CN113788832A - chrysene -base aza-bis [6] helicene compound and application thereof in hole transport material and solar cell - Google Patents

chrysene -base aza-bis [6] helicene compound and application thereof in hole transport material and solar cell Download PDF

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CN113788832A
CN113788832A CN202110930196.4A CN202110930196A CN113788832A CN 113788832 A CN113788832 A CN 113788832A CN 202110930196 A CN202110930196 A CN 202110930196A CN 113788832 A CN113788832 A CN 113788832A
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solar cell
hole transport
spiroalkene
azabicyclo
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CN113788832B (en
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雷鸣
唐泽丰
张雨燕
李天宇
贺丽飞
王鹏
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Zhejiang University ZJU
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Abstract

The invention discloses a
Figure DDA0003210314780000011
Azabicyclo [6] radical]The spiroalkene compound and the application thereof as a hole transport material in a solar cell. The experimental results show that the product prepared by the invention
Figure DDA0003210314780000012
Azabicyclo [6] radical]The energy conversion efficiency of the perovskite solar cell device prepared by taking the spiroalkene compound as the hole transport layer can reach 18.5-21.5%. Meanwhile, the stability of the device is good.

Description

chrysene -base aza-bis [6] helicene compound and application thereof in hole transport material and solar cell
Technical Field
The invention belongs to the field of solar cell materials, and particularly relates to a solar cell
Figure BDA0003210314760000012
Azabicyclo [6] radical]A spiroalkene compound and application thereof in a hole transport material and a solar cell.
Background
Organic-inorganic hybrid Perovskite Solar Cells (PSCs) are rapidly developed due to the advantages of low processing cost, high energy conversion efficiency (PCE) and the like, and the PCE of the Solar Cells exceeds 25% nowadays, and is expected to realize commercialization. However, the stability of the PSC device is one of important factors that restrict commercialization thereof. In the PSCs, a Hole Transport Material (HTM) avoids direct contact between a perovskite layer and a battery anode in the process of hole extraction and transmission, reduces the recombination of electron holes, improves the surface morphology of the perovskite layer, and is a key component of a PSCs device. The HTM with excellent performance should have the following properties (1) HOMO and LUMO energy levels matched with the perovskite layer; (2) high hole mobility and conductivity; (3) low cost of raw materials, simple synthesis and preparation, and stable physicochemical properties under the conditions of high temperature, high light, high humidity and the like. Research shows that the HTM with high glass transition temperature is beneficial to improving the thermal stability of the device.
In the prior art, the most widely used organic hole transport material in perovskite solar cells is mainly 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene (Spiro-OMeTAD). However, the Spiro-OMeTAD has a complex chemical structure, a long synthesis route and high price, and the hole mobility of the material is low, so that the perovskite solar cell has low energy conversion efficiency. P-type doping with lithium bis (trifluoromethylsulfonyl imide) (LiTFSI), t-butylpyridine (t-BP), etc. is usually required to improve the mobility of the hole , but such doping can lead to unstable performance of the battery device and expensive material cost.
Spiroenes are obtained byThe polycyclic aromatic hydrocarbon compound formed by the fusion of the ortho-positions of a plurality of aromatic rings has a unique spiral pi extension structure, the molecular accumulation is easy to generate more intermolecular contacts, the charge mobility is favorably improved, the solubility of molecules is improved, and the solution processing of devices is favorably realized; the invention is based on
Figure BDA0003210314760000013
Two bays (Bay regions) of the molecule extend the pi system through two molecular amino groups
Figure BDA0003210314760000014
Fusion to give azabicyclo [6] in the same bay]The spiroalkene molecule is terminated by an electron Donor (Donor) to obtain a D-pi-D type hole transport material. The invention provides
Figure BDA0003210314760000015
Azabicyclo [6] radical]The migration rate of the spiroalkene hole transport material is proved by experimental results that the material prepared by the invention
Figure BDA0003210314760000016
Azabicyclo [6] radical]The energy conversion efficiency of the perovskite solar cell prepared by taking the spiroalkene compound as the hole transport layer can reach as high as
Figure BDA0003210314760000017
Meanwhile, the glass transition temperature of the materials is high, and the thermal stability of the prepared perovskite solar cell device is good.
