CN104393177B - Solar cell based on Perovskite Phase organic metal halide and preparation method thereof - Google Patents
Solar cell based on Perovskite Phase organic metal halide and preparation method thereof Download PDFInfo
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- CN104393177B CN104393177B CN201410579487.3A CN201410579487A CN104393177B CN 104393177 B CN104393177 B CN 104393177B CN 201410579487 A CN201410579487 A CN 201410579487A CN 104393177 B CN104393177 B CN 104393177B
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- 229910001507 metal halide Inorganic materials 0.000 title claims abstract description 45
- 150000005309 metal halides Chemical class 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 75
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000004065 semiconductor Substances 0.000 claims abstract description 44
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 31
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 28
- 229960004592 isopropanol Drugs 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000000137 annealing Methods 0.000 claims abstract description 6
- 239000002120 nanofilm Substances 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 29
- 230000005540 biological transmission Effects 0.000 claims description 14
- 239000010409 thin film Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000010408 film Substances 0.000 claims description 9
- 230000026030 halogenation Effects 0.000 claims description 7
- 238000005658 halogenation reaction Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 4
- 230000003746 surface roughness Effects 0.000 claims description 4
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000000280 densification Methods 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 40
- 239000000460 chlorine Substances 0.000 abstract description 19
- 239000013078 crystal Substances 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 229910052801 chlorine Inorganic materials 0.000 abstract description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract description 6
- 239000007791 liquid phase Substances 0.000 abstract description 5
- -1 halogen ion Chemical class 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 229910052740 iodine Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 238000010345 tape casting Methods 0.000 description 3
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- PEWKGUDDDAQQCO-UHFFFAOYSA-M N.[I-].C[N+]1=CC=CC=C1 Chemical compound N.[I-].C[N+]1=CC=CC=C1 PEWKGUDDDAQQCO-UHFFFAOYSA-M 0.000 description 1
- NPNMHHNXCILFEF-UHFFFAOYSA-N [F].[Sn]=O Chemical compound [F].[Sn]=O NPNMHHNXCILFEF-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- DRHWBADNSVQEGH-UHFFFAOYSA-L diiodyloxylead Chemical compound O=I(=O)O[Pb]OI(=O)=O DRHWBADNSVQEGH-UHFFFAOYSA-L 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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
- H10K30/80—Constructional details
- H10K30/81—Electrodes
-
- 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
-
- 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
- H10K30/80—Constructional details
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a kind of solar cell based on Perovskite Phase organic metal halide and preparation method thereof, using fine and close titanium dioxide nano-film as electron transfer layer in the solar cell, the recombination-rate surface between electron transfer layer and semiconductor layer can be reduced, the photoelectric conversion rate of photovoltaic device is improved；And the solar cell of the structure can prepare Perovskite Phase organic metal halide semiconductor layer using the full liquid phase synthesizing method of normal temperature and pressure, save energy consumption needed for preparation, reduce the cost of solar cell, during the organic metal halide semiconductor layer of Perovskite Phase is prepared, using two-step synthesis method, pass through the PbX formed between two steps to the first step2Layer carries out second step synthesis again after being soaked in 2 propanol solutions, so as to be mixed with method using chlorine and iodine, by the control to halogen ion concentration and annealing temperature, so during liquid-phase precipitation optimize crystal growth, improve the photovoltaic conversion efficiency of solar cell.
Description
Technical field
The present invention relates to field of photovoltaic technology, and in particular to a kind of solar energy based on Perovskite Phase organic metal halide
Battery and preparation method thereof.
Background technology
Gradually strengthen with progressively exhausted and society the environmental protection consciousness of fossil energy, solar energy power generating has
Chance substitutes fossil energy to meet the electricity needs of people's daily life.Photovoltaic cell is that luminous energy is directly translated into electricity by one kind
The electronic device of energy.
