CN108123000A - A kind of nano-rod shaped antimony selenide solar cell and preparation method thereof - Google Patents
A kind of nano-rod shaped antimony selenide solar cell and preparation method thereof Download PDFInfo
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- CN108123000A CN108123000A CN201711293672.6A CN201711293672A CN108123000A CN 108123000 A CN108123000 A CN 108123000A CN 201711293672 A CN201711293672 A CN 201711293672A CN 108123000 A CN108123000 A CN 108123000A
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- antimony selenide
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- OQRNKLRIQBVZHK-UHFFFAOYSA-N selanylideneantimony Chemical compound [Sb]=[Se] OQRNKLRIQBVZHK-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000002073 nanorod Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 53
- 239000011733 molybdenum Substances 0.000 claims abstract description 53
- 238000000151 deposition Methods 0.000 claims abstract description 43
- 230000008021 deposition Effects 0.000 claims abstract description 32
- 238000000859 sublimation Methods 0.000 claims abstract description 22
- 230000008022 sublimation Effects 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 129
- 239000004065 semiconductor Substances 0.000 claims description 83
- 239000011787 zinc oxide Substances 0.000 claims description 65
- 239000000758 substrate Substances 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 39
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims description 32
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical group OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims description 30
- 229910052787 antimony Inorganic materials 0.000 claims description 17
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 238000002207 thermal evaporation Methods 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 238000007654 immersion Methods 0.000 claims description 6
- 239000011669 selenium Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- 239000005083 Zinc sulfide Substances 0.000 claims description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 4
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 3
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims 1
- 241001148715 Lamarckia aurea Species 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 203
- 239000011521 glass Substances 0.000 description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000010408 film Substances 0.000 description 13
- 238000001755 magnetron sputter deposition Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000013077 target material Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 239000012459 cleaning agent Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- GNZJTRGEKSBAAS-UHFFFAOYSA-N selanylideneantimony;selenium Chemical compound [Se].[Sb]=[Se].[Sb]=[Se] GNZJTRGEKSBAAS-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1876—Particular processes or apparatus for batch treatment of the devices
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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
- 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
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- Sustainable Energy (AREA)
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Abstract
The present invention provides a kind of nano-rod shaped antimony selenide solar cells and preparation method thereof.The structure of the nano-rod shaped antimony selenide solar cell includes being located at edge on molybdenum electrode layer（001）The nano-rod shaped antimony selenide layer of direction growth；The antimony selenide layer is formed by close spaced sublimation equipment fast deposition, and source used is antimony selenide powder.The present invention realizes for the first time to be had（001）The antimony selenide of highly oriented vertical nano bar-shape, the antimony selenide of the structure is highly beneficial for the transmission of electric current, can effectively improve the transmission electric current of solar cell, so as to effectively improve the photoelectric conversion efficiency of device.Using near space equipment sublimation apparatus prepare antimony selenide nanometer rods need not be very high vacuum degree and very high temperature, device simple, preparation process is simple, suitable for industrialized production, has broad application prospects.
Description
Technical field
The present invention relates to photoelectric material and technical field of thin-film solar, specifically a kind of nano-rod shaped selenizing
Antimony solar cell and preparation method thereof.
Background technology
Antimony selenide（Sb2Se3）It is a kind of binary compound material, for energy gap about in 1.2eV, absorption coefficient is general
105cm-1, it is a kind of ideal photovoltaic material, theoretical efficiency can reach 30%.On antimony selenide thin film solar cell device
For the research early start of part in 2014, the time of short 3 years, transfer efficiency has just reached 6.5%, in addition its abundant storage
Amount and environmentally safe characteristic, imply that antimony selenide will become a kind of very promising solar cell absorbed layer material
Material.
