CN105514278A - Bimetal complex perovskite materials, preparation method and application thereof - Google Patents

Bimetal complex perovskite materials, preparation method and application thereof Download PDF

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CN105514278A
CN105514278A CN201511000522.2A CN201511000522A CN105514278A CN 105514278 A CN105514278 A CN 105514278A CN 201511000522 A CN201511000522 A CN 201511000522A CN 105514278 A CN105514278 A CN 105514278A
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metal composite
binary metal
composite perofskite
halide
preparation
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CN105514278B (en
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陈炜
徐尧
王欢
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Hangzhou Zhongneng Photoelectric Technology Co Ltd
Huazhong University of Science and Technology
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Hangzhou Zhongneng Photoelectric Technology Co Ltd
Huazhong University of Science and Technology
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    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses three bimetal complex perovskite materials AB1B2X3(X: Cl, Br or I) and a preparation method thereof, and an application of the bimetal complex perovskite materials in preparation of perovskite solar cells with multiple structures. The bimetal complex perovskite materials, the preparation method and the application thereof belong to the field of a new-material solar cell. The bimetal complex perovskite material is prepared from an organic halide AX (A: CH3NH3<+>, NH2CH=NH2<+>; X: Cl<->, Br<->, I<->), metal halides B1X2, B2X2 (B1:Pb<2+>, B2: Mg<2+>, Ca<2+>, Ba<2+>, Ba<2+>; X: Cl, Br, I), and an organic solvent (N,N-dimethyl formamide DMF, dimethyl sulfoxide DMSO or gamma-butyrrolactone solvent). Compared with existing perovskite materials ABR3 (A: CH3NH3<->, NH2CH=NH2<+>; B: Pb<2+>; X: Cl<->, Br<->, I<->), the bimetal complex perovskite materials, the preparation method and the application thereof have advantages of effectively content of organic lead ions, reducing environment pollution, and facilitating realization of industrial application of perovskite solar cells.

Description

A kind of binary metal composite perofskite material, preparation method and application thereof
Technical field
The invention belongs to perovskite technical field of solar batteries, be specifically related to three kinds of binary metal composite perofskite materials (Mg-Pb, Ca-Pb, Ba-Pb) and this three kinds of material application in heterojunction solar battery, it effectively decreases the toxic heavy metal Pb in perovskite material 2+content, reduces the harm to environment, is conducive to the application of the extensive industrialization of the type battery.
Background technology
Along with the exhaustion day by day of non-renewable energy resources, the continuous increase of energy resource consumption, energy problem has become the significant challenge that the survival and development of current mankind society face.Solar energy is a kind of inexhaustible, nexhaustible non-polluting energy sources, and solar cell is then a kind of efficient apparatus utilizing photovoltaic effect solar energy to be directly converted to electric energy.The novel solar battery of research and development high efficiency, low cost is the technical foundation realizing photovoltaic generation extensive use, is also the important trend of current new energy technology development.
In recent years, the development of new calcium titanium ore solar battery technology rapidly.Liquid calcium titanium ore CH is reported from Japanese Scientists Miyasaka in 2009 3nH 3pbI 3the photoelectric conversion efficiency of solar cell 3.8%, to the perovskite solar battery efficiency of the certifications 20.1% such as Korea S Soek in 2015, perovskite solar battery efficiency promotes very swift and violent, causes the extensive concern of scientific circles and industrial circle.This battery has that raw material sources is extensive, manufacture craft is simple, with low cost and stability advantages of higher, thus probably in photovoltaic industry, becomes a kind of commercially produced product having competitiveness in the near future.
In existing perovskite solar cell, as the perovskite material of light-absorption layer, its metal ion usual 100% is by Pb 2+composition, such as: CH 3nH 3pbI 3, NH 2cH=NH 2pbI 3, CH 3nH 3pbCl 3deng.This perovskite material is because of containing a large amount of toxic heavy metal Pb 2+, there is the problems such as serious environmental pollution, be unfavorable for the extensive commercial application of perovskite solar cell.Therefore, research and develop Mg-Pb, Ca-Pb, Ba-Pb binary metal composite perofskite material to be significant in environmental protection and market-oriented application aspect.
