CN110265551A - A kind of perovskite structure solar cell and preparation method thereof - Google Patents
A kind of perovskite structure solar cell and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 115
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000004528 spin coating Methods 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 29
- 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 claims abstract description 27
- 230000031700 light absorption Effects 0.000 claims abstract description 12
- 230000005540 biological transmission Effects 0.000 claims abstract description 9
- 238000012546 transfer Methods 0.000 claims abstract description 8
- 238000005530 etching Methods 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 238000004381 surface treatment Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 60
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 claims description 37
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 29
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 238000000137 annealing Methods 0.000 claims description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
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- 239000012046 mixed solvent Substances 0.000 claims description 7
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 125000000468 ketone group Chemical group 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 230000005525 hole transport Effects 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 3
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- 238000010422 painting Methods 0.000 claims 1
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- 238000002441 X-ray diffraction Methods 0.000 description 13
- 238000000103 photoluminescence spectrum Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229920002120 photoresistant polymer Polymers 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 5
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- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 3
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- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 230000009102 absorption Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- -1 I-(RX=0.110nm) Chemical class 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 238000002242 deionisation method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000004941 influx Effects 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
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- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000005945 translocation Effects 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of perovskite structure solar cells and preparation method thereof.The perovskite structure solar cell successively includes FTO substrate, TiO2Electron transfer layer, CH3NH3PbI3‑xClxPerovskite light-absorption layer, Spiro-MeOTAD hole transmission layer and Ag electrode, wherein X 0-3.Preparation method includes etching, cleaning FTO substrate, and the barrier layer spin coating TiO2, surface treatment are formed using one-step method or two-step method perovskite on substrate, spin coating Spiro-MeOTAD, Ag are deposited.Perovskite solar cell prepared by the present invention has many advantages, such as that preparation condition is simple, light absorption is strong, low energy consumption, incident photon-to-electron conversion efficiency is high.
Description
Technical field
The present invention relates to a kind of perovskite structure solar cells, belong to technical field of solar cells.
Background technique
Perovskite structure general formula can use ABX3It indicates, generally cube or octahedral structure.In perovskite crystal
In, A ion is located at the center of cubic cell, is surrounded by 12 X ions into coordination cuboctahedron, ligancy 12；B ion position
It is pushed up in the angle of cubic cell, ligancy 6 octahedra at coordination is surrounded by 6 X ions, as shown in the figure.Wherein, A ion and X
Ionic radius is close, collectively forms cubic closest packing (a is octahedron, b cuboctahedron).
The stability of perovskite crystal and the structure being likely to form are mainly by the tolerance factor (t) and the octahedra factor
(μ) is determined.WhereinRA, RB, RX refer respectively to A, B, X original
The radius of son.When meeting 0.81 < t < 1.11 and 0.344 < μ < 0.90, ABX3Compound is perovskite structure；Wherein t=1.0
When formed the highest cubic lattice of symmetry, when t is positioned at 0.89-1.0 between, lattice be rhombohedral structure (trigonal system)；
As t < 0.96, symmetry is changed into orthohormbic structure.
In perovskite solar cell, A ion is commonly referred to as organic cation, and the most common are CH3NH3 +(RA=
0.18nm)；B ion refers to metal cation, mainly there is Pb2+(RB=0.119nm) and Sn2+(RB=0.110nm)；X ion
For halogen family anion, i.e. I-(RX=0.110nm), Cl-(RX=0.181nm) and Br-(RX=0.196nm).
Compared with existing solar cell technology, perovskite material and perovskite solar cell have the advantage that (1) delustring
Coefficient is high and band gap width is suitable.Methylamine lead iodide (CH3NH3PbI3) band gap be about 1.5eV, under AM1.5 solar irradiation
Best band gap magnitude 1.45eV is very close, has high extinction coefficient.Meanwhile passing through doping halogen atom or metal cation
Etc. means, can further adjust the band gap of perovskite material.(2) excellent bipolarity carrier transport properties, in perovskite
The photo-generate electron-hole in portion to can be achieved at room temperature interface and in vivo separation.(3) carrier mobility is high.Wherein electronics
Mobility is about 7.5cm2/ (VS), hole mobility are about 12.5cm2/(V·S).(4) diffusion length is big.(5) open-circuit voltage
It is higher.
Perovskite solar battery can be divided into meso-hole structure and plane forward structure (N-i-P), plane transoid knot at present
Structure (P-i-N).Different device architectures corresponds to different working mechanisms, is conducive to perovskite too to the research of device working mechanism
The promotion of positive energy battery device performance.
According to the difference in carrier moving direction, plane perovskite battery can be roughly divided into two classes: one kind is P-i-N
Type structure battery；One is N-i-P type structure batteries.Calcium titanium ore bed is contacted as photoelectric conversion layer in this kind of structure
The transmission for being respectively completed electrons and holes for two layers.
The semiconductive polymer material of many classics, exciton diffusion length is about 10nm, and organic-inorganic perovskite
CH3NH3Pb3-xClxExciton diffusion length be more than 1 μm, this to have under the premise of not influencing exciton transfer sufficiently thick
Have active layer to realize sufficient light absorption, this is the basis that planar structure is achieved.