Existing patent ZL201610505363.X discloses a kind of high orientation selenizing Sb film and preparation method thereof, adopts
Good edge has been obtained with selenization is carried out to metallic antimony thin film<002>The film of the antimony selenide chain composition of direction growth.It is existing
Have and a kind of p-i-n types antimony selenide solar cell, the structure of the solar cell are disclosed in patent application document CN106898662A
It is top electrode layer, p-type antimony selenide semiconductor layer, intrinsic semiconductor i types layer, n-type antimony selenide semiconductor layer and bottom electrode layer, this
The solar cell of kind structure, on the one hand can reduce the lattice mismatch at pn interfaces, reduce the height brought by interface defect density height
Recombination rate；On the other hand, intrinsic semiconductor i type layers are inserted into homogeneity antimony selenide pn-junction, built is in intrinsic semiconductor i type layers
Extension beneficial to the separation for realizing photo-generated carrier charge, increases the collection efficiency of photo-generated carrier, improves solar cell
Performance.
The photoelectricity and material character of antimony selenide are excellent, are the very potential solar cell materials of a new generation, using selenizing
Antimony is expected to prepare inexpensive, efficient solar cell, this is with important scientific value and application prospect, therefore either
From the preparation still exploration to device architecture, performance optimization etc. of antimony selenide material, all people is worth to go to study.
The content of the invention
An object of the present invention is just to provide a kind of nano-rod shaped antimony selenide solar cell, the antimony selenide layer in the battery
For nano-rod shaped structure, and have（001）Direction is preferably orientated, and can obtain highly efficient electric current, so as to improve battery
Efficiency.
The second object of the present invention is just to provide a kind of preparation method of above-mentioned nano-rod shaped antimony selenide solar cell.
What an object of the present invention was realized in：A kind of nano-rod shaped antimony selenide solar cell, including being located at molybdenum electricity
The upper edge of pole layer（001）The nano-rod shaped antimony selenide layer of direction growth；The antimony selenide layer is quick by close spaced sublimation equipment
It deposits and is formed.The thickness of the antimony selenide layer is 400nm-2000nm.
The molybdenum electrode layer is located on substrate, and substrate can be glass；It is sequentially provided with buffering on the antimony selenide layer
Layer, Window layer and top electrode layer.The buffer layer is cadmium sulfide, cadmium oxide, zinc sulphide, indium sulfide, zinc oxide and titanium dioxide
In one or more.The Window layer includes the indium tin oxide layer of the zinc oxide resistive formation of lower floor and the low-resistance on upper strata, mixes aluminium
Zinc oxide film or boron-doping zinc oxide film.The structure of the solar cell formed is bottom liner type structure, and concrete structure can be：
glass/Mo/Sb2Se3Nanometer rods/CdS/ZnO/AZO/Ag.AZO can be replaced ITO or BZO, Ag top electrode layer can be replaced Au
Or Al top electrode layers.
The present invention forms antimony selenide nano bar-shape on molybdenum electrode layer using close spaced sublimation equipment by fast deposition
Structure, realize has for the first time（001）The antimony selenide of highly oriented vertical nano bar-shape, the antimony selenide of the structure is for electric current
Transmission it is highly beneficial, the transmission electric current of solar cell can be effectively improved, so as to effectively improve device opto-electronic conversion effect
Rate.
The second object of the present invention is to what is be achieved in that：A kind of preparation method of nano-rod shaped antimony selenide solar cell, bag
Include following steps：
A, substrate is cleaned；
B, molybdenum electrode layer is deposited over the substrate using magnetically controlled sputter method；The thickness of the molybdenum electrode layer is 700nm-
1000nm；
C, antimony selenide layer is quickly formed by close spaced sublimation technique on the molybdenum electrode layer using close spaced sublimation equipment；Institute
Antimony selenide layer is stated as edge（001）The nano-rod shaped structure of direction growth, thickness 400nm-2000nm；
D, cadmium sulfide layer is deposited on the antimony selenide layer by immersion method；
E, using magnetically controlled sputter method on the cadmium sulfide layer depositing zinc oxide semiconductor layer；
F, ITO layer, Al-Doped ZnO layer or boron-doping oxidation are deposited on the zinc oxide semiconductor layer using magnetically controlled sputter method
Zinc layers；
G, top electrode layer is deposited on the ITO layer, Al-Doped ZnO layer or boron-doping zinc oxide film using thermal evaporation process.Top electricity
Pole layer can be Au, Ag or Al top electrode layer.
