CN111864072A - Perovskite solar cell and preparation method thereof - Google Patents
Perovskite solar cell and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 164
- 239000011787 zinc oxide Substances 0.000 claims abstract description 82
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000000137 annealing Methods 0.000 claims abstract description 27
- 230000031700 light absorption Effects 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims description 39
- 238000004528 spin coating Methods 0.000 claims description 39
- 239000000758 substrate Substances 0.000 claims description 23
- 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 description 19
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 16
- 239000010931 gold Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 230000005525 hole transport Effects 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 9
- 230000004888 barrier function Effects 0.000 claims description 8
- 239000003599 detergent Substances 0.000 claims description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
- 239000012296 anti-solvent Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000010409 thin film Substances 0.000 abstract description 3
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 238000011049 filling Methods 0.000 abstract description 2
- 238000002161 passivation Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- CASUWPDYGGAUQV-UHFFFAOYSA-M potassium;methanol;hydroxide Chemical compound [OH-].[K+].OC CASUWPDYGGAUQV-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- VWTSXINFCUODBJ-UHFFFAOYSA-L zinc methanol diacetate Chemical compound [Zn++].CO.CC([O-])=O.CC([O-])=O VWTSXINFCUODBJ-UHFFFAOYSA-L 0.000 description 2
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000011701 zinc Substances 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
- 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
- H10K30/353—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 comprising blocking layers, e.g. exciton blocking layers
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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
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- 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
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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
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention provides a perovskite solar cell, and belongs to the field of solar cells. According to the perovskite solar cell provided by the invention, isobutylamine is used as a passivation layer, so that direct contact between zinc oxide and a perovskite light absorption layer is effectively prevented, the thermal stability of the perovskite solar cell is improved, and due to the existence of amino groups in the isobutylamine, the formation of a perovskite thin film with uniform grain size and high crystallinity can be promoted, so that the thermal stability of the perovskite layer is improved, and the perovskite solar cell is kept at high photoelectric conversion efficiency. The data of the examples show that the perovskite solar cell provided by the invention has the efficiency of 18.43 +/-0.91% and the current density of 21.93 +/-0.62 mA/cm2The open circuit voltage is 1.12 +/-0.02V, the filling factor is 75.04 +/-2.31%, and the thermal stability is good after 100 ℃ annealing.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a perovskite solar cell and a preparation method thereof.
Background
In the modern society with energy shortage, people are constantly engaged in the research of new energy sources in order to maintain the sustainable development of human beings. Among various new energy sources, solar energy is undoubtedly one of the most ideal energy sources as a clean, environment-friendly, inexpensive and renewable energy source. There are many ways in which solar energy can be utilized, with the photoelectric effect being of great concern. At present, about 85% of the market share of solar cells is occupied by silicon solar cells, but due to their high price, the application prospects are severely restricted. In recent years, perovskite solar cells have attracted much attention as a new type of solar cells, and since the first report in 2009, the photoelectric conversion efficiency has been increased from 3.8% to 23.3% in as short as a few years.
The perovskite solar cell generally comprises five parts, namely transparent conductive glass, a zinc oxide electron transport layer, a perovskite light absorption layer, a hole transport layer and a metal counter electrode. However, in the prior art, zinc oxide in the perovskite solar cell generates reverse proton decomposition reaction in the forming process of the perovskite light absorption layer to decompose perovskite, and the problem that the high-efficiency zinc oxide based perovskite solar cell cannot be formed due to poor thermal stability exists.
Disclosure of Invention
In view of this, the present invention aims to provide a perovskite solar cell and a preparation method thereof. According to the perovskite solar cell provided by the invention, isobutylamine is used as a barrier layer, so that direct contact between zinc oxide and a perovskite light absorption layer is prevented, and the thermal stability and the higher photoelectric conversion efficiency of the perovskite solar cell are improved.
In order to achieve the above object, the present invention provides the following technical solutions:
the perovskite solar cell comprises a transparent conductive glass substrate, a ZnO compact layer, an IBA barrier layer and CH which are sequentially arranged3NH3PbI3Perovskite light absorption layer, Spiro-MeOTAD hole layer and electrically conductive gold electrode.