By the inspiration of electrostrictive polymer pool structure, planar structure perovskite solar battery can also use reciprocal form structure.It should
In class battery structure, hole transport to transparency conducting layer, and electron-transport is to metal electrode layer.Most common hole mobile material
It is PEDOT:PSS, electron transfer layer is usually fullerene-based material.
Existing perovskite structure prototype battery is influenced by preparation method and its structure, and incident photon-to-electron conversion efficiency is generally 3.8%,
It is relatively inaccessible to 8-10% or more.
Summary of the invention
The technical problems to be solved by the present invention are: how to improve the photoelectric conversion efficiency of perovskite solar battery.
In order to solve the above-mentioned technical problems, the present invention provides a kind of preparation method of perovskite structure solar cell,
It is characterized in that, comprising the following steps:
Step 1): etching FTO substrate: after FTO glass is cut, using adhesive plaster by intermediate locality protection rise as
Electrode, other regions are dipped in zinc powder with hydrochloric acid and are performed etching until etch areas becomes transparent；
Step 2): cleaning FTO substrate: the FTO substrate that will have been etched removes protection adhesive plaster, is carried out just with surfactant
Step washes removing surface impurity by rubbing with the hands, then by FTO substrate be sequentially placed into cleaning agent, deionized water, acetone, alcohol, in deionized water
Ultrasonic cleaning；
Step 3): spin coating TiO2Barrier layer: the FTO substrate surface cleaned is dried up, and being sent into pretreatment chamber makes it generate O2
Plasma, using n-butyl alcohol will be bis- (levulinic ketone group) diisopropyl metatitanic acid ester solution dilute to obtain TiO2Precursor solution,
By TiO2Precursor solution is spin-coated on FTO substrate, is then annealed；
Step 4): surface treatment: by TiCl4It is added in mixture of ice and water, is configured to TiCl4Aqueous solution obtains step 3)
Substrate be immersed in TiCl4After being handled in aqueous solution, drying；After surface-treated substrate is rinsed with deionized water,
Drying, annealing；
Step 5): perovskite is formed on the substrate that step 4) obtains using one-step method or two-step method；
The one-step method are as follows: PCBM is dissolved in chlorobenzene and forms solution, which is spin-coated on substrate, is annealed, so
Afterwards on PCBM substrate spin coating organic and inorganic perovskite solution precursor solution, annealing become perovskite substrate from transparent
Brown；The precursor solution of organic and inorganic perovskite solution includes the PbCl for being dissolved in the in the mixed solvent of DMSO and GBL2、PbI2
And CH3NH3I；
The two-step method are as follows: by PbI2It is dissolved in DMF and forms solution, which is spin-coated on substrate, anneal, then
By PbI2After substrate isopropyl alcohol, it is immersed in CH3NH3In I solution, drying is taken out, is formed in substrate surface
CH3NH3PbI3, anneal, it used to isopropyl alcohol again, dry up, anneal again, make CH3NH3PbI3Further crystallization；
Step 6): the spin coating Spiro-MeOTAD on the substrate that step 5) obtains dries in the shade；
Step 7): Ag is deposited in the substrate surface that step 6) is obtained.
Preferably, in the step 1) FTO substrate in Decon-90 cleaning agent, deionized water, acetone, alcohol, deionization
Respectively it is cleaned by ultrasonic in water 15 minutes.
Preferably, the cleaning agent in the step 2) is the Decon-90 of volumetric concentration 10%.
Preferably, in the step 3) spin coating specific steps are as follows: using n-butyl alcohol will be bis- (levulinic ketone group) diisopropyl
Base metatitanic acid ester solution dilutes the TiO for respectively obtaining 0.15M, 0.3M concentration2Precursor solution, first spin coating 0.15M TiO2Presoma
Solution is primary, annealing；It is then spin coated onto 0.3M TiO2Precursor solution, annealing；Last spin coating 0.3M TiO2Precursor solution moves back
Fire.
Preferably, the precursor solution of organic and inorganic perovskite solution includes being dissolved in DMSO and GBL in the step 5)
The PbCl of in the mixed solvent2 39mg/mL、PbI2 581mg/mL、CH3NH3The in the mixed solvent of I 209mg/mL, DMSO and GBL
The volume ratio of DMSO and GBL is 3:7；Spin coating process are as follows: first with the revolving speed forward spin coating 20s of 1000rpm, then with 4000rpm
Revolving speed after rotate and apply 40s, wherein revolving speed reaches the 20s after 4000rpm and toluene is added dropwise on substrate to inhibit perovskite knot
It is brilliant.
Preferably, Spiro-MeOTAD includes the following component mixed in proportion: 1mL chlorobenzene, 90mg in the step 6)
Spiro-MeOTAD, 45 μ L concentration are the Li-TFSI acetonitrile solution of 170mg/mL, and 75 μ L concentration are the FK-102 second of 100mg/mL
Nitrile solution and 10 μ L tBP；Spin coating revolving speed is 2000rpm.
