CN116709877A - Lead halide film and preparation method and application thereof - Google Patents
Lead halide film and preparation method and application thereof Download PDFInfo
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- 150000004820 halides Chemical class 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000012266 salt solution Substances 0.000 claims abstract description 24
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 22
- 238000001704 evaporation Methods 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 238000001771 vacuum deposition Methods 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- -1 formamidine ions Chemical class 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 27
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 230000000670 limiting effect Effects 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 238000002161 passivation Methods 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 230000033764 rhythmic process Effects 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 129
- 239000010410 layer Substances 0.000 description 78
- 230000000052 comparative effect Effects 0.000 description 24
- 239000000843 powder Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 239000002346 layers by function Substances 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- 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 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910005855 NiOx Inorganic materials 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 description 1
- VOWZMDUIGSNERP-UHFFFAOYSA-N carbamimidoyl iodide Chemical compound NC(I)=N VOWZMDUIGSNERP-UHFFFAOYSA-N 0.000 description 1
- 238000000224 chemical solution deposition Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000313 electron-beam-induced deposition Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910021472 group 8 element Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- JAHFQMBRFYOPNR-UHFFFAOYSA-N iodomethanamine Chemical compound NCI JAHFQMBRFYOPNR-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004544 sputter deposition Methods 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
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- H—ELECTRICITY
- 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
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
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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
- H10K30/50—Photovoltaic [PV] devices
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/811—Controlling the atmosphere during processing
-
- 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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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
The application belongs to the technical field of solar cells, and particularly relates to a lead halide film, a preparation method and application thereof. The application provides a composite lead halide film comprising a lead halide film layer with a compact structure and a lead halide film layer with a loose structure through limiting the porosity, and the lead halide film with the composite structure has the advantages that the lead halide film layer with the loose structure is favorable for better permeation of organic ammonium salt solution, the compact lead halide film layer is favorable for slow reaction of the organic ammonium salt solution with the organic ammonium salt solution, the porous lead halide film layer is used for controlling the permeation rhythm of the organic ammonium salt solution and the compact lead halide film layer is used for slowing down the reaction with the organic ammonium salt solution to improve the crystallization process of perovskite, and in this way, the high-quality perovskite film layer can be prepared, and meanwhile, the compact lead halide film layer can form a passivation layer to improve the performance of a perovskite solar cell.
Description
Technical Field
The application belongs to the technical field of solar cells, and particularly relates to a lead halide film, a preparation method and application thereof.
Background
The perovskite material has the advantages of high absorption coefficient, long carrier diffusion length, high carrier migration speed, low exciton binding energy, high defect tolerance, adjustable band gap and the like, and has larger application in the field of solar cells. Today, the energy conversion efficiency of perovskite solar cells has risen from the original 3.8% to 26%. The quality of the perovskite thin film has an important influence on the performance of the perovskite solar cell. In the traditional method for preparing the perovskite film, the one-step spin coating method generally only can prepare the perovskite film with small area, and has the defects of small perovskite crystal grains, many pinholes and the like. While the combination of vacuum deposition of lead halide method and slit coating solution organic ammonium salt solution (iodoformamidine FAI, iodomethylamine MAI, cesium iodide CsI, etc.) method to prepare perovskite thin film is a promising method, long perovskite thin film can be formed on crystalline silicon surface.
However, in the vacuum deposition method adopted at present, there is a problem that the ratio of the reaction cannot be well grasped, the excessively thick lead halide film causes a problem that the lead halide cannot be fully reacted with the organic solution, the excessively thin lead halide film causes an excessive amount of the organic solution to dissolve the film, and the like, and the reaction speed of the lead halide film and the organic ammonium salt solution is also not easy to control, resulting in poor crystallinity of the perovskite film, thereby affecting the performance of the perovskite solar cell.
Disclosure of Invention
Accordingly, the technical problem to be solved by the present application is to overcome the above-mentioned drawbacks of the metal halide films of the prior art, thereby providing a lead halide film, and a preparation method and application thereof.
