CN113549169A - A kind of phenylfluorene amine polymer hole transport material and preparation method and application thereof - Google Patents

A kind of phenylfluorene amine polymer hole transport material and preparation method and application thereof Download PDF

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CN113549169A
CN113549169A CN202110658624.2A CN202110658624A CN113549169A CN 113549169 A CN113549169 A CN 113549169A CN 202110658624 A CN202110658624 A CN 202110658624A CN 113549169 A CN113549169 A CN 113549169A
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殷成蓉
高晗
潘正武
邹勤
彭大瑞
李仁志
王建浦
黄维
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Nanjing Tech University
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Abstract

开了一种苯基芴胺类聚合物空穴传输材料其制备方法和应用。通过向聚乙烯基咔唑（PVK）侧链引入N‑甲氧基苯基‑二甲基芴胺基团，设计合成了苯基芴胺功能化的PVK聚合物空穴传输材料。本发明所述聚合物空穴传输材料合成成本低、具有很好的溶解性、成膜性、较高的空穴迁移率以及与钙钛矿相匹配的能级，将其作为无掺杂聚合物空穴传输材料应用于反式准二维钙钛矿太阳能电池中，获得较高的功率转化效率。

Figure 202110658624

A preparation method and application of a phenylfluorenamine polymer hole transport material are disclosed. Phenylfluorenamine functionalized PVK polymer hole transport material was designed and synthesized by introducing N-methoxyphenyl-dimethylfluorenamine group into the side chain of polyvinylcarbazole (PVK). The polymer hole transport material of the invention has low synthesis cost, good solubility, film formation, high hole mobility and energy level matching with perovskite, and is used as a non-doped polymer Material-hole transport materials are used in trans quasi-two-dimensional perovskite solar cells to obtain high power conversion efficiency.

Figure 202110658624

Description

Phenylfluorenamine polymer hole transport material and preparation method and application thereof
Technical Field
The invention belongs to the field of novel hole transport materials of perovskite solar cells, and particularly relates to a structure and synthesis of a phenylfluorenamine polymer hole transport material and application of the phenylfluorenamine polymer hole transport material in a trans-perovskite solar cell.
Background
Perovskite Solar Cells (PSCs) adopt organic-inorganic hybrid metal halides with perovskite crystal structures as light-absorbing layers, have attracted attention since 2009 due to simple preparation methods, low production cost and excellent photoelectric properties, and have rapidly increased energy conversion efficiency (PCE) from 3.8% to 25.5%, becoming the third-generation emerging photovoltaic technology which is the most attractive and rapidly developed worldwide. The major structures of PSCs can be classified into the conventional (n-i-p) and trans (p-i-n) types. The conventional n-i-p type PSCs usually use n-type mesoporous TiO2As an electron transport material, high temperature heat treatment is required; by reducing the thickness of the via layer, the hysteresis of the device is more severe, and these disadvantages increase the manufacturing cost of the conventional structure PSCs and limit the reliability of the device performance. Compared with conventional PSCs, the trans-PSCs have reverse device structures and charge transmission directions, have better device stability, smaller hysteresis effect, can be manufactured at low temperature, are suitable for flexible substrates, and can be mixed with silicon or copper (In, Ga) Se2The advantages of photovoltaic technology integration and the like show advantages in the development of commercial large-area PSCs in the future. At present, the efficiency of the small-area trans-PSCs reaches the certification value of 22.75 percent, the efficiency of the micro-module exceeds 18 percent, and the aperture area is 19.276cm2。
Hole Transport Materials (HTMs) are important for both conventional and trans-PSCs as important interfacial layers between the perovskite crystals and the electrodes, and HTMs play a very important role in promoting the extraction and transport of holes, and inhibiting the recombination of carriers at the interfaces between perovskites and HTMs, and can effectively improve the performance of devices. However, for many of the reported HTMs, a chemical doping process is typically required to improve hole mobility/conductivity, which not only increases the overall cost of the device, but also compromises the long-term stability of the device. Therefore, the development of low cost HTMs without doping any additives has become one of the major demands for large area commercial applications of conventional and trans-PSCs in recent years. Among them, polymer undoped HTMs are receiving attention because of their advantages of high heat resistance, strong hydrophobicity, strong thin film processing ability, compatibility with web printing technology, and good device efficiency and stability in different types of device structures. Two classes of polymers, PEDOT PSS and poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTAA), are still the most commonly used HTMs in trans-PSCs, and the currently most efficient trans-PSCs are also prepared based on PTAA. However, stability problems due to acidity and hygroscopicity of PEDOT: PSS, as well as the high cost of PTAA ($ 1980/g), also greatly hampered the development of large area trans PSCs. Compared with the traditional conventional device, the polymer undoped HTMs have less application research in trans-PSCs, the device performance of the polymer undoped HTMs can not be compared with that of a doped PTAA device, and the research on the interface relation between the polymer HTMs and a perovskite layer is not systematic enough. There is therefore still a need to further develop new strategies to design new undoped polymer HTMs for low cost, high performance, stable, large area trans PSCs applications.
