CN109096163B - Organic molecular material, synthesis method thereof and application of organic molecular material as hole transport layer - Google Patents
Organic molecular material, synthesis method thereof and application of organic molecular material as hole transport layer Download PDFInfo
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Abstract
The invention belongs to the technical field of organic functional materials, relates to an organic molecular material, a synthetic method thereof and application of the organic molecular material as a hole transport layer, and discloses an organic molecular material with two molecular ends symmetrically connected with bis (4- (methylthio) phenyl) amine, a preparation method and application thereof, wherein the structural formula is shown as a formula I or a formula II. They have good solubility in common organic solvents and can be used for preparing high-quality films by a solution spin coating method. The F1 and F2 organic molecular materials are applied to the forward perovskite solar cell as hole transport layers, the energy conversion efficiency can reach 12.28 percent and 3.96 percent respectively, and the energy conversion efficiency of the F1 organic molecular material applied to a reverse device can reach 15.04 percent.
Description
Technical Field
The invention belongs to the technical field of organic functional materials, and particularly relates to an organic molecular material with two molecular ends symmetrically connected with bis (4- (methylthio) phenyl) amine, a synthetic method thereof and application of the organic molecular material as a hole transport layer material.
Background
In the utilization of solar energy, the most important concept is solar power generation (PV) in addition to photothermal conversion. In recent years, organic-inorganic Perovskite Solar Cells (PSCs) have been rapidly developed, and 2009 japanese scientist Tsutomu Miyasaka for the first time found that perovskites have the function of absorbing sunlight similar to dyes, and applied to solar cells, energy conversion efficiency (PCE) of 3.8% was achieved (a.kojima, k.teshima, y.shiral, t.miyasaka, j.am.chem.soc.2009,131: 6050-. In less than a decade, scientists have been exploring more than 20% of perovskite solar cells (w.s.yang, j.h.noh, n.j.jeon, y.c.kim, s.ryu, j.seo, s.i.seok, Science,2015,348: 1234-. The perovskite solar cell has high efficiency, low cost, solution processing and excellent photoelectric conversion performance; meanwhile, the perovskite material has the advantages of strong absorption, high mobility, long carrier service life, adjustable band gap, capability of being processed in various modes and the like, so that the perovskite material becomes a solar cell technology which is the most promising to replace an inorganic silicon cell. In high performance PSCs, the Hole Transport Material (HTM) plays a key role in extracting and transporting holes from the perovskite material to the counter electrode. Hole transport materials used in perovskite solar cells can be broadly classified into three categories. The first is inorganic and organometallic compounds; the second type is organic conjugated polymer, which has higher hole transport performance and good film forming performance, so the organic conjugated polymer can be used as hole transport material in PSCs, the organic conjugated polymer used in PSCs can be roughly divided into two types, one type is donor polymer with higher hole mobility used in organic solar cells, and the other type is conjugated polymer containing triphenylamine unit specially designed as hole transport material; the third, and relatively most widely studied, class is the solution spin-coatable organic molecular hole transport materials. The organic molecular material has the advantages that the polymer can be prepared by solution processing and spin coating, the structure is diversified, and simultaneously, the batch difference is avoided due to the determined structure, the purification is convenient, and the repeatability is high. The organic molecule HTM can be roughly classified into a Spiro-type organic molecule hole transport material, a star-type organic molecule hole transport material, and a linear organic molecule hole transport material according to the size and configuration of the molecule. Currently, the most widely applied organic molecular hole transport material in perovskite solar cells is based on spirobifluorenyl bulky molecule Spiro-OMeTAD, and the highest efficiency of mesoporous perovskite solar cells based on the material in a doped state can reach 20.8% (D.Bi, W.Tress, M.Gratzel, A.Hagfeldt et al.Sci.adv.2016,2: e 1501170). A large number of organic molecules HTM are synthesized and applied to PSCs, and the final aim is to seek a material capable of replacing Spiro-OMeTAD, meet the requirements of high efficiency, low synthesis cost and improvement on the stability of corresponding devices.
Disclosure of Invention
The invention aims to provide organic molecular materials F1 and F2 with bis (4- (methylthio) phenyl) amine symmetrically connected at two molecular ends and a preparation method thereof.
The structural general formula of the organic molecular material F1 provided by the invention is shown as a formula I, and the structural general formula of F2 is shown as a formula II:
in the formula I or II, R is straight-chain alkyl with 6 carbon atoms in total.
