CN111864072B - Perovskite solar cell and preparation method thereof - Google Patents
Perovskite solar cell and preparation method thereof Download PDFInfo
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- CN111864072B CN111864072B CN201910347241.6A CN201910347241A CN111864072B CN 111864072 B CN111864072 B CN 111864072B CN 201910347241 A CN201910347241 A CN 201910347241A CN 111864072 B CN111864072 B CN 111864072B
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- 238000002360 preparation method Methods 0.000 title description 6
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims abstract description 52
- 230000031700 light absorption Effects 0.000 claims abstract description 11
- 239000011521 glass Substances 0.000 claims description 14
- 239000010931 gold Substances 0.000 claims description 11
- 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 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 140
- 239000011787 zinc oxide Substances 0.000 abstract description 70
- 238000000137 annealing Methods 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 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
- 239000010409 thin film Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 238000004528 spin coating Methods 0.000 description 33
- 230000005525 hole transport Effects 0.000 description 19
- 239000000758 substrate Substances 0.000 description 19
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 7
- 239000003599 detergent Substances 0.000 description 7
- 229910003002 lithium salt Inorganic materials 0.000 description 7
- 159000000002 lithium salts Chemical class 0.000 description 7
- 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
- 239000012296 anti-solvent Substances 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- -1 N, N-bis (4-methoxyphenyl) amino Chemical group 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001590 oxidative effect 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
- 238000004140 cleaning Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 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
- 238000003756 stirring Methods 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
- JKSIBASBWOCEBD-UHFFFAOYSA-N N,N-bis(4-methoxyphenyl)-9,9'-spirobi[fluorene]-1-amine Chemical compound COc1ccc(cc1)N(c1ccc(OC)cc1)c1cccc2-c3ccccc3C3(c4ccccc4-c4ccccc34)c12 JKSIBASBWOCEBD-UHFFFAOYSA-N 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
- 230000006978 adaptation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 239000002245 particle Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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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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- 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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
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, the isobutylamine is used as the passivation layer, so that the zinc oxide is effectively prevented from being in direct contact with the perovskite light absorption layer, the thermal stability of the perovskite solar cell is improved, and due to the existence of amino groups in the isobutylamine, the perovskite thin film with uniform grain size and high crystallinity can be promoted to be formed, and the perovskite solar cell can maintain higher photoelectric conversion efficiency while the thermal stability of the perovskite layer is improved. 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 2 The 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 ℃.
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 modern society of energy shortage, research on new energy has been pursued in order to maintain sustainable development of human beings. Among various new energy sources, solar energy is certainly one of the most ideal energy sources as a clean, environment-friendly and inexpensive renewable energy source. There are many ways to utilize solar energy, and the photoelectric effect is widely focused. Currently, about 85% of the market share of solar cells is occupied by silicon solar cells, but the application prospect is severely limited due to the high price of the solar cells. In recent years, perovskite solar cells have attracted attention from many scientific researchers as a novel solar cell, and since the first report in 2009, the photoelectric conversion efficiency has been improved from 3.8% to 23.3% in a short period of time.
Perovskite solar cells generally consist of 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 process of forming the perovskite light absorption layer, so that perovskite is decomposed, 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 the above, an object of the present invention is to provide a perovskite solar cell and a method of manufacturing the same. According to the perovskite solar cell provided by the invention, the isobutylamine is used as the barrier layer, so that zinc oxide is prevented from being in direct contact with the perovskite light absorption layer, and the thermal stability and 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:
a perovskite solar cell comprises a transparent conductive glass substrate, a ZnO compact layer, an IBA barrier layer and a CH which are sequentially arranged 3 NH 3 PbI 3 A perovskite light absorption layer, a Spiro-MeOTAD hole layer and a conductive gold electrode.
Preferably, the thickness of the IBA barrier layer is 30-70 nm.