The strategy of combining the main chain of the non-conjugated polyethylene with the side chains of the hole transport groups with different structures is utilized, the method has advantages in constructing novel non-conjugated side chain polymer undoped HTMs, and the prepared polymer HTMs have the advantages of low synthesis cost, strong thin film processing capacity, good wettability, transparent windows in visible regions and the like, and can obtain better device performance in the aspects of conventional and trans PSCs. The phenylfluorenylamine group has better mobility, can adjust the energy level of molecules and the like, and is used for constructing high-performance micromolecule HTMs to be applied to PSCs with conventional structures. At present, polymer HTMs based on phenylfluorenylamines are not reported, and a phenylfluorenylamine non-conjugated side chain polymer hole transport material is designed and synthesized by introducing an N-methoxyphenyl-dimethylfluorenylamine group into a polyvinyl carbazole (PVK) side chain and is applied to trans-PSCs.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the provided phenylfluoreneamine polymer hole transport material can be applied to novel undoped polymers HTMs, and can realize the application of trans PSCs with low cost, high performance, stability and large area.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: the structural formula of the provided phenylfluoreneamine polymer hole transport material is as follows:
Figure BDA0003114354550000021
wherein n is any number from 1 to 1000.
The preparation method of the phenylfluoreneamine polymer hole transport material comprises the following synthetic route:
Figure BDA0003114354550000022
the method comprises the following specific steps:
(1) synthesis of intermediate i and intermediate i': reacting the raw material I (or the raw material I'), the raw material II, sodium tert-butoxide, palladium acetate and a toluene solution of a tri-tert-butylphosphine solution at 65-85 ℃ for 3-6 hours under the protection of nitrogen, and cooling to room temperature. Extracting with saturated sodium chloride solution and dichloromethane, drying with anhydrous magnesium sulfate, filtering, distilling under reduced pressure, and purifying by column chromatography to obtain intermediate I and intermediate I' in the form of light yellow powder;
(2) synthesis of intermediate ii and intermediate ii': dissolving intermediate i (or intermediate i'), potassium hydroxide and p-diphenol in toluene: and (3) reacting the mixed solution of isopropanol (1, 6-10)) at 65-85 ℃ until all the intermediate I (or the intermediate I ') is converted into the intermediate II and the intermediate II' (6-15 hours). Cooling to room temperature, carrying out rotary drying on the isopropanol-toluene mixed solution under reduced pressure, washing by using a saturated sodium chloride solution and dichloromethane, extracting, drying by using anhydrous magnesium sulfate, filtering, and carrying out reduced pressure distillation to obtain a crude product. Recrystallizing with ethanol (methanol)/dichloromethane to obtain intermediate II and intermediate II' in form of light yellow powder;
(3) synthesis of PVCz-DFMeNPh and PVCz-FMeNPh: and under the anhydrous and oxygen-free conditions, initiating the intermediate II (or the intermediate II') and azobisisobutyronitrile (ethanol recrystallization) solution in toluene (or tetrahydrofuran, N-methyl pyrrolidone) at 60-65 ℃ for 2-3 hours, and reacting at 80-85 ℃ for 3-5 days. After the reaction is finished, cooling to room temperature, crystallizing by using methanol, filtering, drying, and extracting by using acetone for three days to obtain yellow PVCz-DFMeNPh and PVCz-FMeNPh.
In addition, the invention also provides application of the phenylfluoreneamine polymer material in a hole transport material, and particularly application of the phenylfluoreneamine polymer material prepared into a hole transport layer applied to a trans-form quasi-two-dimensional perovskite solar cell. For example, the trans-form quasi-two-dimensional perovskite solar cell device is in an ITO glass/hole transport layer/quasi-two-dimensional perovskite/electron transport layer (PC61 BM)/chromium (Cr)/gold (Au), wherein the hole transport layer is made of the phenylfluorenamine polymer hole transport material provided by the invention.
The preparation method of the trans-form quasi-two-dimensional perovskite solar cell based on the phenylfluorene amine polymer hole transport material comprises the following steps:
(1) cleaning: ultrasonically cleaning an ITO glass substrate for 10-20 minutes by adopting acetone, deionized water and ethanol in sequence, and then using N2Blowing the residual solvent on the ITO surface by using an air gun, then carrying out oxygen plasma treatment for 10-15 minutes, and then transferring the ITO glass substrate to a nitrogen glove box;
(2) preparation of hole transport layer: weighing 2-15 mg of the phenylfluoreneamine polymer hole transport material according to claim 1, completely dissolving in 1mL of chlorobenzene solution, uniformly dropwise adding a proper amount of the solution onto an ITO glass substrate, spin-coating at 3000-5000 rpm for 10-20 seconds, and annealing at 90-110 ℃ for 10-15 minutes;
(3) preparation of perovskite layer: and cooling the obtained ITO/hole transport layer substrate to room temperature, preheating for 3-5 minutes at 120-140 ℃, taking 50 mu l of perovskite solution to fully pave the ITO/hole transport layer substrate, spin-coating for 10-20 seconds at 3000-5000 rpm, and annealing for 10-15 minutes at 90-100 ℃ to prepare the perovskite layer. Wherein the perovskite solution is prepared by mixing 3-bromine-benzyl ammonium iodide or 3-chlorobenzyl ammonium iodide, methyl amine chloride and lead iodide in N, N' -dimethylformamide according to a certain molar ratio;
(4) preparation of an electron transport layer: cooling the obtained ITO/hole transport layer/perovskite substrate to room temperature, preparing PC61BM into a 20mg/mL solution, then taking 30 mul of PC61BM solution to fully spread the ITO/hole transport layer/perovskite substrate, and spin-coating at 800-1200 rpm for 30-50 seconds;
(5) preparing an electrode: and (3) placing the substrate in a vacuum evaporation box, and respectively evaporating Cr (about 6nm) and Au (about 80nm) on the PC61BM layer to prepare the required trans-form quasi-two-dimensional perovskite solar cell.