Reference documents:
1.Green,M.A.；Ho-Baillie,A.；Snaith,H.J.,The Emergence of Perovskite Solar Cells[J].Nature Photonics 2014,8(7),506-514.
2.National Renewable Energy Laboratory.(NREL)Best Research-Cell Efficiencies,https://www.nrel.gov/pv/assets/pdfs/best-research-cell-efficiencies.20200104.pdf.
3.Li,D.；Zhang,D.；Lim,K.-S.；Hu,Y.；Rong,Y.；Mei,A.；Park,N.-G.；Han,H.,A Review on Scaling Up Perovskite Solar Cells[J].Advanced Functional Materials 2020,31,2008621.
4.Sheibani,E.；Yang,L.；Zhang,J.,Recent Advances in Organic Hole Transporting Materials for Perovskite Solar Cells[J].Solar RRL 2020,4,2000461.
5.Hawash,Z.；Ono,L.K.；Qi Y.B.Recent Advances in Spiro-MeOTAD Hole Transport Material and Its Applications in Organic–Inorganic Halide Perovskite Solar Cells[J].Adv.Mater.Interfaces 2018,5,1700623.
6.Asghara,M.I.；Zhang J.；Wang H.；Lund P.D.,Device Stability of Perovskite Solar Cells–A Review[J].Renewable&Sustainable Energy Reviews 2017,77,131-146.
7.Shen,Y.,Chen,C.F.Helicenes:Synthesis and Applications[J].Chem.Rev.2012,112,1463-1535.
disclosure of Invention
The invention aims to overcome the defects of the prior art and discloses a method for preparing a novel anti-counterfeiting paper
Figure BDA0003210314760000022
Azabicyclo [6] radical]A spiro-based hole transport material and its use in solar cells.
In order to achieve the purpose, the invention specifically adopts the following technical scheme:
in a first aspect, the present invention provides a method
Figure BDA0003210314760000023
Azabicyclo [6] radical]The spiroalkene compound DA6-HTM has a structural formula shown in a formula I:
Figure BDA0003210314760000021
wherein:
r is selected from H, C1-C16 alkyl or Cl-C16 alkoxy; d is selected from diamine groups:
Figure BDA0003210314760000031
r' is selected from H, C1-C16 alkyl or Cl-C16 alkoxy.
Preferably, the DA6-HTM is in the form of DA6-BMCA-C6, DA6-BMCA-C8, DA6-BDBA or DA6-BDNA, and the structural formulas are shown as formulas II to V respectively:
Figure BDA0003210314760000032
Figure BDA0003210314760000041
in a second aspect, the present invention provides a method as defined in any one of the above aspects of the first aspect
Figure BDA0003210314760000042
Azabicyclo [6] radical]Use of spiroalkene compounds as hole transport materials.
In a third aspect, the present invention provides a perovskite solar cell, wherein the hole transport layer material of the solar cell is as defined in any one of the above first aspects
Figure BDA0003210314760000043
Azabicyclo [6] radical]A spiroalkene compound.
Preferably, the electrode sequentially comprises a substrate, a transparent oxide electrode, an electron transport layer, a photoactive layer, a hole transport layer and a metal electrode from top to bottom.
Further, the electron transport layer material is titanium dioxide.
Further, the photoactive layer material is perovskite.
Prepared by the invention
Figure BDA0003210314760000044
Azabicyclo [6] radical]The energy conversion efficiency of the perovskite solar cell prepared by taking the spiroalkene compound as the hole transport layer can reach 18.5% -21.5%, wherein the energy conversion efficiency of DA6-BMCAThe content was 19.4%. Meanwhile, the glass transition temperature of the materials is high, and the thermal stability of the prepared perovskite solar cell device is good. Accordingly, the invention
Figure BDA0003210314760000045
Azabicyclo [6] radical]The spiroalkene compound is used as a hole transport material of the perovskite solar cell to promote charge transport, and the energy conversion efficiency and stability of the solar cell are improved.
Drawings
FIG. 1 is a schematic view of a structure of a PSC device in which a hole transport layer is made of a material
Figure BDA0003210314760000046
Azabicyclo [6] radical]The spiroalkene compound has electronic transmission layer of titania and optical active layer of perovskite.
FIG. 2 is a J-V curve of a PSCs device based on DA 6-BMCA-C6.
FIG. 3 is a PCE change curve of an aging process of a perovskite solar cell device with a hole transport layer based on DA6-BMCA-C6 under a dark condition of 60 ℃ for 21 days.