The present invention also provides the perovskite structure sun electricity of the preparation method of above-mentioned perovskite structure solar cell preparation
Pond successively includes FTO substrate, TiO2Electron transfer layer, CH3NH3PbI3-xClxPerovskite light-absorption layer, the hole Spiro-MeOTAD
Transport layer and Ag electrode, wherein X 0-3.
Preferably, the Spiro-MeOTAD hole transmission layer with a thickness of 300-500nm, CH3NH3PbI3-xClxCalcium titanium
Mine light-absorption layer with a thickness of 400-600nm, TiO2Electron transfer layer with a thickness of 10-30nm
Perovskite solar cell prepared by the present invention is simple with preparation condition, light absorption is strong, low energy consumption, photoelectric conversion effect
The advantages that rate is high.
Compared with prior art, beneficial effects of the present invention are as follows:
(1) perovskite battery model, the performance and thickness of hole transport layer of perovskite solar battery, perovskite are established
Light-absorption layer thickness has much relations, and little with the thickness relationship of electron transfer layer.Preferable battery performance in order to obtain, it should
Increase thickness of hole transport layer, it is appropriate to increase calcium titanium ore bed thickness, while the thickness of electron transfer layer is minimized, to realize
Fill factor (FF), short-circuit current density (JSC) promotion, keep open-circuit voltage (Voc) stabilization, finally obtain higher turn
Change efficiency (Eff).
(2) preparation and optimization method that perovskite solar battery has active layer and device are explored, plane transoid is prepared for
Perovskite solar cell device, standard MAPbI3The energy conversion efficiency (PCE) of perovskite solar battery is more than 10%；It is logical
The component for advanced optimizing perovskite precursor liquid is crossed, and uses modifying interface method, standard MAPbI3-xClxPerovskite solar energy
The energy conversion efficiency (PCE) of battery is up to 14.3%.
(3) groped by technique of the two-step method to plane perovskite solar battery, and realize 4.67%
Energy conversion efficiency, the component by adjusting Cl element in precursor solution convert the energy of plane perovskite solar battery
Improved efficiency is to 9.53%；One-step method advanced optimizes plane perovskite solar cell, first by using one-step method
Solvent engineering and optimization TiO2The thickness on barrier layer, obtains 10.77% energy conversion efficiency, and TiO2The compound resistance of/PCBM
The addition of barrier further reduced the Interface composites of device to improve the J of devicesc, it is finally obtained 19.421% turn
Change efficiency.
Detailed description of the invention
Fig. 1 is the schematic cross-section for the perovskite structure solar cell that the present invention obtains；
Fig. 2 is TiO under different rotating speeds in embodiment 12The XRD diagram of substrate；
Fig. 3 is the XRD diagram of PCBM substrate under different rotating speeds in embodiment 1；
Fig. 4 is TiO in embodiment 12, PCBM and CH3NH3PbI3-xClxThe XRD diagram of substrate；
Fig. 5 is the TiO obtained under different rotating speeds in embodiment 12The comparison diagram of the SEM image of substrate；Wherein, turn of a, d
Speed is 2k RPM, and the revolving speed of b, e are 4k RPM, and the revolving speed of c, f are 6k RPM；
Fig. 6 is in embodiment 1 with the comparison diagram of the SEM image of the PCBM substrate of different rotating speeds preparation；Wherein, the revolving speed of a
For 2k RPM, the revolving speed of b is 4k RPM, and the revolving speed of c is 6k RPM；
Fig. 7 is the TiO prepared in embodiment 1 with 2k, 4k, 6k revolving speed2The PL image of substrate；
Fig. 8 is in embodiment 1 with the PL image of the PCBM substrate of 2k, 4k, 6k revolving speed preparation；
Fig. 9 is TiO in embodiment 12The PL image of substrate and PCBM substrate；
Figure 10 is TiO in embodiment 22、PbI1+xCl1-x、CH3NH3PbI2+xCl1-xThe XRD diagram of substrate；
Figure 11 is TiO in embodiment 22、PbI1+xCl1-x、CH3NH3PbI2+xCl1-xAnd Spiro-MeOTAD substrate SEM shines
The comparison diagram of piece；
Figure 12 is TiO in embodiment 22、PbI1+xCl1-x、CH3NH3PbI2+xCl1-xAnd the purple of Spiro-MeOTAD substrate
Outside-visible light optical absorption spectra.
Specific embodiment
In order to make the present invention more obvious and understandable, hereby with preferred embodiment, and attached drawing is cooperated to be described in detail below.
