CN106748832B - Hole mobile material based on two fluorenes of spiral shell [3,3] heptane -2,6- spiral shells - Google Patents
Hole mobile material based on two fluorenes of spiral shell [3,3] heptane -2,6- spiral shells Download PDFInfo
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- CN106748832B CN106748832B CN201710028795.0A CN201710028795A CN106748832B CN 106748832 B CN106748832 B CN 106748832B CN 201710028795 A CN201710028795 A CN 201710028795A CN 106748832 B CN106748832 B CN 106748832B
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Abstract
The invention discloses one kind with two fluorenes of spiral shell [3,3] 2,6 spiral shell of heptane be core, methoxy substitution diphenylamines be the novel hole transport material of modification group and the application in perovskite solar cell, belong to solar cell material preparation field.The cost of material that the preparation of novel hole transport material of the present invention is utilized is low, synthetic method is simply, conveniently, synthesized hole mobile material shows by test, electrochemical property test and the heat stability testing of photophysical property, hole mobile material better performances, energy level can be matched with Perovskite Phase, show that synthesized hole mobile material can be applied in perovskite solar cell, and heat endurance is good.The present invention also produces perovskite solar cell device using the novel hole transport material, and carries out photovoltaic performance test, the results show that can reach 12.95% electricity conversion, therefore, has extraordinary application prospect.
Description
Technical field
The invention belongs to organic photoelectrical material field, and specially one kind is core, first with two fluorenes of spiral shell [3.3] heptane -2,6- spiral shell
Novel hole transport material of the diphenylamines for modification group of epoxide substitution and the application in perovskite solar cell.
Background technology
Since the new century is entered, there occurs great variety for global energy composition.The various new energy flourishes, constantly
Shake the leading position of the traditional fossil energy based on oil, coal.Wherein solar energy industry development is particularly swift and violent,
As the important component of novel energy.
In recent years, new all solid state plane solar cell-perovskite solar cell due to its high transfer efficiency,
The equal simple preparation process of liquid/gas and the advantages that extremely low processing cost, causes the great attention of international academic community.Mesh
Before, perovskite solar cell becomes one of research hotspot important in current photovoltaic art.This battery by transparency electrode,
Electron transfer layer, perovskite light-absorption layer, hole transmission layer, five part of metal electrode are formed.Its hole-transporting layer is as a kind of
All solid state electrolyte, can avoid former I/I with perovskite band structure perfect adaptation3-Electrolyte decomposition perovskite light-absorption layer
The problem of bringing, and then improve the stability and process repeatability of perovskite battery（Sci. Rep., 2012, 2, 591）.
Preferable hole transmission layer should have high hole transport efficiency, high thermodynamic stability, good dissolubility and film forming,
There is certain hydrophobicity to protect perovskite absorbed layer at the same time（Phys. Chem. Lett., 2013, 4(21), 3623-
3630）.
At present, the use of most and commercialized hole mobile material is 2,2 ', 7,7 '-four [N, N- bis-（4- methoxybenzenes
Base）Amino] two fluorenes of -9,9 '-spiral shell（spiro-OMeTAD）.However, except its potential HTM feature, spiro-OMeTAD's answers
Heterozygosis is into high cost and low carrier mobility may hinder its large-scale application in PSC, because it includes five reactions
Step is, it is necessary to low temperature（-78℃）And sensitivity（N-BuLi or Grignard Reagent）And aggressivity（Br2）Reagent, total recovery are less than
30%（Chem. Rev. 107 (2007) 1011）, in addition, it is desirable to which the spiro-OMeTAD of high-purity distillation obtains high property
Can device（Angew. Chem. Int. Ed. 54 (2015) 11409）.Therefore, it is badly in need of developing low-cost and more direct at present
Synthetic route so that efficiently small molecule HTM as in solar cell application be spiro-OMeTAD substitute.
