CN108321300A - A kind of perovskite thin film of admixed with additives and its preparation method and application - Google Patents
A kind of perovskite thin film of admixed with additives and its preparation method and application Download PDFInfo
- Publication number
- CN108321300A CN108321300A CN201810119782.9A CN201810119782A CN108321300A CN 108321300 A CN108321300 A CN 108321300A CN 201810119782 A CN201810119782 A CN 201810119782A CN 108321300 A CN108321300 A CN 108321300A
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- China
- Prior art keywords
- solvent
- ion
- perovskite
- additive
- thin film
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- 239000000654 additive Substances 0.000 title claims abstract description 159
- 239000010409 thin film Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 230000000996 additive effect Effects 0.000 claims abstract description 106
- -1 halide ion Chemical class 0.000 claims abstract description 30
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims description 172
- 239000010408 film Substances 0.000 claims description 44
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 38
- 239000000758 substrate Substances 0.000 claims description 38
- 239000000376 reactant Substances 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 27
- 150000002500 ions Chemical class 0.000 claims description 25
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 24
- 239000012296 anti-solvent Substances 0.000 claims description 21
- 229910001507 metal halide Inorganic materials 0.000 claims description 21
- 150000005309 metal halides Chemical class 0.000 claims description 21
- 238000007792 addition Methods 0.000 claims description 20
- 238000001704 evaporation Methods 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 20
- 150000001298 alcohols Chemical class 0.000 claims description 18
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 18
- 238000000151 deposition Methods 0.000 claims description 18
- 230000008021 deposition Effects 0.000 claims description 18
- 150000002148 esters Chemical class 0.000 claims description 18
- 150000008282 halocarbons Chemical class 0.000 claims description 18
- 229930195733 hydrocarbon Natural products 0.000 claims description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims description 18
- 150000002576 ketones Chemical class 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
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- 150000003457 sulfones Chemical class 0.000 claims description 18
- 150000003462 sulfoxides Chemical class 0.000 claims description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000000460 chlorine Substances 0.000 claims description 17
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- 150000001408 amides Chemical class 0.000 claims description 16
- 230000008020 evaporation Effects 0.000 claims description 16
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052794 bromium Inorganic materials 0.000 claims description 15
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 15
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- 239000011248 coating agent Substances 0.000 claims description 13
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 12
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 12
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- 125000003368 amide group Chemical group 0.000 claims description 12
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- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 12
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- RYXHOMYVWAEKHL-UHFFFAOYSA-N astatine atom Chemical compound [At] RYXHOMYVWAEKHL-UHFFFAOYSA-N 0.000 claims description 12
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 12
- 229910052793 cadmium Inorganic materials 0.000 claims description 12
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052792 caesium Inorganic materials 0.000 claims description 12
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical group [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 12
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 12
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 12
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 12
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- 239000011133 lead Substances 0.000 claims description 12
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 12
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- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 12
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- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 229910052699 polonium Inorganic materials 0.000 claims description 12
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 claims description 12
- 238000003672 processing method Methods 0.000 claims description 12
- 229910052703 rhodium Inorganic materials 0.000 claims description 12
- 239000010948 rhodium Substances 0.000 claims description 12
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052701 rubidium Inorganic materials 0.000 claims description 12
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical group [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 12
- 229910052711 selenium Inorganic materials 0.000 claims description 12
- 239000011669 selenium Substances 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 238000004528 spin coating Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910052716 thallium Inorganic materials 0.000 claims description 12
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 12
- 239000011135 tin Substances 0.000 claims description 12
- 229910052718 tin Inorganic materials 0.000 claims description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- 239000010937 tungsten Substances 0.000 claims description 12
- 229910052725 zinc Inorganic materials 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
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- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 4
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- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 4
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 3
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
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- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 3
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- HAYXDMNJJFVXCI-UHFFFAOYSA-N arsenic(5+) Chemical compound [As+5] HAYXDMNJJFVXCI-UHFFFAOYSA-N 0.000 claims description 3
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- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 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
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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
- H10K71/30—Doping active layers, e.g. electron transporting layers
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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
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Inorganic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
The present invention relates to a kind of perovskite thin films of admixed with additives, and doped with additive in the perovskite thin film, the additive is the stabilizer that metal ions M is formed with halide ion G.The invention also discloses a kind of preparation method and application of the perovskite thin film of admixed with additives, by in the preparation process of perovskite thin film, mix suitable additive, inhibit the movement of iodide ion in perovskite thin film material by additive, to have the function that stabilizing material itself so that the long-time stability of the perovskite battery thus prepared get a promotion, and improve the performance of perovskite battery, so that its service life significantly extends, but also promote industrialized production.
Description
Technical field
The invention belongs to perovskite technical field of solar batteries, more particularly to are related to a kind of perovskite of admixed with additives
Film and its preparation method and application.
Background technology
Solar cell is a kind of electrooptical device, is converted solar energy into electrical energy using the photovoltaic effect of semiconductor.
It is developed so far, solar power generation has become the most important regenerative resource in addition to hydroelectric generation and wind-power electricity generation.It is current in
Commercialized semiconductor has monocrystalline silicon, polysilicon, non-crystalline silicon, cadmium telluride, copper indium gallium selenide etc., but energy consumption is big, of high cost mostly.
In recent years, a kind of perovskite solar cell receives significant attention, and this perovskite solar cell is with organic gold
Category halide is light absorbing layer.Perovskite molecule is ABX3The cuboctahedron structure of type, as shown in Figure 1.Such material preparation
Thin-film solar cells simple process, production cost it is low, stablize and high conversion rate, so far from 2009, photoelectric conversion efficiency
It is promoted to 22% or more from 3.8%, be higher than commercialized crystal silicon solar batteries and there is larger cost advantage.
The iodide ion active force that is connected with organo-functional group is weaker in perovskite material, thus is easy to disconnect.After disconnection solely
Vertical iodide ion is easy movement, so as to cause the aging of perovskite material, leads to the deterioration of device performance.
