CN105405973A - Mesoscopic solar cell based on perovskite-kind light absorption material and preparation method thereof - Google Patents

Mesoscopic solar cell based on perovskite-kind light absorption material and preparation method thereof Download PDF

Info

Publication number
CN105405973A
CN105405973A CN201510728751.XA CN201510728751A CN105405973A CN 105405973 A CN105405973 A CN 105405973A CN 201510728751 A CN201510728751 A CN 201510728751A CN 105405973 A CN105405973 A CN 105405973A
Authority
CN
China
Prior art keywords
layer
solar cell
perovskite
light absorbent
ether
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201510728751.XA
Other languages
Chinese (zh)
Inventor
韩宏伟
刘通发
梅安意
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huazhong University of Science and Technology
Original Assignee
Huazhong University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Huazhong University of Science and Technology filed Critical Huazhong University of Science and Technology
Priority to CN201510728751.XA priority Critical patent/CN105405973A/en
Publication of CN105405973A publication Critical patent/CN105405973A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The invention discloses a mesoscopic solar cell based on a perovskite-kind light absorption material. The mesoscopic solar cell comprises a glass substrate, a transparent conductive layer, a hole blocking layer, an electron transport layer and a back electrode; and the hole blocking layer is a compact layer, the electron transport layer is a porous thin film, a porous electron blocking layer is further disposed between the electron transport layer and the back electrode, and the electron transport layer and the electron blocking layer are filled with the perovskite-kind light absorption material. Or the mesoscopic solar cell comprises a glass substrate, a transparent conductive layer, a hole transport layer and a back electrode; and the hole transport layer is a porous thin film, a compact electron blocking layer is further disposed between the hole transport layer and the transparent conductive layer, and the hole transport layer is filled with the perovskite-kind light absorption material. The invention further discloses a preparation method of the mesoscopic solar cell. The cell has optimized structure, the filled perovskite material in mesoporous is more, morphology is good, charge transmission performance is improved, cell photoelectric conversion efficiency is greatly improved, and long-term illumination stability of the cell is substantially improved.