In photovoltaic field, silica-based solar cell has been successfully realized commercialization.However, silicon substrate during silicon materials
The basis of solar cell, and the purification of silicon and production process usually require to carry out under high temperature and high pressure environment, power consumption is high, causes
The high cost of silica-based solar cell.
In recent years, with the further investigation to photovoltaic semiconductors material, the organic metal halide using Perovskite Phase is generation
The novel thin film solar cell of table progressively possesses industrialized possibility.The organic metal halide solar energy of Perovskite Phase
Battery is lied prostrate, with good photovoltaic efficiency.Yang Yang professors team such as UCLA universities successfully develops current laboratory light
Organic metal halide solar-energy photo-voltaic cell of the conversion efficiency highest based on Perovskite Phase is lied prostrate, its photovoltaic conversion efficiency is up to
19.3%.
The organic metal halide solar-energy photo-voltaic cell of existing Perovskite Phase is generally stepped construction, from bottom to up successively
Including substrate, electron transfer layer, Perovskite Phase organic metal halide semiconductor layer, hole transmission layer and to electrode.
Document J.Burschka, N.Pellet, S.J.Moon, R.Humphry-Baker, P.Gao,
M.K.Nazeeruddin, M.Gratzel, Nature, 2013,499,316 disclose a kind of Perovskite Phase organic metal halide
The preparation method of semiconductor layer, it is specific as follows：20~40nm compact titanium dioxide layer is formed first on substrate, then in the layer
It is upper that nano titania porous structure layer of the granular size for 20nm is formed by spin-coating method, it is then porous in nano titania
Lead iodide layer is sprawled on structure sheaf, finally by lead iodide (PbI2) layer and methylpyridinium iodide ammonia (CH3NH3I) calcium titanium is made in solution reaction
Ore deposit phase organic metal iodide (CH3NH3PbI3) semiconductor layer.
This method has the following disadvantages：In semiconductor forming process, its used halogens is iodine, due to iodine
High-dissolvability in the solution, causes the growth rate for changing semiconductor crystal to be difficult to be controlled, finally obtained semiconductor layer
Crystallite dimension it is less than normal, there are a large amount of crystal boundaries and be unfavorable for the transmission in electronics and hole, thus reduce the photovoltaic of semiconductor
Performance.
In addition, to ensure that device surface is completely covered in Perovskite Phase organic metal halide, existing electron transfer layer is more
Titanium dioxide nano-film using rough surface, with loose structure.Pass through spin coating titania nanoparticles formation dioxy
Change titanium nano-porous structure, complex process is unfavorable for carrying out commercialization large-scale production.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of solar energy based on Perovskite Phase organic metal halide
Battery and preparation method thereof.
A kind of solar cell based on Perovskite Phase organic metal halide, includes substrate, electronics successively from bottom to up
Transport layer, Perovskite Phase organic metal halide semiconductor layer, hole transmission layer and to electrode layer, the electron transfer layer is causes
Close titanium dioxide nano-film, the surface roughness of the compact titanium dioxide nano thin-film is less than 20nm.
The test condition of surface roughness is as follows：
Tester is Alpha-step D-500 step instruments, 1 micron of probe radius, probe pressure 2mg, error range
5nm。
The effect of electron transfer layer is to form Ohmic contact with electro-conductive glass, plays a part of electric transmission.Simultaneously can also
Enough change the imbibition characteristic of conductive glass surface, reach the effect of the semiconductor light-absorption layer pattern of control cover it.Simultaneously
Energy isolation of semiconductor layer and electrode, play a part of passivated surface complex centre.
Compared with the electron transfer layer of existing nano titania loose structure, compact titanium dioxide nano thin-film is more suitable
The growth of Perovskite Phase organic metal halide crystal is closed, crystalline size is added, reduces the quantity of crystal boundaries.In addition,
Compact titanium dioxide nano thin-film also reduces its contact area with Perovskite Phase organic metal halide crystal, is conducive to drop
Recombination-rate surface between low electron transfer layer and semiconductor layer, so improve photovoltaic device open-circuit voltage and filling because
Son, reaches the effect for improving photoelectric conversion rate.
