CN117276398A - Sb (Sb) 2 (S,Se) 3 Sb on the surface of the film 2 O 3 Reduction method and solar cell preparation method thereof - Google Patents
Sb (Sb) 2 (S,Se) 3 Sb on the surface of the film 2 O 3 Reduction method and solar cell preparation method thereof Download PDFInfo
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- 230000009467 reduction Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- NYYSPVRERVXMLJ-UHFFFAOYSA-N 4,4-difluorocyclohexan-1-one Chemical compound FC1(F)CCC(=O)CC1 NYYSPVRERVXMLJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011521 glass Substances 0.000 claims abstract description 17
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- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 59
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
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- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 8
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 8
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 claims description 8
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- KLDGLPRBBANWAW-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate;trihydrate Chemical compound O.O.O.[K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O KLDGLPRBBANWAW-UHFFFAOYSA-J 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- IYKVLICPFCEZOF-UHFFFAOYSA-N selenourea Chemical compound NC(N)=[Se] IYKVLICPFCEZOF-UHFFFAOYSA-N 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
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- 239000010937 tungsten Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- 230000002194 synthesizing effect Effects 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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 potential barriers
- 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 potential barriers the potential barriers being only of the PN heterojunction type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
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- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention belongs to the field of solar cells and semiconductor photovoltaics, and particularly relates to a Sb 2 (S,Se) 3 Sb on the surface of the film 2 O 3 A reduction method and a solar cell preparation method. Preparing Sb with uniform thickness on CdS surface by using hydrothermal reaction method 2 (S,Se) 3 Doping formamidine sulfinic acid with proper concentration into precursor solution, and generating Sb on the surface of the film prepared by a chemical hydrothermal method 2 O 3 Reduction to give a film having Glass/FTO/CdS/Sb 2 (S,Se) 3 Sb of a structure of/Spiro-OMeTAD/Au 2 (S,Se) 3 The solar cell has better photoelectric conversion performance.
Description
Technical Field
The invention belongs to the field of solar cells and semiconductor photovoltaics, and in particular relates toSb (Sb) 2 (S,Se) 3 Sb on the surface of the film 2 O 3 A reduction method and a solar cell preparation method.
Background
Antimony chalcogenide is widely studied as a light absorbing material due to its phase stability, earth abundance, low toxicity, high efficiency, low cost, and excellent solar properties. Sb (Sb) 2 (S,Se) 3 Is a material with a one-dimensional crystal structure, the one-dimensional structure is favorable for inhibiting recombination loss of a typical thin film solar cell, and meanwhile, sb 2 (S,Se) 3 The film with high absorption coefficient and thickness of about five hundred nanometers can achieve the optimal absorption. These functions further enhance their competitiveness as a novel non-toxic photovoltaic absorber material with high efficiency and low cost.
Sb 2 (S,Se) 3 As a novel low-cost, low-toxicity and stable inorganic semiconductor thin film solar cell material, the material has excellent light, electricity and material characteristics, namely large light absorption coefficient>10 5 cm -1 ) Adjustable band gap (about 1.1-1.7 eV), high single junction theory conversion efficiency>30%); high carrier mobility, simple phase, low crystal growth temperature, etc. At present Sb 2 (S,Se) 3 PCE of solar cells steadily grows year by year, and Sb is generated along with further development and maturity of battery technology 2 (S,Se) 3 The solar cell has wide application prospect.
Current preparation of Sb 2 (S,Se) 3 The film can be prepared by chemical hydrothermal method, spin coating method, chemical water bath method, vertical gas phase transportation method, pulse laser deposition method, etc. Chemical hydrothermal synthesis of Sb 2 (S,Se) 3 Is a relatively common method, and the highest efficiency under the system is maintained at present by the method for synthesizing Sb 2 (S,Se) 3 . However, the method is influenced by the reaction conditions such as temperature, pressure, content and components of precursor reactants, reaction time, temperature rising rate and the like, so that the crystal structure, the crystal grain purity and the crystal morphology of the synthetic material are still difficult to control. Under the influence of water oxygen parameters, the prepared Sb 2 (S,Se) 3 Antimony oxide exists on the surface of the film,this affects the crystallinity of the film, resulting in Sb being produced 2 (S,Se) 3 The defect concentration of the film is large, and the subsequent Sb is affected 2 (S,Se) 3 Photoelectric conversion efficiency of the thin film solar cell. Thus reducing Sb 2 (S,Se) 3 Antimony oxide on the surface of the film becomes very important.