The phenylfluorenamine polymer hole transport material prepared by the invention has the following advantages and beneficial effects:
(1) the phenylfluorenamine polymer hole transport material prepared by the invention has better solubility in solvents such as dimethyl sulfoxide, N' -dimethylformamide, toluene, chlorobenzene, dichloromethane and the like;
(2) the phenylfluorenamine polymer hole transport material prepared by the invention has low raw material cost and simple preparation process, and is suitable for industrial production;
(3) the phenylfluorenamine polymer hole transport material prepared by the invention has high decomposition temperature and good thermal stability. Meanwhile, the film forming property is good, the film forming agent has good wettability with a perovskite precursor solvent, and the film forming agent is helpful for crystallization and film forming of perovskite;
(4) the phenylfluorenamine polymer hole transport material prepared by the method has good mobility, and is beneficial to extraction and transport of holes;
(5) the prepared phenylfluorenamine polymer hole transport material has a deeper HOMO energy level matched with perovskite;
(6) the phenylfluorenamine polymer hole transport material prepared by the invention can be used for trans-form quasi-two-dimensional perovskite solar cells without doping any additive, has the photoelectric conversion efficiency of 18.44 percent, is better than the current common PTAA (the photoelectric conversion efficiency is 16.65 percent under the same condition), has repeatability, and shows that the compound has good application prospect.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiment(s) of the invention and together with the description serve to explain the invention without limiting the invention.
FIG. 1 shows UV absorption spectrum and fluorescence emission spectrum of PVCz-FMeNPh or PVCz-DFMeNPh film;
FIG. 2 is a thermogravimetric plot of PVCz-FMeNPh or PVCz-DFMeNPh;
FIG. 3 is a differential thermal curve for PVCz-FMeNPh or PVCz-DFMeNPh;
FIG. 4 is a graph of ionization energy measurements for PVCz-FMePh, PVCz-DFMeNPh, and PTAA;
FIG. 5 shows the structure of a quasi-two-dimensional perovskite solar cell made of PVCz-FMePh, PVCz-DFMeNPh and PTAA;
FIG. 6 is a graph of current versus voltage for a quasi-two-dimensional perovskite solar cell made of PVCz-FMePh, PVCz-DFMeNPh, and PTAA;
FIG. 7 is a diagram of a distribution of photovoltaic parameters of a quasi-two-dimensional perovskite solar cell made of PVCz-FMePh, PVCz-DFMeNPh and PTAA.
Detailed Description
The present invention is further illustrated by the following specific examples, which are provided for the purpose of illustration only and are not intended to be limiting. Any modification, equivalent replacement, and improvement made within the principle of the present invention should be included in the present invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. The materials, reagents and the like used are commercially available unless otherwise specified.
Example 1 Synthesis of PVCz-FMeNPh
The synthetic route is as follows:
Figure BDA0003114354550000041
(1) synthesis of intermediate i': mixing the raw material I' (from)The preparation method comprises the steps of reacting 3-bromo-carbazole with 1, 2-dichloroethane under the catalysis of potassium carbonate and potassium hydroxide for 6 hours, and then recrystallizing to obtain the compound; 0.924g, 3mmol) and a raw material II (self-made, obtained by reacting 9, 9-dimethyl-2-bromofluorene and 4-methoxyaniline in the presence of sodium tert-butoxide and a palladium catalyst for 24 hours; 1.041g, 3.3mmol), sodium tert-butoxide (0.24g, 2.5mmol), palladium acetate (21mg, 0.09mmol) and tri-tert-butylphosphine (18mg, 0.09mmol) were charged in a 100ml flask, evacuated and charged with nitrogen, 60ml of toluene was added as a solvent, reacted at 85 ℃ for 6 hours and then cooled to room temperature. Extraction was performed using saturated sodium chloride solution and dichloromethane, dried over anhydrous magnesium sulfate, filtered, distilled under reduced pressure, and purified by column chromatography to give intermediate i' (1.36g, 83.5% yield) as a pale yellow powder.1H NMR(400MHz,DMSO-d6)δ8.05(d,J＝7.7Hz,1H),7.96(d,J＝2.1Hz,1H),7.67-7.61(m,3H),7.58(d,J＝8.3Hz,1H),7.45-7.42(m,2H),7.26-7.23(m,2H),7.21-7.13(m,2H),7.11(s,1H),7.09(s,1H),7.00(d,J＝2.2Hz,1H),6.92(d,J＝9.1Hz,2H),6.75(d,J＝8.3,2.2Hz,1H),4.76(t,J＝6.0Hz,2H),4.06(t,J＝5.9Hz,2H),3.74(s,3H),1.30(s,6H).13C NMR(101MHz,DMSO-d6)δ155.90,155.01,153.31,149.35,141.50,141.21,140.21,139.23,137.69,131.35,127.49,126.77,126.51,126.45,125.55,123.79,123.05,122.47,121.26,121.02,119.62,119.49,119.10,118.38,115.41,114.05,111.27,110.24,55.72,46.77,44.76,43.69,27.47.
