CN113421978B - Preparation method of magnetic perovskite film with weak magnetic field effect - Google Patents
Preparation method of magnetic perovskite film with weak magnetic field effect Download PDFInfo
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- 230000005426 magnetic field effect Effects 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 239000002073 nanorod Substances 0.000 claims abstract description 37
- 238000004528 spin coating Methods 0.000 claims abstract description 37
- 239000011521 glass Substances 0.000 claims abstract description 23
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000010408 film Substances 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 37
- 238000000137 annealing Methods 0.000 claims description 30
- 239000010409 thin film Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 11
- 229910052593 corundum Inorganic materials 0.000 claims description 10
- 239000010431 corundum Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 230000031700 light absorption Effects 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000011010 flushing procedure Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000003980 solgel method Methods 0.000 abstract 1
- 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 description 8
- 239000010931 gold Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- XKKVXDJVQGBBFQ-UHFFFAOYSA-L zinc ethanol diacetate Chemical compound C(C)O.C(C)(=O)[O-].[Zn+2].C(C)(=O)[O-] XKKVXDJVQGBBFQ-UHFFFAOYSA-L 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F13/00—Apparatus or processes for magnetising or demagnetising
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
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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
- Y02E10/549—Organic PV cells
Abstract
The invention discloses a preparation method of a magnetic perovskite film with weak magnetic field effect, which comprises the steps of firstly preparing a ZnO nano rod array film on an FTO conductive glass substrate, and then coating TiO on the ZnO nano rod array film by adopting a sol-gel method 2 Obtaining ZnO@TiO 2 A nanorod array film; then adopting a two-step continuous solution deposition method, spin-coating PbI on the surface of the film 2 Precursor solution, re-immersed in CoI 2 ‑CH 3 NH 3 I, isopropanol solution reacts, then the film is annealed and simultaneously applied with weak magnetic field to prepare CH with weak magnetic field 3 NH 3 Pb 0.9 Co 0.1 I 3 A film; the invention applies weak magnetic field to CH 3 NH 3 Pb 0.9 Co 0.1 I 3 The perovskite is modified, so that the photovoltaic performance, the humidity stability, the heat stability and the light stability of the corresponding battery can be obviously improved, and the commercialization of the perovskite is facilitated.
Description
Technical Field
The invention belongs to the technical field of solar cell preparation, and particularly relates to a preparation method of a perovskite solar cell light absorption layer, in particular to a preparation method of a magnetic perovskite film with weak magnetic field effect.
Background
Perovskite has excellent charge transport property, long carrier diffusion length, full spectrum absorption, high absorption coefficient and other photoelectric properties, and has been widely used in the field of solar cellsGeneral attention is paid. These advantages enable them to effectively capture photons and achieve photoelectric conversion. Since 2009, organic-inorganic hybrid perovskite solar cells have rapidly developed, with a rapid increase in Photoelectric Conversion Efficiency (PCE) from 3.8% to 25.5%. However, organic-inorganic hybrid perovskites are extremely susceptible to factors such as moisture, light, heat, oxygen, etc. in the air, resulting in decomposition of the perovskite material. Therefore, the long-term stability of the perovskite-type solar cell is suppressed, and the perovskite-type solar cell becomes a major bottleneck for further commercialization. In order to solve the problem, the perovskite thin film and the corresponding solar cell stability are improved by doping magnetic cobalt ions in the perovskite and applying a weak magnetic field effect, a new thought is provided for improving the performance of the perovskite solar cell, and a valuable reference is provided for promoting the commercialization of the perovskite solar cell. The research result of the invention shows that the CH is improved 3 NH 3 PbI 3 The morphology, structure, optical performance, stability and stability of perovskite thin film and corresponding device.
Disclosure of Invention
The invention aims to provide a method for improving the stability of a perovskite solar cell, and the core of the method is a preparation method of a magnetic perovskite film with weak magnetic field effect.
The preparation method of the magnetic perovskite film with the weak magnetic field effect can comprise the following steps:
(1) Spin-coating 95-105 mu L of ethanol solution of zinc acetate with the mass concentration of 0.005-0.007 g/mL onto an FTO conductive glass substrate subjected to ultraviolet ozone treatment, spin-coating for 30s at 3000r/min for 3 times, and annealing at 150 ℃ for 15min; spin-coating for 30s at 3000r/min, spin-coating for 3 times, and annealing at 150 ℃ for 15min; and finally spin-coating for 30s at 3000r/min, spin-coating for 3 times, and annealing at 350 ℃ for 45min to obtain the ZnO seed layer taking the FTO conductive glass as the substrate.