Description

Jie based on perovskite light absorbent sees solar cell and preparation method thereof
Technical field
The present invention relates to a kind of sight solar cell device and manufacture method thereof of being situated between, belong to technical field of solar batteries.
Background technology
The sight solar cell that is situated between is that a kind of mesoporous nanocrystalline material that adopts is as the solar cell of light anode.In this solar cell, light absorbent is adsorbed on mesoporous nanocrystalline electrode as light anode, on the one hand the photoelectron of generation be injected into mesoporous nanocrystalline electrode and transfer in conductive substrates, on the other hand by the hole that generates by forming photoelectric current in hole transport layer transports to hole collection layer.Because meso-porous nano electrode has very large specific area, therefore can adsorb abundant light absorbent thus obtain larger photoelectric current, there is very high theoretical efficiency.
All the time, semiconductor nano light absorbent obtains in Jie's sight area of solar cell and widely applies.This is not only because semiconductor nano light absorbent has larger optical cross section, and can change its energy gap by regulating the grain size of these light absorbents within the specific limits, thus changes the open circuit voltage of battery device.Although have very high theoretical efficiency based on the solar cell device of this kind of semiconductor nano light absorbent, in fact these materials are still faced with the great number of issues such as poor stability, Carrier Recombination be short.
Perovskite nanometer light-absorbing semiconductor material has that light absorption range is wide, absorption coefficient is high, Carrier Recombination is long and the many merits such as good stability, is widely used in all solid state Jie sees in solar cell device as light absorbent.In theory, all solid state Jie's sight solar cell device photoelectric conversion efficiency based on this perovskite light absorbent can up to 30%.
CN103441217A discloses a kind of Jie based on perovskite light absorbent and sees solar cell device and preparation method thereof, this Jie sees solar cell device and comprises substrate and stack gradually in this suprabasil hole blocking layer, meso-porous nano crystal layer, dielectric spacer layer and mesoporous hole collection layer, wherein, perovskite semi-conducting material is all filled with in meso-porous nano crystal layer, dielectric spacer layer and mesoporous hole collection layer.This Jie sees solar cell device and takes the method for all print to be prepared from, adopt perovskite nanocrystal as active light absorbent, be filled in meso-porous nano crystal layer, dielectric spacer layer and mesoporous hole collection layer by dripping painting mode, and utilize the hole-conductive performance of himself to form hole transmission layer in mesoporous dielectric spacer layer, directly by hole transport in hole collection layer, avoid the use of organic P-type material.In addition, its material adopting mesoporous carbon etc. relatively inexpensive, as hole collection layer, effectively simplifies the preparation technology of solar cell device and reduces cost of manufacture.
But, its open circuit voltage of the battery of this structure and fill factor, curve factor very low, its photoelectric conversion efficiency is generally no more than 7%, and well below theoretical conversion efficiencies, and its long-term light durability is poor, and cell performance decay is serious.
CN104091889A discloses a kind of Jie based on perovskite light absorbent and sees solar cell device, it by arranging one deck hole transport material in battery layers, thus more effectively can collect hole, compared to adopting carbon back electrode as hole collection layer before, substantially increase the collection efficiency in hole, battery performance is effectively improved.Although the battery device of this structure, its battery performance and transformation efficiency are all greatly improved, be still situated between with perovskite and see solar cell theoretical efficiency and there is larger gap, the space that battery performance and efficiency are still improved.
Summary of the invention
The object of the invention is to the above defect for prior art or Improvement requirement, a kind of Jie based on perovskite light absorbent is provided to see solar cell and preparation method thereof, it is by arranging electronic barrier layer and adopting novel perovskite semi-conducting material to fill, battery structure is optimized, the perovskite material of mesoporous inside is filled more simultaneously, its pattern is better, charge transport properties improves, thus cell photoelectric conversion efficiency is improved greatly, the long-term light durability of battery significantly improves.
According to one aspect of the present invention, a kind of Jie based on perovskite light absorbent is provided to see solar cell, wherein, this Jie sees solar cell and comprises substrate of glass and set gradually transparency conducting layer, hole blocking layer, electron transfer layer and back electrode on the glass substrate, described hole blocking layer is compacted zone, and described electron transfer layer is porous membrane;
It is characterized in that, the electronic barrier layer with porous is also provided with between described electron transfer layer and back electrode, perovskite light absorbent is filled with in described electron transfer layer and electronic barrier layer, can make described electron transfer layer and electronic barrier layer after illumination, produce hole and electronics, wherein electronics because of the existence of described electronic barrier layer can only through described electron transfer layer and hole blocking layer one-way transmission to transparency conducting layer, hole because of described hole blocking layer can only through described electronic barrier layer one-way transmission to back electrode, thus reduce the compound in electronics and hole, make Jie see solar cell and there is high-photoelectric transformation efficiency and long-term light durability.
As improvement of the present invention, also comprise the dielectric spacer layer with porous, on the electron transport layer, described electronic barrier layer is stacked to be arranged between this dielectric spacer layer and back electrode, and is filled with perovskite light absorbent in its stacked setting.
As improvement of the present invention, described electronic barrier layer is by the also rear formation of sintering of the precursor liquid at described electron transfer layer or dielectric spacer layer surface-coated electronic barrier layer, or the also rear formation of sintering of the nano particle slurry of coating electronic barrier layer.
As improvement of the present invention, described back electrode is porous membrane, and described electronic barrier layer passes through the precursor liquid at described back electrode surface-coated electronic barrier layer and sinter formation after infiltrating into electron transfer layer or dielectric spacer layer surface.
According to one aspect of the present invention, a kind of Jie based on perovskite light absorbent is provided to see solar cell, wherein, this Jie sees solar cell and comprises substrate of glass and the transparency conducting layer hole transmission layer set gradually on the glass substrate and back electrode, wherein, described hole transmission layer is porous membrane
It is characterized in that, fine and close electronic barrier layer is also provided with between described hole transmission layer and transparency conducting layer, perovskite light absorbent is filled with in described hole transmission layer, can make this hole transmission layer after illumination, produce hole and electronics, wherein electronics because of the existence of described electronic barrier layer can only through described hole transmission layer one-way transmission to back electrode, and described hole through described electronic barrier layer one-way transmission to transparency conducting layer, thus reduce the compound in electronics and hole, make Jie see solar cell and there is high-photoelectric transformation efficiency and long-term light durability.
As improvement of the present invention, also comprise the hole blocking layer with the dielectric spacer layer of porous, the electron transfer layer of porous or porous, it is arranged between hole transmission layer and back electrode, and is filled with perovskite light absorbent.
As improvement of the present invention, also comprise the dielectric spacer layer with porous and the electron transfer layer of arranged stacked, or the dielectric spacer layer of arranged stacked and hole blocking layer, or the electron transfer layer with porous of arranged stacked and hole blocking layer, above-mentioned each layer is arranged between hole transmission layer and back electrode, and is filled with perovskite light absorbent.
As improvement of the present invention, also comprise the dielectric spacer layer with porous of arranged stacked, electron transfer layer and hole blocking layer, above-mentioned each layer is arranged between hole transmission layer and back electrode, and is filled with perovskite light absorbent.
As improvement of the present invention, described hole blocking layer by applying the precursor liquid also rear formation of sintering on coating cap rock, or the also rear formation of sintering of the nano particle slurry of coating hole blocking layer.
As improvement of the present invention, described back electrode is porous membrane, and described hole blocking layer passes through the precursor liquid at described back electrode surface-coated hole blocking layer and sinter formation after infiltrating into coating cap rock surface.
As improvement of the present invention, described electronic barrier layer is cupric oxide, cuprous oxide, tungsten oxide, doping cupric oxide, doped tungsten oxide, at least one in doped with Cu ScO2, doped with Cu YO2, doped with Cu InO2, doped with Cu AlO2, doped with Cu CrO2, doped with Cu MO2, doped with Cu WO2 and doped with Cu GaO2.
As improvement of the present invention, described doped chemical can be at least one in beryllium, magnesium, calcium, strontium, barium, zinc and cadmium.
As improvement of the present invention, described perovskite semi-conducting material is R xa yb zx (mx+ny+lz)/h, wherein, x is positive number, y and z is nonnegative number, and m, n, l and h are respectively R, and the chemical valence price of A, B and X is (hereinafter referred to as RABX xyztt=(mx+ny+lz)/h), wherein R is organic group containing protonated amido, amidino groups and/or ammonium root, A is at least one group in methylamine, carbonamidine and alkali family cation or ion, B is the cation of at least one in lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, tellurium, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium and astatine, X for containing iodine, bromine, chlorine, with in at least one anion.
At perovskite RABX xyztthe effect of middle R improves traditional perovskite material ABX 3moisture resistance, crystallization shape and carrier transmission performance, thus reduce the encapsulation requirement to device, and improve photoelectric conversion efficiency and the stability in use of perovskite material.
As improvement of the present invention, described R preferably has structure R 1-R 2-R 3group, wherein R 1for halogens, oxygen group elements, nitrogen group element ,-NH 2,-NH 3,-N=C (NH 2)=NH 2,-C=NHNH 2or-C=NHNH 3in at least one, R 2for in C1-C30 a kind of linearly, or branched alkyl, cycloalkyl in C3-C12, heterocycle in C1-C12, unsaturated alkyl in C2-C8, aryl in C6-C12, aralkyl in C6-C30, alkylaryl in C6-C30, iso-aryl in C1-C12, at least one in alkyl iso-aryl in C6-C30 and these organic groups of alkyl heterocyclic in C6-C30, or be halogen, hydroxyl, carboxyl, carbonyl, nitro, aldehyde, nitrous acid, sulfonic acid, acid amides, ketone, ether, nitrile, isocyanides, hydrazone, sulfydryl, phosphine, oxime, the at least one of azo group and amido modified above-mentioned organic group, R 3for-COOH ,-OSiOH ,-O 3pOH and-O 2one or more in SOH.