(2) Synthesis of intermediate II': intermediate I' (1.08g, 2mmol), potassium hydroxide (0.898g, 16mmol) and p-diphenol (22mg, 0.2mmol) were dissolved in toluene: in the mixed solution of isopropanol (1: 8), the reaction is carried out at 85 ℃ until the intermediate I 'is completely converted into the intermediate II', and the reaction time is 10 hours. Cooling to room temperature, carrying out rotary drying on the isopropanol-toluene mixed solution under reduced pressure, washing by using a saturated sodium chloride solution and dichloromethane, extracting, drying by using anhydrous magnesium sulfate, filtering, and carrying out reduced pressure distillation to obtain a crude product. Recrystallization from ethanol (methanol)/dichloromethane gave intermediate ii' (860mg, 84.9% yield) as a pale yellow powder.1H NMR(400MHz,DMSO-d6)δ8.09(d,J＝7.7Hz,1H),7.97(d,J＝2.2Hz,1H),7.85(d,J＝8.5,4.4Hz,2H),7.68-7.55(m,3H),7.51-7.43(m,2H),7.30-7.18(m,4H),7.14-7.09(m,2H),7.06(d,J＝2.0Hz,1H),6.96-6.91(m,2H),6.81(d,J＝8.3,2.0Hz,1H),5.60(d,J＝15.9Hz,1H),5.11(d,J＝9.1Hz,1H),3.76(s,3H),1.32(s,6H).13C NMR(101MHz,Chloroform-d)δ155.65,155.02,153.44,148.78,141.95,141.79,139.97,139.36,135.93,132.31,129.58,126.99,126.48,126.33,126.06,125.14,124.81,123.80,122.47,120.66,120.50,120.42,119.18,117.01,115.65,114.76,111.45,110.57,101.58,55.60,46.85,29.82,27.24.
(3) Synthesis of PVCz-FMeNPh: under anhydrous and oxygen-free conditions, adding the intermediate II' (300mg) and azobisisobutyronitrile (ethanol recrystallization; 3mg) with the mass ratio of 1% of the monomer into solution toluene (or tetrahydrofuran, N-methylpyrrolidone), freeze-drying with liquid nitrogen, vacuumizing for 1 minute, filling nitrogen, repeating for three times, and sealing. After 2 hours of initiation at 65 ℃ the reaction was carried out for three days at 85 ℃. After the reaction is finished, the mixture is cooled to room temperature, crystallized by using methanol (ethanol)/dichloromethane, filtered, dried, extracted by using acetone as a solvent for three days by a Soxhlet extractor to obtain yellow PVCz-FMeNPh (180 mg). The polymer PVCz-FMeNPh had a number average molecular weight Mn of 13437, a weight average molecular weight Mw of 17435, and a polydispersity index PDI of 1.30.
Example 2 Synthesis of PVCz-DFMeNPh
The synthetic route is as follows:
Figure BDA0003114354550000051
(1) synthesis of intermediate i: raw material I (self-made, prepared by reacting 3, 6-dibromo-carbazole with 1, 2-dichloroethane for 6 hours under the catalysis of potassium carbonate and potassium hydroxide and then recrystallizing, 0.589g, 1.52mmol), raw material II (1.1g, 3.5mmol), sodium tert-butoxide (0.336g, 3.5mmol), palladium acetate (28mg, 0.12mmol) and tri-tert-butylphosphine (24mg, 0.12mmol) are added into a 100ml flask, the flask is vacuumized and filled with nitrogen, 60ml of toluene is added as a solvent, the mixture reacts at 85 ℃ for 6 hours and then is cooled to room temperature. Extraction was performed using saturated sodium chloride solution and dichloromethane, dried over anhydrous magnesium sulfate, filtered, distilled under reduced pressure, and purified by column chromatography to give intermediate i (1.12g, 86.2% yield) as a pale yellow powder.1H NMR(400MHz,DMSO-d6)δ7.89(d,J＝2.1Hz,2H),7.68-7.52(m,6H),7.41(d,J＝7.3Hz,2H),7.27-7.14(m,6H),7.09-7.04(m,4H),6.95(d,J＝2.1Hz,2H),6.91-6.85(m,4H),6.70(d,J＝8.3,2.1Hz,2H),4.75(t,J＝5.6Hz,2H),4.07(t,J＝5.9Hz,2H),3.71(s,6H),1.26(s,12H).13C NMR(101MHz,DMSO-d6)δ155.89(s),154.92(s),153.26(s),149.30(s),141.39(s),140.18(s),139.23(s),138.33(s),131.22(s),127.45(s),126.83(s),126.39(s),125.82(s),123.54(s),122.99(s),121.20(s),119.44(s),118.79(d,J＝21.6Hz),115.36(s),113.85(s),111.39(s),55.67(s),46.72(s),31.51(s),27.44(s),22.61(s).