(2) 25 mM-100 mM Zn salt water solution and 0.001-0.006 g/mL mass concentrationAqueous polyvinylpyrrolidone solution according to Zn 2+ The molar ratio of polyvinylpyrrolidone is 1: 2-2: 1, mixing to obtain a mixed solution;
(3) Adding ammonia water into the mixed solution prepared in the step (2), and regulating the pH value to 9-11 to obtain the growth solution.
(4) Immersing the ZnO seed layer prepared in the step (1) and taking the FTO conductive glass as a substrate in the growth solution prepared in the step (3) on a suspension bracket in a horizontal inversion manner, carrying out water bath reaction for 4-12min at the temperature of 95-105 ℃, washing with deionized water, and cleaning with N 2 Drying to obtain the substrate.
(5) Placing the substrate taken out in the step (4) on a corundum boat, placing the corundum boat in a tube furnace, and placing the corundum boat in O 2 Heating from room temperature to 350-450 ℃ at a heating rate of 5 ℃/min under the flow of 10-50mL/min, and oxidizing and sintering for 10-60 min.
(6) And (3) naturally cooling the substrate treated in the step (5) to room temperature, repeatedly rinsing in deionized water, and airing in air to obtain the ZnO nano rod array film taking the FTO conductive glass as a base.
(7) Horizontally inverting the ZnO nano rod array film prepared in the step (6) on a suspension frame, putting the suspension frame into a solution of which the volume ratio is 1mL:50 mL-1 mL and 120mL of tetrabutyl titanate and isopropanol are uniformly mixed, adding 100-140 mu L of deionized water, magnetically stirring and reacting for 4-8 h, taking out, washing with isopropanol, and annealing for 30min at 450 ℃. After cooling, the titanium tetrachloride aqueous solution with the volume ratio of 1/500-1/1000 is treated by ice water bath for 30min, and then the film is annealed for 30min at 450 ℃ to obtain ZnO@TiO taking FTO conductive glass as a substrate 2 A nanorod array film.
(8) 0.2305 g-0.6915 g PbI 2 Dissolving in DMF (N, N-dimethylformamide)/DMSO (dimethyl sulfoxide) mixed solvent with the volume ratio of 8:1-10:1, and magnetically stirring for 30min at 70 ℃. Then filtering with polytetrafluoroethylene filter head with pore size of 0.2 μm to obtain PbI with molar concentration of 0.5-1.5M 2 Precursor solution. 0.1801 to 0.2222g of CH 3 NH 3 I and 0.005-0.015 g of CoI 2 Dissolving in isopropanol to obtain CH 3 NH 3 I：CoI 2 CH with a molar ratio of 8:1-12:1 3 NH 3 I-CoI 2 Isopropyl alcohol solution.
(9) Taking PbI prepared in the step (8) 2 150 mu L of precursor solution is spin-coated for 30s at 3000r/min to ZnO@TiO subjected to ultraviolet ozone treatment 2 Soaking the surface of the nanorod array film in isopropanol for 1min, taking out, spin-coating for 30s at 3000r/min to spin-dry excessive liquid, and annealing at 70 ℃ for 30min. Placing the CH prepared in the step (8) 3 NH 3 I-CoI 2 The reaction is carried out in isopropanol solution for 40s to 100s, the excessive liquid is spin-coated for 30s at 3000r/min after being taken out, the annealing is carried out for 1 to 5min at the temperature of 80 ℃ to 110 ℃, 2 magnet blocks of 10cm x 1cm are placed at the position which is 0.1 to 1cm away from the top of the film at the same time to apply the weak magnetic field effect, after the annealing is finished, the weak magnetic field effect is continuously applied for 10 to 40min, and CH with the weak magnetic field effect is obtained 3 NH 3 Pb 0.9 Co 0.1 I 3 A film.
In the step (1) of the present invention, zn (CH) may be used as the Zn salt 3 COO) 2 ·2H 2 O、ZnCl 2 Or Zn (NO) 3 ) 2 . The average molecular weight of the polyvinylpyrrolidone is 1,300,000.
