CN116768784B - Organic semiconductor material containing fluorenylcarbazole amine electron donor, preparation method and application - Google Patents
Organic semiconductor material containing fluorenylcarbazole amine electron donor, preparation method and applicationInfo
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Abstract
本发明涉及有机半导体材料技术领域，旨在提供一种含芴咔唑胺电子给体的有机半导体材料、制备方法及应用。该有机半导体材料可用作钙钛矿太阳电池的空穴输运层材料，是由包含四个电子受体的中心骨架和四个电子给体组成；所述电子受体为六元环结构，且在中心骨架中呈对称布置；所述电子给体是N‑(9,9‑二甲基‑9H‑芴‑2‑基)‑9‑甲基‑9H‑咔唑‑3‑胺，且与六元环结构一一对应地相连。本发明有机半导体材料具有最高占据分子轨道能级较高、玻璃化转变温度高、电导率高、可溶液加工等性质，可用于制备能量转换效率高、热稳定性好的钙钛矿太阳电池。采用该材料作为空穴输运材料的钙钛矿太阳电池的平均能量转换效率和热老化后器件能量转换效率的保有率均有优异表现。
The present invention relates to the technical field of organic semiconductor materials, and is intended to provide an organic semiconductor material, preparation method and application containing a fluorenecarbazole amine electron donor. The organic semiconductor material can be used as a hole transport layer material for a perovskite solar cell, and is composed of a central skeleton comprising four electron acceptors and four electron donors; the electron acceptors are a six-membered ring structure and are symmetrically arranged in the central skeleton; the electron donor is N-(9,9-dimethyl-9H-fluorene-2-yl)-9-methyl-9H-carbazole-3-amine, and is connected in a one-to-one correspondence with the six-membered ring structure. The organic semiconductor material of the present invention has properties such as a high highest occupied molecular orbital energy level, a high glass transition temperature, high electrical conductivity, and solution processability, and can be used to prepare a perovskite solar cell with high energy conversion efficiency and good thermal stability. The average energy conversion efficiency of a perovskite solar cell using the material as a hole transport material and the retention rate of the device energy conversion efficiency after thermal aging are both excellent.
Description
Technical Field
The invention belongs to the technical field of organic semiconductor materials, and particularly relates to an organic semiconductor material containing fluorene carbazole amine electron donor, a preparation method and application thereof.
Background
The lead halide-based semiconductor material with perovskite structure contains widely distributed elements on the earth surface and high content. Through a solution processing method, a polycrystalline semiconductor film with high defect tolerance can be deposited, and the polycrystalline semiconductor film has excellent sunlight capturing and carrier transporting properties. Methylamine lead iodide, formamidine lead iodide, cesium lead iodide and related alloy perovskite can be used as a light absorption layer of a solar cell for realizing efficient conversion from solar energy to electric energy. In recent years, lead-based perovskite-formamidine lead iodine with wider spectral response and higher thermal decomposition temperature is increasingly paid attention to. Thanks to the continuous improvement of the processing method for regulating and controlling the properties of formamidine lead-iodine perovskite film components, crystallinity, grain size, morphology and the like, the energy conversion efficiency of preparing the single-junction perovskite solar cell in a laboratory by using the spiro-OMeTAD as a hole transport material is over 25 percent,
According to international test standards, solar cells are required to meet high temperature operating conditions up to 85 ℃. However, the high temperatures of 85 ℃ exceed the current capacity of these high efficiency batteries. Although perovskite solar cells that are thermally tolerant of 85 ℃ can be fabricated using some other hole transport layer, the initial efficiency of these devices is not yet high enough. Heretofore, it has remained a great challenge to produce perovskite solar cells that are thermally stable for long periods of time at 85 ℃ with efficiencies greater than 24%.
For thermally stable, efficient perovskite solar cells, the choice of suitable electron transport layers and hole transport layers is also critical, in addition to the perovskite light absorbing layer. For perovskite solar cells employing oxide electron transport layers such as TiO 2 or SnO 2, the solution processable organic hole transport layer should possess the following basic characteristics:
(1) The method can form a compact, uniform and thick enough film on the surface of the perovskite so as to avoid micro-area contact between the metal anode and the perovskite and cause rapid charge recombination.