Substrate, electron transfer layer, the material of hole transmission layer and thickness can be using existing in the solar cell of the present invention
Some materials and thickness.Wherein substrate is generally transparent conducting glass, such as indium tin oxide (ITO, Indium Tin Oxides) or
The electro-conductive glass of person's fluorine tin-oxide (FTO, Fluorine Doped Tin Oxide).The material of hole transmission layer is Spiro-
OMeTAD (2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) amino]-fluorenes of 9,9'- spiral shells two), thickness is 300~500nm.
Electrode layer 5 can use Ag (silver), Au (gold) or conductive carbon, and thickness is 60nm.
The thickness of the electron transfer layer is 150~350nm.
In the solar cell of the present invention, electron transfer layer plays conduction electronics and completely cuts off hole, it is necessary to according to electricity
The structure and electron transport property reasonable set thickness of sub- transport layer.The usage amount of too thick increase raw material and add need not
The internal resistance wanted, the too thin risk that completely can not uniformly cover substrate surface, there are shorted devices.
The Perovskite Phase organic metal halide is CH3NH3PbI3-nCln, n is 0.005~0.1.
Contain a small amount of chlorine (Cl) in Perovskite Phase organic metal halide, at the initial stage generated in crystal, Cl ions are due to molten
Xie Du is relatively low, it is easier to is separated out from solution and combines to form nucleus with lead ion, and then can promote crystal growth, is optimized
Semiconductor crystal, improve solar cell conversion efficiency.
Present invention also offers the preparation method of above-mentioned solar cell, electron transfer layer, calcium are sequentially prepared on substrate
Titanium ore phase organic metal halide semiconductor layer, hole transmission layer and to electrode layer, are made by the steps electron transfer layer：
Substrate is surface-treated, then makes the ethanol solution of titanium dioxide film forming on the substrate after surface treated
And calcined, that is, obtain compact titanium dioxide nano thin-film.
Preferably, being surface-treated using surfactant and ozone-plasma to substrate.Lived first by surface
Property agent cleaning substrate, then recycle ozone-plasma method etching transparent substrates surface.
Surface treatment mainly for thoroughly removing may adhere to surface organic pollution and increase can be played
The surface work function of substrate, the purpose of the surface wetting characteristic of improvement substrate, so that reaching improves the electronics being grown on substrate
The quality of transport layer, plays reduction intrinsic impedance, improves the effect of the photovoltaic conversion efficiency of solar cell.
The ethanol solution of titanium dioxide film forming on the substrate after surface treated is made using knife coating in the present invention, now
The film layer of formation is processing amorphous state.The organic solvent of residual in amorphous state film is removed by calcination processing and made
The amorphous state layer crystallization of titanium dioxide, obtains the titanium dioxide nano-film of crystalline state.
Preferably, the calcining heat is 450~600 DEG C.Excessive titanium dioxide can be formed when calcining heat is too high
Titanium nucleus number, causes the monocrystalline size reduction of titanium dioxide, crystal boundaries increase, and then reduce electrical conductivity；Calcining heat
When too low, then it can not effectively make the mono-crystalline structures to form titanium dioxide, cause low conductivity.
