CN113943301A - Metalloporphyrin hole transport material for perovskite solar cell - Google Patents

Metalloporphyrin hole transport material for perovskite solar cell Download PDF

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CN113943301A
CN113943301A CN202010693410.4A CN202010693410A CN113943301A CN 113943301 A CN113943301 A CN 113943301A CN 202010693410 A CN202010693410 A CN 202010693410A CN 113943301 A CN113943301 A CN 113943301A
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CN113943301B (en
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麦绮伦
高鹏
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Xiamen Zhongke Yanyang New Materials Co.,Ltd.
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Abstract

The invention provides a metalloporphyrin hole transport material for a perovskite solar cell. The metalloporphyrin hole transport material has a structure shown in a formula (I):
Figure DDA0002590173970000011
the metalloporphyrin hole transport material is simple in synthesis steps, and the synthesized material has good high molar extinction coefficient, low synthesis cost, solubility, excellent film forming property and stability, and is beneficial to improving the stability of the perovskite battery and the photoelectric conversion efficiency.

Description

Metalloporphyrin hole transport material for perovskite solar cell
Technical Field
The invention belongs to the technical field of perovskite solar cells, and particularly relates to a metalloporphyrin hole transport material for a perovskite solar cell, and a preparation method and application thereof.
Background
In recent years, due to energy crisis and environmental problems, development of new energy is urgently required to break through the imminent dilemma. Solar energy has great advantages as an inexhaustible new energy source. If the energy absorbed by the earth surface can be sufficiently converted into electric energy to be stored, the energy is directly one of the best choices for solving the earth energy supply problem and the environmental problem. Therefore, in recent years, research on solar cells has been receiving much attention. At present, the development of solar cells has been diversified, and the solar cells are mainly classified into the following generations:
the first generation solar cells are mainly monocrystalline silicon, polycrystalline silicon, thin film-amorphous silicon and the like. From the application perspective, commercial monocrystalline silicon and polycrystalline silicon solar cells become mainstream nowadays, but due to the limitation of material purity and preparation process, the conversion efficiency is difficult to improve and the cost is difficult to reduce; although the amorphous silicon solar cell can be produced in a large area and has low cost, the amorphous silicon solar cell is limited due to low conversion efficiency and poor stability. And following the first generation solar cell, the second generation solar cell is mainly thin film type-cadmium telluride, thin film type-copper indium gallium selenide and the like. Its advantages are wide light absorbing range, high stability, no light attenuation, low power consumption, low temp loss coefficient, low sensitivity to shielding object and short recovery time. However, the compounds are extremely toxic and have great harm to the environment, so that the commercial production of the compounds is limited, and the third generation of low-cost and high-efficiency solar cells are inoculated. The third generation solar cell mainly comprises a dye-sensitized solar cell, an organic solar cell, a quantum dot sensitized solar cell, a perovskite solar cell and the like. Among them, the perovskite solar cell is heteroleptic, and the efficiency is increased from 3.8% to 25.2% nowadays in a short period of several years. It has become a hot spot of research in recent years because of its high photoelectric conversion efficiency. The last fourth generation solar cell is a tandem solar cell developed on the basis of the previous three generations of solar cells, which is typically a physical stack of two or even more types of solar cells. Due to the difference between the wavelengths that can be utilized, the efficiency after lamination can be made greater than the efficiency alone, thus breaking through the theoretical efficiency limit of the solar cell.
Among the numerous solar cells, perovskite solar cells (solar cells) have attracted attention in recent years as the most rapidly-developed solar cells, and their efficiency is expected to be even higher than that of shouldered single crystal silicon solar cells. The perovskite solar cell mainly comprises conductive glass (FTO/ITO), electron transport layers (ETMs), perovskite light absorption layers, hole transport layers (HTMs) and metal electrodes. In addition to perovskite light absorbing layers and electron transporting layers, hole transporting layers also play an important role in perovskite solar cells. The hole transport layer is arranged between the perovskite light absorption layer and the metal electrode, and mainly aims to block the transmission of electrons, increase the hole transmission and prevent the direct contact between the perovskite material and the electrode from causing a quenching phenomenon, so that the hole transport layer matched with the energy levels of the perovskite material and the metal electrode can separate the electrons and holes at the interface of the functional layer, reduce the charge recombination, facilitate the hole transmission and further improve the performance of the battery.