As improvement of the present invention, described perovskite semi-conducting material can be applied in solar cells, can as the light absorbing zone in solar cell, at least one in N-type layer or P-type layer.
As improvement of the present invention, described perovskite semi-conducting material can be applied in LED, OLED or electronic devices and components.
As improvement of the present invention, described perovskite semi-conducting material can be prepared by following methods: (1) prepares RX, halogen acids and R molecular reaction are obtained halate, particularly, can by molecule R and hydroiodic acid frozen water mix bathe in fully react, revolve steaming, use absolute ether washing and precipitating, obtain hydriodate; (2) get its halate appropriate together with MAX with lead halide PbX 2be obtained by reacting perovskite precursor solution, particularly, preferably stoichiometrically weigh halate RX, MAX and lead halide PbX respectively 2, add appropriate gamma-butyrolacton wherein, stir and make it fully react, obtain perovskite precursor solution; (3) dry presoma solvent and can obtain perovskite material.
As improvement of the present invention, described perovskite semi-conducting material can be prepared by following methods: stoichiometrically by MAX, lead halide PbX 2have in the acetonitrile of dense halogen acid solution with R molecular melting to dense halogen acids or dropping, under inert gas shielding, slow solvent flashing obtains perovskite crystal.
As improvement of the present invention, the precursor solution of the perovskite light absorbent of described filling is at perovskite RABX xyztin precursor liquid, add the additional material and the mixture that formed that can improve perovskite semi-conducting material pattern and filling effect, improve the performance of solar cell.
As improvement of the present invention, the mole of the additional material of described interpolation and perovskite RABX xyztthe ratio of mole (0,2] between.
As improvement of the present invention, described additional material comprise hydrogen halides or its solution, halogenated hydrocarbons, halogenated heterocyclic, halogenated aromatic compound, the different aromatic compound of halo, sulfo-hydrocarbon, halo alkyl, halo alkyl amidine, sulfo-heterocycle, sulfo-aromatic, the different aromatic compound of sulfo-, ammonium sulfide and ammonium halide one or more.
Solvent in perovskite precursor liquid adopts mixed solvent, and it is beta-propiolactone, gamma-butyrolacton, δ-valerolactone, DMF, DMA, N, N-dimethylpropionamide, N, N-diethylformamide, N, N-diethyl acetamide, N, N-diethyl propionamide, dimethyl sulfoxide (DMSO), tetramethylene sulfoxide, pentamethylene sulfoxide, hexa-methylene sulfoxide, tetramethylene urea, N, N-dimethacrylate urea, hexamethyl phosphoramide, 1-METHYLPYRROLIDONE, N-ethyl pyrrolidone, carrene, benzene, toluene, dimethylbenzene, methane, ethane, propane, butane, pentane, hexane, octane, cyclohexane, cyclohexanone, toluene cyclohexanone, ether, acetone, butanone, acetic acid, acetic anhydride, dioxane, chloroform, carbon tetrachloride, ethyl acetate, oxolane, pyridine, benzinum, n-butanol, isopropyl alcohol, nitrobenzene, chlorobenzene, dichloro-benzenes, carrene, ether, expoxy propane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, the positive acetone of methyl, isobutyl acetate, 2-nitropropane, n-butyl acetate, propylene glycol monomethyl ether, methyl isoamyl ketone, methyl amyl acetate, n-butyl propionate, propylene glycol methyl ether acetate, pentyl acetate, methyl-n-amyl ketone, isobutyl isobutyrate, ethoxy ether, cyclohexanone, glycol monobutyl ether, propylene glycol monopropyl ether, ethyl cellosolve acetate, isobutyrone, glycol propyl ether, diacetone alcohol, butyl glycol ether, propandiol butyl ether, formic acid-2-ethylhexyl ester, butyl glycol ether acetic acid esters, dipropylene glycol methyl ether, glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ether, diethylene glycol propyl ether, glycol hexyl ether, diethylene glycol ether acetic acid esters, butyl, ethylene glycol-2-ethyl hexyl ether is coated with, butyl acetic acid esters, the third two single phenyl ethers, espeleton, methylisobutylketone, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, phenol, methyl alcohol, ethanol, isopropyl alcohol, normal propyl alcohol, 2-butanols, isobutanol, methyl isobutyl carbinol, amylalcohol, cyclohexanol, naphtha, 100# solvent naphtha, 150# solvent naphtha, 200# solvent naphtha, styrene, perchloroethylene, trichloroethylene, two kinds in ethylene glycol ether and triethanolamine or more.
As improvement of the present invention, the filling of described perovskite semi-conducting material, both can with directly filling perovskite RABX xyztthe mode of precursor liquid realizes, also can with first filling B zx zl/hprecursor liquid, recharges R xa yx mx+ny/hthe mode of precursor liquid realizes.
As improvement of the present invention, described filling realizes by precursor solution being penetrated into after back electrode surface-coated each porous layer or before preparing back electrode, directly the coating of its precursor solution is penetrated into each porous layer and realize.
According to another aspect of the invention, a kind of Jie of above-mentioned perovskite light absorbent is provided to see the preparation method of solar cell, wherein, prepared by one or more modes combined during each semiconductor layer adopts printing, spin coating, spraying, blade coating, hydro-thermal or 3D to print.
As improvement of the present invention, described electron transfer layer is at least one in titanium dioxide, zinc oxide, tin oxide, niobium oxide, barium stannate, PCBM and corresponding dopant.
As improvement of the present invention, described dielectric spacer layer is at least one in zirconia, silicon dioxide, aluminium oxide, indium oxide, gallium oxide, cadmium sulfide and corresponding dopant.
As improvement of the present invention, described dorsum electrode layer is electric conducting material, can be at least one in carbon, gold, silver, aluminium, copper, nickel, iron, zinc, magnesium, calcium, titanium, vanadium, chromium, manganese, cobalt, tungsten and gallium.
As improvement of the present invention, described dorsum electrode layer is electric conducting material, preferably adopts at least one in carbon, aluminium, copper, nickel and cobalt material.
As improvement of the present invention, described dorsum electrode layer preferably adopts the mixture of graphite, carbon black and inorganic oxide, and wherein the effect of inorganic oxide is binding agent between material with carbon element and as the interface-modifying layer between perovskite and material with carbon element.
The hole-conductive performance that the present invention can make full use of perovskite semi-conducting material self directly by hole transport to dorsum electrode layer, the electric transmission simultaneously produced in increase electronic barrier layer reduction perovskite to back electrode, and uses novel perovskite semi-conducting material RABX xyztand use the perovskite precursor liquid formula improved, solve current solar cell properties not high, stability can not meet market demands, requires too high technical problem to battery packaging technology.
In general, the above technical scheme conceived by the present invention compared with prior art, has following beneficial effect:
(1) in battery structure, electronic barrier layer is provided with in the present invention, electronics is stopped towards the transmission in a direction, can only flow to another direction, and hole just in time in contrast, thus greatly improve electric current and the voltage of inside battery, make its efficiency and stability have large increase.
(2) electronic barrier layer in the present invention does not need to adopt traditional makes very fine and close form, still porous membrane structure is adopted, so wherein also can fill perovskite light absorbent, thus make described electron transfer layer and electronic barrier layer all can produce hole and electronics after illumination, improve current efficiency.
(3) in the present invention, perovskite semi-conducting material is the perovskite semi-conducting material optimized, itself or the mixture adding additional material wherein and formed, or the precursor solution forming perovskite semi-conducting material is mixed solvent, thus it is more that the perovskite material of the mesoporous inside being filled into each layer can be made to fill, its pattern is better, and charge transport properties improves.
Accompanying drawing explanation
Fig. 1 is for seeing solar battery structure schematic diagram according to Jie based on perovskite light absorbent constructed by first embodiment of the invention;
Fig. 2 is for seeing solar battery structure schematic diagram according to Jie based on perovskite light absorbent constructed by second embodiment of the invention;
Fig. 3 is for seeing solar battery structure schematic diagram according to Jie based on perovskite light absorbent constructed by third embodiment of the invention;
Fig. 4 is for seeing solar battery structure schematic diagram according to Jie based on perovskite light absorbent constructed by fourth embodiment of the invention;
Fig. 5 is for seeing solar battery structure schematic diagram according to Jie based on perovskite light absorbent constructed by fifth embodiment of the invention;
Fig. 6 is for seeing solar battery structure schematic diagram according to Jie based on perovskite light absorbent constructed by sixth embodiment of the invention;
Fig. 7 is for seeing solar battery structure schematic diagram according to Jie based on perovskite light absorbent constructed by seventh embodiment of the invention;
Fig. 8 is for seeing solar battery structure schematic diagram according to Jie based on perovskite light absorbent constructed by eighth embodiment of the invention;
Fig. 9 is for seeing solar battery structure schematic diagram according to Jie based on perovskite light absorbent constructed by ninth embodiment of the invention;
Figure 10 is for seeing solar battery structure schematic diagram according to Jie based on perovskite light absorbent constructed by tenth embodiment of the invention;
Figure 11 sees solar battery structure schematic diagram according to Jie based on perovskite light absorbent of the present invention;
In all of the figs, identical Reference numeral is used for representing identical element or structure, wherein: 1 is substrate, and 2 is electro-conductive glass, 3 and 3 ' hole blocking layer, 4 and 4 ' is electron transfer layer, and 5 is dielectric spacer layer, 6 and 6 ' is electronic barrier layer, and 7 is back electrode, and 8 ' is hole transmission layer.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with accompanying drawing, the present invention is further elaborated.Only in order to explain the present invention when relating to instantiation if illustrate herein, do not limit the present invention.In addition, if below in described each execution mode of the present invention involved technical characteristic do not form conflict each other and just can mutually combine.
Solar cell device structure is seen as shown in Figure 1, the transparency conducting layer 2, hole blocking layer 3, electron transfer layer 4 and the back electrode 7 that comprise substrate of glass 1 and be successively set in this substrate of glass 1 according to Jie constructed by one embodiment of the invention.Wherein, hole blocking layer 3 is compacted zone, and electron transfer layer 4 is porous membrane, is provided with the electronic barrier layer 6 with porous between electron transfer layer 4 and back electrode 7.
Perovskite light absorbent is filled with in electron transfer layer 4 and electronic barrier layer 6, can make electron transfer layer 4 and electronic barrier layer 6 after illumination, produce hole and electronics, wherein electronics because of the existence of described electronic barrier layer 6 can only through described electron transfer layer 4 and hole blocking layer 3 one-way transmission to transparency conducting layer 2, hole because of described hole blocking layer 3 can only through described electronic barrier layer 6 one-way transmission to back electrode 7, thus reduce the compound in electronics and hole, improve cell photoelectric conversion efficiency and long-term light durability.