The specification of the FTO conductive glass is 20mm 25mm, the square resistance is 14Ω, and the light transmittance is more than or equal to 90%.
The invention adopts a novel two-step continuous deposition method, which is characterized in that 3 NH 3 PbI 3 Co doping during perovskite thin film growth 2+ Ions and weak magnetic field are applied to prepare the magnetic CH 3 NH 3 Pb 1-x Co x I 3 A film. The research result shows that by doping Co 2+ Ions and applying weak magnetic field to improve CH 3 NH 3 PbI 3 The perovskite thin film has the advantages of morphology, structure, optical performance, stability and photovoltaic performance of the corresponding solar cell. The research provides a new thought for improving the performances of perovskite films and devices, and provides a valuable reference for promoting commercialization of perovskite films and devices.
Drawings
FIG. 1 is a field emission scanning electron microscope image of a perovskite thin film: (a) CH (CH) 3 NH 3 PbI 3 ；(b)CH 3 NH 3 Pb 0.9 Co 0.1 I 3 WOMF (no magnetic field effect); (c) CH (CH) 3 NH 3 Pb 0.9 Co 0.1 I 3 WMF (weak magnetic field effect); (d) CH (CH) 3 NH 3 Pb 0.9 Co 0.1 I 3 SMF (strong magnetic field effect).
FIG. 2 shows the deposition of ZnO@TiO 2 XRD pattern of perovskite thin film on nanorod array.
FIG. 3 (a) is CH 3 NH 3 PbI 3 ，CH 3 NH 3 Pb 0.9 Co 0.1 I 3 WOMF (no magnetic field effect), CH 3 NH 3 Pb 0.9 Co 0.1 I 3 WMF (Weak magnetic field action), CH 3 NH 3 Pb 0.9 Co 0.1 I 3 -ultraviolet-visible absorption spectrum of SMF (strong magnetic field effect) perovskite thin film; FIG. 3 (b) is CH 3 NH 3 PbI 3 ，CH 3 NH 3 Pb 0.9 Co 0.1 I 3 WOMF (no magnetic field effect), CH 3 NH 3 Pb 0.9 Co 0.1 I 3 WMF (Weak magnetic field action), CH 3 NH 3 Pb 0.9 Co 0.1 I 3 -fluorescence spectrum of SMF (strong magnetic field effect) perovskite thin film.
FIG. 4 shows perovskite thin film (a) CH stored in air for 0 to 72 hours 3 NH 3 PbI 3 ；(b)CH 3 NH 3 Pb 0.9 Co 0.1 I 3 WOMF (no magnetic field effect); (c) CH (CH) 3 NH 3 Pb 0.9 Co 0.1 I 3 WMF (weak magnetic field effect); (d) CH (CH) 3 NH 3 Pb 0.9 Co 0.1 I 3 XRD pattern of SMF (strong magnetic field effect); (e) Normalized intensity of XRD characteristic diffraction peaks corresponding to perovskite (110) crystal planes.
FIG. 5 is CH 3 NH 3 PbI 3 ，CH 3 NH 3 Pb 0.9 Co 0.1 I 3 WOMF (no magnetic field effect), CH 3 NH 3 Pb 0.9 Co 0.1 I 3 WMF (weak magnetic field effect), CH 3 NH 3 Pb 0.9 Co 0.1 I 3 -J-V curve of SMF (strong magnetic field effect) perovskite solar cell.
FIG. 6 is CH 3 NH 3 PbI 3 ，CH 3 NH 3 Pb 0.9 Co 0.1 I 3 WOMF (no magnetic field effect), CH 3 NH 3 Pb 0.9 Co 0.1 I 3 WMF (Weak magnetic field action), CH 3 NH 3 Pb 0.9 Co 0.1 I 3 - (a) humidity stability of the SMF (strong magnetic field effect) perovskite solar cell; (b) thermal stability; (c) Light stability
Detailed Description
The present invention will be specifically described with reference to the following examples.
