CN113549169B - Phenylfluorenamine polymer hole transport material and preparation method and application thereof - Google Patents
Phenylfluorenamine polymer hole transport material and preparation method and application thereof Download PDFInfo
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Abstract
A phenylfluorenamine polymer hole transport material, its preparation method and application are disclosed. N-methoxyphenyl-dimethylfluorenamine groups are introduced into a polyvinyl carbazole (PVK) side chain, so that the phenylfluorenamine functionalized PVK polymer hole transport material is designed and synthesized. The polymer hole transport material has low synthesis cost, good solubility, good film forming property, high hole mobility and energy level matched with perovskite, and is applied to trans-form quasi-two-dimensional perovskite solar cells as an undoped polymer hole transport material to obtain high power conversion efficiency.
Description
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 absorption layers, since 2009, the perovskite solar cells are concerned due to simple preparation methods, low production cost and excellent photoelectric properties, and the energy conversion efficiency (PCE) is rapidly increased from 3.8% to 25.5%, so that the perovskite solar cells become the third-generation emerging photovoltaic technology which is most concerned and developed most rapidly all over the world. 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 TiO 2 As an electron transport material, high temperature heat treatment is required; while by reducing the thickness of the via layer, the delay of the deviceHysteresis is more severe and these drawbacks increase the cost of fabrication of conventional structure PSCs and limit the reliability of their 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) Se 2 The 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 19.276cm 2 。
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, chemical doping processes are 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 needs 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), remain the most commonly used HTMs of trans-PSCs, and the currently most efficient trans-PSCs are also prepared based on PTAA. However, the acidic and hygroscopic nature of PEDOT: PSS leads to stability problems and the high cost of PTAA ($ 1980/g) has also significantly hindered 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:
wherein n is any number from 1 to 1000.
The preparation method of the phenylfluoreneamine polymer hole transport material comprises the following synthetic route:
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 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: isopropanol (1 (6-10)) mixed solution is reacted at 65-85 ℃ until the intermediate I (or the intermediate I ') is completely 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: under the anhydrous and oxygen-free conditions, the intermediate II (or the intermediate II') and azobisisobutyronitrile (ethanol recrystallization) solution are initiated for 2 to 3 hours at a temperature of between 60 and 65 ℃ and then reacted for 3 to 5 days at a temperature of between 80 and 85 ℃. 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 (PC 61 BM)/chromium (Cr)/gold (Au) structure, wherein the hole transport layer is made of the phenylfluorene amine 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: sequentially ultrasonically cleaning an ITO glass substrate for 10-20 minutes by adopting acetone, deionized water and ethanol, and then using N 2 Blowing 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 phenylfluorene amine polymer hole transport material of claim 1, completely dissolving the material 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 be paved on 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. 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 a 20mg/mL solution of PC61BM, then spreading 30 microliter of the PC61BM solution on 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 6 nm) and Au (about 80 nm) 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 method 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 high 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 method can be used for a trans-form quasi-two-dimensional perovskite solar cell without doping any additive, has the photoelectric conversion efficiency of 18.44 percent, is better than that of the conventional common PTAA (the photoelectric conversion efficiency is 16.65 percent under the same condition), has repeatability, and shows that the compound has a 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 embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
FIG. 1 shows the UV absorption spectrum and fluorescence emission spectrum of PVCz-FMePh 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:
