried out under conditions of coarse vacuum has nitrogen protection.
Wherein, described step 2) in, the amount of sulfur powder/selenium powder used is 0.05-5g.
Wherein, the temperature of described sulfuration/selenization is 400 DEG C-580 DEG C, and heating rate is 10 DEG C/min-1000 DEG C/min, sulfur
Change/selenizing temperature retention time is 10-60min.
Wherein, described copper zinc germanium sulfur/copper zinc germanium selenium film thickness is 0.5-3 μm.
The invention allows for the copper zinc germanium sulfur/copper zinc germanium selenium absorbing layer of thin film solar cell prepared by aforementioned preparation process,
Its structure includes glass substrate, and is sequentially deposited at the first metal layer in described glass substrate, the second metal level, the 3rd gold medal
Belong to layer；Described the first metal layer, the second metal level, the 3rd metal level are respectively Cu metal level, Zn metal level, Ge metal level
Any one.
The present invention, on soda-lime glass substrate, first prepares CuZnGe metal initialization layer with magnetron sputtering method, then carries out vulcanizing/selenizing
Process.Have an advantage in that: 1, use simple substance target to carry out layering sputtering, can by the regulation sputtering sedimentation time, thus realize adjusting
Control the component ratio of described copper zinc germanium sulfur/copper zinc germanium selenium thin film.In the present invention, magnetron sputtering uses simple substance copper target, simple substance zinc target and
Elemental Germanium target.In prior art, elemental Germanium target seldom applies in magnetron sputtering.2, preparation process completes the most under vacuum conditions,
Good environmental basis is provided for preparing the thin film of high-quality.3, avoid the toxic gas such as use hydrogen sulfide/Selenium hydride., carry
The high safety of plated film.4, element mineral resources contained by prepared copper zinc germanium sulfur/copper zinc germanium selenium thin film is enriched.5, magnetic control is used to spatter
The method penetrated prepares copper zinc germanium sulfur/copper zinc germanium selenium thin film can obtain the thin film of high compactness and high evenness, and easily realizes industrialization
Produce.Absorbing layer of thin film solar cell prepared by the present invention has abundant raw material source, environmentally friendly, radioprotective antidamping
Ability is strong, and good stability, preparation technology is simple, it is adaptable to the advantage of industrialized production.
Accompanying drawing explanation
Fig. 1 is the structural representation of the copper zinc germanium S film solar battery obsorbing layer that the present invention prepares；
Fig. 2 is the XRD figure of the copper zinc germanium S film solar battery obsorbing layer that the present invention prepares；
Fig. 3 is the SEM figure of the copper zinc germanium S film solar battery obsorbing layer that the present invention prepares；
Fig. 4 is the pictorial diagram of the copper zinc germanium S film solar battery obsorbing layer that the present invention prepares.
Detailed description of the invention
In conjunction with specific examples below and accompanying drawing, the present invention is described in further detail, and the protection content of the present invention is not limited to
In following example.Under the spirit and scope without departing substantially from inventive concept, those skilled in the art it is conceivable that change and advantage
All it is included in the present invention, and with appending claims as protection domain.Implement the process of the present invention, condition, examination
Agent, experimental technique etc., outside the lower content mentioned specially, be universal knowledege and the common knowledge of this area, the present invention
Content is not particularly limited.
As it is shown in figure 1,1-glass substrate；2-the first metal layer；3-the second metal level；4-the 3rd metal level.
Embodiment:
1, clean glass substrate 1: use acetone, ethanol and deionized water to carry out ultrasonic cleaning successively, be positioned over after having cleaned
Deionized water preserves, uses front nitrogen gun to dry up.
2, in argon atmosphere, magnetically controlled sputter method is used to deposit copper simple substance layer 2, zinc simple substance layer 3 successively in glass substrate 1
With germanium simple substance layer 4, as shown in Figure 1；The time of sputtering is respectively 130s, 160s, 120s, the metallic film of available stratiform
Presoma, the preparation of layered metallic film presoma is to carry out under vacuum, and magnetron sputtered vacuum degree is 1 × 10-4Pa
Below.Wherein copper target, the splash-proofing sputtering process parameter of zinc target and germanium target is: sputtering power 80W, sputtering pressure 1.2Pa.
