CN110845503A - Preparation and application of arylamine substituted benzodiindole organic hole transport material - Google Patents
Preparation and application of arylamine substituted benzodiindole organic hole transport material Download PDFInfo
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Abstract
The invention discloses a preparation method and application of an arylamine substituted benzodiindole organic hole transport material, and belongs to the field of perovskite solar cell application. The hole transport material disclosed by the invention is simple in synthetic route, cheap and easily available in raw materials, easy to purify, high in solubility and good in stability, and can be used as the hole transport material to be applied to trans-planar perovskite solar cells. The trans-form planar perovskite solar cell prepared by using the arylamine substituted benzodiindole organic hole transport material designed by the invention has higher photoelectric conversion efficiency and good stability. The arylamine substituted benzodiindole organic hole transport material provided by the invention provides a new choice for a hole transport material based on a trans-planar perovskite solar cell.
Description
Technical Field
The invention belongs to the technical field of organic functional materials, and particularly relates to an arylamine substituted benzodiindole organic hole transport material, a preparation method thereof, and application thereof in a trans-planar perovskite solar cell.
Background
Since the first reports of perovskite solar cells by japanese scientists Miyasaka et al in 2009 (j.am. chem. soc.2009, 131, 6050-. At present, the record of the photoelectric conversion efficiency of the perovskite solar cell exceeds 25.0% (www.nrel.gov/pv/cell-efficiency. html), and the technical innovation of the photovoltaic industry brings new hopes and has wide application prospects. The Hole Transport Material (HTM) is an important component of the high-efficiency perovskite solar cell, and the development, design and preparation of the hole transport layer material with simplicity and excellent performance have very important significance for the development of the perovskite solar cell.
Polythiophene organic hole transport materials, such as PEEOT: PSS (polyethylenedioxythiophene: poly (p-styrenesulfonic acid)) is commonly used for preparing trans-planar perovskite solar cells and can obtain higher photoelectric conversion efficiency. However, PEEOT: PSS is easy to absorb moisture, and has acidity to corrode the transparent conductive electrode, so that the stability of the perovskite solar cell is reduced. The arylamine compound is often used as an electron donor to be applied to the design of organic photoelectric materials, and the arylamine hole transport material is widely applied to perovskite solar cells and obtains high photoelectric conversion efficiency. A series of advances are made in the application of the arylamine hole transport material in the trans-planar perovskite solar cell. However, the conventional arylamine hole material based on the trans-planar perovskite solar cell has certain absorption in a visible light region, so that the effective light absorption of the perovskite material is reduced, and the improvement of the photoelectric conversion efficiency of a device is not facilitated. In addition, the development of the high-efficiency hole transport material with simple preparation and low cost has very important significance for the industrialization of the perovskite solar cell.
Disclosure of Invention
The invention constructs a novel organic hole transport material by using benzodiindole as a core and arylamine group substitution through molecular design, and is applied to a trans-planar perovskite solar cell. The hole transport material is white powder, is not absorbed in a visible light region, has a molecular energy level matched with a perovskite material, is good in solubility, high in stability, easy to synthesize and has potential application value. The invention avoids the invalid light absorption of the hole transport material in the trans-planar perovskite solar cell, thereby improving the photoelectric property of the perovskite solar cell, improving the stability of the cell and reducing the manufacturing cost of the cell.
The invention also aims to provide a preparation method of the arylamine substituted benzodiindole compound, which has the advantages of simple preparation operation process, mild reaction condition, higher yield, simple purification process and high application value.
The invention provides an arylamine substituted benzodiindole organic hole transport material, which has a structural general formula (II):
formula (II), R1Is C1～C6Any one of an alkane chain; r2Is an electron donating group such as triphenylamine, dimethoxy triphenylamine, phenyl carbazole and the like, and is specifically one of the following structures:
the synthesis method of the arylamine substituted benzodiindole organic hole transport material comprises the following steps: carrying out condensation reaction on N-alkyl indole and 4, 4' -dibromobenzil to obtain a benzodiazole intermediate 1; the intermediate 1 and arylamine boric acid ester are subjected to Suzuki coupling reaction, and arylamine substituted benzodiindole organic hole transport materials LGY-1, LGY-2, LGY-3 and LGY-4 are finally obtained.