In order to further increase perovskite battery efficiency, have and researched and proposed new battery structure, or material interface into
Row modification, and explore new material.It also researchs and proposes, the high efficiency of perovskite battery has benefited from the optimization shape of material itself
Looks and quality are a kind of effective methods using additive to improve film quality and be precisely controlled perovskite crystal grain.
The application of additive can assist the formation of nucleus evenly, and influence the crystallization process of material.Using the benefit of additive
Including smooth film surface can be prepared, surface coverage is improved, grain size is controlled, to increase the parallel connection of perovskite battery
Resistance, and then achieve the purpose that increase battery efficiency.
Existing perovskite thin film additive mainly has a polymer, fullerene, metal halogen salt, inorganic acid, and solvent is organic
Haloid, nano-particle and other type additives.These methods have effectively regulated and controled the crystallization process of perovskite, obtain surface
Fine and close smooth film, to improve the performance and long-time stability of perovskite battery.But existing additive cannot but press down
Iodide ion movement processed, cannot prevent the aging of perovskite material.
Therefore, the prior art is further improved and perfect.
Invention content
Technical problem to be solved by the present invention lies in provide perovskite thin film and its preparation side of a kind of admixed with additives
Method and application mix suitable additive in the preparation process of perovskite thin film, inhibit the shifting of iodide ion by additive
It is dynamic, to have the function that stable perovskite thin film material itself, provide a kind of calcium titanium of the active layer with admixed with additives
Mine film and perovskite solar cell.
The invention is realized in this way a kind of perovskite thin film of admixed with additives is provided, in the perovskite thin film
Doped with additive, the stabilizer that the additive is formed for metal ions M with halide ion G, Formula MG,
In, the metal ions M include rare earth ion, lithium ion, sodium ion, potassium ion, hydrogen ion, calcium ion, magnesium ion, barium from
Son, any one ion in aluminium ion, or including univalent copper ion, bivalent cupric ion, monovalence silver ion, ferrous iron from
Son, ferric ion, divalent manganesetion, tetravalence manganese ion, sexavalence manganese ion, septivalency manganese ion, zinc ion, monovalence nickel ion,
It is any one in bivalent nickel ion, cobalt ions, titanium ion, chromium ion, hafnium ion, tantalum ion, zirconium ion, molybdenum ion, niobium ion
Kind ion, or including ammonium ion, BF3Ion, B2H6It is any one in ion, arsenic ion, antimony ion, electron deficient pi bond ion
Kind ion, the halide ion G are any one ion in iodine, bromine, chlorine.
Due in the preparation process of perovskite thin film, can locally generate iodine vacancy, and the presence in iodine vacancy can promote
The migration of iodide ion in perovskite, therefore, introducing these additives MG can promote being uniformly distributed for iodine that can effectively reduce
Iodine vacancy.The general metal halide smaller using radius, can effectively reduce the iodine vacancy concentration in perovskite thin film.
Further, the additive MG is by way of solution hybrid mode or altogether steaming or anti-solvent mode or lamination side
Formula is incorporated into perovskite thin film.
Further, the electron deficient pi bond ion includes tetracyanoethylene ion, ketene compounds ion.
The invention is realized in this way also providing a kind of preparation side of the perovskite thin film of foregoing admixed with additives
Method includes the following steps：
Step S11, perovskite solution is prepared；
Step S12, additive MG, 70 DEG C of heating stirring 2h are added in the perovskite solution, and it is mixed to obtain perovskite additive
Close liquid；
Step S13, any one processing method adds the perovskite in being continuously coated with or spray by spin coating, blade coating, slit
Adding agent mixed liquor to be coated in deposition has one layer of film layer containing perovskite additive mixed liquor of formation on the substrate of transport layer, and
The film layer is made annealing treatment to obtain the perovskite thin film layer of admixed with additives；
In step s 11, it is mixed in the perovskite solution containing at least one bivalent metal halide predecessor BX2It is molten
Liquid, solution and organic solvent containing at least one reactant A X, B is divalent metal：Lead, tin, tungsten, copper, zinc,
Any one cation in gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X are
At least any one anion in iodine, bromine, chlorine, astatine, A be caesium, rubidium, amido, amidino groups or alkali family at least any one,
The organic solvent includes main solvent and solvent additive, and the main solvent is that can dissolve metal halide and other additive acyls
Amine solvent, sulfone class/sulfoxide type solvents, esters solvent, hydro carbons, halogenated hydrocarbon solvent, alcohols solvent, ketones solvent, ethers are molten
Any one in agent, aromatic hydrocarbon solvent, the solvent additive are that amide solvent, sulfone class/sulfoxide type solvents, esters are molten
In agent, hydro carbons, halogenated hydrocarbon solvent, alcohols solvent, ketones solvent, ether solvent, aromatic hydrocarbon at least any one；Described
In perovskite solution, predecessor BX2A concentration of 0.5 ~ 2mol/L of solution, reactant A X additions are predecessor BX2Mole
0 ~ 100%, solvent additive and predecessor BX2Molar ratio be 0 ~ 300%；
In step s 12, the incorporation of the additive MG is predecessor BX20.01 ~ 5-20% of mole.