Embodiment 1
A kind of preparation method of one-step method perovskite structure solar cell:
(1) etch FTO substrate: FTO glass is cut to 25mm × 30mm, then using adhesive plaster by intermediate 10mm ×
The locality protection of 30mm rises as electrode, and other regions are dipped in zinc powder with hydrochloric acid and performed etching until etch areas becomes
It is bright；
(2) FTO substrate: the FTO substrate that will have been etched is cleaned, protection adhesive plaster is removed, is carried out tentatively with surfactant
Wash removing surface impurity by rubbing with the hands, be then sequentially placed into FTO substrate, the Decon-90 cleaning agent of 10% volumetric concentration, deionized water,
Acetone, alcohol are successively cleaned by ultrasonic 15 minutes in deionized water；
(3) spin coating TiO2Barrier layer: the FTO substrate cleaned is dried up with nitrogen gun, is sent into pretreatment chamber in 3Pa or less
Chamber pressure is adjusted to 60Pa using the flow of 30sccm, then startup power supply generates O2Plasma handles 15 minutes, makes
With 1-butanol will be bis- (levulinic ketone group) diisopropyl metatitanic acid ester solution be diluted to the TiO of 0.15M and 0.3M concentration respectively2
Precursor solution, it is primary using KW-4A photoresist spinner spin coating 0.15M precursor solution, the substrate after spin coating is then placed on 125 DEG C
Thermal station on anneal 5min, spin coating 0.3M precursor solution, 125 DEG C of annealing 5min, last spin coating 0.3M presoma are molten again
Liquid, 500 DEG C of annealing 15min；
(4) it is surface-treated: by TiCl4It is added in mixture of ice and water, is configured to the TiCl that concentration is 20mM4Aqueous solution will move back
The TiO of excessive fire2Substrate is immersed in TiCl4In aqueous solution, it is put into 70 DEG C of processing 45min of convection oven；
(5) it anneals: by surface-treated TiO2Substrate is rinsed with deionized water, and is dried up with nitrogen gun, 500 DEG C of annealing
15min；
(6) spin coating PCBM decorative layer: PCBM is dissolved in the solution for forming 10mg/mL in chlorobenzene, is used in glove box
Photoresist spinner, with the speed spin coating 45s of 6000rpm；
(7) it anneals: the substrate of the complete PCBM of spin coating is placed in 100 DEG C of thermal station the 5min that anneals；
(8) spin coating perovskite active layer: the precursor solution formula of organic and inorganic perovskite solution is as follows:
The PbCl of 39mg2, the PbI of 581mg2, the CH of 209mg3NH3I and 1ml DMSO (is mixed with the mixed solvent of GBL
The volume ratio of DMSO and GBL is 3:7 in solvent)；EZ6 photoresist spinner spin coating precursor solution is used, in glove box with 1000rpm
Forward spin coating 20s, then apply 40s to rotate after 4000rpm, the particularly 20s after revolving speed reaches 4000rpm is to base
Toluene is added dropwise to inhibit the crystallization of perovskite on piece；
(9) annealing of calcium titanium ore bed: the substrate of spun perovskite material is placed in 100 DEG C of thermal station and is annealed
12min, it can be found that substrate becomes dark-brown from transparent quickly during annealing；
(10) spin coating Spiro-MeOTAD hole transmission layer；
(11) composition of Spiro-MeOTAD spin coating is as follows: 1ml chlorobenzene is as solvent, the Spiro-MeOTAD of 90mg
As solute, the Li-TFSI acetonitrile solution of the 170mg/mL of 45 μ L, the FK-102 acetonitrile solution of the 100mg/mL of 75 μ L, 10 μ L
TBP；
(12) spin coating is carried out in air using KW-4A photoresist spinner, spin coating rate is 2000rpm, time 45s；
(13) it dries in the shade: resulting substrate being placed in the culture dish wrapped up with masking foil, 12h is placed in drying box；
(14) evaporate Ag electrode: substrate is put into fixture after drying in the shade and is sent into metal coating room by substrate, and chamber pressure is evacuated to
10-5Pa hereinafter, withRate vapor deposition 100nm Ag；
(15) device detection: the device of preparation is taken out from metal coating room, with U.S.'s renewable energy Laboratory Calibration
Normal cell test macro is calibrated, device is then connected to test macro, scanning range is -1.2V-1.2V, is taken
Sampling point is 100, and setting delay is 10ms, to obtain each performance parameter of device.
Substrate obtained above is subjected to correlated performance test.
1, it estimates
There is mirror-reflection in gained substrate surface, illustrates it with preferable uniformity.
2, x ray diffraction (XRD) is analyzed and researched
By Fig. 2,3 as it can be seen that the revolving speed for changing substrate spin coating does not significantly change the position of diffraction maximum in the XRD diagram picture of substrate
It sets, this is because the thickness of PCBM material is very thin in the device of preparation, thus stronger 37.74 ° and 51.50 ° of peaks pair
It should be in the diffraction maximum of FTO substrate.And 26.52 ° and 36.71 ° of two peaks it is then corresponding be TiO2The diffraction maximum of film, and showing should
Film is anatase crystal.
From fig. 4, it can be seen that forming CH3NH3PbI3-xClxAfter material, occur in XRD diagram picture 14.17 °, 28.51 ° with
And 31.95 ° of three diffraction maximums, correspond respectively to CH3NH3PbI3-xClx<110>,<220>and<310>crystal orientation, while this
Mean the CH of preparation3NH3PbI3-xClxMaterial is tetragonal phase, and lattice constant isAnd
The PbI of 12.72 ° of appearance2Peak this means that in material also contain very small amount of PbI2, these PbI2To CH3NH3PbI3-xClx
Material has played the J that passivation is conducive to devicescRaising.