(2) The highest occupied molecular orbital energy level should be higher than the valence band top of the perovskite to ensure that the excited perovskite injects holes into it at a sufficiently fast rate.
(3) Has proper hole concentration, mobility and conductivity to reduce the internal resistance of the battery, and simultaneously ensures that the interface charge recombination of the perovskite and the hole transport layer is as slow as possible.
(4) When heated, the mechanical property of the hole transport layer is not mutated, and the morphology is not degraded.
(5) Can reduce diffusion and migration of endogenous and exogenous substances.
The first report of spiro-OMeTAD was made in 1997 by the German Ma Pugao molecular institute and by the developer of Hoechst company. The spiro-OMeTAD is composed of a spirobifluorene (spirobi [ fluorene ], SBF) central backbone and 4 dimethoxydiphenylamine (OMeDPA) electron donors. The structural origin of the spiro-OMeTAD can be traced back to the beginning of the 20 th century. As early as 1910, the nobel chemical prize acquirer, the german chemist Wieland professor, etc., synthesized OMeDPA for the first time. In 1930, clarkson and Gomberg at the university of Michigan, U.S. reported the synthesis of SBF. In 1998, gratzel et al, the university of Loose and Loose university of Switzerland, doped with an oxidant during the deposition of amorphous films, achieved a breakthrough in the efficiency of solid dye-sensitized solar cells. Since 2012, energy conversion efficiency records of perovskite solar cells were created several times from research teams at home and abroad using spiro-ome tad as a hole transport layer. The reason for this is that in addition to the fact that the spiro-ome tad is a commercially available material, it is highly likely to be related to the proper energy level, hole concentration, hole mobility, morphology and slow interfacial charge recombination of the doped films. However, a not inconsiderable fact is that the glass transition temperature of the spiro-OMeTAD is only slightly above 120 ℃. After doping, the glass transition temperature is usually lower, and the hole transport layer based on the spiro-OMeTAD is easy to crystallize and crack when being heated for a long time at 85 ℃. Severe morphological degradation results in a significant decay in device efficiency. In recent years, new hole transport materials based on spirobifluorene and other electron donors have been reported, but the overall quality factors of these materials, including film forming properties, energy levels, hole transport properties, glass transition temperatures, etc., have been lacking. For example, jeon et al report that a hole transporting material consisting of SBF and electron donor fluorenylmethoxy amine, abbreviated as DM, has a perovskite solar cell based on DM with a thermal stability of 60 ℃. DM has a higher glass transition temperature of 161℃than the spiro-OMeTAD, but has a reduced hole transport property.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and providing an organic semiconductor material containing fluorenylcarbazole amine electron donor, a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following solutions:
an organic semiconductor material containing fluorene carbazole amine electron donor is provided, which consists of a central skeleton containing four electron acceptors and four electron donors, wherein the electron acceptors are of six-membered ring structures and are symmetrically arranged in the central skeleton, and the electron donors are N- (9, 9-dimethyl-9H-fluoren-2-yl) -9-methyl-9H-carbazole-3-amine and are connected with the six-membered ring structures in a one-to-one correspondence manner.
As a preferable mode of the present invention, the central skeleton is any one of spirobifluorene, bifluorene, dibenzoflexion and tetralyene.
As a preferable scheme of the invention, the structural general formula of the organic semiconductor material is any one of the formula (I), the formula (II), the formula (III) and the formula (IV):
wherein R 1、R2、R3 is optionally methyl, ethyl or propyl.
