CN106129143B - A kind of high orientation selenizing Sb film and preparation method thereof - Google Patents

A kind of high orientation selenizing Sb film and preparation method thereof Download PDF

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CN106129143B
CN106129143B CN201610505363.XA CN201610505363A CN106129143B CN 106129143 B CN106129143 B CN 106129143B CN 201610505363 A CN201610505363 A CN 201610505363A CN 106129143 B CN106129143 B CN 106129143B
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film
selenizing
antimony
high orientation
preparation
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CN106129143A (en
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唐江
冷美英
何粟
何一粟
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WUHAN INDUSTRIAL INSTITUTE FOR OPTOELECTRONICS Co Ltd
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    • H—ELECTRICITY
    • H01—BASIC ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00—Semiconductor devices sensitive to infra-red 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 infra-red 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 infra-red 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
    • H—ELECTRICITY
    • H01—BASIC ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00—Semiconductor devices sensitive to infra-red 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 infra-red radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/0445—PV modules or arrays of single PV cells including thin film solar cells, e.g. single thin film a-Si, CIS or CdTe solar cells
    • H—ELECTRICITY
    • H01—BASIC ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00—Semiconductor devices sensitive to infra-red 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
    • 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 belongs to photoelectric material and thin-film solar cells preparation field, a kind of high orientation selenizing Sb film and preparation method thereof is disclosed, good selenizing Sb film is especially orientated, the high orientation selenizing Sb film is one-dimensional chain material, and good orientation is edge<002>The film of the antimony selenide chain composition of direction growth.The preparation method, specially two steps, including：Antimony metal film is prepared using thermal evaporation or other method, selenium is then carried out（Sulphur）Change the method for processing.Method in the present invention, can obtain the selenizing Sb film being well orientated, and be hopeful to obtain more efficient antimony selenide thin-film solar cells, and simple and easy to apply, with low cost.