Example 1
(1) Spin-coating 100 mu L of zinc acetate ethanol solution with the mass concentration of 0.005g/mL on an FTO conductive glass substrate subjected to ultraviolet ozone treatment, spin-coating for 30s at 3000r/min for 3 times, and annealing at 150 ℃ for 15min; spin-coating for 30s at 3000r/min, spin-coating for 3 times, and annealing at 150 ℃ for 15min; and finally spin-coating for 30s at 3000r/min, spin-coating for 3 times, and annealing at 350 ℃ for 45min to obtain the ZnO seed layer taking the FTO conductive glass as the substrate.
(2) 25mM Zn aqueous solution and polyvinylpyrrolidone aqueous solution with mass concentration of 0.0015g/mL were added as Zn 2+ The molar ratio of polyvinylpyrrolidone is 1:1, mixing to obtain a mixed solution;
(3) Adding ammonia water into the mixed solution prepared in the step (2), and regulating the pH value to 9 to obtain a growth solution.
(4) Horizontally inverting the ZnO seed layer prepared in the step (1) and taking the FTO conductive glass as a substrate, immersing the ZnO seed layer in the growth liquid prepared in the step (3) on a suspension frame, reacting for 10min in a water bath at 99 ℃, washing with deionized water, and cleaning with N 2 Drying to obtain the substrate.
(5) Placing the substrate taken out in the step 4 on a corundum boat, placing the corundum boat in a tube furnace, and placing the corundum boat in O 2 And (3) under the condition of the flow rate of 25mL/min, heating from room temperature to 420 ℃ at a heating rate of 5 ℃/min, and oxidizing and sintering for 30min.
(6) And (3) naturally cooling the substrate treated in the step (5) to room temperature, repeatedly rinsing in deionized water at 90 ℃, and airing in air to obtain the ZnO nano-rod array film taking the FTO conductive glass as a base.
(7) And (3) horizontally inverting the ZnO nano rod array film prepared in the step (6) on a suspension frame, putting the suspension frame into a solution of which the volume ratio is 1mL to 90mL and butyl titanate and isopropanol are uniformly mixed, adding 120 mu L of deionized water, magnetically stirring and reacting for 5h, taking out, washing with isopropanol, and annealing for 30min at 450 ℃. After cooling, the titanium tetrachloride aqueous solution with the volume ratio of 1/700 is treated by ice water bath for 30min, and then the film is annealed for 30min at 450 ℃ to obtain ZnO@TiO taking FTO conductive glass as a substrate 2 A nanorod array film.
(8) To a certain quality of PbI 2 Dissolved in a mixed solvent of DMF (N, N-dimethylformamide)/DMSO (dimethyl sulfoxide) in a volume ratio of 8:1, and magnetically stirred for 30min at 70 ℃. Then filtering with a polytetrafluoroethylene filter head with a pore diameter of 0.2 μm to obtain PbI with a molar concentration of 0.5M 2 Precursor solution. 0.1801g of CH 3 NH 3 I and 0.0091g CoI 2 Dissolving in isopropanol to obtain CH 3 NH 3 I：CoI 2 CH with a molar ratio of 10:1 3 NH 3 I-CoI 2 Isopropyl alcohol solution.
(9) Taking PbI prepared in the step (8) 2 150 mu L of precursor solution is spin-coated for 30s at 3000r/min to ZnO@TiO after ultraviolet ozone treatment 2 Soaking the surface of the nanorod array film in isopropanol for 1min, taking out, spin-coating for 30s at 3000r/min to spin-dry excessive liquid, and annealing at 70 ℃ for 30min. Placing the CH prepared in the step (8) 3 NH 3 I-CoI 2 And (3) carrying out reaction for 50s in isopropanol solution, spin-coating for 30s at 3000r/min after taking out, spin-drying redundant liquid, annealing for 1min at 80 ℃, and simultaneously placing 2 magnet blocks of 10cm x 1cm at a position which is 0.2cm away from the top of the film, and applying a weak magnetic field effect. After the annealing is finished, continuing the weak magnetic field action for 20min to obtain CH with the weak magnetic field action 3 NH 3 Pb 0.9 Co 0.1 I 3 A film; in addition, we also performed control examples without magnetic field effect and with strong magnetic field effect, respectivelyThe magnetic field effect is that 5 magnet blocks with the length of 10cm and the length of 1cm are placed at the position which is 0.2cm away from the position just above the film, the strong magnetic field effect is exerted, and after annealing is finished, the strong magnetic field effect is exerted for 20min; other conditions are the same;
(10) Transferring 40 mu L of Spiro-OMeTAD cobalt-based spin-coating liquid by a liquid transferring gun, and dripping the solution onto the FTO/ZnO@TiO prepared in the step (9) adsorbed on a vacuum chuck 2 CH of nano rod array/weak magnetic field action 3 NH 3 Pb 0.9 Co 0.1 I 3 Spin-coating the film substrate for 30s at 3000r/min to obtain FTO/ZnO@TiO 2 CH of nano rod array/weak magnetic field action 3 NH 3 Pb 0.9 Co 0.1 I 3 The film is a cobalt-doped Spiro-OMeTAD hole transport layer of the substrate.