Therefore, the application provides the following technical scheme:
the application provides a lead halide film, which comprises a first lead halide film layer and a second lead halide film layer which are stacked, wherein the porosity of the first lead halide film layer is 1-30%, and the porosity of the second lead halide film layer is 40-60%.
Typically, without limitation, the first lead halide film layer may have a porosity of 1%,3%,5%,10%,13%,15%,18%,20%,22%,24%,26%,28%, 30%, etc.; the porosity of the second lead halide film layer may be 40%,41%,43%,45%,48%,50%,53%,55%,58%, or 60%, etc.
Optionally, the thickness ratio of the first lead halide film layer to the second lead halide film layer is (0.2-5): 1. typically, without limitation, the thickness ratio of the first lead halide film layer to the second lead halide film layer may be 0.2:1,0.4:1,0.6:1,0.8:1,1:1,1.3:1,1.5:1,1.8:1,2:1,2.2:1,2.5:1,2.8:1,3:1,3.5:1,4:1,4.5:1 or 5:1, etc.
Optionally, the thickness of the first lead halide film layer is 80-500 nm; and/or the thickness of the second lead halide film layer is 200-600 nm.
Typically, without limitation, the thickness of the first lead halide film layer can be 80nm,100nm,120nm,140nm,150nm,180nm,200nm,230nm,250nm,280nm,300nm,350nm,400nm,420nm,450nm, 500nm, or the like; the thickness of the second lead halide film layer may be 200nm,220nm,250nm,280nm,300nm,330nm,350nm,380nm,400nm,450nm,500nm,520nm,550nm, 600nm, or the like.
Optionally, the composition of the first lead halide film layer and the second lead halide film layer is independently selected from at least one of lead chloride, lead iodide and lead bromide.
The application provides a preparation method of a lead halide film, which comprises the following steps:
s1, preparing a first lead halide film layer with the porosity of 1-30% on a substrate;
s2, preparing a second lead halide film layer with the porosity of 40-60% on the first lead halide film layer.
The substrate is not particularly limited in the present application, and those skilled in the art can specifically determine the substrate according to the actual application situation. For example, when applied to the preparation process of a perovskite solar cell with a trans structure, the substrate is a first electrode, and the first electrode may be ITO (In-doped SnO 2 ) Or FTO (F doped SnO) 2 ) Etc.
Optionally, preparing a first lead halide film layer by adopting an evaporation method, wherein in the step S1, the evaporation speed of the lead halide is 0.5-1.2 nm/S, and the vacuum degree is 10 -3 ～10 -5 Pa；
And/or preparing a second lead halide film layer by adopting an evaporation method, wherein in the step S2, the evaporation speed of the lead halide is 0.5-1.2 nm/S, and the vacuum degree is 10 -3 ～10 -5 Pa。
It should be noted that the vacuum degree is 10 -3 ～10 -5 Pa can refer to the vacuum degree which needs to be achieved by the reaction chamber before the film plating starts, and the application does not limit the matched vacuum system.
Typically, but not limited to, the evaporation rate of the lead halide in steps S1 and S2 may be 0.5nm/S,0.6nm/S,0.7nm/S,0.8nm/S,0.9nm/S,1nm/S,1.1nm/S, 1.2nm/S, etc.
Optionally, in step S1, no gas is introduced during the deposition process; or, introducing nitrogen or rare gas, wherein the introduced amount is 10-50 mL/min; typically, but not limited to, the nitrogen or rare gas may be introduced at a rate of 10mL/min,20mL/min,30mL/min,40mL/min,50 mL/min, etc.
And/or, in the step S2, ammonia gas is introduced in the vacuum deposition process, wherein the introducing amount is 20-60 mL/min. Typically, but not limited to, the ammonia gas may be introduced at 20mL/min,25mL/min,30mL/min,40mL/min,50mL/min, 60mL/min, etc.