The content of the invention
The technical problem to be solved in the present invention is overcome the shortcomings of above-mentioned existing hole mobile material, there is provided one kind synthesis into
This low, excellent in efficiency hole mobile material substitutes spiro-OMeTAD.
The present invention adopts the following technical scheme that realization：
One kind is based on the hole mobile material of two fluorenes of spiral shell [3,3] heptane -2,6- spiral shell, and structure is as follows：
。
The preparation method of the above-mentioned hole mobile material based on two fluorenes of spiral shell [3.3] heptane -2,6- spiral shell, including：By 2,2 ', 7,
7 '-four bromo- two fluorenes of spiral shell [3.3] heptane -2,6- spiral shells, 4,4 '-dimethoxy diphenylamines, organic base, palladium catalyst and Phosphine ligands mix
To close, add toluene, be uniformly mixed, the lower back flow reaction of nitrogen protection, reaction solution is dry through washing after the completion of reaction, crosses pillar,
Desolventizing, recrystallization, obtains compound 2,2 ', 7,7 '-four（Double -4- the methoxyphenyls of N, N-）- spiral shell [3.3] heptane -2,6- spiral shells
Two fluorenes.
Further, the organic base is potassium tert-butoxide or sodium tert-butoxide.
Further, the palladium catalyst is palladium, Pd2dba3（Three（Dibenzalacetone）Two palladiums）、Pd(PPh3)4（Four
（Triphenylphosphine）Palladium）In one kind.
Further, the Phosphine ligands are tri-butyl phosphine or three o-methyl-phenyl phosphines.
Further, the temperature of the back flow reaction is 105 DEG C ~ 110 DEG C, 24 ~ 36h of return time.
Further, the solvent of the recrystallization is one kind in n-hexane, toluene, ethyl acetate, petroleum ether, dichloromethane
Or any two kinds of mixture.
The application, for core, is drawn with 2,2 ', 7,7 '-four bromo- two fluorenes of spiral shell [3.3] heptane -2,6- spiral shell in its 2,2 ', 7,7 ' position
Enter the diaryl-amine group with methoxy substitution.Diaryl-amine is the preferable group for having efficient hole transport performance, it is possible to provide compared with
High carrier mobility；And on the one hand two fluorenes core of spiral shell [3.3] heptane -2,6- spiral shell can increase material dissolubility, on the other hand make
It so can greatly improve the film forming of material with hydrophobic function, while protect calcium titanium ore bed, and then improve cell photoelectric
Transformation efficiency and stability.The present invention has designed and synthesized the inexpensive loop coil of referred to as SDF-OMeTAD by two-step reaction
[3.3] two fluorenes of heptane -2,6-（SDF）Base hole mobile material, relative to known spiro-OMeTAD, SDF-OMeTAD is in halogen
Change and the SnO of cryogenic fluid processing is utilized in lead plane perovskite solar cell2As electron transfer layer, in 100mWcm-2,
There is the open-circuit voltage of 1.04V under AM 1.5G solar lightings, obtain 11.62% photoelectric conversion efficiency. SDF-OMeTAD
It will promote it in film organic-inorganic perovskite solar cell into one from the simple synthesis of commercially available starting material
Step exploitation, and electricity conversion is up for further optimization.
The invention also discloses the hole mobile material based on two fluorenes of spiral shell [3.3] heptane -2,6- spiral shells in perovskite solar energy
Application in battery device.
The present invention also provides a kind of preparation method of perovskite solar cell device, including：
FTO glass substrates are cleaned, are dry, and spare with the processing of ultraviolet-ozone device；It is then spin coated onto SnCl2·2H2O's
Ethanol solution, 180 DEG C of calcinations, form SnO2Electron transfer layer；FTO glass substrates are transferred in glove box again, spin coating PbI2
DMF solution, 90 DEG C drying, the FTO glass substrates of above-mentioned drying are finally immersed in CH3NH3In the aqueous isopropanol of I, isopropyl
After alcohol elution, 70 DEG C dry and cool down spare.The chlorobenzene solution based on two fluorene compound of spiral shell [3.3] heptane -2,6- spiral shell is prepared, and
Add Li-TFSI（Two（Trifluoromethane sulfonic acid acyl）Imine lithium）Acetonitrile solution and 4- tert .-butylpyridines, will be above-mentioned prepared
Solution carries out spin coating operation, and is transferred to vacuum evaporation room evaporation Au electrodes, and perovskite solar cell device is made.