(1) According to the reference method (org. biomol. chem., 2008, 6, 1738-1742), N-alkyl indole, 4' -dibromobenzil, p-toluenesulfonic acid and anhydrous toluene are added into a dry double-mouth bottle, the mixture is uniformly stirred at room temperature under the protection of nitrogen, then heated and reacted overnight, and the mixture is cooled to room temperature after the reaction is finished. And (3) after the solvent toluene is dried by spinning, adding water into the residue, extracting with dichloromethane, washing with saturated saline solution, collecting an organic phase, adding anhydrous sodium sulfate, drying, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and drying in vacuum to obtain the benzodiindole intermediate 1.
(2) Dissolving the intermediate 1 in 1, 4-dioxane, adding arylamine borate, potassium carbonate water solution and tetrakis (triphenylphosphine) palladium, uniformly stirring at room temperature under the protection of nitrogen, heating, and reacting overnight. After the reaction is finished, cooling to room temperature. And (2) after solvent toluene is dried in a spinning mode, adding water into the residue, extracting with dichloromethane, washing with saturated saline solution, collecting an organic phase, adding anhydrous sodium sulfate, drying, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and drying in vacuum to obtain the arylamine substituted benzodiindole organic hole transport materials LGY-1, LGY-2, LGY-3 and LGY-4.
The synthetic process comprises the following steps:
R1is C1～C6Any one of an alkane chain; r2Is an electron donating group such as triphenylamine, dimethoxy triphenylamine, phenyl carbazole and the like, and is specifically one of the following structures:
in the step (1), the molar ratio of 4, 4' -dibromobenzil, N-alkyl indole and p-methylbenzenesulfonic acid is 1: 2.5: 0.2, the reaction temperature is 110 ℃, and the reaction time is 10-24 h.
In the step (2), the molar ratio of the intermediate 1 to the arylamine borate is 1: 2-4, the reaction temperature is 70-110 ℃, and the reaction time is 10-24 hours.
The arylamine substituted benzodiindole organic hole transport material prepared by the invention is used as a hole transport layer to be applied to a perovskite solar cell, the perovskite solar cell is composed of a transparent conductive substrate, a hole transport layer, a perovskite absorption layer, an electron transport layer, an electron buffer layer and a metal electrode, and the method specifically comprises the following steps:
(1) cutting a transparent conductive substrate into a fixed size, carrying out etching treatment, respectively carrying out ultrasonic cleaning on the etched conductive substrate in different solvents, and then carrying out ultraviolet ozone treatment on the substrate;
(2) preparing a hole transport layer from the aromatic amine substituted benzodiindole organic hole transport material on the treated transparent conductive substrate by a spin coating method;
(3) moving the conductive substrate coated with the hole transport layer into a glove box, and spin-coating the perovskite precursor liquid on the hole transport layer by a spin-coating method to form a perovskite absorption layer;
(4) spin-coating a solution of an electron transport material on the perovskite absorption layer by a spin coating method to form an electron transport layer;
(5) depositing an electron buffer material on the electron transport layer by a vacuum evaporation method;
(6) and depositing a metal electrode on the hole transport layer by a vacuum evaporation method.
The transparent conductive substrate is one of FTO conductive glass, ITO conductive glass or a flexible substrate;
the hole transport material solution is prepared by dissolving 20mg of hole transport material in 1mL of chlorobenzene; the perovskite precursor liquid is prepared by the following steps: will CH3NH3I and PbI2Mixing and dissolving in dimethyl sulfoxide according to the molar ratio of 1: 1, and stirring for 1-3 hours at 50 ℃ to obtain CH3NH3PbI3The dimethylsulfoxide solution of (1);
the electron transport material solution is prepared by dissolving 20mg of electron transport material PCBM ([6, 6] -phenyl-C61-butyl acid methyl ester) in 1mL of chlorobenzene;
the electron buffer material is lithium fluoride.
The metal electrode is one of gold and silver.
The invention has the following advantages:
the organic hole transport material designed by the invention adopts benzodiindole groups as synthetic building blocks, the synthetic route is simple, and the raw materials are cheap and easy to obtain. The organic hole transport material is easy to purify, good in solution solubility, high in photo-thermal stability and excellent in performance; the arylamine substituted benzodiindole organic hole transport material designed and developed by the invention is colorless powder, and almost does not absorb in a visible light region; the trans-form planar perovskite solar cell prepared by adopting the arylamine substituted benzodiindole organic hole transport material designed and developed by the invention has higher photoelectric conversion efficiency and device stability; the arylamine substituted benzodiindole organic hole transport material designed by the invention provides a new hole transport material selection for preparing a high-efficiency stable trans-planar perovskite solar cell.