It should be specifically noted that, for convenience of description, understanding and considering the practical application scenario of the disclosed solution, the present application defines the amount of the corresponding gas (such as the above-mentioned nitrogen gas, ammonia gas, etc.) in the chamber during the film plating process by defining the gas inlet amount. The above limitation on the gas inlet amount is, for example, 10-50 mL/min and 20-60 mL/min, the corresponding coating chamber volumes are all 4 cubic meters, and the operation of the vacuum system is kept consistent with the start of coating during the coating process. Those skilled in the art will appreciate that in the case of determining the volume of the coating chamber, the limitation of the flow rate of the gas introduced in this embodiment is only of explicit significance. Based on this description, the person skilled in the art has been able to ascertain the limiting effect of the gas introduction on the concentration of the respective gas in the reaction chamber during the coating process and to repeat the respective technical solution. Moreover, when the volume of the reaction chamber and the vacuumizing capacity of the corresponding vacuum system are changed, a person skilled in the art can keep the concentration of the corresponding gas in the reaction chamber unchanged in the film coating process by adjusting the gas inlet amount, so that the claimed technical effect of the application is achieved, and the adjustment still belongs to the scope of the application. In addition, the volume of the test chamber used in the subsequent embodiments of the present application is the same as that described herein, and no description is given.
The application also provides a perovskite film layer, which is obtained by depositing an organic ammonium salt solution on the surface of the lead halide film or the lead halide film prepared by the preparation method, and then annealing.
Optionally, in the organic amine salt solution, the cations of the solute include formamidine ions and/or methylamine ions;
and/or anions of the solute include at least one of chloride, bromide, or iodide;
and/or the solvent in the organic ammonium salt solution comprises at least one or more of isopropanol and dimethyl sulfoxide (DMSO);
and/or the concentration of the organic ammonium salt solution is 0.2-0.8 mol/mL; typically, but not limited to, the concentration of the organic ammonium salt solution may be 0.2mol/mL,0.3mol/mL,0.4mol/mL,0.5mol/mL,0.6mol/mL,0.7mol/mL, 0.8mol/mL, etc.
And/or the deposition method comprises a solution method or a vacuum evaporation method; preferably, the solution method includes at least one of a knife coating method, a spraying method, or a dipping method;
and/or the annealing temperature is 120-150 ℃ and the annealing time is 40-60 min. Typically, but not limited to, the annealing temperature may be 120 ℃,130 ℃,140 ℃,150 ℃, etc., and the annealing time may be 40min,45min,50min,55min, 60min, etc.
The application also provides a perovskite solar cell, which comprises the perovskite film layer.
In the present application, the rare gas means an elemental gas corresponding to all the group VIII elements of the periodic table of elements, and is also referred to as an inert gas. The rare gas used includes: argon, helium, and the like.
The perovskite solar cell provided by the application has the components and the preparation methods of other film layers except the perovskite film layer, which are all conventional in the field. The perovskite solar cell may have a formal structure or a trans structure.
Typically, but not by way of limitation, perovskite solar cells of formal structure include a first electrode/electron transport layer/perovskite layer/hole transport layer/second electrode. The perovskite solar cell with the trans structure comprises a first electrode/a hole transport layer/a perovskite layer/an electron transport layer/a second electrode.
Wherein the first electrode may be ITO (In-doped SnO 2 ) Or FTO (F doped SnO) 2 ). The thickness range is 600-800 nm.
The hole transport layer comprises Spiro-OMeTAD, PEDOT: PSS, and NiO x Or CuO, etc. The preparation method can adopt a solution spin coating method, a magnetron sputtering method, a chemical vapor deposition method and the like. The thickness range is 10-40 nm.
The composition of the electron transport layer may include TiO 2 、ZnO、SnO 2 、WO 3 Or fullerenes and derivatives thereof, and the like. The preparation method can adopt solution spin coating, thermal evaporation, atomic layer deposition, chemical bath deposition and the like. The thickness range is 5-15 nm.
The composition of the second electrode may include Cu, ag, au, al, or the like. The preparation method can adopt thermal evaporation, electron beam deposition, screen printing or the like. The thickness range is 80-100 nm.