A method for preparing an organic molecular material of formula I, comprising the steps of: under the catalytic action of tris (dibenzylideneacetone) dipalladium (0), tri-tert-butylphosphine tetrafluoroborate and sodium tert-butoxide, carrying out Buchwald-Hartwig reaction on a compound shown in a formula III and a compound shown in a formula IV, namely, carrying out reflux reaction after mixing in a toluene solution to obtain a solution containing the organic molecular material shown in the formula I, and purifying to obtain the organic molecular material shown in the formula I.
In the formula III, R is linear alkyl with the total number of carbon atoms of 6.
In the method, the feeding molar ratio of the compound shown in the formula III to the compound shown in the formula IV is 1: 2-2.2, preferably 1: 2.2.
The feeding molar ratio of the tris (dibenzylideneacetone) dipalladium (0) to the compound shown in the formula III is 0.01-0.02: 1, and preferably 0.02: 1.
The feeding molar ratio of the tri-tert-butylphosphine tetrafluoroborate to the compound shown as the formula III is 0.015-0.03: 1, preferably 0.03: 1.
The feeding molar ratio of the sodium tert-butoxide to the compound shown in the formula III is 2-3: 1, preferably 3: 1.
The reaction time is 12 to 48 hours, preferably 12 hours.
The method also comprises the following purification steps: and (2) cooling the solution containing the organic molecular material shown in the formula I to room temperature, extracting, combining organic phases, washing with saturated sodium chloride aqueous solution, drying with anhydrous magnesium sulfate, evaporating the solvent in vacuum, and purifying by using a chromatographic column through a mixed solvent of ethyl acetate and petroleum ether in a volume ratio of 1:20(v: v) to obtain the organic molecular material shown in the formula I.
A method for preparing an organic molecular material represented by formula II, similar to the method for preparing formula I, comprises the following steps: under the catalytic action of tris (dibenzylideneacetone) dipalladium (0), tri-tert-butylphosphine tetrafluoroborate and sodium tert-butoxide, carrying out Buchwald-Hartwig reaction on a compound shown in a formula IV and a compound shown in a formula V, namely, carrying out reflux reaction after mixing in a toluene solution to obtain a solution containing the organic molecular material shown in the formula II, and purifying to obtain the organic molecular material shown in the formula II.
In formula V, R is as defined in formulas I and II.
In the method, the feeding molar ratio of the compound shown as the formula V to the compound shown as the formula IV is 1: 2-2.2, preferably 1: 2.2.
The feeding molar ratio of the tris (dibenzylideneacetone) dipalladium (0) to the compound shown in the formula V is 0.01-0.02: 1, and preferably 0.02: 1.
The feeding molar ratio of the tri-tert-butylphosphine tetrafluoroborate to the compound shown as the formula V is 0.015-0.03: 1, preferably 0.03: 1.
The feeding molar ratio of the sodium tert-butoxide to the compound shown in the formula V is 2-3: 1, preferably 3: 1.
The reflux reaction time is 12-48 hours, preferably 12 hours.
The method also comprises the following purification steps: and cooling the solution containing the organic molecular material shown in the formula II to room temperature, then extracting, combining organic phases, washing with saturated sodium chloride aqueous solution, drying with anhydrous magnesium sulfate, evaporating the solvent in vacuum, and purifying by using a chromatographic column through a mixed solvent of dichloromethane and petroleum ether with the volume ratio of 1:3(v: v) to obtain the organic molecular material shown in the formula II.
The invention also provides a method for preparing the monomer shown in the formula IV, which comprises the following steps: mixing the compounds shown in the formulas VI and VII, tris (dibenzylideneacetone) dipalladium, 1,1' -bis (diphenylphosphino) ferrocene (DPPF), sodium tert-butoxide and dried toluene in a reactor, refluxing for 12-24 hours (preferably 12 hours) at 90-110 ℃ (preferably 90 ℃) under the protection of nitrogen to obtain a reaction mixed solution, cooling to room temperature, dissolving in dichloromethane, washing with saturated sodium chloride aqueous solution, drying with anhydrous magnesium sulfate, evaporating the solvent in vacuum, and purifying with a chromatographic column by using an ethyl acetate/petroleum ether (1/15, V/V) mixed solution to obtain a yellow solid, namely the compound shown in the formula IV. Wherein the molar ratio of the reaction raw materials is a compound shown in formula VI: a compound represented by formula vii ═ 1:1 to 1.2, preferably 1: 1.2.
