CN114574193A - Method for extracting residual lead iodide from lead halogen perovskite material - Google Patents
Method for extracting residual lead iodide from lead halogen perovskite material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 91
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 9
- 150000002367 halogens Chemical class 0.000 title 1
- 239000002243 precursor Substances 0.000 claims abstract description 166
- 150000003839 salts Chemical class 0.000 claims abstract description 137
- -1 amine salt Chemical class 0.000 claims abstract description 95
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical class CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 78
- 238000000137 annealing Methods 0.000 claims abstract description 58
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 239000010408 film Substances 0.000 claims description 91
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 49
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 30
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 10
- 230000005525 hole transport Effects 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 7
- 125000001475 halogen functional group Chemical group 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- TWZBHHYMSPBSBI-UHFFFAOYSA-N [I-].[NH4+].C(=N)N Chemical compound [I-].[NH4+].C(=N)N TWZBHHYMSPBSBI-UHFFFAOYSA-N 0.000 claims description 3
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 2
- VRNINGUKUJWZTH-UHFFFAOYSA-L lead(2+);dithiocyanate Chemical compound [Pb+2].[S-]C#N.[S-]C#N VRNINGUKUJWZTH-UHFFFAOYSA-L 0.000 claims description 2
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 2
- WWAFREDGOYFDCU-UHFFFAOYSA-N [Br-].[NH4+].C(=N)N Chemical compound [Br-].[NH4+].C(=N)N WWAFREDGOYFDCU-UHFFFAOYSA-N 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- VOWZMDUIGSNERP-UHFFFAOYSA-N carbamimidoyl iodide Chemical compound NC(I)=N VOWZMDUIGSNERP-UHFFFAOYSA-N 0.000 claims 1
- JAHFQMBRFYOPNR-UHFFFAOYSA-N iodomethanamine Chemical compound NCI JAHFQMBRFYOPNR-UHFFFAOYSA-N 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000007547 defect Effects 0.000 abstract description 9
- 239000000284 extract Substances 0.000 abstract 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 143
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 99
- 238000004528 spin coating Methods 0.000 description 65
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 52
- 238000002360 preparation method Methods 0.000 description 43
- 230000031700 light absorption Effects 0.000 description 41
- 230000000052 comparative effect Effects 0.000 description 29
- 238000003756 stirring Methods 0.000 description 29
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 description 24
- 239000002904 solvent Substances 0.000 description 24
- 238000001816 cooling Methods 0.000 description 22
- 238000010586 diagram Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 7
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 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 5
- SXGBREZGMJVYRL-UHFFFAOYSA-N butan-1-amine;hydrobromide Chemical compound [Br-].CCCC[NH3+] SXGBREZGMJVYRL-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 description 3
- 125000002496 methyl group Chemical class [H]C([H])([H])* 0.000 description 3
- 229940117803 phenethylamine Drugs 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910001516 alkali metal iodide Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical class C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- LLWRXQXPJMPHLR-UHFFFAOYSA-N methylazanium;iodide Chemical class [I-].[NH3+]C LLWRXQXPJMPHLR-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- LPJKDVHMUUZHRY-UHFFFAOYSA-N octadec-9-enylazanium;chloride Chemical compound Cl.CCCCCCCCC=CCCCCCCCCN LPJKDVHMUUZHRY-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
- C09K11/665—Halogenides with alkali or alkaline earth metals
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Abstract
The invention discloses a method for extracting residual lead iodide from a lead-halogen perovskite material, which comprises the following steps: coating a lead salt precursor solution on a substrate, and carrying out annealing crystallization treatment to form a lead salt film; sequentially coating the amine salt precursor solution and the oleylamine salt precursor solution on the lead salt film to form a perovskite precursor film; and annealing and crystallizing the substrate and the perovskite precursor film in an atmospheric environment to form the perovskite material. The method extracts residual lead iodide in the lead-halogen perovskite material from the grain boundary to the surface of the perovskite crystal grain, reduces the defect state density, and the prepared perovskite material can effectively improve the photoelectric conversion efficiency of the perovskite solar photovoltaic device to 24.28% at most and obviously improve the stability of the perovskite device.
Description
Technical Field
The invention belongs to the field of photoelectronic materials and devices, and particularly relates to a method for extracting residual lead iodide from a lead-halogen perovskite material.
Background
The organic-inorganic hybrid perovskite solar cell has the efficiency comparable with that of a silicon solar cell in short time of about ten years, has low material preparation cost, and is favored by the majority of scientific research personnel. Perovskite solar cells have also achieved a lot of research results in terms of stability and efficiency. The perovskite light absorption material has the advantages of high carrier mobility, adjustable band gap, solution preparation, high absorption coefficient and the like, so that the perovskite solar cell with high performance can be obtained by regulating and controlling the components of the perovskite material. Furthermore, defects can also be passivated by introducing a modifying material. Researches have proved that lead iodide can effectively passivate defect states of perovskite, thereby improving the performance of devices; however, too much lead iodide also causes instability problems. Therefore, how to balance performance and stability is a problem to be optimized and explored. The charge transmission capability of the perovskite material is improved, the defect state density is reduced, the key strategy for improving the performance and stability of the device is provided, the lead iodide is a p-type material, the charge transmission capability can be effectively improved by inducing the distribution of the lead iodide at the surface grain boundary of the perovskite in the prior art, but the charge transmission of the perovskite material is not perfect and the defect states are many at present.
Disclosure of Invention
Aiming at the problems of imperfect charge transmission and many defect states of the existing perovskite material, the invention discovers that oleylamine salt is coated on the unannealed perovskite precursor film and then annealed, so that lead iodide at the grain boundary of the perovskite film can be extracted to the surface of perovskite crystal grains, thereby effectively improving the charge transmission performance, enabling the perovskite film to have quicker charge extraction capability and less defect state density, improving the working stability, being used for preparing a solar photovoltaic device, having the conversion efficiency as high as 23.2 percent and the filling factor reaching more than 84 percent.