The technical scheme of the application has the following advantages:
the lead halide film provided by the application provides a composite lead halide film comprising a lead halide film layer with a compact structure and a lead halide film layer with a loose structure through limiting the porosity. The lead halide film with the composite structure has the advantages that the lead halide film with the loose structure is beneficial to better permeation of the organic ammonium salt solution, the dense lead halide film is beneficial to slow reaction of the organic ammonium salt solution with the lead halide film, the porous lead halide film is used for controlling the permeation rhythm of the organic ammonium salt solution and slowing down the reaction with the organic ammonium salt solution to improve the crystallization process of perovskite, and meanwhile, the perovskite film with high quality can be prepared in the mode, and meanwhile, the dense lead halide film which is not fully reacted during preparation of the perovskite film can also be used as a passivation layer to improve the performance of a perovskite solar cell.
According to the preparation method of the lead halide film, a small amount of nitrogen and rare gas or different gases are introduced in the vacuum deposition process to form a compact lead halide film layer, and then a small amount of ammonia gas is introduced to coordinate with lead halide to form a loose lead halide film layer, so that the lead halide film with a loose/compact structure can be finally formed. According to the preparation method, the porosity or the compactness of the film layer is controlled by introducing different gases, so that the composite lead halide film with different morphologies and various structures can be prepared, and the composite lead halide film can be better reacted with an organic ammonium salt solution in the preparation of the perovskite film layer, so that the quality of the perovskite film layer is further improved.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present application, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of a lead halide film provided in example 1 of the present application;
FIG. 2 is an SEM image of a perovskite film layer provided in example 1 of the application;
FIG. 3 is a J-V plot of the perovskite solar cell provided in example 1 of the application;
FIG. 4 is a J-V plot of the perovskite solar cell provided in example 2 of the application;
FIG. 5 is a J-V plot of the perovskite solar cell provided in example 3 of the application;
FIG. 6 is a J-V plot of the perovskite solar cell provided in example 4 of the application;
FIG. 7 is a J-V plot of the perovskite solar cell provided in example 5 of the application;
FIG. 8 is a J-V plot of the perovskite solar cell provided in example 6 of the application;
FIG. 9 is a J-V plot of the perovskite solar cell provided in example 7 of the application;
FIG. 10 is a J-V plot of the perovskite solar cell provided in example 8 of the application;
FIG. 11 is an SEM image of a lead halide film provided in comparative example 1 of the present application;
FIG. 12 is an SEM image of a perovskite film layer provided in comparative example 1 of the application;
fig. 13 is a J-V plot of the perovskite solar cell provided in comparative example 1 of the application.
FIG. 14 is a J-V plot of the perovskite solar cell provided in comparative example 2 of the application;
fig. 15 is a J-V plot of the perovskite solar cell provided in comparative example 3 of the application.
Detailed Description
The following examples are provided for a better understanding of the present application and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the application, any product which is the same or similar to the present application, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present application.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a lead halide film, and the preparation method and specific operation parameters thereof are as follows:
vacuumizing the vacuum deposition equipment to 10 -4 Pa, evaporating PbI at a rate of 1.2nm/s 2 Solid powder, nitrogen is flushed at a speed of 30mL/min to obtain compact PbI 2 Film (thickness 420nm, porosity 20%) and further evaporating PbI at a rate of 1.2nm/s 2 The solid powder is flushed with ammonia gas at a speed of 20mL/min to obtain loose PbI 2 Film (thickness 210nm, porosity 50%) and final PbI with compact/loose structure composite layer 2 A film as shown in fig. 1.
The embodiment also provides a preparation method of the perovskite solar cell, which comprises the following specific steps and operation parameters:
(1) Using magnetron sputtering apparatus, the glass was cleaned in a clean FTO conductive glass (30X 30cm in size 2 FTO thickness of 800 nm) is coated with a layer of NiO with a thickness of 20nm x The film has magnetron sputtering parameters that the air pressure of the magnetron sputtering chamber is 0.5Pa, the deposition rate of NiOx is 0.04A/s, and the sputtering power is 800W.
