CN110776434B - Hole transport material based on tetraaryl butadiene and preparation method and application thereof - Google Patents

Hole transport material based on tetraaryl butadiene and preparation method and application thereof Download PDF

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CN110776434B
CN110776434B CN201910934817.9A CN201910934817A CN110776434B CN 110776434 B CN110776434 B CN 110776434B CN 201910934817 A CN201910934817 A CN 201910934817A CN 110776434 B CN110776434 B CN 110776434B
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邵光
陈剑
余惠娟
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Shenzhen Research Institute of Sun Yat Sen University
National Sun Yat Sen University
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Abstract

The invention discloses a hole transport material based on tetraaryl butadiene, wherein the chemical general formula of the hole transport material is shown as a formula (I); the hole transport material is an organic small molecule which takes tetraphenylbutadiene, tetrathiophenylbutadiene or tetrafuranbutadiene as a core and takes diphenylamine, triphenylamine, carbazole, phenothiazine or phenoxazine substituted by alkoxy or alkylthio as a side group. The hole transport material disclosed by the invention is simple to synthesize, low in cost and has the potential of large-scale production, has good photoelectric property and thermal stability, can be used as the hole transport material to be applied to photoelectric devices such as organic photoconductive drums, OLED displays and solar cells, and has a wide application prospect.

Description

Hole transport material based on tetraaryl butadiene and preparation method and application thereof
Technical Field
The invention relates to the technical field of photoelectric materials, in particular to a hole transport material of tetraaryl butadiene, and a preparation method and application thereof.
Background
With the economic development and technological progress, photoelectric materials have covered aspects of life and work, such as Organic Photoconductors (OPCs) in laser printers, Organic Light-Emitting diodes (OLEDs) in displays, and Hole-Transporting materials (HTMs) in solar cells.
OPC refers to a semiconductor material that causes formation and migration of photogenerated carriers when irradiated with light. The organic photoconductor drum is a photoelectric imaging device prepared by coating OPC on the surface of a conductive aluminum cylinder, is an insulator in the dark, can maintain certain electrostatic charge, becomes a conductor after being irradiated by light with certain wavelength, releases the charge through an aluminum base to form an electrostatic latent image, and is a key part for printing and copying. Early photoconductive materials were inorganic substances such as selenium and cadmium sulfide, high in price and toxicity, and now replaced by low-price and low-toxicity OPC. Currently, the types of HTM in OPC are mainly aromatic amines, stilbenes, biphenyls, and the like. In addition, since the appearance of OLEDs in 1987, research in related fields has been vigorously made, and particularly in the field of displays, the OLEDs have the advantages of active light emission, wide viewing angle, wide color gamut, fast response, small thickness, good flexibility, high contrast and resolution, high light emission efficiency, and the like, and are well known to have the potential to replace liquid crystal displays. The HTM is very critical to the realization of the above advantages, and can improve the efficiency of hole migration, increase the concentration of holes in the light emitting layer, block electrons in the light emitting layer, further improve the probability of exciton formation by the combination of electrons and holes, and increase the light emitting efficiency of the device. The organic small molecule HTM applied to the OLED mainly includes: compounds containing fluorene and heterofluorene structures; triphenylamines, carbazoles and other molecules rich in N atoms, metal complexes and the like. Meanwhile, the current mainstream fossil energy is difficult to meet the requirements of social sustainable development due to the defects of limited reserves, serious pollution and the like, and the development and utilization of solar energy which is safe, clean and nearly unlimited in reserves becomes an increasingly urgent problem. Perovskite solar cells are a new star in the photovoltaic field, and the efficiency of the perovskite solar cells reaches 24.2%, so that the perovskite solar cells become a popular research topic in the energy field. As an important component of high efficiency perovskite solar cells, HTMs ensure that holes are efficiently extracted and transported, limiting the recombination of photogenerated carriers.
Currently, the predominant HTMs are 2,2 ', 7,7 ' -tetrakis (N, N-p-methoxyanilino) -9,9 ' -spirobifluorene (spiro-omatad) and poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTAA), but they involve complicated and expensive synthesis and purification steps, limited to laboratory studies. Therefore, research on the HTM with simple synthesis and purification, low cost and excellent performance has important significance for realizing commercialization of the perovskite battery.
Disclosure of Invention
The present invention is directed to overcoming the above-mentioned drawbacks and deficiencies of the prior art and to providing a hole transport material based on tetraarylbutadiene.
The invention also aims to provide a preparation method of the hole transport material based on the tetraarylbutadiene.
The invention further aims to provide application of the hole transport material based on the tetraarylbutadiene.
The above object of the present invention is achieved by the following technical solutions:
a tetraarylbutadiene-based hole transport material having a general chemical formula as shown in formula (I):
Figure BDA0002221292900000021
wherein Ar is a benzene ring, a thiophene ring or a furan ring, R is diphenylamine, triphenylamine, carbazole, phenothiazine or phenoxazine substituted by alkoxy or alkylthio, and n is 1-6.
The hole transport material is an organic micromolecule which takes tetraphenylbutadiene, tetrathiophenylbutadiene or tetrafuranbutadiene as a core and takes diphenylamine, triphenylamine, carbazole, phenothiazine or phenoxazine substituted by alkoxy or alkylthio as a side group. The planar structure of butadiene is favorable for forming good intermolecular pi-pi accumulation, and meanwhile, a plurality of nodes are provided for the jumping of holes among molecules by more N atom centers, and the two nodes are both favorable for improving the hole mobility. The photoelectric property of the hole transport material can be regulated and controlled by regulating the types of the aryl and the peripheral groups of the core. The thermal stability, solubility and film-forming property of the hole-transporting material can be controlled by increasing or decreasing the length of the terminal alkoxy group and alkylthio group. The hole transport material has good photoelectric property and thermal stability, and can be used as a hole transport material to be applied to photoelectric devices such as organic photoconductive drums, OLED displays and solar cells.