Raw material of the present invention can synthesize commercially or according to the prior art.
Beneficial effects of the present invention are as follows：
1st, compound of the present invention is of low cost, synthetic route is simple, yield is high, is easy to purify, and is very beneficial for
Industrialized production.
2nd, compound dissolubility and better heat stability of the present invention, glass transition temperature is higher, can be formed
Good amorphous membrance, is conducive to the stabilization of battery properties.
3rd, electricity conversion of the compound of the present invention in perovskite solar cell device is higher, illustrates this
Invent the hole mobile material that the compound is a kind of function admirable.
Present invention design is reasonable, and the cost of material that the preparation of the novel hole transport material is utilized is low, synthetic method letter
Singly, conveniently, synthesized hole mobile material passes through test, electrochemical property test and the heat stability testing of photophysical property
Show, hole mobile material better performances, energy level can be matched with Perovskite Phase, show that synthesized hole mobile material can be answered
For in perovskite solar cell, and heat endurance is good.
The present invention also produces perovskite solar cell device using the novel hole transport material, and carries out photovoltaic
It can test, the results show that 12.95% electricity conversion can be reached, therefore, there is extraordinary application prospect.
Brief description of the drawings
Fig. 1 shows the synthetic route and structure of compound of the present invention.
Fig. 2 represents absorption curve figure of the compound of the present invention in dichloromethane solution.
Fig. 3 represents cyclic voltammetry curve figure of the compound of the present invention in acetonitrile solution.
Fig. 4 represents the TGA curves of compound of the present invention.
Fig. 5 represents the DSC curve of compound of the present invention.
Fig. 6 represents knot of the compound of the present invention as perovskite solar cell device made of hole mobile material
Composition.
Fig. 7 represents that compound of the present invention is close as the electric current of perovskite solar cell made of hole mobile material
Degree-voltage curve.
Embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1
Prepare 2,2 ', 7,7 '-four（Double -4- the methoxyphenyls of N, N-）Two fluorenes of-spiral shell [3.3] heptane -2,6- spiral shell, structure is as schemed
1：
Reaction scheme is as follows：
Step 1：
2,7- dibromos fluorenes (3.24g, 10mmol) is added in super dry tetrahydrofuran (100mL), is added several times at 50 DEG C
Enter sodium hydride (0.6g, 25mmol) and stir 1h afterwards.Again by the tetrahydrofuran solution of penta tetrabromo of season (0.86g, 2.21mmol) two
It is slowly dropped into a hour in system.After being added dropwise, anti-12h is stirred at 65 DEG C.After reaction solution is cooled to room temperature, decompression
Solvent evaporated, reaction mixture are washed with deionized water successively with dichloromethane solution, organic phase, anhydrous MgSO4It is dry, filtering.