(2) And (3) synthesizing an intermediate II: intermediate i (0.86g, 1mmol), potassium hydroxide (0.449g, 8mmol) and p-diphenol (11mg, 0.1mmol) were dissolved in toluene: in the mixed solution of isopropanol (1: 8), the reaction is carried out at 85 ℃ until the intermediate I is completely converted into the intermediate II, and the reaction time is 10 hours. Cooling to room temperature, carrying out rotary drying on the isopropanol-toluene mixed solution under reduced pressure, washing by using a saturated sodium chloride solution and dichloromethane, extracting, drying by using anhydrous magnesium sulfate, filtering, and carrying out reduced pressure distillation to obtain a crude product. Recrystallization from ethanol (methanol)/dichloromethane afforded intermediate ii as a pale yellow powder (640mg, 78.1% yield).1H NMR(400MHz,DMSO-d6)δ7.87(d,J＝2.2Hz,2H),7.82(d,J＝8.8Hz,2H),7.63-7.52(m,5H),7.41(d,J＝7.3Hz,2H),7.28-7.15(m,6H),7.09-7.04(m,4H),6.98(d,J＝2.1Hz,2H),6.91-6.86(m,4H),6.74(d,J＝8.3,2.1Hz,2H),5.56(d,J＝15.9,0.9Hz,1H),5.08(d,J＝9.4,0.8Hz,1H),3.70(s,6H),1.26(s,12H).13C NMR(101MHz,Chloroform-d)δ155.61,154.96,153.41,141.90,139.33,136.48,132.26,126.95,126.24,126.02,125.14,124.85,122.43,120.46,119.16,117.32,115.55,114.76,111.48,55.56,46.81,29.82,27.22.
(3) Synthesis of PVCz-DFMeNPh: under anhydrous and oxygen-free conditions, adding the intermediate II (300mg) and azobisisobutyronitrile (ethanol recrystallization; 3mg) with the mass ratio of 1% of the monomer into solution toluene (or tetrahydrofuran, N-methylpyrrolidone), freeze-drying with liquid nitrogen, vacuumizing for 1 minute, filling nitrogen, repeating for three times, and sealing. After 2 hours of initiation at 65 ℃ the reaction was carried out for three days at 85 ℃. After the reaction, the reaction mixture was cooled to room temperature, crystallized using methanol (ethanol)/dichloromethane, suction-filtered and dried, and then extracted with acetone as a solvent in a Soxhlet extractor for three days to obtain yellow PVCz-DFMeNPh (160 mg). The polymer PVCz-DFMeNPh had a number average molecular weight Mn of 17787, a weight average molecular weight Mw of 24037 and a polydispersity index PDI of 1.35.
Example 3 absorption emission Spectroscopy determination of PVCz-FMePh and PVCz-DFMeNPh
Preparation of thin film samples of PVCz-FMePh and PVCz-DFMeNPh A chlorobenzene solution with a solubility of 7mg/mL was spin coated on quartz plates by means of a spin coater. The absorption spectrum and emission spectrum of the PVCz-FMeNPh and PVCz-DFMeNPh films were measured using a SHIMADZUUV-1750 type spectrophotometer and a Hitachi F-4600 type fluorescence spectrometer, and the results are shown in FIG. 1. Measuring the absorption peaks of PVCz-FMeNPh at 317nm and 355nm and the maximum emission peak at 439nm in the thin film state; the absorption peaks of PVCz-DFMeNPh are located at 319nm and 356nm, and the maximum emission peak is located at 450 nm.
Example 4 thermal stability testing of PVCz-FMePh and PVCz-DFMeNPh
Thermogravimetric analysis Test (TGA): PVCz-FMeNPh and PVCz-DFMeNPh decomposition temperatures were measured using a METTLER TOLEDO TGA2 thermogravimeter. During the test, the nitrogen flow rate was set at 50cm3And/min as purging and protection, the heating rate is set to 10 ℃/min. The sample needs to be dried in advance, the mass is 3-5mg, and the test result is shown in figure 2. Differential scanning calorimetry test (DSC): PVCz-FMeNPh and PVCz-DFMeNPh glass transition temperature analyses Shimadzu DSC-60A differential calorimeter was used. In the test process, nitrogen is used as a blowing and protecting function, and the flow rates are respectively set to be 40cm3Min and 60cm3And/min. The sample is heated from 30 ℃ to 350 ℃, the heating rate is 10 ℃/min, and the cooling rate is 20 ℃/min. The sample needs to be dried in advance, the mass is 3-5mg, and the test result is shown in figure 3.
PVCz-FMeNPh and PVCz-DFMeNPh have no distinct glass transition peaks and 5% thermogravimetric weight loss temperatures of 415.53 ℃ and 423.62 ℃ as measured by DSC and TGA.
Example 5 ionization energy determination of PVCz-FMePh, PVCz-DFMeNPh and PTAA
Photoelectron spectroscopy test (YPS): ionization energies of PVCz-FMePh, PVCz-DFMeNPh and PTAA were tested using the IPS-4 ionization energy measurement system, and the test results are shown in FIG. 4.