Preferably, Ar is
Figure BDA0002221292900000031
R is
Figure BDA0002221292900000032
Preferably, Ar is
Figure BDA0002221292900000033
R is
Figure BDA0002221292900000034
Figure BDA0002221292900000035
n＝1～6。
More preferably, n ═ 1, i.e., R is 4,4 '-dimethoxydiphenylamine or 4, 4' -dimethoxytriphenylamine, gives a hole transport material represented by CJ-03 or CJ-04 as follows:
Figure BDA0002221292900000041
the preparation method of the hole transport material CJ-03 or CJ-04 comprises the following steps:
s1, under the protection of inert gas, 4' -dibromobenzophenone and methyl triphenyl phosphonium bromide react under the condition of strong alkali to obtain an olefination compound 1;
s2, reacting the compound 1 with paraformaldehyde and hydrogen bromide under the protection of inert gas to obtain a bromomethylated compound 2;
s3, reacting the compound 2 with triethyl phosphite under the protection of inert gas to obtain a Wittig reagent compound 3;
s4, reacting the compound 3 with 4, 4' -dibromo benzophenone under the protection of inert gas under a strong alkali condition to obtain a compound 4;
s5, under the protection of inert gas, reacting the compound 4 with 4, 4' -dimethoxydiphenylamine under the action of strong base and a catalyst to obtain a hole transport material CJ-03; or reacting the compound 4 with 4,4 '-dimethoxy-4' -triphenylamine borate under the action of a weak base and a catalyst to obtain the hole transport material CJ-04.
Preferably, in the step S1, the molar ratio of the 4, 4' -dibromobenzophenone to the methyl triphenyl phosphonium bromide is 1: 2-3, and the reaction is carried out for 38-40 h at 20-25 ℃; the strong base is potassium tert-butoxide and the solvent is tetrahydrofuran.
Preferably, in the step S2, the molar ratio of the compound 1 to the paraformaldehyde to the hydrogen bromide is 1: 1.5-2, and the reaction is carried out at 45-55 ℃ for 25-30 h; the solvent is acetic acid.
Preferably, in the step S3, the molar ratio of the compound 2 to the triethyl phosphite is 1: 2-3, and the reaction is carried out at 105-115 ℃ for 30-35 h; in the step S4, the molar ratio of the compound 3 to the 4, 4' -dibromobenzophenone is 1: 1-1.5, the reaction is carried out at 20-25 ℃ for 50-55 h, the alkali is sodium hydride, and the solvent is tetrahydrofuran.
Preferably, in step S5, the molar ratio of the compound 4 to 4, 4' -dimethoxydiphenylamine is 1: 4-5, the reaction is carried out at 115-125 ℃ for 45-50 h, the base is sodium tert-butoxide, the catalyst is palladium acetate and tri-tert-butylphosphine, and the solvent is toluene; the molar ratio of the compound 4 to 4,4 '-dimethoxy-4' -triphenylamine borate is 1: 7-8, the reaction is carried out at the temperature of 80-90 ℃ for 50-55 h, the alkali is potassium carbonate, the catalyst is tetrakis (triphenylphosphine) palladium, and the solvent is tetrahydrofuran and water.
Preferably, the preparation method of the 4,4 '-dimethoxy-4' -triphenylamine borate comprises the following steps:
s1, under the protection of inert gas, reacting 4-iodoanisole with aniline under the action of strong base and a catalyst to obtain a compound 5;
s2, reacting the compound 5 with N-bromosuccinimide under the protection of inert gas to obtain a brominated compound 6;
s3, under the protection of inert gas, reacting the compound 6 with triisopropyl borate under a strong alkali condition to obtain a boric acid compound 7, namely 4,4 '-dimethoxy-4' -triphenylamine borate.
Preferably, in the step S1, the molar ratio of 4-iodoanisole to aniline is 2-3: 1, the reaction is carried out at 125-135 ℃ for 45-55 h, the base is potassium tert-butoxide, and the catalyst is 1, 10-phenanthroline monohydrate and cuprous iodide.
Preferably, in step S2, the molar ratio of compound 5 to N-bromosuccinimide is 1: 1-1.2, the reaction is carried out at 0-25 ℃ for 35-40 h, and the solvent is N, N-dimethylformamide.
Preferably, in step S3, the molar ratio of the compound 6 to triisopropyl borate is 1:3, the reaction is carried out at-78-25 ℃ for 20-25 h, the base is n-butyllithium, and the solvent is tetrahydrofuran.
Preferably, the inert gas in the above reaction step is argon.
The application of any one of the hole transport materials in the preparation of perovskite solar cells, OLEDs or organic photoconductor drums.
The invention also provides a perovskite solar cell which comprises a glass substrate, a conductive layer, an electron transport layer, a light absorption layer, a hole transport layer and an electrode layer, and is characterized in that the hole transport layer is made of any of the tetraarylbutadiene-based hole transport materials.
Preferably, the conductive substrate is FTO glass, and the FTO glass is partitioned into a positive electrode region and a negative electrode region by etching.
Preferably, the electron transport layer is titanium dioxide (TiO)2)。
Preferably, the light absorbing layer is iodoplumbum methylamine.
Preferably, the electrode is gold (Au).
The preparation method of the perovskite solar cell comprises the following steps:
(1) and protecting the FTO glass conducting layer by using an adhesive tape, reserving a space with the width of 6mm, and cleaning after etching.
(2) Pasting adhesive tape with the width of 5mm on the opposite surface of the etching tape, and spin-coating TiO2And (4) compacting a layer and calcining.
(3) Pasting adhesive tape with the width of 5mm on the opposite surface of the etching tape, and spin-coating TiO2Mesoporous layer, calcining.
(4) And (3) pasting an adhesive tape with the width of 5mm on the opposite surface of the etching tape, spin-coating the perovskite precursor solution in a glove box, and annealing.
(5) Spin coating the HTM solution, i.e., spin coating any of the tetraarylbutadiene based hole transport materials described above.
(6) Plating electrodes and oxidizing.
Preferably, in the step (1), the FTO specification is 20mm × 20mm × 2.4mm, 7 Ω, and 83% of light transmittance, hydrochloric acid (4M) and zinc powder are used for etching, and the cleaning is performed by sequentially performing ultrasonic treatment with a detergent, deionized water, propanol, and methanol for 20min each.