Description

A kind of high orientation selenizing Sb film and preparation method thereof
Technical field
The invention belongs to photoelectric material and thin-film solar cells preparation field, and in particular to a kind of high orientation antimony selenide Film and preparation method thereof.
Background technology
Antimony selenide（Sb2Se3）It is that a kind of very promising film photovoltaic absorbs layer material, it has suitable energy gap 1 ~ 1.2eV, big absorptivity（Shortwave absorptivity>105 cm-1）, raw material are nontoxic and rich reserves, but several up to date Year antimony selenide thin-film solar cells just begins with international literature and recorded and report.
Antimony selenide is the special strip material of comparison, therefore the mobility in its all directions has significant difference, and is moved Shifting rate decides diffusion length to influence electric current again.Solar battery efficiency N=Voc*Jsc*FF, Jsc therein are electric current Density, is to influence one of key factor of battery conversion efficiency.Patent document 1（CN 105324863 A）Describe a kind of film The manufacture method of solar cell and thin-film solar cells, the purpose of the invention be there is provided a kind of photoelectric transformation efficiency it is high, The especially manufacture method of the high thin-film solar cells of open-circuit voltage and thin-film solar cells.The thin film solar of the invention Battery there is negative electrode, anode, the photoelectric conversion layer being configured between the negative electrode and the anode and be configured at the negative electrode with Electron transfer layer between the photoelectric conversion layer, the photoelectric conversion layer has containing organic semi-conductor position and contained The position of antimony trisulfide and/or antimony selenide, between the photoelectric conversion layer and the electron transfer layer, is configured with containing rare earth The layer of dvielement and/or the race's element of the periodic table of elements the 2nd.But the technical scheme of the patent document 1 has the drawback that：Its Battery structure is extremely complex, antimony selenide effect wherein and indefinite and performance does not have significant change.
Patent document 2（CN 104638036 A）A kind of high photoresponse near infrared photodetector is described, its feature exists In：Concrete structure is transparent inert substrate/selenizing Sb film/electrode, and wherein selenizing Sb film is through selenization later Selenizing Sb film；The rear selenization is：Selenizing Sb film is made annealing treatment in selenium atmosphere, wherein：The selenium atmosphere The selenium steam partial pressure enclosed is 1~10000Pa, and annealing temperature is 150~400 DEG C, and processing time is 5~30min；Or One layer of selenium is deposited in antimony selenide film surface, is then made annealing treatment again, wherein：The thickness of the selenium of deposition be 1~ 500nm, annealing temperature is 150~400 DEG C, and annealing time is 10~60min.The high photoresponse near infrared light electricity of the invention The abundant raw materials of detector, cheap, technique is simple, economical, workable, and with high sensitivity.But this is special The problem of technical scheme of sharp document 2 is present be：The method is post-processing approach, compared with preparing the method for antimony selenide herein more Selenizing Sb film for complexity, and the method preparation can not possess favourable<002>Orientation.
The content of the invention
It is an object of the invention to the shortcoming for overcoming prior art, there is provided a kind of high orientation selenizing Sb film and its preparation Method, method of the invention, which can be prepared, to be orientated excellent selenizing Sb film to obtain high short-circuit current density.
It is thin that a further object of the present invention is that the shortcoming for overcoming prior art includes the high orientation antimony selenide there is provided one kind The solar cell of film.
In order to realize first purpose of the present invention, the present invention is adopted the following technical scheme that：
A kind of high orientation selenizing Sb film, it is characterised in that the selenizing Sb film is to use to enter metallic antimony thin film The selenizing Sb film that row selenization is well orientated, as edge<002>The film of the antimony selenide chain composition of direction growth.
A kind of preparation method of high orientation selenizing Sb film as described above, specific steps include：
The first step, metallic antimony thin film is prepared using thermal evaporation：The evaporation technology of the metallic antimony is that source temperature is 500 ~ 800 DEG C, substrate heating temperature is normal temperature ~ 200 DEG C, and evaporation time is 10 ~ 30min, and vacuum is 10-2 ~ 10- 4Pa；
Second step, selenization obtains selenizing Sb film after being carried out to metallic antimony thin film, and the rear selenization is：By gold Category Sb film is made annealing treatment in selenium atmosphere, wherein：The selenium steam partial pressure of the selenium atmosphere is 1~10000Pa, annealing temperature Spend for 300~450 DEG C, processing time is 12~30min.
The a further object of the present invention is to provide a kind of antimony selenide thin-film solar cells, it is characterised in that including above-mentioned The high orientation selenizing Sb film that the preparation method of the high orientation selenizing Sb film is obtained.
Compared with prior art, the present invention has following beneficial effect：Height is prepared in metallic antimony selenizing method of the present invention to take The method and antimony selenide thin-film solar cells of tropism selenizing Sb film, the surface topography and X-ray diffraction of selenizing Sb film have Significantly change, crystallite dimension becomes big to micron order, with<002>For highest peak or secondary strong peak, the change to energy gap is smaller, makes It somewhat broadens and has more suitably energy gap.The electric current that the preparation method can improve antimony selenide thin-film solar cells is close Degree and fill factor, curve factor, so that efficiency is increased substantially.