When antimony selenide layer is prepared in step c, sedimentary origin used is antimony selenide powder（Antimony selenide powder can pass through antimony selenide
Particulate abrasive forms）Or selenizing antimony particle, the size of sedimentary origin is 10 μm of -10mm.The temperature of sedimentary origin is controlled at 300 DEG C -700
DEG C, substrate temperature is controlled at 200 DEG C -500 DEG C.Air pressure in close spaced sublimation equipment is maintained at below 10Pa.
Antimony selenide nanometer rods are obtained using close spaced sublimation technique present invention firstly provides a kind of, and applied to antimony selenide
In solar cell, and apply in the solar cell absorbed layer of bottom liner structure.Compared with current battery, the present invention can be effective
The short circuit current flow of antimony selenide solar cell is improved, and then improves the transfer efficiency of antimony selenide solar cell.Meanwhile use near space
Equipment sublimation apparatus prepare antimony selenide nanometer rods need not be very high vacuum degree and very high temperature, device simple, prepare
Process is simple, suitable for industrialized production, has broad application prospects.
Description of the drawings
Fig. 1 is the structure diagram of the solar cell prepared by the embodiment of the present invention 1.
Fig. 2 is the XRD diagram of the solar cell prepared by the embodiment of the present invention 1.
Fig. 3 is the SEM figures of the solar cell prepared by the embodiment of the present invention 1.
Fig. 4 is the IV figures of the solar cell prepared by the embodiment of the present invention 1.
Fig. 5 is the EQE figures of the solar cell prepared by the embodiment of the present invention 1.
Specific embodiment
Example below is for being further described the present invention, but embodiment is not the present invention any type of limit
It is fixed.
Embodiment 1
As shown in Figure 1, the structure for the bottom liner type solar cell that the present embodiment is provided is glass substrate successively from top to bottom
（Glass）, molybdenum electrode layer（Mo）, antimony selenide layer（Sb2Se3）, cadmium sulfide layer（CdS）, zinc oxide film（i-ZnO）, mix the oxidation of aluminium
Zinc layers（Azo）, silver-colored top electrode layer（Ag）.
The preparation process of the solar cell is as follows：
（1）Clean substrate
Substrate is used glass as, glass is impregnated into 12h in electronic cleaning agent solution first, is then taken out, with a large amount of
Deionized water rinsing is clean, is finally dried up with nitrogen.
（2）Deposit molybdenum electrode layer
Molybdenum electrode layer is deposited using magnetron sputtering technique：The glass substrate cleaned up is fixed on specimen holder, is put into vacuum
In chamber, chamber vacuum degree reaches 5 × 10-4It is 4N using purity after Pa（Purity is 99.99%）Molybdenum target material, be filled with certain
Inert gas, in 0.1-10 Pa（It is 0.6Pa in the present embodiment）It is sputtered under pressure, obtains thickness on a glass substrate
For the molybdenum electrode layer of 900nm.The thickness that molybdenum electrode layer is prepared in other embodiment can be 700-1000 nm.
（3）Depositing p-type antimony selenide semiconductor layer
The equipment used in this step is close spaced sublimation equipment, and p is deposited using thermal evaporation techniques in close spaced sublimation equipment
Type antimony selenide semiconductor layer：The sample of above-mentioned glass substrate/molybdenum electrode layer is fixed on specimen holder, close spaced sublimation is put into and sets
In standby vacuum chamber, after chamber vacuum degree reaches below 10Pa, the antimony selenide powder that purity is 4N is utilized（As sedimentary origin,
Or sublimation source）, 2min is evaporated according to pre-set temperature, the temperature of sedimentary origin is kept during evaporation under this pressure
Between 300 DEG C -700 DEG C（Sedimentary origin rises to 300 DEG C by room temperature needs about 2min, and rising to 500 DEG C by 300 DEG C needs 2min left
It is right）, substrate temperature is maintained between 200 DEG C -500 DEG C（Substrate rises to 300 DEG C of need about 2min by room temperature）, on molybdenum electrode layer
The p-type antimony selenide semiconductor layer of fast deposition 1500nm thickness.The thickness of p-type antimony selenide semiconductor layer can be in other embodiment
400-2000nm.P-type antimony selenide semiconductor layer is as absorbed layer and existing in solar cell.