FIG. 4 comparison of stability of perovskite solar cell devices based on BA7-BMCA-C6 and DA6-BMCA-C6 (room temperature, AM 1.5G, 100mW cm)-2)。
Detailed Description
The invention will be further elucidated and described with reference to the drawings and specific embodiments.
According to the invention
Figure BDA0003210314760000053
Azabicyclo [6] radical]The structural formula of the spiroalkene hole transport material is as follows:
Figure BDA0003210314760000051
wherein:
r is selected from H, C1-C16 alkyl or Cl-C16 alkoxy;
d is selected from diamine groups, and specifically comprises:
Figure BDA0003210314760000052
r' is selected from H, C1-C16 alkyl or Cl-C16 alkoxy.
According to the invention
Figure BDA0003210314760000054
Azabicyclo [6] radical]The spiroalkene compound is used as a hole transport material of the perovskite solar cell to promote charge transport, and the energy conversion efficiency and stability of the solar cell are improved.
To the prepared compound of formula I
Figure BDA0003210314760000055
Azabicyclo [6] radical]The cavity mobility of the spiroalkene compound DA6-HTM is measured, and the distribution range of the cavity mobility is as follows: 4.36X 10-5～8.25×10-4 cm2 V-1。
The following examples will help to understand the present invention, but the scope of the present invention is not limited to the contents of the following examples:
example 1 Synthesis of DA6-BMCA
Figure BDA0003210314760000056
Azabicyclo [6] radical]The synthetic route of the spiroalkene compound DA6-BMCA is as follows:
Figure BDA0003210314760000061
in the above synthetic route, the synthetic method of the compounds 1-6 is as follows:
compound 1(6, 12-dibromo)
Figure BDA0003210314760000064
) The synthesis of (2):
Figure BDA0003210314760000062
mixing the raw materials
Figure BDA0003210314760000065
(2.0g, 228.3g/mol, 8.8mmol) was added to a 150mL sealed tube containing 70mL chloroform, liquid bromine (1.4mL, 3.1g/mL, 4.2g, 159.8g/mol, 26.3mmol) was dissolved in 10mL chloroform, added to the sealed tube, slowly heated to 80 ℃ for reaction for 16h, cooled to room temperature after completion of the reaction, and 50mL Na was added2S2O3The reaction was quenched with aqueous solution (0.1mol/L, 150mL) and dibromo was further treated with 100mL of poor solvent methanol
Figure BDA0003210314760000066
All precipitate was filtered under reduced pressure, the filtrate was again treated with aqueous sodium hydroxide solution to give a crude filter cake, and toluene was recrystallized to give 3.1g of a white solid (compound 1) in a yield of 90.4%. The structural characterization data for the synthesized compound 1 is as follows:
1H NMR(500MHz,THF-d8)δ9.19–9.18(s,2H),8.93–8.92(d,J＝8.0Hz,2H),8.43–8.42(d,J＝7.6Hz,2H),7.84–7.76(m,4H).13C NMR(126MHz,THF-d8)δ130.70,130.67,128.34,128.31,127.95,127.89,127.65,125.36,123.75,122.95ppm.
synthesis of Compound 2:
Figure BDA0003210314760000063
compound 1(2.0g, 386.1g/mol, 5.2mmol) and 1-chloro-2-aminonaphthalene (2.8g, 177.6g/mol, 15.6mmol), Pd (OAc)2(34.9mg, 224.5g/mol, 15.5% mmol), DPEPhOS (251.0mg, 538.6g/mol, 0.5mmol), NaO (t-Bu) (2.5g, 96.0g/mol, 25.9mmol) were added to a 200mL single-neck round-bottom flask, 100mL of toluene was added as solvent, heated under argon atmosphere at 120 ℃ under reflux for 16h, after completion of the reaction, cooled to room temperature, the catalyst and base were filtered off with celite, the filtrate was concentrated and recrystallized with THF to give 2.4g of a white solid (Compound 2) in 2.4g yield79.6 percent. The structural characterization data for the synthesized compound 2 is as follows:
1H NMR(500MHz,THF-d8)δ8.79–8.78(d,J＝8.4Hz,2H),8.76–8.75(s,2H),8.27–8.26(d,J＝8.3Hz,2H),8.18–8.17(d,J＝8.5Hz,2H),7.75–7.72(m,4H),7.68–7.65(dd,J＝8.4,6.8Hz,2H),7.60–7.54(m,6H),7.32–7.31(dd,J＝8.0,6.5Hz,2H),7.09–7.08(d,J＝8.9Hz,2H).13C NMR(126MHz,THF-d8)δ142.55,137.95,133.51,133.01,131.04,131.03,130.62,129.53,128.94,128.72,128.36,128.35,127.95,125.19,125.07,124.52,123.72,119.10,117.43.HR-MS(ESI)m/z calcd.For(C38H24Cl2N2):578.1317.Found:578.1301.FT-IR:2956,2922,2852,1626,1597,1504,1474,1434,1351,1321,1293,1252,1025,988,863,811.