Preferably, the thickness of the IBA barrier layer is 30-70 nm.
Preferably, the thickness of the ZnO dense layer is 30-60 nm.
Preferably, the thickness of the conductive gold electrode is 80-100 nm.
The invention also provides a preparation method of the perovskite solar cell in the technical scheme, which comprises the following steps:
(1) under the ultrasonic condition, sequentially cleaning a transparent conductive glass substrate by using a detergent, acetone, isopropanol, ethanol and deionized water, and then drying by using nitrogen to obtain a pretreated substrate;
(2) spin-coating a zinc oxide precursor solution on the surface of the pretreatment substrate to obtain FTO/ZnO;
(3) spin-coating an IBA solution on the surface of the ZnO layer of the FTO/ZnO obtained in the step (2) to obtain FTO/ZnO/IBA;
(4) spin-coating CH on the surface of IBA layer in FTO/ZnO/IBA obtained in the step (3)3NH3PbI3Annealing the perovskite precursor solution to obtain FTO/ZnO/IBA/CH3NH3PbI3；
(5) The FTO/ZnO/IBA/CH obtained in the step (4)3NH3PbI3Middle CH3NH3PbI3Spin coating a cavity transport layer precursor solution on the surface of the layer, and oxidizing to form a cavity transport layer to obtain FTO/ZnO/IBA/CH3NH3PbI3a/spiro-OMeTAD precursor solution comprising 2, 2 ', 7, 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino]-9, 9' -spirobifluorene, chlorobenzene, lithium salts and tetra-tert-butylpyridine;
(6) and (5) depositing Au on the surface of the hole transport layer formed in the step (5) to be used as a counter electrode, and obtaining the perovskite solar cell.
Preferably, CH is spin-coated in the step (4)3NH3PbI3And adding an anti-solvent dropwise when the perovskite precursor solution is prepared.
Preferably, the temperature of the annealing treatment in the step (4) is 60-100 ℃, and the time of the annealing treatment is 5-10 min.
Preferably, the step (2) further comprises, after the spin coating: and annealing the spin-coated sample, wherein the annealing temperature is 180-200 ℃, and the annealing time is 10-15 min.
The invention provides a perovskite solar cell which comprises a transparent conductive glass substrate, a ZnO compact layer, an IBA barrier layer and CH which are sequentially arranged3NH3PbI3Perovskite light absorption layer, Spiro-MeOTAD hole layer and electrically conductive gold electrode. The invention provides a perovskite solar cell, and belongs to the field of solar cells. The perovskite solar cell provided by the invention uses isobutylamine as a passivation layer, effectively prevents zinc oxide from being in direct contact with a perovskite light absorption layer, improves the thermal stability of the perovskite solar cell, and has amino groups in the isobutylamineThe perovskite thin film with uniform grain size and high crystallinity can be promoted to be formed, and the thermal stability of the perovskite layer is improved, and meanwhile, the perovskite solar cell keeps high photoelectric conversion efficiency. The data of the examples show that the perovskite solar cell provided by the invention has the efficiency of 18.43 +/-0.91% and the current density of 21.93 +/-0.62 mA/cm 2The open circuit voltage is 1.12 +/-0.02V, the filling factor is 75.04 +/-2.31%, and the thermal stability is good after annealing at 100 ℃ (room temperature is 26 ℃, and the humidity is 52% RH).
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Fig. 1 is a schematic diagram of a cell structure of a perovskite solar cell provided by the present invention;
FIG. 2 shows ZnO/IBA/CH prepared in example 1 of the present invention3NH3PbI3XRD pattern of (a);
FIG. 3 shows ZnO/IBA/CH prepared in example 1 of the present invention3NH3PbI3SEM picture of (1);
FIG. 4 is a graph of the J-V characteristics of a perovskite solar cell prepared in example 1 of the present invention;
fig. 5 is a thermal stability graph of the perovskite solar cell prepared in example 1 of the present invention.