The technical scheme provided by the invention is as follows:
a method of extracting residual lead iodide from a lead-halo perovskite material, comprising the steps of:
coating a lead salt precursor solution on a substrate, and carrying out annealing crystallization treatment to form a lead salt film;
sequentially coating the amine salt precursor solution and the oleylamine salt precursor solution on the lead salt film to form a perovskite precursor film; and
and annealing and crystallizing the substrate and the perovskite precursor film in an atmospheric environment to form the perovskite material.
According to the method, excessive lead iodide is extracted to the surface of the perovskite crystal grain instead of the grain boundary, so that the perovskite material has more excellent performance in a solar photovoltaic device.
The method further comprises the following post-processing steps: and coating the chloroform solution of the oleylamine salt on the surface of the perovskite material. Although the quantity and the form of the lead iodide on the surface of the perovskite crystal grain are not obviously changed in the post-treatment step, the performance of the perovskite solar photovoltaic device can be obviously improved.
In particular embodiments, the lead salt is one or more of lead (II) iodide, lead (II) thiocyanate, lead (II) chloride, lead (II) bromide.
According to some embodiments, the lead salt precursor solution comprises an iodide salt, wherein the iodide salt is one or more of formamidine ammonium iodide, methyl ammonium iodide, and an alkali metal iodide salt.
In a particular embodiment, the lead salt is lead (II) iodide and the lead salt precursor solution comprises methyl amine iodide.
In a particular embodiment, the lead salt is lead (II) iodide and the lead salt precursor solution comprises CsI.
According to some embodiments, the amine salt is one or more of formamidine iodized amine, formamidine chlorinated amine, methyl amidine brominated amine, methyl iodized amine, methyl chlorinated amine, methyl brominated amine.
According to some embodiments, the oleylamine salt precursor solution has a concentration of the halogenated oleylamine salt of 0.05mg/mL to 0.4 mg/mL.
In a particular embodiment, the oleylamine salt precursor solution has a concentration of the halogenated oleylamine salt of from 0.075mg/mL to 0.3 mg/mL.
In a particular embodiment, the concentration of the halogenated oleylamine salt in the oleylamine salt precursor solution is 0.15 mg/mL.
In a particular embodiment, the oleylamine salt is a halogenated oleylamine salt, such as an oleylamine bromide, an oleylamine iodide, an oleylamine chloride, particularly preferably an oleylamine chloride (hereinafter abbreviated as oleylamine chloride).
According to some embodiments, the temperature of the annealing crystallization treatment in the atmospheric environment is greater than or equal to 50 ℃ and less than or equal to 300 ℃, and the absolute humidity of the atmospheric environment is greater than or equal to 30% and less than or equal to 40%.
In a particular embodiment, the temperature of the annealing crystallization treatment in the atmospheric environment is 150 ℃ and the absolute humidity of the atmospheric environment is 35%.
According to some embodiments, a method of preparing a perovskite material comprises the steps of:
will PbI2Dissolving in an organic solvent to form a lead salt precursor solution;
dissolving amine salt in isopropanol to form amine salt precursor solution;
dissolving oleylamine chloride in a chloroform solvent to form oleylamine salt precursor solution;
spin-coating the lead salt precursor solution on a substrate, and annealing to room temperature to obtain PbI2A film;
in PbI2Sequentially spin-coating amine salt precursor solution and oleylamine salt precursor solution on the film to form a perovskite precursor film;
and annealing the substrate covered with the perovskite precursor film in an atmospheric environment to obtain the perovskite material.
In a particular embodiment, the organic solvent is a mixed solvent of DMF and DMSO.
In a specific embodiment, the concentration of the amine salt in the amine salt precursor solution is regulated and controlled according to different components;
in a particular embodiment, PbI is prepared2The annealing temperature of the film is 70 ℃, and the time is 1 min;
in a particular embodiment, the spin-coating rotation speed of the oleylamine salt precursor solution is 4000rpm for 30 s.
In a specific embodiment, the preparation method is used for preparing a perovskite light absorption layer in a perovskite solar photovoltaic device, and a matrix spin-coated by a lead salt precursor solution is an electron transport layer.
According to some embodiments, the present invention provides a perovskite material prepared based on the above method, the perovskite material being an organic-inorganic hybridPerovskite (FAPBI)3)x(MAPbI3)1-x, lead iodide hardly exists between crystal boundaries, the lead iodide is enriched on the surface of perovskite crystal grains, and the lead iodide is enriched in organic-inorganic hybrid perovskite (FAPBI) between the crystal boundaries3)x(MAPbI3)1-x has a lower defect state density.
According to some embodiments, the invention provides a perovskite solar photovoltaic device based on the perovskite material, which comprises an ITO glass substrate, a tin dioxide transport layer, the perovskite material prepared by the above method, a hole transport layer and a top electrode layer from bottom to top.
In a particular embodiment, the tin dioxide transport layer is 30nm thick, the perovskite material is 600nm thick, the hole transport layer is 80nm thick and the top electrode layer is 80nm thick.
In particular embodiments, the perovskite material is an organic-inorganic hybrid perovskite (FAPbI)3)x(MAPbI3)1-x。
The invention has the beneficial effects that:
1. compared with the situation that the perovskite material is not treated by an oleylamine salt precursor solution, the perovskite material obtained after the residual lead iodide is extracted from the lead halide perovskite material has more excellent charge transmission performance and lower defect state density;
2. the method for extracting the residual lead iodide from the lead-halogen perovskite material is simple and has good repeatability;
3. after the residual lead iodide is extracted from the lead-halogen perovskite material, the photoelectric conversion efficiency (up to 23.2%) of the perovskite solar photovoltaic device is effectively improved, the filling factor and the open-circuit voltage are mainly improved, and the method has great application development potential.