Summary of the invention
For the problem of environmental pollution of current plumbous halogen perovskite solar cell, the application provides three kinds low lead content perovskite materials and preparation method, and at the various application processes of area of solar cell, while the photoelectric conversion efficiency ensureing battery, promote the environmental friendliness development of perovskite solar cell.
The present invention proposes three kinds of Mg-Pb, Ca-Pb, Ba-Pb composite perofskite materials, and described material is perovskite structure, and its expression formula can be used represent, wherein 0<m<1, A are or in one; B 1for Pb 2+; B 2for Mg 2+, Ca 2+or Ba 2+in one; X is at least Cl -, Br -or I -in one.
Preferably, described material is by halogenated methyl amine (or halogenation carbonamidine), lead halide, magnesium halide (or calcium halide, calcium halide), be dissolved in N, in dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) or gamma-butyrolacton solvent, then solvent evaporation is obtained.
Preferably, in described material, two kinds of metal halide (B 1x 2, B 2x 2) amount of substance sum, be 1:1 ~ 1:3 with the ratio of the amount of substance of organohalogen compounds (halogenated methyl amine or halogenation carbonamidine); In described two kinds of metal halide admixture, B 1x 2(lead halide) proportion is 10 ~ 90%, B 2x 2(magnesium halide, calcium halide or calcium halide) proportion is 90 ~ 10%; Described two kinds of metal halide (B 1x 2, B 2x 2), organohalogen compounds (halogenated methyl amine or halogenation carbonamidine) are dissolved in DMF (DMF), dimethyl sulfoxide (DMSO) (DMSO) or gamma-butyrolacton solvent, described two kinds of metal halide (B 1x 2, B 2x 2), organohalogen compounds (halogenated methyl amine or halogenation carbonamidine) account for 10% ~ 60% of solution gross mass, then by solvent evaporation is obtained B 1-B 2(Mg-Pb, Ca-Pb, Ba-Pb) binary metal composite perofskite material.
According to the present invention, provide a kind of preparation method of Mg-Pb, Ca-Pb, Ba-Pb composite perofskite material of correspondence, this preparation method comprises the following steps:
(1) under room temperature, by B 1x 2(lead halide) and B 2x 2(magnesium halide, calcium halide or calcium halide), by the ratio 1:9 ~ 9:1 of amount of substance, mixes, and forms two kinds of metal halide mixed-powders;
(2) by the mixed-powder described in (1), press ratio 1:1 ~ 1:3 proportioning of amount of substance with organohalogen compounds (halogenated methyl amine or halogenation carbonamidine) crystal, form homogeneous mixture;
(3) at room temperature ~ 130 DEG C, described to (2) mixture is dissolved in N, in dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) or gamma-butyrolacton solvent, be stirred to whole dissolving, then by 60 DEG C ~ 150 DEG C heating anneals 5 minutes ~ 120 minutes by solvent evaporate to dryness, can B be obtained 1-B 2(Mg-Pb, Ca-Pb, Ba-Pb) binary metal composite perofskite material.
Preferably, described halogenated methyl amine is CH 3nH 3cl, CH 3nH 3br or CH 3nH 3the one of I; Described halogenation carbonamidine is NH 2cH=NH 2cl, NH 2cH=NH 2br or NH 2cH=NH 2the one of I; Described lead halide is PbCl 2, PbBr 2or PbI 2one; Described magnesium halide is MgCl 2, MgBr 2or MgI 2in one or more mixing.Described calcium halide is CaCl 2, CaBr 2or CaI 2in one or more mixing.Described barium halide is BaCl 2, BaBr 2or BaI 2in one or more mixing.
The new binary metal composite perofskite material that the present invention proposes, can be applied in the perovskite solar cell of various structures.According to another aspect of the present invention, the present invention illustrates that above-mentioned binary metal composite perofskite material is used for the manufacture method of solar cell by five kinds further.