Evaporated under reduced pressure solvent, product carry out recrystallization purification with chloroform, obtain 2,2 ', 7,7 '-four bromo- spiral shell [3.3] heptane -2,6- spiral shells two
Fluorenes white crystal (1.089g), yield 40%.1H NMR (400 MHz, CDCl3) δ 7.63 (d, J = 1.6 Hz,
4H, Ph), 7.46 (d, J = 8.1 Hz, 4H, Ph), 7.41 (dd, J = 8.1, 1.7 Hz, 4H, Ph),
2.99 (s, 8H, CH2)。
Step 2：
4,4'- dimethoxy diphenylamines is added in the two mouth flask of 50mL（1.43g 6.25mmol）, 2,2 ', 7,7 '-
Four bromo- two fluorenes of spiral shell [3.3] heptane -2,6- spiral shells（0.89g, 1.25mmol）, sodium tert-butoxide（0.86,9.00mmol）, three（Two benzal
Benzylacetone）Two palladiums（0.34g, 0.37mmol）And tri-butyl phosphine（0.23g, 1.12mmol）Mixing.Then, in nitrogen atmosphere
Under, 15mL dry toluenes are added into flask.By reaction mixture under nitrogen atmosphere 110 DEG C be heated to reflux 36 it is small when.Cooling
To room temperature, by reaction mixture dichloromethane and salt water washing, and with anhydrous MgSO4It is dry.After evaporating solvent, residue
Pass through column chromatography（Dichloromethane/n-hexane=2/1）Purifying, obtains dark gray solid（1.30 g）, yield 80%.1H NMR
(400 MHz, CDCl3) δ 7.21 – 6.50 (m, 32H), 3.76 (d, J = 28.7 Hz, 24H), 2.56 –
2.34 (m, 8H), 1.61 (s, 4H), 1.25 (s, 4H), 0.94 – 0.82 (m, 4H)。
Embodiment 2
To the hole mobile material 2,2 ', 7,7 '-four synthesized by embodiment 1（Double -4- the methoxyphenyls of N, N-）- spiral shell
[3.3] two fluorenes of heptane -2,6- spiral shells carries out optical physics（UV absorption）Property, electrochemical property test and heat stability testing.
The results show：The absorption of material is in 300 ~ 420nm（As shown in Figure 2）, HOMO energy levels are -5.28eV, lumo energy
For -2.37eV（As shown in Figure 3）, it is similar to spiro-OMeTAD, matched with Perovskite Phase, heat decomposition temperature is 400 DEG C（Such as figure
Shown in 4）, glass transition temperature is 126.6 DEG C（As shown in Figure 5）, good thermal stability.
Embodiment 3
The perovskite solar cell device of the compound prepared using embodiment 1
Fig. 6 is structure of the compound of the present invention as perovskite solar cell device made of hole mobile material
Figure, device architecture FTO/SnO2/CH3NH3PbI3/HTM/Au.The compound can be used for but not only as hole mobile material
It is limited to such a battery structure.
The production process of the device of the perovskite solar cell：
1st, FTO glass substrates are cleaned, are dry, and spare with the processing of ultraviolet-ozone device.
2nd, SnO is prepared2Electron transfer layer：Spin coating SnCl2·2H2The ethanol solution of O, when 180 DEG C of calcinations 1 are small, forms
SnO2Electron transfer layer.
3rd, calcium titanium ore bed is prepared：Lead iodide is dissolved in DMF first, the concentration of lead iodide is 462mg/mL, and 70 DEG C are heated
Stirring is until PbI2It is completely dissolved, with 0.22 μm of organic membrane filtration, by PbI2Solution drops in SnO2On film, then revolved
Apply, spin coating, which finishes, to be transferred on 90 DEG C of warm tables, and anneal 15min；After heating finishes and is cooled to 25 DEG C, the PbI that will prepare2It is thin
Film soaks in aqueous isopropanol, is placed at once after taking-up in the molten aqueous isopropanol of 6mg/mL iodine methylamines, PbI2Film color
Black is gradually changed into from yellow；Then film is transferred in aqueous isopropanol and slightly rinsed, be spin-coated to solvent volatilization, finally will
It is transferred on 70 DEG C of warm tables the 10min that anneals, that is, obtains organic and inorganic calcium titanium ore bed.