The organic molecular material shown in the formula I or the formula II is used as a hole transport material in the preparation of perovskite solar cells, particularly in the preparation of hole transport layers of the perovskite solar cells, wherein the organic molecules shown in the formula I are used as the hole transport layers to prepare forward and/or reverse photovoltaic devices; and (3) preparing the forward photovoltaic device by using the organic molecules shown in the formula II as a hole transport layer.
The invention has the beneficial effects that:
the invention applies the methylthio unit to the design and synthesis of organic molecule hole transport materials which can be processed by soluble solution, and synthesizes the organic molecule hole transport material with two molecular ends symmetrically connected with bis (4- (methylthio) phenyl) amine. They have good solubility in common organic solvents (such as dichloromethane, trichloromethane, toluene, chlorobenzene and the like), and can prepare high-quality films by a solution method; and can obtain a material with a high purity compared with a polymer material. At the same time, these molecules have suitable HOMO and LUMO energy levels. The organic molecule is used as a hole transport layer to prepare a material based on CH3NH3PbI3The optimized perovskite solar cell has the highest energy conversion efficiency of more than 15%.
Drawings
Fig. 1 is a synthetic route diagram provided by the present invention.
Fig. 2 shows absorption spectra of solid-state thin films prepared from F1 and F2.
FIG. 3 is a schematic diagram of the structure of a perovskite solar cell; wherein fig. 3(a) is a forward perovskite solar cell structure using F1 or F2 as a hole transport layer, and fig. 3(b) is an inverse perovskite solar cell structure using F1 as a hole transport layer.
FIG. 4 is a current-voltage plot of a perovskite solar cell; among them, fig. 4(a) is a current-voltage curve of a forward perovskite solar cell in which a hole transport layer is prepared based on F1 of 15mg/L, fig. 4(b) is a current-voltage curve of an inverse perovskite solar cell in which a hole transport layer is prepared based on F1, and fig. 4(c) is a current-voltage curve of a forward perovskite solar cell in which a hole transport layer is prepared based on F2 of 10 mg/L.
Fig. 5 is a cyclic voltammogram of a compound thin film, in which fig. 5(a) is a cyclic voltammogram based on an F1 thin film, and fig. 5(b) is a cyclic voltammogram based on an F2 thin film.
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1 Synthesis of bis (4- (methylthio) phenyl) amine (Compound of formula IV)
4-Aminothioanisole (formula VII, 3.34g, 24mmol), sodium tert-butoxide (2.69g, 28mmol), tris (dibenzylideneacetone) dipalladium (0.366g, 0.4mmol), 1' -bis (diphenylphosphino) ferrocene (DPPF) (0.332g, 0.6mmol) and 20ml toluene were mixed and stirred at constant temperature of 60 ℃ for 30 min. 4.06g of 4-bromothioanisole (formula VI, 4.06g, 20mmol) are added again, and then the mixture is refluxed at 90 ℃ for 12 hours under the protection of nitrogen. The reaction mixture was cooled to room temperature, deionized water was added, ethyl acetate was extracted three times, the organic phases were combined, followed by washing with saturated aqueous sodium chloride solution, drying over anhydrous magnesium sulfate, and after evaporation of the solvent in vacuo, purification was performed by chromatography using ethyl acetate/petroleum ether (1/15, V/V) to give 3.64g of bis ((methylthio) phenyl) amine as a yellow solid, yield: 69.73 percent. GC/MS:261 (M)+)。
The structure validation data is as follows:1h NMR (500MHz, acetone-d6)(ppm):8.22(s,1H),7.21(m,4H),7.02(m,4H),2.41(s,6H)。
Example 2, 9-dihexyl-N2,N2,N7,N7Synthesis of (e) -tetrakis (4- (methylthio) phenyl) -9H-fluorenyl-2, 7-diamine (F1) (formula i, wherein R ═ C)6H13)
To the flask was added 20ml of toluene, bis (4- (methylthio) phenyl) amine (formula IV, 2.30g, 8.8mmol), 2, 7-dibromo-9, 9-hexylfluorene (formula III, 2g, 4mmol), tris (dibenzylideneacetone) dipalladium (73.2mg, 0.08mmol), tri-tert-butylphosphine tetrafluoroborate (34.8mg, 0.12mmol) and sodium tert-butoxide (1.152g, 12mmol) were added to the flask, and the reaction was stirred in an oil bath for 12 hours. After the solution was cooled, deionized water and dichloromethane were added for extraction three times, the organic phases were combined, and the organic phase was washed twice with saturated aqueous sodium chloride solution. Adding anhydrous magnesium sulfate, drying, and purifying with neutral alumina chromatographic column, eluting with 20:1(v/v) petroleum ether/ethyl acetate. The resulting product was dissolved in acetone and recrystallized from methanol to collect product F1 as a pale yellow solid (2.20g, 64.6%). Compounds were characterized using mass spectrometry and nuclear magnetism as follows. MALDI-TOF m/z 850.2 calculated C53H60N2S4Has a mass to charge ratio of 850.3.