The Perovskite Phase organic metal halide semiconductor layer, which is made by the steps, to be obtained：
(1) PbX is sprawled on described electron transfer layer2DMF (N, N-dimethylformamide N, N- dimethyl
Formamide) solution, form PbX after drying2Layer, the X is Cl or I；
(2) by PbX2It is placed on CH3NH3In Y (methylammonium halide, methyl halogenation ammonia) 2- propanol solutions
20~60s is soaked, in CH after taking-up3NH3Made annealing treatment in Y saturation atmosphere and obtain Perovskite Phase organic metal halide
Semiconductor layer, annealing temperature is 100~150 DEG C, 10~25min of the time under；
Work as PbX2For PbI2When, CH3NH3Y is CH3NH3Cl；Work as PbX2For PbCl2And PbI2Mixture when, CH3NH3Y is
CH3NH3 I。
Step (1) is mixed with the two kinds of different halogens (iodine and chlorine) used in (2), has taken into account iodide high-dissolvability
Advantage and chloride crystals grow controllable advantage, organic gold that thickness and crystal structure are all optimized can be ultimately formed
Belong to halide semiconductor layer.
First by the PbX of step (1) formation in the step (2)2Layer is placed in again after soaking 1~2s in 2- propanol solutions
CH3NH3Y 2- propanol solutions.
Prior art can not overcome organic metal chlorine caused by the low solubility of lead chloride in organic solvent due to it
The problem of compound semiconductor growth layer is difficult, therefore prior art can only use the higher lead iodide of solubility.Although using iodine
Thickness 500n semiconductor layer can be formed by changing lead, but be due to that the growth course of lead iodide crystal is difficult to control to, Perovskite Phase
Organic metal halide semiconductor layer can not uniform overlay electronic transport layer, cause photovoltaic device efficiency to decline.Therefore, in order to
Make to have that iodate lead layer is complete, uniform overlay electronic transmission layer surface, it is necessary to extra to use nano titania porous structure layer.
Although surface coverage can be improved by introducing nano titania porous structure layer, loose structure, which can also cause, is covered in it
On semiconductor layer crystal growth it is irregular, cause the increase of the surface recombination between semiconductor layer and titanium dioxide layer, and then
Reduce the photovoltaic efficiency of device.
The present invention uses two-step method, forms the halogenation lead layer of thickness 500nm amorphous state in step (1) first, then
Halogenation lead layer is surface-treated by using 2- propanol solutions, on the one hand can change the table of the halogenation lead layer of unformed shape
Face characteristic, on the other hand, can wash away the DMF solution remained in halogenation lead layer using 2- propanol solutions, make lead halide
Layer can effectively and CH3NH3Y is combined, and then makes CH3NH3Y molecules are easier to enter halogenation lead layer participation crystal growth, are formed with
Machine metal halide semiconductor layer.Pass through the CH at 100~150 DEG C again3NH3Annealed 15 minutes in Y saturation atmosphere, reach control
The purpose of crystallization temperature processed, highly crystalline quality.
Preferably, working as CH3NH3Y is CH3NH3Cl and CH3NH3During I mixture, CH3NH3Cl and CH3NH3I's rubs
You are than being 1:(1~9).Further preferably, CH3NH3Cl and CH3NH3I mol ratio is 1:9.
Use the PbX of high concentration2DMF solution be in order to scraping blade method can be used disposably to sprawl solution and formed
500nm or so PbX2, PbX in the step (1)2DMF solution in PbX2Concentration be 0.5~1mol/L.It is further excellent
PbX in choosing, the step (1)2DMF solution in PbX2Concentration be 1mol/L.Now, PbX is worked as2For PbI2When, PbI2It is dense
Spend for 1mol/L；Work as PbX2For PbCl2And PbI2Mixture when, PbCl2Concentration be 0.1mol/L, PbI2Concentration be
0.9mol/L。
Further preferably, the CH3NH3CH in Y 2- propanol solutions3NH3Y concentration is 5~15mg/ml, is preferably
10mg/ml。CH3NH3Y concentration can effectively control the speed of Crystallization to reach the purpose for optimizing crystal structure.Adjust chlorine
Concentration of the ion in preparation process can play the important function of optimization crystal structure.