Brief description of the drawings
Fig. 1 is the surface pattern of the metallic antimony thin film of the present invention.
Fig. 2 is the selenium of the good orientation of the present invention（Sulphur）Change the cross-sectional view and surface pattern of Sb film.
Fig. 3 is the selenium of the good orientation of the present invention（Sulphur）Change the photoresponse curve of Sb film.
Fig. 4 is the selenium of the good orientation in the different base of the present invention（Sulphur）Change the X-ray diffraction curve of Sb film.
Fig. 5 is the selenium of the good orientation of the present invention（Sulphur）Change the energy gap curve of Sb film.
Fig. 6 is the selenium of the good orientation of the present invention（Sulphur）Change the x-ray photoelectron power spectrum of Sb film.
Fig. 7 is the selenium of the good orientation by the present invention（Sulphur）Changing the current-voltage of solar cell prepared by Sb film is Efficiency curve.
Embodiment
Form is described in further detail again to the above of the present invention by the following examples, but should not manage this The scope solved as above-mentioned theme of the invention is only limitted to following embodiment, and all technologies realized based on the above of the present invention are equal Belong to the scope of the present invention.
In order to improve current density, the performance of battery is improved, the embodiments of the invention provide a kind of high orientation antimony selenide Film and preparation method thereof, including：The selenizing Sb film is well to be taken using selenization after being carried out to metallic film To selenizing Sb film, as edge<002>The film of the antimony selenide chain composition of direction growth.The high orientation selenizing Sb film For one-dimensional chain material.In the technical scheme, handled using metallic antimony selenized annealing and be orientated to improve with this improved thin film Current density is to reach the lifting of device performance.To make the object, technical solutions and advantages of the present invention clearer, tool is lifted below The present invention is further detailed explanation for body embodiment.
Present invention relates particularly to a kind of high orientation selenizing Sb film and preparation method thereof, existing selenizing Sb film is solved too It is positive can battery short circuit current flow and it is less efficient the problem of.
A kind of high orientation selenizing Sb film, it is characterised in that including：The selenizing Sb film is using thin to metallic antimony Film carries out the selenizing Sb film that selenization is well orientated, as edge<002>It is thin that the antimony selenide chain of direction growth is constituted Film.
The preparation method of the high orientation selenizing Sb film, specific steps include：
The first step, metallic antimony thin film is prepared using thermal evaporation：The evaporation technology of the metallic antimony is that source temperature is 500 ~ 800 DEG C, substrate heating temperature is normal temperature ~ 200 DEG C, and evaporation time is 10 ~ 30min, and vacuum is 10-2 ~ 10- 4Pa；
Second step, selenization obtains selenizing Sb film after being carried out to metallic antimony thin film, and the rear selenization is：By gold Category Sb film is made annealing treatment in selenium atmosphere, wherein：The selenium steam partial pressure of the selenium atmosphere is 1~10000Pa, annealing temperature Spend for 300~450 DEG C, processing time is 12~30min.
The present invention also aims to provide a kind of antimony selenide thin-film solar cells, it is characterised in that including above-mentioned institute State the high orientation selenizing Sb film that the preparation method of high orientation selenizing Sb film is obtained.
In metallic antimony selenizing method of the present invention prepares the method for antimony selenide thin-film solar cells, the surface of selenizing Sb film Pattern and X-ray diffraction are significantly changed, and crystallite dimension becomes big to micron order, with<002>For highest peak or secondary strong peak, to forbidden band The change of width is smaller, it is somewhat broadened and has more suitably energy gap.The processing can improve selenizing Sb film too The current density and fill factor, curve factor of positive energy battery increase substantially so as to efficiency.
It is exemplified below specific embodiment to illustrate the method for present invention improvement antimony selenide orientation, and passes through this method Solar cell has been prepared, but the present invention is not limited to following embodiments.Condition in following embodiments is to test most It is excellent, but the above-mentioned content of the present invention can be applied to after the metallic antimony of improvement antimony selenide orientation in the method for selenizing, with Under only illustrated with preferably treatment conditions.
Embodiment
Step 1: with deionized water, acetone, isopropanol, deionized water cleans each 30 points of electrically conducting transparent FTO glass successively Clock, then dried up with nitrogen gun；
Step 2: depositing 300nm metallic antimony thin film using thermal evaporation, source temperature is 500-600 DEG C, and substrate adds Hot temperature is normal temperature, and evaporation time is 20min；
Orientation is obtained Step 3: being uncapped after being annealed 16 minutes with quartzy lid and 50mg granules of selenium in glove box well Selenizing Sb film.
The solar cell obtained to embodiment carries out performance test respectively, and test result is as shown in table 1.
Performance table of the embodiment as solar cell made from P-type layer of table 1
Voc(V) Jsc (mA/cm2) FF(%) Eff(%) Rs Rsh
TiO2 0.17 2.7 31.7 0.2 456 1036
TiO2 nanosheet 0.28 3.7 29.63 0.3 561 1025
First is classified as the description of N-type layer.