Many materials for producing a hole transport layer have been developed, and among them, the ideal materials for producing a hole transport layer must have the following advantages: (1) the glass transition temperature is higher, so that the phase transition is avoided; (2) good hole mobility; (3) energy level matching with perovskite materials ensures that holes can be effectively injected and transmitted at each interface; (4) the stability is good; (5) the production cost is low, and the commercialization is easy; (6) good dissolving power and film forming property, etc.
Among them, the most widely used material for preparing the hole transport layer is 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD). Although it has the advantages of good film forming property, etc., it also has some disadvantages, such as complicated synthesis steps, poor hole transport capability, low hole mobility, poor stability, etc.
Currently, to improve the hole transport ability, the conductivity and hole mobility are generally improved by adding chemical dopants and oxidants to the materials, such as the dopants lithium bistrifluoromethanesulfonimide (LiTFSI), 4-tert-Butylpyridine (4-tert-Butylpyridine), and Co3+The complex is used as an oxidant, but the use of the additive not only weakens the stability of the battery, but also increases the hysteresis effect of the battery.
Disclosure of Invention
In order to solve the problems of complex synthesis steps, poor hole transport capacity, low hole mobility, poor stability and the like of the Spiro-OMeTAD, the invention provides a metalloporphyrin hole transport material for a perovskite solar cell, wherein the metalloporphyrin hole transport material for the perovskite solar cell takes a porphyrin metal cluster as the hole transport material for the perovskite solar cell, so that the traditional hole transport material Spiro-OMeTAD can be replaced, and the performance of the perovskite solar cell is improved.
The porphyrin compound is a Conjugated double bond macrocyclic system consisting of 4 pyrroles and 4 unsaturated carbon atoms, has 22 pi electrons and 11 Conjugated double bonds, and is easy to modify and transform substituents. In addition, the porphyrin compound has a rigid structure, not only has good stability, but also has the characteristics of excellent optical property, electrochemical property, bionic property, carrier mobility, thermal stability, wide light absorption range and the like, and has strong absorption in a visible light range. Therefore, the metalloporphyrin hole transport material provided by the invention not only has easily adjustable structure and performance, but also has excellent performance of porphyrin molecules.
The purpose of the invention is realized by the following technical scheme:
a compound having the structure shown in formula (I):
Figure BDA0002590173950000031
wherein F and E are the same or different and are independently selected from the structures shown below,
Figure BDA0002590173950000041
wherein R is44Is composed of
Figure BDA0002590173950000042
X is selected from O or S;R1-R34same or different, independently from each other selected from H, C1-15Alkyl radical, C1-15Alkoxy radical, - [ CH2]m[OC2H4]nOCH3(m＝0～1，n＝1～30)；
A and C are the same or different and are independently selected from one of the following structures (11) or (12):
Figure BDA0002590173950000051
wherein R is35-R40Same or different, independently from each other selected from H, C1-15Alkyl radical, C1-15Alkoxy radical, - [ CH2]m[OC2H4]nOCH3(m＝0～1，n＝1～30)；
M is selected from Zn (II), Cu (II), Eu (III), Mn (III), Fe (III), Ru (III), Co (II) or Co (III).
According to the invention, the structure represented by formula (11) is selected from one of the following structures:
Figure BDA0002590173950000052
wherein R is35-R39Is as defined above.