The invention is realized in this way also providing a kind of preparation side of the perovskite thin film of foregoing admixed with additives
Method includes the following steps：
Step S21, forerunner's additive mixed liquor is prepared：Additive MG, 70 DEG C of heating stirrings are added in perovskite precursor solution
2h；
Step S22, any one processing method adds the forerunner in being continuously coated with or spray by spin coating, blade coating, slit
Agent mixed liquor, which is coated in deposition, one layer of film layer containing forerunner's additive mixed liquor of formation on the substrate of transport layer, and to this
Film layer is made annealing treatment to obtain the perovskite precursor thin film layer of admixed with additives MG；
Step S23, the substrate of the perovskite precursor thin film layer of admixed with additives MG made from step S22 is positioned over film forming
In cavity, the vacuum degree control in film forming cavity is 10-5 Pa~105Between Pa；
Step S24, by the reactant A X powder being previously positioned in film forming cavity heat, heating temperature range be 100 ~
200 DEG C so that perovskite precursor thin film is placed in the steam ambient of reactant A X, while being heated to substrate, the heating of substrate
Temperature control is at 30 DEG C ~ 150 DEG C, and reaction time control is in 10min ~ 120min, reactant A X gas molecules and predecessor BX2Point
Son reaction generates the perovskite thin film of admixed with additives MG, forms perovskite active layer；
In the step s 21, it is mixed in the perovskite precursor solution containing at least one bivalent metal halide predecessor BX2
Solution and organic solvent, B is divalent metal：Lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium,
Any one cation in indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X are at least any one in iodine, bromine, chlorine, astatine
Kind of anion, the organic solvent include main solvent and solvent additive, the main solvent be can dissolve metal halide and its
His additive amide solvent, sulfone class/sulfoxide type solvents, esters solvent, hydro carbons, halogenated hydrocarbon solvent, alcohols solvent, ketone are molten
Any one in agent, ether solvent, aromatic hydrocarbon solvent, the solvent additive are that amide solvent, sulfone class/sulfoxide type are molten
It is at least any one in agent, esters solvent, hydro carbons, halogenated hydrocarbon solvent, alcohols solvent, ketones solvent, ether solvent, aromatic hydrocarbon
Kind；In the perovskite precursor solution, predecessor BX2A concentration of 0.5 ~ 2mol/L of solution, the incorporation of the additive MG
Amount is predecessor BX2The 0.01 ~ 20% of mole, solvent additive and predecessor BX2Molar ratio be 0 ~ 300%；
In step s 24, the A of the reactant A X be caesium, rubidium, amido, amidino groups or alkali family at least any one, reaction
Object AX additions are predecessor BX2The 0 ~ 100% of mole.
The invention is realized in this way also providing a kind of preparation side of the perovskite thin film of foregoing admixed with additives
Method includes the following steps：
Step S31, the substrate of transport layer is placed in film forming cavity deposition, the vacuum degree control in film forming cavity
10-8 Pa~105It between Pa, while being heated to substrate, the heating and temperature control of substrate is at 30 DEG C ~ 150 DEG C；
Step S32, by predecessor BX2, reactant A X, additive MG be respectively placed in different evaporation sources, the evaporation rate of AX
For 0.1 ~ 10/s, BX2Evaporation rate be 0.1 ~ 10/s, the evaporation rate of additive MG is 0.01 ~ 5/s so that predecessor
BX2, reactant A X, additive MG react to each other and generate the perovskite thin film of admixed with additives MG, form perovskite active layer；
In step s 32, the predecessor BX2B be divalent metal：Lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium,
Any one cation in rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X are iodine, bromine, chlorine, astatine, sulphur
At least any one anion in cyanogen root, acetate, the A in the reactant A X are caesium, rubidium, amido, amidino groups or alkali family
In at least any one.
The invention is realized in this way also providing a kind of preparation side of the perovskite thin film of foregoing admixed with additives
Method includes the following steps：
Step S41, additive MG is dissolved in anti-solvent, 60 DEG C of heating stirring 2h, antisolvent addition mixing is prepared
Liquid；
Step S42, perovskite solution is prepared；
Step S43, any one processing method is molten by the perovskite in being continuously coated with or spray by spin coating, blade coating, slit
Liquid, which is coated in deposition, one layer of perovskite thin film layer of formation on the substrate of transport layer；
Step S44, any one in antisolvent addition mixed liquor being continuously coated with or sprayed by spin coating, blade coating, slit
Processing method, which is coated in deposition, to be had on the substrate of perovskite thin film layer, and is made annealing treatment to obtain the calcium doped with additive MG
Titanium ore film layer；
In step S41, the anti-solvent be benzene, toluene, 1,2- dimethylbenzene, 1,3- dimethylbenzene, Isosorbide-5-Nitrae-dimethylbenzene, chlorobenzene, 1,
At least one of 2- dichloro-benzenes, 1,3- dichloro-benzenes, 1,4- dichloro-benzenes, tetrahydrofuran, acetonitrile, ether, amylalcohol；The anti-solvent
The concentration of additive MG is 0.01 ~ 3mol/L in additive mixed liquor；
In step S42, it is mixed in the perovskite solution containing at least one bivalent metal halide predecessor BX2It is molten
Liquid, solution and organic solvent containing at least one reactant A X, B is divalent metal：Lead, tin, tungsten, copper, zinc,
Any one cation in gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X are
At least any one anion in iodine, bromine, chlorine, astatine, thiocyanate, acetate, A are in caesium, rubidium, amido, amidino groups or alkali family
At least any one, the organic solvent includes main solvent and solvent additive, and the main solvent is that can dissolve metal halide
Object and other additive amide solvents, sulfone class/sulfoxide type solvents, esters solvent, hydro carbons, halogenated hydrocarbon solvent, alcohols solvent,
Any one in ketones solvent, ether solvent, aromatic hydrocarbon solvent, the solvent additive are amide solvent, sulfone class/sulfoxide
At least appointing in class solvent, esters solvent, hydro carbons, halogenated hydrocarbon solvent, alcohols solvent, ketones solvent, ether solvent, aromatic hydrocarbon
Meaning is a kind of；In the perovskite solution, predecessor BX2A concentration of 0.5 ~ 2mol/L of solution, before reactant A X additions are
Drive object BX2The 0 ~ 100% of mole, solvent additive and predecessor BX2Molar ratio be 0 ~ 300%.
The invention is realized in this way also providing a kind of perovskite solar cell, the perovskite sun is being prepared
The perovskite thin film of foregoing admixed with additives has been used on energy battery.