Drawings
FIG. 1 is a device structure diagram of a planar perovskite solar photovoltaic device, wherein a 1-ITO glass substrate, a 2-tin dioxide transmission layer, a 3-perovskite light absorption layer, a 4-hole transmission layer, a Spiro-OMeTAD, and a 5-top electrode are arranged;
FIG. 2 is a statistical plot of the performance of the perovskite solar photovoltaic device prepared in example 1;
FIG. 3 is a statistical plot of the performance of the perovskite solar photovoltaic device prepared in example 2;
FIG. 4 is a statistical plot of the performance of the perovskite solar photovoltaic device prepared in example 2;
FIG. 5 is a statistical plot of the performance of the perovskite solar photovoltaic device prepared in example 3;
fig. 6 is a statistical graph of the performance of the perovskite solar photovoltaic device manufactured in comparative example 1.
FIG. 7 is a statistical plot of the performance of the perovskite solar photovoltaic device prepared in example 4;
fig. 8 is a statistical graph of the performance of the perovskite solar photovoltaic device manufactured in comparative example 2.
FIG. 9 is a statistical plot of the performance of the perovskite solar photovoltaic device made in example 5;
fig. 10 is a statistical graph of the performance of the perovskite solar photovoltaic device manufactured in comparative example 3.
FIG. 11 is a topographical view of the perovskite material produced in example 6;
fig. 12 is a morphology map of the perovskite material produced in comparative example 4.
FIG. 13 is a topographical view of the perovskite material produced in example 7;
fig. 14 is a morphology map of the perovskite material produced in comparative example 5.
FIG. 15 is a topographical view of the perovskite material produced in example 8;
fig. 16 is a morphology map of the perovskite material produced in comparative example 6.
FIG. 17 is a topographical view of the perovskite material produced in example 9;
fig. 18 is a morphology map of the perovskite material produced in comparative example 7.
FIG. 19 is a topographical map of the perovskite material produced in example 10.
Fig. 20 is a morphology diagram of the perovskite material prepared in comparative example 8.
Fig. 21 is a morphology map of the perovskite material produced in comparative example 9.
Fig. 22 is a morphology diagram of the perovskite material prepared in comparative example 10.
Fig. 23 is a morphology diagram of the perovskite material produced in comparative example 11.
Fig. 24 is a morphology diagram of the perovskite material prepared in comparative example 12.
Fig. 25 is a morphology map of the perovskite material produced in comparative example 13.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Oleylamine chloride, also known as oleylamine chloride, common name 9-octadecenylamine chloride, CAS number, used in the following examples: 41130-29-4.
Example 1: preparation of perovskite solar photovoltaic device
The structural schematic diagram of the perovskite solar photovoltaic device is shown in fig. 1, and the perovskite solar photovoltaic device comprises an ITO conductive glass substrate, an electron transport layer (hydrogen peroxide modified tin dioxide film), a perovskite light absorption layer, a hole transport layer and a top electrode in sequence from bottom to top, and the preparation method specifically comprises the following steps:
1. cleaning:
in the test, the substrate is cleaned and dried. And (3) cleaning the ITO conductive glass with a proper size by using a cleaning agent, and then washing by using deionized water. Then the ITO conductive glass is placed in an ultrasonic cleaner to be sequentially ultrasonically cleaned by acetone, ethanol and deionized water, and finally, nitrogen is used for blow-drying, so that the ITO conductive glass with a clean surface, namely the substrate required by the embodiment, is obtained.
2. Preparing an electron transport layer:
mixing tin dioxide colloidal solution, deionized water and hydrogen peroxide in a proportion of 1: 4: 1, and then stirring for 24 hours at room temperature to obtain a hydrogen peroxide modified tin dioxide precursor solution; the method comprises the steps of spin-coating a hydrogen peroxide modified tin dioxide precursor solution on a substrate at a rotation speed of 4000rpm for 30s, and then placing the substrate on a hot stage at 180 ℃ for annealing for 30min to obtain a hydrogen peroxide modified tin dioxide thin film with a thickness of about 30nm, wherein the thin film is used as an electron transport layer in the embodiment.
3. Preparing a perovskite light absorption layer:
will PbI2MAI (methyl amine iodide) was dissolved in a DMF and DMSO complex solvent (volume ratio DMF: DMSO ═ 19:1) at a molar concentration of 1.3M and 0.039M, respectively, and stirred at 60 ℃ for 24 hours to obtain a lead salt precursor solution. Wherein DMF and DMSO represent N, N-dimethylformamide and dimethyl sulfoxide, respectively.
Dissolving amine salt consisting of FAI (formamidine ammonium iodide) and MACl (methyl ammonium chloride) in a mass ratio of 60:12 in 1mL of isopropanol, and stirring for 24h at normal temperature to obtain an amine salt precursor solution.
Dissolving oleylamine chloride in chloroform according to the concentration of 0.075mg/mL to obtain oleylamine chloride precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, spin-coating the oleylamine chloride precursor solution on the lead salt film, and annealing at 150 ℃ for 12min in an atmospheric environment with the humidity of about 35% to obtain the component (FAPBI)3)x(MAPbI3)1-xThe light-absorbing layer of the perovskite modified by oleylamine chloride has the thickness of about 700 nm.
4. Preparing a hole transport layer:
preparing 2,2',7,7' -tetra [ N, N-di (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD) on a perovskite light absorption layer as a hole transport layer, wherein the preparation method comprises the following steps: dissolving 520mg of lithium bistrifluoromethylenesulfonate imide (Li-TFSI) in 1mL of acetonitrile, and stirring for 3min to obtain a Li-TFSI acetonitrile solution; then, 72.3mg of 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD) was dissolved in 1mL of chlorobenzene, and 28.8. mu.L of 4-tert-butylpyridine (TBP) and 17.5. mu.L of a Li-TFSI acetonitrile solution were added and stirred at 40 ℃ for 24 hours. The prepared solution was spin coated on the perovskite light absorbing layer at 3000rpm for 20 s. The resulting film is a hole transport layer. The thickness of the hole transport layer was about 80 nm.