synthesis of Compound 3(DA6H)
Figure BDA0003210314760000071
Mixing compound 2(2.0g, 579.5g/mol, 3.5mmol), Pd (OAc)2(78.6mg，224.5g/mol，0.4mmol)、K2CO3(2.9g, 138.0g/mol, 20.7mmol) and P (t-Bu)3·HBF4(200.0mg, 290.0g/mol, 0.7mmol) is added into a 300mL single-neck round-bottom flask, 200mL ultra-dry N, N-dimethylacetamide (DMAc) is taken as a reaction solvent, the mixture is stirred and reacted for 24 hours under the protection of argon and the heating condition of 130 ℃, after the reaction is completed, the reaction solution is extracted by DCM (30mL multiplied by 3), and the organic phase is extracted by anhydrous Na2SO4After drying, filtration and rotary evaporation gave the crude product which was purified by column separation over alumina eluting with THF and toluene (2: 1 by volume) to give 472.1mg of a yellow solid (compound 3) in 27.0% yield. The structural characterization data for the synthesized compound 3 is as follows:
1H NMR(500MHz,THF-d8)δ11.99–11.98(s,2H),8.55–8.54(d,J＝8.0Hz,2H),8.42–8.41(d,J＝8.3Hz,2H),7.97-7.96(d,J＝7.9Hz,2H),7.89–7.88(dd,J＝12.7,8.7Hz,2H),7.83–7.82(d,J＝8.4Hz,2H),7.62–7.59(m,2H),7.32–7.29(m,2H),7.25–7.22(m,2H),7.11–7.10(dd,J＝11.7,4.5Hz,2H).13C NMR(126MHz,THF-d8)δ134.85,131.36,128.66,128.00,127.45,127.14,126.26,125.65,123.94,123.73,122.24,122.12,121.98,120.42,119.49,118.64,116.92,111.84,111.17ppm.HR-MS(ESI)m/z calcd.For(C38H22N2):506.1783.Found:506.1778.FT-IR:2957,2924,2853,1667,1531,1454,1397,1262,1023,897,804,756,717,669.
synthesis of Compound 4(DA 6-C6):
Figure BDA0003210314760000081
dissolving compound 3(472.1mg, 506.6g/mol, 0.9mmol) in ultra-dry DMF and 50mL of ultra-dry THF (volume ratio 1:1), slowly adding NaH (446.4mg, 24g/mol, 18.6mmol), stirring under argon for 10min, adding iodohexane (789.0mg, 212.1g/mol, 3.7mmol), stirring at room temperature for 3h, slowly adding water (300mL) after the reaction is completed, quenching the reaction, adding DCM (50 mL. times.3), extracting, and using anhydrous Na as organic phase2SO4Drying, filtering, rotary evaporating to obtain crude product, separating with silica gel column, and eluting with toluene and petroleum ether (1:8) to obtain 503.8mg of yellow powder (compound 4) with yield of 98.0%. The structural characterization data for the synthesized compound 4 is as follows:
1H NMR(500MHz,THF-d8)δ8.64–8.63(d,J＝8.3Hz,2H),8.40–8.39(d,J＝8.5,2H),8.02–8.01(d,J＝9.0Hz,2H),7.97–7.95(dd,J＝11.9,5.0Hz,4H),7.83–7.81(d,J＝8.5Hz,2H),7.60–7.59(dd,J＝8.3,6.8,2H),7.30–7.29(dd,J＝7.9,6.7,2H),7.21–7.20(dd,J＝8.2,6.8,2H),7.06–7.05(dd,J＝8.4,6.8,2H),5.23–5.17(m,2H),5.07–5.00(m,2H),2.48–2.32(m,4H),1.79–1.76(m,4H),1.60–1.53(m,4H),1.50–1.43(m,4H),0.98–(t,J＝7.3Hz,6H).13C NMR(126MHz,THF-d8)δ136.02,130.85,128.79,128.67,127.99,126.64,126.25,125.28,124.08,123.64,122.71,122.22,122.20,120.67,120.23,119.37,115.99,112.28,109.31,44.12,29.75,28.79,24.77,20.78,11.57ppm.HR-MS(MALDI-TOF)m/z calcd.For(C50H46N2):674.3661.Found:674.3657.FT-IR:2925,2852,1616,1524,1442,1398,1288,1217,1023,798,750,715,629.