Preferably, the thickness of the ZnO compact 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, which comprises the following steps:
(1) Under the ultrasonic condition, cleaning the 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 zinc oxide precursor solution on the surface of the pretreated substrate to obtain FTO/ZnO;
(3) Spin-coating IBA solution on the surface of the ZnO layer of the FTO/ZnO obtained in the step (2) to obtain the FTO/ZnO/IBA;
(4) Spin-coating CH on the surface of IBA layer in the FTO/ZnO/IBA obtained in the step (3) 3 NH 3 PbI 3 Annealing treatment is carried out after the perovskite precursor solution to obtain FTO/ZnO/IBA/CH 3 NH 3 PbI 3 ；
(5) FTO/ZnO/IBA/CH obtained in the step (4) 3 NH 3 PbI 3 Middle CH 3 NH 3 PbI 3 Spin-coating a hole transport layer precursor solution on the surface of the layer, oxidizing to form a hole transport layer to obtain FTO/ZnO/IBA/CH 3 NH 3 PbI 3 The hole transport layer precursor solution comprises 2,2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino group]-9,9' -spirobifluorene, chlorobenzene, lithium salts and tetra-tert-butylpyridine;
(6) And (3) depositing Au on the surface of the hole transport layer formed in the step (5) to serve as a counter electrode, so as to obtain the perovskite solar cell.
Preferably, in the step (4), CH is spin-coated 3 NH 3 PbI 3 And (3) dropwise adding an antisolvent 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, after spin coating in the step (2), the method further comprises: and (3) carrying out annealing treatment on the spin-coated sample, wherein the temperature of the annealing treatment is 180-200 ℃, and the time of the annealing treatment 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 a CH which are arranged in sequence 3 NH 3 PbI 3 A perovskite light absorption layer, a Spiro-MeOTAD hole layer and a 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 takes the isobutylamine as the passivation layer, effectively prevents zinc oxide from being in direct contact with the perovskite light absorption layer, improves the thermal stability of the perovskite solar cell, and can promote the formation of a perovskite film with uniform grain size and high crystallinity due to the existence of amino groups in the isobutylamine, and can also ensure that the perovskite solar cell keeps while improving the thermal stability of the perovskite layerHigh 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 2 The open circuit voltage is 1.12+/-0.02V, the filling factor is 75.04 +/-2.31 percent, and the thermal stability is good after annealing at 100 ℃ (room temperature 26 ℃ and humidity 52%RH).
Drawings
The invention will be described in further detail with reference to the drawings and the detailed description.
Fig. 1 is a schematic diagram of a cell structure of a perovskite solar cell provided by the invention;
FIG. 2 shows the ZnO/IBA/CH prepared in example 1 of the present invention 3 NH 3 PbI 3 An XRD pattern of (b);
FIG. 3 is a ZnO/IBA/CH prepared in example 1 of the present invention 3 NH 3 PbI 3 SEM images of (a);
FIG. 4 is a graph of J-V characteristics of perovskite solar cell as prepared in example 1 of the invention;
fig. 5 is a graph showing the thermal stability 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 a CH which are arranged in sequence 3 NH 3 PbI 3 A perovskite light absorption layer, a Spiro-MeOTAD hole layer and a conductive gold electrode.
In the invention, the thickness of the IBA barrier layer is preferably 30-90 nm.
In the present invention, the thickness of the ZnO dense layer is preferably 30 to 60nm, more preferably 50nm.
In the present invention, the CH 3 NH 3 PbI 3 The thickness of the perovskite light absorbing layer is preferably 400 to 750nm.
The source of the transparent conductive glass substrate (FTO) is not particularly limited, and commercially available products known to those skilled in the art may be used.