Preferably, in the step (2), the TiO2The preparation method of the compact layer comprises the following steps: titanium tetraisopropoxide (125 μ L) was added to ethanol (845 μ L) to give solution a; hydrochloric acid (2M, 11.6. mu.L) was added to ethanol (845. mu.L), solution B; dropwise adding the solution B into the stirred solution A; the spin coating procedure is 3000r/min and 50 s; the calcining procedure is 30-500 ℃, 60min, 500 ℃ and 30 min.
Preferably, in the step (3), the TiO2The preparation method of the mesoporous layer comprises the following steps: diluting titanium dioxide slurry (18 NR-T) in ethanol (w/w ═ 1/7); the spin coating program is 5000r/min and 30 s; the calcining procedure is 30-500 ℃, 60min, 500 ℃, 30 min.
Preferably, in step (4), the perovskite precursor solution is prepared by the following method: will PbI2(1.2mmol/mL) and CH3NH3I (1.2mmol/mL) was dissolved in DMF/DMSO (v/v ═ 4/1). The spin-coating procedure is 3000r/min and 55s, and chlorobenzene (100 mu L) is dropwise added into the middle of the film after the spin-coating procedure is started for 8 s; the annealing procedure is 100 ℃ for 20 min.
Preferably, in the step (5), the HTM solution is prepared by: dissolving HTM (CJ-03, CJ-04, or spiro-OMeTAD), Li-TFSI, FK209, and t-BP in chlorobenzene; the spin coating procedure was 5000r/min, 30 s.
Preferably, in the step (6), the electrode plating method is magnetron sputtering. The electrode is gold (Au). The oxidation procedure is as follows: oxidizing in air with relative humidity less than 10% for 12.0 h.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a novel hole transport material, which is an organic micromolecule taking tetraphenylbutadiene, tetrathiophenebutadiene or tetrafuranbutadiene as a core and taking diphenylamine, triphenylamine, carbazole, phenothiazine or phenoxazine substituted by alkoxy or alkylthio as a side group. The hole transport material disclosed by the invention is simple to synthesize, low in cost and has the potential of large-scale production, has good photoelectric property and thermal stability, can be used as the hole transport material to be applied to photoelectric devices such as organic photoconductive drums, OLED displays and solar cells, and has a wide application prospect.
Drawings
FIG. 1 shows the synthesis routes of CJ-03 and CJ-04 hole transport materials of the present invention.
FIG. 2 is a drawing of Compound 1 of example 1 of the present invention1H NMR Spectrum (300MHz, CDCl)3)。
FIG. 3 is a drawing of Compound 2 of example 1 of the present invention1H NMR Spectrum (400MHz, CDCl)3)。
FIG. 4 is a drawing of Compound 2 of example 1 of the present invention13C NMR Spectroscopy (100MHz, CDCl)3)。
FIG. 5 is a drawing of Compound 3 of example 1 of the present invention1H NMR Spectrum (400MHz, CDCl)3)。
FIG. 6 is a drawing of Compound 3 of example 1 of the present invention13C NMR Spectrum (125MHz, CDCl)3)。
FIG. 7 is a drawing of Compound 3 of example 1 of the present invention31P NMR Spectrum (162MHz, CDCl)3)。
FIG. 8 is a HRMS spectrum of Compound 3 of example 1 of the present invention.
FIG. 9 is a drawing of Compound 4 of example 1 of the present invention1H NMR Spectrum (400MHz, CDCl)3)。
FIG. 10 is a photograph of Compound 4 of example 1 of the present invention13C NMR Spectroscopy (100MHz, CDCl)3)。
FIG. 11 shows a hole transporting material CJ-03 of the invention1H NMR Spectrum (400MHz, CDCl)3)。
FIG. 12 shows a hole transporting material CJ-03 of the invention13C NMR Spectroscopy (100MHz, CDCl)3)。
FIG. 13 is a HRMS spectrum of a hole transporting material CJ-03 of the present invention.
FIG. 14 shows Compound 5 of example 2 of the present invention1H NMR Spectrum (400MHz, CDCl)3)。
FIG. 15 is a drawing of Compound 6 of example 2 of the present invention1H NMR Spectrum (400MHz, CDCl)3)。
FIG. 16 shows a hole transporting material CJ-04 of the invention1H NMR Spectrum (400MHz, CDCl)3)。
FIG. 17 shows a hole transporting material CJ-04 of the invention13C NMR Spectroscopy (100MHz, CDCl)3)。
FIG. 18 shows the HRMS spectrum of a hole transporting material CJ-04 according to the present invention.
FIG. 19 shows UV-VISIBLE absorptions and fluorescence spectra (1.0X 10) of hole transport materials CJ-03, CJ-04, and spiro-OMeTAD in dichloromethane–5M)。
FIG. 20 shows UV-VIS absorption spectra and fluorescence spectra of hole transport materials CJ-03, CJ-04 and spiro-OMeTAD normalized to 1.0X 10 in methylene chloride solution–5M)。
FIG. 21 shows a fluorescence spectrum (1.0X 10) of a hole transporting material CJ-03 in methylene chloride–5M；λex＝ 450nm，λem518 nm; slit: 3.0nm, 3.0 nm).
FIG. 22 shows a fluorescence spectrum (1.0X 10) of a hole transporting material CJ-04 in methylene chloride–5M；λex＝438nm，λem540 nm; slit: 3.0nm, 3.0 nm).
FIG. 23 shows the fluorescence spectrum (1.0X 10) of the hole transport material spiro-OMeTAD in dichloromethane–5M；λex＝384nm，λem423 nm; slit: 3.0nm, 3.0 nm).
FIG. 24 shows spin coating of CJ-03, CJ-04, and spiro-OMeTAD on TiO2/MAPbI3Uv-vis absorption spectrum on the film.
FIG. 25 shows cyclic voltammograms of hole transport materials CJ-03, CJ-04, and spiro-OMeTAD in dichloromethane (1.0X 10)-4M) and the energy level diagram of each component in the PSC. (a) Cyclic voltammetry curves; (b) energy level diagram.