The structure validation data is as follows:1h NMR (500MHz, acetone-d6)(ppm):7.68(d,2H),7.27-7.24(m,8H),7.18(d,2H),7.07-7.04(m,8H),7.02-7.00(q,2H),2.50(s,12H),1.88-1.85(m,4H),1.32-1.17(m,4H),1.13-1.11(m,8H),0.87(t,6H),0.77-0.72(m,4H).13C NMR (acetone-d)6,500MHz)(ppm):153.10,147.30,146.45,137.42,132.80,129.18,125.09,124.42,121.16,120.18,55.96,40.81,32.39,30.55,30.40,30.37,30.24,30.09,24.75,23.32,16.57,14.49.
The compound is well dissolved in common solvents such as trichloromethane, toluene, chlorobenzene and the like.
The absorption spectrum of the organic molecular material F1 solid film prepared in this example is shown in FIG. 2. The compound F1 thin film is prepared by dissolving F1 in an organic solvent to obtain an F1 solution, and then forming a film on a quartz plate by adopting a solution spin coating method, wherein the absorption of the F1 compound thin film is mainly concentrated at 305-430nm, the absorption margin is about 427nm, and the corresponding optical band gap is 2.90 eV.
FIG. 5(a) is based onCyclic voltammogram of F1 film. The measurement was carried out by directly dissolving F1 in tetrabutylammonium hexafluorophosphate acetonitrile solution with Ag/AgCl as a reference electrode. The initial oxidation potential was found to be 0.18v from the figure, and then represented by the formula HOMO ═ E (E)ox onset+4.71)(eV)＝-4.89eV,LOMO＝(Eg opt+HOMO)(eV)＝-1.99eV.
Examples 3, 4,9, 9-tetrahexyl-N2,N2,N7,N7-tetrakis (4- (methylthio) benzene) -4, 9-dihydro-s-bisfluorenyl [1,2-b:5,6-b']Synthesis of Bisphthiophene-2, 7-diamine (F2) (formula II, R ═ C)6H13)
20ml of toluene was added to the flask, and bis (4- (methylthio) phenyl) amine (formula IV, 1.49g, 5.72mmol), 2, 7-dibromo-4, 4,9, 9-tetrahexyl-bisfluorenyl [1,2-b:5,6-b']Bithiophene (formula V, 2g, 2.6mmol), tris (dibenzylideneacetone) dipalladium (47.6mg, 0.052mmol), tri-tert-butylphosphine tetrafluoroborate (22.6mg, 0.078mmol) and sodium tert-butoxide (0.749g, 7.8mmol) were added to the flask and stirred in the oil bath for 12 h. After the solution is cooled, deionized water and dichloromethane are added for extraction for three times, organic phases are combined, and the organic phase is washed twice by saturated sodium chloride aqueous solution. Adding anhydrous magnesium sulfate, drying, and purifying with neutral alumina chromatographic column, eluting with 3:1(v/v) petroleum ether/dichloromethane. The resulting product was dissolved in acetone and recrystallized from methanol to collect product F2 as a dark yellow solid (1.58g, 54.2%). Compounds were characterized by mass spectrometry. C68H84N2S6Exact Mass (1120.52), MS (MADI-TOF) (1122.3). MALDI-TOF m/z1122.3. calculated C68H84N2S6Has a mass to charge ratio of 1120.52.
The structure validation data is as follows:1h NMR (500MHz, acetone-d6)(ppm):7.11(d,10H),7.03(d,10H),2.57(t,8H),2.46(s,12H),1.60(m,8H),1.36(m,24H),0.90(t,12H).
The compound is well dissolved in common solvents such as trichloromethane, toluene, chlorobenzene and the like.
The absorption spectrum of the organic molecular hole transport material F2 solid film prepared in this example is shown in FIG. 2. The F2 film is prepared by dissolving F2 in an organic solvent to obtain an F2 solution, and then forming a film on a quartz plate by adopting a solution spin coating method, wherein the compound F2 film has wide absorption between 307 nm and 460nm, the absorption margin is about 450nm, and the corresponding optical band gap is 2.75 eV.