Drawings
FIG. 1 shows the molecular structures of hole-transporting materials LGY-1, LGY-2, LGY-3, LGY-4 synthesized in examples 1 and 2 of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of a hole-transporting material LGY-1 synthesized in example 1 of the present invention;
FIG. 3 is a nuclear magnetic resonance carbon spectrum of a hole-transporting material LGY-1 synthesized in example 1 of the present invention;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of a hole-transporting material LGY-2 synthesized in example 1 of the present invention;
FIG. 5 is a nuclear magnetic resonance carbon spectrum of a hole-transporting material LGY-2 synthesized in example 1 of the present invention;
FIG. 6 is a nuclear magnetic resonance hydrogen spectrum of a hole-transporting material LGY-3 synthesized in example 1 of the present invention;
FIG. 7 is a nuclear magnetic resonance carbon spectrum of a hole-transporting material LGY-3 synthesized in example 1 of the present invention;
FIG. 8 is a nuclear magnetic resonance hydrogen spectrum of a hole-transporting material LGY-4 synthesized in example 2 of the present invention;
FIG. 9 is a nuclear magnetic resonance carbon spectrum of a hole-transporting material LGY-4 synthesized in example 2 of the present invention;
FIG. 10 is a graph showing UV-VIS absorption spectra of hole transporting materials LGY-1, LGY-2, LGY-3, LGY-4 synthesized in examples 1 and 2 of the present invention. As can be seen, the hole-transporting materials LGY-1, LGY-2, LGY-3, LGY-4 have strong absorption in the ultraviolet region and almost no absorption in the visible region;
FIG. 11 is a thermogravimetric analysis Test (TGA) curve of the hole transporting materials LGY-1, LGY-2, LGY-3, LGY-4 synthesized in examples 1, 2 of the present invention. As can be seen from the figure, the hole-transporting materials LGY-1-4 have decomposition temperatures of 400 ℃, which shows that the materials have high thermal stability, and LGY-1 and LGY-2 have higher thermal stability than LGY-3 and LGY-4;
FIG. 12 is a J-V plot of perovskite solar cells of hole transport materials LGY-1, LGY-2, LGY-3, LGY-4 synthesized in examples 1, 2 of the present invention, with voltage on the abscissa and current density on the ordinate. The LGY-1 based perovskite solar cell achieved a photoelectric conversion efficiency (current density (J) of 17.59%SC) Is 21.90mA/cm2Voltage (V)OC) 1.043V, 0.77 Fill Factor (FF); LGY-2 based perovskite solar cells achieved a 15.56% photoelectric conversion efficiency (J)SCIs 20.98mA/cm2，VOC1.036V, FF 0.77); the LGY-3 based perovskite solar cell achieves a photoelectric conversion efficiency (J) of 18.40%SCIs 21.95mA/cm2，VOC1.061V, FF 0.79); the LGY-4 based perovskite solar cell achieves a photoelectric conversion efficiency (J) of 14.47 percentSCIs 20.84mA/cm2，VOC0.992V, FF 0.70);
FIG. 13 is a graph showing stability tests of perovskite solar cells of hole transport materials LGY-1, LGY-2, LGY-3 and LGY-4 synthesized in examples 1 and 2 of the present invention. The results show that the trans-planar perovskite solar cells based on the hole transport materials LGY-1, LGY-2, LGY-3 and LGY-4 have better stability.