Claims (3)

1. a kind of high orientation selenizing Sb film, it is characterised in that the selenizing Sb film is to be carried out using to metallic antimony thin film The selenizing Sb film that selenization is well orientated, the selenizing Sb film is edge<002>The antimony selenide chain group of direction growth Into film.
2. a kind of preparation method of the high orientation selenizing Sb film described in claim 1, it is characterised in that specific steps bag Include：
The first step, metallic antimony thin film is prepared using thermal evaporation：The evaporation technology of the metallic antimony be source temperature be 500~ 800 DEG C, substrate heating temperature is normal temperature~200 DEG C, and evaporation time is 10~30min, and vacuum is 10-2~10-4Pa；
Second step, selenization obtains selenizing Sb film after being carried out to metallic antimony thin film, and the rear selenization is：By metallic antimony Film is made annealing treatment in selenium atmosphere, wherein：The selenium steam partial pressure of the selenium atmosphere is 1~10000Pa, and annealing temperature is 300~450 DEG C, processing time is 12~30min.
3. a kind of antimony selenide thin-film solar cells, it is characterised in that including high orientation selenizing Sb film described in claim 2 The obtained high orientation selenizing Sb film of preparation method.
CN201610505363.XA 2016-07-01 2016-07-01 A kind of high orientation selenizing Sb film and preparation method thereof Active CN106129143B (en)

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CN106920863B (en) * 2017-03-21 2018-05-11 华中科技大学 A kind of back surface processing method of antimony selenide thin-film solar cells
CN106910797B (en) * 2017-03-23 2017-12-29 华中科技大学 The method of Zinc oxide-base bottom induced orientation growth selenizing Sb film
CN106917068B (en) * 2017-03-29 2019-05-07 福建师范大学 Solar battery obsorbing layer Sb is prepared based on magnetron sputtering and rear selenizing2Se3The method of film
CN107275441A (en) * 2017-06-20 2017-10-20 湖南商学院 A kind of preparation method of photodetector
CN107937969A (en) * 2017-11-14 2018-04-20 中南大学 A kind of GN Sb2Se3The preparation method of laminated film
CN108493276A (en) * 2018-01-30 2018-09-04 河北大学 A kind of antimony selenide method for manufacturing thin film and device
CN109518149B (en) * 2019-01-07 2020-11-20 重庆大学 Preparation method of antimony selenide photoelectric film preferentially growing along (002) direction
CN110117769A (en) * 2019-05-20 2019-08-13 陕西科技大学 A kind of preparation method of selenizing tin thin film
CN111020487B (en) * 2019-11-21 2021-02-26 华中科技大学 Method for preparing film of quasi-one-dimensional structure material with controllable orientation
CN111560583A (en) * 2020-05-05 2020-08-21 东北电力大学 Induction (Sb)4Se6)nMethod for preparing antimony selenide photoelectric film with longitudinally-grown molecular chain
CN112376113B (en) * 2020-10-28 2022-02-11 河南大学 Antimony selenide crystal, preparation method and application thereof
CN114164399A (en) * 2021-11-08 2022-03-11 华中科技大学 Antimony selenide film with one-dimensional chain crystal structure and method for improving hole concentration of antimony selenide film

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KR20100085769A (en) * 2009-01-21 2010-07-29 재근 이 Cds/cdte thin film solar cells and manufacturing method thereof
CN104638036B (en) * 2014-05-28 2017-11-10 武汉光电工业技术研究院有限公司 High photoresponse near infrared photodetector
CN105479848B (en) * 2014-10-11 2017-06-16 华中科技大学 A kind of Sb2(Sex,S1‑x)3Alloy firm and preparation method thereof

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