synthesis of Compound 5(DA6-C6-2 Br):
Figure BDA0003210314760000091
compound 4(503.8mg, 551.7g/mol, 0.9mmol) was added to a 100mL single neck round bottom flask, DCM50mL was added to dissolve it completely, NBS (321.0mg, 178.0g/mol, 1.8mmol) was added and stirred at room temperature for 1h, after completion of the reaction Na was added2S2O3The reaction was quenched with aqueous solution (0.1mol/L, 50mL), the reaction was extracted with DCM (20 mL. times.3), and the organic phase was washed with anhydrous Na2SO4Drying, filtering, rotary evaporating to obtain crude product, separating with silica gel column, and eluting with toluene and petroleum ether (volume ratio of 1:8) to obtain yellow solid (compound 5)562.5mg, with yield of 90.0%. The structural characterization data for the synthesized compound 5 is as follows:
1H NMR(500MHz,CDCl3)δ8.44–8.43(dd,J＝8.3,5.0Hz,4H),8.31–8.29(d,J＝8.4Hz,2H),8.18–8.16(s,2H),7.85–7.83(d,J＝8.4Hz,2H),7.56–7.54(dd,J＝7.6Hz,2H),7.45–7.42(dd,J＝7.6Hz,2H),7.24–7.20(m,2H),7.15–7.12(dd,J＝7.7Hz,2H),5.02–4.96(m,2H),4.81–4.75(m,2H),2.41–2.25(m,4H),1.72–1.86(m,4H),1.55–1.50(m,4H),1.47–1.42(m,4H),0.98–0.96(t,J＝7.2Hz,6H).13C NMR(126MHz,CDCl3)δ137.65,133.57,131.09,130.94,129.39,127.95,127.77,126.39,125.69,125.15,125.03,124.53,122.55,121.42,120.39,118.35,115.82,114.30,46.89,31.96,31.06,27.18,23.11,14.48.HR-MS(MALDI-TOF)m/z calcd.For(C50H44Br2N2):830.1871.Found:830.122.FT-IR:2926,2852,1714,1499,1469,1424,1335,948,858,698.
synthesis of Compound 6(DA 6-BMCA-C6):
Figure BDA0003210314760000092
compound 5(500.0mg, 832.7g/mol, 0.6mmol), starting intermediate BMCA (675.9mg, 375.5g/mol, 1.8mmol), Pd2(dba)3(55.0mg，916.0g/mol，0.06mmol)、P(t-Bu)3·HBF4(34.8mg, 290.0g/mol, 0.1mmol) and NaO (t-Bu) (288.0mg, 96.0g/mol, 3.0mmol) were added to a 200mL single neck round bottom flask, 100mL of toluene was added, and the reaction was refluxed at 120 ℃ under argon overnight. After the reaction is completed, the reaction product is cooled to room temperature, the catalyst and the alkali are filtered by diatomite, the filtrate is subjected to rotary evaporation and concentration and then is separated by a silica gel column, and the yellow solid (compound 6)597.6mg can be obtained by eluting the solution by THF-petroleum ether (the volume ratio is 1:3), and the yield is 70%. The structural characterization data for synthesized compound 6 is as follows:
1H NMR(500MHz,THF-d8)δ8.59–8.54(m,4H),8.43–8.41(m,2H),7.99–7.96(m,4H),7.95–7.93(m,2H),7.89–7.86(m,6H),7.55–7.53(m,2H),7.42–7.38(m,12H),7.35–7.33(m,4H),7.25–7.23(m,2H),7.11–7.08(m,2H),7.04–6.98(m,6H),5.03–4.97(m,2H),4.87–4.80(m,2H),3.86(s,12H),2.21–2.17(m,4H),1.47–1.41(m,4H),1.24–1.21(m,4H),1.14–1.09(m,J＝7.4Hz,4H),0.70–0.68(t,J＝7.3Hz,6H).13C NMR(125MHz,THF-d8)δ145.42,144.31,142.48,139.22,137.95,133.77,131.37,131.24,130.81,128.26,128.19,126.30,126.23,126.04,125.32,125.01,124.80,124.36,123.55,123.35,123.30,122.73,121.98,120.98,118.92,116.84,115.14,115.10,112.53,109.70,108.98,46.52,32.13,31.30,30.47,28.97,27.27,14.03.HR-MS(MALDI-TOF)m/z calcd.For(C102H84N8):1420.6819.Found:1420.8735.