Compared with prior art, the advantage of the invention is that：
(a) using fine and close titanium dioxide nano-film group as electron transfer layer, electron transfer layer and calcium titanium are advantageously reduced
The contact area of ore deposit phase organic metal halide crystal, it is possible to decrease the surface recombination speed between electron transfer layer and semiconductor layer
Rate, it is possible to increase the open-circuit voltage and fill factor, curve factor of photovoltaic device, and then improve the effect of photoelectric conversion rate；
(b) Perovskite Phase organic metal halide semiconductor layer uses the full liquid phase synthesizing method of normal temperature and pressure, reduces preparation
Required energy consumption, reduces the cost of solar cell；
(c) during the organic metal halide semiconductor layer of Perovskite Phase is prepared, using two-step synthesis method, by
To the PbX of first step formation between two steps2Layer carries out second step synthesis again in 2- propanol solutions after soaking layer, so as to adopt
Method is mixed with two kinds of halogens (chlorine and iodine), it is excellent by the control to halogen ion concentration, and then during liquid-phase precipitation
Change the growth of crystal, and then the quality of Perovskite Phase organic metal halide semiconductor layer can be improved, be further able to improve
The photovoltaic conversion efficiency of solar cell.
Brief description of the drawings
Fig. 1 is the structure chart of the solar cell of the present embodiment；
Fig. 2 is the i-v curve of solar cell.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be described in detail.
Embodiment 1
Fig. 1 for the present embodiment solar cell structure chart, from bottom to up successively include substrate 1, electron transfer layer 2,
Perovskite Phase organic metal halide semiconductor layer 3, hole transmission layer 4 and to electrode layer 5.
Substrate 1 is indium tin oxide glass in the present embodiment.Electron transfer layer 2 is compact titanium dioxide nano thin-film, its
Surface roughness is less than 10nm, and thickness is 350nm.The thickness of Perovskite Phase organic metal halide semiconductor layer 3 is 350nm,
And the Perovskite Phase organic metal halide is CH3NH3PbI3-nCln, n is 0.05 in the present embodiment.The material of hole transmission layer 4
For Spiro-OMeTAD (2,2', 7,7'- tetra- [N, N- bis- (4- methoxyphenyls) amino]-fluorenes of 9,9'- spiral shells two), thickness is
350nm.The material of electrode layer 5 is Au, and thickness is 60nm.
The solar cell of the present embodiment is made by the steps：
(S1) electron transfer layer is prepared on substrate
First by surfactant washing substrate, ozone-plasma processing substrate surface is then recycled, after the completion of, adopt
Make film that the ethanol solution of titanium dioxide is formed after 350nm on surface treated substrate with knife coating and forged at 450 DEG C
Burn 20 minutes, that is, obtain compact titanium dioxide nano thin-film as electron transfer layer；
(S2) Perovskite Phase organic metal halide semiconductor layer is prepared on the electron transport layer
(1) PbX is sprawled on the electron transport layer2DMF solution, dry after formed 300nm after PbX2Layer, X is Cl or I；
(2) by PbX2It is placed on CH3NH320s is soaked in Y 2- propanol solutions, taking-up is placed in 150 DEG C of CH3NH3Y's is full
The CH that room temperature obtains Perovskite Phase is cooled to after the 15min that annealed in atmosphere3NH3PbI2.95Cl0.05Film is used as Perovskite Phase
Organic metal halide semiconductor layer；Work as PbX2For PbI2When, CH3NH3Y is CH3NH3Cl；Work as PbX2For PbCl2And PbI2It is mixed
During compound, CH3NH3Y is CH3NH3I。
X is I in the present embodiment, and Y is Cl.PbX2DMF solution in PbX2Concentration be 460mg/ml (i.e. 1mol/L),
CH3NH3CH in Y 2- propanol solutions3NH3Y concentration is 10mg/ml.
(S3) using the Spiro- that formation thickness is 350nm on knife coating Perovskite Phase organic metal halide semiconductor layer
OMeTAD films are as hole transmission layer, and wherein Spiro-OMeTAD structural formula is as follows：
(S4) thickness 60nm Au is deposited with as to electrode layer on hole transmission layer using thermal evaporation, by each layer (substrate,
Electron transfer layer, Perovskite Phase organic metal halide semiconductor layer and hole pass transport layer) assemble to form solar energy
Battery.
