CN106025085B - Based on Spiro OMeTAD/CuXPerovskite solar cell of S composite hole transporting layers and preparation method thereof - Google Patents

Based on Spiro OMeTAD/CuXPerovskite solar cell of S composite hole transporting layers and preparation method thereof Download PDF

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CN106025085B
CN106025085B CN201610566473.7A CN201610566473A CN106025085B CN 106025085 B CN106025085 B CN 106025085B CN 201610566473 A CN201610566473 A CN 201610566473A CN 106025085 B CN106025085 B CN 106025085B
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spiro
ometad
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CN106025085A (en
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方国家
雷红伟
郑小璐
杨光
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Wuhan University WHU
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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    • H—ELECTRICITY
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    • 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
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
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    • 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

Abstract

The invention discloses one kind to be based on Spiro OMeTAD/CuxPerovskite solar cell of S composite hole transporting layers and preparation method thereof, including transparent conductive substrate, Oxide Electron transport layer, perovskite light-absorption layer, composite hole transporting layer and metal electrode, composite hole transporting layer obtain in the following manner：Formerly one layer of Spiro OMeTAD layer of spin coating on perovskite light-absorption layer, then high-purity copper sulfide powder is deposited on Spiro OMeTAD layers by Vacuum sublimation, obtains p-type CuxS films and the compound hole transmission layer of Spiro OMeTAD layers, wherein, 1≤x≤2.The composite hole transporting layer hole carrier mobility is up to 0.1 cm2V•s−1, and it is very hydrophobic, contact angle reaches 92 °, and the water stability of device greatly improves.Using the plane perovskite thin film cell photoelectric conversion efficiency of composite hole transporting layer of the invention up to 14%, device decay in 1000 hours is less than 10%, and this better than individually uses Spiro OMeTAD or CuxS is the device of hole transmission layer.

Description

Based on Spiro-OMeTAD/CuXThe perovskite solar cell of S composite hole transporting layers And preparation method thereof
Technical field
The present invention relates to one kind to be based on Spiro-OMeTAD/CuxThe perovskite solar cell of S composite hole transporting layers and Its preparation method, belong to photoelectron material and devices field.
Background technology
Since 21 century, with the development of society and the raising of human living standard, the mankind increasingly increase to the demand of the energy Add, the gradual exhaustion of the non-renewable energy resources such as coal, oil, natural gas.Energy problem is in the urgent need to address.Solar energy have cleaning, The many merits such as green and inexhaustible, nexhaustible, thus there is vast potential for future development.At present, all kinds of solar cells The technology of preparing of middle silica-based solar cell is more ripe, and electricity conversion is more than 20%.But expensive price limit its Further widely apply；Inorganic multivariate compound based solar battery, which can be stablized, effectively utilizes sunshine, efficiency high, into This is low, easily large-scale production, but complicated component is difficult to control.DSSC is cheap, efficiency comparison is high, makes work Skill requires low, lasted a long time, but after solidification for electrolyte, it is difficult to ensure higher energy conversion efficiency.Organic solar electricity Pond cost is cheap, it is simple to prepare, but electricity conversion is limited at present.