FIG. 26 is a thermogravimetric analysis of the hole transport materials CJ-03 and CJ-04 (scan rate of 10K/min, N)2Atmosphere).
FIG. 27 is a DSC curve of the hole transport materials CJ-03 and CJ-04 (scan rate of 10K/min, N)2Atmosphere).
FIG. 28 is MAPbI3And MAPbI3The steady state fluorescence spectrum and the time resolved fluorescence spectrum of the HTM film.
Fig. 29 is a structural view of a perovskite solar cell.
FIG. 30 is a reverse scan J-V curve for cells of CJ-03, CJ-04, and spiro-OMeTAD.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
The following examples are illustrative of the method of synthesizing the hole transport material of the present invention, and the method of the present invention is not limited to the substances in the figures.
EXAMPLE 1 Synthesis of Compound CJ-03
The synthesis route of CJ-03 is shown in FIG. 1, and the specific synthesis steps are as follows:
(1) synthesis of Compound 1
Figure BDA0002221292900000081
4, 4' -dibromobenzophenone (1700.1mg, 5.000mmol, 1.00equiv.), methyl triphenyl phosphonium bromide (3574.7mg, 10.007mmol, 2.00equiv.), potassium tert-butoxide (1129.1mg, 10.062mmol, 2.01equiv.) and tetrahydrofuran (20mL) were added to a two-necked round bottom flask, stirred and reacted at room temperature for 39.5h under argon protection. The solvent was distilled off under reduced pressure, and a white solid (1257.0mg, 74.37%) was obtained by separation by column chromatography (petroleum ether/ethyl acetate 50/1, v/v), which was compound 1.
Process for preparation of Compound 11The H NMR spectrum is shown in FIG. 2:1H NMR(300MHz,CDCl3):δ(TMS, ppm)＝7.47(d,J＝9.0Hz,4H),7.18(d,J＝9.0Hz,4H),5.46(s,2H)。
(2) synthesis of Compound 2
Figure BDA0002221292900000091
Compound 1(343.5mg, 1.016mmol, 1.00equiv.), paraformaldehyde (46.0mg, 1.532mmol, 1.51equiv.), a solution of hydrogen bromide in acetic acid (33 wt.%, 0.3mL, 1.657mmol, 1.63equiv.) and acetic acid (4mL) were added to a two-necked round bottom flask, stirred, heated to 50 ℃, and reacted for 27.5h under argon shield. Water was added to the reaction mixture, followed by extraction with dichloromethane, drying of the extract over anhydrous magnesium sulfate, filtration, and removal of the solvent from the filtrate by distillation under reduced pressure, followed by column chromatography (petroleum ether/ethyl acetate 50/1, v/v) to give a white oily liquid (448.0mg, 92.32%), which is compound 2.
Process for preparation of Compound 21The H NMR spectrum is shown in FIG. 3:1H NMR(400MHz,CDCl3):δ(TMS,ppm) ＝7.56(d,J＝8.0Hz,2H),7.42(d,J＝8.0Hz,2H),7.13(d,J＝8.0Hz,2H),7.08(d, J＝8.0Hz,2H),6.33(t,J＝8.0Hz,1H),3.99(d,J＝8.0Hz,2H)；
process for preparation of Compound 213The C NMR spectrum is shown in FIG. 4:13C NMR(100MHz,CDCl3):δ(ppm)＝ 143.88,139.52,136.40,131.82,131.47,131.06,129.16,124.65,122.55,122.39, 30.12。
(3) synthesis of Compound 3
Figure BDA0002221292900000092
Compound 2(448.0mg, 1.040mmol, 1.00equiv.) and triethyl phosphite (0.36mL, 2.099mmol, 2.02equiv.) were added to a single-neck round bottom flask, stirred, heated to 110 ℃, and reacted under argon for 32.0 h. The reaction mixture was distilled under reduced pressure until dried, and the residue was separated by column chromatography (petroleum ether/ethyl acetate ═ 1/1, v/v) to give a pale yellow oily liquid (418.6mg, 82.45%) which was compound 3.
Process for preparation of Compound 31The H NMR spectrum is shown in FIG. 5:1H NMR(400MHz,CDCl3):δ(TMS,ppm) ＝7.53(d,J＝8.0Hz,2H),7.40(d,J＝8.0Hz,2H),7.11(d,J＝8.0Hz,2H),7.07(d, J＝8.0Hz,2H),6.14–6.08(m,1H),4.13–4.05(m,4H),2.68(d,J＝8.0Hz,1H),2.63 (d,J＝8.0Hz,1H),1.31(t,J＝8.0Hz,6H)；
process for preparation of Compound 313The C NMR spectrum is shown in FIG. 6:13C NMR(125MHz,CDCl3):δ(ppm)＝ 143.44(d,J＝15.0Hz),140.33(d,J＝2.5Hz),137.29(d,J＝2.5Hz),131.69,131.55, 131.46,131.31,128.89,121.79(d,J＝16.3Hz),118.66(d,J＝11.3Hz),61.94(d,J＝ 6.3Hz),28.43(d,J＝140.0Hz),16.42(d,J＝6.3Hz)；
process for preparation of Compound 331The P NMR spectrum is shown in FIG. 7:31P NMR(162MHz,CDCl3):δ(ppm)＝ 23.17；
the HRMS spectrum of compound 3 is shown in figure 8: HRMS (ESI) M/z: [ M + H ]]+Calcd for C19H22Br2O3P:486.9668；found:486.9667。
(4) Synthesis of Compound 4
Figure BDA0002221292900000101
Compound 3(3048.6mg, 6.245mmol, 1.00equiv.), 4' -dibromobenzophenone (2336.5mg, 6.872mmol, 1.10equiv.), sodium hydride (455.6mg, 18.983mmol, 3.04equiv.) and tetrahydrofuran (16mL) were added to a single-neck round-bottom flask, stirred, and reacted at room temperature for 51.5h under argon atmosphere. The solvent was distilled off under reduced pressure, and a yellow solid (4532.1mg, 97.66%) was obtained by separation by column chromatography (petroleum ether/dichloromethane ═ 10/1, v/v), which was compound 4.