the hole mobility of the prepared DA6-BMCA-C6 is measured, and the hole mobility is as follows: 8.25X 10- 4cm2V-1. DA6-BMCA-C6 has a Tg of 233 ℃ as measured by Differential Scanning Calorimetry (DSC) over another
Figure BDA0003210314760000102
Aza [7 ] yl]194 ℃ of spiroalkene compound BA 7-BMCA-C6.
Figure BDA0003210314760000103
Aza [7 ] yl]The structural formula of the spiroalkene compound BA7-BMCA-C6 is as follows:
Figure BDA0003210314760000101
example 2 Synthesis of DA 6-BMCA-C8:
DA6-BMCA-C8 was synthesized by the procedure of example 1 using Compound 3 as a starting material. The synthetic route is as follows:
Figure BDA0003210314760000111
the structural characterization data for compound DA6-BMCA-C8 are as follows:
1H NMR(500MHz,THF-d8)δ8.59–8.55(m,4H),8.43–8.40(m,2H),7.99–7.96(m,4H),7.95–7.92(m,2H),7.89–7.86(m,6H),7.55–7.53(m,2H),7.42–7.38(m,12H),7.35–7.33(m,4H),7.25–7.23(m,2H),7.11–7.08(m,2H),7.04–6.97(m,6H),5.03–4.97(m,1H),4.87–4.80(m,1H),3.86–3.83(s,12H),3.53-3.50(m,4H),2.21–2.16(m,4H),1.47–1.41(m,4H),1.24–1.21(m,4H),1.14–1.09(m,J＝7.4Hz,4H),0.85-0.83(t,J＝7.0Hz,6H),0.68-0.66(t,J＝7.0Hz,6H).13C NMR(125MHz,THF-d8)δ145.43,144.32,142.49,139.23,137.96,133.76,131.38,131.24,130.81,128.26,128.18,126.32,126.24,126.06,125.32,125.02,124.82,124.38,123.56,123.37,123.31,122.73,121.98,120.98,118.92,116.84,115.14,115.10,112.53,109.70,108.98,46.53,32.15,31.31,30.48,29.86,28.96,27.29,14.06.HR-MS(MALDI-TOF)m/z calcd.For(C106H92N8):1477.9488.Found:1477.9525.
the hole mobility of the prepared DA6-BMCA-C8 is measured, and the hole mobility is as follows: 6.23X 10- 4cm2V-1. The Tg of DA6-BMCA-C8 was 225 ℃ as determined by Differential Scanning Calorimetry (DSC).
Example 3 synthesis of DA 6-BDBA:
DA6-BDBA was synthesized by referring to the procedure in example 1 using compound 5 as a starting material. The reaction equation is as follows:
Figure BDA0003210314760000112
the structural characterization data for the synthesized compound DA6-BDBA is as follows:
1H NMR(500MHz,THF-d8)δ8.79–8.64(m,4H),7.93–7.95(m,2H),7.89–7.86(m,6H),7.42–7.38(m,16H),7.36–7.28(m,4H),7.11(dd,10,5Hz,2H),5.03–4.97(m,2H),4.87–4.80(m,2H),3.83(s,12H),2.22–2.17(m,4H),1.46–1.41(m,4H),1.24–1.20(m,4H),1.13–1.09(m,J＝7.4Hz,4H),0.70–0.68(t,J＝7.3Hz,6H).13C NMR(125MHz,THF-d8)δ145.43,144.32,142.48,139.22,137.96,133.78,131.37,130.81,128.26,126.30,126.05,125.33,124.80,123.55,123.30,122.73,121.98,120.99,118.92,116.84,115.10,55.85,46.52,32.13,31.31,28.97,27.27,14.02.HR-MS(MALDI-TOF)m/z calcd.For(C78H72N4O4):1129.4508.Found:1129.4585.
the hole mobility of the prepared DA6-BDBA is measured, and the hole mobility is as follows: 6.25X 10-5cm2V-1. The Tg of DA6-BDBA was 195 ℃ as determined by Differential Scanning Calorimetry (DSC).