Disclosure of Invention
In order to solve the problems, the invention provides a Sb 2 (S,Se) 3 Sb on the surface of the film 2 O 3 Reduction method and solar cell preparation method thereof, and existing chemical hydrothermal method for synthesizing Sb is eliminated 2 (S,Se) 3 Sb generated on the surface of the film 2 O 3 。
The invention adopts the technical scheme that:
sb (Sb) 2 (S,Se) 3 Sb on the surface of the film 2 O 3 A method of reduction comprising the steps of:
(1) Prefabricating a buffer layer CdS substrate: placing the cleaned FTO conductive glass with the conductive surface facing upwards in an ozone treatment machine for treatment, vertically attaching the treated FTO conductive glass to a glass backboard, and then placing the FTO conductive glass into a quartz square cylinder filled with a mixed solution of thiourea, cadmium sulfate and ammonia water for water bath reaction;
(2) Post-treatment of CdS film: taking the fully dissolved CdCl by a pipetting gun 2 The anhydrous methanol solution is used for placing the CdS film substrate prepared in the step (1) into a spin coater, and CdCl is added dropwise 2 An anhydrous methanol solution is dynamically spin-coated in an air atmosphere; then, measuring an anhydrous methanol solution, and controlling spin coating parameters to be unchanged for spin coating; annealing in air after spin coating, naturally cooling, taking down, and carrying out ozone treatment by using an ozone treatment machine;
(3)Sb 2 (S,Se) 3 preparation of film and Sb 2 O 3 And (3) reduction: separately weighing antimony potassium tartrate trihydrate (C8H 8 K 2 O 12 Sb 12 ·3H 2 O), ethylenediamine tetraacetic acid (C) 10 H 18 N 2 O 8 ) Ammonium fluoride (NH) 4 F) And formamidine sulfinic acid (NH) 2 C(＝NH)SO 2 H) Put and putAdding the mixture into deionized water, and stirring the mixture until the mixture is clear; then weighing sodium thiosulfate pentahydrate (Na) 2 S 2 O 3 ·5H 2 O) is put into the solution, stirred until the sodium thiosulfate pentahydrate is dissolved, and then selenourea ((H) is added 2 N 2 ) C=se), sufficiently stirring and dissolving to prepare a precursor solution; placing the substrate CdS film prepared in the step (2) in a polytetrafluoroethylene reaction kettle liner towards the inner wall of the liner, pouring a precursor solution into the liner, sealing, and performing hydrothermal reaction;
(4) After the reaction is finished, the reaction kettle is naturally cooled to room temperature, and flowing N is used 2 Blow-drying the obtained Sb 2 (S,Se) 3 A film; annealing in nitrogen atmosphere, and taking off after the annealing is finished and naturally cooled.
Preferably, the FTO conductive glass is cleaned in step (1): sequentially carrying out ultrasonic treatment by using deionized water, acetone, isopropanol and ethanol; ultrasound finishing using flowing N 2 And drying the FTO conductive glass piece by piece for standby.
Preferably, the mixed solution required by the water bath reaction in the step (1) is prepared from deionized water, 0.75M thiourea solution, 0.015M cadmium sulfate solution and 25% ammonia water solution; wherein the content of the thiourea solution, the cadmium sulfate solution and the ammonia water solution accounts for 10 to 15 percent of the total volume of the mixed solution.
Preferably, the water bath reaction temperature in the step (1) is 65-80 ℃ and the reaction time is 8-14min.
Preferably, the rotating speed of the spin coater in the step (2) is 3700rpm/min, the real-time spin coating speed is 3700rpm, and the spin coating time is 30s.
Preferably, the preparation method of the precursor solution in the step (3) comprises the following steps: 267.1mg of antimony potassium tartrate trihydrate, 50mg of ethylenediamine tetraacetic acid, 25mg of ammonium fluoride and 0.86-43.24mg of formamidine sulfinic acid are put into 40ml of deionized water, stirred and mixed for 30-60min at a rotating speed of 2000rpm, so that the medicine is completely dissolved, the solution is stirred until the medicine is clear, 794.2mg of sodium thiosulfate pentahydrate is weighed and added into the solution, the solution is fully dissolved, then 20mg of selenourea is added, and the precursor solution is prepared after the solution is fully stirred and dissolved. Dissolving in the precursorThe formamidine sulfinic acid is added into the liquid to reduce Sb 2 (S,Se) 3 Sb on the surface of the film 2 O 3 Is a target of (a).