XRD tests are carried out to prepared p-type antimony selenide semiconductor layer, acquired results are shown in Fig. 2.P-type antimony selenide is partly led
Body layer carries out SEM tests, and acquired results are shown in Fig. 3.As seen from Figure 3, the antimony selenide layer prepared by the present invention is in erected shape
Nanometer stick array structure, and the antimony selenide layer edge（001）Direction has the preferable orientation of growth.
（4）Deposit cadmium sulfide n-type semiconductor layer
Cadmium sulfide n-type semiconductor layer is deposited using immersion method：By above-mentioned glass substrate/molybdenum electrode layer/p-type antimony selenide semiconductor layer
Sample be fixed on specimen holder, in vulcanization cadmium solution between 50-90 DEG C（The present embodiment is 60 DEG C）Deposit 10-20min（This
It is about 14min in embodiment）, sample is taken out, then is dried up with nitrogen using deionized water rinsing for a period of time.Cadmium sulfide n-type half
Conductor layer is buffer layer.Buffer layer can also be cdo layer, zinc sulfide layer, vulcanization indium layer, zinc oxide in other embodiment
Layer or titanium dioxide layer are a variety of in cadmium sulfide, cadmium oxide, zinc sulphide, indium sulfide, zinc oxide and titanium dioxide.
（5）Deposition intrinsic ZnO semiconductor layers
Using magnetron sputtering technique deposition intrinsic ZnO semiconductor layers：Above-mentioned glass substrate/molybdenum electrode layer/p-type antimony selenide is partly led
The sample of body layer/cadmium sulfide n-type semiconductor layer is fixed on specimen holder, is put into vacuum chamber, and chamber vacuum degree reaches 5 ×
10-4After Pa, using the intrinsic ZnO target material that purity is 4N, in 0.1-10 Pa（Experiment uses about 0.33Pa）It is carried out under pressure
Sputtering, deposition thickness is the intrinsic ZnO semiconductor layers of 90 nm thickness in cadmium sulfide n-type semiconductor layer.
（6）Deposition mixes the zinc oxide n-type semiconductor layer of aluminium
The zinc oxide n-type semiconductor layer of aluminium is mixed using magnetron sputtering technique deposition：By above-mentioned glass substrate/molybdenum electrode layer/p-type selenium
The sample for changing antimony semiconductor layer/cadmium sulfide n-type semiconductor layer/intrinsic zinc oxide semiconductor layer is fixed on specimen holder, is put into true
In plenum chamber, chamber vacuum degree reaches 5 × 10-4After Pa, using the zinc oxide target for mixing aluminium that purity is 4N, in 0.1-10 Pa
（Experiment uses about 0.15Pa）It is sputtered under pressure, deposition thickness is thick for 400nm on intrinsic zinc oxide semiconductor layer
The zinc oxide n-type semiconductor layer for mixing aluminium.
Step（5）The intrinsic ZnO semiconductor layers formed be resistive formation, step（6）What is formed mixes the zinc oxide n-type of aluminium
Semiconductor layer is low resistivity layer, and both resistive formation and low resistivity layer collectively form Window layer.
（7）Deposit Ag top electrode layers
Using thermal evaporation techniques（Equipment used herein is common thermal evaporation apparatus）Deposit Ag top electrode layers：By step（6）It obtains
Sample be fixed on specimen holder, be put into vacuum chamber, chamber vacuum degree reaches 5 × 10-4It is 4N's using purity after Pa
Filamentary silver, 10-3It is evaporated under pressure, deposition thickness is the Ag top electrode layers of 200 nm on sample, is thus prepared for selenizing
The nano-rod shaped solar cell of antimony.IV and EQE tests are carried out to prepared solar cell, resulting structures are shown in Fig. 4 and Fig. 5.By Fig. 4
It can be seen that, the battery efficiency in the present invention has reached 6.35%, this is also photoelectric conversion efficiency pretty good at present.
Embodiment 2
The structure for the bottom liner type solar cell that the present embodiment is provided is followed successively by from the bottom to top：Glass substrate, molybdenum electrode layer, selenizing
Antimony layer, cadmium sulfide layer, zinc oxide film, the zinc oxide film for mixing aluminium, aluminium top electrode layer.