5. Preparing a top electrode:
and (4) taking an Au electrode with the evaporation thickness of about 80nm on the hole transport layer as a top electrode to obtain the perovskite solar photovoltaic device.
And (3) testing: in AM1.5, the effective area of the active layer is 0.0557cm2The perovskite solar photovoltaic device is tested under the condition of (1). The obtained statistical graph of the photoelectric conversion efficiency parameters is shown in fig. 2.
Example 2: preparation of perovskite solar photovoltaic device
The structural schematic diagram of the perovskite solar photovoltaic device of the embodiment is shown in fig. 1, and in the preparation method, except that the preparation steps of the perovskite light absorption layer are different from those in embodiment 1, the embodiment further performs post-treatment on the perovskite light absorption layer:
preparing a perovskite light absorption layer:
will PbI2And MAI was dissolved in a DMF and DMSO complex solvent (volume ratio DMF: DMSO ═ 19:1) at a molar concentration of 1.3M and 0.039M, respectively, and stirred at 60 ℃ for 24 hours to obtain a lead salt precursor solution.
Dissolving amine salt consisting of FAI and MACl in a mass ratio of 60:12 in 1mL of isopropanol, and stirring for 24h at normal temperature to obtain an amine salt precursor solution.
Dissolving oleylamine chloride in chloroform according to the concentration of 0.15mg/mL to obtain oleylamine chloride precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, spin-coating the oleylamine chloride precursor solution on the amine salt precursor solution, and annealing at 150 ℃ for 12min in an atmospheric environment with the humidity of about 35% to obtain the component (FAPBI)3)x(MAPbI3)1-xThe light-absorbing layer A is a perovskite light-absorbing layer A modified by oleylamine chloride, and the thickness of the perovskite light-absorbing layer A is about 700 nm.
And (3) post-treatment: dissolving oleylamine chloride in chloroform according to the concentration of 3mg/mL to obtain oleylamine chloride post-treatment solution; and spin-coating the oleylamine chloride post-treatment solution on the surface of the perovskite light absorption layer for 30s at the speed of 4000rpm to obtain the perovskite light absorption layer B. The observation shows that the quantity and the form of the lead iodide on the surface of the crystal grains of the perovskite light absorption layer B do not obviously change relative to the perovskite light absorption layer A.
And respectively preparing a hole transmission layer and a top electrode on the perovskite light absorption layer A and the perovskite light absorption layer B to obtain a perovskite solar photovoltaic device A and a perovskite solar photovoltaic device B.
And (3) testing: in AM1.5, the effective area of the active layer is 0.0557cm2The perovskite solar photovoltaic device is tested under the condition of (1). The statistical graph of the photoelectric conversion efficiency parameters of the perovskite solar photovoltaic device A is shown in fig. 3, the statistical graph of the photoelectric conversion efficiency parameters of the perovskite solar photovoltaic device B is shown in fig. 4, and after the perovskite light absorption layer is subjected to post-treatment, the performance of the perovskite solar photovoltaic device is further improved. And the stability of the perovskite solar photovoltaic device B is obviously improved compared with that of the perovskite solar photovoltaic device A, and 80% of initial efficiency is still maintained under the continuous working condition for 1000 hours.
Example 3: preparation of perovskite solar photovoltaic device
The schematic structural diagram of the perovskite solar photovoltaic device of the embodiment is shown in fig. 1, and the preparation method only comprises the preparation steps of the perovskite light-absorbing layer, which are different from those of the embodiment 1:
preparing a perovskite light absorption layer:
will PbI2And MAI was dissolved in a DMF and DMSO complex solvent (volume ratio DMF: DMSO ═ 19:1) at a molar concentration of 1.3M and 0.039M, respectively, and stirred at 60 ℃ for 24 hours to obtain a lead salt precursor solution.
Dissolving amine salt consisting of FAI and MACl in a mass ratio of 60:12 in 1mL of isopropanol, and stirring for 24h at normal temperature to obtain an amine salt precursor solution.
Dissolving oleylamine chloride in chloroform according to the concentration of 0.30mg/mL to obtain oleylamine chloride precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; lead saltCooling the film to room temperature, spin-coating the prepared amine salt precursor solution on the film, spin-coating the oleylamine chloride precursor solution on the film, and annealing at 150 ℃ for 12min in an atmospheric environment with the humidity of about 35% to obtain the component (FAPBI)3)x(MAPbI3)1-xThe light-absorbing layer of the perovskite modified by oleylamine chloride has the thickness of about 700 nm.
And (3) testing: in AM1.5, the effective area of the active layer is 0.0557cm2The perovskite solar photovoltaic device is tested under the condition of (1). The obtained statistical graph of the photoelectric conversion efficiency parameters is shown in fig. 5.
Comparative example 1: preparation of perovskite solar photovoltaic device
The structural schematic diagram of the perovskite solar photovoltaic device of the comparative example is shown in fig. 1, and the preparation method only comprises the preparation steps of the perovskite light absorption layer, which are different from those in example 1:
preparing a perovskite light absorption layer:
will PbI2And MAI was dissolved in a DMF and DMSO complex solvent (volume ratio DMF: DMSO ═ 19:1) at a molar concentration of 1.3M and 0.039M, respectively, and stirred at 60 ℃ for 24 hours to obtain a lead salt precursor solution.
Dissolving amine salt consisting of FAI and MACl in a mass ratio of 60:12 in 1mL of isopropanol, and stirring for 24h at normal temperature to obtain an amine salt precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, and annealing at 150 deg.C in atmosphere with humidity of about 35% for 12min to obtain the final product (FAPBI)3)x(MAPbI3)1-xThe thickness of the perovskite light absorption layer is about 700 nm.