3, field emission scanning electron microscope (SEM) is analyzed and researched
As seen from Figure 5, the TiO when revolving speed is 2k and 4k RPM2Apparent pin hole is not occurred on substrate, but works as and turns
Speed is raised to TiO after 6k RPM2Substrate surface starts pin hole occur, and the presence of these pin holes can cause FTO cathode and Ag
Anode directly contacts so as to cause shorted devices, even if the table for directly contacting these pin holes does not occur for FTO cathode and Ag anode
Planar defect can also reduce the J of device as surface recombination centersc。
The TiO after revolving speed is raised to 6k RPM2Substrate surface starts pin hole occur, so in the preparation process of device
It is middle to control revolving speed in 4k RPM.Meanwhile revolving speed being controlled in 4k RPM, in TiO2With different revolving speed spin coatings on substrate
PCBM, it is as shown in Figure 6 with the SEM image of the PCBM substrate of different rotating speeds preparation.As seen from Figure 6, it is prepared with different revolving speeds
Any pin hole is not found on PCBM.
4, atomic force microscope (AFM) is analyzed and researched
The PCBM of different revolving speed preparations is had studied by AFM to CH3NH3PbI3-xClxThe influence of the surface RMS of material.
By comparing the CH that RMS is respectively 15.6nm, 15.3nm, 16.0nm3NH3PbI3-xClxThe three-dimensional afm image and two dimension of substrate are opened up
Image discovery is flutterred, the RMS of three substrates is almost consistent, illustrates the insertion of PCBM substantially to CH3NH3PbI3-xClxThe table of material
Face pattern does not have any influence.
It is can analyze out by XRD, SEM and AFM result, improve TiO2Spin speed be not conducive to material surface
The control of pattern, and be inserted into PCBM material and can be very good to make up this point, it can be in higher TiO2Spin speed under obtain
Preferable surface topography is obtained, and the insertion of PCBM material will not influence CH3NH3PbI3-xClxThe surface appearance of material.
5, ultraviolet-visible diffuse reflectance spectrum (UV-Vis) is analyzed and researched
Pass through TiO under research different rotating speeds2The transmitance of PCBM substrate can under the transmitance and different rotating speeds of substrate
Know, increases preparation TiO2When spin speed can make TiO2Surface generates pin hole, these pin holes can be such that incident light scatters, no
It, can be by CH to reduce conducive to the transmission of light3NH3PbI3-xClxThe intensity for the light that material absorbs.PCBM as insert layer,
There is also certain light absorptions for itself；Lower spin speed can also make the PCBM of preparation thicker, so that reducing can be by
CH3NH3PbI3-xClxThe intensity for the light that material absorbs.Therefore in order to guarantee TiO2The light transmission rate of/PCBM composite barrier should
Higher PCBM spin speed is kept as far as possible.
Pass through the CH prepared on research different rotating speeds PCBM substrate3NH3PbI3-xClxThe absorption spectrum of material is it is found that PCBM
There is positive influence to the absorption of incident light；With the increase CH of spin speed3NH3PbI3-xClxThe influx and translocation of material, and AFM
As a result have shown that this time experiment PCBM substrate RMS it is almost consistent, further related to PCBM material itself there is
Light absorption, this is also the reason that PCBM is widely used in organic solar batteries.
6, photoluminescence spectra (PL) is analyzed and researched
On the basis of transmission spectrum and absorption spectra, the present embodiment is again to TiO2It is carried out with the photoluminescence spectrum of PCBM substrate
Measurement, the wavelength of excitation are 515nm.
As seen from Figure 7, by increasing TiO2The spin speed of substrate, it can be found that occurring varying strength at 518nm
The peak PL, and the intensity at the peak PL is with TiO2The increase of the spin speed of substrate and weaken, since the energy of excitation wave is less than
TiO2Forbidden bandwidth, thus be TiO at the peak PL of 518nm2Defect peak.In order to study PCBM insert layer to TiO2The shadow of substrate
It rings, the present embodiment is prepared for PCBM substrate again with different revolving speeds.By Fig. 8,9 as it can be seen that when PCBM is spin-coated on TiO2On substrate
After, obviously decaying occurs in the peak PL, it means that TiO2Had occurred between PCBM the transmission of electronics so as to cause
The decaying at the peak PL.
Conclusion: optimizing the component of perovskite precursor liquid in one-step technology, mixes suitable lead chloride, simultaneously
Modifying interface is carried out, the battery of structure as shown in Figure 1, J are prepared forSCIt improves to 22.23 ± 0.50mA/cm2, Voc improve to
1.02 ± 0.01V, FF are 80.6 ± 1.3%, and average PCE is promoted to 18.0%, and optimal device efficiency is up to 18.9%.