(2) NiO was deposited on the substrate using a vacuum deposition apparatus (PVD) as described above x Evaporating a PbI layer with a compact structure/loose structure composite layer on the film 2 A film.
(3) A solution of the organic ammonium salt (90 mg/mL FAI, 6.4mg/mL MAI, 9mg/mL MACl in a 98.8% isopropyl alcohol+1.2% DMSO mixture) was knife coated onto the PbI of the dense/loose structure composite layer using a knife coater 2 The film surface was coated with 60. Mu.L of the coating composition at a coating speed of 6mm/s.
(4) The wet film after the completion of the reaction was transferred to a heating stage at 150℃and heated for 40 minutes to obtain a perovskite film layer, as shown in FIG. 2, it can be seen from the figure that the thickness of the perovskite film layer was 482.1nm.
(5) Placing perovskite film layer into evaporation equipment, vacuum degree of the equipment is kept to be 5 multiplied by 10 -4 Pa or below, sequentially evaporating C with thickness of 30nm 60 The rates of 6nm thick bath copper (BCP, CAS number: 4733-39-5), 90nm thick Cu were maintained at 0.1A/s,0.2A/s and 0.5A/s, respectively.
(6) The prepared perovskite solar energy is tested, and specific test parameters are as follows: light intensity: 1 sun, area: 1cm 2 Voltage: -1V-1.05V, interval: as shown in FIG. 3, a 0.02V (hereinafter, the same) J-V curve can give a perovskite solar cell (1 cm) having an efficiency of 15.11% 2 ) This is at a higher level in the two-step process for the production of perovskite solar cells.
Example 2
The embodiment provides a lead halide film, and the preparation method and specific operation parameters thereof are as follows:
vacuumizing the vacuum deposition equipment to 10 -4 Pa, evaporating PbBr at a rate of 1.2nm/s 2 Solid powder, nitrogen is flushed at a speed of 30mL/min to obtain compact PbBr 2 Film (thickness 400nm, porosity 18%) and further evaporation of PbBr at a rate of 1.2nm/s 2 The solid powder is flushed with ammonia gas at a speed of 20mL/min to obtain loose PbBr 2 Film (thickness 200nm, porosity 52%) and finally PbBr with compact/loose structure composite layer 2 A film.
The embodiment also provides a preparation method of the perovskite solar cell except PbBr with a compact structure/loose structure composite layer 2 The preparation of the other functional layers except for the film was the same as in example 1.
The prepared perovskite solar energy is tested, and a perovskite solar cell (1 cm) with the efficiency of 16.40% can be obtained 2 )。
Example 3
The embodiment provides a lead halide film, and the preparation method and specific operation parameters thereof are as follows:
vacuumizing the vacuum deposition equipment to 10 -4 Pa, evaporating PbI at a rate of 0.6nm/s 2 Solid powder, nitrogen is flushed at a speed of 10mL/min to obtain compact PbI 2 Film (thickness 150nm, porosity 10%) and further evaporation of PbI at a rate of 0.6nm/s 2 Solid powder, and ammonia gas is injected at a speed of 50mL/min to obtain loose PbI 2 Film (thickness 300nm, porosity 60%) and finally PbI with compact/loose structure composite layer 2 A film.
The embodiment also provides a preparation method of the perovskite solar cell except PbI with a compact structure/loose structure composite layer 2 The preparation of the other functional layers except for the film was the same as in example 1.
The prepared perovskite solar energy is tested, and a perovskite solar cell (1 cm) with the efficiency of 15.48% can be obtained 2 )。
Example 4
The embodiment provides a lead halide film, and the preparation method and specific operation parameters thereof are as follows:
vacuumizing the vacuum deposition equipment to 10 -4 Pa, evaporating PbI at a rate of 0.6nm/s 2 Solid powder, nitrogen is flushed at a speed of 30mL/min to obtain compact PbI 2 Film (thickness 210nm, porosity 17%) and further evaporating PbI at a rate of 1.2nm/s 2 The solid powder is flushed with ammonia gas at a speed of 20mL/min to obtain loose PbI 2 Film (thickness 210nm, porosity 49%) and finally PbI with compact/loose structure composite layer 2 A film.