3, metallic film presoma and the sulfur powder that quality is 0.5g of stratiform are positioned in graphite, in coarse vacuum and there is nitrogen
Carrying out vulcanizing treatment under protection, temperature rises to 550 DEG C from room temperature, and heating rate is 25 DEG C/min, insulation 20～30min, so
Rear Temperature fall.Final available copper zinc germanium S film solar battery obsorbing layer, thickness is about 1 μm.
Copper zinc germanium sulfur thin film XRD figure as shown in Figure 2, its 2 θ is 29.119 °, 48.199 °, 48.635 ° and 57.305 °
Place all have diffraction maximum, correspond respectively to (112), (220) in standard card JCPDF25-0327 (custerite phase compound),
And (116)/(312) diffraction index (204).The SEM of copper zinc germanium S film solar battery obsorbing layer of the present invention schemes such as Fig. 3
Shown in, its material object is as shown in Figure 4.
In another embodiment, other operating conditions ibid, use magnetically controlled sputter method to deposit zinc list successively in glass substrate 1
Matter layer 2, copper simple substance layer 3 and germanium simple substance layer 4.It is also possible that use magnetically controlled sputter method deposit Germanium in glass substrate 1 successively
Simple substance layer 2, zinc simple substance layer 3 and copper simple substance layer 4.In the present invention, glass substrate 1 is sequentially depositing Cu metal level, Zn gold
Belong to layer, the order of Ge metal level can change, and is followed successively by Cu metal level 1-Zn metal level 2-Ge metal including sedimentary sequence
Layer 3, or Zn metal level 1-Cu metal level 2-Ge metal level 3, or Ge metal level 1-Cu metal level 2-Zn metal level
3, or Ge metal level 1-Zn metal level 2-Cu metal level 3, or other etc..
In other embodiments, ibid, wherein, the air pressure of sputtering is 0.2Pa to other operating conditions, it is also possible to for 2Pa；Power
Density is 1w/cm2, it is also possible to for 6w/cm2.The amount of sulfur powder/selenium powder used is 0.05g, it is also possible to for 5g.Described sulfuration/selenium
The temperature that change processes is 400 DEG C, it is also possible to be 580 DEG C；Heating rate is 10 DEG C/min, it is also possible to be 1000 DEG C/min；Sulfur
Change/selenizing temperature retention time is 10min, it is also possible to for 60min；The copper zinc germanium sulfur prepared/copper zinc germanium selenium thin-film solar cells
The thickness of absorbed layer is 0.5 μm, it is also possible to be 3 μm.
Claims (8)
1. the preparation method of copper zinc germanium sulfur/copper zinc germanium selenium absorbing layer of thin film solar cell, it is characterised in that described method is by such as
Lower step is carried out:
1) use magnetically controlled sputter method, the glass substrate (1) cleaned up deposits the first metal layer (2), the second metal
Layer (3), the 3rd metal level (4), obtain the metallic film presoma of stratiform；Wherein, described the first metal layer (2), second
Metal level (3), the 3rd metal level (4) be respectively Cu metal level, Zn metal level, Ge metal level any one；
2) layered metallic film presoma and sulfur powder/selenium powder are placed in graphite, carry out vulcanizing/selenization, obtain
Described copper zinc germanium sulfur/copper zinc germanium selenium absorbing layer of thin film solar cell；
Described step 1) in, using Cu simple substance target, metallic film presoma prepared by Zn simple substance target and Ge simple substance target；
Described step 1) in, the most described the first metal layer (2), the second metal level (3), the 3rd metal level (4)
Sedimentary sequence variable；
Described sulfuration/selenization is carried out under conditions of coarse vacuum has nitrogen protection.