And (3) testing: in AM1.5, the effective area of the active layer is 0.0557cm2The perovskite solar photovoltaic device is tested under the condition of (1). The obtained statistical graph of the photoelectric conversion efficiency parameters is shown in fig. 6.
Example 4: preparation of perovskite solar photovoltaic device
The structural schematic diagram of the perovskite solar photovoltaic device of the embodiment is shown in fig. 1, and the preparation method only comprises the preparation steps of the perovskite light absorption layer, which are different from those of the embodiment 1:
preparing a perovskite light absorption layer:
will PbI2Dissolving the mixture in a DMF and DMSO composite solvent (volume ratio of DMF to DMSO: 19:1) at a molar concentration of 1.3M, and stirring at 60 ℃ for 24 hours to obtain a lead salt precursor solution.
Dissolving amine salt consisting of MAI and MACl in a mass ratio of 60:14 in 1mL of isopropanol, and stirring for 24h at normal temperature to obtain an amine salt precursor solution.
Dissolving oleylamine chloride in chloroform according to the concentration of 0.15mg/mL to obtain oleylamine chloride precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, spin-coating the oleylamine chloride precursor solution on the amine salt precursor solution, and annealing at 110 ℃ for 12min in an atmospheric environment with the humidity of about 35% to obtain the MAPbI component3The light-absorbing layer of the perovskite modified by oleylamine chloride has the thickness of about 600 nm.
And (3) testing: in AM1.5, the effective area of the active layer is 0.0557cm2The perovskite solar photovoltaic device is tested under the condition of (1). The obtained statistical graph of the photoelectric conversion efficiency parameters is shown in fig. 7.
Comparative example 2: preparation of perovskite solar photovoltaic device
The structural schematic diagram of the perovskite solar photovoltaic device of the comparative example is shown in fig. 1, and the preparation method only comprises the preparation steps of the perovskite light absorption layer, which are different from those in example 1:
preparing a perovskite light absorption layer:
will PbI2The mixture was dissolved in a DMF and DMSO complex solvent (volume ratio DMF: DMSO 19:1) at a molar concentration of 1.3M, and stirred at 60 ℃ for 24h to obtain a lead salt precursor solution.
Dissolving amine salt consisting of MAI and MACl in a mass ratio of 60:14 in 1mL of isopropanol, and stirring for 24h at normal temperature to obtain an amine salt precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, and annealing at 110 ℃ for 12min in an atmospheric environment with the humidity of about 35% to obtain the MAPbI3The thickness of the perovskite light absorption layer is about 600 nm.
And (3) testing: in AM1.5, the effective area of the active layer is 0.0557cm2The perovskite solar photovoltaic device is tested under the condition of (1). The obtained statistical graph of the photoelectric conversion efficiency parameters is shown in fig. 8.
Example 5: preparation of perovskite solar photovoltaic device
The schematic structural diagram of the perovskite solar photovoltaic device of the embodiment is shown in fig. 1, and the preparation method only comprises the preparation steps of the perovskite light-absorbing layer, which are different from those of the embodiment 1:
preparing a perovskite light absorption layer:
will PbI2And CsI is dissolved in a DMF and DMSO composite solvent (volume ratio DMF: DMSO ═ 19:1) according to molar concentrations of 1.3M and 0.065M respectively, and the mixture is stirred for 24 hours at 60 ℃ to obtain a lead salt precursor solution.
Dissolving amine salt consisting of FAI, MAI and MACl in a mass ratio of 60:5:12 in 1mL of isopropanol, and stirring at normal temperature for 24h to obtain an amine salt precursor solution.
Dissolving oleylamine chloride in chloroform according to the concentration of 0.15mg/mL to obtain oleylamine chloride precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, spin-coating the oleylamine chloride precursor solution on the amine salt precursor solution, and annealing at 150 ℃ for 12min in an atmospheric environment with the humidity of about 35% to obtain the lead salt film with the Cs componentxFAyMA1-x-yPbI3Oleylamine chloride modified perovskiteAnd the thickness of the perovskite light absorption layer is about 600 nm.
And (3) testing: in AM1.5, the effective area of the active layer is 0.0557cm2The perovskite solar photovoltaic device is tested under the condition of (1). The obtained statistical graph of the photoelectric conversion efficiency parameters is shown in fig. 9.
Comparative example 3: preparation of perovskite solar photovoltaic device
The structural schematic diagram of the perovskite solar photovoltaic device of the comparative example is shown in fig. 1, and the preparation method only comprises the preparation steps of the perovskite light absorption layer, which are different from those in example 1:
preparing a perovskite light absorption layer:
will PbI2And CsI is dissolved in a DMF and DMSO composite solvent (volume ratio DMF: DMSO ═ 9:1) according to molar concentrations of 1.3M and 0.065M respectively, and the mixture is stirred for 24 hours at 60 ℃ to obtain a lead salt precursor solution.
Dissolving amine salt consisting of FAI, MAI and MACl in a mass ratio of 60:5:12 in 1mL of isopropanol, and stirring at normal temperature for 24h to obtain an amine salt precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, and annealing at 150 ℃ for 12min in an atmospheric environment with the humidity of about 35% to obtain the product with the component CsxFAyMA1-x-yPbI3The thickness of the perovskite light absorption layer is about 600 nm.
And (3) testing: in AM1.5, the effective area of the active layer is 0.0557cm2The perovskite solar photovoltaic device is tested under the conditions of (1). The obtained statistical graph of the photoelectric conversion efficiency parameters is shown in fig. 10.
Example 6: preparation of perovskite materials
Will PbI2Dissolving the mixture in a DMF and DMSO composite solvent (volume ratio of DMF to DMSO: 19:1) at a molar concentration of 1.3M, and stirring at 60 ℃ for 24 hours to obtain a lead salt precursor solution.