The perovskite battery of latest find is quickly grown in recent years, due to very high electricity conversion, at home It is outer to cause unprecedented huge research boom, and have been achieved for many achievements in research.Perovskite light absorbent has height Carrier mobility, band gap is adjustable, solwution method prepare and high absorption coefficient, so perovskite battery can obtain it is high Short circuit battery, open-circuit voltage and fill factor, curve factor.Document report highest perovskite battery efficiency is by external Michael at present Gratzel et al. is published in the research of the cation doping on perovskite photovoltaic cell on EES magazines, organic using tradition Hole transmission layer, achieve 22.1% electricity conversion (Michael Saliba, Taisuke Matsui, Ji-Youn Seo,Konrad Domanski,Juan-Pablo Correa-Baena,Mohammad Khaja Nazeeruddin,Shaik M. Zakeeruddin,Wolfgang Tress,Antonio Abate,Anders Hagfeldt and Michael Cesium-containing triple cation perovskite solar cells:improved stability,reproducibility and high efficiency,EnergyEnviron.Sci.,2016,9,1989- 1997)。
Traditional efficient perovskite battery typically using organic hole material Spiro-OMeTAD as hole transmission layer, Through achieving very high efficiency.Although this organic cavity transmission layer can play a part of stopping electronics, transporting holes, from The hole mobility of body is not high, even if being doped with inorganic lithium salts or other additives, mobility also only has 10-4cm2V·s-1。 It is such a and doping lithium salts or other additives easily cause hole transmission layer to form hole during spin coating and subsequent oxidation Hole easily causes gold electrode to be contacted with the direct of perovskite, causes device performance to reduce.More disadvantageously, such lithium salts or its Its additive is hydrophilic, and this is unfavorable for the long-term water stability of device.So if a kind of new height can be found Mobility and stable performance, hydrophobic inorganic hole transporter are significant for the development to perovskite battery.On The hole transmission layer of inorganic hole-transporting layer or organo-mineral complexing at home and abroad only has very in perovskite using current A small amount of report, replace Spiro-OMeTAD to make the hole transmission layer of perovskite photovoltaic cell with inorganic material at present, use The peak efficiency that CuSCN is obtained is 12.4% (Peng Qin, Soichiro Tanaka, Seigo Ito, Nicolas Tetreault,Kyohei Manabe,Hitoshi Nishino,Mohammad Khaja Nazeeruddin&MichaelInorganic hole conductor-based lead halide perovskite solar cells with 12.4%conversion efficiency, Nature Communications 5,3834).But CuSCN is dissolved in alkali, certainly Right environment stability inferior is poor, so while achieve preferable efficiency but also there are problems that in terms of long-time stability, It is not too much optimistic in commercial Application.The electricity conversion of perovskite solar cell has reached industrialized and wanted now Ask, but also have many problems to need to solve in terms of preparation technology, cost, particularly stability.So in order to realize calcium titanium Ore deposit solar cell efficient and stably, if the Gao Qian of the easy preparation of organic material, high efficiency and inorganic material can be combined Shifting rate, stability, developing a kind of hole transmission layer of organo-mineral complexing will be significant.
The content of the invention
Problem to be solved by this invention is migrated for existing perovskite thin film photovoltaic cell organic cavity transmission layer The problems such as rate is low, stability is poor, there is provided a kind of perovskite thin film photovoltaic cell based on organo-mineral complexing hole transmission layer and Its preparation method.
Main contents of the present invention：The p-type semiconductor Cu prepared using Vacuum sublimationxS, it is prepared for Spiro- OMeTAD/CuxS organic-inorganic two-layer compound hole transmission layers prepare perovskite solar cell.Contrast traditional perovskite Solar cell, the invention provides a kind of Spiro-OMeTAD/CuxPerovskite thin film photovoltaic electrics of the S as hole transmission layer Pond and preparation method thereof, this method cause the transformation efficiency of photovoltaic cell and long term device stability to be improved.
Technical scheme provided by the invention is specific as follows：
One kind is based on Spiro-OMeTAD/CuxThe perovskite solar cell of S composite hole transporting layers, including transparent lead Electric substrate and stack gradually in the metal oxide electron transport layer in transparent conductive substrate, perovskite light-absorption layer, hole transport Layer and metal electrode layer；It is characterized in that：Described hole transmission layer obtains in the following manner：First in perovskite light-absorption layer Upper one layer of Spiro-OMeTAD layer of spin coating, then high-purity copper sulfide powder is deposited on by Spiro- by Vacuum sublimation On OMeTAD layers, p-type Cu is obtainedxS films and the compound hole transmission layer of Spiro-OMeTAD layers, wherein, 1≤x≤2.
Described CuxS is CuS, Cu1.75S、Cu1.8S、Cu1.96S、Cu2One kind in S.
Described p-type CuxThe thickness of S films is 20-70nm.
Described hole transmission layer obtains especially by the following manner：Prepare the 2,2' containing 68mM first, 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) amino] two fluorenes of -9,9'- spiral shells, 26mM bis trifluoromethyl sulfonic acid Asia acid amides lithium and 55mM uncle 4- The Spiro-OMeTAD precursor solutions of butyl-pyridinium, solvent are that volume ratio is 10：1 chlorobenzene/acetonitrile mixture；Then will match somebody with somebody The Spiro-OMeTAD precursor solutions made are equably spin-coated on perovskite light-absorption layer with photoresist spinner, form Spiro- OMeTAD layers；Finally the vulcanization copper powders of high-purity are deposited on by Vacuum sublimation in vacuum coating equipment On Spiro-OMeTAD layers, p-type Cu is obtainedxS films and the compound hole transmission layer of Spiro-OMeTAD layers.