The solar cell of the present embodiment is in 100mW/cm2AM1.5 sunshines under i-v curve such as Fig. 2 in it is real
Apply shown in the corresponding curve of example 1.Its volt-ampere of performance curve is shown in Table 1.
Table 1
Embodiment 2
The structure of the solar cell of the present embodiment is same as Example 1, and preparation method is same as Example 1, and institute is different
Be that step (S2) prepares Perovskite Phase organic metal halide semiconductor layer on the electron transport layer when, will in step (2)
PbX2It is placed on CH3NH3Soaked in Y 2- propanol solutions before 20s first by PbX2Be placed in 2- propanol solutions soak 1~2s with
To PbX2Layer is surface-treated, and the substrate of step (1) directly is placed in into 1~2s of immersion in 2- propanol solutions during practical operation.
The solar cell of the present embodiment is in 100mW/cm2AM1.5 sunshines under i-v curve such as Fig. 2 in it is real
Apply shown in the corresponding curve of example 2.Its volt-ampere of performance curve is shown in Table 1.
Embodiment 3
The structure of the solar cell of the present embodiment is same as Example 1, and preparation method is identical in embodiment 2, and institute is different
Be PbX in step (1)2For PbCl2And PbI2Mixture, and PbCl2And PbI2Mixture mol ratio be 1:9.Step
Suddenly the CH in (2)3NH3Y is CH3NH3 I。
The solar cell of the present embodiment is in 100mW/cm2AM1.5 sunshines under i-v curve such as Fig. 2 in it is real
Apply shown in the corresponding curve of example 3.Its volt-ampere of performance curve is shown in Table 1.
Comparative example
The structure of the solar cell of this comparative example is same as Example 1, except that electron transfer layer 2 is from the bottom to top
Include compact titanium dioxide nano thin-film and poriferous titanium dioxide nano thin-film successively.
Preparation method is same as Example 1, except that during the electron transfer layer of step (S1) formation titanium dioxide, needing
Nano titania porous structure layer is re-formed in fine and close titanic oxide electronic transport layer, it is concretely comprised the following steps 20nm
The titania nanoparticles (model Dyesol 18NRT, Dyesol) of size are dissolved in ethanol solution that (concentration is 2:7 matter
Amount ratio), using spin-coating method formation 200nm liquid-phase precipitation layers, then under 500 DEG C of environment, annealing is cooled to room temperature after 15 minutes, most
End form is into nano titania porous structure layer (i.e. poriferous titanium dioxide nano thin-film).Step (S2) is made on the electron transport layer
During standby Perovskite Phase organic metal halide semiconductor layer, X and Y are I (i.e. PbX2For PbI2, CH3NH3Y is CH3NH3I), most
End form into Perovskite Phase organic metal halide semiconductor layer be CH3NH3PbI3Film.
It is real in i-v curve such as Fig. 2 of the solar cell of this comparative example under 100mW/cm2 AM1.5 sunshines
Apply shown in the corresponding curve of example 3.Its volt-ampere of performance curve is shown in Table 1.
From Fig. 2 and table 1, open-circuit voltage can be increased using the combination of different halogens, solar-electricity is improved
The photovoltaic conversion efficiency in pond.Perovskite Phase organic metal halide is prepared on electron transfer layer in solar cell preparation process
During semiconductor layer, by being simply surface-treated (first PbX2 is placed on 1~2s of immersion in 2- propanol solutions), can effectively it reduce
Increase open-circuit voltage and fill factor, curve factor while manufacturing cycle, improve battery efficiency.