Process for preparation of Compound 41The H NMR spectrum is shown in FIG. 9:1H NMR(400MHz,CDCl3):δ(TMS,ppm) ＝7.55(d,J＝8.0Hz,4H),7.37(d,J＝8.0Hz,4H),7.14(d,J＝8.0Hz,4H),7.00(d, J＝8.0Hz,4H),6.65(s,2H)；
process for preparation of Compound 413The C NMR spectrum is shown in FIG. 10:13C NMR(100MHz,CDCl3):δ(ppm)＝ 142.72,140.60,137.95,132.17,131.68,131.47,129.21,126.04,122.16,122.03。
(5) synthesis of Compound CJ-03
Figure BDA0002221292900000111
A two-necked round bottom flask was charged with a toluene (1.4mL) solution of Compound 4(675.5mg, 1.002mmol, 1.00equiv.), 4' -dimethoxydiphenylamine (1103.0mg, 4.811mmol, 4.80equiv.), palladium acetate (34.4mg, 0.153 mmol, 0.15equiv.), sodium tert-butoxide (1930.4mg, 20.087mmol, 20.05equiv.), tri-tert-butylphosphine (140mg, 0.692mmol, 0.69equiv.), and toluene (25 mL), stirred, heated to 120 ℃ and reacted under argon protection for 48.0 h. The solvent was removed by distillation under the reduced pressure, and the residue was separated by column chromatography (petroleum ether/tetrahydrofuran 4/1, v/v) to give 1066.5mg of a yellow solid, yield 83.97%, i.e., compound CJ-03. The product was further purified by recrystallization (methanol/dichloromethane) and used to make cells.
Process for preparation of compound CJ-031The H NMR spectrum is shown in FIG. 11:1H NMR(400MHz,CDCl3):δ(TMS, ppm)＝7.10–7.04(m,24H),6.90(d,J＝8.0Hz,4H),6.83–6.78(m,20H),6.71(s, 2H),3.78(s,24H)；
process for preparation of compound CJ-0313The C NMR spectrum is shown in FIG. 12:13C NMR(100MHz,CDCl3):δ (ppm)＝155.81,155.77,147.67,147.65,140.90,140.77,135.06,132.17,131.40, 128.25,126.63,126.59,124.36,119.69,119.64,114.62,55.44；
the HRMS spectrum of compound CJ-03 is shown in FIG. 13: HRMS (ESI) M/z [ M ]]+Calcd for C84H74N4O8:1266.5501；found:1266.5502。
EXAMPLE 2 Synthesis of Compound CJ-04
The synthetic route of CJ-04 is shown in FIG. 1, and the specific synthetic steps are as follows: wherein the steps (1) to (4) are the same as in example 1;
(5) synthesis of Compound 5
Figure BDA0002221292900000121
To a two-necked round bottom flask were added 4-iodoanisole (2458.4mg, 10.505mmol, 2.06equiv.), 1, 10-phenanthroline monohydrate (199.4mg, 1.006mmol, 0.20equiv.), cuprous iodide (191.8mg, 1.007mmol, 0.20equiv.), potassium tert-butoxide (3370.6mg, 30.038mmol, 5.89equiv.), aniline (474.9mg, 5.099mmol, 1.00equiv.), and toluene (40mL), stirred, heated to 130 ℃ and refluxed for 39.0h under argon shield. The solvent was distilled off under reduced pressure, and a yellow solid (946.4mg, 60.78%) was isolated by column chromatography (petroleum ether/ethyl acetate 50/1, v/v), which was compound 5.
Process for preparation of Compound 51The H NMR spectrum is shown in FIG. 14:1H NMR(400MHz,CDCl3):δ(TMS,ppm) ＝7.16(t,J＝8.0Hz,2H),7.04(d,J＝8.0Hz,4H),6.93(d,J＝8.0Hz,2H),6.85(t,J ＝8.0Hz,1H),6.81(d,J＝8.0Hz,4H),3.78(s,6H)。
(6) synthesis of Compound 6
Figure BDA0002221292900000122
Compound 5(226.7mg, 0.742mmol, 1.00equiv.) and N, N-dimethylformamide (2mL) were added to a single-neck round-bottom flask, stirred, and a solution of N-bromosuccinimide (147.3mg, 0.828mmol, 1.12equiv.) in N, N-dimethylformamide (8mL) was added at 0 ℃ and reacted under protection of argon from light (0 ℃ C.: 1.0 h; 0 ℃ C. to room temperature: 38.5 h). Water was added to the reaction mixture, extracted with ethyl acetate, the extract was dried over anhydrous magnesium sulfate, filtered, the solvent of the filtrate was distilled off under reduced pressure, and a yellow solid (285.1mg, 99.99%) was obtained by column chromatography (petroleum ether/dichloromethane ═ 4/1, v/v).
Process for preparation of Compound 61The H NMR spectrum is shown in FIG. 15:1H NMR(400MHz,CDCl3):δ(TMS,ppm) ＝7.23(d,J＝8.0Hz,2H),7.03(d,J＝8.0Hz,4H),6.82(d,J＝8.0Hz,4H),6.79(d, J＝8.0Hz,2H),3.79(s,6H)。
(7) synthesis of Compound 7
Figure BDA0002221292900000131
Adding compound 6(1374.2mg, 3.576mmol, 1.00equiv.) and tetrahydrofuran (12mL) into a single-neck round-bottom flask under the protection of argon, stirring, cooling to-78 ℃, adding n-butyllithium n-hexane solution (2.5M, 3.0mL, 2.10equiv.), reacting for 1.5h, adding triisopropyl borate (2.5mL, 10.834mmol, 3.03equiv.), reacting for 2.5h, stopping cooling, naturally heating for 1.0h, transferring to room temperature, and reacting for 18.0 h. To the reaction mixture was added dilute hydrochloric acid to make it acidic, followed by extraction with dichloromethane, drying of the organic layer over anhydrous magnesium sulfate, filtration, and removal of the solvent from the filtrate by distillation under the reduced pressure to give a green oily liquid (1525.0mg), Compound 7, which was used directly in the next reaction.