2. the preparation method of copper zinc germanium sulfur/copper zinc germanium selenium absorbing layer of thin film solar cell as claimed in claim 1, it is characterised in that
Described step 1) in, the air pressure of sputtering is 0.2-2Pa, and power density is 1-6w/cm2。
3. the preparation method of copper zinc germanium sulfur/copper zinc germanium selenium absorbing layer of thin film solar cell as claimed in claim 1, it is characterised in that
Described step 1) in, the preparation of the metallic film presoma of stratiform is carried out under vacuum.
4. the preparation method of copper zinc germanium sulfur/copper zinc germanium selenium absorbing layer of thin film solar cell as claimed in claim 3, it is characterised in that
The vacuum of described magnetron sputtering is 1 × 10-4Below Pa.
5. the preparation method of copper zinc germanium sulfur/copper zinc germanium selenium absorbing layer of thin film solar cell as claimed in claim 1, it is characterised in that
Described step 2) in, the amount of sulfur powder/selenium powder used is 0.05-5g.
6. the preparation method of copper zinc germanium sulfur/copper zinc germanium selenium absorbing layer of thin film solar cell as claimed in claim 1, it is characterised in that
The temperature of described sulfuration/selenization is 400 DEG C-580 DEG C, and heating rate is 10 DEG C/min-1000 DEG C/min, and sulfuration/selenizing is incubated
Time is 10-60min.
7. the preparation method of copper zinc germanium sulfur/copper zinc germanium selenium absorbing layer of thin film solar cell as claimed in claim 1, it is characterised in that
Described copper zinc germanium sulfur/copper zinc germanium selenium film thickness is 0.5-3 μm.
8. copper zinc germanium sulfur/copper zinc germanium selenium thin-film solar cells suction that the preparation method as described in any one of claim 1-7 obtains
Receive layer.
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| CN201410392589.4A CN104157734B (en) | 2014-08-11 | 2014-08-11 | A kind of preparation method of copper zinc germanium sulfur/copper zinc germanium selenium absorbing layer of thin film solar cell |
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| CN104157734A CN104157734A (en) | 2014-11-19 |
| CN104157734B true CN104157734B (en) | 2016-09-14 |
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| CN1547239A (en) * | 2003-12-05 | 2004-11-17 | 南开大学 | Method for preparing selenide or sulfide semiconductor film material of copper-indium-gallium |
| CN101805890A (en) * | 2009-12-14 | 2010-08-18 | 中南大学 | Method for in-situ growth of Cu2ZnSnS4 photovoltaic thin film |
| CN103107243A (en) * | 2013-02-03 | 2013-05-15 | 电子科技大学 | Copper zinc tin sulfur thin film preparation method with doping process adopted |
| CN103165748A (en) * | 2013-02-28 | 2013-06-19 | 宁波大学 | Method of preparing copper-zinc tin-sulphur solar cell absorbed layer thin film |
| CN103762257A (en) * | 2014-01-17 | 2014-04-30 | 华东师范大学 | Method for manufacturing copper-zinc-tin-sulfide absorbing layer thin film and copper-zinc-tin-sulfide solar cell |
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| US20140113403A1 (en) * | 2012-08-27 | 2014-04-24 | Intermolecular Inc. | High efficiency CZTSe by a two-step approach |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1547239A (en) * | 2003-12-05 | 2004-11-17 | 南开大学 | Method for preparing selenide or sulfide semiconductor film material of copper-indium-gallium |
| CN101805890A (en) * | 2009-12-14 | 2010-08-18 | 中南大学 | Method for in-situ growth of Cu2ZnSnS4 photovoltaic thin film |
| CN103107243A (en) * | 2013-02-03 | 2013-05-15 | 电子科技大学 | Copper zinc tin sulfur thin film preparation method with doping process adopted |
| CN103165748A (en) * | 2013-02-28 | 2013-06-19 | 宁波大学 | Method of preparing copper-zinc tin-sulphur solar cell absorbed layer thin film |
| CN103762257A (en) * | 2014-01-17 | 2014-04-30 | 华东师范大学 | Method for manufacturing copper-zinc-tin-sulfide absorbing layer thin film and copper-zinc-tin-sulfide solar cell |
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