The invention is realized in this way also providing a kind of perovskite solar cell, the perovskite sun is being prepared
Perovskite thin film prepared by the preparation method of the perovskite thin film of foregoing admixed with additives is used in energy cell process.
Compared with prior art, the perovskite thin film of admixed with additives and its preparation method and application of the invention, in calcium
In the preparation process of titanium ore film, suitable additive is mixed, iodide ion in perovskite thin film material is inhibited by additive
Movement, to have the function that stable perovskite thin film material itself so that the perovskite battery thus prepared it is long-term steady
Qualitative to get a promotion, service life significantly extends, but also promotes industrialized production.
Description of the drawings
Fig. 1 is schematic arrangement in prior art perovskite thin film；
Fig. 2 is perovskite inside solar energy battery structural schematic diagram prepared by the present invention；
Fig. 3 is Cu+And IElectron outside nucleus track schematic diagram；
Fig. 4 is the J-V curve graphs of perovskite solar cell prepared by the present invention；
Fig. 5 is 3000 hours damp and hot testing efficiency decay patterns of perovskite solar cell working prepared by the present invention；
Fig. 6 is 5000 hours illumination decay patterns of perovskite solar cell prepared by the present invention.
Specific implementation mode
In order to make technical problems, technical solutions and advantages to be solved be more clearly understood, tie below
Accompanying drawings and embodiments are closed, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only
To explain the present invention, it is not intended to limit the present invention.
The invention discloses a kind of perovskite thin films of admixed with additives, doped with addition in the perovskite thin film
Agent, the additive are the stabilizer that metal ions M is formed with halide ion G, Formula MG, wherein the metal
Ion M includes in rare earth ion, lithium ion, sodium ion, potassium ion, hydrogen ion, calcium ion, magnesium ion, barium ions, aluminium ion
Any one ion, or including univalent copper ion, bivalent cupric ion, monovalence silver ion, ferrous ion, ferric ion,
Divalent manganesetion, tetravalence manganese ion, sexavalence manganese ion, septivalency manganese ion, zinc ion, monovalence nickel ion, bivalent nickel ion, cobalt from
Any one ion in son, titanium ion, chromium ion, hafnium ion, tantalum ion, zirconium ion, molybdenum ion, niobium ion, or including
Ammonium ion, BF3Ion, B2H6Any one ion in ion, arsenic ion, antimony ion, electron deficient pi bond ion, the halogen
Ion G is any one ion in iodine, bromine, chlorine.The electron deficient pi bond ion includes tetracyanoethylene ion, ketene chemical combination
Object ion.
According to lewis acid-base theories, the halide ion G in additive（Especially iodide ion）It, can be with lone pair electrons
It is complexed with the atom with unoccupied orbital, to inhibit the migration of perovskite thin film material halide ion.
Due in the preparation process of perovskite thin film, can locally generate iodine vacancy, and the presence in iodine vacancy can promote
Therefore the migration of iodide ion in perovskite introduces additive and promotes being uniformly distributed for iodine that can effectively reduce iodine vacancy, generally
Using the smaller metal halide of radius, such as potassium iodide, the iodine vacancy concentration in perovskite can be effectively reduced.Therefore, make
Iodide ion can be inhibited to move with additive disclosed by the invention, to improve the long-time stability of perovskite battery.
In the above-described embodiments, the additive MG by way of solution hybrid mode or altogether steaming or anti-solvent mode or
Stacked system is incorporated into perovskite thin film.
The invention also discloses a kind of preparation method of the perovskite thin film of foregoing admixed with additives, including it is as follows
Step：
Step S11, perovskite solution is prepared.
Step S12, additive MG, 70 DEG C of heating stirring 2h are added in the perovskite solution, obtain perovskite addition
Agent mixed liquor.
Step S13, any one processing method is by the calcium titanium in being continuously coated with or spray by spin coating, blade coating, slit
Mine additive mixed liquor, which is coated in deposition, one layer of film containing perovskite additive mixed liquor of formation on the substrate of transport layer
Layer, and the film layer is made annealing treatment to obtain the perovskite thin film layer of admixed with additives MG.
In step s 11, it is mixed in the perovskite solution containing at least one bivalent metal halide predecessor BX2
Solution, solution and organic solvent containing at least one reactant A X, B is divalent metal：Lead, tin, tungsten, copper,
Any one cation in zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X
For at least any one anion in iodine, bromine, chlorine, astatine, A is at least any one in caesium, rubidium, amido, amidino groups or alkali family
Kind, the organic solvent includes main solvent and solvent additive, and the main solvent is that can dissolve metal halide and other additions
Agent amide solvent, sulfone class/sulfoxide type solvents, esters solvent, hydro carbons, halogenated hydrocarbon solvent, alcohols solvent, ketones solvent, ether
Any one in class solvent, aromatic hydrocarbon solvent, can be mainly n,N-Dimethylformamide（DMF）, dimethyl sulfoxide (DMSO)（DMSO）、
N-Methyl pyrrolidone（NMP）, gamma-butyrolacton（GBL）In any one；The solvent additive is amide solvent, sulfone
In class/sulfoxide type solvents, esters solvent, hydro carbons, halogenated hydrocarbon solvent, alcohols solvent, ketones solvent, ether solvent, aromatic hydrocarbon
At least any one, mainly can be DMSO, NMP, 1,8- diiodo-octanes（DIO）, n-cyclohexyl-2-pyrrolidone（CHP）, chlorine
Benzene（CB）, one or more of toluene；In the perovskite solution, predecessor BX2A concentration of 0.5 ~ 2mol/L of solution,
Reactant A X additions are predecessor BX2The 0 ~ 100% of mole, solvent additive and predecessor BX2Molar ratio be 0 ~ 300%.
In step s 12, the incorporation of the additive MG is predecessor BX2The 0.01 ~ 20% of mole.