(8) Synthesis of Compound CJ-04
Figure BDA0002221292900000132
To a single neck round bottom flask was added compound 4(168.9mg, 0.251mmol, 1.00equiv.), compound 7(658.4mg, 1.886mmol, 7.51equiv.), tetrakis (triphenylphosphine) palladium (60.1mg, 0.052 mmol, 0.21equiv.), aqueous potassium carbonate (2M, 1.3mL, 10.36equiv.), and tetrahydrofuran (20mL), stirred, heated to 85 ℃ and refluxed under argon for 52.5 h. The solvent was distilled off under reduced pressure, and a yellow solid (182.1mg, 46.15%) was isolated by column chromatography (petroleum ether/dichloromethane ═ 1/1, v/v), which was compound CJ-04. The product was further purified by recrystallization (acetonitrile/dichloromethane) and used to prepare batteries.
Of compound CJ-041The H NMR spectrum is shown in FIG. 16:1H NMR(400MHz,CDCl3):δ(TMS, ppm)＝7.61(d,J＝8.0Hz,4H),7.50(d,J＝8.0Hz,4H),7.43–7.36(m,12H), 7.26–7.24(m,4H),7.11–7.06(m,16H),7.02(d,J＝8.0Hz,4H),6.95(d,J＝8.0Hz, 4H),6.90(s,2H),6.86–6.82(m,16H),3.80(s,12H),3.79(s,12H)；
of compound CJ-0413The C NMR spectrum is shown in FIG. 17:13C NMR(100MHz,CDCl3):δ (ppm)＝155.86,148.19,148.09,143.24,140.88,140.81,140.69,139.72,139.67, 138.05,132.47,132.35,131.24,128.17,127.37,127.24,126.59,126.54,126.05, 120.83,120.59,114.69,55.45；
the HRMS spectrum of compound CJ-04 is shown in FIG. 18: HRMS (ESI) M/z [ M ]]+Calcd for C108H90N4O8:1570.6753；found:1570.6761。
Performance testing
The hole transport materials CJ-03 and CJ-04 synthesized in examples 1 and 2 were subjected to photo-physical properties (UV, fluorescence) and electrochemical performance tests as follows:
(1) ultraviolet-visible absorption spectrum and fluorescence spectrum test: testing with an ultraviolet-visible-near infrared spectrophotometer (SHIMADZU UV-3600) and a fluorescence spectrometer (SHIMADZU RF5301 PC); the hole transport materials CJ-03, CJ-04, and spiro-OMeTAD were formulated to be 1.0X 10, respectively–5M in methylene chloride, and measuring the ultraviolet-visible absorption spectrum and the fluorescence excitation-emission spectrum of the samples. UV-VISIBLE ABSORPTION SPECTRUM AND FLUORESCENCE SPECTRUM (1.0X 10) OF CJ-03, CJ-04, and spiro-OMeTAD in dichloromethane–5M) As shown in FIG. 19, all three HTMs have two absorption bands in the region of 260 to 500nm, and CJ-03 also has a weak absorption peak in the region of 340 to 390 nm. The absorption band of 260 to 330nm originates from the electronic transition of triphenylamine, and the absorption band of 330 to 500nm originates from the pi-pi transition of the whole molecule.
Ultraviolet-visible absorption and fluorescence spectra normalized for CJ-03, CJ-04, and spiro-OMeTAD (dichloromethane solution, 1.0X 10–5M) intersection wavelengths (λ) of CJ-03, CJ-04, and spiro-OMeTAD as shown in FIG. 20intersection) 476, 470 and 406nm, respectively, according to the band gap Egap＝1240/λintersectionTo obtain E of the threegap2.61, 2.64 and 3.05eV, respectively.
Fluorescent light of CJ-03 in dichloromethaneSpectrum (1.0X 10)–5M；λex＝450nm，λem518 nm; slit: 3.0nm, 3.0nm) as shown in fig. 21; fluorescence spectrum (1.0X 10) of CJ-04 in dichloromethane–5 M；λex＝438nm，λem540 nm; slit: 3.0nm, 3.0nm) as shown in fig. 22; fluorescence spectrum of spiro-OMeTAD in dichloromethane (1.0X 10)–5M；λex＝384nm，λem423 nm; slit: 3.0nm, 3.0nm) is shown in fig. 23. Maximum emission wavelength (λ)em) The increase from 518nm (CJ-03) to 540nm (CJ-04) is attributed to the increased conjugation system. CJ-03 and CJ-04 both have large Stokes shifts of 68 and 102nm, respectively, indicating that the molecules undergo significant structural deformation when excited. Due to the rigid spiro unit, the Stokes shift of spiro-OMeTAD is only 39 nm. These results indicate that the propeller-shaped tetraphenylbutadiene core favors increased Stokes shifts compared to the rigid spiro core, while larger Stokes shifts favor pore filling of the HTM, enhancing the hole extraction efficiency of the PSC.
CJ-03, CJ-04, and spiro-OMeTAD were spin-coated on TiO2/MAPbI3The UV-vis absorption spectrum on the film was obtained using a SHIMADZU UV-3600 UV-vis-nir spectrophotometer, and the results are shown in fig. 24. The absorption ranges from visible light up to the near infrared region. Initial absorption wavelength (. lamda.)onset780nm) corresponds to MAPbI3The band gap of (a). The three HTMs have an enhanced absorption band between 360 and 500nm due to the superimposed characteristic absorption of the respective components. The lower absorbance of CJ-03 and CJ-04 compared to spiro-OMeTAD is an advantageous property for ideal HTM, which reduces the absorption loss of incident photons.