Described transparent conductive substrate is FTO electro-conductive glass or ITO electro-conductive glass；Described metal oxide electron transmission Layer is SnO2Film；Described perovskite light-absorption layer is CH3NH3PbI3Film；Described metal electrode layer is gold electrode.
Prepared by one kind above-mentioned is based on Spiro-OMeTAD/CuxThe side of the perovskite solar cell of S composite hole transporting layers Method, comprise the following steps：
(1) using semiconductor technology cleaning transparent conductive substrate, dried up with nitrogen；
(2) metal oxide electron transport layer is prepared in transparent conductive substrate after cleaning；
(3) perovskite light-absorption layer is prepared in metal oxide electron transport layer；
(4) first one layer of Spiro-OMeTAD layer of spin coating on perovskite light-absorption layer, then will be high-purity by Vacuum sublimation Degree vulcanization copper powders are deposited on Spiro-OMeTAD layers, obtain p-type CuxS films and the compound hole of Spiro-OMeTAD layers Transport layer, wherein, 1≤x≤2；
(5) evaporation prepares metal electrode layer on hole transmission layer.
The step (4) specifically includes following steps：The 2,2' containing 68mM, [(the 4- first of N, N- bis- of 7,7'- tetra- are prepared first Phenyl) amino] two fluorenes of -9,9'- spiral shells, 26mM bis trifluoromethyl sulfonic acid Asia acid amides lithium and 55mM 4- tert .-butylpyridines Spiro-OMeTAD precursor solutions, solvent are that volume ratio is 10：1 chlorobenzene/acetonitrile mixture；Then will prepare Spiro-OMeTAD precursor solutions are equably spin-coated on perovskite light-absorption layer with photoresist spinner, form Spiro-OMeTAD layers； The vulcanization copper powders of high-purity are finally deposited on by Spiro-OMeTAD layers by Vacuum sublimation in vacuum coating equipment On, obtain p-type CuxS films and the compound hole transmission layer of Spiro-OMeTAD layers.
The condition of Vacuum sublimation depositing copper sulphide powder is in step (4)：It is described vulcanization copper powders purity be 99.99%；Base vacuum is 10-4Pa；Heated current is 30~45A, and evaporation time is 30s~3min.
The step (2) specifically includes following steps：First by 0.025~0.2mol/L SnCl2·2H2O ethanol solutions Stirring 10~40 minutes, obtains metal oxide precursor solution；The metal oxide precursor solution whirl coating that will be prepared Machine is equably spin-coated in the transparent conductive substrate cleaned up；Finally annealed 1 hour under 180 degrees celsius, obtain gold Belong to Oxide Electron transport layer；
The step (3) specifically includes following steps：First by CH3NH3I and PbI2In molar ratio 1:1 is dissolved in dimethyl In formamide, stirred 24 hours under 60 degrees Celsius, obtain perovskite precursor solution；Then the perovskite presoma that will be prepared Solution is equably spin-coated in the metal oxide electron transport layer by annealing with photoresist spinner；Most after 60 degrees Celsius of annealing 2 Minute, annealed 5 minutes in 100 degrees Celsius.
It is above-mentioned to be based on Spiro-OMeTAD/CuxThe perovskite solar cell of S composite hole transporting layers is in photoelectric field Application.
The present invention has advantages below and beneficial effect：
(1) present invention prepares one kind by simple, the inexpensive method of step and is based on new organo-mineral complexing hole The perovskite solar cell of the efficient stable of transport layer, the device of preparation have fine electricity conversion and stability, Be advantageous to the application and popularization of technology.
(2) present invention uses hole transmission layer of the organic/inorganic composite material as perovskite solar cell, organic layer For Spiro-OMeTAD, inorganic layer is p-type semiconductor CuxS, the hole transmission layer holoe carrier of the organo-mineral complexing are moved Shifting rate is up to 0.1cm2V·s-1, for plane perovskite thin film cell photoelectric conversion efficiency up to 14%, device decay in 1000 hours is small In 10%, this better than individually uses Spiro-OMeTAD or CuxS is the device of hole transmission layer, is greatly increased too The photoelectric transformation efficiency and stability of positive energy battery.