Dissolving amine salt consisting of FAI, MAI and MACl in a mass ratio of 60:5:12 in 1mL of isopropanol, and stirring at normal temperature for 24h to obtain an amine salt precursor solution.
Dissolving oleylamine chloride in chloroform according to the concentration of 0.15mg/mL to obtain oleylamine chloride precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, spin-coating the oleylamine chloride precursor solution on the amine salt precursor solution, and annealing at 145 ℃ for 12min in an atmospheric environment with the humidity of about 35% to obtain the component FAxMA1-xPbI3The light-absorbing layer of the perovskite modified by oleylamine chloride has the thickness of about 600 nm.
The perovskite material is shown in the figure 11, and lead iodide is mainly and intensively distributed on the surface of perovskite crystal grains.
Comparative example 4: preparation of perovskite materials
Will PbI2The mixture was dissolved in a DMF and DMSO complex solvent (volume ratio DMF: DMSO 19:1) at a molar concentration of 1.3M, and stirred at 60 ℃ for 24h to obtain a lead salt precursor solution.
Dissolving amine salt consisting of FAI, MAI and MACl in a mass ratio of 60:5:12 in 1mL of isopropanol, and stirring at normal temperature for 24h to obtain an amine salt precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, and annealing at 145 ℃ for 12min in an atmospheric environment with the humidity of about 35% to obtain the product with the component FAxMA1-xPbI3The thickness of the perovskite light absorption layer is about 600 nm.
The perovskite material is shown in the figure 12, and lead iodide is mainly and intensively distributed on grain boundaries.
Example 7: preparation of perovskite materials
Will PbI2Dissolving at a molar concentration of 1.3M in a DMF/DMSO composite solvent (volume ratio of DMF: DMSO: 19:1)And stirring for 24 hours at the temperature of 60 ℃ to obtain a lead salt precursor solution.
Dissolving amine salt consisting of MAI and MACl in a mass ratio of 60:13 in 1mL of isopropanol, and stirring for 24h at normal temperature to obtain an amine salt precursor solution.
Dissolving oleylamine chloride in chloroform according to the concentration of 0.15mg/mL to obtain oleylamine chloride precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, spin-coating the oleylamine chloride precursor solution on the amine salt precursor solution, and annealing at 145 ℃ for 12min in an atmospheric environment with the humidity of about 35% to obtain the MAPbI component3The light-absorbing layer of the perovskite modified by oleylamine chloride has the thickness of about 600 nm.
The perovskite material is shown in the figure 13, and lead iodide is mainly and intensively distributed on the surface of perovskite crystal grains.
Comparative example 5: preparation of perovskite materials
Will PbI2The mixture was dissolved in a DMF and DMSO complex solvent (volume ratio DMF: DMSO 19:1) at a molar concentration of 1.3M, and stirred at 60 ℃ for 24h to obtain a lead salt precursor solution.
Dissolving amine salt consisting of MAI and MACl in a mass ratio of 60:13 in 1mL of isopropanol, and stirring for 24h at normal temperature to obtain an amine salt precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, and annealing at 145 ℃ for 12min in an atmospheric environment with the humidity of about 35% to obtain the MAPbI3The thickness of the perovskite light absorption layer is about 600 nm.
The perovskite material is shown in the figure 14, and lead iodide is mainly and intensively distributed on the grain boundary.
Example 8: preparation of perovskite materials
Will PbI2The mixture was dissolved in a DMF and DMSO complex solvent (volume ratio DMF: DMSO 19:1) at a molar concentration of 1.3M, and stirred at 60 ℃ for 24h to obtain a lead salt precursor solution.
Dissolving amine salt consisting of FAI and MACl in a mass ratio of 60:13 in 1mL of isopropanol, and stirring for 24h at normal temperature to obtain an amine salt precursor solution.
Dissolving oleylamine chloride in chloroform according to the concentration of 0.15mg/mL to obtain oleylamine chloride precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, spin-coating the oleylamine chloride precursor solution on the amine salt precursor solution, and annealing at 145 ℃ for 12min in an atmospheric environment with the humidity of about 35% to obtain the FAPBI3The light-absorbing layer of the perovskite modified by oleylamine chloride has the thickness of about 600 nm.
The perovskite material is shown in the figure 15, and lead iodide is mainly and intensively distributed on the surface of perovskite crystal grains.
Comparative example 6: preparation of perovskite materials
Will PbI2The mixture was dissolved in a DMF and DMSO complex solvent (volume ratio DMF: DMSO 19:1) at a molar concentration of 1.3M, and stirred at 60 ℃ for 24h to obtain a lead salt precursor solution.
Dissolving amine salt consisting of FAI and MACl in a mass ratio of 60:13 in 1mL of isopropanol, and stirring for 24h at normal temperature to obtain an amine salt precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, and annealing at 145 ℃ for 12min in an atmospheric environment with the humidity of about 35% to obtain the FAPBI3The thickness of the perovskite light absorption layer is about 600 nm.
The perovskite material is shown in the figure 16, and lead iodide is mainly and intensively distributed on grain boundaries.
Example 9: preparation of perovskite materials
Will PbI2And CsI is dissolved in a DMF and DMSO composite solvent (volume ratio DMF: DMSO ═ 9:1) according to molar concentrations of 1.3M and 0.065M respectively, and the mixture is stirred for 24 hours at 60 ℃ to obtain a lead salt precursor solution.
Dissolving amine salt consisting of FAI, MAI and MACl in a mass ratio of 60:5:12 in 1mL of isopropanol, and stirring at normal temperature for 24h to obtain an amine salt precursor solution.