The invention provides the first and apply the method that above-mentioned binary metal composite perofskite material prepares solar cell, comprise the following steps:
The preparation of step (1) hole blocking layer
On the electro-conductive glass having plated fluorine doped tin oxide FTO, under 400 DEG C ~ 600 DEG C conditions, by the isopropyl titanate aqueous isopropanol of 0.01mol/L ~ 0.05mol/L, by the fine and close TiO that the method deposition 20nm ~ 100nm of thermal spraying is thick 2hole blocking layer;
The preparation of step (2) electron transfer layer
At described TiO 2on barrier layer, by the TiO that silk screen printing 200nm ~ 1000nm is thick 2nano-particle layer, under 450 DEG C ~ 550 DEG C conditions, anneals 0.5 hour ~ 2 hours, forms the mesoporous TiO of 200nm ~ 1000nm 2electron transfer layer;
The preparation of step (3) mesoporous insulating barrier
To include diameter is 10nm ~ 50nmZrO 2nano particle or Al 2o 3the slurry of nano particle, by silk screen printing on the electron transport layer, under 450 DEG C ~ 550 DEG C conditions, sinters 0.5 hour ~ 2 hours, forms the mesoporous insulating barrier of 200nm ~ 1000nm;
Step (4) carbon is to the preparation of electrode
Will by nano carbon black, graphite powder and ZrO 2the carbon pastes of nano adhesive composition, by silk screen printing on mesoporous insulating barrier, under 400 DEG C ~ 500 DEG C conditions, sinters 0.5 hour ~ 2 hours, and forming thickness is that the carbon of 5 μm ~ 20 μm is to electrode;
Step (5) fills binary metal composite perofskite material
By described binary metal composite perofskite heating materials to 50 DEG C ~ 130 DEG C, get 1 μ L ~ 100 μ L and drop in the carbon of described solar cell to electrode surface, then with 60 DEG C ~ 150 DEG C heating temperatures 10 minutes ~ 120 minutes, make this kind of binary metal composite perofskite material solvent volatilization, obtain solid-state binary metal composite perofskite solar cell.
The invention provides the second and apply the method that above-mentioned binary metal composite perofskite material prepares solar cell, comprise the following steps:
The preparation of step (1) hole blocking layer
On the electro-conductive glass having plated fluorine doped tin oxide FTO, under 400 DEG C ~ 600 DEG C conditions, by the isopropyl titanate aqueous isopropanol of 0.01mol/L ~ 0.05mol/L, by the fine and close TiO that the method deposition 20nm ~ 100nm of thermal spraying is thick 2hole blocking layer;
The preparation of step (2) electron transfer layer
On the described barrier layer prepared, the TiO that silk screen printing one deck 50nm ~ 500nm is thick 2nano particle, under 450 DEG C ~ 550 DEG C conditions, anneals 0.5 hour ~ 2 hours, forms one deck and is about the mesoporous TiO of 50nm ~ 500nm 2electron transfer layer;
The preparation of step (3) binary metal composite perofskite material light-absorption layer
Get binary metal composite perofskite solution spin coating described in 50 μ L ~ 1000 μ L on the electron transport layer, under 70 DEG C ~ 150 DEG C conditions, heat 10 minutes ~ 120 minutes, binary metal composite perofskite material solvent is volatilized and forms the binary metal composite perofskite material light-absorption layer of one deck 200nm ~ 1000nm;
The preparation of step (4) hole transmission layer
By P3HT (or Spiro-MeOTAD, PTAA, CuI, CuSCN solution), be spin-coated on described perovskite light-absorption layer, form 50nm ~ 200nm hole transmission layer;
The preparation of step (5) metal counter electrode
Use vacuum evaporation coating film device, evaporation a layer thickness is Au or the Ag electrode of 60nm ~ 150nm on the hole transport layer, obtains solid-state binary metal composite perofskite solar cell.
The invention provides the third and apply the method that above-mentioned binary metal composite perofskite material prepares solar cell, comprise the following steps:
The preparation of step (1) hole blocking layer
On the electro-conductive glass having plated fluorine doped tin oxide FTO, under 400 DEG C ~ 600 DEG C conditions, by the isopropyl titanate aqueous isopropanol of 0.01mol/L ~ 0.05mol/L, by the fine and close TiO that the method deposition 20nm ~ 100nm of thermal spraying is thick 2hole blocking layer;
The preparation of step (2) binary metal composite perofskite material light-absorption layer
The binary metal composite perofskite solution got described in 50 μ L ~ 1000 μ L is spin-coated on hole blocking layer, under 70 DEG C ~ 150 DEG C conditions, heat 10 minutes ~ 120 minutes, binary metal composite perofskite material solvent is volatilized and forms the binary metal composite perofskite material light-absorption layer of one deck 200nm ~ 1000nm;
The preparation of step (3) hole transmission layer
By P3HT (or Spiro-MeOTAD, PTAA, CuI, CuSCN solution), be spin-coated on described perovskite light-absorption layer, form 50nm ~ 200nm hole transmission layer;
The preparation of step (4) metal counter electrode
Use vacuum evaporation coating film device, evaporation a layer thickness is Au or the Ag electrode of 60nm ~ 150nm on the hole transport layer, obtains solid-state binary metal composite perofskite solar cell.