The invention also discloses a kind of preparation method of the perovskite thin film of foregoing admixed with additives, including it is as follows
Step：
Step S21, forerunner's additive mixed liquor is prepared：Additive MG, 70 DEG C of heating stirrings are added in perovskite precursor solution
2h。
Step S22, any one processing method is by the forerunner in being continuously coated with or spray by spin coating, blade coating, slit
Additive mixed liquor, which is coated in deposition, one layer of film layer containing forerunner's additive mixed liquor of formation on the substrate of transport layer, and
The film layer is made annealing treatment to obtain the perovskite precursor thin film layer of admixed with additives MG.
Step S23, the substrate of the perovskite precursor thin film layer of admixed with additives MG made from step S22 is positioned over film
In molding cavity, the vacuum degree control in film forming cavity is 10-5 Pa-105Between Pa.
Step S24, the reactant A X powder being previously positioned in film forming cavity is heated, heating temperature range is
100 ~ 200 DEG C so that perovskite precursor thin film is placed in the steam ambient of reactant A X, while being heated to substrate, substrate
At 30 DEG C ~ 150 DEG C, the reaction time controls in 10min ~ 120min, reactant A X gas molecules and predecessor heating and temperature control
BX2Molecule reaction generates the perovskite thin film of admixed with additives MG, forms perovskite active layer.Obtained perovskite light-absorption layer
Thickness is 200 ~ 500nm.
In the step s 21, it is mixed in the perovskite precursor solution containing at least one bivalent metal halide forerunner
Object BX2Solution and organic solvent, B is divalent metal：Lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium,
Any one cation in silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X be iodine, bromine, chlorine, in astatine at least
Any one anion, the organic solvent include main solvent and solvent additive, and the main solvent is that can dissolve metal halide
Object and other additive amide solvents, sulfone class/sulfoxide type solvents, esters solvent, hydro carbons, halogenated hydrocarbon solvent, alcohols solvent,
Any one in ketones solvent, ether solvent, aromatic hydrocarbon solvent, the solvent additive are amide solvent, sulfone class/sulfoxide
At least appointing in class solvent, esters solvent, hydro carbons, halogenated hydrocarbon solvent, alcohols solvent, ketones solvent, ether solvent, aromatic hydrocarbon
Meaning is a kind of；In the perovskite precursor solution, predecessor BX2A concentration of 0.5 ~ 2mol/L of solution, the additive MG's
Incorporation is predecessor BX2The 0.01 ~ 20% of mole, solvent additive and predecessor BX2Molar ratio be 0 ~ 300%.
In step s 24, the A of the reactant A X be caesium, rubidium, amido, amidino groups or alkali family at least any one,
Reactant A X additions are predecessor BX2The 0 ~ 100% of mole.
The invention also discloses a kind of preparation method of the perovskite thin film of foregoing admixed with additives, including it is as follows
Step：
Step S31, the substrate of transport layer is placed in film forming cavity deposition, the vacuum degree control in film forming cavity
10-8 Pa-105It between Pa, while being heated to substrate, the heating and temperature control of substrate is at 30 DEG C ~ 150 DEG C.
Step S32, by predecessor BX2, reactant A X, additive MG be respectively placed in different evaporation sources, the evaporation of AX
Rate is 0.1 ~ 10/s, BX2Evaporation rate be 0.1 ~ 10/s, the evaporation rate of additive MG is 0.01 ~ 5/s so that preceding
Drive object BX2, reactant A X, additive MG react to each other and generate the perovskite thin film of admixed with additives MG, form perovskite activity
Layer.
In step s 32, the predecessor BX2B be divalent metal：Lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic,
In selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium any one cation, X be iodine, bromine, chlorine,
At least any one anion in astatine, thiocyanate, acetate, the A in the reactant A X be caesium, rubidium, amido, amidino groups or
In alkali family at least any one.
The invention also discloses a kind of preparation method of the perovskite thin film of foregoing admixed with additives, including it is as follows
Step：
Step S41, additive MG is dissolved in anti-solvent, 60 DEG C of heating stirring 2h, the mixing of anti-solvent stabilizer is prepared
Liquid；
Step S42, perovskite solution is prepared.
Step S43, any one processing method is by the calcium titanium in being continuously coated with or spray by spin coating, blade coating, slit
Mineral solution, which is coated in deposition, one layer of perovskite thin film layer of formation on the substrate of transport layer.
Step S44, arbitrary in antisolvent addition mixed liquor being continuously coated with or sprayed by spin coating, blade coating, slit
A kind of processing method, which is coated in deposition, to be had on the substrate of perovskite thin film layer, and is made annealing treatment to obtain doped with additive MG
Perovskite thin film layer.
In step S41, the anti-solvent is benzene, toluene, 1,2- dimethylbenzene, 1,3- dimethylbenzene, Isosorbide-5-Nitrae-dimethylbenzene, chlorine
At least one of benzene, 1,2- dichloro-benzenes, 1,3- dichloro-benzenes, 1,4- dichloro-benzenes, tetrahydrofuran, acetonitrile, ether, amylalcohol；It is described
The concentration of additive MG is 0.01 ~ 3mol/L in antisolvent addition mixed liquor.
In step S42, it is mixed in the perovskite solution containing at least one bivalent metal halide predecessor BX2
Solution, solution and organic solvent containing at least one reactant A X, B is divalent metal：Lead, tin, tungsten, copper,
Any one cation in zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X
For at least any one anion in iodine, bromine, chlorine, astatine, thiocyanate, acetate, A is caesium, rubidium, amido, amidino groups or alkali family
In at least any one, the organic solvent includes main solvent and solvent additive, and the main solvent is that can dissolve metal halogen
Compound and other additive amide solvents, sulfone class/sulfoxide type solvents, esters solvent, hydro carbons, halogenated hydrocarbon solvent, alcohols are molten
Any one in agent, ketones solvent, ether solvent, aromatic hydrocarbon solvent, the solvent additive be amide solvent, sulfone class/
In sulfoxide type solvents, esters solvent, hydro carbons, halogenated hydrocarbon solvent, alcohols solvent, ketones solvent, ether solvent, aromatic hydrocarbon extremely
Lack any one；In the perovskite solution, predecessor BX2A concentration of 0.5 ~ 2mol/L of solution, reactant A X additions
It is predecessor BX2The 0 ~ 100% of mole, solvent additive and predecessor BX2Molar ratio be 0 ~ 300%.