According to the invention, R35-R40Same or different, independently from each other selected from H, C4-8Alkyl radical, C4-8Alkoxy radical, - [ CH2]m[OC2H4]nOCH3(m＝0～1，n＝2～10)。
According to the invention, R35-R40Same or different, independently from each other selected from H, C4H9O-、C8H17O-。
According to the invention, R1-R34Same or different, independently from each other selected from H, C1-8Alkyl radical, C1-8Alkoxy radical, - [ CH2]m[OC2H4]nOCH3(m＝0～1，n＝1～10)。
According to the invention, R1-R34Same or different, independently from each other selected from H, CH3O-。
Illustratively, the compound represented by the formula (1) is selected from the following compounds:
Figure BDA0002590173950000061
in the metalloporphyrin hole transport material provided by the invention, a porphyrin ring can be connected with electron donating groups such as diphenylamine, triphenylamine and the like, and a compound containing diphenylamine and triphenylamine systems has very good electron transport characteristics and good light stability, so that the metalloporphyrin hole transport material is very suitable to be used as a transport layer material of current carriers. In order to avoid the phenomenon that porphyrin molecules are gathered on the surface of a semiconductor to reduce the photoelectric conversion efficiency, the porphyrin ring can be connected with a larger substituent group, such as hydrophobic carbon chains of an oxygen alkyl chain, a sulfur alkyl chain and the like, so that on one hand, the solubility of the porphyrin hole transport material is improved, on the other hand, the long carbon chain can also play a role in protecting a perovskite layer from being damaged, and the stability and the photoelectric conversion efficiency of the perovskite solar cell are improved.
The invention also provides a preparation method of the compound, and the synthetic route is as follows:
Figure BDA0002590173950000071
the method comprises the following steps:
(1) mixing dipyrromethane and a compound shown as a formula 8, and reacting to prepare a compound shown as a formula 9;
(2) mixing a compound shown as a formula 9 with a metal salt, and carrying out a metallization reaction to prepare a compound shown as a formula 10;
(3) mixing the compound shown in the formula 10 with N-bromosuccinimide, and carrying out bromination reaction to prepare the compound shown in the formula 11;
(4) mixing the compound shown in the formula 11 with EH and FH (ethylene-vinyl acetate) to perform a Suzuki reaction or a Buchwald-Hartwig coupling reaction to prepare the compound shown in the formula I; or, reacting the compound represented by the formula 11 with
Figure BDA0002590173950000072
Mixing, and carrying out Suzuki reaction to prepare the compound shown in the formula I; wherein E and F are as defined above.
According to the invention, in step (1), the temperature of the reaction is room temperature, such as 20-35 ℃; the reaction time is 2 to 8 hours, such as 5 hours.
The reaction is prepared in the presence of a dichloromethane organic solvent and trifluoroacetic acid.
The reaction is carried out under the protection of nitrogen atmosphere.
The molar ratio of the dipyrromethane to the compound shown in the formula 8 is 1: 1.
According to the present invention, in the step (2), the molar ratio of the compound represented by the formula 9 to the metal salt is 1: 10.
The metal salt is selected from zinc acetate dihydrate, nickel acetate tetrahydrate, ferric bromide, manganese acetate, cupric acetate, magnesium bromide and europium acetate.
The organic solvent in the metallization reaction process can be different organic solvents selected according to different metal salts; for example, when the metal salt is selected from zinc acetate dihydrate, the organic solvent is selected from dichloromethane, the reaction temperature is room temperature, and the reaction time is 1-5 hours; for example, when the metal salt is selected from nickel acetate tetrahydrate, iron bromide, manganese acetate, copper acetate and magnesium bromide, the organic solvent is selected from N, N-dimethylformamide, and the reaction is carried out under reflux overnight.
According to the present invention, in the step (3), the bromination is carried out in the presence of methylene chloride.
The reaction was carried out under a nitrogen atmosphere.
The reaction temperature is room temperature, and the reaction time is 0.5-2 hours.
The molar ratio of the compound shown in the formula 10 to the N-bromosuccinimide is 1: 2.2.
For example, the compound represented by formula 10(0.482 mmol) is dissolved in dichloromethane and stirred, then N-bromosuccinimide (NBS) (1.06 mmol) is dissolved in dichloromethane and slowly added dropwise to the stirred solution, and the reaction is carried out under nitrogen for 1 hour; then, removing the solvent under reduced pressure to obtain a residue, and purifying by silica gel column chromatography with dichloromethane/n-hexane as eluent; finally in MeOH/CH2Cl2And (4) recrystallizing to obtain the compound shown in the formula 11.
According to the present invention, in step (4), the molar ratio of the compound represented by formula 11 to EH and FH is 1: 3. A compound represented by the formula 11 and
Figure BDA0002590173950000091
in a molar ratio of 1: 3.
K is also added in the reaction process2CO3、Pd(PPh3)4(ii) a Said K2CO3The molar ratio of the compound represented by the formula 11 to the compound represented by the formula is (1: 10); the Pd (PPh)3)4The molar ratio to the compound represented by formula 11 was (1: 0.16).