As A preferable scheme of the invention, the organic semiconductor material consists of spirobifluorene, bifluorene, dibenzochrysene or tetralyene serving as A central framework and N- (9, 9-dimethyl-9H-fluoren-2-yl) -9-methyl-9H-carbazole-3-amine serving as an electron donor, wherein the general structural formulA of the organic semiconductor material is any one of the formulA (I-A), the formulA (II-A), the formulA (III-A) and the formulA (IV-A):
The invention further provides a preparation method of the organic semiconductor material containing fluorene carbazole amine electron donor, which comprises the steps of adding a central skeleton halogenide, N- (9, 9-dimethyl-9H-fluorene-2-yl) -9-methyl-9H-carbazole-3-amine, tris (dibenzylideneacetone) dipalladium, tetra-tert-butylphosphine borate and sodium tert-butoxide into toluene according to a molar ratio of 1:5:0.2:0.4:5 under the protection of nitrogen, heating to 120 ℃ while stirring, then reacting for 12 hours, standing, cooling to room temperature after the reaction is finished, and separating and purifying by column chromatography to obtain a solid, namely the organic semiconductor material.
As a preferred embodiment of the present invention, the center skeleton halogeno is any one of 2,2', 7' -tetrabromo-9, 9 '-spirobifluorene, 2',7 '-tetrabromo-9, 9' -bifluorene, 3,6,11,14-tetrabromodibenzochrysene or 2,7,10,15-tetrachlorotetraene.
The invention also provides an application method of the organic semiconductor material containing fluorene carbazole amine electron donor, which is used as a hole transport layer material of a perovskite solar cell.
When the perovskite solar cell is prepared, firstly adding the organic semiconductor material, bis (trifluoro-sulfonimide) tert-butylpyridinium and tert-butylpyridinium into chlorobenzene to obtain a hole transport layer solution, and then rotating for 30s at 4000rpm by a dynamic spin coating method to deposit the organic semiconductor material on a perovskite layer to obtain the hole transport layer.
The invention also provides a perovskite solar cell device which uses the organic semiconductor material containing fluorene carbazole amine electron donor as a hole transport layer material, wherein the perovskite solar cell device has a multilayer structure and sequentially comprises an ITO conductive glass layer, an electron transport layer, a perovskite light absorption layer, a hole transport layer and a metal electrode from bottom to top.
Brief description of the principles of the invention:
The invention discloses several organic semiconductor materials, which respectively take spirobifluorene, bifluorene, dibenzochrysene or tetralyene as a central framework and 4 fluorenylcarbazole amines as electron donors. For example, the organic semiconductor material (SBF-FC) of the product of the invention takes spirobifluorene as a central framework and 4N- (9, 9-dimethyl-9H-fluoren-2-yl) -9-methyl-9H-carbazole-3-amine as electron donor. After the dimethoxy diphenylamine is replaced by the rigid fluorenylcarbazole amine electron donor, the SBF-FC molecule is not easy to twist or twist, so that the glass transition temperature is obviously higher than that of the spiro-OMeTAD, and the fluorenylcarbazole amine electron donor has a larger conjugated system, which brings the SBF-FC with larger average molecular mass center distance, smaller reforming energy and smaller energy disorder degree, so that the hole mobility of the fluorenyl-FC is higher than that of the spiro-OMeTAD. In addition, the SBF-FC has higher highest occupied molecular orbit energy level, and the fluorenylcarbazole amine electron donor does not affect the solubility of the SBF-FC molecules, so that under the same material processing conditions, the SBF-FC presents a complete and uniform film, in contrast to a spiro-OMeTAD hole transport layer which presents a small number of nanoscale holes.
The test shows that when the SBF-FC is used as a hole transport layer of a perovskite solar cell, the average energy conversion efficiency of the cell reaches 24.5%, which is possibly related to the excellent hole transport performance of the SBF-FC and slow interfacial charge recombination of the perovskite/hole transport layer. At the same time, the cell shows good 85 ℃ tolerance, which can be attributed to the fact that after aging, the hole transport layer based on the SBF-FC product of the invention remains morphologically intact and the degradation of the perovskite of the light absorbing layer is effectively inhibited.
Compared with the prior art, the invention has the beneficial effects that:
1. the organic semiconductor material containing fluorene carbazole amine provided by the invention has the characteristics of higher highest occupied molecular orbit energy level, high glass transition temperature, high conductivity, solution processing and the like, and can be used for preparing perovskite solar cells with high energy conversion efficiency and good thermal stability.
2. The average energy conversion efficiency of the perovskite solar cell taking several organic semiconductor materials containing fluorene carbazole amine electron donor as hole transport materials prepared by the invention reaches 24.5%, and the retention rate of the energy conversion efficiency of the device after 500 hours of 85 ℃ heat aging is more than 90%.