4th, hole transmission layer is prepared：Prepare 2,2 ', 7,7 '-four（Double -4- the methoxyphenyls of N, N-）- spiral shell [3.3] heptane -2,
The concentration of two fluorenes of 6- spiral shells is the chlorobenzene solution of 72.3mg/mL, adds two kinds of dopants：29μL 520mg/mL Li-TFSI（Two
（Trifluoromethane sulfonic acid acyl）Imine lithium）Acetonitrile solution and 28.8 μ L 4- tert .-butylpyridines, 20 DEG C stirring 1h.
5 and then by step（4）Prepared solution is spun to step（3）Calcium titanium ore bed on.Vacuum evaporation room is placed in,
Vacuum evaporation metal Au, is made perovskite solar cell device.
Fig. 7 for compound of the present invention and tradition spiro-OMeTAD as perovskite made of hole mobile material too
The Current density-voltage contrast curve of positive energy battery.
The results show：Short circuit current flowJ scFor 19.061mA/cm2, open-circuit voltageV ocIt is for 1.095eV, fill factor, curve factor FF
0.62, electricity conversion PCE are 12.95%.And there is the space further optimized, have a good application prospect.
Embodiment 4
Prepare 2,2 ', 7,7 '-four（Double -4- the methoxyphenyls of N, N-）Two fluorenes of-spiral shell [3.3] heptane -2,6- spiral shell, it is as follows：
4,4'- dimethoxy diphenylamines is added in the two mouth flask of 50mL（1.43g 6.25mmol）, 2,2 ', 7,7 '-
Four bromo- two fluorenes of spiral shell [3.3] heptane -2,6- spiral shells（0.89g, 1.25mmol）, sodium tert-butoxide（0.86g, 9.00mmol）, three（Two is sub-
Benzylacetone）Two palladiums（0.34g, 0.37mmol）And tri-butyl phosphine（0.23g, 1.12mmol）Mixing.Then, in nitrogen atmosphere
Under, 15mL dry toluenes are added into flask.By reaction mixture under nitrogen atmosphere 110 DEG C be heated to reflux 24 it is small when.Cooling
To room temperature, by reaction mixture dichloromethane and salt water washing, and with anhydrous MgSO4It is dry.After evaporating solvent, residue
Pass through column chromatography（Dichloromethane/petroleum ether=2/1）Purifying, obtains dark gray solid（0.89g）, yield 55%.1H NMR
(400 MHz, CDCl3) δ 7.21 – 6.50 (m, 32H), 3.76 (d, J = 28.7 Hz, 24H), 2.56 –
2.34 (m, 8H), 1.61 (s, 4H), 1.25 (s, 4H), 0.94 – 0.82 (m, 4H)。
Embodiment 5
Prepare 2,2 ', 7,7 '-four（Double -4- the methoxyphenyls of N, N-）Two fluorenes of-spiral shell [3.3] heptane -2,6- spiral shell, it is as follows：
4,4'- dimethoxy diphenylamines is added in the two mouth flask of 50mL（1.72g 7.50mmol）, 2,2 ', 7,7 '-
Four bromo- two fluorenes of spiral shell [3.3] heptane -2,6- spiral shells（0.89g, 1.25mmol）, sodium tert-butoxide（0.86g, 9.00mmol）, three（Two is sub-
Benzylacetone）Two palladiums（0.34g, 0.37mmol）And tri-butyl phosphine（0.23g, 1.12mmol）Mixing.Then, in nitrogen atmosphere
Under, 15mL dry toluenes are added into flask.By reaction mixture under nitrogen atmosphere 110 DEG C be heated to reflux 24 it is small when.Cooling
To room temperature, by reaction mixture dichloromethane and salt water washing, and with anhydrous MgSO4It is dry.After evaporating solvent, residue