The reaction was heated to reflux for 8h, cooled to room temperature, concentrated to remove the solvent, and purified by column Chromatography (CH)2Cl2Hexane) to obtain the compound shown in the formula I.
The invention also provides the application of the compound, which is used for a hole transport material of the perovskite solar cell.
The invention also provides a hole transport material of the perovskite solar cell, and the material comprises the compound.
The invention has the beneficial effects that:
the invention provides a metalloporphyrin hole transport material for a perovskite solar cell. The metalloporphyrin hole transport material is simple in synthesis steps, and the synthesized material has good high molar extinction coefficient, low synthesis cost, solubility, excellent film forming property and stability, and is beneficial to improving the stability of the perovskite battery and the photoelectric conversion efficiency.
Drawings
FIG. 1 is a schematic diagram of a structure of a perovskite solar cell based on a porphyrin hole transport material.
Fig. 2 is a graph of photocurrent density versus voltage for the perovskite solar cells of example 2 of the present invention and comparative example 1.
Fig. 3 is a cross-sectional scanning electron micrograph of compound 1 prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1 Synthesis of porphyrin hole transport materials
Figure BDA0002590173950000101
Dipyrromethane (41.0 mmol) and compound 8(41.0 mmol) were dissolved in anhydrous oxygen-free dichloromethane (DCM,5.4 l) and trifluoroacetic acid (37.3 mmol) was added. The solution was stirred at 23 ℃ for 5 hours, after which dichlorodicyano-p-benzoquinone (DDQ) (62.1 mmol) was added to form a mixture, which was stirred for an additional 2 hours and purified by silica gel column chromatography using Dichloromethane (DCM)/n-Hexane (Hexane) (1:2) as eluent to give the crude product, which was finally purified in MeOH/CH2Cl2Medium recrystallization afforded compound 9 as a purple solid (5.31 g, 32%).
By CH2Cl2(500 ml) Compound 9(5.13 mmol) was dissolvedMol), then a solution of zinc acetate dihydrate (51.3 mmol) in MeOH (50 ml) was added thereto. After 10 hours of reaction, DCM/H was added2And (4) extracting, concentrating an organic layer, and performing silica gel column chromatography to obtain a mauve solid compound 10 (98%).
Compound 10(0.482 mmol) was dissolved in a stirred solution of dichloromethane (400 ml), then N-bromosuccinimide (NBS) (1.06 mmol) was dissolved in dichloromethane (DCM,300 ml), slowly added dropwise to the stirred solution, and reacted under nitrogen for 1 hour. Subsequently, the solvent was removed under reduced pressure to obtain a residue, which was purified by silica gel column chromatography using dichloromethane/n-hexane (1:2) as an eluent. Finally in MeOH/CH2Cl2Medium recrystallization afforded compound 11 as a purple solid (0.48 g, 83%).
Compound 11(0.123 mmol) and 60% NaH (1.23 mmol) were dissolved in THF (30 mL), stirred for 5min, and compound 12(1.23 mmol), Pd (OAc) were added2(0.062 mmol) and DPEphos (0.074 mmol), heated at reflux for 4h, cooled to room temperature, concentrated to remove the solvent, and purified by column Chromatography (CH)2Cl2Hexane 1:3) to give compound 1 (38%) as a green solid. Identification and analysis of the Green solid Compound 11H NMR(CDCl3,500MHz):δH＝9.20(d,J＝4.5Hz,4H),8.82(d,J＝4.5Hz,4H),7.20(d,J＝2.0Hz,4H),7.19-7.140(m,8H),6.67(s,2H),6.62(d,J＝9.0Hz,8H),3.98(t,J＝6.5Hz,8H),3.57(s,J＝9.0Hz,12H),1.80-1.71(m,8H),1.48(m,8H),1.36(m,34H),0.89-0.77(m,12H)。
Taking compound 11(0.123 mmol) and compound 13(0.37 mmol), compound K is added2CO3(1.23 mmol), Pd (PPh)3)4(0.02 mmol) in THF (30 mL)/H2O (10 ml), heated under reflux for 8h, cooled to room temperature, concentrated to remove the solvent, and purified by column Chromatography (CH)2Cl2Hexane 1:1) to give compound 2 as a purple solid (74%). Identification and analysis1H NMR(CDCl3,500MHz):δH＝9.07(s,8H),8.08-7.92(m,4H),7.44-7.38(m,4H),7.36(d,J＝9.0Hz,8H),7.32-7.26(m,4H),4.10(t,J＝7.0Hz,4H),3.87-3.73(m,12H),1.93-1.78(m,8H),1.55-1.44(m,8H),1.40-1.17(m,34),0.93-0.79(m,12H)。
The method for producing compound 3 is different from the method for producing compound 1 and the method for producing compound 4 is different from the method for producing compound 2 in the number of carbon atoms in compound 8.