Specific preparation process is as follows：
（1）Clean substrate
Substrate is used glass as, glass is impregnated into 12h in electronic cleaning agent solution first, is then taken out, with a large amount of
Deionized water rinsing is clean, is finally dried up with nitrogen.
（2）Deposit molybdenum electrode layer
Molybdenum electrode layer is deposited using magnetron sputtering technique：The glass substrate cleaned up is fixed on specimen holder, is put into vacuum
In chamber, chamber vacuum degree reaches 5 × 10-4After Pa, using the molybdenum target material that purity is 4N, splashed under 0.1-10 Pa pressure
It penetrates, obtains the molybdenum electrode layer that thickness is 700-1000 nm on a glass substrate.
（3）Depositing p-type antimony selenide semiconductor layer
Using thermal evaporation techniques depositing p-type antimony selenide semiconductor layer：The sample of above-mentioned glass substrate/molybdenum electrode layer is fixed on sample
It on product frame, is put into the vacuum chamber of close spaced sublimation equipment, is 4N's using purity after chamber vacuum degree reaches below 10Pa
Antimony selenide powder（It is formed by antimony selenide particulate abrasive）Or selenizing antimony particle, wherein antimony selenide powder or the ruler of selenizing antimony particle
Very little is 10 μm of -10mm, according to pre-set temperature under this pressure（It is 300 DEG C -700 DEG C to deposit source temperature, underlayer temperature
For 200 DEG C -500 DEG C）1-3min is evaporated, the p-type antimony selenide semiconductor of fast deposition 400-2000nm on molybdenum electrode layer
Layer.The p-type antimony selenide semiconductor layer formed is edge（001）The nanometer stick array structure of direction growth.
（4）Deposit cadmium sulfide n-type semiconductor layer
Cadmium sulfide n-type semiconductor layer is deposited using immersion method：By above-mentioned glass substrate/molybdenum electrode layer/p-type antimony selenide semiconductor layer
Sample be fixed on specimen holder, 10-20min is deposited between 50-90 °C in vulcanization cadmium solution, takes out sample, using go from
Sub- water rinses a period of time, then is dried up with nitrogen.
（5）Deposition intrinsic ZnO semiconductor layers
Using magnetron sputtering technique deposition intrinsic ZnO semiconductor layers：Above-mentioned glass substrate/molybdenum electrode layer/p-type antimony selenide is partly led
The sample of body layer/cadmium sulfide n-type semiconductor layer is fixed on specimen holder, is put into vacuum chamber, and chamber vacuum degree reaches 5 ×
10-4 After Pa, using the intrinsic ZnO target material that purity is 4N, sputtered under 0.1-10 Pa pressure, partly led in cadmium sulfide n-type
Deposition thickness is the intrinsic ZnO semiconductor layers of 80-100 nm on body layer.
（6）Deposition mixes the zinc oxide n-type semiconductor layer of aluminium
The zinc oxide n-type semiconductor layer of aluminium is mixed using magnetron sputtering technique deposition：By above-mentioned glass substrate/molybdenum electrode layer/p-type selenium
The sample for changing antimony semiconductor layer/cadmium sulfide n-type semiconductor layer/intrinsic zinc oxide semiconductor layer is fixed on specimen holder, is put into true
In plenum chamber, chamber vacuum degree reaches 5 × 10-4 After Pa, using the zinc oxide target for mixing aluminium that purity is 4N, in 0.1-10 Pa
It is sputtered under pressure, deposition thickness is that the zinc oxide n-type for mixing aluminium of 300-500nm is partly led on intrinsic zinc oxide semiconductor layer
Body layer.
（7）Depositing Al top electrode layer
Using thermal evaporation techniques（Equipment used herein is common thermal evaporation apparatus）Depositing Al top electrode layer：By step（6）It obtains
Sample be fixed on specimen holder, be put into vacuum chamber, chamber vacuum degree reaches 5 × 10-4It is 4N's using purity after Pa
Aluminium wire, 10-4-10-2It is evaporated under Pa pressure, deposition thickness is the Al top electrode layers of 200 nm on sample, is thus made
Obtain the nano-rod shaped solar cell of antimony selenide.