(1) Synthesis of intermediate i': a raw material I' (self-made, prepared by reacting 3-bromo-carbazole with 1, 2-dichloroethane for 6 hours under the catalysis of potassium carbonate and potassium hydroxide and then recrystallizing, 0.924g, 3mmol), a raw material II (self-made, prepared by reacting 9, 9-dimethyl-2-bromofluorene and 4-methoxyaniline for 24 hours under the catalysis of sodium tert-butoxide and palladium catalysts), 1.041g,3.3mmol, sodium tert-butoxide (0.24g, 2.5mmol), palladium acetate (211mg, 0.09mmol) and tri-tert-butylphosphine (18mg, 0.09mmol) are added into a 100ml flask, the flask is vacuumized and filled with nitrogen, 60ml of toluene is added as a solvent, and the mixture is cooled to room temperature after reacting for 6 hours at 85 ℃. Extraction with saturated sodium chloride solution and dichloromethane, drying over anhydrous magnesium sulfate, filtration, distillation under reduced pressure, and purification by column chromatography gave intermediate i' (1.36g, 83.5% yield) as a pale yellow powder. 1 H NMR(400MHz,DMSO-d 6 )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). 13 C NMR(101MHz,DMSO-d 6 )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. Cooling to room temperature, spinning the isopropanol-toluene mixed solution under reduced pressure, washing with saturated sodium chloride solution and dichloromethane, extracting, drying with anhydrous magnesium sulfate, filtering, and distilling under reduced pressure to obtain a crude product. Recrystallization from ethanol (methanol)/dichloromethane gave intermediate ii' (860 mg,84.9% yield) as a pale yellow powder. 1 H NMR(400MHz,DMSO-d 6 )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). 13 C 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 anaerobic conditions, adding the intermediate II' (300 mg) and azobisisobutyronitrile (ethanol recrystallization; 3 mg) with the mass ratio of 1% of 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 at 65 ℃ initiation, the reaction was carried out at 85 ℃ for three days. 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:
(1) Synthesis of an intermediate I: a 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), a 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 is reacted for 6 hours at 85 ℃, and then the mixture 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. 1 H NMR(400MHz,DMSO-d 6 )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). 13 C NMR(101MHz,DMSO-d 6 )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. 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 obtainIntermediate II (640mg, 78.1% yield) as a pale yellow powder. 1 H NMR(400MHz,DMSO-d 6 )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). 13 C 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 anaerobic conditions, adding the intermediate II (300 mg) and azobisisobutyronitrile (ethanol recrystallization; 3 mg) with the mass ratio of 1% of 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 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 at 319nm and 356nm, and the maximum emission peak is 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 thermogravimetric instrument. Test procedureIn the nitrogen gas flow rate was set at 50cm 3 Min, as a purging and protection action, the heating rate was 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 for blowing and protecting, and the flow rates are respectively set to be 40cm 3 Min and 60cm 3 And/min. The sample is heated from 30 ℃ to 350 ℃, the temperature rise rate is 10 ℃/min, and the temperature drop 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.
By testing DSC and TGA tests, PVCz-FMeNPh and PVCz-DFMeNPh have no obvious glass transition peaks, and the 5% thermal weight loss temperatures are 415.53 ℃ and 423.62 ℃.
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 results are shown in FIG. 4.
The HOMO energy level of PVCz-FMeNPh can be obtained by YPS spectrum and is-5.56 eV, and the LUMO energy level is calculated to be-2.67 eV according to the combined 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 the perovskite precursor solvent have orthogonal solubility, and can have good wettability with the perovskite precursor solvent in the preparation of a trans-device and maintain the uniform and compact film appearance. Application of PVCz-FMePh and PVCz-DFMeNPh as undoped non-conjugated polymer hole transport materials in reverse direction in comparison with common PTAAFormula quasi two-dimensional perovskite solar cell (1 cm) 2 ) The structure of the device is ITO glass/a hole transport layer/a quasi-two-dimensional perovskite layer/an electron transport layer (PC 61 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:
the perovskite precursor solution is prepared in advance, and the specific process comprises the steps of adding 1mmol of 3-bromo-benzylamine into a reaction bottle, adding 20ml of anhydrous ethanol to dissolve the 3-bromo-benzylamine, dropwise adding 1mmol of hydroiodic acid while stirring, reacting at 0 ℃ for 2 hours, raising the temperature to 60 ℃, evaporating the solvent to obtain a solid, washing the solid with diethyl ether for three times, and finally placing the solid in a vacuum drying oven at 30 ℃ for 12 hours. The obtained 3-bromo-benzyl ammonium iodide, MAC1 and PbI 2 According to the proportion 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 sequence, and then using N 2 Blowing 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 the ITO/hole transport layer substrate for 3 minutes at 140 ℃, taking 50 mu l of perovskite precursor solution, paving the perovskite precursor solution on the ITO/hole transport layer substrate, spin-coating the perovskite precursor solution at 5000rpm for 20 seconds, and annealing the perovskite precursor solution at 90 ℃ for 15 minutes 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 the 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 6 nm) and gold (about 80 nm) 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/cm 2 The 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 measurement was performed, the light intensity was calibrated using a Newport standard silicon cell 91150, and the device was in forward and reverse scan mode, with a scan rate of 0.02V/s. The current density-voltage curve after the test is shown in fig. 6.