After adding dichloromethane and 15% HCl to compound 1(0.18g,0126mmol), stirring for 30 min, adding water for extraction, and concentrating the organic layer to obtain compound 17, dissolving it in dichloromethane (27mL), adding copper acetate (0.252g,1.26mmol), dissolving it in methanol (12mL), heating under reflux for 1.5 hr, draining, and extracting with water to obtain compound 5 (99%) as a green solid.
Figure BDA0002590173950000121
Example 2
Step one, pretreatment process of FTO glass
And (2) etching by using zinc powder and dilute hydrochloric acid, ultrasonically cleaning the etched glass by using deionized water, ethanol and acetone for 15 minutes, putting the glass into an oven to dry the glass, finally cleaning the glass by using plasma for 10 minutes, and then placing the glass in a dry place for later use.
Step two, device preparation
The invention is suitable for the perovskite battery with a front-side illumination mesoporous structure and a planar structure (n-i-p).
The cell structure is TCO/electron transport layer/perovskite photoactive layer/porphyrin hole transport layer/gold or silver electrode. The preparation method comprises the following steps:
firstly, a Compact Layer (c-TiO) of titanium dioxide is coated on FTO glass in a spin mode2) And after annealing at 450 ℃ for 30 minutes, spin-coating mesoporous titanium dioxide (m-TiO)2) Then, the temperature is raised to 500 ℃ and then returned to 70 ℃, and then the plasma is cleaned for 10 minutes and then sent into a device preparation glove box.
Preparing a perovskite solution: mixing lead iodide (PbI)21.1M) and bromine iodide (PbBr)20.2M) was dissolved in a mixed solution of dimethylformamide (DMF, 880. mu.L) and dimethyl sulfoxide (DMSO, 220. mu.L), stirred at 70 ℃ for 2 hours,finally formamidine iodide (FAI,1.0M) and methylamine bromide (MABr,0.2M) were added.
The formulated perovskite solution was spin coated on conductive glass (1000 revolutions per minute (rpm), 10 seconds; 6000 revolutions per minute (rpm), 25 seconds), and the anti-solvent chlorobenzene (200 μ L) was added for the remaining 10 seconds(s) of the final spin, followed by annealing at 100 ℃ for 1 hour.
20mg of compound 1 prepared in example 1 was dissolved in 1 ml of chlorobenzene and spin-coated onto the surface of the annealed perovskite layer (6000 revolutions per minute (rpm), 20 seconds).
The thickness of the gold-plated electrode is 80 nm.
Example 3
The other example is the same as example 2 except that compound 2 is used instead of compound 1 in example 2.
Example 4
The other example is the same as example 2 except that compound 3 is used instead of compound 1 in example 2.
Example 5
The other example is the same as example 2 except that compound 4 is used instead of compound 1 in example 2.
Comparative example 1
The other operations were the same as example 2 except that the material of the hole transport layer was 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD).
Test example 1
The solar cells prepared in the above examples 2-5 and comparative example 1 were subjected to performance test under the condition of simulating 1 sun, the test standard was IEC 60904-3Ed.2AM1.5G, and the irradiance during the test was 1000 + -100W/m2The temperature during the test was 25. + -. 2 ℃. The test results are shown in table 1 below.