(2) Electrochemical properties:
cyclic voltammetric testing of compounds electrochemical workstations (Zahner Zennium) and three-electrode systems were used: the working electrode is a platinum wire electrode; the counter electrode is a platinum sheet electrode; the reference electrode is Ag/Ag+Electrode (0.01M silver nitrate acetonitrile solution). The concentration of the solution is 1.0X 10–4M, 0.1M tetrabutylammonium hexafluorophosphate as supporting electrolyte. Circulation of CJ-03, CJ-04 and spiro-OMeTAD in dichloromethaneVoltammogram (1.0X 10)–4M) is shown in fig. 25 (a). CJ-03 and CJ-04 both have two pairs of redox peaks, and the cyclic voltammograms of both are highly reversible, indicating their excellent electrochemical stability. E of HTM1/2Calculated from the first redox potential: e1/2＝(Eox+Ered)/2. E of HTM and spiro-OMeTAD1/2The difference of (d) is calculated from the following equation: delta E1/2＝E1/2(HTM)–E1/2(spiro-OMeTAD). The HOMO energy level of the HTM is calculated from the following equation: eHOMO(HTM)＝EHOMO(spiro-OMeTAD)–ΔE1/2. Calculated according to the HOMO level (-5.22 eV) of spiro-OMeTAD reported in the literature, the HOMO levels of CJ-03 and CJ-04 are-5.18 eV and-5.44 eV, respectively. HOMO energy level ratio MAPbI of CJ-033Is high (-5.43 eV), the hole transfer can be promoted. The higher HOMO level of CJ-03 than spiro-OMeTAD indicates a lower open circuit voltage in PSC. In contrast, the HOMO level ratio MAPbI of CJ-043Is energetically unfavorable for hole extraction and therefore unfavorable for photovoltaic performance, as shown in the subsequent photovoltaic performance section. In view of the aforementioned EgapUsing the equation: eLUMO＝EHOMO+EgapThe LUMO energy levels of CJ-03, CJ-04, and spiro-OMeTAD were found to be-2.57, -2.80, and-2.17 eV, respectively. MAPbi3And the energy barrier between the HTM at the LUMO level is expected to prevent electron backflow and reduce electron-hole recombination. The energy levels of the components in the PSC are shown in fig. 25 (b).
(3) Thermal analysis
The test condition of the thermogravimetric analysis (NETZSCH STA 449F 3 Jupiter) is N2And (3) the atmosphere, wherein the temperature rise interval is 35-900 ℃, and the temperature rise rate is 10.0K/min. The results of thermogravimetric analysis of CJ-03 and CJ-04 are shown in FIG. 26. Decomposition temperature (T)d) Temperature at 5% weight loss, T of CJ-03 and CJ-04d417.5 and 423.3 c, respectively, indicating good thermal stability of the two materials.
Differential Scanning Calorimetry (DSC) (NETZSCH DSC 204F1 Phoenix) test at N2The heating and cooling are carried out in the atmosphere, and the heating and cooling rates are both 10.0K/min. DSC curves of CJ-03 and CJ-04As shown in fig. 27. For CJ-03, the first heating showed a melting point of 299.3 ℃ and a crystallization peak (T) appeared at the time of coolingc255.4 deg.C), the second heating showed a melting point of 299.1 deg.C. For CJ-04, the first heating showed a melting point of 171.8 ℃, no crystallization peak at the time of temperature reduction, and the second heating showed a glass transition temperature (T)g) The temperature was 154.1 ℃.
In conclusion, the electrochemical, photo-physical and thermal properties of the hole transport materials CJ-03 and CJ-04 are shown in Table 1, which indicates that CJ-03 and CJ-04 have excellent photo-physical, electrochemical and thermal stability properties.
TABLE 1 electrochemical, photophysical, and thermal properties of HTM
Figure BDA0002221292900000161
MAPbI3And MAPbI3Steady-state and time-resolved fluorescence spectra of the/HTM films were obtained using an Edinburgh FLS980 fluorescence spectrometer, with results as shown in FIG. 28, and double-exponential fit parameters for the time-resolved fluorescence spectra as shown in Table 2. With pure MAPbI3In contrast to the membrane, MAPbI was observed3Enhanced fluorescence quenching of the HTM film indicates that the HTM efficiently extracts the photogenerated holes of the perovskite in the excited state. The quenching ability of the three HTMs is in the order CJ-03>spiro-OMeTAD>CJ-04. The strongest quenching ability of CJ-03 can be attributed to its HOMO level and MAPbI3Maximum energy level difference (driving force) at the valence band top of (a); the weakest quenching ability of CJ-04 can be attributed to its HOMO level and MAPbI3Is mismatched at the top of the valence band. In addition, a double exponential fit to the fluorescence decay curve yields the fluorescence lifetime (τ). Pure MAPbI3The τ of the film was longest and was 122.91 ns. After introduction of HTM, τ was reduced to 10.12ns (CJ-03), 16.45ns (spiro-OMeTAD) and 49.71ns (CJ-04), consistent with quenching effects in the steady-state fluorescence spectrum.
TABLE 2 double exponential fitting parameters for time resolved fluorescence spectroscopy
Figure BDA0002221292900000171
Example 3 preparation of perovskite solar cell
TiO2The preparation method of the compact layer comprises the following steps: titanium tetraisopropoxide (125 μ L) was added to ethanol (845 μ L) to give a solution a. Hydrochloric acid (2M, 11.6. mu.L) was added to ethanol (845. mu.L), solution B. Dropwise adding the solution B into the stirred TiO in the solution A2The preparation method of the mesoporous layer comprises the following steps: the titanium dioxide slurry (18 NR-T) was diluted in ethanol (w/w ═ 1/7).
The preparation method of the perovskite precursor solution comprises the following steps: will PbI2(1.2mmol/mL) and CH3NH3I (1.2mmol/mL) was dissolved in DMF/DMSO (v/v ═ 4/1).
The preparation method of the HTM solution comprises the following steps: HTM [ CJ-03(60.0mg), CJ-04(60.0mg) or spiro-OMeTAD (72.3mg) ], Li-TFSI (9.1mg), FK209 (15% molar ratio with respect to HTM) and t-BP (28.8. mu.L) were dissolved in chlorobenzene (1 mL).