The embodiment also provides a preparation method of the perovskite solar cell except PbI with a compact structure/loose structure composite layer 2 The preparation of the other functional layers except for the film was the same as in example 1.
The prepared perovskite solar energy was tested, and a perovskite solar cell (1 cm) with an efficiency of 16.49% could be obtained 2 )。
Example 5
The embodiment provides a lead halide film, and the preparation method and specific operation parameters thereof are as follows:
vacuumizing the vacuum deposition equipment to 10 -4 Pa, evaporating PbI at a rate of 1.2nm/s 2 Solid powder, nitrogen is flushed at a speed of 30mL/min to obtain compact PbI 2 Film (thickness 80nm, porosity 20%) and further evaporation of PbI at a rate of 1.2nm/s 2 The solid powder is flushed with ammonia gas at a speed of 20mL/min to obtain loose PbI 2 Film (thickness 400nm, porosity 50%) and final PbI with compact/loose structure composite layer 2 A film.
The embodiment also provides a preparation method of the perovskite solar cell except PbI with a compact structure/loose structure composite layer 2 The preparation of the other functional layers except for the film was the same as in example 1.
The prepared perovskite solar energy is tested, and a perovskite solar cell (1 cm) with the efficiency of 16.18% can be obtained 2 )。
Example 6
The embodiment provides a lead halide film, and the preparation method and specific operation parameters thereof are as follows:
vacuumizing the vacuum deposition equipment to 10 -4 Pa, evaporating PbI at a rate of 1.2nm/s 2 Solid powder, nitrogen is flushed at a speed of 30mL/min to obtain compact PbI 2 Film (thickness 500nm, porosity 20%) and further evaporation of PbI at a rate of 1.2nm/s 2 The solid powder is flushed with ammonia gas at a speed of 20mL/min to obtain loose PbI 2 Film (thickness 200nm, porosity 50%) and final PbI with compact/loose structure composite layer 2 A film.
The embodiment also provides a preparation method of the perovskite solar cell except PbI with a compact structure/loose structure composite layer 2 The preparation of the other functional layers except for the film was the same as in example 1.
The prepared perovskite solar energy is tested, and a perovskite solar cell (1 cm) with the efficiency of 15.82% can be obtained 2 )。
Example 7
This example provides a lead halide film, its preparation method and specific operating parameters are the same as in example 1.
The present embodiment also provides a method for manufacturing a perovskite solar cell, which is different from embodiment 1 only in that the organic ammonium salt solution has the following composition: FAI:35mg/mL, MAI:2.5mg/mL MACl:3.5mg/mL of a 0.245g 98.5% isopropyl alcohol+0.5% DMSO mixture.
The prepared perovskite solar energy was tested, and a perovskite solar cell (1 cm) with an efficiency of 15.54% could be obtained 2 )。
Example 8
This example provides a lead halide film, its preparation method and specific operating parameters are the same as in example 1.
The present embodiment also provides a method for manufacturing a perovskite solar cell, which is different from embodiment 1 only in that in step (4), the wet film completely reacted is transferred to a heating table at 120 ℃ and heated for 40min to obtain a perovskite film layer.
The prepared perovskite solar energy is tested, and a perovskite solar cell (1 cm) with the efficiency of 14.38% can be obtained 2 )。
Comparative example 1
The comparative example provides a lead halide film, the preparation method and specific operating parameters thereof are as follows:
vacuumizing the vacuum deposition equipment to 10 -4 Pa, evaporating PbI at a rate of 1.2nm/s 2 Solid powder forming single morphology PbI 2 Thin film, (thickness 430nm, porosity 11%) as shown in fig. 11.
The comparative example also provides a method for preparing a perovskite solar cell: pbI removal 2 The microstructure of the perovskite film layer obtained in example 1 is shown in fig. 12.