Preferably, in the step (3), the substrate CdS thin film is placed in the polytetrafluoroethylene reaction kettle liner towards the inner wall of the liner, and the inclination angle of the substrate is 60 degrees.
Preferably, the hydrothermal reaction temperature in the step (3) is 135-140 ℃ and the reaction time is 140min.
Preferably, the annealing temperature in the step (4) is 350 ℃, and the annealing time is 15-20min.
The invention also provides a Sb 2 (S,Se) 3 Solar cell with structure of Glass/FTO/CdS/Sb 2 (S,Se) 3 Spiro-OMeTAD/Au wherein Sb 2 (S,Se) 3 The structural layer is obtained through the steps (1) to (4).
Above-mentioned Sb 2 (S,Se) 3 The preparation method of the solar cell comprises the following steps:
(5) Sb produced in step (4) 2 (S,Se) 3 Spin-coating a Spiro-OMeTAD solution on the film;
(6) After spin coating, the partial Spiro-OMeTAD and Sb are respectively corroded by acetonitrile solution, potassium hydroxide solution and concentrated hydrochloric acid diluted solution 2 (S,Se) 3 And CdS film to expose the electrode fully;
(7) After the electrode is corroded, evaporating the Au electrode by using high-vacuum thermal evaporator equipment to obtain Sb 2 (S,Se) 3 Thin film solar cells.
Preferably, the acceleration of the spin coating in the step (5) is 3000-500rpm/min, the spin coating rotating speed is 3000-3500rpm, and the spin coating time is 30s.
Preferably, in the step (6), the concentration of the potassium hydroxide solution used for electrode corrosion is 5M, the diluted solution of the concentrated hydrochloric acid is a mixed solution of the concentrated hydrochloric acid and water according to the volume ratio of 1:1, and the acetonitrile solution is anhydrous acetonitrile.
Preferably, the specific method for evaporating the Au electrode in the step (7) is as follows: weighing 0.14g of gold with purity of 99.99% and placing in a tungsten boat, and pumping after the rotation speed of a molecular pump reaches a certain valueVacuum to below 8 x 10 -4 After Pa, 52A current is used first/s) is evaporated for 20min, followed by a 66A current (++>/s) is evaporated for 20min until the gold is completely evaporated.
Compared with the prior art, the invention has the advantages that 2 (S,Se) 3 Formamidine sulfinic acid with proper concentration is doped in the precursor solution of the film to lead Sb generated on the surface of the film prepared by a chemical hydrothermal method 2 O 3 And (5) reduction. Formamidine sulfinic acid can reduce Sb generated in chemical hydrothermal reaction 2 O 3 . After the vibration of the Sb-O bond is weakened, the vibration of the Sb-S bond is relatively enhanced, and the Sb can be improved to a certain extent 2 (S,Se) 3 Crystallinity of the thin film, and Sb having a quasi-one-dimensional crystal structure and excellent in crystallinity and photoelectric properties was produced 2 (S,Se) 3 A film. At the same time, surface Sb 2 O 3 Reduction is equivalent to reducing impurities on the surface of the absorption layer, is beneficial to improving interface contact between the hole transport layer and the light absorption layer, reduces interface loss, and simultaneously has the surface Sb 2 O 3 Reduction of Sb 2 (S,Se) 3 The defect concentration of the film component is reduced, the energy band arrangement of the device is facilitated, and the Sb obtained based on the film is enhanced 2 (S,Se) 3 The transmission capability of PN junction electron-hole pairs in the solar cell is improved, and the photoelectric conversion performance of the device is further improved.
The invention provides a Sb 2 (S,Se) 3 Sb on the surface of the film 2 O 3 Reduction method and application thereof to Sb 2 (S,Se) 3 The preparation of solar cells is otherwise not reported in the patent or non-patent literature.
Description of the drawings:
FIG. 1 is a diagram of Sb prepared by adding various amounts of formamidine sulfinic acid 2 (S,Se) 3 A thin film solar cell PCE box diagram;
FIG. 2 is a graph of Sb produced by adding various amounts of formamidine sulfinic acid 2 (S,Se) 3 A thin film solar cell J-V graph;
FIG. 3 is a diagram of Sb prepared in example 1 and example 2 2 (S,Se) 3 Raman analysis of the film;
FIG. 4 shows Sb prepared in example 1 (left) and example 2 (right) 2 (S,Se) 3 SEM image of the film.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in various other embodiments according to the present invention, or simply change or modify the design structure and thought of the present invention, which fall within the protection scope of the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention will be further described in detail with reference to examples:
example 1
The clean FTO conductive glass subjected to ozone treatment for 15min is vertically stuck on a glass backboard with the conductive surface facing upwards, and then placed into a quartz square jar filled with a mixed solution of thiourea, cadmium sulfate and ammonia water to react in a water bath at 65 ℃ for 14min. In the mixed solution, 20mL of each of a 0.75M thiourea solution, a 0.015M cadmium sulfate solution and a 25% ammonia solution, 140mL of deionized water were used.