(11) Under high vacuum (5×10) -5 Pa) under FTO/ZnO@TiO 2 CH of nano rod array/weak magnetic field action 3 NH 3 Pb 0.9 Co 0.1 I 3 Thermally evaporating a layer of gold (Au) with the thickness of 80nm on a Spiro-OMeTAD substrate as a cathode to obtain the structure of FTO/ZnO@TiO 2 CH of nano rod array/weak magnetic field action 3 NH 3 Pb 0.9 Co 0.1 I 3 Perovskite solar cell of/Spiro-OMeTAD/Au.
FIG. 1 is a field emission scanning electron microscope image of a perovskite thin film: (a) CH (CH) 3 NH 3 PbI 3 ；(b)CH 3 NH 3 Pb 0.9 Co 0.1 I 3 WOMF (no magnetic field effect); (c) CH (CH) 3 NH 3 Pb 0.9 Co 0.1 I 3 WMF (weak magnetic field effect); (d) CH (CH) 3 NH 3 Pb 0.9 Co 0.1 I 3 SMF (strong magnetic field effect).
FIG. 2 shows the deposition of ZnO@TiO 2 XRD pattern of perovskite thin film on nanorod array.
FIG. 3 (a) is CH 3 NH 3 PbI 3 ，CH 3 NH 3 Pb 0.9 Co 0.1 I 3 WOMF (no magnetic field effect), CH 3 NH 3 Pb 0.9 Co 0.1 I 3 WMF (Weak magnetic field action), CH 3 NH 3 Pb 0.9 Co 0.1 I 3 -ultraviolet-visible absorption spectrum of SMF (strong magnetic field effect) perovskite thin film; FIG. 3 (b) is CH 3 NH 3 PbI 3 ，CH 3 NH 3 Pb 0.9 Co 0.1 I 3 WOMF (no magnetic field effect), CH 3 NH 3 Pb 0.9 Co 0.1 I 3 WMF (Weak magnetic field action), CH 3 NH 3 Pb 0.9 Co 0.1 I 3 -fluorescence spectrum of SMF (strong magnetic field effect) perovskite thin film.
FIG. 4 shows perovskite thin film (a) CH stored in air for 0 to 72 hours 3 NH 3 PbI 3 ；(b)CH 3 NH 3 Pb 0.9 Co 0.1 I 3 WOMF (no magnetic field effect); (c) CH (CH) 3 NH 3 Pb 0.9 Co 0.1 I 3 WMF (weak magnetic field effect); (d) CH (CH) 3 NH 3 Pb 0.9 Co 0.1 I 3 XRD pattern of SMF (strong magnetic field effect); (e) Normalized intensity of XRD characteristic diffraction peaks corresponding to perovskite (110) crystal planes.
FIG. 5 is CH 3 NH 3 PbI 3 ，CH 3 NH 3 Pb 0.9 Co 0.1 I 3 WOMF (no magnetic field effect), CH 3 NH 3 Pb 0.9 Co 0.1 I 3 WMF (Weak magnetic field action), CH 3 NH 3 Pb 0.9 Co 0.1 I 3 -J-V curve of SMF (strong magnetic field effect) perovskite solar cell.
FIG. 6 is CH 3 NH 3 PbI 3 ，CH 3 NH 3 Pb 0.9 Co 0.1 I 3 WOMF (no magnetic field effect), CH 3 NH 3 Pb 0.9 Co 0.1 I 3 WMF (Weak magnetic field action), CH 3 NH 3 Pb 0.9 Co 0.1 I 3 - (a) humidity stability of the SMF (strong magnetic field effect) perovskite solar cell; (b) thermal stability; (c) light stability.