The invention also discloses a kind of perovskite solar cells, are used on preparing the perovskite solar cell
The perovskite thin film of foregoing admixed with additives.
The invention also discloses a kind of perovskite solar cells, during preparing the perovskite solar cell
On use foregoing admixed with additives perovskite thin film preparation method prepare perovskite thin film.
With reference to specific embodiment come illustrate the present invention perovskite thin film of admixed with additives and preparation method thereof and
Using.
Example 1, a kind of preparation method of perovskite solar cell.
Attached perovskite inside solar energy battery structural schematic diagram shown in Fig. 2 is please referred to, is included the following steps：
（1）By the ito glass plate of 5 × 5cm successively through liquid detergent, deionized water, acetone, each cleaning 30min of isopropanol ultrasound, then
Use N2After drying 10min is handled through UV O-zone；
（2）NiO films are prepared as electron transfer layer；
（3）Prepare the metal halide precursor liquid of doping or modification：By the PbI of 461mg2（1mmol）, 19.05mg cuprous iodides
CuI（0.1mmol）It is dissolved in the DMF solution of 1mL, 60 DEG C of heating stirring 2h, 20uL chlorobenzenes is added, it is for use after mixing completely；
（4）The PbI of doping is prepared by slot coated using the precursor liquid of preparation2Film；
（5）Metal halide film obtained is placed in film forming cavity, using vacuum pump control pressure 10-5Pa~
105Pa, MABr heating and temperature control are at 100 DEG C ~ 200 DEG C, and substrate heating temperature control is at 30 DEG C ~ 150 DEG C, MABr gas molecules
With PbI2Reaction generates the perovskite thin film of doping
（6）It is dissolved in chlorobenzene with solwution method deposition electron transfer layer PCBM, PCBM on substrate, 10mg/mL obtains thick 30nm
PCBM layers；
（7）Perovskite solar cell is made in evaporation metal conductive layer Ag electrodes.
It please refers to shown in Fig. 3, attached drawing 3 is Cu+And IElectron outside nucleus trajectory diagram.From diagram as can be seen that Cu+With INetwork
It closes, to inhibit the migration of halide ion in perovskite thin film material.
Embodiment 2
（1）The FTO glass plates of 10 × 10cm are respectively cleaned into 30min through liquid detergent, deionized water, acetone, isopropanol ultrasound successively,
N is used again2After drying 10min is handled through UV O-zone；
（2）CuSCN films are prepared as hole transmission layer；
（3）Prepare the perovskite solution added with additive：By the PbI of 461mg2（1mmol）, 159mg MAI（1mmol）It is molten
Solution adds the anhydrous DMSO of 68uL in the DMF solution of 1mL, and adds 36.9mg cuprous bromides CuBr as additive, 70 DEG C
Heating stirring 2h, it is for use after mixing completely；
（4）Stably-doped dose of perovskite thin film, and 60 ~ 150 DEG C are prepared by slot coated using the perovskite solution of doping
Anneal 10 ~ 120min, and thickness is 200 ~ 600nm；
（5）Redeposited electron transfer layer ZnO, 20 ~ 50nm of thickness on substrate；
（6）Perovskite solar cell is made in evaporation metal conductive layer Au electrodes.
Embodiment 3
（1）The ito glass plate of 30 × 40cm is respectively cleaned into 30min through liquid detergent, deionized water, acetone, isopropanol ultrasound successively,
N is used again2After drying 10min is handled through UV O-zone；
（2）PEDOT films are prepared as hole transmission layer；
（3）There is the substrate of transport layer to be placed in film forming cavity deposition, the vacuum degree control in film forming cavity is 10-8 Pa~105It between Pa, while being heated to substrate, the heating and temperature control of substrate is at 30 DEG C ~ 150 DEG C；By PbI2, MAI, addition
Agent stannous chloride CuCl is respectively placed in different evaporation sources, and the evaporation rate of MAI is 1/s, PbI2Evaporation rate be 1.1
The evaporation rate of/s, stannous chloride are 0.02/s so that PbI2, MAI, stannous chloride reaction generate Doped ions stabilizers
Perovskite thin film forms perovskite active layer, thickness 550nm；
（4）Redeposited electron transfer layer tin oxide, 5 ~ 40nm of thickness on substrate；
（5）Perovskite solar cell is made in evaporation metal conductive layer Al electrodes.
Embodiment 4
（1）By the ito glass plate of 5 × 5cm successively through liquid detergent, deionized water, acetone, each cleaning 30min of isopropanol ultrasound, then
Use N2After drying 10min is handled through UV O-zone；
（2）Tungsten oxide film is prepared as hole transmission layer；
（3）Prepare perovskite solution：By the PbI of 461mg2（1mmol）, 159mg MAI（1mmol）The DMF for being dissolved in 1mL is molten
In liquid, 1, the 8- diiodo-octanes of 100uL are added, 70 DEG C of heating stirring 1h are for use after mixing completely；
（4）Prepare antisolvent addition mixed liquor：The iron iodide of 33.1mg is dissolved in 1mL anti-solvent chlorobenzenes, 60 DEG C are stirred
2h is mixed, it is for use after dissolving completely；
（5）Perovskite thin film is prepared by knife coating on the hole transport layer, and is added the anti-solvent of preparation by knife coating
Agent mixed liquor is coated on perovskite thin film surface, heating anneal, and heating temperature is 60 ~ 120 DEG C, and heating time is 2 ~ 60min, system
Obtain the perovskite thin film of Doped ions stabilizer；
（6）It is dissolved in adjacent 2 chlorobenzenes with solwution method deposition electron transfer layer PC71BM, PC71BM on substrate, 15mg/mL is obtained
To the PC71BM layers of thick 40nm；
（7）Perovskite solar cell is made in evaporation metal conductive layer Ag electrodes.