Embodiment 3
The structure for the bottom liner type solar cell that the present embodiment is provided is followed successively by from the bottom to top：Glass substrate, molybdenum electrode layer, selenizing
Antimony layer, cadmium sulfide layer, zinc oxide film, indium tin oxide transparent conductive semiconductor film layer, silver-colored top electrode layer.
Specific preparation process is as follows：
（1）Clean substrate
Substrate is used glass as, glass is impregnated into 12h in electronic cleaning agent solution first, is then taken out, with a large amount of
Deionized water rinsing is clean, is finally dried up with nitrogen.
（2）Deposit molybdenum electrode layer
Molybdenum electrode layer is deposited using magnetron sputtering technique：The glass substrate cleaned up is fixed on specimen holder, is put into vacuum
In chamber, chamber vacuum degree reaches 5 × 10-4After Pa, using the molybdenum target material that purity is 4N, splashed under 0.1-10 Pa pressure
It penetrates, obtains the molybdenum electrode layer that thickness is 700-1000 nm on a glass substrate.
（3）Depositing p-type antimony selenide semiconductor layer
Using thermal evaporation techniques depositing p-type antimony selenide semiconductor layer：The sample of above-mentioned glass substrate/molybdenum electrode layer is fixed on sample
It on product frame, is put into the vacuum chamber of close spaced sublimation equipment, is 4N's using purity after chamber vacuum degree reaches below 10Pa
Antimony selenide powder or selenizing antimony particle, according to pre-set temperature under this pressure（It is 300 DEG C -700 to deposit source temperature
DEG C, underlayer temperature is 200 DEG C -500 DEG C）1-3min is evaporated, the p-type selenium of fast deposition 400-2000nm on molybdenum electrode layer
Change antimony semiconductor layer.The p-type antimony selenide semiconductor layer formed is edge（001）The nano bar-shape structure of direction growth.
（4）Deposit cadmium sulfide n-type semiconductor layer
Cadmium sulfide n-type semiconductor layer is deposited using immersion method：By above-mentioned glass substrate/molybdenum electrode layer/p-type antimony selenide semiconductor layer
Sample be fixed on specimen holder, 10-20min is deposited between 50-90 °C in vulcanization cadmium solution, takes out sample, using go from
Sub- water rinses a period of time, then is dried up with nitrogen.
（5）Deposition intrinsic ZnO semiconductor layers
Using magnetron sputtering technique deposition intrinsic ZnO semiconductor layers：Above-mentioned glass substrate/molybdenum electrode layer/p-type antimony selenide is partly led
The sample of body layer/cadmium sulfide n-type semiconductor layer is fixed on specimen holder, is put into vacuum chamber, and chamber vacuum degree reaches 5 ×
10-4 After Pa, using the intrinsic ZnO target material that purity is 4N, sputtered under 0.1-10 Pa pressure, partly led in p-type antimony selenide
Deposition thickness is the intrinsic ZnO semiconductor layers of 80-100 nm on body layer.
（6）Deposit ITO nesa coating layer
ITO nesa coating layer is deposited using magnetron sputtering technique（Indium tin oxide transparent conductive semiconductor film）：By above-mentioned glass
The sample of glass substrate/molybdenum electrode layer/p-type antimony selenide semiconductor layer/cadmium sulfide n-type semiconductor layer/intrinsic zinc oxide semiconductor layer
It is fixed on specimen holder, is put into vacuum chamber, chamber vacuum degree reaches 5 × 10-4 After Pa, the ITO that purity is 4N is utilized（Oxygen
Change indium tin）Target is sputtered under 0.1-10 Pa pressure, and thickness is obtained on intrinsic zinc oxide semiconductor layer as 300-400
The ITO nesa coating layer of nm.
（7）Deposit Ag top electrode layers
Using thermal evaporation techniques（Equipment used herein is common thermal evaporation apparatus）Deposit Ag top electrode layers：By step（6）It obtains
Sample be fixed on specimen holder, be put into vacuum chamber, chamber vacuum degree reaches 5 × 10-4It is 4N's using purity after Pa
Filamentary silver, 10-4-10-2 It is evaporated under Pa pressure, deposition thickness is the Ag top electrode layers of 200 nm on sample, is thus made
The nano-rod shaped solar cell of antimony selenide.