Detailed Description
The invention provides a perovskite solar cell which comprises a transparent conductive glass substrate, a ZnO compact layer, an IBA barrier layer and CH which are sequentially arranged3NH3PbI3Perovskite light absorption layer, Spiro-MeOTAD hole layer and electrically conductive gold electrode.
In the invention, the thickness of the IBA barrier layer is preferably 30-90 nm.
In the invention, the thickness of the ZnO dense layer is preferably 30-60 nm, and more preferably 50 nm.
In the present invention, the CH3NH3PbI3The thickness of the perovskite light absorption layer is preferably 400-750 nm.
The source of the transparent conductive glass substrate (FTO) is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
The invention also provides a preparation method of the perovskite solar cell in the technical scheme, which comprises the following steps:
(1) under the ultrasonic condition, sequentially cleaning a transparent conductive glass substrate by using a detergent, acetone, isopropanol, ethanol and deionized water, and then drying by using nitrogen to obtain a pretreated substrate;
(2) spin-coating a zinc oxide precursor solution on the surface of the pretreatment substrate to obtain FTO/ZnO;
(3) spin-coating an IBA solution on the surface of the ZnO layer of the FTO/ZnO obtained in the step (2) to obtain FTO/ZnO/IBA;
(4) spin-coating CH on the IBA layer surface of the FTO/ZnO/IBA obtained in the step (3)3NH3PbI3Annealing the perovskite precursor solution to obtain FTO/ZnO/IBA/CH3NH3PbI3；
(5) The FTO/ZnO/IBA/CH obtained in the step (4)3NH3PbI3Middle CH3NH3PbI3After the surface of the layer is coated with a cavity transport layer precursor solution in a spin coating mode, oxidizing for a period of time to form a cavity transport layer, and obtaining FTO/ZnO/IBA/CH3NH3PbI3a/spiro-OMeTAD precursor solution comprising 2, 2 ', 7, 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino]-9, 9' -spirobifluorene, chlorobenzene, lithium salts and tetra-tert-butylpyridine;
(6) And (5) depositing Au on the surface of the hole transport layer formed in the step (5) to be used as a counter electrode, and obtaining the perovskite solar cell.
Under the ultrasonic condition, the transparent conductive glass substrate is sequentially cleaned by a detergent, acetone, isopropanol, ethanol and deionized water, and then dried by nitrogen to obtain the pretreated substrate. The dosage of the detergent, acetone, isopropanol, ethanol and deionized water is not specially limited, and the transparent conductive glass substrate can be cleaned. In the present invention, the detergent is preferably a detergent.
The power and time of the ultrasonic wave are not particularly limited in the present invention, and the ultrasonic power and time well known to those skilled in the art may be adopted, specifically, for example, 30min per ultrasonic cleaning.
In the present invention, the pre-treated substrate is preferably treated with oxygen plasma prior to use. In the present invention, the time of the oxygen plasma treatment is preferably 5 min. In the present invention, oxygen plasma treatment can increase the hydrophilicity of the FTO surface.
After the pretreated substrate is obtained, the invention spin-coats the zinc oxide precursor solution on the surface of the pretreated substrate to obtain FTO/ZnO. The composition of the zinc oxide precursor solution and the content of zinc oxide in the zinc oxide precursor solution are not particularly limited in the present invention, and the zinc oxide precursor solution known to those skilled in the art can be used. In the present invention, the zinc oxide precursor solution preferably includes zinc oxide nanoparticles, n-butanol, methanol, and chloroform. In the invention, the volume ratio of n-butanol, methanol and chloroform in the zinc oxide precursor solution is preferably 14: 1: 1.5.
In the present invention, the zinc oxide precursor solution is preferably filtered before use, and the filtering is more preferably performed by using a 0.45 μm PVDF filter head.