Technical scheme and beneficial effect are described in detail above-described embodiment, Ying Li
Solution is to the foregoing is only presently most preferred embodiment of the invention, is not intended to limit the invention, all principle models in the present invention
Interior done any modification, supplement and equivalent etc. are enclosed, be should be included within the scope of the present invention.
Claims (4)
1. a kind of preparation method of the solar cell based on Perovskite Phase organic metal halide, is included on substrate and makes successively
Standby electron transfer layer, Perovskite Phase organic metal halide semiconductor layer, hole transmission layer and to electrode layer, it is characterised in that
The electron transfer layer is made by the steps：
Substrate is surface-treated, the ethanol solution of titanium dioxide film forming and is carried out on surface treated substrate
Calcining, that is, obtain compact titanium dioxide nano thin-film；
The Perovskite Phase organic metal halide semiconductor layer, which is made by the steps, to be obtained：
(1) PbX is sprawled on described electron transfer layer2DMF solution, dry after form PbX2Layer, the PbX2For PbI2, or
For PbCl2And PbI2Mixture；
(2) by PbX2It is placed on CH3NH320~60s is soaked in Y 2- propanol solutions, in CH after taking-up3NH3Enter in Y saturation atmosphere
Row annealing obtains Perovskite Phase organic metal halide semiconductor layer, and annealing temperature is 100~150 DEG C, time
For 10~25min；
Work as PbX2For PbI2When, CH3NH3Y is CH3NH3Cl；Work as PbX2For PbCl2And PbI2Mixture when, CH3NH3Y is
CH3NH3I；
First by the PbX of step (1) formation in the step (2)2Layer is placed in CH again after soaking 1~2s in 2- propanol solutions3NH3Y
2- propanol solutions；
The solar cell prepared, includes substrate, electron transfer layer, Perovskite Phase organic metal halogenation successively from bottom to up
Thing semiconductor layer, hole transmission layer and to electrode layer, the electron transfer layer are compact titanium dioxide nano thin-film, the densification
The surface roughness of titanium dioxide nano-film is less than 20nm；The Perovskite Phase organic metal halide is CH3NH3PbI3- nCln, n is 0.005~0.1；The thickness of the electron transfer layer is 150~350nm.
2. the preparation method of solar cell as claimed in claim 1, it is characterised in that the calcining heat is 450~600
℃。
3. the preparation method of solar cell as claimed in claim 2, it is characterised in that PbX in the step (1)2DMF
PbX in solution2Concentration be 0.5~1mol/L.
4. the preparation method of solar cell as claimed in claim 3, it is characterised in that the CH3NH3Y 2- propanol solutions
Middle CH3NH3Y concentration is 5~15mg/ml.
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| CN105280819A (en) * | 2015-06-16 | 2016-01-27 | 郑州大学 | Planar heterojunction perovskite solar cell and preparation method thereof |
| CN104993060B (en) * | 2015-07-20 | 2017-08-25 | 苏州大学 | Annealing-free perovskite type solar cell and preparation method thereof |
| CN105206749A (en) * | 2015-08-31 | 2015-12-30 | 中国电子科技集团公司第四十八研究所 | Perovskite solar cell and preparation process thereof |
| US10790096B2 (en) * | 2015-09-11 | 2020-09-29 | Okinawa Institute Of Science And Technology School Corporation | Formation of lead-free perovskite film |
| EP3416206B1 (en) * | 2017-06-16 | 2022-10-05 | Korea Research Institute of Chemical Technology | Perovskite solar cell with wide band-gap and fabrication method thereof |
| CN107452879A (en) * | 2017-09-13 | 2017-12-08 | 武汉理工大学 | A kind of perovskite solar cell with silver/titanium dioxide nano composite material dense film |
| RU2692110C1 (en) * | 2018-09-20 | 2019-06-21 | АО "Красноярская ГЭС" | Method of forming perovskite-like material film |
| RU2694086C1 (en) * | 2018-12-25 | 2019-07-09 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" | Hybrid photoconverter modified with maxenes |
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