(3) Spiro-OMeTAD/Cu of the present inventionxS composite hole transporting layers are very hydrophobic, and contact angle reaches 92 °, makes device Water stability greatly improve.
Brief description of the drawings
Fig. 1 is the device junction composition of perovskite solar cell, wherein, 1-transparent conductive substrate, 2-metal oxide Electron transfer layer, 3-perovskite light-absorption layer, 4-Spiro-OMeTAD/CuxS composite hole transporting layers, 5-metal electrode layer.
Fig. 2 is the current density voltage curve figure that perovskite solar cell is made in embodiment 1.
Fig. 3 is the current density voltage curve figure that perovskite solar cell is made in embodiment 2.
Fig. 4 is the current density voltage curve figure that perovskite solar cell is made in embodiment 3.
Fig. 5 is the current density voltage curve figure that perovskite solar cell is made in embodiment 4.
Fig. 6 is the current density voltage curve figure that perovskite solar cell is made in embodiment 5.
Fig. 7 is the current density voltage curve figure that perovskite solar cell is made in embodiment 6.
Fig. 8 is the current density voltage curve figure that perovskite solar cell is made in embodiment 7.
Fig. 9 is the stability test result figure that perovskite solar cell is made in embodiment 8.
Embodiment
The present invention is further described with reference to embodiment, the description be intended merely to better illustrate the present invention rather than It is limited.The present invention is not limited to particular example and embodiment as described herein.Technology in any this area Personnel are easy to be further improved without departing from the spirit and scope of the present invention and perfect, both fall within the present invention Protection domain.
Embodiment 1：
(1) cleaning of transparent conductive substrate：First FTO Conducting Glass is cleaned, be dried up in experiment.First will Electro-conductive glass cuts into required size with glass cutter, is first cleaned up with cleaning agent after well cutting, then use deionized water Rinse.Then put it into ultrasonic cleaner, spend in acetone, ethanol, ionized water and be cleaned by ultrasonic successively, finally use nitrogen again Air-blowing is done, you can obtains testing the clean transparent conductive substrate in required surface.
(2) preparation of metal oxide electron transport layer：By 0.1mol/L SnCl2·2H2O ethanol solutions stirring 30 Minute, obtain metal oxide precursor solution；The metal oxide precursor solution prepared is equably revolved with photoresist spinner Apply on conductive substrates, annealed one hour under 180 degrees celsius after getting rid of, obtain metal oxide electron transport layer.
(3) prepared by perovskite light-absorption layer：By CH3NH3I and PbI2In molar ratio 1:1 is dissolved in dimethylformamide, and 60 Stirred 24 hours under degree Celsius, obtain perovskite precursor solution；Then the perovskite precursor solution whirl coating that will be prepared Machine is equably spin-coated on the SnO by annealing2On electron transfer layer, first annealed 2 minutes at 60 c after getting rid of, then Annealed 5 minutes under 100 degrees Celsius, obtain perovskite light-absorption layer.
(4) preparation of organic cavity transmission layer：One layer of spin coating prepares in advance on perovskite light-absorption layer with photoresist spinner Organic cavity transmission layer solution (the 2,2' containing 68mM, 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) amino] -9,9'- spiral shells two The mixed solution of the 4- tert .-butylpyridines of fluorenes, 26mM bis trifluoromethyl sulfonic acid Asia acid amides lithium and 55mM.Solvent for use is volume Than for 10：1 chlorobenzene and the mixed liquor of acetonitrile).
(5) preparation of metal electrode layer：The sample for preparing hole transmission layer is placed in vacuum evaporation apparatus and passes through heat Evaporation technology evaporates one layer of gold film electrode.
(6) test：In AM1.5, active layer effective area is 0.09cm2Under conditions of battery is tested.Obtain Photoelectric transformation efficiency parameter is：Open-circuit voltage 1.07V, short-circuit current density 17.46mA/cm2, fill factor, curve factor 0.60, conversion effect Rate 11.21%.
Embodiment 2：
(1) cleaning of transparent conductive substrate：With embodiment 1.
(2) preparation of metal oxide electron transport layer：With embodiment 1.
(3) perovskite light-absorption layer (CH3NH3PbI3Layer) preparation：With embodiment 1.