Pass through column chromatography（Dichloromethane/petroleum ether=2/1）Purifying, obtains dark gray solid（1.07g）, yield 66%.1H NMR
(400 MHz, CDCl3) δ 7.21 – 6.50 (m, 32H), 3.76 (d, J = 28.7 Hz, 24H), 2.56 –
2.34 (m, 8H), 1.61 (s, 4H), 1.25 (s, 4H), 0.94 – 0.82 (m, 4H)。
Embodiment 6
Prepare 2,2 ', 7,7 '-four（Double -4- the methoxyphenyls of N, N-）Two fluorenes of-spiral shell [3.3] heptane -2,6- spiral shell, it is as follows：
4,4'- dimethoxy diphenylamines is added in the two mouth flask of 50mL（1.72g 7.50mmol）, 2,2 ', 7,7 '-
Four bromo- two fluorenes of spiral shell [3.3] heptane -2,6- spiral shells（0.89g, 1.25mmol）, sodium tert-butoxide（0.86g, 9.00mmol）, three（Two is sub-
Benzylacetone）Two palladiums（0.34g, 0.37mmol）And tri-butyl phosphine（0.23g, 1.12mmol）Mixing.Then, in nitrogen atmosphere
Under, 15mL dry toluenes are added into flask.By reaction mixture under nitrogen atmosphere 110 DEG C be heated to reflux 36 it is small when.Cooling
To room temperature, by reaction mixture dichloromethane and salt water washing, and with anhydrous MgSO4It is dry.After evaporating solvent, residue
Pass through column chromatography（Dichloromethane/petroleum ether=2/1）Purifying, obtains dark gray solid（1.20g）, yield 74%.1H NMR
(400 MHz, CDCl3) δ 7.21 – 6.50 (m, 32H), 3.76 (d, J = 28.7 Hz, 24H), 2.56 –
2.34 (m, 8H), 1.61 (s, 4H), 1.25 (s, 4H), 0.94 – 0.82 (m, 4H)。
Embodiment 7
Prepare 2,2 ', 7,7 '-four（Double -4- the methoxyphenyls of N, N-）Two fluorenes of-spiral shell [3.3] heptane -2,6- spiral shell, it is as follows：
4,4'- dimethoxy diphenylamines is added in the two mouth flask of 50mL（1.72g 7.50mmol）, 2,2 ', 7,7 '-
Four bromo- two fluorenes of spiral shell [3.3] heptane -2,6- spiral shells（0.89g, 1.25mmol）, sodium tert-butoxide（0.86g, 9.00mmol）, three（Two is sub-
Benzylacetone）Two palladiums（0.34g, 0.37mmol）And tri-butyl phosphine（0.23g, 1.12mmol）Mixing.Then, in nitrogen atmosphere
Under, 15mL dry toluenes are added into flask.By reaction mixture under nitrogen atmosphere 110 DEG C be heated to reflux 24 it is small when.Cooling
To room temperature, by reaction mixture dichloromethane and salt water washing, and with anhydrous MgSO4It is dry.After evaporating solvent, residue
Pass through column chromatography（Dichloromethane/n-hexane=2/1）Purifying, obtains dark gray solid（1.30g）, yield 80%.1H NMR
(400 MHz, CDCl3) δ 7.21 – 6.50 (m, 32H), 3.76 (d, J = 28.7 Hz, 24H), 2.56 –
2.34 (m, 8H), 1.61 (s, 4H), 1.25 (s, 4H), 0.94 – 0.82 (m, 4H)。
It should be noted last that the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although ginseng
It is described in detail according to the embodiment of the present invention, it will be understood by those of ordinary skill in the art that, to technical scheme
Technical scheme is modified or replaced equivalently, without departure from the spirit and scope of technical scheme, it should all cover claim
In protection domain.