Example 4 synthesis of DA 6-BDNA:
DA6-BDNA was synthesized by following the procedure of example 1 using Compound 5 as a starting material. The reaction equation is as follows:
Figure BDA0003210314760000121
the structural characterization data of compound DA6-BDNA is as follows:
1H NMR(500MHz,THF-d8)δ8.70–8.64(m,4H),8.43–8.41(m,2H),7.95–7.93(m,2H),7.89–7.85(m,6H),7.55–7.51(m,2H),7.42–7.38(m,12H),7.35–7.33(m,4H),7.25–7.23(m,2H),7.11–7.09(m,2H),7.04–6.98(m,6H),5.03–4.97(m,2H),4.87–4.80(m,2H),3.82(s,12H),2.22–2.17(m,4H),1.46–1.41(m,4H),1.25–1.22(m,4H),1.13–1.09(m,J＝7.4Hz,4H),0.70(t,J＝7.3Hz,6H).13C NMR(125MHz,THF-d8)δ145.43,144.32,142.47,139.21,137.96,133.76,131.36,131.25,130.80,128.25,126.31,126.05,125.33,124.81,123.54,123.31,122.72,121.99,120.97,118.93,116.85,115.15,115.11,55.83,46.53,32.12,31.31,30.48,28.98,27.27,14.02.HR-MS(MALDI-TOF)m/z calcd.For(C94H80N4O4):1329.6900.Found:1329.6987.
the hole mobility of the prepared DA6-BDNA is measured, and the hole mobility is as follows: 1.23X 10-4cm2V-1. The Tg of DA6-BDNA was 203 ℃ as determined by Differential Scanning Calorimetry (DSC).
Example 5 preparation of solar cell device:
the FTO glass was cleaned in turn with detergent, deionized water, acetone, ethanol and isopropanol in an ultrasonic instrument for 10 minutes each time. Dissolving 0.6mL of diisopropyl di (acetylacetonate) titanate and 0.4mL of acetylacetone in 9mL of absolute ethanol to prepare a precursor solution, and depositing the prepared precursor solution on FTO by a spray pyrolysis method at 450 ℃ by taking oxygen as a carrier gas to form dense TiO with the thickness of 30nm2And (3) a layer. Adding commercial TiO2The paste (30NR-D) and absolute ethyl alcohol were diluted at a mass ratio of 1:6, and then at 2000rpm s-1Spin coating for 10s at a rotating speed to make the mesoporous TiO2Depositing on a substrate to form 200 nm-thick mesoporous TiO2And (3) a layer. Drying at 80 deg.C for 10min, and adding TiO2The film was thermally annealed at 450 ℃ for 30min under a dry air flow to remove organic components, and then subjected to ultraviolet-ozone treatment for 30 min. Dissolving 1.30M PbI2, 1.19M FAI and 0.14M PbBr in mixed solution of DMSO/DMF (volume ratio of 1:4)2And 0.14M MABr and 0.07M CsI (FAPbI)3)0.875(MAPbBr3)0.075(CsPbI3)0.05(PbI2)0.03 perovskite precursor solution, followed by the preparation of a perovskite layer in a glove under a flow of dry air with a relative humidity of less than 2%, in two successive steps at 200rpm s-1Spin at 10s and 2000rpm s-1The perovskite precursor solution is deposited on the electron transport layer by spin coating for 30s at the rotating speed. 150 μ L of chlorobenzene was dropped on the rotating light-absorbing layer 15s before the end of the procedure, and then the perovskite layer was thermally annealed at 120 ℃ for 1h to complete the preparation of the perovskite layer.