The film absorption of this compound was broader in absorption width and red-shifted in absorption position than that of F1 film.
FIG. 5(b) is a cyclic voltammogram based on F2 film. And (3) coating the trichloromethane solution of F2 on a glassy carbon electrode, taking Ag/AgCl as a reference electrode, airing to form a film, and then placing the film in a tetrabutyl ammonium hexafluorophosphate acetonitrile solution for measurement. The initial oxidation potential and initial reduction potential were found to be 0.23v from the graph and then represented by the formula HOMO ═ E (E)ox onset+4.71)(eV)＝-4.94eV,LOMO＝(Eg opt+HOMO)(eV)＝-2.19eV.
Example 4 photovoltaic properties of perovskite solar cells based on the Forward orientation of F1 or F2 as hole transport layer and the reverse orientation of F1 as hole transport material
Preparation of CH-based hole transport layer with F1 or F2 as hole transport layer3NH3PbI3Perovskite solar cell device. Fig. 3 is a schematic diagram of the structure of a forward and reverse perovskite solar cell device, respectively.
The structure of the forward device is FTO/compact TiO2/CH3NH3PbI3Undoped F1 or F2/Au.
The structure of the reverse device is ITO/undoped F1/CH3NH3PbI3/PC61BM/Al
The forward device preparation method comprises the following steps: the FTO glass is ultrasonically washed by deionized water, ethanol and acetone for 15min and then cleaned by oxygen plasma for 10 min. FTO glass soaked in 200mM TiCl4Adding the FTO into the solution, placing the FTO in a drying oven at 70 ℃ for 1 hour, then cleaning FTO glass by using deionized water and ethanol, and then placing the FTO in the drying oven at 100 ℃ for drying for 1 hour. 0.228g of CH are weighed3NH3I and 0.663g PbI2Dissolving in 1.2ml of DMAC and NMP mixed solution (DMAC: NMP is 5:1) in a glove box at 60 ℃ with stirring to obtain CH3NH3PbI3Spin coating the precursor solution to obtainThe solution was used after filtration through a 0.20um PTFE filter. With bl-TiO2The FTO glass of the layer was placed in a glove box and CH was spin-coated at low speed 1000rpm (15s) and high speed 6000rpm (55s)3NH3PbI3Dripping 500ul chlorobenzene solution rapidly at high speed of 25s, stopping rotation, annealing at 100 deg.C for 5min, cooling FTO glass sheet to room temperature, spin-coating hole transport material at 5000rpm (30s), dissolving hole transport material in 1ml chlorobenzene, and finally adding water at 1.0 × 10-4And (3) evaporating a layer of gold electrode with the thickness of 80nm on the cavity layer by thermal evaporation under the pressure Pa. The preparation process of the positive perovskite battery is that the maximum effective area of the battery is 0.07cm2. In filling with N2AM1.5G intensity (100 mW/cm) using xenon lamp solar simulator in glove box (Takara Shuzo)2) Three parameters of open-circuit voltage, short-circuit current and fill factor of the prepared solar cell device were tested, and the xenon lamp solar simulator was calibrated in the National Renewable Energy Laboratory (NREL) using a silicon diode (with KG5 visible filter).
The preparation method of the reverse device comprises the following steps: and ultrasonically washing the ITO glass for 15min by using a detergent, ethanol and acetone in sequence, drying the ITO glass by using dry air, and carrying out UVO treatment for 20 min. The hole-transporting material was then spin-coated at 5000rpm (40s) and dissolved in 1ml of chlorobenzene. Then annealed in a glove box at 100 ℃ for 5 min. PdI spin coating at 3500rpm2After 20s, CH is added dropwise3NH3I, annealing at 90 ℃ for 8min after the operation is finished. PC with a solubility of 7mg/mL was spin coated by 1500rpm61BM chloroform solution at 1.0 × 10- 4An aluminum electrode with a thickness of 80nm was deposited on the hole layer by thermal evaporation under Pa pressure. The preparation process of the whole perovskite battery is that the maximum effective area of the battery is 0.07cm2. In filling with N2AM1.5G intensity (100 mW/cm) using xenon lamp solar simulator in glove box (Takara Shuzo)2) Three parameters of open-circuit voltage, short-circuit current and fill factor of the prepared solar cell device were tested, and the xenon lamp solar simulator was calibrated in the National Renewable Energy Laboratory (NREL) using a silicon diode (with KG5 visible filter).