Example 2
(1) Spin-coating 100 mu L of an ethanol solution of zinc acetate with the mass concentration of 0.007g/mL on an FTO conductive glass substrate subjected to ultraviolet ozone treatment, spin-coating for 30s at 3000r/min, spin-coating for 3 times, and annealing at 150 ℃ for 15min; spin-coating for 30s at 3000r/min, spin-coating for 3 times, and annealing at 150 ℃ for 15min; and finally spin-coating for 30s at 3000r/min, spin-coating for 3 times, and annealing at 350 ℃ for 45min to obtain the ZnO seed layer taking the FTO conductive glass as the substrate.
(2) 100mM Zn aqueous solution and polyvinylpyrrolidone aqueous solution with mass concentration of 0.006g/mL were treated as Zn 2+ The molar ratio of polyvinylpyrrolidone is 1:1, mixing to obtain a mixed solution;
(3) Adding ammonia water into the mixed solution prepared in the step (2), and regulating the pH value to 11 to obtain a growth solution.
(4) Immersing the ZnO seed layer prepared in the step (1) and taking the FTO conductive glass as a substrate in the growth liquid prepared in the step (3) on a suspension bracket in a horizontal inversion manner, reacting for 6min in a water bath at 100 ℃, washing with deionized water, and cleaning with N 2 Drying to obtain the substrate.
(5) Placing the substrate taken out in the step 4 on a corundum boat, placing the corundum boat in a tube furnace, and placing the corundum boat in O 2 And (3) under the condition of 30ml/min of flow, heating from room temperature to 450 ℃ at a heating rate of 5 ℃/min, and oxidizing and sintering for 20min.
(6) And (3) naturally cooling the substrate treated in the step (5) to room temperature, repeatedly rinsing in deionized water at 90 ℃, and airing in air to obtain the ZnO nano-rod array film taking the FTO conductive glass as a base.
(7) And (3) horizontally inverting the ZnO nano rod array film prepared in the step (6) on a suspension frame, putting the suspension frame into a solution of which the volume ratio is 1mL to 110mL and butyl titanate and isopropanol are uniformly mixed, adding 130 mu L of deionized water, magnetically stirring and reacting for 7h, taking out, washing with isopropanol, and annealing for 30min at 450 ℃. After cooling, the titanium tetrachloride aqueous solution with the volume ratio of 1/900 is treated by ice water bath for 30min, and then the film is annealed for 30min at 450 ℃ to obtain ZnO@TiO taking FTO conductive glass as a substrate 2 A nanorod array film.
(8) To a certain quality of PbI 2 Dissolved in DMF/DMSO mixed solvent with volume ratio of 10:1, and magnetically stirred at 70 ℃ for 30min. Then using polytetrafluoroethylene with the pore diameter of 0.2 mu mFiltering by using an olefin filter head to obtain PbI with the molar concentration of 1.3M 2 Precursor solution. 0.2222g of CH 3 NH 3 I and 0.0093g of CoI 2 Dissolving in isopropanol, stirring at room temperature for 30min to obtain CH 3 NH 3 I：CoI 2 CH with a molar ratio of 12:1 3 NH 3 I-CoI 2 Isopropyl alcohol solution.
(9) 150. Mu.L PbI 2 Spin-coating the precursor solution to ZnO@TiO prepared in the step (7) through ultraviolet ozone treatment 2 Spin-coating the surface of the nanorod array film for 30s at 3000r/min, immersing in isopropanol for 1min, taking out, spin-drying the excessive liquid, and annealing at 70 ℃ for 30min. Put into CH 3 NH 3 I-CoI 2 And (3) reacting in isopropanol solution for 80s, taking out, spin-coating for 30s at 3500r/min, and spin-drying redundant liquid. Then placing the substrate on a heating table for annealing at 100 ℃ for 4min, placing 2 magnet blocks of 10cm x 1cm at a position 0.5cm away from the top of the film during annealing, applying a weak magnetic field effect, and continuously applying the weak magnetic field effect for 40min after the annealing is finished to obtain the film with FTO/ZnO@TiO 2 The nanorod array is CH with weak magnetic field effect of the substrate 3 NH 3 Pb 1-x Co x I 3 A film.