Embodiment 4
The structure for the bottom liner type solar cell that the present embodiment is provided is followed successively by from the bottom to top：Glass substrate, molybdenum electrode layer, selenizing
Antimony layer, cadmium sulfide layer, zinc oxide film, the zinc oxide film of boron-doping, silver-colored top electrode layer.
Specific preparation process is as follows：
（1）Clean substrate
Substrate is used glass as, glass is impregnated into 12h in electronic cleaning agent solution first, is then taken out, with a large amount of
Deionized water rinsing is clean, is finally dried up with nitrogen.
（2）Deposit molybdenum electrode layer
Molybdenum electrode layer is deposited using magnetron sputtering technique：The glass substrate cleaned up is fixed on specimen holder, is put into vacuum
In chamber, chamber vacuum degree reaches 5 × 10-4After Pa, using the molybdenum target material that purity is 4N, splashed under 0.1-10 Pa pressure
It penetrates, obtains the molybdenum electrode layer that thickness is 700-1000 nm on a glass substrate.
（3）Depositing p-type antimony selenide semiconductor layer
Using thermal evaporation techniques depositing p-type antimony selenide semiconductor layer：The sample of above-mentioned glass substrate/molybdenum electrode layer is fixed on sample
It on product frame, is put into the vacuum chamber of close spaced sublimation equipment, is 4N's using purity after chamber vacuum degree reaches below 10Pa
Antimony selenide powder or selenizing antimony particle, according to pre-set temperature under this pressure（It is 300 DEG C -700 to deposit source temperature
DEG C, underlayer temperature is 200 DEG C -500 DEG C）1-3min is evaporated, the p-type antimony selenide of 400-2000nm is deposited on molybdenum electrode layer
Semiconductor layer.The p-type antimony selenide semiconductor layer formed is edge（001）The nano bar-shape structure of direction growth.
（4）Deposit cadmium sulfide n-type semiconductor layer
Cadmium sulfide n-type semiconductor layer is deposited using immersion method：By above-mentioned glass substrate/molybdenum electrode layer //p-type antimony selenide semiconductor
The sample of layer is fixed on specimen holder, and 10-20mins is deposited between 50-90 °C in vulcanization cadmium solution, takes out sample, using going
Ionized water rinses a period of time, then is dried up with nitrogen.
（5）Deposition intrinsic ZnO semiconductor layers
Using magnetron sputtering technique deposition intrinsic ZnO semiconductor layers：Above-mentioned glass substrate/molybdenum electrode layer/p-type antimony selenide is partly led
The sample of body layer/cadmium sulfide n-type semiconductor layer is fixed on specimen holder, is put into vacuum chamber, and chamber vacuum degree reaches 5 ×
10-4After Pa, using the intrinsic ZnO target material that purity is 4N, sputtered under 0.1-10 Pa pressure, partly led in p-type antimony selenide
Deposition thickness is the intrinsic ZnO semiconductor layers of 80-100 nm on body layer.
（6）Deposit the zinc oxide n-type semiconductor layer of boron-doping
Using the zinc oxide n-type semiconductor layer of magnetron sputtering technique deposition boron-doping（BZO）, by above-mentioned glass substrate/molybdenum electrode layer/
The sample of p-type antimony selenide semiconductor layer/cadmium sulfide n-type semiconductor layer/intrinsic zinc oxide semiconductor layer is fixed on specimen holder, is put
In vacuum chamber, chamber vacuum degree reaches 5 × 10-4After Pa, using the zinc oxide target for the boron-doping that purity is 4N, in 0.1-10
It is sputtered under Pa pressure, deposition thickness is the zinc oxide n-type half of the boron-doping of 300-400nm on intrinsic zinc oxide semiconductor layer
Conductor layer.