Dissolving oleylamine chloride in chloroform according to the concentration of 0.15mg/mL to obtain oleylamine chloride precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, spin-coating the oleylamine chloride precursor solution on the amine salt precursor solution, and annealing at 150 ℃ for 12min in an atmospheric environment with the humidity of about 35% to obtain the product with the Cs componentxFAyMA1-x-yPbI3The light-absorbing layer of the perovskite modified by oleylamine chloride has the thickness of about 600 nm.
The perovskite material is shown in the figure 17, and lead iodide is mainly and intensively distributed on the surface of perovskite crystal grains.
Comparative example 7: preparation of perovskite materials
Will PbI2And CsI is dissolved in a DMF and DMSO composite solvent (volume ratio DMF: DMSO ═ 9:1) according to molar concentrations of 1.3M and 0.065M respectively, and the mixture is stirred for 24 hours at 60 ℃ to obtain a lead salt precursor solution.
Dissolving amine salt consisting of FAI, MAI and MACl in a mass ratio of 60:5:12 in 1mL of isopropanol, and stirring at normal temperature for 24h to obtain an amine salt precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, and annealing at 150 ℃ for 12min in an atmospheric environment with the humidity of about 35% to obtain the product with the component CsxFAyMA1-x-yPbI3The thickness of the perovskite light absorption layer is about 600 nm.
The perovskite material is shown in the figure 18, and lead iodide is mainly and intensively distributed on grain boundaries.
Example 10: preparation of perovskite materials
Will PbI2And MAI was dissolved in a DMF and DMSO complex solvent (volume ratio DMF: DMSO ═ 19:1) at a molar concentration of 1.3M and 0.039M, respectively, and stirred at 60 ℃ for 24 hours to obtain a lead salt precursor solution.
Dissolving amine salt consisting of FAI and MACl in a mass ratio of 60:12 in 1mL of isopropanol, and stirring for 24h at normal temperature to obtain an amine salt precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, and annealing at 150 deg.C in atmosphere with humidity of about 35% for 12min to obtain the final product (FAPBI)3)x(MAPbI3)1-xThe thickness of the perovskite light absorption layer is about 700 nm.
The morphology of the perovskite material is shown in fig. 19, and lead iodide is mainly and intensively distributed in the grain boundary.
Comparative example 8: preparation of perovskite materials
Will PbI2MAI was dissolved in a DMF and DMSO complex solvent (volume ratio DMF: DMSO ═ 19:1) at a molar concentration of 1.3M and 0.039M, respectively, and stirred at 60 ℃ for 24 hours, and oleylamine chloride was added thereto at a mass concentration of 0.09mg/mL, to obtain a lead salt precursor solution.
Dissolving amine salt consisting of FAI and MACl in a mass ratio of 60:12 in 1mL of isopropanol, and stirring for 24h at normal temperature to obtain an amine salt precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, and then carrying out the spin-coating in an atmospheric environment with the humidity of about 35 percentAnnealing at 150 deg.C for 12min to obtain component (FAPbI)3)x(MAPbI3)1-xThe thickness of the perovskite light absorption layer is about 700 nm.
The perovskite material is shown in the figure 20, and lead iodide is mainly and intensively distributed on grain boundaries.
Comparative example 9: preparation of perovskite materials
Will PbI2And MAI was dissolved in a DMF and DMSO complex solvent (volume ratio DMF: DMSO ═ 19:1) at a molar concentration of 1.3M and 0.039M, respectively, and stirred at 60 ℃ for 24 hours to obtain a lead salt precursor solution.
Dissolving amine salt consisting of FAI and MACl in a mass ratio of 60:12 in 1mL of isopropanol, stirring at normal temperature for 24h, and adding oleylamine chloride according to a mass concentration of 0.09mg/mL to obtain an amine salt precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, and annealing at 150 deg.C in atmosphere with humidity of about 35% for 12min to obtain the final product (FAPBI)3)x(MAPbI3)1-xThe thickness of the perovskite light absorption layer is about 700 nm.
The perovskite material is shown in the figure 21, and lead iodide is mainly and intensively distributed on grain boundaries. Comparative example 10: preparation of perovskite materials
Will PbI2And MAI was dissolved in a DMF and DMSO complex solvent (volume ratio DMF: DMSO ═ 19:1) at a molar concentration of 1.3M and 0.039M, respectively, and stirred at 60 ℃ for 24 hours to obtain a lead salt precursor solution.
Dissolving amine salt consisting of FAI and MACl in a mass ratio of 60:12 in 1mL of isopropanol, and stirring for 24h at normal temperature to obtain an amine salt precursor solution.
PEAI (phenethyl amine iodide) is dissolved in isopropanol according to the mass concentration of 0.15mg/mL to obtain a precursor solution of the phenethyl amine iodide.
Uniformly spin-coating the prepared lead salt precursor solution on a spin coaterAn electron transport layer; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, spin-coating the phenethyl amine iodide precursor solution on the lead salt film, and annealing at 150 ℃ for 12min in an atmospheric environment with the humidity of about 35% to obtain the component (FAPBI)3)x(MAPbI3)1-xThe thickness of the perovskite light absorption layer is about 700 nm.
The perovskite material is shown in the figure 22, lead iodide is mainly and intensively distributed at the grain boundary, namely PEAI has no function of extracting lead iodide.
Comparative example 11: preparation of perovskite materials
Will PbI2And MAI was dissolved in a DMF and DMSO complex solvent (volume ratio DMF: DMSO ═ 19:1) at a molar concentration of 1.3M and 0.039M, respectively, and stirred at 60 ℃ for 24 hours to obtain a lead salt precursor solution.
Dissolving amine salt consisting of FAI and MACl in a mass ratio of 60:12 in 1mL of isopropanol, and stirring for 24h at normal temperature to obtain an amine salt precursor solution.