Claims (10)
1. one kind is based on the hole mobile material of two fluorenes of spiral shell [3,3] heptane -2,6- spiral shell, it is characterised in that：With following molecule
Structural formula：
Explanation:Explanation:Explanation:Explanation:Explanation:Explanation: F:Force builds the big-Li Hui student's case original text structural formulas .jpg of cloud in January, 2017 science and engineering。
2. the preparation method of the hole mobile material according to claim 1 based on two fluorenes of spiral shell [3,3] heptane -2,6- spiral shell,
It is characterized in that：It is prepared by the following method：
By 2,2 ', 7,7 '-four bromo- two fluorenes of spiral shell [3.3] heptane -2,6- spiral shells, 4,4 '-dimethoxy diphenylamines, organic base, palladium chtalyst
Agent and Phosphine ligands mixing, add toluene, are uniformly mixed, the lower back flow reaction of nitrogen protection, after the completion of reaction reaction solution through washing,
It is dry, pillar is crossed, desolventizing, recrystallization, obtains compound 2,2 ', 7,7 '-four（Double -4- the methoxyphenyls of N, N-）- spiral shell [3.3]
Two fluorenes of heptane -2,6- spiral shells.
3. the preparation method of the hole mobile material according to claim 2 based on two fluorenes of spiral shell [3,3] heptane -2,6- spiral shell,
It is characterized in that：2,2 ', 7,7 '-four bromo- two fluorenes of spiral shell [3.3] heptane -2,6- spiral shells, 4,4 '-dimethoxy diphenylamines, organic base,
The molar ratio of palladium catalyst and Phosphine ligands is 1:5:7.2:0.3:0.9.
4. the preparation side of the hole mobile material based on two fluorenes of spiral shell [3,3] heptane -2,6- spiral shells according to Claims 2 or 3
Method, it is characterised in that：The organic base is sodium tert-butoxide or potassium tert-butoxide.
5. the preparation side of the hole mobile material based on two fluorenes of spiral shell [3,3] heptane -2,6- spiral shells according to Claims 2 or 3
Method, it is characterised in that：The palladium catalyst is palladium, Pd2dba3、Pd(PPh3)4In one kind.
6. the preparation side of the hole mobile material based on two fluorenes of spiral shell [3,3] heptane -2,6- spiral shells according to Claims 2 or 3
Method, it is characterised in that：The Phosphine ligands are tri-butyl phosphine or three o-methyl-phenyl phosphines.
7. the preparation side of the hole mobile material based on two fluorenes of spiral shell [3,3] heptane -2,6- spiral shells according to Claims 2 or 3
Method, it is characterised in that：The temperature of the back flow reaction is 105 DEG C ~ 110 DEG C, return time 24-36h.
8. the preparation side of the hole mobile material based on two fluorenes of spiral shell [3,3] heptane -2,6- spiral shells according to Claims 2 or 3
Method, it is characterised in that：The solvent of the recrystallization is n-hexane, one kind in toluene, ethyl acetate, petroleum ether, dichloromethane
Or any two kinds of mixture.
It is 9. a kind of as claimed in claim 1 based on two fluorene compound of spiral shell [3.3] heptane -2,6- spiral shells in perovskite solar cell
Application in device.
A kind of 10. preparation method of perovskite solar cell device, it is characterised in that：Include the following steps：
（1）, FTO glass substrates clean, be dry, it is and spare with the processing of ultraviolet-ozone device；
（2）, spin coating SnCl2·2H2The ethanol solution of O, 180 DEG C of calcinations, form SnO2Electron transfer layer；
（3）, spin coating PbI on FTO glass substrates2DMF solution, 90 DEG C of drying, finally soak the FTO glass substrates of above-mentioned drying
Not in CH3NH3In the aqueous isopropanol of I, after isopropanol elution, 70 DEG C dry and cool down spare；
（4）, prepare claim 1 described in the hole mobile material based on two fluorenes of spiral shell [3.3] heptane -2,6- spiral shells chlorobenzene it is molten
Liquid, and add two（Trifluoromethane sulfonic acid acyl）The acetonitrile solution and 4- tert .-butylpyridines of imine lithium；
（5）, above-mentioned prepared solution is subjected to spin coating operation, and be transferred to vacuum evaporation room evaporation Au electrodes, perovskite be made
Solar cell device.
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