It please refers to shown in attached drawing 4, Fig. 5 and Fig. 6, attached drawing 4, attached drawing 5 and attached drawing 6 are the preparation method using the present invention respectively
The test data chart of the perovskite battery of the admixed with additives of preparation.From attached drawing 4 it can be seen that the admixed with additives of the present invention
Perovskite solar cell there is excellent photoelectric conversion performance, efficiency is up to 19.22%（PCE）.From attached drawing 5 it can be seen that originally
The solar cell long-time stability of the admixed with additives of invention are excellent, and 3000 hours behind efficiency attenuations are small under wet heat condition
In the 3% of starting efficiency.From attached drawing 6 it can be seen that the solar cell of the admixed with additives of the present invention is 5000 under illumination condition
Hour behind efficiency attenuation is less than the 5% of starting efficiency.From above-mentioned data it can be clearly seen that being prepared using the method for the present invention
The stability of perovskite solar cell greatly improve so that its service life significantly extends.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (9)
1. a kind of perovskite thin film of admixed with additives, which is characterized in that doped with additive, institute in the perovskite thin film
It is the stabilizer that metal ions M is formed with halide ion G, Formula MG, wherein the metal ions M to state additive
Including arbitrary in rare earth ion, lithium ion, sodium ion, potassium ion, hydrogen ion, calcium ion, magnesium ion, barium ions, aluminium ion
A kind of ion, or including univalent copper ion, bivalent cupric ion, monovalence silver ion, ferrous ion, ferric ion, divalent
Manganese ion, tetravalence manganese ion, sexavalence manganese ion, septivalency manganese ion, zinc ion, monovalence nickel ion, bivalent nickel ion, cobalt ions,
Any one ion in titanium ion, chromium ion, hafnium ion, tantalum ion, zirconium ion, molybdenum ion, niobium ion, or including ammonium root
Ion, BF3Ion, B2H6Any one ion in ion, arsenic ion, antimony ion, electron deficient pi bond ion, the halide ion
G is any one ion in iodine, bromine, chlorine.
2. the perovskite thin film of admixed with additives as described in claim 1, which is characterized in that the additive MG passes through solution
Hybrid mode steams mode or anti-solvent mode or stacked system is incorporated into perovskite thin film altogether.
3. the perovskite thin film of admixed with additives as described in claim 1, which is characterized in that the electron deficient pi bond ion packet
Include tetracyanoethylene ion, ketene compounds ion.
4. a kind of preparation method of the perovskite thin film of admixed with additives as claimed in claim 1 or 2, which is characterized in that packet
Include following steps：
Step S11, perovskite solution is prepared；
Step S12, additive MG, 70 DEG C of heating stirring 2h are added in the perovskite solution, and it is mixed to obtain perovskite additive
Close liquid；
Step S13, any one processing method adds the perovskite in being continuously coated with or spray by spin coating, blade coating, slit
Adding agent mixed liquor to be coated in deposition has one layer of film layer containing perovskite additive mixed liquor of formation on the substrate of transport layer, and
The film layer is made annealing treatment to obtain the perovskite thin film layer of admixed with additives MG；
In step s 11, it is mixed in the perovskite solution containing at least one bivalent metal halide predecessor BX2It is molten
Liquid, solution and organic solvent containing at least one reactant A X, B is divalent metal：Lead, tin, tungsten, copper, zinc,
Any one cation in gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X are
At least any one anion in iodine, bromine, chlorine, astatine, A be caesium, rubidium, amido, amidino groups or alkali family at least any one,
The organic solvent includes main solvent and solvent additive, and the main solvent is that can dissolve metal halide and other additive acyls
Amine solvent, sulfone class/sulfoxide type solvents, esters solvent, hydro carbons, halogenated hydrocarbon solvent, alcohols solvent, ketones solvent, ethers are molten
Any one in agent, aromatic hydrocarbon solvent, the solvent additive are that amide solvent, sulfone class/sulfoxide type solvents, esters are molten
In agent, hydro carbons, halogenated hydrocarbon solvent, alcohols solvent, ketones solvent, ether solvent, aromatic hydrocarbon at least any one；Described
In perovskite solution, predecessor BX2A concentration of 0.5 ~ 2mol/L of solution, reactant A X additions are predecessor BX2Mole
0 ~ 100%, solvent additive and predecessor BX2Molar ratio be 0 ~ 300%；
In step s 12, the incorporation of the additive MG is predecessor BX2The 0.01 ~ 20% of mole.