The HOMO energy level of PVCz-FMeNPh can be obtained to be-5.56 eV through YPS spectrum, and the LUMO energy level is calculated to be-2.67 eV by combining the absorption band edge; the HOMO energy level of the PVCz-DFMeNPh is-5.39 eV, and the LUMO energy level is calculated to be-2.58 eV by combining the absorption band edge; the HOMO level of the PTAA was-5.24 eV, and the LUMO level was calculated to be-2.29 eV in combination with the absorption band edge.
Example 6PVCz-FMeNPh, PVCz-DFMeNPh and PTAA as hole transport layers were applied to trans-quasi two-dimensional perovskite solar cells.
The PVCz-FMeNPh and PVCz-DFMeNPh polymer monomers prepared by the method are very easy to dissolve in perovskite precursor solvents, and films with more holes are very easy to form in the preparation process of trans-devices. The PVCz-FMeNPh and PVCz-DFMeNPh polymers and perovskite precursor solvents have orthogonal solubility, and can have good wettability with the perovskite precursor solvents in the preparation of trans-devices and maintain uniform and compact film morphology. PVCz-FMePh and PVCz-DFMeNPh as undoped non-conjugated polymer hole transport materials are applied to trans-form quasi-two-dimensional perovskite solar cells (1 cm) in comparison with common PTAA2) The structure of the device is ITO glass/hole transport layer/quasi-two-dimensional perovskite layer/electron transport layer (PC61 BM)/chromium (Cr)/gold (Au), and the structure is shown in FIG. 5.
The manufacturing method of the trans-form quasi-two-dimensional perovskite solar cell comprises the following steps:
before the preparation, a perovskite precursor solution needs to be prepared in advance, and the specific process is as follows, 1mmol of 3-bromo-benzylamine is added into a reaction bottle, 20ml of absolute ethyl alcohol is added to dissolve the 3-bromo-benzylamine, 1mmol of hydroiodic acid is dropwise added while stirring, after the reaction is carried out for 2 hours at the temperature of 0 ℃, the temperature is raised to 60 ℃, the solvent is evaporated to obtain a solid, the solid is washed with ethyl ether for three times, and finally the solid is placed in a vacuum drying oven at the temperature of 30 ℃ for 12 hours. The obtained 3-bromo-benzyl ammonium iodide, MAC1 and PbI2According to the weight ratio of 2.5: 4.2: 5.2 mol ratio in N, N' -dimethylformamide, and stirring for 8 hours at 60 ℃ to obtain the perovskite precursor solution.
(1) Cleaning: firstly, ultrasonically cleaning an ITO glass substrate for 15 minutes by adopting acetone, deionized water and ethanol in turn,then using N2Blowing the residual solvent on the ITO surface to dry by an air gun, then carrying out oxygen plasma treatment for 10 minutes, and then transferring the ITO glass substrate into a nitrogen glove box to ensure the surface of the ITO glass substrate to be clean so as to carry out further manufacturing steps;
(2) preparation of hole transport layer: 5mg of PVCz-DFMeNPh (or PVCz-FMeNPh) synthesized in this paper was completely dissolved in 1mL of chlorobenzene solution, and 20. mu.l of the solution of PVCz-DFMeNPh (or PVCz-FMeNPh) was uniformly dropped on an ITO glass substrate, spin-coated at 5000rpm for 20 seconds, and then annealed at 100 ℃ for 10 minutes.
(3) Preparation of perovskite layer: and cooling the obtained ITO/hole transport layer substrate to room temperature, preheating for 3 minutes at 140 ℃, taking 50 mu l of perovskite precursor solution to be paved on the ITO/hole transport layer substrate, spin-coating for 20 seconds at 5000rpm, and annealing for 15 minutes at 90 ℃ to prepare the perovskite layer.
(4) Preparation of an electron transport layer: the ITO/hole transport layer/quasi-two-dimensional perovskite layer substrate obtained above was cooled to room temperature, PC61BM was prepared as a 20mg/mL solution, and then 30. mu.L of a PC61BM solution was spread over the ITO/hole transport layer/quasi-two-dimensional perovskite layer substrate and spin-coated at 1000rpm for 40 seconds.
(5) Preparing an electrode: and (3) putting the substrate in a mask plate, putting the mask plate in a vacuum evaporation box, and respectively evaporating chromium (about 6nm) and gold (about 80nm) on the PC61BM layer to prepare the required quasi-two-dimensional perovskite solar cell.
The power of the solar simulator is adjusted to be 100mw/cm2The AM1.5G radiation standard is simulated, and the current and voltage values of the device are read by a computer connected with a Keithley2450 power supply meter. Before the current density-voltage curve measurements were taken, the light intensity was calibrated using a Newport standard silicon cell 91150, the device was in forward and reverse scan mode, and the scan rate was 0.02V/s. The current density-voltage curve after the test is shown in fig. 6.
The open circuit voltage of the positive scanning of the trans-perovskite solar cell device corresponding to the PTAA commonly used for the trans-device at present is 1.2V, and the short circuit current is 17.04mA/cm2The fill factor is 79%, and the photoelectric conversion efficiency is 16.07% (the open-circuit voltage of reverse scan is 1.2V, and the short-circuit current is 16.04 mA/cm)2The fill factor was 83%, and the photoelectric conversion efficiency was 16.65%).