The invention has no special limitation on the particle size and the source of the zinc oxide nanoparticles, and the preparation method of the zinc oxide nanoparticles, which is well known to those skilled in the art, is adopted, and specifically, KOH is dissolved in methanol to prepare a potassium hydroxide methanol solution; zn (CH) is added under the condition of water bath at 65 DEG C3COO)2·2H2Dissolving O in methanol to obtain a zinc acetate methanol solution; dropwise adding the potassium hydroxide methanol solution into the zinc acetate methanol solution, continuously stirring and reacting for 2.5 hours under the water bath condition, and washing the obtained product with methanol for 2-3 times to remove residual ions to obtain the zinc oxide nanoparticles.
In the present invention, when potassium hydroxide is dissolved, the ratio of potassium hydroxide to methanol is preferably 0.29 g: 13 mL; when dissolving zinc acetate, the ratio of zinc acetate to methanol is preferably 0.59 g: 25 mL.
In the invention, the speed of the spin coating is preferably 3000-4000 rpm, more preferably 3500-3600 rpm, and the time of the spin coating is preferably 30 s.
In the invention, the spin coating is preferably performed for 4-5 times so as to reach the thickness range of the zinc oxide dense layer.
In the present invention, after the spin coating is completed, it is preferable to further include: and annealing the spin-coated sample, wherein the annealing temperature is preferably 150-200 ℃, more preferably 180-190 ℃, and the annealing time is preferably 10-30 min, more preferably 10-15 min. In the invention, the annealing treatment can enable the ZnO dense layer to be combined with the pretreated substrate more firmly.
After the FTO/ZnO is obtained, spin-coating an IBA solution on the surface of the ZnO layer of the FTO/ZnO to obtain the FTO/ZnO/IBA.
In the invention, the spin-coating speed of the IBA solution is preferably 2000-4000 rpm, more preferably 2500-3000 rpm, and the spin-coating time is preferably 25-35 s, more preferably 30 s.
After the FTO/ZnO/IBA is obtained, the surface of the IBA layer in the FTO/ZnO/IBA is spin-coated with CH3NH3PbI3Annealing the perovskite precursor solution to obtain FTO/ZnO/IBA/CH3NH3PbI3。
In the present invention, the spin coating CH3NH3PbI3The anti-solvent is preferably added dropwise to the perovskite precursor solution.
In the present invention, the perovskite precursor solution comprises PbI2、CH3NH3I (MAI), DMF and DMSO. The invention is about the PbI2、CH3NH3I. The amount ratio of DMF to DMSO is not particularly limited, and in specific examples, the amount ratio of DMF to DMSO is 0.462g of PbI2、0.15897gCH3NH3I. Perovskite precursor solution was obtained by conventional mixing of 0.6g dmf and 0.078g dmso.
In the invention, the speed of the spin coating of the perovskite precursor solution is preferably 2500-4000 rpm, more preferably 3000-3500 rpm, and the time of the spin coating is preferably 30-40 s, more preferably 40 s. In the present invention, it is preferable to add an antisolvent dropwise from the start of spin coating for 15 seconds to accelerate crystallization. The anti-solvent used in the present invention is not particularly limited, and those known to those skilled in the art, such as diethyl ether or chlorobenzene, can be used.
Deposition of CH3NH3PbI3After perovskite light absorption layer, annealing treatment is carried out on the obtained product to obtain FTO/ZnO/IBA/CH3NH3PbI3. In the invention, the temperature of the annealing treatment is preferably 50-110 ℃, more preferably 90-100 ℃, and the time of the annealing treatment is preferably 5-30 min, more preferably 10-15 min. In the present invention, the annealing treatment can promote perovskite crystallization.
Obtaining FTO/ZnO/IBA/CH3NH3PbI3Then, the invention is in the FTO/ZnO/IBA/CH3NH3PbI3Middle CH3NH3PbI3Spin coating a cavity transport layer precursor solution on the surface of the layer, and oxidizing to form a cavity transport layer to obtain FTO/ZnO/IBA/CH3NH3PbI3a/spiro-OMeTAD precursor solution comprising 2, 2 ', 7, 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino]-9, 9' -spirobifluorene (spiro-OMeTAD), chlorobenzene, lithium salts and tetra-tert-butylpyridine (TBP).