Embodiment 2
A kind of preparation method of two-step method perovskite structure solar cell:
(1) etch FTO substrate: the FTO glass used in this experiment is cut to 25mm*30mm size, then makes
The locality protection of intermediate 10mm*30mm is risen as electrode with adhesive plaster, other regions are dipped in zinc powder with hydrochloric acid and performed etching
Until etch areas becomes transparent；
(2) FTO substrate: the FTO substrate that will have been etched is cleaned, protection adhesive plaster is removed, is carried out tentatively with surfactant
Wash removing surface impurity by rubbing with the hands, be then sequentially placed into FTO substrate, the Decon-90 cleaning agent of 10% volume fraction, deionized water,
Acetone, alcohol are successively cleaned by ultrasonic 15 minutes in deionized water；
(3) spin coating TiO2Barrier layer: the FTO substrate cleaned is dried up with nitrogen gun, is sent into pretreatment chamber in 3Pa or less
Chamber pressure is adjusted to 60Pa using the flow of 30sccm, then startup power supply generates O2Plasma handles 15 minutes, makes
With 1-butanol will be bis- (levulinic ketone group) diisopropyl metatitanic acid ester solution be diluted to the concentration TiO of 0.15M and 0.3M respectively2
Precursor solution, it is primary using KW-4A photoresist spinner spin coating 0.15M precursor solution, the substrate after spin coating is then placed on 125 DEG C
Thermal station on anneal 5min, spin coating 0.3M precursor solution, 125 DEG C of annealing 5min, last spin coating 0.3M presoma are molten again
Liquid, 500 DEG C of annealing 15min；
(4) it is surface-treated: by TiCl4It is added in mixture of ice and water, is configured to the TiCl that concentration is 20mM4Aqueous solution will move back
The TiO of excessive fire2Substrate is immersed in TiCl4In aqueous solution, it is put into 70 DEG C of processing 45min of convection oven；
(5) it anneals: by surface-treated TiO2Substrate is rinsed with deionized water, and is dried up with nitrogen gun, 500 DEG C of annealing
15min；
(6) spin coating PbI2Solution: by PbI2Be dissolved in DMF formed concentration be 1M solution, using KW-4A photoresist spinner into
Row spin coating, spin coating revolving speed 2000rpm, spin-coating time 45s；
(7) it anneals: by PbI2Substrate is placed on 90 DEG C of baking close annealing 15min；
(8) it impregnates and forms perovskite: the PbI of excessive fire will be moved back2Substrate isopropyl alcohol 2s, then by PbI2Substrate is impregnated
In the CH of 20mg/mL3NH3In I solution, and it is put into 70 DEG C of oven 20min, forms CH3NH3PbI3；
(9) it anneals: the CH that will have been impregnated3NH3PbI3Substrate uses isopropyl alcohol again, and is dried up with nitrogen gun, then by shape
At CH3NH3PbI3Substrate, which is placed in 90 DEG C of thermal station the 45min that anneals, makes CH3NH3PbI3Further crystallization；
(10) spin coating Spiro-MeOTAD hole transmission layer；
(11) composition of Spiro-MeOTAD spin coating is as follows: 1ml chlorobenzene is as solvent, the Spiro-MeOTAD of 90mg
As solute, the Li-TFSI acetonitrile solution of the 170mg/mL of 45 μ L, the FK-102 acetonitrile solution of the 100mg/mL of 75 μ L, 10 μ L
TBP；
(12) spin coating is carried out in air using KW-4A photoresist spinner, spin coating rate is 2000rpm, time 45s；
(13) it dries in the shade: resulting substrate being placed in the culture dish wrapped up with masking foil, 12h is placed in drying box；
(14) evaporate Ag electrode: substrate is put into fixture after drying in the shade and is sent into metal coating room by substrate, and chamber pressure is evacuated to
10-5Pa hereinafter, withRate vapor deposition 100nm Ag；
(15) device detection: the device of preparation is taken out from metal coating room, with U.S.'s renewable energy Laboratory Calibration
Normal cell test macro is calibrated, device is then connected to test macro, scanning range is -1.2V---1.2V,
Sample point is 100, and setting delay is 10ms, to obtain each performance parameter of device.
Substrate obtained above is subjected to correlated performance test.
1, x ray diffraction (XRD) is analyzed and researched
In the experiment of two-step method, by PbI2On spin coating PbI again2/PbCl2Mixed solution adjust acquisition
The surface topography of inorganic thin film, then CH obtained is studied by XRD3NH3PbI2+xCl1-xOrganic and inorganic perovskite thin film
Crystalline nature, the substrate for carrying out XRD characterization have TiO2、PbI1+xCl1-x、CH3NH3PbI2+xCl1-x, corresponding XRD spectrum is such as Figure 10 institute
Show.
As seen from Figure 10,37.90 ° and 51.66 ° of peak corresponds to FTO substrate, and 26.58 ° correspond to TiO with 33.81 ° of peak2
Characteristic peak, due to TiO2It is very thin, so the intensity at two peaks is all very weak, but it may determine that the high temperature by 500 DEG C
Annealing, TiO2Crystal form be anatase crystal；Correspond to PbI at 12.72 ° of very strong peaks1+xCl1-x<001>crystal orientation spy
Levy peak；And after the immersion for completing two-step method, correspond to CH at the strong peak that 14.15 ° occur3NH3PbI2+xCl1-xMaterial <
There is CH in 28.48 °, 31.87 ° and 42.60 ° three places in 110 > crystal orientation3NH3PbI2+xCl1-xThe characteristic peak of material, point
It Dui Yingyu not CH3NH3PbI2+xCl1-x<220><310><330>of material, it means that prepared CH3NH3PbI2+xCl1-xMaterial
Material is tetragonal phase, and lattice constant isBy Scherrer formula, we can be further
Calculate CH3NH3PbI2+xCl1-xThe grain size of organic and inorganic perovskite material is in 250~350nm.