The prepared perovskite solar energy was tested, and a J-V curve is shown in FIG. 13, so that a perovskite solar cell (1 cm) with an efficiency of 13.89% could be obtained 2 )。
Comparative example 2
The comparative example provides a lead halide film, the preparation method and specific operating parameters thereof are as follows:
vacuumizing the vacuum deposition equipment to 10 -4 Pa, evaporating PbI at a rate of 1.2nm/s 2 The solid powder is flushed with ammonia gas at a speed of 20mL/min to obtain loose PbI 2 Film (thickness 210nm, porosity 61%) and further evaporation of PbI at a rate of 1.2nm/s 2 Solid powder, nitrogen is flushed at a speed of 30mL/min to obtain compact PbI 2 Film (thickness 420nm, porosity 17%) and finally PbI with loose structure/compact structure composite layer 2 A film.
The comparative example also provides a method for preparing a perovskite solar cell: pbI removal 2 The preparation of the other functional layers except for the film was the same as in example 1.
The prepared perovskite solar energy was tested, and a perovskite solar cell (1 cm) with an efficiency of 11.01% was obtained 2 )。
Comparative example 3
The comparative example provides a lead halide film, the preparation method and specific operating parameters thereof are as follows:
vacuumizing the vacuum equipment to 10 4 Pa, starting to regulate the evaporation rate of the lead iodide, first depositing 550nm at a deposition rate of 1nm/s, then depositing 80nm at a deposition rate of 0.05nm/s, and then stopping the deposition, in such a way that a composite PbI is obtained 2 The comparative film example also provides a method for preparing a perovskite solar cell: pbI removal 2 The preparation of the other functional layers except for the film was the same as in example 1.
The prepared perovskite solar energy is tested, and a perovskite solar cell (1 cm) with the efficiency of 11.45% can be obtained 2 )。
The J-V graphs of perovskite solar cells provided in each example and comparative example are shown in FIGS. 3-10 and 13-15, and specific performance parameters are shown in the following table:
TABLE 1
| Case (B) | Current (mA) | Voltage (V) | Fill factor (%) | Photoelectric conversion efficiency (%) |
| Example 1 | 22.57 | 0.90 | 73.84 | 15.11 |
| Example 2 | 23.19 | 0.95 | 74.33 | 16.40 |
| Example 3 | 22.79 | 0.90 | 75.14 | 15.48 |
| Example 4 | 22.76 | 0.98 | 73.48 | 16.49 |
| Example 5 | 22.89 | 0.97 | 72.65 | 16.18 |
| Example 6 | 22.76 | 1.00 | 70.02 | 15.82 |
| Example 7 | 22.89 | 0.97 | 70.06 | 15.54 |
| Example 8 | 23.11 | 0.88 | 70.10 | 14.38 |
| Comparative example 1 | 21.77 | 0.89 | 71.02 | 13.88 |
| Comparative example 2 | 20.90 | 0.89 | 59.13 | 11.01 |
| Comparative example 3 | 19.24 | 1.03 | 57.43 | 11.45 |
Comparative example 1 and comparative example 1, pbI of the dense structure/loose structure composite layer can be seen from SEM sectional view 2 Grains of film-formed perovskite (FIG. 2) compared to PbI of single morphology 2 The grains formed (fig. 12) are larger and more complete. From the comparison of the results in table 1, it is understood that the battery efficiency in example 1 is much higher than that in comparative example 1. Thus, pbI is produced in a dense/loose structure composite layer 2 The thin film is more beneficial to obtaining a high-quality perovskite solar cell.
As can be seen from example 2, a dense structure/loose structure composite layer of PbBr 2 The thin film can still obtain a perovskite solar cell with high efficiency, which shows that the method has universality. It can be seen from examples 3 and 4 that the lead halide thin films of the dense/loose composite layers prepared by different processes can still obtain high-performance perovskite solar cells, which shows that the friendly structure is suitable for different processes. As can be seen from example 5, when the thickness ratio of the two film layers is 0.2:1, the thinner compact first lead halide film layer can help the organic solution to react slowly, and form a passivation layer, and the thicker loose second lead halide film layer is favorable for the organic solution to permeate quickly, so that the perovskite solar cell with high efficiency can be obtained. As can be seen from example 6, when the thickness ratio of the two film layers is 2.5:1, the lead halide film of the formed compact structure/loose structure composite layer can still obtain a perovskite solar cell with high performance. From example 7, it can be seen that the organic ammonium salt solution with different concentrations can still react better with the composite lead halide film proposed by the scheme, which shows that the scheme can be more widely used for different solutions and has more universality.