5. a kind of preparation method of the perovskite thin film of admixed with additives as claimed in claim 1 or 2, which is characterized in that packet
Include following steps：
Step S21, forerunner's additive mixed liquor is prepared：Additive MG, 70 DEG C of heating stirrings are added in perovskite precursor solution
2h；
Step S22, any one processing method adds the forerunner in being continuously coated with or spray by spin coating, blade coating, slit
Agent mixed liquor, which is coated in deposition, one layer of film layer containing forerunner's additive mixed liquor of formation on the substrate of transport layer, and to this
Film layer is made annealing treatment to obtain the perovskite precursor thin film layer of admixed with additives MG；
Step S23, the substrate of the perovskite precursor thin film layer of admixed with additives MG made from step S22 is positioned over film forming
In cavity, the vacuum degree control in film forming cavity is 10-5 Pa~105Between Pa；
Step S24, by the reactant A X powder being previously positioned in film forming cavity heat, heating temperature range be 100 ~
200 DEG C so that perovskite precursor thin film is placed in the steam ambient of reactant A X, while being heated to substrate, the heating of substrate
Temperature control is at 30 DEG C ~ 150 DEG C, and reaction time control is in 10min ~ 120min, reactant A X gas molecules and predecessor BX2Point
Son reaction generates the perovskite thin film of admixed with additives MG, forms perovskite active layer；
In the step s 21, it is mixed in the perovskite precursor solution containing at least one bivalent metal halide predecessor BX2
Solution and organic solvent, B is divalent metal：Lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium,
Any one cation in indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X are at least any one in iodine, bromine, chlorine, astatine
Kind of anion, the organic solvent include main solvent and solvent additive, the main solvent be can dissolve metal halide and its
His additive amide solvent, sulfone class/sulfoxide type solvents, esters solvent, hydro carbons, halogenated hydrocarbon solvent, alcohols solvent, ketone are molten
Any one in agent, ether solvent, aromatic hydrocarbon solvent, the solvent additive are that amide solvent, sulfone class/sulfoxide type are molten
It is at least any one in agent, esters solvent, hydro carbons, halogenated hydrocarbon solvent, alcohols solvent, ketones solvent, ether solvent, aromatic hydrocarbon
Kind；In the perovskite precursor solution, predecessor BX2A concentration of 0.5 ~ 2mol/L of solution, the incorporation of the additive MG
Amount is predecessor BX2The 0.01 ~ 20% of mole, solvent additive and predecessor BX2Molar ratio be 0 ~ 300%；
In step s 24, the A of the reactant A X be caesium, rubidium, amido, amidino groups or alkali family at least any one, reaction
Object AX additions are predecessor BX2The 0 ~ 100% of mole.
6. a kind of preparation method of the perovskite thin film of admixed with additives as claimed in claim 1 or 2, which is characterized in that packet
Include following steps：
Step S31, the substrate of transport layer is placed in film forming cavity deposition, the vacuum degree control in film forming cavity
10-8 Pa~105It between Pa, while being heated to substrate, the heating and temperature control of substrate is at 30 DEG C ~ 150 DEG C；
Step S32, by predecessor BX2, reactant A X, additive MG be respectively placed in different evaporation sources, the evaporation rate of AX is
0.1 ~ 10/s, BX2Evaporation rate be 0.1 ~ 10/s, the evaporation rate of additive MG is 0.01 ~ 5/s so that predecessor
BX2, reactant A X, additive MG react to each other and generate the perovskite thin film of admixed with additives MG, form perovskite active layer；
In step s 32, the predecessor BX2B be divalent metal：Lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium,
Any one cation in rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X are iodine, bromine, chlorine, astatine, sulphur
At least any one anion in cyanogen root, acetate, the A in the reactant A X are caesium, rubidium, amido, amidino groups or alkali family
In at least any one.
7. a kind of preparation method of the perovskite thin film of admixed with additives as claimed in claim 1 or 2, which is characterized in that packet
Include following steps：
Step S41, additive MG is dissolved in anti-solvent, 60 DEG C of heating stirring 2h, antisolvent addition mixing is prepared
Liquid；
Step S42, perovskite solution is prepared；
Step S43, any one processing method is molten by the perovskite in being continuously coated with or spray by spin coating, blade coating, slit
Liquid, which is coated in deposition, one layer of perovskite thin film layer of formation on the substrate of transport layer；
Step S44, any one in antisolvent addition mixed liquor being continuously coated with or sprayed by spin coating, blade coating, slit
Processing method, which is coated in deposition, to be had on the substrate of perovskite thin film layer, and is made annealing treatment to obtain the calcium doped with additive MG
Titanium ore film layer；
In step S41, the anti-solvent be benzene, toluene, 1,2- dimethylbenzene, 1,3- dimethylbenzene, Isosorbide-5-Nitrae-dimethylbenzene, chlorobenzene, 1,
At least one of 2- dichloro-benzenes, 1,3- dichloro-benzenes, 1,4- dichloro-benzenes, tetrahydrofuran, acetonitrile, ether, amylalcohol；The anti-solvent
The concentration of additive MG is 0.01 ~ 3mol/L in additive mixed liquor；
In step S42, it is mixed in the perovskite solution containing at least one bivalent metal halide predecessor BX2It is molten
Liquid, solution and organic solvent containing at least one reactant A X, B is divalent metal：Lead, tin, tungsten, copper, zinc,
Any one cation in gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X are
At least any one anion in iodine, bromine, chlorine, astatine, thiocyanate, acetate, A are in caesium, rubidium, amido, amidino groups or alkali family
At least any one, the organic solvent includes main solvent and solvent additive, and the main solvent is that can dissolve metal halide
Object and other additive amide solvents, sulfone class/sulfoxide type solvents, esters solvent, hydro carbons, halogenated hydrocarbon solvent, alcohols solvent,
Any one in ketones solvent, ether solvent, aromatic hydrocarbon solvent, the solvent additive are amide solvent, sulfone class/sulfoxide
At least appointing in class solvent, esters solvent, hydro carbons, halogenated hydrocarbon solvent, alcohols solvent, ketones solvent, ether solvent, aromatic hydrocarbon
Meaning is a kind of；In the perovskite solution, predecessor BX2A concentration of 0.5 ~ 2mol/L of solution, before reactant A X additions are
Drive object BX2The 0 ~ 100% of mole, solvent additive and predecessor BX2Molar ratio be 0 ~ 300%.
8. a kind of perovskite solar cell, which is characterized in that used on preparing the perovskite solar cell as
The perovskite thin film of admixed with additives as claimed in claim 1 or 2.
9. a kind of perovskite solar cell, which is characterized in that used during preparing the perovskite solar cell
Perovskite thin film prepared by the preparation method of the perovskite thin film of the admixed with additives as described in the claim 4 or 5 or 6 or 7.
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