The preparation of the hole-transporting layer was also carried out in a glove box with a flow of dry air at a relative humidity of less than 2%, respectively synthesized in the above examples
Figure BDA0003210314760000132
Azabicyclo [6] radical]The spiroalkene compound is used as a hole transport material, the hole transport material is doped with 0.5 equivalent of HTFSI (bis (trifluoromethylsulfonyl) amide) and 3.3 equivalents of t-BP (tert-butylpyridine) to prepare a 30mM chlorobenzene solution, and then the mixture is subjected to s-stirring at 4000rpm-1Spin coating at a rotation speed of 20s, depositing the film on the annealed perovskite film, and finally performing vacuum evaporation of a layer of gold with a thickness of 120nm to obtain the final product
Figure BDA0003210314760000133
Azabicyclo [6] radical]The perovskite solar cell device with the hole transport layer made of the spiroalkene compound is manufactured, and the structure of the perovskite solar cell device is shown in figure 1.
In this example, 4 kinds of the compounds synthesized in examples 1 to 4 were used
Figure BDA0003210314760000134
Azabicyclo [6] radical]And preparing a hole transport layer by using spiroalkene compounds DA6-BMCA-C6, DA6-BMCA-C8, DA6-BDBA or DA6-BDNA to obtain four types of solar cell devices. The photovoltaic performance test is carried out on four types of perovskite solar cell devices, and the results are as follows:
TABLE 1 differs by
Figure BDA0003210314760000135
Azabicyclo [6] radical]Photovoltaic performance parameters of perovskite solar cell device with hole transport layer made of spiroalkene compound
Figure BDA0003210314760000131
In which fig. 2 exemplarily shows the J-V curve of a perovskite solar cell device based on a hole transport layer prepared from DA 6-BMCA-C6.
Example 6 stability testing:
the stability test results are shown in FIG. 3, and the PCE retention rate of the DA 6-BMCA-based PSCs after aging at 60 ℃ for 21 days in the dark is 77%.
After being stored for 30 days under the conditions of dry air atmosphere and room temperature, the perovskite solar cell device based on DA6-BMCA-C6 as a hole transport layer and another perovskite solar cell device
Figure BDA0003210314760000141
Aza [7 ] yl]Stability test (room temperature, AM 1.5G, 100mW cm) is carried out on the perovskite solar cell device with the spiroalkene compound BA7-BMCA-C6 as the hole transport layer-2). The perovskite solar cell device based on BA7-BMCA-C6 and serving as a hole transport layer is the same as the perovskite solar cell device based on DA6-BMCA-C6 and serving as a hole transport layer in example 2 except that the hole transport layer is BA 7-BMCA-C6. The stability test results are shown in fig. 4, and the PCE retention rates of the two solar cell devices are 93.1% and 81.3%, respectively. The perovskite solar cell device based on DA6-BMCA-C6 is proved to have better stability compared with the perovskite solar cell device based on BA 7-BMCA-C6.
The above-described embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, the technical scheme obtained by adopting the mode of equivalent replacement or equivalent transformation is within the protection scope of the invention.

Claims (7)

1. A kind of
Figure FDA0003210314750000014
Azabicyclo[6]The structural formula of the spiroalkene compound is shown as the formula I:
Figure FDA0003210314750000011
wherein:
r is selected from H, C1-C16 alkyl or Cl-C16 alkoxy; d is selected from diamine groups:
Figure FDA0003210314750000012
r' is selected from H, C1-C16 alkyl or Cl-C16 alkoxy.
2. The method of claim 1
Figure FDA0003210314750000015
Azabicyclo [6] radical]The spiroalkene compound is characterized in that the structural formula is as shown in any one of formula II to formula V:
Figure FDA0003210314750000013
Figure FDA0003210314750000021
3. a process as claimed in claim 1 or 2
Figure FDA0003210314750000022
Azabicyclo [6] radical]Use of spiroalkene compounds as hole transport materials.
4. A perovskite solar cell, characterized in that the hole transport layer material of the solar cell is as defined in claim 1 or 2
Figure FDA0003210314750000023
Azabicyclo [6] radical]A spiroalkene compound.
5. The perovskite solar cell according to claim 4, which consists of a substrate, a transparent oxide electrode, an electron transport layer, a photoactive layer, a hole transport layer and a metal electrode in this order from top to bottom.
6. The perovskite solar cell of claim 5, wherein the electron transport layer material is titanium dioxide.
7. The perovskite solar cell of claim 5, wherein the photoactive layer material is a perovskite.
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