TABLE 1
Figure BDA0002590173950000141
The intensity of a light is 100mW cm-2Lighting (AM 1.5G lower)
As can be seen from table 1, the better solubility of the carbon chains of examples 2-5 compared to the carbon chains increases the current value and voltage value, and structurally, examples 4 and 5 have inferior voltage values due to the mismatch between the energy levels of the perovskite energy and the energy levels of the perovskite.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A compound having the structure shown in formula (I):
Figure FDA0002590173940000011
wherein F and E are the same or different and are independently selected from the structures shown below,
Figure FDA0002590173940000012
wherein R is44Is composed of
Figure FDA0002590173940000021
X is selected from O or S; r1-R34Same or different, independently from each other selected from H, C1-15Alkyl radical, C1-15Alkoxy radical, - [ CH2]m[OC2H4]nOCH3(m＝0～1，n＝1～30)；
A and C are the same or different and are independently selected from one of the following structures (11) or (12):
Figure FDA0002590173940000022
wherein R is35-R40Identical or different, independently of one anotherSelected from H, C1-15Alkyl radical, C1-15Alkoxy radical, - [ CH2]m[OC2H4]nOCH3(m＝0～1，n＝1～30)；
M is selected from Zn (II), Cu (II), Eu (III), Mn (III), Fe (III), Ru (III), Co (II) or Co (III).
2. The compound of claim 1, wherein the structure of formula (11) is selected from one of the following structures:
Figure FDA0002590173940000023
wherein R is35-R39Is as defined above.
3. A compound according to claim 1 or 2, wherein R35-R40Same or different, independently from each other selected from H, C4-8Alkyl radical, C4-8Alkoxy radical, - [ CH2]m[OC2H4]nOCH3(m＝0～1，n＝2～10)。
Preferably, R35-R40Same or different, independently from each other selected from H, C4H9O-、C8H17O-。
4. A compound according to any one of claims 1-3, wherein R1-R34Same or different, independently from each other selected from H, C1-8Alkyl radical, C1-8Alkoxy radical, - [ CH2]m[OC2H4]nOCH3(m＝0～1，n＝1～10)。
Preferably, R1-R34Same or different, independently from each other selected from H, CH3O-。
5. The compound according to any one of claims 1 to 4, wherein the compound represented by formula (1) is selected from the following compounds:
Figure FDA0002590173940000041
6. a process for the preparation of a compound according to any one of claims 1 to 5, the synthetic route being as follows:
Figure FDA0002590173940000051
the method comprises the following steps:
(1) mixing dipyrromethane and a compound shown as a formula 8, and reacting to prepare a compound shown as a formula 9;
(2) mixing a compound shown as a formula 9 with a metal salt, and carrying out a metallization reaction to prepare a compound shown as a formula 10;
(3) mixing the compound shown in the formula 10 with N-bromosuccinimide, and carrying out bromination reaction to prepare the compound shown in the formula 11;
(4) mixing the compound shown in the formula 11 with EH and FH (ethylene-vinyl acetate) to perform a Suzuki reaction or a Buchwald-Hartwig coupling reaction to prepare the compound shown in the formula I; or, reacting the compound represented by the formula 11 with
Figure FDA0002590173940000052
Mixing, and carrying out Suzuki reaction to prepare the compound shown in the formula I; wherein E and F are as defined above.
7. The method according to claim 6, wherein the reaction is carried out in the presence of an organic solvent such as methylene chloride and trifluoroacetic acid in step (1).
Preferably, the molar ratio of dipyrromethane to compound of formula 8 is 1: 1.
Preferably, in the step (2), the molar ratio of the compound represented by the formula 9 to the metal salt is 1: 10.
Preferably, the metal salt is selected from zinc acetate dihydrate, nickel acetate tetrahydrate, iron bromide, manganese acetate, copper acetate, magnesium bromide, europium acetate.
8. The production method according to claim 6 or 7, wherein, in the step (3), the bromination is carried out in the presence of methylene chloride.
The molar ratio of the compound shown in the formula 10 to the N-bromosuccinimide is 1: 2.2.
Preferably, in step (4), the molar ratio of the compound represented by formula 11 to EH and FH is 1: 3. A compound represented by the formula 11 and
Figure FDA0002590173940000061
in a molar ratio of 1: 3.
9. Use of a compound according to any one of claims 1 to 5 for a hole transport material for a perovskite solar cell.
10. A hole transport material for a perovskite solar cell, the material comprising a compound as claimed in any one of claims 1 to 5.
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