The invention has no special limitation on the dosage of 2, 2 ', 7, 7 ' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9, 9 ' -spirobifluorene, chlorobenzene, lithium salt and tetra-tert-butylpyridine in the hole transport layer precursor solution, and the solution for preparing the hole transport layer, which is well known to those skilled in the art, can be adopted. In the present example, specifically, 0.072g of spiro-OMeTAD was dissolved in 1mL of chlorobenzene, and 18.8. mu.L of lithium salt (0.052g + 100. mu.L of acetonitrile) and 28.8. mu.L of TBP were added thereto, followed by stirring at room temperature to obtain a clear pale yellow cavity layer precursor solution.
In the invention, the spin coating speed of the hole transport layer precursor solution is preferably 2500-4000 rpm, more preferably 3000rpm, and the spin coating time is preferably 20-40 s, more preferably 30 s.
In the invention, the spin coating amount of the hole transport layer precursor solution is preferably 75-80 muL.
In the present invention, the Relative Humidity (RH) of air at the time of oxidation is preferably less than 40%.
In the invention, the time for oxidation is preferably 24-36 h, and more preferably 30-32 h. In the present invention, the oxidation ensures complete oxidation of the hole transport layer.
After the hole transport layer is formed, Au is deposited on the surface of the hole transport layer to be used as a counter electrode, and the perovskite solar cell is obtained. In the present invention, the deposition is preferably evaporation-coating using a vacuum coater.
The perovskite solar cell and the preparation method thereof provided by the invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the invention.
FIG. 1 is a schematic structural diagram of a perovskite solar cell provided by the invention, which comprises a transparent conductive glass substrate, a ZnO dense layer, an IBA barrier layer and CH which are sequentially arranged3NH3PbI3Perovskite light absorption layer, Spiro-MeOTAD hole layer and electrically conductive gold electrode.
Example 1
The FTO glass is sequentially cleaned by detergent, acetone, isopropanol, ethanol and deionized water for 30min in an ultrasonic mode, then the glass is dried for standby by a nitrogen gun, and the glass is treated by oxygen plasma for five minutes before use.
0.29g of KOH was dissolved in 13mL of a methanol solution to prepare a solution 1; 0.59g of Zn (CH)3COO)2·2H2Adding O into 25mL of methanol solution, and stirring and dissolving at 65 ℃ in a water bath to form a solution 2; dropwise adding the solution 1 into the solution 2, continuously stirring and reacting for 2.5h under the water bath condition, washing the obtained nanoparticles for 2-3 times by using methanol to remove residual ions, dissolving the nanoparticles in 14mL of n-butanol, 1mL of methanol and 1.5mL of chloroform to form a ZnO precursor solution to obtain a zinc oxide precursor solution, and filtering the zinc oxide precursor solution by using a 0.45-micrometer PVDF filter head before use.
Taking 100 mu L of the ZnO precursor solution, spin-coating the ZnO precursor solution on a clean FTO glass substrate, wherein the spin-coating speed is 3000rpm, and the spin-coating time is 30 s; then annealing at 180 ℃ for 10min on a heating plate; this process was repeated 4 times to obtain a ZnO thin film of optimum thickness, the thickness of which was 50 nm.
Taking 100 mu L of IBA solution, carrying out spin coating deposition on the FTO/ZnO solution at the speed of 4000rpm for 30s to obtain the FTO/ZnO/IBA.
0.462g of PbI was weighed out separately2And 0.15897g MAI, followed by the addition of solvent 0.6g DMF and 0.078g DMSO to make up the perovskite precursor solution. Depositing 100 mu L of perovskite precursor solution on FTO/ZnO/IBA, wherein the spin-coating speed is 4000rpm, the spin-coating time is 30s, dropwise adding an anti-solvent at the 20 th s in the spin-coating process, and then annealing for 10min at the temperature of 100 ℃ to obtain the FTO/ZnO/IBA/CH3NH3PbI3。
0.072g of spiro-OMeTAD was dissolved in 1mL of chlorobenzene, and 18.8. mu.L of lithium salt (0.026g of lithium salt + 50. mu.L of acetonitrile) and 28.8. mu.L of 4-tert-butylpyridine were added. The spin-coating speed is 4000rpm, the spin-coating time is 40s, and FTO/ZnO/IBA/CH is obtained3NH3PbI3/spiro-MeOTAD。
Using a vacuum coating instrument to evaporate 0.15g of gold on FTO/ZnO/IBA/CH by thermal evaporation3NH3PbI3on/spiro-MeOTAD, the gold electrode thickness was 80 nm.