Preferably, as shown in Figure 2, can also have the dielectric spacer layer 5 of porous, it is stacked is arranged on electron transfer layer 4, and electronic barrier layer 6 is stacked to be arranged between this dielectric spacer layer 5 and back electrode 7, and is filled with perovskite light absorbent.
Preferably, electronic barrier layer 6 is by being formed after the precursor liquid at described electron transfer layer 4 or dielectric spacer layer 5 surface-coated electronic barrier layer 6 also sintering.Or by being formed after the nano particle slurry at described electron transfer layer 4 or dielectric spacer layer 5 surface-coated electronic barrier layer 6 also sintering.
Preferably, back electrode 7 is porous membrane, and described electronic barrier layer 6 passes through the precursor liquid at described back electrode 7 surface-coated electronic barrier layer 6 and sinter formation after infiltrating into electron transfer layer 4 or dielectric spacer layer 5 surface.
Solar cell device structure is seen as shown in Figure 3 according to Jie constructed by another embodiment of the present invention, comprise substrate of glass 1 and be successively set on transparency conducting layer 2, hole transmission layer 8 ' and the back electrode 7 in this substrate of glass 1, hole transmission layer 8 ' is porous membrane.
Fine and close electronic barrier layer 6 ' is also provided with between hole transmission layer 8 ' and transparency conducting layer 2, perovskite light absorbent is filled with in hole transmission layer 8 ', can make this hole transmission layer 8 ' after illumination, produce hole and electronics, wherein electronics because of the existence of described electronic barrier layer 6 ' can only through described hole transmission layer 8 ' one-way transmission to back electrode 7, and hole through described electronic barrier layer 6 ' one-way transmission to transparency conducting layer 2, thus reduce the compound in electronics and hole, improve cell photoelectric conversion efficiency and long-term light durability.
As Figure 4-Figure 6, in the battery device of this embodiment, also can comprise dielectric spacer layer 5, the electron transfer layer 4 ' of porous or the hole blocking layer 3 ' of porous with porous, it is arranged between hole transmission layer 8 ' and back electrode 7, and is filled with perovskite light absorbent.
Or, as Figure 7-9, comprise the dielectric spacer layer 5 with porous and the electron transfer layer 4 ' of arranged stacked, or the dielectric spacer layer 5 of arranged stacked and hole blocking layer 3 ', or the electron transfer layer 4 ' with porous of arranged stacked and hole blocking layer 3 ', it is arranged between hole transmission layer 8 ' and back electrode 7, and is filled with perovskite light absorbent.
Or, as shown in Figure 10, comprise the dielectric spacer layer 5 with porous of arranged stacked, electron transfer layer 4 ' and hole blocking layer 3 ', dielectric spacer layer 5, electron transfer layer 4 ' and this order of three layers of hole blocking layer 3 ' also can be exchanged, above-mentioned stepped construction its be arranged between hole transmission layer 8 ' and back electrode 7, and be filled with perovskite light absorbent.
Preferably, hole blocking layer 3 ' by applying the precursor liquid also rear formation of sintering on its coating cap rock, or the also rear formation of sintering of the nano particle slurry of coating hole blocking layer 3 '.
Preferably, back electrode 7 is porous membrane, and hole blocking layer 3 ' passes through the precursor liquid at back electrode 7 surface-coated hole blocking layer 3 ' and sinter formation after infiltrating into coating cap rock surface.
Below in conjunction with concrete example, the preparation method seeing solar cell that is situated between is described in detail.
embodiment 1
Device in the present embodiment take glass as substrate 1, transparent electro-conductive glass 2 is set thereon, then after depositing certain thickness such as 50nm titanium dioxide hole blocking layer 3 thereon, electron transfer layer 4 (such as titanium dioxide) is prepared successively from bottom to top, electronic barrier layer 6 (preferential oxidation tungsten) and dorsum electrode layer 7 (preferred material with carbon element) in the mode of silk screen printing.
In electron transfer layer 4, nano titanium oxide grain size is such as 18nm, and titanium dioxide layer thickness is such as about 1 μm.In electronic barrier layer 6, the granular size of tungsten oxide is such as 30 nanometers, and thickness is such as about 1 μm.The mesoporous conductive film that dorsum electrode layer 7 is preferably graphite, carbon black is made, thickness is such as about 10 μm.By a certain amount of such as 40 μ L perovskites (PEA) 2(CH 3nH 3) 40pb 41cl 10i 114(PEA represents phenyl ethylamine, lower same) precursor liquid (30wt%) is sprayed on dorsum electrode layer 7, leaves standstill and fully infiltrates into after in titanium dioxide nanocrystalline film until it for one minute, dry at uniform temperature such as 50 DEG C.Test shows, gained battery device is at 100mW/cm 2under simulated solar irradiation, efficiency is 18.5%.
embodiment 2
Device in the present embodiment take glass as substrate 1, transparent electro-conductive glass 2 is set thereon, then after depositing certain thickness such as 50nm titanium dioxide hole blocking layer 3 thereon, electron transfer layer 4 (such as titanium dioxide) is prepared successively from bottom to top in the mode of silk screen printing, dielectric spacer layer 5 (such as zirconium dioxide), electronic barrier layer 6 (preferential oxidation tungsten) and dorsum electrode layer 7 (preferred aluminum).
In the present embodiment, nano titanium oxide grain size is such as 18nm, and titanic oxide electronic transport layer 4 thickness is such as about 1 μm.Zirconium dioxide grain size is such as 40nm, and insulation gap layer thickness is such as about 1 μm.In electronic barrier layer 6, the granular size of tungsten oxide is such as 30 nanometers, and thickness is such as 100 nanometers.Aluminum back electrode layer is the mesoporous conductive film that the flakey aluminium of 20 micron diameters is made, and thickness is such as about 10 μm.By a certain amount of such as 4 μ L perovskites (5-AVA) 2(CH 3nH 3) 40pb 41i 124(5-AVA represents 5-aminovaleric acid, lower same) precursor liquid (30wt%) drips on dorsum electrode layer 7, leaves standstill and fully infiltrate into after in titanium dioxide nanocrystalline film until it for one minute, dries at uniform temperature such as 50 DEG C.Test shows, gained battery device is at 100mW/cm 2under simulated solar irradiation, efficiency is 17.9%.
With do not have 100 nanometer thickness tungsten oxide hole transmission layer device compared with, efficiency rises to 17.9% by 12.5%, this can not be strengthened by light absorption and cause, because most light by 2 micron thickness be filled in perovskite material inside titanium dioxide and zirconium dioxide absorb, the lifting of efficiency is mainly brought by the obvious lifting of short circuit current, fill factor, curve factor and open circuit voltage.
In the various embodiments described above, electronic barrier layer 6 is also by the also rear formation of sintering of the precursor liquid at described electron transfer layer 4 or dielectric spacer layer 5 surface-coated electronic barrier layer 6, or the also rear formation of sintering of the nano particle slurry of coating electronic barrier layer 6.
embodiment 3
Device in the present embodiment take glass as substrate 1, arranges transparent electro-conductive glass 2 thereon, and the mode printed with 3D from bottom to top prepares 30nm titanium dioxide dense layer 3, titanic oxide electronic transport layer 4, tungsten oxide electronic barrier layer 6 successively.By a certain amount of such as 100 μ L perovskites (PEA) 2(CH 3nH 3) 40pb 41cl 10i 114(PEA represents phenyl ethylamine, lower same) precursor liquid (40wt%) is spin-coated on above-mentioned semiconductor layer, leaves standstill and fully infiltrates into after in titanium dioxide nanocrystalline film until it for one minute, dry at uniform temperature such as 50 DEG C, printing carbon dorsum electrode layer 7.Test shows, gained battery device is at 100mW/cm 2under simulated solar irradiation, efficiency is 20.5%.
embodiment 4
Device in the present embodiment take glass as substrate 1, transparent electro-conductive glass 2 is set thereon, then deposit certain thickness such as 50nm thereon and mix magnesium tungsten oxide compacted zone as electronic barrier layer 6 ', then molybdenum oxide hole transmission layer 8 ' is prepared successively in the mode of silk screen printing from bottom to top, carbon dorsum electrode layer 7, after sintering, the precursor liquid of magnesium aluminium oxide copper is mixed in printing, sintering.
The mesoporous conductive film that carbon electrode hole collection layer is graphite, carbon black is made, thickness is such as about 10 μm.Tungsten oxide precursor liquid is such as the aqueous solution of tungsten chloride.By a certain amount of such as 4 μ L perovskites (PEA) 2(CH 3nH 3) 40pb 41(BF 4) 10i 114precursor liquid (30wt%) drips on carbon mesoporous film, leaves standstill and fully infiltrates into after in titanium dioxide nanocrystalline film until it for one minute, dries at uniform temperature such as 50 DEG C.Test shows, gained battery device is at 100mW/cm 2under simulated solar irradiation, efficiency is 18.9%.
embodiment 5
Device in the present embodiment take glass as substrate 1, transparent electro-conductive glass 2 is set thereon, after deposition certain thickness such as 50nm mixes magnesium tungsten oxide compacted zone 6 ', nickel oxide hole transmission layer 8 ' is prepared successively from bottom to top in the mode of silk screen printing, titanic oxide electronic transport layer 4 ', carbon dorsum electrode layer 7.
In electron transfer layer 4 ', nano titanium oxide grain size is such as 18nm, and titanium dioxide layer thickness is such as about 1 μm.In tungsten oxide electronic barrier layer, the granular size of tungsten oxide is such as 30 nanometers, and thickness is such as about 1 μm.The mesoporous conductive film that carbon electrode hole collection layer is graphite, carbon black is made, thickness is such as about 10 μm.By a certain amount of such as 4 μ L perovskites (PEA) 2(CH 3nH 3) 40pb 41i 124precursor liquid (30wt%) drips on carbon mesoporous film, leaves standstill and fully infiltrates into after in titanium dioxide nanocrystalline film until it for one minute, dries at uniform temperature such as 50 DEG C.Test shows, gained battery device is at 100mW/cm 2under simulated solar irradiation, efficiency is 19.1%.
embodiment 6
Device in the present embodiment take glass as substrate 1, transparent electro-conductive glass 2 is set thereon, after deposition certain thickness such as 50nm tungsten oxide compacted zone 6 ', nickel oxide hole transmission layer 8 ' is prepared successively from bottom to top in the mode of silk screen printing, zirconium dioxide dielectric spacer layer 5, titanic oxide electronic transport layer 4 ', nickel dorsum electrode layer 7.
Nano titanium oxide grain size is such as 18nm, and titanium dioxide layer thickness is such as about 1 μm.The granular size of zirconium dioxide is such as 30 nanometers, and thickness is such as about 1 μm.By a certain amount of such as 4 μ L perovskites (5-AVA) 2(CH 3nH 3) 40pb 41(BF 4) 10i 114precursor liquid (30wt%) drips on carbon mesoporous film, leaves standstill and fully infiltrates into after in titanium dioxide nanocrystalline film until it for one minute, dries at uniform temperature such as 50 DEG C.Test shows, gained battery device is at 100mW/cm 2under simulated solar irradiation, efficiency is 18.9%.
embodiment 7
Device in the present embodiment take glass as substrate 1, transparent electro-conductive glass 2 is set thereon, after deposition certain thickness such as 50nm tungsten oxide compacted zone 6 ', nickel oxide hole transmission layer 8 ' is prepared successively from bottom to top in the mode of silk screen printing, zirconium dioxide dielectric spacer layer 5, niobium oxide hole blocking layer 3 ', nickel dorsum electrode layer 7.