(4) preparation of hole transmission layer：The same embodiment of preparation process of organic cavity transmission layer (Spiro-OMeTAD layers) 1, one layer of inorganic hole transporter Cu is then evaporated in vacuo on Spiro-OMeTAD layersxS：3mg vulcanization copper powders are weighed, are treated Thermal evaporation vacuum coating equipment base vacuum is better than 10-4Pa, electric current 40A are heated, evaporation time 30s.
(5) preparation of metal electrode layer：The sample for preparing hole transmission layer is placed in vacuum evaporation apparatus and passes through heat Evaporation technology evaporates one layer of gold film electrode.
(6) test：In AM1.5, active layer effective area is 0.09cm2Under conditions of to the perovskite solar energy for preparing Battery is tested.The photoelectric transformation efficiency parameter of acquisition is：Open-circuit voltage 1.1V, short-circuit current density 20.31mA/cm2, fill out Fill the factor 62.16, conversion efficiency 14%.
Embodiment 3：
(1) cleaning of transparent conductive substrate：With embodiment 1.
(2) preparation of metal oxide electron transport layer：With embodiment 1.
(3) perovskite light-absorption layer (CH3NH3PbI3Layer) preparation：With embodiment 1.
(4) preparation of hole transmission layer：One layer of inorganic hole transporter Cu is evaporated directly on perovskite light-absorption layerxS。 30mg vulcanization copper powders are weighed, treat that thermal evaporation vacuum coating equipment base vacuum is better than 10-4Pa, electric current 30A are heated, evaporation time 3 min。
(5) preparation of metal electrode layer：The sample of the hole transmission layer prepared is placed in vacuum evaporation apparatus and passed through Thermal evaporation process evaporates one layer of gold film electrode.
(6) test：In AM 1.5, active layer effective area is 0.09cm2Under conditions of to the perovskite sun for preparing Energy battery is tested.The photoelectric transformation efficiency parameter of acquisition is：Open-circuit voltage 0.6V, short-circuit current density 14.54mA/cm2, Fill factor, curve factor 0.36, conversion efficiency 3.14%.
Embodiment 4：
(1) cleaning of transparent conductive substrate：With embodiment 1.
(2) preparation of metal oxide electron transport layer：With embodiment 1.
(3) perovskite light-absorption layer (CH3NH3PbI3Layer) preparation：With embodiment 1.
(4) preparation of hole transmission layer：Organic cavity transmission layer Spiro-OMeTAD preparation is the same as embodiment 1；Then exist Evaporation prepares one layer of inorganic hole transporter Cu on Spiro-OMeTAD layersxS：10mg vulcanization copper powders are weighed, treat thermal evaporation Vacuum coating equipment base vacuum is better than 10-4Pa, electric current 45A are heated, evaporation time 1min.
(5) preparation of metal electrode layer：The sample for preparing hole transmission layer is placed in vacuum evaporation apparatus and passes through heat Evaporation technology evaporates one layer of gold film electrode.
(6) test：In AM1.5, active layer effective area is 0.09cm2Under conditions of to the perovskite solar energy for preparing Battery is tested, and the photoelectric transformation efficiency parameter of acquisition is：Open-circuit voltage 1.07V, short-circuit current density 19.68mA/cm2, Fill factor, curve factor 0.47, conversion efficiency 9.9%.
Embodiment 5：
(1) cleaning of transparent conductive substrate：With embodiment 1.
(2) preparation of metal oxide electron transport layer：With embodiment 1.
(3) perovskite light-absorption layer (CH3NH3PbI3Layer) preparation：With embodiment 1.
(4) preparation of hole transmission layer：Organic cavity transmission layer Spiro-OMeTAD preparation then exists with embodiment 1 One layer of inorganic hole transporter Cu is evaporated on Spiro-OMeTAD layersxS：5mg vulcanization copper powders are weighed, treat thermal evaporation Vacuum Deposition Film machine base vacuum is better than 10-4Pa, electric current 40A are heated, evaporation time 2min.
(5) preparation of metal electrode layer：The sample for preparing hole transmission layer is placed in vacuum evaporation apparatus and passes through heat Evaporation technology evaporates one layer of gold film electrode.
(6) test：In AM1.5, active layer effective area is 0.09cm2Under conditions of to the perovskite solar energy for preparing Battery is tested, and the photoelectric transformation efficiency parameter of acquisition is：Open-circuit voltage 1.07V, short-circuit current density 19.55mA/cm2, Fill factor, curve factor 0.56, conversion efficiency 11.71%.