The invention provides the method that solar cell prepared by the 4th kind of above-mentioned binary metal composite perofskite material of application, comprise the following steps:
The preparation of step (1) electronic barrier layer
On the electro-conductive glass having plated fluorine doped tin oxide FTO, under 400 DEG C ~ 600 DEG C conditions, by the nickel acetylacetonate acetonitrile solution of 0.005mol/L ~ 0.05mol/L, by the fine and close NiO electronic barrier layer that the method deposition 10nm ~ 50nm of thermal spraying is thick;
The preparation of step (2) binary metal composite perofskite material light-absorption layer
The binary metal composite perofskite solution got described in 50 μ L ~ 1000 μ L is spin-coated on electronic barrier layer, under 70 DEG C ~ 150 DEG C conditions, heat 10 minutes ~ 120 minutes, binary metal composite perofskite material solvent is volatilized and forms the binary metal composite perofskite light-absorption layer of one deck 200nm ~ 1000nm;
The preparation of step (3) electron transfer layer
PCBM solution is spin-coated on after on described perovskite light-absorption layer and heats at 70 DEG C ~ 100 DEG C, form the electron transfer layer of one deck 50nm ~ 200nm;
The preparation of step (4) interface-modifying layer
By BCP, LiF, TiO xor the material such as Ca by spin coating or evaporation on the electron transport layer, forms one deck 1nm ~ 20nm interface-modifying layer;
The preparation of step (5) metal counter electrode
On interface-modifying layer, evaporation a layer thickness is Al or the Ag electrode of 60nm ~ 150nm, obtains solid-state binary metal composite perofskite solar cell.
The invention provides the method that solar cell prepared by the 5th kind of above-mentioned binary metal composite perofskite material, comprise the following steps:
The preparation of step (1) hole transmission layer
PEDOT:PSS solution is spin-coated on the ito glass cleaned up, forms one deck 20nm ~ 100nm hole transmission layer;
The preparation of step (2) binary metal composite perofskite material light-absorption layer
The binary metal composite perofskite solution got described in 50 μ L ~ 1000 μ L is spin-coated on hole transmission layer, under 70 DEG C ~ 150 DEG C conditions, heat 10 minutes ~ 120 minutes, binary metal composite perofskite material solvent is volatilized and forms the binary metal composite perofskite material light-absorption layer of one deck 200nm ~ 1000nm;
The preparation of step (3) electron transfer layer
PCBM solution is spin-coated on after on described perovskite light-absorption layer and heats at 70 DEG C ~ 100 DEG C, form the electron transfer layer of one deck 50nm ~ 200nm;
The preparation of step (4) interface-modifying layer
By BCP, LiF, TiO xor the material such as Ca by spin coating or evaporation on the electron transport layer, forms one deck 1nm ~ 20nm interface-modifying layer;
The preparation of step (5) metal counter electrode
On interface-modifying layer, evaporation a layer thickness is Al or the Ag electrode of 60nm ~ 150nm, obtains solid-state binary metal composite perofskite solar cell.
In general, according to binary metal composite perofskite material of the present invention, (structural formula is wherein 0<m<1, A are or in one; B 1for Pb 2+; B 2for Mg 2+, Ca 2+or Ba 2+in one; X is at least Cl -, Br -or I -in one.) and existing plumbous halogen perovskite material (CH 3nH 3pbI 3, NH 2cH=NH 2pbI 3deng) compare, advantage is: magnesium halide, calcium halide, barium halide raw material are easy to get cheapness.With Mg 2+, Ca 2+, Ba 2+part replaces the toxic heavy metal Pb in existing plumbous halogen perovskite material 2+, while the every photoelectric properties of guarantee battery, greatly reduce the harm to environment and human body, be conducive to the extensive commercial application promoting perovskite solar cell.