Nano titanium oxide grain size is such as 18nm, and titanium dioxide layer thickness is such as about 1 μm.The granular size of zirconium dioxide is such as 30 nanometers, and thickness is such as about 1 μm.By a certain amount of such as 4 μ L perovskites (5-AVA) 2(CH 3nH 3) 40pb 41(BF 4) 10i 114precursor liquid (30wt%) drips on carbon mesoporous film, leaves standstill and fully infiltrates into after in titanium dioxide nanocrystalline film until it for one minute, dries at uniform temperature such as 50 DEG C.Test shows, gained battery device is at 100mW/cm 2under simulated solar irradiation, efficiency is 18.9%.
embodiment 8
Device in the present embodiment take glass as substrate 1, transparent electro-conductive glass 2 is set thereon, after deposition certain thickness such as 50nm tungsten oxide compacted zone 6 ', nickel oxide hole transmission layer 8 ' is prepared successively from bottom to top in the mode of silk screen printing, zirconium dioxide dielectric spacer layer 5, titanic oxide electronic transport layer 4 ', niobium oxide hole blocking layer 3 ', cobalt dorsum electrode layer 7.
Nano titanium oxide grain size is such as 18nm, and titanium dioxide layer thickness is such as about 1 μm.The granular size of zirconium dioxide is such as 30 nanometers, and thickness is such as about 1 μm.By a certain amount of such as 4 μ L perovskites (5-AVA) 2(CH 3nH 3) 40pb 41(BF 4) 10i 114precursor liquid (30wt%) drips on carbon mesoporous film, leaves standstill and fully infiltrates into after in titanium dioxide nanocrystalline film until it for one minute, dries at uniform temperature such as 50 DEG C.Test shows, gained battery device is at 100mW/cm 2under simulated solar irradiation, efficiency is 18.9%.
embodiment 9
Device in the present embodiment take glass as substrate 1, transparent electro-conductive glass 2 is set thereon, after deposition certain thickness such as 50nm tungsten oxide compacted zone 6 ', nickel oxide hole transmission layer 8 ' is prepared successively from bottom to top in the mode of silk screen printing, titanic oxide electronic transport layer 4 ', niobium oxide hole blocking layer 3 ', cobalt dorsum electrode layer 7.
Nano titanium oxide grain size is such as 18nm, and titanium dioxide layer thickness is such as about 1 μm.The granular size of zirconium dioxide is such as 30 nanometers, and thickness is such as about 1 μm.By a certain amount of such as 4 μ L perovskites (5-AVA) 2(CH 3nH 3) 40pb 41(BF 4) 10i 114precursor liquid (30wt%) drips on carbon mesoporous film, leaves standstill and fully infiltrates into after in titanium dioxide nanocrystalline film until it for one minute, dries at uniform temperature such as 50 DEG C.Test shows, gained battery device is at 100mW/cm 2under simulated solar irradiation, efficiency is 18.9%.
In fact, in the embodiment of above-mentioned each preparation method, can also after deposited oxide tungsten compacted zone 6 ', only deposited oxide niobium hole blocking layer 3 ' or dielectric spacer layer 5 separately between nickel oxide hole transmission layer 8 ' and cobalt dorsum electrode layer 7.
In the present invention, the material of electronic barrier layer 6,6 ' is not limited to above-described embodiment, can be such as cupric oxide, cuprous oxide, tungsten oxide, doping cupric oxide, doped tungsten oxide, at least one in doped with Cu ScO2, doped with Cu YO2, doped with Cu InO2, doped with Cu AlO2, doped with Cu CrO2, doped with Cu MO2, doped with Cu WO2 and doped with Cu GaO2.Doped chemical can be at least one in beryllium, magnesium, calcium, strontium, barium, zinc and cadmium.
In the present invention, perovskite semi-conducting material is also not limited to above-described embodiment, and it can select chemical formula to be R xa yb zx (mx+ny+lz)/hperovskite semi-conducting material, wherein, x is positive number, y and z is nonnegative number, and m, n, l and h are respectively R, and the chemical valence price of A, B and X is (hereinafter referred to as RABX xyztt=(mx+ny+lz)/h), wherein R is organic group containing protonated amido, amidino groups and/or ammonium root, A is at least one group in methylamine, carbonamidine and alkali family cation or ion, B is the cation of at least one in lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, tellurium, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium and astatine, X for containing iodine, bromine, chlorine, with in at least one anion.
Wherein, described R preferably has structure R 1-R 2-R 3group, wherein R 1for halogens, oxygen group elements, nitrogen group element ,-NH 2,-NH 3,-N=C (NH 2)=NH 2or-N=HCH-NH 3in at least one, R 2for in C1-C30 a kind of linearly, or branched alkyl, cycloalkyl in C3-C12, heterocycle in C1-C12, unsaturated alkyl in C2-C8, aryl in C6-C12, aralkyl in C6-C30, alkylaryl in C6-C30, iso-aryl in C1-C12, at least one in alkyl iso-aryl in C6-C30 and these organic groups of alkyl heterocyclic in C6-C30, or be halogen, hydroxyl, carboxyl, carbonyl, nitro, aldehyde, nitrous acid, sulfonic acid, acid amides, ketone, ether, nitrile, isocyanides, hydrazone, sulfydryl, phosphine, oxime, the at least one of azo group and amido modified above-mentioned organic group, R 3for-COOH ,-OSiOH ,-O 3pOH and-O 2one or more in SOH.
In the present invention, the precursor solution of the perovskite light absorbent of filling is at perovskite RABX xyztin precursor liquid, add the additional material and the mixture that formed that can improve perovskite semi-conducting material pattern and filling effect.The mole of the additional material of described interpolation and perovskite RABX xyztthe ratio of mole (0,2] between.
In the present invention, additional material is not limited to above-described embodiment, in fact its can for comprise hydrogen halides or its solution, halogenated hydrocarbons, halogenated heterocyclic, halogenated aromatic compound, the different aromatic compound of halo, sulfo-hydrocarbon, halo alkyl, halo alkyl amidine, sulfo-heterocycle, sulfo-aromatic, the different aromatic compound of sulfo-, ammonium sulfide and ammonium halide one or more.
In the present invention, the mixed solvent in perovskite precursor liquid can be beta-propiolactone, gamma-butyrolacton, δ-valerolactone, DMF, DMA, N, N-dimethylpropionamide, N, N-diethylformamide, N, N-diethyl acetamide, N, N-diethyl propionamide, dimethyl sulfoxide (DMSO), tetramethylene sulfoxide, pentamethylene sulfoxide, hexa-methylene sulfoxide, tetramethylene urea, N, N-dimethacrylate urea, hexamethyl phosphoramide, 1-METHYLPYRROLIDONE, N-ethyl pyrrolidone, carrene, benzene, toluene, dimethylbenzene, methane, ethane, propane, butane, pentane, hexane, octane, cyclohexane, cyclohexanone, toluene cyclohexanone, ether, acetone, butanone, acetic acid, acetic anhydride, dioxane, chloroform, carbon tetrachloride, ethyl acetate, oxolane, pyridine, benzinum, n-butanol, isopropyl alcohol, nitrobenzene, chlorobenzene, dichloro-benzenes, carrene, ether, expoxy propane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, the positive acetone of methyl, isobutyl acetate, 2-nitropropane, n-butyl acetate, propylene glycol monomethyl ether, methyl isoamyl ketone, methyl amyl acetate, n-butyl propionate, propylene glycol methyl ether acetate, pentyl acetate, methyl-n-amyl ketone, isobutyl isobutyrate, ethoxy ether, cyclohexanone, glycol monobutyl ether, propylene glycol monopropyl ether, ethyl cellosolve acetate, isobutyrone, glycol propyl ether, diacetone alcohol, butyl glycol ether, propandiol butyl ether, formic acid-2-ethylhexyl ester, butyl glycol ether acetic acid esters, dipropylene glycol methyl ether, glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ether, diethylene glycol propyl ether, glycol hexyl ether, diethylene glycol ether acetic acid esters, butyl, ethylene glycol-2-ethyl hexyl ether is coated with, butyl acetic acid esters, the third two single phenyl ethers, espeleton, methylisobutylketone, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, phenol, methyl alcohol, ethanol, isopropyl alcohol, normal propyl alcohol, 2-butanols, isobutanol, methyl isobutyl carbinol, amylalcohol, cyclohexanol, naphtha, 100# solvent naphtha, 150# solvent naphtha, 200# solvent naphtha, styrene, perchloroethylene, trichloroethylene, two kinds in ethylene glycol ether and triethanolamine or more.
In the present invention, the filling of perovskite semi-conducting material, both can with directly filling perovskite RABX xyztthe mode of precursor liquid realizes, also can with first filling B zx zl/hprecursor liquid, recharges R xa yx mx+ny/hthe mode of precursor liquid realizes.Filling can be by precursor solution being penetrated into after back electrode (7) surface-coated each porous layer and realize or directly before back electrode (7) coating of its precursor solution is penetrated into each porous layer and realizing preparing.
In fact, the transformation efficiency seeing solar cell 10-11% based on Jie of perovskite light absorbent due to existing efficiency with can implementation efficiency 20% also there is a big difference, making great efforts in the industry analysis reason always and attempting to reduce this gap.Through a large amount of theoretical researches and test, the present invention creatively finds, photo-generated carrier still has part effectively not to be collected by electrode, causes current loss and parallel resistance to reduce and then reduces fill factor, curve factor, is the too low key reason of transformation efficiency.
Such as, be this typical perovskite light absorbent of bustamentite methylamine perovskite of 1.55eV for band gap, it is 24mA/cm as unijunction solar cell the highest accessible short circuit current 2, open circuit voltage is 1.1V, and fill factor, curve factor is 75%.After bustamentite methylamine perovskite is filled into multichip semiconductor pore membrane, the C film of the superiors is peeled off together with the bustamentite methylamine perovskite inside C film, residue zirconium dioxide, titanium dioxide and scribble the Conducting Glass of hole blocking layer, measure its visible-light absorptivity, find in 350nm-750nm wave-length coverage, absorptivity reaches 90%, reaches 100% in 500nm wavelength annex absorptivity, if separation of charge efficiency and charge collection efficiency all reach 100%, 24mA/cm can be produced 2short-circuit current density.This illustrates that most photon is absorbed, and measures the external quantum efficiency display of gained, and in 350nm-750nm wave-length coverage inside and outside, quantum efficiency only has 85%.The short-circuit current density of device is 16mA/cm 2, this with can implementation value 24mA/cm 2still have larger gap, and open circuit voltage 0.9V allows of no optimist especially, limit the further lifting of efficiency to a great extent.Therefore, can conclude, photo-generated carrier still has part effectively not collected by electrode, causes current loss and parallel resistance reduce and then reduce fill factor, curve factor.Those skilled in the art can know, in bustamentite methylamine, the diffusion length in hole is greater than 1 micron, and the diffusion length of electronics is greater than 100 nanometers.Because hole blocking layer can blocking hole effectively, hole also have collected effectively by hole collection layer, and what therefore cause current loss can only be that electronics is not collected effectively by electron transfer layer and front electrode layer.And when inserting the electron transfer layer of one deck 50 nanometer thickness between carbon electrode and zirconium dioxide membrane, electric current, fill factor, curve factor and voltage significantly decline simultaneously, and this has more absolutely proved light induced electron, and some is not effectively collected but has been injected into dorsum electrode layer.Therefore, in order to obtain, higher efficiency is necessary increases electronic barrier layer between carbon electrode and electron transfer layer.Increase after electronic barrier layer, voltage and current has had large lifting really, and efficiency and stability obtain significant progress, and electronic barrier layer does not need to adopt and traditional makes very fine and close form, still adopts porous membrane structure.
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 (26)