ZnO/IBA/CH was obtained for this example3NH3PbI3When the sample was subjected to XRD and SEM tests, as shown in fig. 2 and 3, respectively, it can be seen from fig. 2 to 3 that the perovskite structure was formed.
The perovskite solar cell prepared in the embodiment is subjected to J-V test, and the result is shown in FIG. 4, the photoelectric conversion efficiency of the device of the perovskite solar cell prepared in the invention is 18.43%, and the current density is 21.93mA/cm2The open circuit voltage was 1.12V and the fill factor was 75.04%.
Fig. 5 is a graph of the thermal stability of the perovskite solar cell prepared in example 1 of the present invention at 100 ℃ annealing (26 ℃ at room temperature and 52% RH in humidity). As can be seen from fig. 5, the perovskite solar cell prepared in this example has excellent thermal stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A perovskite solar cell comprises a transparent conductive glass substrate, a ZnO compact layer, an isobutylamine modified layer and CH which are sequentially arranged3NH3PbI3Perovskite light absorption layer, Spiro-MeOTAD hole layer and electrically conductive gold electrode.
2. The perovskite solar cell of claim 1, wherein the IBA barrier layer has a thickness of 30 to 90 nm.
3. The perovskite solar cell according to claim 1, wherein the ZnO dense layer has a thickness of 30 to 60 nm.
4. The perovskite solar cell according to claim 1, wherein the conductive gold electrode has a thickness of 80 to 100 nm.
5. A method of manufacturing a perovskite solar cell as claimed in any one of claims 1 to 4, comprising the steps of:
(1) under the ultrasonic condition, cleaning a transparent conductive glass substrate by using a detergent, acetone, isopropanol, ethanol and deionized water in sequence, and then drying by using nitrogen to obtain a pretreated substrate;
(2) spin-coating a zinc oxide precursor solution on the surface of the pretreatment substrate to obtain FTO/ZnO;
(3) spin-coating an IBA solution on the surface of the ZnO layer in the FTO/ZnO obtained in the step (2) to obtain FTO/ZnO/IBA;
(4) spin-coating CH on the surface of IBA layer in FTO/ZnO/IBA obtained in the step (3)3NH3PbI3Annealing the perovskite precursor solution to obtain FTO/ZnO/IBA/CH3NH3PbI3；
(5) The FTO/ZnO/IBA/CH obtained in the step (4)3NH3PbI3Middle CH3NH3PbI3Spin coating a cavity transport layer precursor solution on the surface of the layer, and oxidizing to form a cavity transport layer to obtain FTO/ZnO/IBA/CH 3NH3PbI3a/spiro-OMeTAD precursor solution comprising 2, 2 ', 7, 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino]-9, 9' -spirobifluorene, chlorobenzene, lithium salts and tetra-tert-butylpyridine;
(6) and (5) depositing Au on the surface of the hole transport layer formed in the step (5) to be used as a counter electrode, and obtaining the perovskite solar cell.
6. The method according to claim 5, wherein the step (4) comprises spin-coating CH3NH3PbI3And adding an anti-solvent dropwise when the perovskite precursor solution is prepared.
7. The method according to claim 5, wherein the temperature of the annealing treatment in the step (4) is 60 to 100 ℃, and the time of the annealing treatment is 5 to 10 min.
8. The method according to claim 5, wherein the step (2) further comprises, after the spin coating: and annealing the spin-coated sample, wherein the annealing temperature is 180-200 ℃, and the annealing time is 10-15 min.
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