The positive scanning open-circuit voltage of the corresponding trans-perovskite solar cell device of PVCz-FMePh is 1.20V, and the short-circuit current is 17.64mA/cm2The fill factor was 70%, and the photoelectric conversion efficiency was 14.79% (open circuit voltage for reverse scan was 1.20V, short circuit current was 17.29 mA/cm)2The fill factor was 77%, and the photoelectric conversion efficiency was 15.87%).
The positive-scanning open-circuit voltage of a trans-perovskite solar cell device corresponding to PVCz-DFMeNPh is 1.19V, and the short-circuit current is 18.98mA/cm2The fill factor was 81%, and the photoelectric conversion efficiency was 18.24% (open circuit voltage for reverse scan was 1.17V, short circuit current was 18.81 mA/cm)2The filling factor is 84%, the photoelectric conversion efficiency is 18.44%), and the device performance is better than that of the PTAA.
Under the same experimental conditions, the invention respectively collects the statistical data of the photovoltaic parameters of the trans-Quasi-2D PSCs based on PVCz-FMePh, PVCz-DFMeNPh and PTAA from one hundred devices, and as shown in figure 7, the invention shows that the trans-Quasi-2D PSCs device has good repeatability. The average PCEs for trans-Quasi-2D PSCs based on PVCz-FMePh, PVCz-DFMeNPh and PTAA were 14.54%, 16.70% and 15.19%, respectively.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes, substitutions or simple modifications that can be easily made by those skilled in the art within the technical scope of the present invention should be covered within the scope of the present invention.

Claims (4)

1.一种苯基芴胺类聚合物空穴传输材料，其特征在于，所述苯基芴胺类聚合物是以聚乙烯基作为主链和苯基芴胺取代的咔唑为侧链的聚合物分子，其化学结构式如下：1. a phenylfluorene amine polymer hole transport material, is characterized in that, described phenyl fluorene amine polymer is a side chain with polyvinyl as main chain and the carbazole substituted by phenyl fluorene amine A polymer molecule whose chemical structural formula is as follows:
Figure FDA0003114354540000011
Figure FDA0003114354540000011
 其中，n为1～1000中任意数字。Among them, n is any number from 1 to 1000. 2.权利要求1所述的苯基芴胺类聚合物空穴传输材料的制备方法，其合成路线如下所示：2. the preparation method of the phenylfluorene amine polymer hole transport material according to claim 1, its synthetic route is as follows:
Figure FDA0003114354540000012
Figure FDA0003114354540000012
 具体步骤为：The specific steps are: (1)中间体Ⅰ和中间体Ⅰ’的合成：将原料Ⅰ(或原料Ⅰ’)、原料Ⅱ、叔丁醇钠、醋酸钯以及三叔丁基膦溶液甲苯溶液，氮气保护下65～85℃反应3～6小时后冷却至室温。使用饱和氯化钠溶液和二氯甲烷萃取，无水硫酸镁干燥、过滤、减压蒸馏，经过柱层析提纯得到淡黄色粉末的中间体Ⅰ和中间体Ⅰ’；(1) Synthesis of intermediate I and intermediate I': the raw material I (or raw material I'), raw material II, sodium tert-butoxide, palladium acetate and tri-tert-butylphosphine solution toluene solution, under nitrogen protection, 65～85 After reaction at °C for 3-6 hours, it was cooled to room temperature. Using saturated sodium chloride solution and dichloromethane extraction, drying over anhydrous magnesium sulfate, filtering, distillation under reduced pressure, and purifying by column chromatography to obtain intermediate I and intermediate I' as pale yellow powder; (2)中间体Ⅱ和中间体Ⅱ’的合成：将中间体Ⅰ(或中间体Ⅰ’)、氢氧化钾以及对二苯酚溶于甲苯：异丙醇(1：(6～10))混合溶液中，65～85℃下反应至中间体Ⅰ(或中间体Ⅰ’)全部转化为中间体Ⅱ和中间体Ⅱ’(6～15小时)。冷却至室温，减压旋干异丙醇甲苯混合溶液，使用饱和氯化钠溶液和二氯甲烷洗涤、萃取，无水硫酸镁干燥、过滤、减压蒸馏得到粗产物，用乙醇(甲醇)/二氯甲烷重结晶得到淡黄色粉末的中间体Ⅱ和中间体Ⅱ’；(2) Synthesis of intermediate II and intermediate II': Dissolve intermediate I (or intermediate I'), potassium hydroxide and p-diphenol in toluene: isopropanol (1:(6-10)) and mix In the solution, the reaction is carried out at 65-85°C until the intermediate I (or the intermediate I') is completely transformed into the intermediate II and the intermediate II' (6-15 hours). Cooled to room temperature, spin-dried isopropanol-toluene mixed solution under reduced pressure, washed and extracted with saturated sodium chloride solution and dichloromethane, dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure to obtain a crude product, which was washed with ethanol (methanol)/ Recrystallization from dichloromethane gave intermediate II and intermediate II' as light yellow powder; (3)PVCz-DFMeNPh和PVCz-FMeNPh的合成：无水无氧条件下，将中间体Ⅱ(或中间体Ⅱ’)和偶氮二异丁腈(乙醇重结晶)溶液甲苯(或四氢呋喃、N-甲基吡咯烷酮)中，60～65℃引发2～3小时后，80～85℃反应3～5天。