1. see solar cell based on Jie of perovskite light absorbent for one kind, wherein, this Jie sees solar cell and comprises substrate of glass (1) and be successively set on transparency conducting layer (2), hole blocking layer (3), electron transfer layer (4) and the back electrode (7) in this substrate of glass (1), described hole blocking layer (3) is compacted zone, and described electron transfer layer (4) is porous membrane; It is characterized in that,
The electronic barrier layer (6) with porous is also provided with between described electron transfer layer (4) and back electrode (7), perovskite light absorbent is filled with in this electron transfer layer (4) and electronic barrier layer (6), can make described electron transfer layer (4) and electronic barrier layer (6) after illumination, produce hole and electronics, wherein said electronics because of the existence of described electronic barrier layer (6) can only through described electron transfer layer (4) and hole blocking layer (3) one-way transmission to transparency conducting layer (2), described hole because of the existence of described hole blocking layer (3) can only through described electronic barrier layer (6) one-way transmission to back electrode (7), thus reduce the compound in electronics and hole, make Jie see solar cell and there is high-photoelectric transformation efficiency and long-term light durability.
2. a kind of Jie based on perovskite light absorbent according to claim 1 sees solar cell, wherein, also comprise the dielectric spacer layer (5) with porous, it is stacked is arranged on electron transfer layer (4), described electronic barrier layer (6) is stacked to be arranged between this dielectric spacer layer (5) and back electrode (7), and is filled with perovskite light absorbent.
3. a kind of Jie based on perovskite light absorbent according to claim 1 and 2 sees solar cell, wherein, described electronic barrier layer (6) is by the also rear formation of sintering of the precursor liquid at described electron transfer layer (4) or dielectric spacer layer (5) surface-coated electronic barrier layer (6), or the also rear formation of sintering of the nano particle slurry of coating electronic barrier layer (6).
4. a kind of Jie based on perovskite light absorbent according to claim 1 and 2 sees solar cell, wherein, described back electrode (7) is porous membrane, and described electronic barrier layer (6) passes through the precursor liquid at described back electrode (7) surface-coated electronic barrier layer (6) and sinter formation after infiltrating into electron transfer layer (4) or dielectric spacer layer (5) surface.
5. see solar cell based on Jie of perovskite light absorbent for one kind, wherein, this Jie sees solar cell and comprises substrate of glass (1) and be successively set on transparency conducting layer (2), hole transmission layer (8 ') and the back electrode (7) in this substrate of glass (1), wherein, described hole transmission layer (8 ') is porous membrane, it is characterized in that
Fine and close electronic barrier layer (6 ') is also provided with between described hole transmission layer (8 ') and transparency conducting layer (2), perovskite light absorbent is filled with in described hole transmission layer (8 '), can make this hole transmission layer (8 ') after illumination, produce hole and electronics, wherein electronics because of the existence of described electronic barrier layer (6 ') can only through described hole transmission layer (8 ') one-way transmission to back electrode (7), and described hole through described electronic barrier layer (6 ') one-way transmission to transparency conducting layer (2), thus reduce the compound in electronics and hole, make Jie see solar cell and there is high-photoelectric transformation efficiency and long-term light durability.
6. a kind of Jie based on perovskite light absorbent according to claim 5 sees solar cell, wherein, also comprise dielectric spacer layer (5), the electron transfer layer (4 ') of porous or the hole blocking layer (3 ') of porous with porous, it is arranged between hole transmission layer (8 ') and back electrode (7), and is filled with perovskite light absorbent.
7. a kind of Jie based on perovskite light absorbent according to claim 5 sees solar cell, wherein, also comprise the dielectric spacer layer (5) with porous and the electron transfer layer (4 ') of arranged stacked, or the dielectric spacer layer of arranged stacked (5) and hole blocking layer (3 '), or the electron transfer layer (4 ') with porous of arranged stacked and hole blocking layer (3 '), it is arranged between hole transmission layer (8 ') and back electrode (7), and is filled with perovskite light absorbent.
8. a kind of Jie based on perovskite light absorbent according to claim 5 sees solar cell, wherein, also comprise dielectric spacer layer (5), electron transfer layer (4 ') and the hole blocking layer (3 ') with porous of arranged stacked, above-mentioned each layer is arranged between hole transmission layer (8 ') and back electrode (7), and is filled with perovskite light absorbent.
9. a kind of Jie based on perovskite light absorbent according to any one of claim 5-8 sees solar cell, wherein, described hole blocking layer (3 ') by applying the precursor liquid also rear formation of sintering on its coating cap rock, or the also rear formation of sintering of the nano particle slurry of coating hole blocking layer (3 ').
10. a kind of Jie based on perovskite light absorbent according to any one of claim 5-8 sees solar cell, wherein, described back electrode (7) is porous membrane, and described hole blocking layer (3 ') is passed through the precursor liquid at described back electrode (7) surface-coated hole blocking layer (3 ') and sinter formation after being infiltrated into coating cap rock surface.
11. a kind of Jie based on perovskite light absorbent according to any one of claim 1-10 see solar cell, wherein, described electronic barrier layer (6,6 ') is cupric oxide, cuprous oxide, tungsten oxide, doping cupric oxide, doped tungsten oxide, at least one in doped with Cu ScO2, doped with Cu YO2, doped with Cu InO2, doped with Cu AlO2, doped with Cu CrO2, doped with Cu MO2, doped with Cu WO2 and doped with Cu GaO2.
12. a kind of Jie based on perovskite light absorbent according to claim 11 see solar cell, and wherein, described doped chemical can be at least one in beryllium, magnesium, calcium, strontium, barium, zinc and cadmium.
13. a kind of Jie based on perovskite light absorbent according to any one of claim 1-12 see solar cell, and wherein, described perovskite semi-conducting material is R xa yb zx (mx+ny+lz)/hwherein, x is positive number, y and z is nonnegative number, m, n, l and h is respectively R, A, the chemical valence price (t=(mx+ny+lz)/h) of B and X, wherein R is organic group containing protonated amido, amidino groups and/or ammonium root, and A is at least one group in methylamine, carbonamidine and alkali family cation or ion, B is the cation of at least one in lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, tellurium, osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium and astatine, X for containing iodine, bromine, chlorine, with in at least one anion.
14. a kind of Jie based on perovskite light absorbent according to claim 13 see solar cell, and wherein, described R preferably has structure R 1-R 2-R 3group, wherein R 1for halogens, oxygen group elements, nitrogen group element ,-NH 2,-NH 3,-N=C (NH 2)=NH 2,-C=NHNH 2or-C=NHNH 3in at least one, R 2for in C1-C30 a kind of linearly, or branched alkyl, cycloalkyl in C3-C12, heterocycle in C1-C12, unsaturated alkyl in C2-C8, aryl in C6-C12, aralkyl in C6-C30, alkylaryl in C6-C30, iso-aryl in C1-C12, at least one in alkyl iso-aryl in C6-C30 and these organic groups of alkyl heterocyclic in C6-C30, or be halogen, hydroxyl, carboxyl, carbonyl, nitro, aldehyde, nitrous acid, sulfonic acid, acid amides, ketone, ether, nitrile, isocyanides, hydrazone, sulfydryl, phosphine, oxime, the at least one of azo group and amido modified above-mentioned organic group, R 3for-COOH ,-OSiOH ,-O 3pOH and-O 2one or more in SOH.
15. a kind of Jie based on perovskite light absorbent according to any one of claim 1-10 see solar cell, and wherein, the precursor solution of the perovskite light absorbent of described filling is at perovskite RABX xyztin precursor liquid, add the additional material and the mixture that formed that can improve perovskite semi-conducting material pattern and filling effect.
16. a kind of Jie based on perovskite light absorbent according to claim 15 see solar cell, wherein, and the mole of the additional material of described interpolation and perovskite RABX xyztthe ratio of mole (0,2] between.
17. a kind of Jie based on perovskite light absorbent according to claim 15 or 16 see solar cell, wherein, described additional material comprise hydrogen halides or its solution, halogenated hydrocarbons, halogenated heterocyclic, halogenated aromatic compound, the different aromatic compound of halo, sulfo-hydrocarbon, halo alkyl, halo alkyl amidine, sulfo-heterocycle, sulfo-aromatic, the different aromatic compound of sulfo-, ammonium sulfide and ammonium halide one or more.
18. a kind of Jie based on perovskite light absorbent according to any one of claim 1-17 see solar cell, and wherein, the solvent in described perovskite precursor liquid adopts mixed solvent, and it is beta-propiolactone, gamma-butyrolacton, δ-valerolactone, DMF, DMA, N, N-dimethylpropionamide, N, N-diethylformamide, N, N-diethyl acetamide, N, N-diethyl propionamide, dimethyl sulfoxide (DMSO), tetramethylene sulfoxide, pentamethylene sulfoxide, hexa-methylene sulfoxide, tetramethylene urea, N, N-dimethacrylate urea, hexamethyl phosphoramide, 1-METHYLPYRROLIDONE, N-ethyl pyrrolidone, carrene, benzene, toluene, dimethylbenzene, methane, ethane, propane, butane, pentane, hexane, octane, cyclohexane, cyclohexanone, toluene cyclohexanone, ether, acetone, butanone, acetic acid, acetic anhydride, dioxane, chloroform, carbon tetrachloride, ethyl acetate, oxolane, pyridine, benzinum, n-butanol, isopropyl alcohol, nitrobenzene, chlorobenzene, dichloro-benzenes, carrene, ether, expoxy propane, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, the positive acetone of methyl, isobutyl acetate, 2-nitropropane, n-butyl acetate, propylene glycol monomethyl ether, methyl isoamyl ketone, methyl amyl acetate, n-butyl propionate, propylene glycol methyl ether acetate, pentyl acetate, methyl-n-amyl ketone, isobutyl isobutyrate, ethoxy ether, cyclohexanone, glycol monobutyl ether, propylene glycol monopropyl ether, ethyl cellosolve acetate, isobutyrone, glycol propyl ether, diacetone alcohol, butyl glycol ether, propandiol butyl ether, formic acid-2-ethylhexyl ester, butyl glycol ether acetic acid esters, dipropylene glycol methyl ether, glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ether, diethylene glycol propyl ether, glycol hexyl ether, diethylene glycol ether acetic acid esters, butyl, ethylene glycol-2-ethyl hexyl ether is coated with, butyl acetic acid esters, the third two single phenyl ethers, espeleton, methylisobutylketone, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, phenol, methyl alcohol, ethanol, isopropyl alcohol, normal propyl alcohol, 2-butanols, isobutanol, methyl isobutyl carbinol, amylalcohol, cyclohexanol, naphtha, 100# solvent naphtha, 150# solvent naphtha, 200# solvent naphtha, styrene, perchloroethylene, trichloroethylene, two kinds in ethylene glycol ether and triethanolamine or more.
19. a kind of Jie based on perovskite light absorbent according to any one of claim 1-18 see solar cell, and wherein, the filling of described perovskite semi-conducting material, both can with direct filling perovskite RABX xyztthe mode of precursor liquid realizes, also can with first filling B zx zl/hprecursor liquid, recharges R xa yx mx+ny/hthe mode of precursor liquid realizes.
20. a kind of Jie based on perovskite light absorbent according to any one of claim 1-19 see solar cell, wherein, described filling is by precursor solution being penetrated into after back electrode (7) surface-coated each porous layer and realize or directly before back electrode (7) coating of its precursor solution is penetrated into each porous layer and realizing preparing.
Jie based on perovskite light absorbent according to any one of 21. 1 kinds of claim 1-20 sees the preparation method of solar cell, wherein, prepared by one or more modes combined during each semiconductor layer adopts printing, spin coating, spraying, blade coating, hydro-thermal or 3D to print.
22. preparation methods according to claim 21, wherein, described electron transfer layer (4,4 ') is titanium dioxide, at least one in zinc oxide, tin oxide, niobium oxide, barium stannate, PCBM and corresponding dopant.
23. preparation methods according to claim 20 or 21, wherein, described dielectric spacer layer (5) is zirconia, at least one in silicon dioxide, aluminium oxide, indium oxide, gallium oxide, cadmium sulfide and corresponding dopant.
24. preparation methods according to any one of claim 20-23, wherein, described back electrode (7) is electric conducting material, can be at least one in carbon, gold, silver, aluminium, copper, nickel, iron, zinc, magnesium, calcium, titanium, vanadium, chromium, manganese, cobalt, tungsten and gallium.
25. preparation methods according to any one of claim 20-24, wherein, described back electrode (7) preferably adopts at least one in carbon, aluminium, copper, nickel and cobalt material.
26. preparation methods according to any one of claim 20-25, wherein, described back electrode (7) preferably adopts the mixture of graphite, carbon black and inorganic oxide, and wherein the effect of inorganic oxide is binding agent between material with carbon element and as the interface-modifying layer between perovskite and material with carbon element.
CN201510728751.XA 2015-10-30 2015-10-30 Mesoscopic solar cell based on perovskite-kind light absorption material and preparation method thereof Pending CN105405973A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510728751.XA CN105405973A (en) 2015-10-30 2015-10-30 Mesoscopic solar cell based on perovskite-kind light absorption material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510728751.XA CN105405973A (en) 2015-10-30 2015-10-30 Mesoscopic solar cell based on perovskite-kind light absorption material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN105405973A true CN105405973A (en) 2016-03-16