Drawings
FIG. 1 is A DSC curve of A fluorene carbazole amine electron donor-containing organic semiconductor material of formulA (I-A), formulA (II-A), formulA (III-A) and formulA (IV-A) as measured by Differential Scanning Calorimetry (DSC);
FIG. 2 is A cyclic voltammogram of the measured fluorene carbazole amine electron donor-containing organic semiconductor materials of formulA (I-A), formulA (II-A), formulA (III-A) and formulA (IV-A) and the calculated highest occupied molecular orbital energy levels;
Fig. 3 is a schematic diagram of a device structure of the perovskite solar cell provided by the invention.
Fig. 4 is a graph showing voltage-current curves of the perovskite solar cell prepared in example 1 of the present invention before and after aging at 85 ℃ for 500 hours.
Fig. 5 is a graph showing voltage-current curves of the perovskite solar cell prepared in the comparative example before and after aging at 85 ℃ for 500 hours.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
Synthesis of the target compound of formula (I-A);
2,2', 7' -tetrabromo-9, 9' -spirobifluorene (474 mg,0.75 mmol), N- (9, 9-dimethyl-9H-fluoren-2-yl) -9-methyl-9H-carbazol-3-amine (1.46 g,3.75 mmol), tris (dibenzylideneacetone) dipalladium (137 mg,0.15 mmol), tri-tert-butylphosphine tetrafluoroborate (87 mg,0.30 mmol) and sodium tert-butoxide (360 mg,3.75 mmol) were added together to 50mL of anhydrous toluene under the protection of argon, the reaction system was heated to 120℃with continuous stirring, the reaction was continued for 12H, after the reaction was completed, the reaction solution was allowed to stand and cool to room temperature, the reaction solvent was removed by rotary evaporation under reduced pressure, then 100mL of distilled water was added to the system, methylene chloride was used for extraction (three times with 100mL of methylene chloride each time), the organic phase was combined by rotary evaporation under reduced pressure to obtain a crude product, the column chromatography was purified by using a volume ratio of 2:1 tetrahydrofuran mixed solvent as a white solid compound of the formula I (about 1g, 18 g) was obtained.
And (3) carrying out structural characterization on the obtained target organic semiconductor material formula (I-A) by adopting nuclear magnetic resonance, mass spectrometry and elemental analysis methods, wherein the high-resolution mass spectrometry analysis result is [ M ] + = 1861.8404.
The nmr characterization data were as follows:
1H NMR(400MHz,THF-d8)δ:8.01(d,J＝1.9Hz,4H),7.97(d,J＝7.9Hz,4H),7.56(d,J＝7.4Hz,4H),7.52(d,J＝8.4Hz,4H),7.45–7.31(m,16H),7.31–7.25(m,12H),7.18(td,J＝7.5,1.0Hz,4H),7.13(td,J＝7.5,1.0Hz,4H),7.09–7.04(m,4H),6.99–6.90(m,8H),6.78(dd,J＝8.5,2.2Hz,4H),3.78(s,12H),1.55(s,24H).
13C NMR(100MHz,THF-d8)δ:155.78,154.51,151.19,149.33,148.49,142.83,140.63,140.33,139.67,136.40,134.06,127.77,127.01,126.74,126.70,124.96,123.75,123.27,122.95,122.61,121.48,121.37,120.80,120.09,119.80,119.78,117.78,117.49,110.56,109.54,47.69,29.37,27.90.
the glass transition temperature of the prepared target organic semiconductor material of formula (I-A) was measured and found to be 222 ℃.
The conductivity of the prepared target organic semiconductor material of the formula (I-A) is measured, the air oxidation natural doping is 0.28 mu S cm -1, and the doping accelerator is 49 mu S cm -1 after the doping accelerator is introduced.
Example 2
Synthesis of the target compound of formula (II-A);
In this example, 2', 7' -tetrabromo-9, 9 '-spirobifluorene was changed to 2,2',7 '-tetrabromo-9, 9' -bifluorene, and the remaining reaction processes, reagent names and reagent amounts were the same as in example 1.