Accompanying drawing explanation
Fig. 1 is CH obtained by embodiment 1 3nH 3pb 1-xmg xi 3the XRD figure of perovskite thin film;
Fig. 2 is CH obtained by embodiment 2 3nH 3pb 1-xca xi 3the XRD figure of perovskite thin film;
Fig. 3 is CH obtained by embodiment 3 3nH 3pb 1-xba xi 3the XRD figure of perovskite thin film;
Fig. 4 is CH obtained by embodiment 2 3nH 3pb 1-xca xi 3the UV-vis absorption spectrum figure of perovskite thin film;
Fig. 5 is perovskite solar battery structure schematic diagram, and wherein, 1 electrically conducting transparent substrate, 2 hole blocking layers, 3 electron transfer layers, 4 porous dielectric layers and 5 carbon are to electrode;
Fig. 6 is perovskite solar battery structure schematic diagram, wherein, and 1 electrically conducting transparent substrate, 2 hole blocking layers, 3 electron transfer layers, 6 perovskite light-absorption layers, 7 hole transmission layers and 8 metal counter electrode;
Fig. 7 is perovskite solar battery structure schematic diagram, wherein, and 1 electrically conducting transparent substrate, 2 hole blocking layers, 6 perovskite light-absorption layers, 7 hole transmission layers and 8 metal counter electrode;
Fig. 8 is perovskite solar battery structure schematic diagram, wherein, and 1 electrically conducting transparent substrate, 9 electronic barrier layers, 6 perovskite light-absorption layers, 3 electron transfer layers, 10 interface-modifying layer and 8 metal counter electrode;
Fig. 9 is perovskite solar battery structure schematic diagram, wherein, and 1 electrically conducting transparent substrate, 7 hole transmission layers, 6 perovskite light-absorption layers, 3 electron transfer layers, 10 interface-modifying layer, 8 metal counter electrode;
The current density voltage curve figure of Figure 10 perovskite solar cell obtained by embodiment 4;
The current density voltage curve figure of Figure 11 perovskite solar cell obtained by embodiment 5;
The current density voltage curve figure of Figure 12 perovskite solar cell obtained by embodiment 6;
The current density voltage curve figure of Figure 13 perovskite solar cell obtained by embodiment 7;
The current density voltage curve figure of Figure 14 perovskite solar cell obtained by embodiment 8.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1, comprises the steps:
(1) under room temperature, by PbI 2with MgI 2powder is 9:1 Homogeneous phase mixing by the ratio of amount of substance;
(2) by the mixed-powder described in (1), with CH 3nH 3i crystal press amount of substance than 1:1 proportioning, formed homogeneous mixture;
(3) be dissolved in DMF (DMF) solvent by the mixture described in (2), stirred at ambient temperature, until all dissolve, obtains CH 3nH 3pb 0.9mg 0.1i 3composite perofskite solution;
(4) get the solution that 2ml (3) obtains, revolve Tu on sheet glass, then 60 DEG C of heating anneals 120 minutes by solvent evaporate to dryness, obtain CH 3nH 3pb 0.9mg 0.1i 3composite perofskite thin-film material.
Embodiment 2, comprises the steps:
(1) under room temperature, by PbI 2with CaI 2powder is 9:1 Homogeneous phase mixing by the ratio of amount of substance;
(2) by the mixed-powder described in (1), with CH 3nH 3i crystal press amount of substance than 1:2 proportioning, formed homogeneous mixture;
(3) mixture described in (2) is dissolved in dimethyl sulfoxide (DMSO) (DMSO) solvent, stirs at 100 DEG C, until all dissolve, obtain CH 3nH 3pb 0.9ca 0.1i 3composite perofskite solution;
(4) get the solution that 2ml (3) obtains, revolve Tu on sheet glass, then 100 DEG C of heating anneals 60 minutes by solvent evaporate to dryness, obtain CH 3nH 3pb 0.9ca 0.1i 3composite perofskite thin-film material.