A perovskite solar cell containing a hole transport material CJ-03 or CJ-04 consists of a conductive substrate, an electron transport layer, a light absorption layer, a hole transport layer and an electrode, the structure of the perovskite solar cell is shown in figure 27, and the preparation method comprises the following steps:
(1) and protecting the FTO glass conductive layer by using an adhesive tape, keeping a space of 6mm, covering zinc powder, and dropwise adding hydrochloric acid (4M) for etching. Ultrasonic washing with detergent, deionized water, acetone and ethanol sequentially (each for 20 min).
(2) Pasting adhesive tape with the width of 5mm on the opposite surface of the etching tape, and spin-coating TiO2And (3) tearing off the adhesive tape and then calcining the compact layer (3000r/min, 50 s) (30-500 ℃, 60 min; 500 ℃, 30 min.).
(3) After cooling, an adhesive tape with a width of 5mm is pasted on the opposite surface of the etching tape, and TiO is spin-coated2The mesoporous layer (5000r/min, 30s) is calcined after the adhesive tape is torn off (30-500 ℃, 60 min; 500 ℃, 30 min.).
(4) After cooling, a 5mm wide tape was attached to the opposite side of the etched tape, transferred to a glove box, and the perovskite precursor solution (3000r/min, 55s) was spin coated, and chlorobenzene (100 μ L) was added dropwise to the middle of the film after 8s from the start of the spin coating procedure. Annealing (100 deg.C, 20min) in a heating table.
(5) After cooling, the HTM solution was spin coated (5000r/min, 30 s).
(6) Tearing off the adhesive tape, and utilizing magnetron sputtering to plate gold electrodes; and oxidizing the device (air with the relative humidity less than 10% and oxidizing for 12.0h) to obtain the perovskite solar cell, wherein the structure is shown in figure 29.
Performance testing
The perovskite solar cell prepared in example 3 was tested and the current density-voltage curve (J-V currents) of the device was determined by AM 1.5G (100mW cm) provided by a source meter (Keithley 2400) in a solar simulator (ABET Sun 3000)–2) Obtained under illumination, and the area of the battery is 0.09cm2The light intensity before the test is corrected by a standard silicon battery, the scanning speed is 0.2V/s, and the scanning direction is reverse scanning.
The reverse scan J-V curves for cells CJ-03, CJ-04, and spiro-OMeTAD are shown in FIG. 30, with photovoltaic parameters as shown in Table 3, with cells based on spiro-OMeTAD having the highest efficiency (16.53%), followed by cells based on CJ-03 (14.67%) and CJ-04 (8.93%).
TABLE 3 photovoltaic parameters based on CJ-03, CJ-04, and spiro-OMeTAD cells
Figure BDA0002221292900000181
In conclusion, after the hole transport material prepared by the invention is applied to the perovskite solar cell, the photoelectric conversion efficiency of the CJ-03-based cell is high (14.67%), the CJ-03-based cell is close to that of the spiro-OMeTAD-based cell (16.53%), and the CJ-03-based cell has a good application prospect.

Claims (9)

1. A tetraarylbutadiene-based hole transport material having a general chemical formula of formula (I):
Figure FDA0002793358370000011
ar is
Figure FDA0002793358370000012
R is
Figure FDA0002793358370000013
n＝1～6。
2. The tetraarylbutadiene-based hole transport material of claim 1, wherein the hole transport material has the following structural formula CJ-03 or CJ-04:
Figure FDA0002793358370000014
3. a method for producing the hole transport material according to claim 2, comprising the steps of:
s1, under the protection of inert gas, 4' -dibromobenzophenone and methyl triphenyl phosphonium bromide react under the condition of strong alkali to obtain an olefination compound 1;
s2, reacting the compound 1 with paraformaldehyde and hydrogen bromide under the protection of inert gas to obtain a bromomethylated compound 2;
s3, reacting the compound 2 with triethyl phosphite under the protection of inert gas to obtain a Wittig reagent compound 3;
s4, reacting the compound 3 with 4, 4' -dibromo benzophenone under the protection of inert gas under a strong alkali condition to obtain a compound 4;
s5, under the protection of inert gas, reacting the compound 4 with 4, 4' -dimethoxydiphenylamine under the action of strong base and a catalyst to obtain a hole transport material CJ-03; or reacting the compound 4 with 4,4 '-dimethoxy-4' -triphenylamine borate under the action of a weak base and a catalyst to obtain the hole transport material CJ-04.
4. The preparation method according to claim 3, wherein in step S1, the molar ratio of 4, 4' -dibromobenzophenone to methyl triphenyl phosphonium bromide is 1: 2-3, and the reaction is carried out at 20-25 ℃ for 38-40 h.
5. The preparation method according to claim 3, wherein in step S2, the molar ratio of the compound 1 to the paraformaldehyde to the hydrogen bromide is 1: 1.5-2, and the reaction is carried out at 45-55 ℃ for 25-30 h.
6. The preparation method according to claim 3, wherein in step S3, the molar ratio of the compound 2 to the triethyl phosphite is 1: 2-3, and the reaction is carried out at 105-115 ℃ for 30-35 h; in the step S4, the molar ratio of the compound 3 to the 4, 4' -dibromobenzophenone is 1: 1-1.5, and the reaction is carried out for 50-55 h at 20-25 ℃.
7. The preparation method according to claim 3, wherein in step S5, the molar ratio of compound 4 to 4, 4' -dimethoxydiphenylamine is 1: 4-5, and the reaction is carried out at 115-125 ℃ for 45-50 h; the molar ratio of the compound 4 to 4,4 '-dimethoxy-4' -triphenylamine borate is 1: 7-8, and the reaction is carried out for 50-55 h at the temperature of 80-90 ℃.
8. Use of the hole transport material according to any of claims 1-2 for the preparation of perovskite solar cells, OLEDs or organic photoconductor drums.
9. A perovskite solar cell comprising a glass substrate, a conductive layer, an electron transport layer, a light absorbing layer, a hole transport layer and an electrode layer, wherein the hole transport layer is composed of the tetraarylbutadiene-based hole transport material according to any one of claims 1 to 2.
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