The synthetic route and the structural formula of the final product are shown as follows:
And (3) carrying out structural characterization on the obtained target compound shown in the formula (II-A) by adopting nuclear magnetic resonance, mass spectrometry and elemental analysis methods, wherein the high-resolution mass spectrometry analysis result is [ M+Na ] + = 1896.8305.
The nmr characterization data were as follows:
1H NMR(400MHz,THF-d8)δ:7.86(s,4H),7.61(d,J＝8.2Hz,4H),7.55(s,4H),7.40(d,J＝7.9Hz,4H),7.32–7.17(m,20H),7.13(t,J＝7.8Hz,4H),7.06(t,J＝7.8Hz,4H),6.99–6.93(m,4H),6.90–6.82(m,16H),6.72(d,J＝8.7Hz,4H),3.70(s,12H),1.43(s,24H).
13C NMR(100MHz,THF-d8)δ:155.70,154.42,149.94,148.31,142.80,142.76,140.77,140.56,140.44,139.36,137.29,133.05,127.71,127.45,126.79,126.63,126.28,124.83,123.80,123.74,123.26,121.46,121.40,121.05,120.80,120.03,119.66,119.15,116.19,110.65,109.55,47.53,29.33,27.53.
the glass transition temperature of the prepared target organic semiconductor material of formula (II-A) was measured and found to be 242 ℃.
The conductivity of the prepared target organic semiconductor material of formula (II-A) was measured, and the air oxidation natural doping was 0.20. Mu.S cm -1, and after the doping accelerator was introduced, 41. Mu.S cm -1.
Example 3
Synthesis of the target compound of formula (III-a):
In this example, 2', 7' -tetrabromo-9, 9' -spirobifluorene was changed to 3,6,11,14-tetrabromodibenzo-dioptric acid as compared with example 1, and the remaining reaction processes, reagent names and reagent amounts were kept the same as in example 1.
The synthetic route and the structural formula of the final product are shown as follows:
And (3) carrying out structural characterization on the obtained target compound shown in the formula (III-A) by adopting nuclear magnetic resonance, mass spectrometry and elemental analysis methods, wherein the high-resolution mass spectrometry analysis result is [ M+Na ] + = 1896.8311.
The nmr characterization data were as follows:
1H NMR(400MHz,THF-d8)δ:8.39–8.33(m,8H),7.92(dd,J＝10.3,4.7Hz,8H),7.59(d,J＝7.4Hz,4H),7.46–7.41(m,12H),7.38–7.30(m,8H),7.28–7.19(m,8H),7.19–7.06(m,16H),6.90(dd,J＝8.5,1.8Hz,4H),3.65(s,12H),1.49(s,24H).
13C NMR(100MHz,THF-d8)δ:155.81,154.44,149.52,147.57,142.76,140.45,139.52,133.70,130.86,129.84,129.08,128.82,127.72,127.00,126.92,126.62,125.05,124.91,124.64,123.76,123.23,122.15,121.76,121.49,121.40,120.20,119.78,119.65,117.05,110.69,109.56,47.56,29.33,27.53.
The glass transition temperature of the prepared target organic semiconductor material of formula (III-A) was measured and found to be 246 ℃.
The conductivity of the prepared target organic semiconductor material of formula (III-A) is measured, the air oxidation natural doping is 0.32 mu S cm -1, and the doping accelerator is introduced into the material to be 53 mu S cm -1.
Example 4
Synthesis of target Compound of formulA (IV-A)
Compared with example 1, 2', 7' -tetrabromo-9, 9' -spirobifluorene is changed into 2,7,10,15-tetrachlorotetraene in the present example, and the rest reaction process, reagent name and reagent dosage are the same as those in example 1.
The synthetic route and the structural formula of the final product are shown as follows:
the structural characterization of the obtained target compound (IV-A) is carried out by adopting nuclear magnetic resonance, mass spectrometry and elemental analysis methods, and the high-resolution mass spectrometry analysis result is [ M ] + = 1849.8448.