Embodiment 3, comprises the steps:
(1) under room temperature, by PbI 2with BaI 2powder is 9:1 Homogeneous phase mixing by the ratio of amount of substance;
(2) by the mixed-powder described in (1), with CH 3nH 3i crystal press amount of substance than 1:3 proportioning, formed homogeneous mixture;
(3) mixture described in (2) is dissolved in gamma-butyrolacton solvent, stirs at 130 DEG C, until all dissolve, obtain CH 3nH 3pb 0.9ba 0.1i 3composite perofskite solution;
(4) get the solution that 2ml (3) obtains, revolve Tu on sheet glass, then 150 DEG C of heating anneals 5 minutes by solvent evaporate to dryness, obtain CH 3nH 3pb 0.9ba 0.1i 3composite perofskite thin-film material.
Embodiment 4, comprises the steps:
(1) cleaning step: select sheet resistance to be 5 ~ 25 Ω, transmitance is substrate at the FTO glass of 70 ~ 90%, then successively with the cleaning of liquid detergent, distilled water, ethanol and acetone;
(2) preparation of hole blocking layer: on the electro-conductive glass having plated fluorine doped tin oxide FTO, under 460 DEG C of conditions, by the isopropyl titanate aqueous isopropanol of 0.05mol/L, by the fine and close TiO that the method deposition 20nm of thermal spraying is thick 2hole blocking layer.Spray rear continuation to anneal at such a temperature 2 hours;
(3) electron transfer layer preparation process: at described TiO 2on barrier layer, by the TiO that silk screen printing 500nm is thick 2nano-particle layer, under 500 DEG C of conditions, anneals 2 hours, forms the mesoporous TiO of 500nm 2electron transfer layer;
(4) mesoporous insulating barrier preparation process: will include diameter is 50nmAl 2o 3the slurry of nano particle, by silk screen printing on the electron transport layer, sinters 2 hours, forms the mesoporous insulating barrier of 1000nm at 500 DEG C;
(5) carbon is to electrode preparation process: will by nano carbon black, graphite powder and ZrO 2the mode double exposure of the carbon pastes silk screen printing of nano adhesive composition, on described mesoporous insulating barrier, under 400 DEG C of conditions, sinters 1 hour, and forming thickness is that the carbon of 10 μm is to electrode;
(6) Ca-Pb binary metal composite perofskite solution preparation step is with (1) ~ (3), the wherein PbI of embodiment 2 2: CaI 2be respectively 9:1,8:2,7:3,6:4,5:5;
(7) Ca-Pb binary metal composite perofskite is filled: the Ca-Pb binary metal composite perofskite solution after the carbon of described solar cell instills 2 μ L heating to electrode surface, heat 30 minutes at 75 DEG C, make solvent evaporates obtain solid-state Ca-Pb binary metal composite perofskite solar cell.
Embodiment 5, comprises the steps:
(1) cleaning step: select sheet resistance to be 5 ~ 25 Ω, transmitance is substrate at the FTO glass of 70 ~ 90%, then successively with the cleaning of liquid detergent, distilled water, ethanol and acetone;
(2) preparation process of hole blocking layer: on the electro-conductive glass having plated fluorine doped tin oxide FTO, under 500 DEG C of conditions, by the isopropyl titanate aqueous isopropanol of 0.01mol/L, by the fine and close TiO that the method deposition 100nm of thermal spraying is thick 2hole blocking layer;
(3) preparation process of electron transfer layer: on the described barrier layer prepared, the TiO that silk screen printing one deck 150nm is thick 2nano particle, under 550 DEG C of conditions, anneals 1.5 hours, forms one deck and is about the mesoporous TiO of 150nm 2electron transfer layer;
(4) Mg-Pb binary metal composite perofskite solution preparation step: by PbI 2with MgBr 2form mixture, wherein PbI 2accounting for mol ratio is 70%, CH 3nH 3i therewith mixture in molar ratio 1:2 be dissolved in gamma-butyrolacton solvent, at 120 DEG C stir, until all dissolve, obtain Mg-Pb binary metal composite perofskite solution;
(5) preparation process of Mg-Pb binary metal composite perofskite material light-absorption layer: get Mg-Pb binary metal composite perofskite solution spin coating described in 150 μ L on the electron transport layer, under 100 DEG C of conditions, heat 30 minutes, after solvent evaporates, form the Mg-Pb binary metal composite perofskite material light-absorption layer of one deck 100nm;
(6) preparation process of hole transmission layer: with configure by P3HT, be spin-coated on perovskite light-absorption layer, form about 100nm hole transmission layer;
(7) preparation process of metal counter electrode: use vacuum evaporation coating film device, evaporation a layer thickness is the Au electrode of 60nm on the hole transport layer, obtains solid-state binary metal composite perofskite solar cell.