Detailed Description
Example 1:
the synthesis of hole transport materials LGY-1, LGY-2, LGY-3, LGY-4 and their application in perovskite solar cells:
R1is C1～C6Any one of an alkane chain; r2Is an electron donating group such as triphenylamine, dimethoxy triphenylamine, phenyl carbazole and the like, and is specifically one of the following structures:
(1) r in intermediate 11In the case of methyl, 1a is used as the starting material, and the synthesis method is reported in the literature, reference 1a (org. biomol. chem., 2008, 6, 1738-1742) was prepared by adding 50mL of anhydrous toluene, 50mL of N-methylindole, 1.11g (8.16mmol), 4, 4' -dibromobenzil, 1g (2.72mmol), and 104mg (0.55mmol) of p-toluenesulfonic acid to a 50mL two-neck round-bottom flask equipped with a condenser tube under nitrogen protection. Heating to 100 ℃, and reacting for 12 h. The mixture was cooled to room temperature, and after toluene was removed as a solvent, water was added to the residue, followed by extraction with dichloromethane, washing with saturated brine, collection of the organic phase, drying with anhydrous sodium sulfate, removal of the organic solvent under reduced pressure, separation and purification of the resulting solid, and vacuum drying, whereby intermediate 1a, 968mg (yield: 60.1%) was obtained.1H NMR(CDCl3，600MHz)：δ8.62(d，J＝7.8Hz，1H)，7.50(t，J＝6.6Hz，2H)，7.46(d，J＝8.4Hz，2H)，7.43(d，J＝8.4Hz，1H)，7.32-7.39(m，4H)，7.10(dd，J1＝8.4Hz，J2＝16.2Hz，4H)，6.96(t，J＝7.2Hz，1H)，6.57(d，J＝7.8Hz，1H)，4.51(s，3H)，3.30(s，3H).13C NMR(CDCl3，600MHz)：δ142.45，141.93，139.15，138.96，137.73，137.25，134.20，133.86，132.15，131.47，130.75，124.77，124.24，124.23，122.82，121.23，121.21，121.03，120.82，119.70，119.56，116.84，114.94，109.169，107.657，35.57，33.34.HR-MS：(ESI)m/z：C32H22Br2N2Calculated value 592.0150; found 592.0128.
(2) Intermediate 1a, 500mg (0.84mmol) was dissolved in 1, 4-dioxane, triphenylamine borate, 783mg (2.11mmol), aqueous potassium carbonate (2mol/L), tetrakis (triphenylphosphine) palladium, 98mg (0.085mmol) were added, stirred uniformly under nitrogen at room temperature, then heated, and reacted overnight. After the reaction is finished, cooling to room temperature. Spin-drying toluene as solvent, adding water into the residue, extracting with dichloromethane, washing with saturated saline solution, collecting organic phase, adding anhydrous sodium sulfate, drying, removing organic solvent under reduced pressure, separating and purifying the obtained solid, and vacuum drying to obtain the final product with benzoindole as core structure440mg of the organic hole-transporting material LGY-1 (yield: 56.7%).1H NMR(CDCl3，600MHz)：δ8.64(d，J＝7.8Hz，1H)，7.57(q，J＝9.0Hz，4H)，7.51(t，J＝9.0Hz，3H)，7.48(t，J＝6.6Hz，3H)，7.43(d，J＝7.8Hz，1H)，7.33-7.36(m，3H)，7.30-7.32(m，3H)，7.25-7.28(m，8H)，7.11-7.16(m，12H)，7.03(t，J＝7.8Hz，4H)，6.91(t，J＝7.2Hz，1H)，6.68(d，J＝7.8Hz，1H)，4.54(s，3H)，3.35(s，3H).13CNMR(CDCl3，600MHz)：δ147.84，147.80，147.31，147.24，142.51，141.99，139.57，138.91，138.41，138.40，137.52，137.18，135.60，134.90，134.58，132.78，130.92，129.39，127.67，127.60，126.02，125.30，124.66，124.49，124.41，124.38，124.28，123.97，123.01，122.95，122.76，121.36，121.01，119.53，119.33，118.14，115.28，109.35，109.01，107.42，35.61，33.22.HR-MS：(ESI)m/z：C68H50N4Calculated value 922.4035; found 922.4021.