Family

ID=55471345

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510728751.XA Pending CN105405973A (en) 2015-10-30 2015-10-30 Mesoscopic solar cell based on perovskite-kind light absorption material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN105405973A (en)

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105977386A (en) * 2016-07-04 2016-09-28 陕西煤业化工技术研究院有限责任公司 Perovskite solar cell of nano metal oxide hole transport layer and preparation method thereof
CN105977385A (en) * 2016-07-01 2016-09-28 湘潭大学 Waterproof copper-based perovskite solar cell and manufacturing method thereof
CN106206956A (en) * 2016-09-07 2016-12-07 中国工程物理研究院材料研究所 A kind of preparation method of novel copper-containing ion perovskite thin film
CN106449989A (en) * 2016-12-01 2017-02-22 苏州大学 Perovskite solar battery and preparation method thereof
CN106935710A (en) * 2017-03-27 2017-07-07 华中科技大学 A kind of perovskite solar cell with High-current output under extremely low temperature
CN107180914A (en) * 2017-06-20 2017-09-19 陕西科技大学 A kind of preparation method of perovskite thin film battery
CN107240645A (en) * 2017-06-21 2017-10-10 南开大学 The preparation of perovskite Ge particle organic inorganic composite solar battery
CN107275488A (en) * 2017-06-12 2017-10-20 清华大学 A kind of precursor solution of nanocrystalline/perovskite hybrid material
CN107482119A (en) * 2017-06-29 2017-12-15 华中光电技术研究所（中国船舶重工集团公司第七七研究所） A kind of perovskite solar cell and preparation method thereof
CN107546326A (en) * 2016-06-24 2018-01-05 云南科威液态金属谷研发有限公司 Low-melting-point metal electrode type perovskite solar cell
CN108682740A (en) * 2018-03-21 2018-10-19 苏州协鑫纳米科技有限公司 Perovskite battery and preparation method thereof
CN109103337A (en) * 2018-07-13 2018-12-28 华中科技大学 A kind of technique and its application using bustamentite carbonamidine as solar battery light-absorption layer
CN109103331A (en) * 2018-08-15 2018-12-28 四川省新材料研究中心 A kind of perovskite solar battery and preparation method thereof based on mesoporous inorganic hole mobile material
CN109346601A (en) * 2018-11-26 2019-02-15 南京理工大学 The preparation method of the multiple resistive memristor of full-inorganic perovskite
CN110120454A (en) * 2019-05-10 2019-08-13 电子科技大学 Application, solar battery and the preparation method of organic acid and/or alcohol in preparation solar cell interface adjusting control agent
CN110311039A (en) * 2019-06-28 2019-10-08 河南大学 A kind of Nb- stannic oxide nanometer presoma utilizes it as the method that electron transfer layer prepares perovskite solar battery
CN110446761A (en) * 2017-03-20 2019-11-12 锡克拜控股有限公司 Barium stannate material, safe ink composition and its security feature of luminescence generated by light Fe2O3 doping
CN110581222A (en) * 2018-06-11 2019-12-17 湖北万度光能有限责任公司 Preparation method of solar cell
CN110660920A (en) * 2018-06-28 2020-01-07 湖北万度光能有限责任公司 Method for manufacturing perovskite solar cell
CN110660917A (en) * 2018-06-29 2020-01-07 湖北万度光能有限责任公司 Method for forming mesoscopic solar cell electron transport layer
JP2020504455A (en) * 2017-10-24 2020-02-06 ▲華▼中科技大学Ｈｕａｚｈｏｎｇ Ｕｎｉｖｅｒｓｉｔｙ Ｏｆ Ｓｃｉｅｎｃｅ Ａｎｄ Ｔｅｃｈｎｏｌｏｇｙ Ferroelectric reinforced solar cell and method of manufacturing the same
CN111653672A (en) * 2020-06-15 2020-09-11 安徽大学 Lattice-matched heterojunction composite film, preparation method and perovskite solar cell
CN112397617A (en) * 2019-08-19 2021-02-23 Tcl集团股份有限公司 Doped tungsten oxide nano material, preparation method thereof and inorganic hole transport material
CN112552185A (en) * 2020-11-12 2021-03-26 华中科技大学鄂州工业技术研究院 Preparation method of phenylethylamine silver indium bromide, semiconductor radiation detector and preparation method
CN112582544A (en) * 2019-09-27 2021-03-30 南京工业大学 Method for preparing perovskite film based on additive engineering and photoelectric application thereof
CN113363391A (en) * 2021-05-24 2021-09-07 桂林电子科技大学 Carbon-based full-printing perovskite solar cell based on ionic liquid additive and preparation method thereof
CN113707815A (en) * 2021-08-03 2021-11-26 深圳市华星光电半导体显示技术有限公司 Perovskite device, preparation method thereof and perovskite layer precursor liquid
CN114645327A (en) * 2022-02-11 2022-06-21 上海大学 Perovskite single crystal and growth method thereof
CN114695681A (en) * 2022-03-30 2022-07-01 电子科技大学 Tin-based perovskite solar cell, preparation method and green solvent system
WO2023054016A1 (en) * 2021-09-30 2023-04-06 住友化学株式会社 Photoelectric conversion element
WO2023097646A1 (en) * 2021-12-03 2023-06-08 宁德时代新能源科技股份有限公司 Perovskite solar cell, and photovoltaic assembly
CN116904192A (en) * 2023-07-05 2023-10-20 华中科技大学鄂州工业技术研究院 Preparation method and application of all-inorganic perovskite quantum dot

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013171520A1 (en) * 2012-05-18 2013-11-21 Isis Innovation Limited Optoelectronic device comprising perovskites
CN103441217A (en) * 2013-07-16 2013-12-11 华中科技大学 Mesoscopic solar cell based on perovskite light absorption material and manufacturing method thereof
CN104091889A (en) * 2014-07-24 2014-10-08 华中科技大学 Semi-conductor perovskite solar cell and preparing method thereof
CN104409636A (en) * 2014-11-18 2015-03-11 天津理工大学 Perovskite thin-film solar cell with three-dimensional ordered mesopore support layer
WO2015031944A1 (en) * 2013-09-04 2015-03-12 Dyesol Ltd A photovoltaic device
CN104662625A (en) * 2012-05-18 2015-05-27 埃西斯创新有限公司 Optoelectronic devices with organometal perovskites with mixed anions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013171520A1 (en) * 2012-05-18 2013-11-21 Isis Innovation Limited Optoelectronic device comprising perovskites
CN104662625A (en) * 2012-05-18 2015-05-27 埃西斯创新有限公司 Optoelectronic devices with organometal perovskites with mixed anions
CN103441217A (en) * 2013-07-16 2013-12-11 华中科技大学 Mesoscopic solar cell based on perovskite light absorption material and manufacturing method thereof
WO2015031944A1 (en) * 2013-09-04 2015-03-12 Dyesol Ltd A photovoltaic device
CN104091889A (en) * 2014-07-24 2014-10-08 华中科技大学 Semi-conductor perovskite solar cell and preparing method thereof
CN104409636A (en) * 2014-11-18 2015-03-11 天津理工大学 Perovskite thin-film solar cell with three-dimensional ordered mesopore support layer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
荣耀光等: "全固态介观太阳能电池:从染料敏化到钙钛矿", 《化学学报》 *