The nmr characterization data were as follows:
1H NMR(400MHz,THF-d8)δ:7.86(d,J＝6.6Hz,8H),7.51(d,J＝7.5Hz,4H),7.45(d,J＝8.3Hz,4H),7.37–7.29(m,8H),7.28–7.17(m,16H),7.13(t,J＝7.5Hz,4H),7.06(t,J＝7.5Hz,4H),6.98(s,4H),6.91(t,J＝7.2Hz,8H),6.86(s,8H),3.79(s,12H),1.43(s,12H),1.35(s,12H).
13C NMR(100MHz,THF-d8)δ:155.91,154.56,149.41,148.77,144.16,142.77,140.89,140.33,139.50,136.07,134.39,130.10,127.79,127.06,126.65,126.22,124.93,123.71,123.42,123.29,121.83,121.47,121.42,120.06,119.69,119.25,118.54,110.48,109.46,47.67,29.32,27.93,27.56.
The glass transition temperature of the prepared target organic semiconductor material of formulA (IV-A) was measured and found to be 222 ℃.
The conductivity of the prepared target organic semiconductor material of formulA (IV-A) was measured, and the air oxidation natural doping was 0.02. Mu.S cm -1, and after the doping accelerator was introduced, 6.3. Mu.S cm -1.
The method and effect of the organic semiconductor material synthesized according to the present invention as a hole transport material in a perovskite photovoltaic device will be described in detail below with reference to examples 5, 6, and 7.
Example 5 preparation of perovskite solar cell
Indium Tin Oxide (ITO) glass is first laser etched and then subjected to a series of ultrasonic cleaning with detergent, deionized water, acetone and ethanol. The cleaned ITO substrate is then treated with ultraviolet ozone. For the electron transport layer, a 3wt% SnO 2 colloidal solution was spin coated onto the ITO substrate and heated at 150 ℃ for 30 minutes. Subsequently, a DMF/DMSO (volume ratio of 9:1) solution containing 1.5MPbI 2 and 0.075M RbCl was spin coated onto the electron transport layer and heated at 70 ℃ for 1 minute. After cooling to room temperature, a solution of formamidine iodide: methylamine chloride (90 mg:13.5mg in 1ml isopropanol) was spin-coated and heated at 150 ℃ for 30 minutes to give a FAPbI 3 perovskite layer. For the passivation layer, 5mg of phenethylamine iodide was dissolved in 1mL of isopropanol and spin-coated onto the perovskite surface. For the hole transporting layer, 50mg mL -1 of an organic semiconductor material product of formulA (I-A), formulA (II-A), formulA (III-A) or formulA (IV-A), 8.82mg mL -1 bis (trifluorosulfonimide) t-butylpyridinium and 132mM t-butylpyridinium were added to 1mL of chlorobenzene to prepare A hole transporting layer solution, and then the hole transporting layer solution was deposited on the perovskite layer by dynamic spin coating at 4000rpm for 30 s. Finally, a gold layer of about 100nm thick was thermally evaporated under vacuum of 1×10 -4 Pa to complete the fabrication of the battery. The structural schematic of the perovskite solar cell is shown in fig. 3, and the effective area of the cell is 0.258cm 2.
Example 6 energy efficiency test
The perovskite solar cell prepared in example 5 was tested for voltage-current curve under the irradiation of AM1.5G simulated sunlight with an illumination intensity of 100mW cm -2 to obtain energy conversion efficiency, and the results are shown in the following table:
| Organic semiconductor material | Energy conversion efficiency |
| Formula (I-A) | 24.7% |
| Formula (II-A) | 24.2% |
| Formula (III-A) | 24.1% |
| FormulA (IV-A) | 21.0% |
Example 7 aging test of perovskite solar cell
The packaged batteries were stored in an oven at 85 ℃ to evaluate long term thermal stability, with the ambient relative humidity outside the oven being 45% -85%. The cells were removed from the oven at intervals for measurement.