Embodiment 6, comprises the steps:
(1) cleaning step: select sheet resistance to be 5 ~ 25 Ω, transmitance is substrate at the FTO glass of 70 ~ 90%, then successively with the cleaning of liquid detergent, distilled water, ethanol and acetone;
(2) preparation process of hole blocking layer: on the electro-conductive glass having plated fluorine doped tin oxide FTO, under 600 DEG C of conditions, by the isopropyl titanate aqueous isopropanol of 0.25mol/L, by the fine and close TiO that the method deposition 100nm of thermal spraying is thick 2hole blocking layer;
(3) Ba-Pb binary metal composite perofskite solution preparation step: by PbI 2with BaCl 2form mixture, wherein PbI 2accounting for mol ratio is 70%, CH 3nH 3i therewith mixture in molar ratio 1:1 be dissolved in gamma-butyrolacton solvent, at 120 DEG C stir, until all dissolve, obtain Ba-Pb binary metal composite perofskite solution;
(4) preparation of Ba-Pb binary metal composite perofskite material light-absorption layer: the Ba-Pb binary metal composite perofskite solution got described in 100 μ L is spin-coated on hole blocking layer, under 120 DEG C of conditions, heat 30 minutes, after solvent evaporates, form the Ba-Pb binary metal composite perofskite light-absorption layer of one deck 500nm;
(5) preparation process of hole transmission layer: by the Spiro-MeOTAD configured, is spin-coated on described perovskite light-absorption layer, forms about 100nm hole transmission layer;
(6) preparation of metal counter electrode: use vacuum evaporation coating film device, evaporation a layer thickness is the Ag electrode of 60nm on the hole transport layer, obtains solid-state binary metal composite perofskite solar cell.
Embodiment 7, comprises the steps:
(1) cleaning step: select sheet resistance to be 5 ~ 25 Ω, transmitance is substrate at the FTO glass of 70 ~ 90%, then successively with the cleaning of liquid detergent, distilled water, ethanol and acetone;
(2) preparation process of electronic barrier layer: on the electro-conductive glass having plated fluorine doped tin oxide FTO, under 500 DEG C of conditions, by the nickel acetylacetonate acetonitrile solution of 0.025mol/L, by the fine and close NiO electronic barrier layer that the method deposition 50nm of thermal spraying is thick;
(3) Ca-Pb binary metal composite perofskite solution preparation step: by PbI 2with CaI 2form mixture, wherein PbI 2accounting for mol ratio is 80%, NH 2cH=NH 2i therewith mixture in molar ratio 1:1 be dissolved in DMF DMF solvent, at 80 DEG C stir, until all dissolve, obtain Ca-Pb binary metal composite perofskite solution;
(4) preparation process of Ca-Pb binary metal composite perofskite material light-absorption layer: the Ca-Pb binary metal composite perofskite solution got described in 50 μ L is spin-coated on electronic barrier layer, under 70 DEG C of conditions, heat 100 minutes, after solvent evaporates, form the binary metal composite perofskite light-absorption layer of one deck 200nm;
(5) preparation process of electron transfer layer: be spin-coated on by PCBM solution after on described perovskite light-absorption layer, heats at being placed on 70 DEG C, forms the electron transfer layer of one deck 50nm;
(6) preparation process of interface-modifying layer: by BCP by spin coating or evaporation on the electron transport layer, forms one deck 1nm interface-modifying layer;
(7) preparation process of metal counter electrode: evaporation a layer thickness is the Al electrode of 60nm on interface-modifying layer, obtains solid-state binary metal composite perofskite solar cell.