BABr (butyl ammonium bromide) is dissolved into isopropanol according to the mass concentration of 0.15mg/mL to obtain a butyl ammonium bromide precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, spin-coating the butyl ammonium bromide precursor solution on the lead salt film, and annealing at 150 ℃ for 12min in an atmospheric environment with the humidity of about 35% to obtain the component (FAPBI)3)x(MAPbI3)1-xThe thickness of the perovskite light absorption layer is about 700 nm.
The perovskite material is shown in the figure 23, lead iodide is mainly and intensively distributed at the grain boundary, namely BABr has no function of extracting lead iodide.
Comparative example 12: preparation of perovskite materials
Will PbI2MAI was dissolved in DMF and D at molar concentrations of 1.3M and 0.039M, respectivelyAnd (3) stirring the MSO composite solvent (DMF: DMSO: 19:1) at 60 ℃ for 24 hours to obtain a lead salt precursor solution.
Dissolving amine salt consisting of FAI and MACl in a mass ratio of 60:12 in 1mL of isopropanol, and stirring for 24h at normal temperature to obtain an amine salt precursor solution.
And dissolving OABr (oleylamine bromide) into chloroform according to the mass concentration of 0.15mg/mL to obtain an OABr precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, spin-coating the OABr precursor solution on the amine salt precursor solution, and annealing at 150 ℃ for 12min in an atmospheric environment with the humidity of about 35% to obtain the component (FAPBI)3)x(MAPbI3)1-xThe thickness of the perovskite light absorption layer is about 700 nm.
The perovskite material is shown in a topography as figure 24, and lead iodide is mainly and intensively distributed on the surface of perovskite crystal grains.
Comparative example 13: preparation of perovskite materials
Will PbI2And MAI was dissolved in a DMF and DMSO complex solvent (volume ratio DMF: DMSO ═ 19:1) at a molar concentration of 1.3M and 0.039M, respectively, and stirred at 60 ℃ for 24 hours to obtain a lead salt precursor solution.
Dissolving amine salt consisting of FAI and MACl in a mass ratio of 60:12 in 1mL of isopropanol, and stirring for 24h at normal temperature to obtain an amine salt precursor solution.
Dissolving OAI (oleylamine iodide) into chloroform according to the mass concentration of 0.15mg/mL to obtain an OAI precursor solution.
Uniformly spin-coating the prepared lead salt precursor solution on the electron transport layer by using a spin coater; then annealing and crystallizing at 70 ℃ for 1min to obtain a lead salt film; cooling the lead salt film to room temperature, spin-coating the prepared amine salt precursor solution on the lead salt film, spin-coating the OAI precursor solution on the OAI precursor solution, and annealing at 150 ℃ for 12min in an atmospheric environment with the humidity of about 35% to obtain the component (FAPBI)3)x(MAPbI3)1-xThe thickness of the perovskite light absorption layer is about 700 nm.
The perovskite material is shown in the figure 25, and lead iodide is mainly and intensively distributed on the surface of perovskite crystal grains.
The preparation method provided by the invention is simple in process, and can effectively improve the photoelectric conversion efficiency and stability of the device. The photovoltaic device prepared by the invention is applied to the perovskite photovoltaic cell, obtains good effect and has larger application potential.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the spirit and scope of the present invention.
Claims (10)
1. A method for extracting residual lead iodide from a lead-halogen perovskite material is characterized by comprising the following steps:
coating a lead salt precursor solution on a substrate, and carrying out annealing crystallization treatment to form a lead salt film;
sequentially coating an amine salt precursor solution and an oleylamine salt precursor solution on the lead salt film to form a perovskite precursor film; and
annealing the substrate and the perovskite precursor thin film in an atmospheric environment for crystallization to form a perovskite material.
2. The method of extracting residual lead iodide from a lead-halo perovskite material of claim 1, wherein: further comprising the steps of: and coating the chloroform solution of the oleylamine salt on the surface of the perovskite material.
3. The method of extracting residual lead iodide from lead-halo perovskite material of claim 1, wherein: the lead salt is one or more of lead iodide (II), lead thiocyanate (II), lead chloride (II) and lead bromide (II); the amine salt is one or more of formamidine ammonium iodide, formamidine ammonium chloride, formamidine ammonium bromide, methyl amine iodide, methyl amine chloride and methyl amine bromide; the oleyl amine salt is halogenated oleyl amine salt, and the halogenated oleyl amine salt is one or more of oleyl amine chloride, oleyl amine iodide and oleyl amine bromide.
4. A method of extracting residual lead iodide from a lead-halo perovskite material as claimed in any one of claims 1 to 3, wherein: the lead salt precursor solution contains iodide salt, and the iodide salt is one or more of iodomethylamine, iodoformamidine and iodized alkali metal salt.
5. The method of extracting residual lead iodide from a lead-halo perovskite material of claim 1, wherein: the oleylamine salt precursor solution has a halogenated oleylamine salt concentration of 0.05mg/mL to 0.4 mg/mL.
6. The method of extracting residual lead iodide from a lead-halo perovskite material of claim 1, wherein: the oleylamine salt precursor solution has a halogenated oleylamine salt concentration of 0.075mg/mL to 0.3 mg/mL.
7. The method of extracting residual lead iodide from a lead-halo perovskite material of claim 1, wherein: the temperature of the annealing crystallization treatment in the atmospheric environment is more than or equal to 50 ℃ and less than or equal to 150 ℃; the absolute humidity of the atmospheric environment is greater than or equal to 30% and less than or equal to 40%.
8. A perovskite material characterized by: the method for extracting residual lead iodide from the lead-halogen perovskite material as claimed in any one of claims 1 to 7.
9. Use of the perovskite material of claim 8 in the field of solar photovoltaic devices.
10. A perovskite solar photovoltaic device comprises an ITO conductive glass substrate, a hydrogen peroxide modified tin dioxide thin film electron transport layer, the perovskite material according to claim 8, a hole transport layer and a top electrode layer from bottom to top.
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