The voltage-current curve of the battery was tested under the irradiation of AM1.5G simulated sunlight with the illumination intensity of 100mW cm -2, and FIG. 4 is a graph showing the voltage-current curve before and after aging for 500 hours at 85 ℃ of the perovskite solar cell prepared in example 1 of the present invention. The open circuit voltage of the battery before aging is 1.18V, the short circuit current density is 25.9mA cm -2, the filling factor is 80.9%, the energy conversion efficiency is 24.7%, the open circuit voltage of the battery after aging at 85 ℃ for thousands of hours is 1.16V, the short circuit current density is 25.2mA cm -2, the filling factor is 77.3%, the energy conversion efficiency is 22.6%, and the energy conversion efficiency retention rate of the device is 92%.
Comparative example
A perovskite solar cell was prepared by taking a commercially available spiro-OMeTAD as a hole transporting material and then performing a performance test under the same conditions as in example 6, and the result showed that the open circuit voltage of the cell before aging was 1.14V, the short circuit current density was 25.9mA cm -2, the filling factor was 77.6%, the energy conversion efficiency was 22.9%, 85℃and the open circuit voltage of the cell after 500 hours aging was 0.715V, the short circuit current density was 13.3mA cm -2, the filling factor was 43.2%, the energy conversion efficiency was 4.2%, and the device energy conversion efficiency retention was 18.3%. Fig. 5 is a voltage-current curve of the perovskite solar cell prepared by the comparative example at 85 ℃ and before and after 500 hours of aging.
From the test results, the organic semiconductor material is used as a hole transport layer of the perovskite solar cell, has the characteristics of high glass transition temperature and high conductivity, and is far superior to the existing organic semiconductor material or the existing technical scheme in the aspect of 85 ℃ long-term stability.
The above description of the embodiments is provided to aid in understanding the method and core idea of the invention. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (5)
1. An organic semiconductor material containing fluorenocarbazole amine electron donor is characterized in that the organic semiconductor material consists of spirobifluorene, bifluorene, dibenzochrysene or tetralyene serving as a central framework and N- (9, 9-dimethyl-9H-fluoren-2-yl) -9-methyl-9H-carbazole-3-amine serving as an electron donor, wherein the central framework is provided with four six-membered ring structures which are symmetrically arranged, and the four electron donors are connected with the six-membered ring structures serving as electron acceptors in a one-to-one correspondence manner;
The structural general formulA of the organic semiconductor material is any one of the formulA (I-A), the formulA (II-A), the formulA (III-A) and the formulA (IV-A):
2. The preparation method of the fluorene carbazole amine electron donor-containing organic semiconductor material according to claim 1 is characterized by comprising the steps of adding a central skeleton halogenide, N- (9, 9-dimethyl-9H-fluoren-2-yl) -9-methyl-9H-carbazole-3-amine, tris (dibenzylideneacetone) dipalladium, tetra-fluoroboric acid tri-tert-butylphosphine and tert-butyl alcohol sodium together into toluene according to a molar ratio of 1:5:0.2:0.4:5 under the protection of nitrogen, heating to 120 ℃ while stirring, then reacting for 12 hours, standing and cooling to room temperature after the reaction is finished, and separating and purifying by column chromatography to obtain a solid, namely the organic semiconductor material;
The central skeleton halogeno compound is any one of 2,2', 7' -tetrabromo-9, 9 '-spirobifluorene, 2',7 '-tetrabromo-9, 9' -bifluorene, 3,6,11,14-tetrabromodibenzodrone or 2,7,10,15-tetrachlorotetraene.
3. Use of an organic semiconductor material containing a fluorenylcarbazole amine electron donor according to claim 1 as a hole transporting layer material for perovskite solar cells.
4. The method according to claim 3, wherein the hole transporting layer is obtained by adding the organic semiconductor material and bis (trifluorosulfonimide) tert-butylpyridinium and tert-butylpyridinium to chlorobenzene to obtain a hole transporting layer solution, and then depositing the organic semiconductor material on the perovskite layer by dynamic spin coating at 4000rpm for 30 s.
5. The perovskite solar cell device taking the organic semiconductor material containing fluorene carbazole amine electron donor as a hole transport layer material is characterized by having a multi-layer structure, and sequentially comprising an ITO conductive glass layer, an electron transport layer, a perovskite light absorption layer, a hole transport layer and a metal electrode from bottom to top.
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