Embodiment 8, comprises the steps:
(1) cleaning step: select sheet resistance to be 5 ~ 25 Ω, transmitance is substrate at the FTO glass of 70 ~ 90%, then successively with the cleaning of liquid detergent, distilled water, ethanol and acetone;
(2) preparation process of hole transmission layer: PEDOT:PSS solution is spin-coated on the ito glass cleaned up, 100 DEG C of annealing form one deck 20nm hole transmission layer;
(3) Ba-Pb binary metal composite perofskite material preparation process: by PbI 2with BaCl 2form mixture, wherein PbI 2accounting for mol ratio is 80%, NH 2cH=NH 2i therewith mixture in molar ratio 1:1 be dissolved in DMF DMF solvent, at 100 DEG C stir, until all dissolve, obtain Ba-Pb binary metal composite perofskite solution;
(4) preparation process of Ba-Pb binary metal composite perofskite material light-absorption layer: the Ba-Pb binary metal composite perofskite solution got described in 800 μ L is spin-coated on hole transmission layer, under 100 DEG C of conditions, heat 30 minutes, after solvent evaporates, form the binary metal composite perofskite material light-absorption layer of one deck 1000nm;
(5) preparation process of electron transfer layer: PCBM solution is spin-coated on after on described perovskite light-absorption layer and heats 30 minutes at 70 DEG C, form the electron transfer layer of one deck 60nm;
(6) preparation process of interface-modifying layer: by BCP by spin coating or evaporation on the electron transport layer, forms one deck 10nm interface-modifying layer;
(7) preparation process of metal counter electrode: evaporation a layer thickness is the Ag electrode of 60nm on interface-modifying layer, obtains solid-state binary metal composite perofskite solar cell.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (7)

1. a binary metal composite perofskite materials A B 1b 2x 3, it is characterized in that, described binary metal composite perofskite material is perovskite structure, and the expression formula of described binary metal composite perofskite material is wherein 0<m<1, A are +or in one; B 1for Pb 2+; B 2for Mg 2+, Ca 2+or Ba 2+in one; X is at least Cl -, Br -or I -in one.
2. binary metal composite perofskite material as claimed in claim 1, is characterized in that, B 1x 2, B 2x 2the amount of substance sum of two kinds of metal halides, with CH 3nH 3x or NH 2cH=NH 2the ratio of the amount of substance of X is 1:1 ~ 1:3.
3. binary metal composite perofskite material as claimed in claim 1, is characterized in that, in two kinds of metal halide admixture, and B 1x 2proportion is 10 ~ 90%, B 2x 2proportion is 90 ~ 10%.
4. a preparation method for binary metal composite perofskite material, is characterized in that, comprises the steps:
(1) at room temperature by B 1x 2with B 2x 2mix by the ratio 1:9 ~ 9:1 of amount of substance, form two kinds of metal halide mixed-powders; Wherein, B 1x 2for lead halide, B 2x 2for the one in magnesium halide, calcium halide or barium halide;
(2) described mixed-powder and organohalogen compounds crystal are pressed ratio 1:1 ~ 1:3 proportioning of amount of substance, form homogeneous mixture; Wherein, organohalogen compounds are halogenated methyl amine or halogenation carbonamidine;
(3) at room temperature ~ 130 DEG C, described mixture is dissolved in DMF DMF, dimethyl sulfoxide (DMSO) DMSO or gamma-butyrolacton solvent, is stirred to whole dissolving, then by 60 DEG C ~ 150 DEG C heating anneals 5 minutes ~ 120 minutes by solvent evaporate to dryness, can B be obtained 1-B 2binary metal composite perofskite material; Wherein, described B 1-B 2for Mg-Pb, Ca-Pb or Ba-Pb.
5. preparation method as claimed in claim 4, it is characterized in that, described halogenated methyl amine is CH 3nH 3cl, CH 3nH 3br or CH 3nH 3the one of I; Described halogenation carbonamidine is NH 2cH=NH 2cl, NH 2cH=NH 2br or NH 2cH=NH 2the one of I; Described lead halide is PbCl 2, PbBr 2or PbI 2one; Described magnesium halide is MgCl 2, MgBr 2or MgI 2in one or more mixing; Described calcium halide is CaCl 2, CaBr 2or CaI 2in one or more mixing; Described barium halide is BaCl 2, BaBr 2or BaI 2in one or more mixing.
6. the application based on binary metal composite perofskite material according to claim 1.
7. the solar cell based on binary metal composite perofskite material according to claim 1.
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