(10) 60 mu L of the Spiro-OMeTAD cobalt-based spin-coating liquid is removed by a liquid-transferring gun and is dripped into the FTO/ZnO@TiO prepared in the step (9) adsorbed on a vacuum chuck 2 CH of nano rod array/weak magnetic field action 3 NH 3 Pb 1-x Co x I 3 Spin-coating the film substrate for 30s at 3000r/min to obtain FTO/ZnO@TiO 2 CH of nano rod array/weak magnetic field action 3 NH 3 Pb 1-x Co x I 3 The film is a cobalt-doped Spiro-OMeTAD hole transport layer of the substrate.
(11) Under high vacuum (5×10) -5 Pa) under FTO/ZnO@TiO 2 CH of nano rod array/weak magnetic field action 3 NH 3 Pb 1-x Co x I 3 Thermally evaporating a layer of gold (Au) with the thickness of 80nm on a Spiro-OMeTAD substrate as a cathode to obtain the structure of FTO/ZnO@TiO 2 CH of nano rod array/weak magnetic field action 3 NH 3 Pb 1-x Co x I 3 Perovskite solar cell of/Spiro-OMeTAD/Au.
The invention utilizes the weak magnetic field to modify CH 3 NH 3 Pb 0.9 Co 0.1 I 3 The perovskite light absorption layer improves the surface coverage rate, morphology, crystallinity, light absorption performance, surface trap state, defect concentration and air stability of the perovskite film. The efficiency of the perovskite solar cell modified by the action of the weak magnetic field is improved by 17.6 percent compared with that of an unmodified cell. In addition, after 288 hours of standing at 80% high relative humidity, the unpackaged cells with modified, no applied and strong applied magnetic fields maintained 55%, 11% and 13% of their original photoelectric conversion efficiency values, respectively; after heating at 60 ℃ for 68 hours, the unpackaged cells modified by the weak magnetic field effect, not applying the magnetic field effect and applying the strong magnetic field effect maintain 24.8%, 19.2% and 11.3% of their original photoelectric conversion efficiency values, respectively; at 100mW/cm 2 After 60 minutes of continuous illumination, the unpackaged cells modified by the weak magnetic field, without the applied magnetic field, and with the applied strong magnetic field maintained 42.5%, 29.3%, and 29.1% of their original photoelectric conversion efficiency values, respectively. This shows that the device modified by the weak magnetic field has better humidity stability, heat stability and light stability than the perovskite solar cell without the magnetic field effect and the strong magnetic field effect.
Claims (9)
1. The preparation method of the magnetic perovskite film with the weak magnetic field effect is characterized by comprising the following steps of:
1) Preparing a ZnO seed layer on an FTO conductive glass substrate, and then preparing and obtaining a ZnO nano rod array film;
2) Placing the ZnO nanorod array film on a suspension bracket with the surface facing downwards on the sample prepared in the step 1) serving as a substrate, immersing the ZnO nanorod array film in a mixed solution of butyl titanate and isopropanol, adding deionized water, stirring and reacting for 4-8 hours, then flushing with isopropanol, annealing at 450 ℃ for at least 30min, immersing the ZnO nanorod array film in a titanium tetrachloride aqueous solution, treating the ZnO nanorod array film for at least 30min under the ice water bath condition, and then annealing the ZnO nanorod array film at 450 ℃ for at least 30min to obtain ZnO@TiO with FTO conductive glass serving as a substrate 2 NanorodsAn array film;
3) PbI is prepared 2 Dissolving in mixed solvent of DMF and DMSO, filtering with polytetrafluoroethylene filter head with pore size of 0.2 μm to obtain PbI 2 A precursor solution; coI is to 2 、CH 3 NH 3 I (MAI) is dissolved in isopropanol to obtain CH 3 NH 3 I-CoI 2 An isopropanol solution;
4) ZnO@TiO prepared in the step 2) is prepared 2 After the nanorod array film is treated by ultraviolet ozone, pbI is treated 2 Spin-coating the precursor solution onto its surface, immersing the sample in isopropanol, spin-drying, annealing at 70deg.C for at least 30min, and adding CH 3 NH 3 I-CoI 2 The mixture reacts in isopropanol solution for 40 to 100 seconds, is spin-coated and spin-dried after being taken out, and then the sample is annealed for 1 to 5 minutes at the temperature of between 80 and 110 ℃ and simultaneously the thin film is subjected to the action of a weak magnetic field; continuously applying a weak magnetic field to the film for 10-40 min after annealing to obtain FTO/ZnO@TiO 2 The nanorod array is CH with weak magnetic field effect of the substrate 3 NH 3 Pb 1-x Co x I 3 A film; the weak magnetic field is used for applying a magnetic field by placing 2 magnet blocks of 10cm x 1cm at a position 0.1-1 cm away from the position just above the film.