The invention also provides a preparation method of the perovskite solar cell, which comprises the following steps:
(1) Under the ultrasonic condition, cleaning the 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 zinc oxide precursor solution on the surface of the pretreated substrate to obtain FTO/ZnO;
(3) Spin-coating IBA solution on the surface of the ZnO layer of the FTO/ZnO obtained in the step (2) to obtain the FTO/ZnO/IBA;
(4) Spin-coating CH on the IBA layer surface of the FTO/ZnO/IBA obtained in the step (3) 3 NH 3 PbI 3 Annealing treatment is carried out after the perovskite precursor solution to obtain FTO/ZnO/IBA/CH 3 NH 3 PbI 3 ；
(5) FTO/ZnO/IBA/CH obtained in the step (4) 3 NH 3 PbI 3 Middle CH 3 NH 3 PbI 3 After spin coating a hole transport layer precursor solution on the surface of the layer, oxidizing for a period of time to form a hole transport layer to obtain FTO/ZnO/IBA/CH 3 NH 3 PbI 3 The hole transport layer precursor solution comprises 2,2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino group]-9,9' -spirobifluorene, chlorobenzene, lithium salts and tetra-tert-butylpyridine;
(6) And (3) depositing Au on the surface of the hole transport layer formed in the step (5) to serve as a counter electrode, so as to obtain the perovskite solar cell.
Under the ultrasonic condition, the transparent conductive glass substrate is washed by a detergent, acetone, isopropanol, ethanol and deionized water in sequence, and then is dried by nitrogen to obtain the pretreated substrate. The dosage of the detergent, the acetone, the isopropanol, the ethanol and the deionized water is not particularly 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, and ultrasonic power and time well known to those skilled in the art can be adopted, and the ultrasonic wave is specifically cleaned for 30min each time.
In the present invention, the pretreated substrate is preferably treated with oxygen plasma prior to use. In the present invention, the time of the oxygen plasma treatment is preferably 5 minutes. In the present invention, oxygen plasma treatment can increase hydrophilicity of the FTO surface.
After a pretreated substrate is obtained, the invention spin-coats 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, and zinc oxide precursor solutions well known to those skilled in the art may 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 filtration is more preferably performed using a PVDF filter head of 0.45 μm.
The particle size and the source of the zinc oxide nano particles are not particularly limited, and the preparation method of the zinc oxide nano particles, which is well known to those skilled in the art, can be adopted, specifically, KOH is dissolved in methanol to prepare potassium hydroxide methanol solution; under the water bath condition of 65 ℃, zn (CH) 3 COO) 2 ·2H 2 O is dissolved in methanol to obtain zinc acetate methanol solution; and (3) dropwise adding the potassium hydroxide methanol solution into the zinc acetate methanol solution, continuously stirring and reacting for 2.5h under the water bath condition, and washing the obtained product with methanol for 2-3 times to remove residual ions, thereby obtaining the zinc oxide nano particles.
In the present invention, the ratio of potassium hydroxide to methanol is preferably 0.29 g/13 mL when potassium hydroxide is dissolved; when zinc acetate is dissolved, the ratio of zinc acetate to methanol is preferably 0.59 g/25 mL.
In the present invention, the spin-coating speed is preferably 3000 to 4000rpm, more preferably 3500 to 3600rpm, and the spin-coating time is preferably 30s.
In the present invention, the number of spin-coating is preferably 4 to 5 to achieve the thickness range of the zinc oxide dense layer.
In the present invention, it is preferable that the spin coating further comprises: the spin-coated sample is annealed at a temperature of preferably 150 to 200 ℃, more preferably 180 to 190 ℃, and for a time of preferably 10 to 30 minutes, more preferably 10 to 15 minutes. In the invention, the annealing treatment can enable the ZnO compact layer to be firmly combined with the pretreated substrate.
After the FTO/ZnO is obtained, spin-coating IBA solution on the surface of the ZnO layer of the FTO/ZnO to obtain the FTO/ZnO/IBA.
In the present invention, the spin coating speed of the IBA solution is preferably 2000 to 4000rpm, more preferably 2500 to 3000rpm, and the spin coating time is preferably 25 to 35s, more preferably 30s.