Post-treatment of CdS film: taking the fully dissolved CdCl by a pipetting gun 2 Placing the prepared CdS film substrate into a spin coater, setting the rotating speed of 3700rpm/min, spin coating for 30s, starting the spin coater until the rotating speed reaches a set value, and instantly dripping CdCl 2 An anhydrous methanol solution is dynamically spin-coated in an air atmosphere; then, measuring an anhydrous methanol solution, and controlling spin coating parameters to be unchanged for spin coating; annealing in air at 400 ℃ for 10min after spin coating, naturally cooling, taking down, and carrying out ozone treatment for 15min by using an ozone treatment machine.
Sb 2 (S,Se) 3 Preparation of film and Sb 2 O 3 And (3) reduction: respectively weighing 267.1mg of antimony potassium tartrate trihydrate, 50mg of ethylenediamine tetraacetic acid and fluoridationAmmonium 25mg and formamidine sulfinic acid (more than or equal to 98%, batch number F16001, sigma-Aldrich, commercially available) 8.65mg were placed in 40ml deionized water, stirred at 2000rpm/min for 30-60min, and the mixed solution was stirred until clear; then weighing 794.2mg of sodium thiosulfate pentahydrate, putting into the solution, stirring until the sodium thiosulfate pentahydrate is dissolved, adding 20mg of selenourea, and fully stirring for dissolution, thereby preparing a precursor solution; placing the prepared substrate CdS film in a polytetrafluoroethylene reaction kettle liner towards the inner wall of the liner, pouring a precursor solution into the liner, sealing, and performing hydrothermal reaction at 135 ℃ for 140min, wherein the inclination angle of the substrate is 60 degrees.
After the reaction is finished, the reaction kettle is naturally cooled to room temperature, and after the flakes are taken out, flowing N is used 2 Blow-drying the obtained Sb 2 (S,Se) 3 A film; annealing in a nitrogen atmosphere of a glove box, wherein the annealing temperature is 350 ℃, the annealing time is 20min, and the annealing is taken down after the annealing is finished and naturally cooled.
In the prepared Sb 2 (S,Se) 3 The film was spin coated with 20. Mu.L of Spiro-OMeTAD solution.
After spin coating, the partial Spiro-OMeTAD and Sb are respectively corroded by acetonitrile solution, potassium hydroxide solution and concentrated hydrochloric acid diluted solution 2 (S,Se) 3 And CdS film to expose the electrode fully. The spin coating acceleration is 3000-3500rpm/min, the spin coating rotating speed is 3000-3500rpm, and the spin coating time is 30s.
The etching electrode is finished, and the high vacuum thermal evaporator device is used for evaporating the Au electrode, wherein the method for evaporating the Au electrode is to weigh 0.14g of Au (99.9 percent, the technology of gold research in Beijing, the market is available), and the Au electrode is smaller than 5 to 8 multiplied by 10 -4 The substrate prepared in the above step was plated with a layer of Au as an electrode (16 sheets/lot) under vacuum of Pa using a high-vacuum thermal evaporator. The evaporation rate is controlled by adjusting the current, 52A current is used firstEvaporating for 20min, and then using 66A current +.>Evaporating for 20min to a final thickness of about 40About nm, obtain Sb 2 (S,Se) 3 Thin film solar cells.
Sb prepared in this example 2 (S,Se) 3 The thin film solar cell has a photoelectric conversion efficiency of 8.24%.
Example 2
Procedure and process are carried out with reference to example 1, preparation of Sb 2 (S,Se) 3 When the precursor solution of the film is used, formamidine sulfinic acid is not added.
Sb prepared in this example 2 (S,Se) 3 The thin film solar cell has a photoelectric conversion efficiency of 7.89%.