Cited By (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107546326A (en) * 2016-06-24 2018-01-05 云南科威液态金属谷研发有限公司 Low-melting-point metal electrode type perovskite solar cell
CN105977385A (en) * 2016-07-01 2016-09-28 湘潭大学 Waterproof copper-based perovskite solar cell and manufacturing method thereof
CN105977386A (en) * 2016-07-04 2016-09-28 陕西煤业化工技术研究院有限责任公司 Perovskite solar cell of nano metal oxide hole transport layer and preparation method thereof
CN106206956A (en) * 2016-09-07 2016-12-07 中国工程物理研究院材料研究所 A kind of preparation method of novel copper-containing ion perovskite thin film
CN106449989A (en) * 2016-12-01 2017-02-22 苏州大学 Perovskite solar battery and preparation method thereof
CN110446761A (en) * 2017-03-20 2019-11-12 锡克拜控股有限公司 Barium stannate material, safe ink composition and its security feature of luminescence generated by light Fe2O3 doping
US11352517B2 (en) 2017-03-20 2022-06-07 Sicpa Holding Sa Photoluminescent iron-doped barium stannate material, security ink composition and security feature thereof
CN106935710A (en) * 2017-03-27 2017-07-07 华中科技大学 A kind of perovskite solar cell with High-current output under extremely low temperature
CN107275488A (en) * 2017-06-12 2017-10-20 清华大学 A kind of precursor solution of nanocrystalline/perovskite hybrid material
CN107275488B (en) * 2017-06-12 2019-09-27 清华大学 A kind of precursor solution of nanocrystalline/perovskite hybrid material
CN107180914A (en) * 2017-06-20 2017-09-19 陕西科技大学 A kind of preparation method of perovskite thin film battery
CN107240645A (en) * 2017-06-21 2017-10-10 南开大学 The preparation of perovskite Ge particle organic inorganic composite solar battery
CN107240645B (en) * 2017-06-21 2019-06-04 南开大学 The preparation of perovskite-nanometer germanium particle Organic-inorganic composite solar battery
CN107482119A (en) * 2017-06-29 2017-12-15 华中光电技术研究所（中国船舶重工集团公司第七七研究所） A kind of perovskite solar cell and preparation method thereof
US11127535B2 (en) 2017-10-24 2021-09-21 Huazhong University Of Science And Technology Ferroelectric enhanced solar cell and preparation method thereof
JP2020504455A (en) * 2017-10-24 2020-02-06 ▲華▼中科技大学Ｈｕａｚｈｏｎｇ Ｕｎｉｖｅｒｓｉｔｙ Ｏｆ Ｓｃｉｅｎｃｅ Ａｎｄ Ｔｅｃｈｎｏｌｏｇｙ Ferroelectric reinforced solar cell and method of manufacturing the same
JP7012282B2 (en) 2017-10-24 2022-01-28 ▲華▼中科技大学 Ferroelectric reinforced solar cells and their manufacturing methods
CN108682740B (en) * 2018-03-21 2022-02-22 昆山协鑫光电材料有限公司 Perovskite battery and preparation method thereof
CN108682740A (en) * 2018-03-21 2018-10-19 苏州协鑫纳米科技有限公司 Perovskite battery and preparation method thereof
CN110581222A (en) * 2018-06-11 2019-12-17 湖北万度光能有限责任公司 Preparation method of solar cell
CN110660920A (en) * 2018-06-28 2020-01-07 湖北万度光能有限责任公司 Method for manufacturing perovskite solar cell
CN110660917A (en) * 2018-06-29 2020-01-07 湖北万度光能有限责任公司 Method for forming mesoscopic solar cell electron transport layer
CN110660917B (en) * 2018-06-29 2022-11-01 湖北万度光能有限责任公司 Method for forming mesoscopic solar cell electron transport layer
CN109103337A (en) * 2018-07-13 2018-12-28 华中科技大学 A kind of technique and its application using bustamentite carbonamidine as solar battery light-absorption layer
CN109103331A (en) * 2018-08-15 2018-12-28 四川省新材料研究中心 A kind of perovskite solar battery and preparation method thereof based on mesoporous inorganic hole mobile material
CN109346601A (en) * 2018-11-26 2019-02-15 南京理工大学 The preparation method of the multiple resistive memristor of full-inorganic perovskite
CN110120454A (en) * 2019-05-10 2019-08-13 电子科技大学 Application, solar battery and the preparation method of organic acid and/or alcohol in preparation solar cell interface adjusting control agent
CN110311039B (en) * 2019-06-28 2020-06-30 河南大学 Nb-tin dioxide nano precursor and method for preparing perovskite solar cell by using Nb-tin dioxide nano precursor as electron transport layer
CN110311039A (en) * 2019-06-28 2019-10-08 河南大学 A kind of Nb- stannic oxide nanometer presoma utilizes it as the method that electron transfer layer prepares perovskite solar battery
CN112397617A (en) * 2019-08-19 2021-02-23 Tcl集团股份有限公司 Doped tungsten oxide nano material, preparation method thereof and inorganic hole transport material
CN112397617B (en) * 2019-08-19 2022-02-18 Tcl科技集团股份有限公司 Doped tungsten oxide nano material, preparation method thereof and inorganic hole transport material
CN112582544A (en) * 2019-09-27 2021-03-30 南京工业大学 Method for preparing perovskite film based on additive engineering and photoelectric application thereof
CN112582544B (en) * 2019-09-27 2024-05-28 南京工业大学 Method for preparing perovskite film based on additive engineering and photoelectric application thereof
CN111653672A (en) * 2020-06-15 2020-09-11 安徽大学 Lattice-matched heterojunction composite film, preparation method and perovskite solar cell
CN111653672B (en) * 2020-06-15 2022-07-01 安徽大学 Lattice-matched heterojunction composite film, preparation method and perovskite solar cell
CN112552185B (en) * 2020-11-12 2022-04-26 华中科技大学鄂州工业技术研究院 Preparation method of phenylethylamine silver indium bromide, semiconductor radiation detector and preparation method
CN112552185A (en) * 2020-11-12 2021-03-26 华中科技大学鄂州工业技术研究院 Preparation method of phenylethylamine silver indium bromide, semiconductor radiation detector and preparation method
CN113363391A (en) * 2021-05-24 2021-09-07 桂林电子科技大学 Carbon-based full-printing perovskite solar cell based on ionic liquid additive and preparation method thereof
CN113707815B (en) * 2021-08-03 2023-06-30 深圳市华星光电半导体显示技术有限公司 Perovskite device, preparation method thereof and perovskite layer precursor liquid
CN113707815A (en) * 2021-08-03 2021-11-26 深圳市华星光电半导体显示技术有限公司 Perovskite device, preparation method thereof and perovskite layer precursor liquid
WO2023054016A1 (en) * 2021-09-30 2023-04-06 住友化学株式会社 Photoelectric conversion element
WO2023097646A1 (en) * 2021-12-03 2023-06-08 宁德时代新能源科技股份有限公司 Perovskite solar cell, and photovoltaic assembly
CN114645327B (en) * 2022-02-11 2023-11-07 上海大学 Perovskite single crystal and growth method thereof
CN114645327A (en) * 2022-02-11 2022-06-21 上海大学 Perovskite single crystal and growth method thereof
CN114695681A (en) * 2022-03-30 2022-07-01 电子科技大学 Tin-based perovskite solar cell, preparation method and green solvent system
CN116904192A (en) * 2023-07-05 2023-10-20 华中科技大学鄂州工业技术研究院 Preparation method and application of all-inorganic perovskite quantum dot

Similar Documents

Publication Publication Date Title
CN105405973A (en) Mesoscopic solar cell based on perovskite-kind light absorption material and preparation method thereof
Liu et al. Efficient carbon-based CsPbBr 3 inorganic perovskite solar cells by using Cu-phthalocyanine as hole transport material
Nazir et al. Stabilization of perovskite solar cells: recent developments and future perspectives
CN103441217B (en) Jie based on perovskite light absorbent sees solar cell and preparation method thereof
CN101361218B (en) Dye sensitized solar cell and dye sensitized solar cell module
CN204243085U (en) Perovskite-based thin film solar cell
CN103972394B (en) Solid dye sensitized solar cell and solid dye sensitized solar cell module
JP2018026586A (en) Solar cell equipped with light absorbing structure
US20170162811A1 (en) Template enhanced organic inorganic perovskite heterojunction photovoltaic device
US20100294350A1 (en) Photo-electrode comprising conductive non-metal film, and dye-sensitized solar cell comprising the same
US9406446B2 (en) Dye-sensitized solar cell, method of producing the same, and dye-sensitized solar cell module
WO2014180780A1 (en) Organic-inorganic perovskite based solar cell
CN106463624A (en) Photoelectric conversion element
CN106025085A (en) Perovskite solar cell based on Spiro-OMeTAD/CuxS composite hole transport layer and preparation method thereof
US20120085411A1 (en) Photoelectric conversion element and solar cell
EP1667275B1 (en) Dye-sensitized solar cell and dye-sensitized solar cell module
CN108063186A (en) Zinc doping nickel oxide hole transmission layer inverts perovskite solar cell and preparation method
CN105830243A (en) Dye-sensitized solar cell
JP2018019092A (en) Photoelectric conversion element and method for manufacturing the same
CN103733287A (en) Pigment sensitization solar cell
CN106867305B (en) The CeO that a kind of surface is modified2Nano material and product
Guan et al. Fullerene derivative as an additive for highly efficient printable mesoscopic perovskite solar cells
US20110155227A1 (en) Electrolyte composition for photoelectric transformation device and photoelectric transformation device manufactured by using the same
EP2985799A1 (en) Solid state hole transport material
JP2021095307A (en) Anatase-type titanium oxide nanoparticles and method for producing the same, and photoelectric conversion element using anatase-type titanium oxide nanoparticles and method for producing the same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20160316

RJ01 Rejection of invention patent application after publication