After the FTO/ZnO/IBA is obtained, the invention spin-coats CH on the surface of the IBA layer in the FTO/ZnO/IBA 3 NH 3 PbI 3 Annealing treatment is carried out after the perovskite precursor solution to obtain FTO/ZnO/IBA/CH 3 NH 3 PbI 3 。
In the present invention, the spin-coating CH 3 NH 3 PbI 3 The anti-solvent is preferably added dropwise to the perovskite precursor solution.
In the present invention, the perovskite precursor solution comprises PbI 2 、CH 3 NH 3 I (MAI), DMF and DMSO. The invention relates to the PbI 2 、CH 3 NH 3 I. The ratio of DMF to DMSO is not particularly limited, and in particular examples, 0.462gPbI 2 、0.15897gCH 3 NH 3 I. 0.6g DMF and 0.078g DMSO were mixed conventionally to give a perovskite precursor solution.
In the present invention, the speed of spin coating of the perovskite precursor solution is preferably 2500 to 4000rpm, more preferably 3000 to 3500rpm, and the spin coating time is preferably 30 to 40s, more preferably 40s. In the present invention, it is preferable to add an antisolvent dropwise from the start of spin coating to 15s to accelerate crystallization. The kind of the antisolvent is not particularly limited, and the antisolvent well known to those skilled in the art may be used, and specifically, diethyl ether or chlorobenzene.
Deposition of CH 3 NH 3 PbI 3 After the perovskite light absorption layer, the invention carries out annealing treatment on the obtained product to obtain the FTO/ZnO/IBA/CH 3 NH 3 PbI 3 . In the present invention, the temperature of the annealing treatment is preferably 50 to 110 ℃, more preferably 90 to 100 ℃, and the time of the annealing treatment is preferably 5 to 30 minutes, more preferably 10 to 15 minutes. In the present invention, the annealing treatment can promote perovskite crystallization.
Obtaining FTO/ZnO/IBA/CH 3 NH 3 PbI 3 After that, the invention is carried out on the FTO/ZnO/IBA/CH 3 NH 3 PbI 3 Middle CH 3 NH 3 PbI 3 Spin-coating a hole transport layer precursor solution on the surface of the layer, oxidizing to form a hole transport layer to obtain FTO/ZnO/IBA/CH 3 NH 3 PbI 3 The hole transport layer precursor solution comprises 2,2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino group]-9,9' -spirobifluorene (spiro-ome tad), chlorobenzene, lithium salts and tetra-tert-butylpyridine (TBP).
The amount of 2,2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene, chlorobenzene, lithium salt and tetra-tert-butylpyridine in the hole transport layer precursor solution is not particularly limited, and the solution composition for preparing the hole transport layer well known to the person skilled in the art can be adopted. In the examples of the present invention, specifically, for example, 0.072g of the spiro-OMeTAD was dissolved in 1mL of chlorobenzene, 18.8. Mu.L of lithium salt (0.052g+100. Mu.L of acetonitrile) and 28.8. Mu.L of TBP were further added thereto, and the mixture was stirred at room temperature to obtain a clear pale yellow hole layer precursor solution.
In the present invention, the spin-coating speed of the hole transport layer precursor solution is preferably 2500 to 4000rpm, more preferably 3000rpm, and the spin-coating time is preferably 20 to 40s, more preferably 30s.
In the present invention, the spin-coating amount of the hole transport layer precursor solution is preferably 75 to 80. Mu.L.
In the present invention, the Relative Humidity (RH) of the air at the time of oxidation is preferably less than 40%.
In the present invention, the time of the oxidation is preferably 24 to 36 hours, more preferably 30 to 32 hours. In the present invention, the oxidation can ensure complete oxidation of the hole transport layer.
After forming a hole transport layer, depositing Au on the surface of the hole transport layer to serve as a counter electrode to obtain the perovskite solar cell. In the present invention, the deposition is preferably vapor-coated using a vacuum coater.