FIG. 4 shows Sb prepared in example 1 (left) and example 2 (right) 2 (S,Se) 3 SEM image of a film, it can be seen that Sb prepared in example 1 2 (S,Se) 3 The grain boundary of the thin film is reduced, the capability of capturing carriers is reduced, carrier transmission is facilitated, and meanwhile, the electron transmission capability is enhanced, so that the photoelectric performance of the solar cell is improved.
Example 3
Screening of Formamidine Sulfinic Acid (FSA) usage:
procedure and process are carried out with reference to example 1, preparation of Sb 2 (S,Se) 3 When precursor solutions of the films are added, different amounts of formamidine sulfinic acid are respectively 0.86mg, 2.59mg, 4.32mg, 6.05mg, 8.64mg, 25.94mg and 43.24mg.
Table 1 Sb prepared based on different amounts of FSA doping 2 (S,Se) 3 Sb of thin film 2 (S,Se) 3 Photoelectric conversion parameter of solar cell
Example 4
The steps and processes are carried out with reference to example 2, wherein no ozone treatment is carried out for 15min in the post-treatment step of CdS.
Sb prepared in this example 2 (S,Se) 3 The thin film solar cell has a photoelectric conversion efficiency of 7.75%.
Example 5
Sb 2 (S,Se) 3 Screening reaction temperature for film preparation:
the steps and processes are carried out according to example 1, and the hydrothermal reaction is controlled to synthesize Sb 2 (S,Se) 3 The reaction temperature of (2) is 135-150 ℃.
Table 2 below Sb prepared at different reaction temperatures 2 (S,Se) 3 Sb of thin film 2 (S,Se) 3 Photoelectric conversion parameter of solar cell
Example 6
Sb 2 (S,Se) 3 Screening annealing time for film preparation:
the procedure and process are carried out with reference to example 1, controlling Sb 2 (S,Se) 3 The annealing time of the film is 15-25min.
Table 3 attached Sb prepared based on different annealing times 2 (S,Se) 3 Sb of thin film 2 (S,Se) 3 Photoelectric conversion parameter of solar cell
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme and the concept of the present invention, and should be covered by the scope of the present invention.
Claims (9)
1. Sb (Sb) 2 (S,Se) 3 Sb on the surface of the film 2 O 3 A reduction method characterized by comprising the steps of:
(1) Prefabricating a buffer layer CdS substrate: placing the cleaned FTO conductive glass with the conductive surface facing upwards in an ozone treatment machine for treatment, vertically attaching the treated FTO conductive glass to a glass backboard, and then placing the FTO conductive glass into a quartz square cylinder filled with a mixed solution of thiourea, cadmium sulfate and ammonia water for water bath reaction;
(2) Post-treatment of CdS film: taking the fully dissolved CdCl by a pipetting gun 2 The anhydrous methanol solution is used for placing the CdS film substrate prepared in the step (1) into a spin coater, and CdCl is added dropwise 2 An anhydrous methanol solution is dynamically spin-coated in an air atmosphere; then, measuring an anhydrous methanol solution, and controlling spin coating parameters to be unchanged for spin coating; annealing in air after spin coating, naturally cooling, taking down, and carrying out ozone treatment by using an ozone treatment machine;
(3)Sb 2 (S,Se) 3 preparation of film and Sb 2 O 3 And (3) reduction: separately weighing antimony potassium tartrate trihydrate (C8H 8 K 2 O 12 Sb 12 ·3H 2 O), ethylenediamine tetraacetic acid (C) 10 H 18 N 2 O 8 ) Ammonium fluoride (NH) 4 F) And formamidine sulfinic acid (NH) 2 C(＝NH)SO 2 H) Placing the mixture into deionized water, and stirring the mixture until the mixture is clear; then weighing sodium thiosulfate pentahydrate (Na) 2 S 2 O 3 ·5H 2 O) is put into the solution, stirred until the sodium thiosulfate pentahydrate is dissolved, and then selenourea ((H) is added 2 N 2 ) C=se), sufficiently stirring and dissolving to prepare a precursor solution; placing the substrate CdS film prepared in the step (2) in a polytetrafluoroethylene reaction kettle liner towards the inner wall of the liner, pouring a precursor solution into the liner, sealing, and performing hydrothermal reaction;
(4) After the reaction is finished, the reaction kettle is naturally cooled to room temperature, and flowing N is used 2 Blow-drying the obtained Sb 2 (S,Se) 3 A film; annealing in nitrogen atmosphere, and taking off after the annealing is finished and naturally cooled.