（7）Deposit Ag top electrode layers
Using thermal evaporation techniques（Equipment used herein is common thermal evaporation apparatus）Deposit Ag top electrode layers：By step（6）It obtains
Sample be fixed on specimen holder, be put into vacuum chamber, chamber vacuum degree reaches 5 × 10-4 It is 4N's using purity after Pa
Filamentary silver, 10-4-10-2It is evaporated under Pa pressure, deposition thickness is the Ag top electrode layers of 200 nm on sample, is thus made
Obtain the nano-rod shaped solar cell of antimony selenide.
Antimony selenide powder is gone out a kind of nano bar-shape structure by the present invention by close spaced sublimation technique fast deposition, and is applied
In solar cell bottom liner structure, good current transmission characteristic is obtained with this.The present invention is used with fast deposition characteristic
Close spaced sublimation equipment prepares antimony selenide nanorod structure, can obtain preferably（001）The antimony selenide nanorod structure of orientation, to obtain
Highly efficient electric current is taken to provide basis, therefore one is provided to obtain highly efficient antimony selenide solar cell by the present invention
The simple and fast preparation method of kind.
Claims (10)
1. a kind of nano-rod shaped antimony selenide solar cell, it is characterized in that, including being located at edge on molybdenum electrode layer（001）Direction growth
Nano-rod shaped antimony selenide layer；The antimony selenide layer is formed by close spaced sublimation equipment fast deposition.
2. nano-rod shaped antimony selenide solar cell according to claim 1, it is characterized in that, the molybdenum electrode layer is located at substrate
On；It is sequentially provided with buffer layer, Window layer and top electrode layer on the antimony selenide layer.
3. nano-rod shaped antimony selenide solar cell according to claim 2, it is characterized in that, the buffer layer is cadmium sulfide,
One or more in cadmium oxide, zinc sulphide, indium sulfide, zinc oxide and titanium dioxide.
4. nano-rod shaped antimony selenide solar cell according to claim 2, it is characterized in that, the Window layer includes lower floor
Indium tin oxide layer, Al-Doped ZnO layer or the boron-doping zinc oxide film of the low-resistance on zinc oxide resistive formation and upper strata.
5. nano-rod shaped antimony selenide solar cell according to claim 1, it is characterized in that, the thickness of the antimony selenide layer is
400nm-2000nm。
6. a kind of preparation method of nano-rod shaped antimony selenide solar cell, it is characterized in that, include the following steps：
A, substrate is cleaned；
B, molybdenum electrode layer is deposited over the substrate using magnetically controlled sputter method；The thickness of the molybdenum electrode layer is 700nm-
1000nm；
C, antimony selenide layer is formed by close spaced sublimation technique on the molybdenum electrode layer using close spaced sublimation equipment；The selenium
It is edge to change antimony layer（001）The nano-rod shaped structure of direction growth, thickness 400nm-2000nm；
D, cadmium sulfide layer is deposited on the antimony selenide layer by immersion method；
E, using magnetically controlled sputter method on the cadmium sulfide layer depositing zinc oxide semiconductor layer；
F, ITO layer, Al-Doped ZnO layer or boron-doping oxidation are deposited on the zinc oxide semiconductor layer using magnetically controlled sputter method
Zinc layers；
G, top electrode layer is deposited on the ITO layer, Al-Doped ZnO layer or boron-doping zinc oxide film using thermal evaporation process.
7. the preparation method of nano-rod shaped antimony selenide solar cell according to claim 6, it is characterized in that, it is made in step c
During standby antimony selenide layer, sedimentary origin used is antimony selenide powder or selenizing antimony particle, and the wherein size of powder or particle is 10 μ
m-10mm。
8. the preparation method of nano-rod shaped antimony selenide solar cell according to claim 7, it is characterized in that, it is made in step c
During standby antimony selenide layer, at 300 DEG C -700 DEG C, substrate temperature is controlled at 200 DEG C -500 DEG C for the temperature control of sedimentary origin.
9. the preparation method of nano-rod shaped antimony selenide solar cell according to claim 6, it is characterized in that, it is made in step c
During standby antimony selenide layer, the air pressure in close spaced sublimation equipment is maintained at below 10Pa.
10. the preparation method of nano-rod shaped antimony selenide solar cell according to claim 6, it is characterized in that, institute in step g
The top electrode layer of formation is goldentop electrode layer, silver-colored top electrode layer or aluminium top electrode layer.
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