2, field emission scanning electron microscope (FFSEM) is analyzed and researched
TiO is respectively illustrated from upper left, upper right, lower-left, bottom right in Figure 112、PbI1+xCl1-x、CH3NH3PbI2+xCl1-xWith
And Spiro-CH3NH3PbI2+xCl1-xThe SEM photograph of substrate.What can be will be apparent that sees even across TiCl4Surface at
Reason, TiO2Still there is height to rise and fall on surface, while there is also the pin holes of part, and in TiO2One layer of PbI of upper rotation Tu1+ xCl1-xThe phenomenon that after material, the pin hole on surface significantly becomes smaller, while height rises and falls also has obtained a degree of slow
Solution, this is because PbI1+xCl1-xThe thickness of material is greater than TiO2The surface Root Mean Square roughness (RMS) of material；Work as two-step method
After having impregnated, PbI1+xCl1-xCH is transformed on material3NH3PbI2+xCl1-xMaterial, a very direct evidence be exactly
CH3NH3PbI2+xCl1-xThere is no very strong PbI in the XRD spectrum of material1+xCl1-xCharacteristic peak, meanwhile, material is by original stratiform
Piece is to three-dimensional particle transition, this indicates the increase i.e. expansion of crystal of this lattice constant to a certain extent, this is also composed with XRD
Analysis match；When Spiro-MeOTAD is spin-coated on CH3NH3PbI2+xCl1-xAfter on material, with the naked eye just it is observed that
Mirror-reflection, this illustrates that the fluctuating of material surface and pin hole are filled and led up, and can illustrate this well by AFM photo
Point.
3, atomic force microscope (Atomic Force Microscope, AFM) is analyzed and researched
By TiO2、PbI1+xCl1-x、CH3NH3PbI2+xCl1-xAnd Spiro-CH3NH3PbI2+xCl1-xThe AFM photo of substrate
As it can be seen that being spin-coated on the TiO on FTO substrate2RMS be 25.8nm, work as PbI1+xCl1-xIt is coated over TiO2The later RMS in surface is almost
Do not change, and works as and form CH3NH3PbI2+xCl1-xRMS has been significantly increased to 50.6nm after material, illustrates in PbI2To
CH3NH3PbI2+xCl1-xThe structure and lattice constant of crystal are changed when material changes, higher under normal conditions
RMS is unfavorable for the promotion of device performance, uses the Spiro-MeOTAD with stronger hole filling capacity in the present embodiment,
When Spiro-MeOTAD is coated over CH3NH3PbI2+xCl1-xAfter material, the RMS of film is reduced to 4nm significantly, completely
The requirement of preparation plane perovskite solar battery is reached, to ensure that the higher energy conversion of the device finally prepared
Efficiency (PCE).
4, ultraviolet-visible diffuse reflectance spectrum (Ultraviolet-visible Spectroscopy, UV-vis) analysis is ground
Study carefully
Pass through TiO2、PbI1+xCl1-x、CH3NH3PbI2+xCl1-xAnd the ultraviolet-visible light light of Spiro-MeOTAD substrate
Absorption spectra discovery, with the increase TiO of number of layers2、PbI1+xCl1-x、CH3NH3PbI2+xCl1-xThe light absorption of substrate successively increases
By force, but the ultraviolet-visible light optical absorption spectra of Spiro-MeOTAD substrate occurs after the complete Spiro-MeOTAD material of spin coating
Blue shift.Afm image explains this problem, CH well3NH3PbI2+xCl1-xThe RMS of material is very big, big in this way
RMS can make incident light that scattering occur to which the detector inside the photometer that can not be split detects, and work as Spiro-MeOTAD
It is coated over CH3NH3PbI2+xCl1-xRMS is significantly reduced after material, thus has more light to be detected by the detector, institute
The blue shift of absorption curve is had found on ultraviolet-visible light optical absorption spectra with us.
Groped by technique of the two-step method to plane perovskite solar battery, and realizes 4.67% energy
Transfer efficiency, by adjusting the component of Cl element in precursor solution for the energy conversion efficiency of plane perovskite solar battery
It is promoted to 9.53%.On the basis of two-step method, plane perovskite solar cell is advanced optimized using one-step method, it is first
First pass through the solvent engineering and optimization TiO using one-step method2The thickness on barrier layer, we obtain the conversions of 10.77% energy
Efficiency, and TiO2The addition of/PCBM composite barrier further reduced the Interface composites of device to improve the J of devicesc,
It is finally obtained 19.421% transfer efficiency.