The open circuit voltage of the positive scan 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/cm 2 The 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) 2 The 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/cm 2 The 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) 2 The 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/cm 2 The 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) 2 The 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 of 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. The phenylfluorenamine polymer hole transport material is characterized in that the phenylfluorenamine polymer is a polymer molecule which takes polyvinyl as a main chain and phenylfluorenamine substituted carbazole as a side chain, and has the following chemical structural formula:
wherein n is any number from 26 to 1000.
2. The method for preparing a phenylfluorenamine polymer hole transport material according to claim 1, wherein the synthetic route is as follows:
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 'with the raw material II, sodium tert-butoxide, palladium acetate and toluene solution of tri-tert-butylphosphine solution at 65-85 ℃ for 3-6 hours under the protection of nitrogen, 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 an intermediate I or an intermediate I' which is light yellow powder;
(2) Synthesis of intermediate II and intermediate II': dissolving intermediate I or intermediate I', potassium hydroxide and p-diphenol in toluene: isopropanol mixed solution, wherein the ratio of toluene: the isopropanol is 1; reacting at 65-85 ℃ until the intermediate I or the intermediate I ' is completely converted into the intermediate II or the intermediate II ', wherein the reaction time is 6-15 hours, cooling to room temperature, performing rotary drying on the isopropanol and toluene mixed solution under reduced pressure, washing and extracting by using a saturated sodium chloride solution and dichloromethane, drying by using anhydrous magnesium sulfate, filtering, performing reduced pressure distillation to obtain a crude product, and performing recrystallization by using ethanol/dichloromethane or methanol/dichloromethane to obtain the intermediate II or the intermediate II ' which is light yellow powder;
(3) Synthesis of PVCz-DFMeNPh and PVCz-FMeNPh: under anhydrous and anaerobic conditions, placing azodiisobutyronitrile recrystallized from the intermediate II or the intermediate II' and ethanol in toluene or tetrahydrofuran or N-methylpyrrolidone solution, initiating at 60-65 ℃ for 2-3 hours, reacting at 80-85 ℃ for 3-5 days, cooling to room temperature after the reaction is finished, crystallizing by using methanol, carrying out suction filtration and drying, and extracting by using acetone for three days to obtain yellow PVCz-DFMeNPh and PVCz-FMeNPh.
3. The use of the phenylfluorenamine-based polymer hole transport material as claimed in claim 1, wherein the phenylfluorenamine-based polymer is used as an undoped hole transport material in a trans-perovskite solar cell.
4. A method of preparing a trans-perovskite solar cell using the phenylfluorenamine-based polymer material as an undoped hole transport material as claimed in claim 1, characterized by comprising the steps of:
(1) Cleaning: ultrasonically cleaning an ITO glass substrate for 10-20 minutes by adopting acetone, deionized water and ethanol in sequence, and then using N 2 Blowing the residual solvent on the ITO surface by using an air gun, 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 phenylfluorene amine polymer hole transport material of claim 1, completely dissolving the material 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: cooling the ITO/hole transport layer substrate obtained in the step (2) to room temperature, preheating for 3-5 minutes at 120-140 ℃, taking 50 mu l of perovskite solution to be paved on the ITO/hole transport layer substrate, spin-coating for 10-20 seconds at 3000-5000 rpm, annealing for 10-15 minutes at 90-100 ℃ to prepare a perovskite layer, wherein the perovskite solution is prepared into one of 3-bromo-benzyl ammonium iodide or 3-chlorobenzyl ammonium iodide, and is mixed with methyl ammonium chloride and lead iodide in N, N' -dimethylformamide according to a certain molar ratio;
(4) Preparation of an electron transport layer: cooling the ITO/hole transport layer/perovskite substrate obtained in the step (3) to room temperature, preparing PC61BM into a solution of 20mg/mL, then taking 30 mu l of PC61BM solution to fully cover 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 obtained in the step (4) in a vacuum evaporation box, and respectively evaporating Cr and Au on the PC61BM layer, wherein the diameter of Cr particles is less than or equal to 6nm, and the diameter of Au particles is less than or equal to 80nm, and finally obtaining the required trans-perovskite solar cell.
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