2. Sb according to claim 1 2 (S,Se) 3 Sb on the surface of the film 2 O 3 The reduction method is characterized in that in the step (1), FTO conductive glass is cleaned: sequentially using deionized water, acetone, isopropanol and ethanolPerforming sound treatment; ultrasound finishing using flowing N 2 And drying the FTO conductive glass piece by piece for standby.
3. Sb according to claim 1 2 (S,Se) 3 Sb on the surface of the film 2 O 3 The reduction method is characterized in that the mixed solution required by the water bath reaction in the step (1) is prepared from deionized water, 0.75M thiourea solution, 0.015M cadmium sulfate solution and 25% ammonia water solution; wherein, the content of the thiourea solution, the cadmium sulfate solution and the ammonia water solution accounts for 10 to 15 percent of the total volume of the mixed solution;
and/or, the water bath reaction temperature in the step (1) is 65-80 ℃ and the reaction time is 8-14min.
4. Sb according to claim 1 2 (S,Se) 3 Sb on the surface of the film 2 O 3 The reduction method is characterized in that the rotating speed of the spin coater in the step (2) is 3700rpm/min, the real-time spin coating speed is 3700rpm, and the spin coating time is 30s.
5. Sb according to claim 1 2 (S,Se) 3 Sb on the surface of the film 2 O 3 The reduction method is characterized in that the preparation method of the precursor solution in the step (3) comprises the following steps: 267.1mg of antimony potassium tartrate trihydrate, 50mg of ethylenediamine tetraacetic acid, 25mg of ammonium fluoride and 0.86-43.24mg of formamidine sulfinic acid are put into 40ml of deionized water, stirred and mixed for 30-60min at a rotating speed of 2000rpm, so that the medicine is completely dissolved, the solution is stirred until the medicine is clear, 794.2mg of sodium thiosulfate pentahydrate is weighed and added into the solution, the solution is fully dissolved, then 20mg of selenourea is added, and the precursor solution is prepared after the solution is fully stirred and dissolved.
6. Sb according to claim 1 2 (S,Se) 3 Sb on the surface of the film 2 O 3 The reduction method is characterized in that in the step (3), the substrate CdS film is placed in a polytetrafluoroethylene reaction kettle liner towards the inner wall of the liner, and the inclination angle of the substrate is 60 degrees;
and/or, the hydrothermal reaction temperature in the step (3) is 135-140 ℃ and the reaction time is 140min;
and/or, in the step (4), the annealing temperature is 350 ℃, and the annealing time is 15-20min.
7. Sb (Sb) 2 (S,Se) 3 The solar cell is characterized in that the solar cell has the structure of Glass/FTO/CdS/Sb 2 (S,Se) 3 Spiro-OMeTAD/Au wherein Sb 2 (S,Se) 3 Structural layer by Sb as claimed in any one of claims 1 to 6 2 (S,Se) 3 Sb on the surface of the film 2 O 3 Steps (1) to (4) of the reduction method.
8. Sb as defined in claim 7 2 (S,Se) 3 The preparation method of the solar cell is characterized by comprising the following steps:
(5) Sb produced in step (4) 2 (S,Se) 3 Spin-coating a Spiro-OMeTAD solution on the film;
(6) After spin coating, the partial Spiro-OMeTAD and Sb are respectively corroded by acetonitrile solution, potassium hydroxide solution and concentrated hydrochloric acid diluted solution 2 (S,Se) 3 And CdS film to expose the electrode fully;
(7) After the electrode is corroded, evaporating the Au electrode by using high-vacuum thermal evaporator equipment to obtain Sb 2 (S,Se) 3 Thin film solar cells.
9. Sb according to claim 8 2 (S,Se) 3 The preparation method of the solar cell is characterized in that the spin-coating acceleration in the step (5) is 3000-3500rpm/min, the spin-coating rotating speed is 3000-3500rpm, and the spin-coating time is 30s;
and/or, in the step (6), the concentration of the potassium hydroxide solution used for electrode corrosion is 5M, the concentrated hydrochloric acid diluted solution is a mixed solution of concentrated hydrochloric acid and water according to the volume ratio of 1:1, and the acetonitrile solution is anhydrous acetonitrile;
and/or, the specific method for evaporating the Au electrode in the step (7) is as follows: 0.14g of gold with 99.99% purity is weighedPlacing in a tungsten boat, vacuumizing to less than 8X10 when the rotation speed of the molecular pump reaches a certain value -4 After Pa, the 52A current is used firstEvaporating for 20min, and then using 66A current +.>Evaporating for 20min until gold is completely evaporated.
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