Comparative examples 1 and 2 show that the loosening of the first lead halide film layer is unfavorable for slow reaction of the organic solution, which easily results in excessive organic solution, and the densification of the second lead halide film layer is unfavorable for rapid permeation of the organic solution, so that the efficiency of the obtained perovskite solar cell is too low. In contrast to example 1 and comparative example 3, comparative example 3 can produce a larger pore first film layer that can enhance the degree of conversion of metal halides and a flat dense second film layer whose flat surface can enhance the surface flatness of perovskite films, however, it is disadvantageous for permeation of organic amine salt solution, and thus the perovskite solar cell efficiency obtained by this structure is lower than that of example 1, and is not an optimal structure.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present application.
Claims (10)
1. The lead halide film is characterized by comprising a first lead halide film layer and a second lead halide film layer which are stacked, wherein the first lead halide film layer has a porosity of 1-30%, and the second lead halide film layer has a porosity of 40-60%.
2. The lead halide film according to claim 1, wherein the thickness ratio of the first lead halide film layer to the second lead halide film layer is (0.2 to 5): 1.
3. the lead halide film according to claim 1 or 2, wherein the thickness of the first lead halide film layer is 80 to 500nm;
and/or the thickness of the second lead halide film layer is 200-600 nm.
4. A lead halide film according to any one of claims 1 to 3, wherein the first lead halide film layer and the second lead halide film layer are independently composed of at least one member selected from the group consisting of lead chloride, lead iodide and lead bromide.
5. The preparation method of the lead halide film is characterized by comprising the following steps:
s1, preparing a first lead halide film layer with the porosity of 1-30% on a substrate;
s2, preparing a second lead halide film layer with the porosity of 40-60% on the first lead halide film layer.
6. The method for producing a lead halide film as recited in claim 5, wherein the first lead halide film layer is produced by an evaporation method, and in step S1, the evaporation rate of the lead halide is 0.5 to 1.2nm/S, and the vacuum degree is 10 -3 ～10 -5 Pa；
And/or preparing a second lead halide film layer by adopting an evaporation method, wherein in the step S2, the evaporation speed of the lead halide is 0.5-1.2 nm/S, and the vacuum degree is 10 -3 ～10 -5 Pa。
7. The method for producing a lead halide film as claimed in claim 6, wherein in step S1, no gas is introduced during the deposition; or, introducing nitrogen or rare gas, wherein the introduced amount is 10-50 mL/min;
and/or, in the step S2, ammonia gas is introduced in the vacuum deposition process, wherein the introducing amount is 20-60 mL/min.
8. A perovskite film layer, characterized in that the surface of the lead halide film prepared by the lead halide film according to any one of claims 1 to 4 or the preparation method according to any one of claims 5 to 7 is deposited with an organic ammonium salt solution, and the film layer is obtained by annealing.
9. The perovskite membrane layer of claim 8, wherein in the organic amine salt solution, cations of the solute include formamidine ions and/or methylamine ions;
and/or anions of the solute include at least one of chloride, bromide, or iodide;
and/or the solvent in the organic ammonium salt solution comprises isopropanol;
and/or the concentration of the organic ammonium salt solution is 0.2-0.8 mol/mL;
and/or the deposition method comprises a solution method or a vacuum evaporation method; preferably, the solution method includes at least one of a knife coating method, a spraying method, or a dipping method;
and/or the annealing temperature is 120-150 ℃ and the annealing time is 40-60 min.
10. A perovskite solar cell comprising the perovskite film layer of claim 9.
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