Fig. 4(a) and (b) are current-voltage curves for a forward device and a reverse device, respectively, based on F1. Based on the forward devices prepared with different concentrations of F1, the open-circuit voltage of the device (F1 of 15 mg/mL) is preferably 0.95V, and the short-circuit current is 18.39mA/cm2The filling factor is 70.27%, and the energy conversion efficiency is 12.28%; the open-circuit voltage of the inverter is 1.04V, and the short-circuit current is 21,18mA/cm2The fill factor was 68% and the energy conversion efficiency was 15.04%. (c) Based on the current-voltage curves of the forward devices with different concentrations of F2, the open-circuit voltage of the device (F2 of 10.00 mg/ml) is preferably 0.9V and the short-circuit current is preferably 11.62mA/cm2The fill factor was 37.72%, and the energy conversion efficiency was 3.96%.
The invention is described with reference to specific embodiments and examples. However, the invention is not limited to only the described embodiments and examples. One of ordinary skill in the art will recognize, based on the teachings herein, that many modifications and substitutions can be made without departing from the scope of the invention, which is defined by the claims.
Claims (6)
1. The application of the organic molecular material as a hole transport layer in the preparation of a photovoltaic device is characterized in that the structural formula of the organic molecular material is a compound shown as follows:
r is straight-chain alkyl with the total number of carbon atoms of 6;
the organic molecules are used as a hole transport layer to prepare a forward photovoltaic device.
2. Use of the organic molecular material according to claim 1 as hole transport layer in the preparation of a photovoltaic device, characterized in that: the synthesis method comprises the following steps:
under the catalytic action of tris (dibenzylideneacetone) dipalladium (0), tri-tert-butylphosphine tetrafluoroborate and sodium tert-butoxide, carrying out Buchwald-Hartwig reaction on a compound shown in a formula V and a compound shown in a formula IV, namely, carrying out reflux reaction after mixing in a toluene solution to obtain a solution containing an organic molecular material, and purifying to obtain the organic molecular material;
(formula IV)
(formula V)
In the formula V, R is linear alkyl with the total number of carbon atoms of 6.
3. Use of the organic molecular material according to claim 2 as hole transport layer in the preparation of a photovoltaic device, characterized in that: the feeding molar ratio of the compound shown as the formula V to the compound shown as the formula IV is 1: 2-2.2;
the feeding molar ratio of the tris (dibenzylideneacetone) dipalladium (0) to the compound shown in the formula V is 0.01-0.02: 1;
the feeding molar ratio of the tri-tert-butylphosphine tetrafluoroborate to the compound shown in the formula V is 0.015-0.03: 1;
the feeding molar ratio of the sodium tert-butoxide to the compound shown in the formula V is 2-3: 1;
the reflux reaction time is 12-48 hours.
4. Use of the organic molecular material according to claim 2 as a hole transport layer in the preparation of a photovoltaic device, characterized in that the purification step is: cooling the solution containing the organic molecule hole transport material to room temperature, extracting, combining organic phases, washing with saturated sodium chloride aqueous solution, drying with anhydrous magnesium sulfate, evaporating the solvent in vacuum, and purifying by using a chromatographic column with a mixed solvent to obtain an organic molecule material; the purification by chromatography column adopts a mixed solvent of dichloromethane and petroleum ether with the volume ratio of 1: 3.
5. Use of the organic molecular material according to claim 2 as hole transport layer in the preparation of a photovoltaic device, characterized in that: the synthesis method of the compound shown in the formula IV comprises the following steps: mixing a compound shown as a formula VI, a formula VII, tris (dibenzylideneacetone) dipalladium, 1,1' -bis (diphenylphosphino) ferrocene (DPPF), sodium tert-butoxide and dried toluene in a reactor, heating to 90-110 ℃ under the protection of nitrogen, refluxing for 12-24 hours to obtain a reaction mixed solution, cooling to room temperature, extracting, combining organic phases, washing with saturated sodium chloride aqueous solution, drying with anhydrous magnesium sulfate, evaporating the solvent in vacuum, and then adopting ethyl acetate and petroleum ether in a volume ratio of 1: 15, purifying the mixed solution by a chromatographic column to obtain a yellow solid, namely the compound shown in the formula IV; wherein the molar ratio of the reaction raw materials is a compound shown in formula VI: compound of formula vii = 1:1 to 1.2;
(VI) (formula VII)
6. Use according to claim 1, characterized in that: the photovoltaic device is based on CH3NH3PbI3The perovskite solar cell of (1).
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