Embodiment 6：
(1) cleaning of transparent conductive substrate：With embodiment 1.
(2) preparation of metal oxide electron transport layer：With embodiment 1.
(3) perovskite light-absorption layer (CH3NH3PbI3Layer) preparation：With embodiment 1.
(4) preparation of hole transmission layer：Organic cavity transmission layer Spiro-OMeTAD preparation then exists with embodiment 1 One layer of inorganic hole transporter Cu is evaporated on Spiro-OMeTAD layersxS：15mg vulcanization copper powders are weighed, treat thermal evaporation vacuum Coating machine base vacuum is better than 10-4Pa, electric current 42A are heated, evaporation time 2min30s.
(5) preparation of metal electrode layer：The sample for preparing hole transmission layer is placed in vacuum evaporation apparatus and passes through heat Evaporation technology evaporates one layer of gold film electrode.
(6) test：In AM1.5, active layer effective area is 0.09cm2Under conditions of to the perovskite solar energy for preparing Battery is tested.The photoelectric transformation efficiency parameter of acquisition is：Open-circuit voltage 1.06V, short-circuit current density 19.17mA/cm2, Fill factor, curve factor 0.48, conversion efficiency 9.75%.
Embodiment 7：
(1) cleaning of transparent conductive substrate：With embodiment 1.
(2) preparation of metal oxide electron transport layer：With embodiment 1.
(3) perovskite light-absorption layer (CH3NH3PbI3Layer) preparation：With embodiment 1.
(4) preparation of hole transmission layer：Not spin coating Spiro-OMeTAD, one layer of inorganic hole is evaporated directly on perovskite Transmission material CuxS：5mg vulcanization copper powders are weighed, treat that thermal evaporation vacuum coating equipment base vacuum is better than 10-4Pa, electric current 40A add Heat, evaporation time 50s.
(5) preparation of metal electrode layer：The sample for preparing hole transmission layer is placed in vacuum evaporation apparatus and passes through heat Evaporation technology evaporates one layer of gold film electrode.
(6) test：In AM1.5, active layer effective area is 0.09cm2Under conditions of to the perovskite solar energy for preparing Battery is tested.The photoelectric transformation efficiency parameter of acquisition is：Open-circuit voltage 0.64V, short-circuit current density 14.55mA/cm2, Fill factor, curve factor 0.48, conversion efficiency 4.47%.
Embodiment 8：
Test the device 30% humidity stability of lower 1000 hours in atmosphere.Contrast the Spiro-OMeTAD/ of the present invention CuxThe perovskite thin film photovoltaic cell of S composite hole transporting layers and the Spiro-OMeTAD hole transmission layer perovskites of routine are thin Film photovoltaic cell.Using Spiro-OMeTAD/CuxS device 1000h decay is less than 10%, using Spiro-OMeTAD device Part 1000h decays to 20%.

Claims (10)

1. one kind is based on Spiro-OMeTAD/CuxThe perovskite solar cell of S composite hole transporting layers, including electrically conducting transparent lining Bottom and stack gradually in the metal oxide electron transport layer in transparent conductive substrate, perovskite light-absorption layer, hole transmission layer with And metal electrode layer；It is characterized in that：Described hole transmission layer obtains in the following manner：First revolved on perovskite light-absorption layer One layer of Spiro-OMeTAD layer is applied, then high-purity copper sulfide powder is deposited on by Spiro-OMeTAD layers by Vacuum sublimation On, obtain p-type CuxS films and the compound hole transmission layer of Spiro-OMeTAD layers, wherein, 1≤x≤2.
2. according to claim 1 be based on Spiro-OMeTAD/CuxThe perovskite solar-electricity of S composite hole transporting layers Pond, it is characterised in that：Described CuxS is CuS, Cu1.75S、Cu1.8S、Cu1.96S、Cu2One kind in S.
3. according to claim 1 be based on Spiro-OMeTAD/CuxThe perovskite solar-electricity of S composite hole transporting layers Pond, it is characterised in that：Described p-type CuxThe thickness of S films is 20-70nm.