The perovskite solar cell and the method for manufacturing the same according to the present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
FIG. 1 is a schematic diagram of a perovskite solar cell according to the present invention, comprising a transparent conductive glass substrate, a ZnO dense layer, an IBA barrier layer, and CH, which are sequentially arranged 3 NH 3 PbI 3 A perovskite light absorption layer, a Spiro-MeOTAD hole layer and a conductive gold electrode.
Example 1
The FTO glass is sequentially ultrasonically cleaned for 30min by using a detergent, acetone, isopropanol, ethanol and deionized water, then the glass is dried for standby by using a nitrogen gun, and is treated by oxygen plasma for five minutes before being used.
Solution 1 was prepared by dissolving 0.29g of KOH in 13mL of methanol solution; 0.59g of Zn (CH) 3 COO) 2 ·2H 2 O is added into 25mL of methanol solution, and is stirred and dissolved under the water bath condition of 65 ℃ to form solution 2; dropwise adding the solution 1 into the solution 2, continuously stirring under the water bath condition for reacting for 2.5 hours, washing the obtained nano particles with methanol for 2-3 times to remove residual ions, dissolving the nano particles in 14mL of n-butanol, 1mL of methanol and 1.5mL of chloroform to form a ZnO precursor solution, and filtering the ZnO precursor solution by using a PVDF filter head with the thickness of 0.45 mu m before using the ZnO precursor solution.
Taking 100 mu L of the ZnO precursor solution, and 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 30s; subsequently annealing on a heating plate at 180 ℃ for 10min; this procedure was repeated 4 times to obtain a ZnO film of optimal thickness, the thickness of the film being 50nm.
100 mu L of IBA solution is taken and spin-coated on FTO/ZnO, the spin-coating speed is 4000rpm, and the spin-coating time is 30s, so that the FTO/ZnO/IBA is obtained.
0.462g of PbI was weighed out separately 2 And 0.15897g MAI, then 0.6g DMF and 0.078g DMSO were added to make up the perovskite precursor solution. Depositing 100 mu L of perovskite precursor solution on FTO/ZnO/IBA, spin-coating at 4000rpm for 30s, dripping antisolvent at 20s in the spin-coating process, and annealing at 100deg.C for 10min to obtain FTO/ZnO/IBA/CH 3 NH 3 PbI 3 。
0.072g of spiro-OMeTAD was dissolved in 1mL of chlorobenzene, and 18.8. Mu.L of lithium salt (0.026 g of lithium salt+50. Mu.L of acetonitrile) and 28.8. Mu.L of 4-tert-butylpyridine were added. Spin coating speed is 4000rpm, spin coating time is 40s, and FTO/ZnO/IBA/CH is obtained 3 NH 3 PbI 3 /spiro-MeOTAD。
0.15g of gold is evaporated on an FTO/ZnO/IBA/CH by a vacuum film plating instrument and thermal evaporation 3 NH 3 PbI 3 on/spiro-MeOTAD, the gold electrode thickness was 80nm.
For the embodiment, znO/IBA/CH is prepared 3 NH 3 PbI 3 The sample was subjected to XRD and SEM tests, as shown in FIGS. 2 and 3, respectively, and as can be seen from FIGS. 2 to 3, a perovskite structure was formed.
The perovskite solar cell prepared in this example was 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/cm 2 The open circuit voltage was 1.12V and the fill factor was 75.04%.
Fig. 5 is a graph showing the thermal stability of the perovskite solar cell prepared in example 1 of the present invention at 100 ℃ annealing (room temperature 26 ℃, humidity 52% rh). As can be seen from fig. 5, the perovskite solar cell prepared in this example has excellent thermal stability.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (1)
1. A perovskite solar cell comprises a transparent conductive glass base, a ZnO compact layer, an isobutylamine modification layer, a CH3NH3PbI3 perovskite light absorption layer, a Spiro-MeOTAD hole layer and a conductive gold electrode which are sequentially arranged.
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| CN107104189A (en) * | 2016-02-23 | 2017-08-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | perovskite thin film solar cell and preparation method thereof |
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