Claims (8)
1. a kind of preparation method of perovskite structure solar cell, which comprises the following steps:
Step 1): etching FTO substrate: after FTO glass is cut, intermediate locality protection is risen as electricity using adhesive plaster
Pole, other regions are dipped in zinc powder with hydrochloric acid and are performed etching until etch areas becomes transparent；
Step 2): cleaning FTO substrate: the FTO substrate that will have been etched removes protection adhesive plaster, is tentatively rubbed with the hands with surfactant
Surface impurity is removed in washout, and FTO substrate is then sequentially placed into cleaning agent, deionized water, acetone, alcohol, ultrasound in deionized water
Cleaning；
Step 3): spin coating TiO2Barrier layer: the FTO substrate surface cleaned is dried up, and being sent into pretreatment chamber makes it generate O2Deng from
Daughter, using n-butyl alcohol will be bis- (levulinic ketone group) diisopropyl metatitanic acid ester solution dilute to obtain TiO2Precursor solution, by TiO2
Precursor solution is spin-coated on FTO substrate, is then annealed；
Step 4): surface treatment: by TiCl4It is added in mixture of ice and water, is configured to TiCl4Aqueous solution, the base that step 3) is obtained
Piece is immersed in TiCl4After being handled in aqueous solution, drying；After surface-treated substrate is rinsed with deionized water, drying,
Annealing；
Step 5): perovskite is formed on the substrate that step 4) obtains using one-step method or two-step method；
The one-step method are as follows: PCBM is dissolved in chlorobenzene and forms solution, which is spin-coated on substrate, anneals, then exists
The precursor solution of spin coating organic and inorganic perovskite solution on PCBM substrate, annealing make perovskite substrate become brown from transparent；
The precursor solution of organic and inorganic perovskite solution includes the PbCl for being dissolved in the in the mixed solvent of DMSO and GBL2、PbI2And
CH3NH3I；
The two-step method are as follows: by PbI2It is dissolved in DMF and forms solution, which is spin-coated on substrate, anneal, then will
PbI2After substrate isopropyl alcohol, it is immersed in CH3NH3In I solution, drying is taken out, is formed in substrate surface
CH3NH3PbI3, anneal, it used to isopropyl alcohol again, dry up, anneal again, make CH3NH3PbI3Further crystallization；
Step 6): the spin coating Spiro-MeOTAD on the substrate that step 5) obtains dries in the shade；
Step 7): Ag is deposited in the substrate surface that step 6) is obtained.
2. the preparation method of perovskite structure solar cell as described in claim 1, which is characterized in that in the step 1)
FTO substrate is respectively cleaned by ultrasonic 15 minutes in Decon-90 cleaning agent, deionized water, acetone, alcohol, deionized water.
3. the preparation method of perovskite structure solar cell as described in claim 1, which is characterized in that in the step 2)
Cleaning agent is the Decon-90 of volumetric concentration 10%.
4. the preparation method of perovskite structure solar cell as described in claim 1, which is characterized in that rotation in the step 3)
The specific steps of painting are as follows: using n-butyl alcohol will bis- (levulinic ketone group) diisopropyl metatitanic acid ester solution dilute respectively obtain 0.15M,
The TiO of 0.3M concentration2Precursor solution, first spin coating 0.15M TiO2Precursor solution is primary, annealing；It is then spin coated onto 0.3M TiO2
Precursor solution, annealing；Last spin coating 0.3M TiO2Precursor solution, annealing.
5. the preparation method of perovskite structure solar cell as described in claim 1, which is characterized in that have in the step 5)
The precursor solution of the inorganic perovskite solution of machine-includes the PbCl for being dissolved in the in the mixed solvent of DMSO and GBL2 39mg/mL、PbI2
581mg/mL、CH3NH3The volume ratio of the in the mixed solvent DMSO and GBL of I 209mg/mL, DMSO and GBL are 3:7；Spin coating process
Are as follows: first with the revolving speed forward spin coating 20s of 1000rpm, 40s then is applied to rotate after the revolving speed of 4000rpm, wherein revolving speed reaches
Toluene is added dropwise on substrate to inhibit perovskite crystalline in 20s after 4000rpm.
6. the preparation method of perovskite structure solar cell as described in claim 1, which is characterized in that in the step 6)
Spiro-MeOTAD includes the following component mixed in proportion: 1mL chlorobenzene, 90mg Spiro-MeOTAD, and 45 μ L concentration are
The Li-TFSI acetonitrile solution of 170mg/mL, 75 μ L concentration are the FK-102 acetonitrile solution and 10 μ L tBP of 100mg/mL；Spin coating turns
Speed is 2000rpm.
7. perovskite structure made from the preparation method of perovskite structure solar cell as claimed in any one of claims 1 to 6 is too
Positive electricity pond, which is characterized in that the perovskite structure solar cell successively includes FTO substrate, TiO2Electron transfer layer,
CH3NH3PbI3-xClxPerovskite light-absorption layer, Spiro-MeOTAD hole transmission layer and Ag electrode, wherein X 0-3.
8. perovskite structure solar cell as claimed in claim 7, which is characterized in that the Spiro-MeOTAD hole transport
Layer with a thickness of 300-500nm, CH3NH3PbI3-xClxPerovskite light-absorption layer with a thickness of 400-600nm, TiO2Electron transfer layer
With a thickness of 10-30nm.
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