反应结束冷却至室温，使用甲醇析晶，抽滤烘干后，使用丙酮抽提三天得到黄色的PVCz-DFMeNPh和PVCz-FMeNPh。(3) Synthesis of PVCz-DFMeNPh and PVCz-FMeNPh: Under anhydrous and anaerobic conditions, intermediate II (or intermediate II') and azobisisobutyronitrile (recrystallized from ethanol) were dissolved in toluene (or tetrahydrofuran, N - methylpyrrolidone), after initiation at 60-65°C for 2-3 hours, the reaction is performed at 80-85°C for 3-5 days. After the reaction was completed, it was cooled to room temperature, crystallized with methanol, dried with suction, and extracted with acetone for three days to obtain yellow PVCz-DFMeNPh and PVCz-FMeNPh. 3.权利要求1所述的苯基芴胺类聚合物空穴传输材料的应用，所述苯基芴胺类聚合物可以作为无掺杂空穴传输材料应用于反式钙钛矿太阳能电池中。3. The application of the phenylfluorene amine polymer hole transport material according to claim 1, the phenyl fluorene amine polymer can be used as a non-doped hole transport material in trans perovskite solar cells . 4.权利要求1中所述的苯基芴胺类聚合物材料作为无掺杂空穴传输材料制备反式钙钛矿太阳能电池的方法，其特征在于包含以下步骤:4. the phenylfluorene amine polymer material described in claim 1 prepares the method for trans perovskite solar cell as undoped hole transport material, it is characterized in that comprising the following steps: (1)清洗：采用丙酮，去离子水和乙醇依次超声清洗ITO玻璃基片10～20分钟，然后使用N2气枪将ITO表面残留溶剂吹干，再进行10～15分钟的氧等离子体处理，随后将ITO玻璃基片转移到氮气手套箱；(1) Cleaning: Use acetone, deionized water and ethanol to ultrasonically clean the ITO glass substrate for 10 to 20 minutes in turn, then use an N2 air gun to dry the residual solvent on the ITO surface, and then perform oxygen plasma treatment for 10 to 15 minutes. The ITO glass substrate was subsequently transferred to a nitrogen glove box; (2)空穴传输层的制备：称取2～15mg的权利要求1所述的苯基芴胺类聚合物空穴传输材料完全溶于1mL的氯苯溶液中，取适量溶液均匀的滴加到ITO玻璃基片上，以3000～5000rpm旋涂10～20秒，再以90～110℃退火10～15分钟；(2) Preparation of hole transport layer: Weigh 2-15 mg of the phenylfluorenamine polymer hole transport material according to claim 1 and completely dissolve it in 1 mL of chlorobenzene solution, take an appropriate amount of the solution and add it dropwise evenly On the ITO glass substrate, spin coating at 3000-5000rpm for 10-20 seconds, and then anneal at 90-110°C for 10-15 minutes; (3)钙钛矿层的制备：将上述得到的ITO/空穴传输层基底冷却至室温，以120～140℃预热3～5分钟，取50μl钙钛矿溶液铺满ITO/空穴传输层基底，以3000～5000rpm旋涂10～20秒，再以90～100℃退火10～15分钟，制备成钙钛矿层。其中钙钛矿溶液配制为3-溴-苄基碘化铵或者3-氯苄基碘化铵、甲基氯化胺、碘化铅按照一定摩尔比例混合于N,N'-二甲基甲酰胺中；(3) Preparation of perovskite layer: Cool the ITO/hole transport layer substrate obtained above to room temperature, preheat at 120-140°C for 3-5 minutes, and take 50 μl of perovskite solution to cover the ITO/hole transport layer The substrate is spin-coated at 3000-5000 rpm for 10-20 seconds, and then annealed at 90-100° C. for 10-15 minutes to prepare a perovskite layer. The perovskite solution is prepared as 3-bromo-benzyl ammonium iodide or 3-chlorobenzyl ammonium iodide, methyl ammonium chloride, and lead iodide mixed in N,N'-dimethylmethane according to a certain molar ratio amide; (4)电子传输层的制备：将上述得到的ITO/空穴传输层/钙钛矿基底冷却至室温，将PC61BM配置成20mg/mL的溶液，然后取30μl的PC61BM溶液铺满ITO/空穴传输层/钙钛矿基底，以800～1200rpm旋涂30～50秒；(4) Preparation of electron transport layer: The ITO/hole transport layer/perovskite substrate obtained above was cooled to room temperature, PC61BM was prepared into a 20 mg/mL solution, and then 30 μl of PC61BM solution was taken and covered with ITO/holes Transmission layer/perovskite substrate, spin-coated at 800-1200 rpm for 30-50 seconds; (5)电极的制备：将上述的基片置于真空蒸镀箱内，分别将Cr(～6nm)和Au(～80nm)蒸镀在PC61BM层上，制得所需的反式钙钛矿太阳能电池。(5) Preparation of electrodes: the above-mentioned substrate was placed in a vacuum evaporation box, and Cr (~6nm) and Au (~80nm) were evaporated on the PC61BM layer respectively to obtain the desired trans perovskite. Solar battery.
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