2. The method for producing a low-intensity magnetic field-induced magnetic perovskite thin film according to claim 1, wherein in the step 3), pbI 2 PbI in precursor solution 2 Molar concentration is 0.5-1.5M, CH 3 NH 3 I-CoI 2 MAI and CoI in isopropanol solution 2 The molar ratio of (2) is 8:1 to 12:1.
3. the method for preparing a magnetic perovskite thin film with weak magnetic field effect according to claim 1, wherein in the step 1), the FTO conductive glass is used as a substrate to prepare a ZnO seed layer, specifically: dripping 95-105 mu L of ethanol solution of zinc acetate with the mass concentration of 0.005-0.007 g/mL onto an FTO conductive glass substrate subjected to ultraviolet ozone treatment, spin-coating for 30s at 3000r/min for 3 times, and annealing at 150 ℃ for 15min; repeating the spin coating and annealing processes; and after the last spin coating, annealing for 45min at 350 ℃ to obtain the ZnO seed layer taking the FTO conductive glass as the substrate.
4. The method for preparing a magnetic perovskite thin film with weak magnetic field effect according to claim 1, wherein the preparation of the ZnO nano rod thin film in the step 1) is specifically as follows: 25 mM-100 mM of Zn salt water solution and 0.001-0.006 g/mL of polyvinylpyrrolidone water solution are mixed according to Zn 2+ The molar ratio of polyvinylpyrrolidone is 1: 2-2: 1, mixing to obtain a mixed solution; ammonia water is added, the pH value is regulated to 9-11, and growth liquid is obtained; the ZnO seed layer surface is inverted downwards and is immersed in the growth solution on a suspension bracket, water bath reaction is carried out for 4-12min at the temperature of 95-105 ℃, deionized water is used for washing, and N is used for washing 2 Drying to obtain a substrate; placing the substrate on a corundum boat, placing in a tube furnace, and placing in O 2 Heating from room temperature to 350-450 ℃ at a heating rate of 5 ℃/min under the flow of 10-50mL/min, oxidizing and sintering for 10-60 min, naturally cooling, repeatedly rinsing with deionized water, and airing in air to obtain the ZnO nano-rod array film taking FTO conductive glass as a substrate.
5. The method for preparing a low-intensity magnetic field-induced magnetic perovskite thin film according to claim 4, wherein the Zn salt is Zn (CH 3 COO) 2 ·2H 2 O、ZnCl 2 Or Zn (NO) 3 ) 2 The method comprises the steps of carrying out a first treatment on the surface of the The average molecular weight of the polyvinylpyrrolidone is 1,300,000.
6. The method for preparing a weak magnetic field magnetic perovskite thin film according to claim 1, wherein the volume ratio of butyl titanate to isopropyl alcohol in the mixed solution of step 2) is 1ml:50ml to 1ml:120ml, and the volume ratio of deionized water to butyl titanate is 100-140 μl:1mL.
7. The method for producing a low-intensity magnetic field-applied magnetic perovskite thin film according to claim 1, wherein the volume fraction of the titanium tetrachloride aqueous solution in the step 2) is 1/500 to 1/1000.
8. The method for producing a low-intensity magnetic field-applied magnetic perovskite thin film according to claim 1, wherein in the step 4), znO@TiO 2 150 mul PbI is dripped on the surface of the nano rod array film 2 Spin-coating the precursor solution at 3000r/min for 30s, and immersing the precursor solution in isopropanol for at least 1min after spin-coating; spin-coating and spin-drying in the step is to spin-coat for 30s at 3000r/min, and spin-dry redundant liquid.
9. A perovskite solar cell, characterized in that the magnetic perovskite thin film prepared by the method according to any one of claims 1 to 8 is used as a light absorption layer.
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