4. according to claim 1 be based on Spiro-OMeTAD/CuxThe perovskite solar-electricity of S composite hole transporting layers Pond, it is characterised in that：Described hole transmission layer obtains especially by the following manner：The 2,2' containing 68mM, 7,7'- are prepared first The fluorenes of four [N, N- bis- (4- methoxyphenyls) amino] -9,9'- spiral shells two, 26mM bis trifluoromethyl sulfonic acid Asia acid amides lithium and 55mM The Spiro-OMeTAD precursor solutions of 4- tert .-butylpyridines, solvent are that volume ratio is 10：1 chlorobenzene/acetonitrile mixture；Then The Spiro-OMeTAD precursor solutions prepared are equably spin-coated on perovskite light-absorption layer with photoresist spinner, form Spiro- OMeTAD layers；The vulcanization copper powders of high-purity are finally deposited on by Spiro- by Vacuum sublimation in vacuum coating equipment On OMeTAD layers, p-type Cu is obtainedxS films and the compound hole transmission layer of Spiro-OMeTAD layers.
5. according to claim 1 be based on Spiro-OMeTAD/CuxThe perovskite solar-electricity of S composite hole transporting layers Pond, it is characterised in that：Described transparent conductive substrate is FTO electro-conductive glass or ITO electro-conductive glass；Described metal oxide electricity Sub- transport layer is SnO2Film；Described perovskite light-absorption layer is CH3NH3PbI3Film；Described metal electrode layer is gold electricity Pole.
6. it is a kind of prepare described in claim any one of 1-5 based on Spiro-OMeTAD/CuxThe calcium titanium of S composite hole transporting layers The method of ore deposit solar cell, it is characterised in that comprise the following steps：
(1) using semiconductor technology cleaning transparent conductive substrate, dried up with nitrogen；
(2) metal oxide electron transport layer is prepared in transparent conductive substrate after cleaning；
(3) perovskite light-absorption layer is prepared in metal oxide electron transport layer；
(4) first one layer of Spiro-OMeTAD layer of spin coating on perovskite light-absorption layer, then by Vacuum sublimation by high-purity sulphur Change copper powders to be deposited on Spiro-OMeTAD layers, obtain p-type CuxS films and the compound hole transport of Spiro-OMeTAD layers Layer, wherein, 1≤x≤2；
(5) evaporation prepares metal electrode layer on hole transmission layer.
7. according to the method for claim 6, it is characterised in that the step (4) specifically includes following steps：Prepare first The fluorenes of 2,2' containing 68mM, 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) amino] -9,9'- spiral shells two, 26mM bis trifluoromethyl sulphur The Spiro-OMeTAD precursor solutions of the sub- acid amides lithium of acid and 55mM 4- tert .-butylpyridines, solvent are that volume ratio is 10：1 chlorine Benzene/acetonitrile mixture；Then the Spiro-OMeTAD precursor solutions prepared are equably spin-coated on perovskite with photoresist spinner On light-absorption layer, Spiro-OMeTAD layers are formed；Finally in vacuum coating equipment by Vacuum sublimation by the sulphur of high-purity Change copper powders to be deposited on Spiro-OMeTAD layers, obtain p-type CuxS films and the compound hole transport of Spiro-OMeTAD layers Layer.
8. the method according to claim 6 or 7, it is characterised in that：Vacuum sublimation depositing copper sulphide powder in step (4) End condition be：The purity of the vulcanization copper powders is 99.99%；Base vacuum is 10-4Pa；Heated current is 30~45A, is steamed The hair time is 30s~3min.
9. the method according to claim 6 or 7, it is characterised in that：The step (2) specifically includes following steps：First By 0.025~0.2mol/L SnCl2·2H2O ethanol solutions stir 10~40 minutes, obtain metal oxide precursor solution； The metal oxide precursor solution prepared is equably spin-coated in the transparent conductive substrate cleaned up with photoresist spinner；Most Annealed 1 hour under 180 degrees celsius afterwards, obtain metal oxide electron transport layer；
The step (3) specifically includes following steps：First by CH3NH3I and PbI2In molar ratio 1:1 is dissolved in dimethyl formyl In amine, stirred 24 hours under 60 degrees Celsius, obtain perovskite precursor solution；Then the perovskite precursor solution that will be prepared Equably it is spin-coated on photoresist spinner in the metal oxide electron transport layer by annealing；Most annealed 2 minutes after 60 degrees Celsius, Annealed 5 minutes in 100 degrees Celsius.
10. described in claim any one of 1-5 based on Spiro-OMeTAD/CuxThe perovskite sun of S composite hole transporting layers Can application of the battery in photoelectric field.
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