(3) Intermediate 1a, 100mg (0.168mmol) was dissolved in 1, 4-dioxane, phenylcarbazole borate, 187mg (0.505mmol), aqueous potassium carbonate (2mol/L), tetrakis (triphenylphosphine) palladium, 25mg (0.022mmol) were added, stirred uniformly under nitrogen at room temperature, then heated, and reacted overnight. After the reaction is finished, cooling to room temperature. After toluene as a solvent was dried by spinning, water was added to the residue, followed by extraction with dichloromethane, washing with saturated brine, collecting the organic phase, drying with anhydrous sodium sulfate, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and drying under vacuum to obtain 110mg (yield: 70.1%) of organic hole transporting material LGY-2 having a benzindole core structure.1H NMR(CDCl3，600MHz)：δ8.67(d，J＝8.4Hz，1H)，8.45(s，1H)，8.38(s，1H)，8.17(dd，J1＝7.8Hz，J2＝12Hz，2H)，7.74(t，J＝9.6Hz，3H)，7.68(d，J＝9.6Hz，1H)，7.65(s，1H)，7.64(s，1H)，7.56-7.62(m，8H)，7.51(t，J＝8.4Hz，3H)，7.44-7.48(m，8H)，7.40-7.42(m，7H)，7.35-7.37(m，2H)，7.24-7.28(m，2H)，6.95(t，J＝7.2Hz，1H)，6.78(d，J＝8.4Hz，1H)，4.56(s，3H)，3.43(s，3H).13C NMR(CDCl3，600MHz)：δ142.55，142.07，141.45，140.46，140.00，139.99，139.72，138.64，137.83，137.78，137.25，137.23，135.79，133.23，132.98，132.88，131.02，130.02，127.59，127.57，127.17，127.15，126.87，126.20，126.15，126.12，125.50，125.40，124.77，124.48，124.04，124.02，123.96，123.68，123.62，122.78，121.48，121.09，120.57，120.52，120.17，120.15，119.56，119.31，118.79，118.73，118.33，115.40，110.10，110.01，109.98，109.38，109.02，107.45，35.64，33.37.HR-MS：(ESI)m/z：C74H50N4Calculated value 994.4035; found 994.4012.
(4) Intermediate 1a, 100mg (0.168mmol) was dissolved in 1, 4-dioxane, dimethoxytriphenylamine borate, 218mg (0.505mmol), aqueous potassium carbonate (2mol/L), tetrakis (triphenylphosphine) palladium, 25mg (0.022mmol) were added, stirred uniformly under nitrogen at room temperature, then heated, and reacted overnight. After the reaction is finished, cooling to room temperature. After toluene as a solvent was dried by spinning, water was added to the residue, followed by extraction with dichloromethane, washing with saturated brine, collecting the organic phase, drying with anhydrous sodium sulfate, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and drying under vacuum to obtain 114mg (yield: 65.0%) of an organic hole transporting material LGY-3 having a benzindole core structure.1H NMR(CDCl3，600MHz)：δ8.64(d，J＝8.4Hz，1H)，7.47-7.53(m，6H)，7.42-7.45(m，5H)，7.33(q，J＝8.4Hz，2H)，7.29(dd，J1＝7.8Hz，J2＝11.4Hz，4H)，7.06-7.09(m，8H)，6.98-7.02(m，4H)，6.90(t，J＝7.2Hz，1H)，6.83-6.85(m，8H)，6.68(d，J＝7.8Hz，1H)，4.53(s，3H)，3.80(s，12H)，3.34(s，3H).13C NMR(CDCl3，600MHz)：δ155.93，155.89，148.23，148.17，142.51，142.01，141.165，141.09，139.62，138.59，138.57，137.16，135.72，132.91，132.74，132.57，130.87，127.41，127.34，126.54，126.50，125.83，125.12，124.69，124.45，123.93，122.75，121.39，121.37，121.23，121.03，119.50，119.29，118.26，115.31，114.82，109.33，108.98，107.38，55.63，35.61，33.24.HR-MS：(ESI)m/z：C72H58N4O4Calculated value 1042.4458; found 1042.4436.
Example 2:
(1) r in intermediate 11In the case of n-hexyl, denoted 1b, the synthesis has not been reported and we refer to the synthesis of intermediate 1a for preparation. 50mL of anhydrous toluene, N-N-hexylindole, 820mg (4.08mmol), 4, 4' -dibromobenzil, 500mg (1.36mmol), p-toluenesulfonic acid, 52mg (0.272mmol) were added to a 50mL two-necked round-bottomed flask equipped with a condenser under nitrogen. Then, the mixture was heated to 100 ℃ and reacted for 12 hours, the mixture was cooled to room temperature, the solvent toluene was spin-dried, water was added to the residue, extraction was performed with dichloromethane, washing was performed with saturated brine, the organic phase was collected, anhydrous sodium sulfate was added thereto, the organic solvent was removed under reduced pressure, and the obtained solid was separated, purified and vacuum-dried to obtain intermediate 1b, 1890mg (yield: 63.1%).1H NMR(CDCl3，600MHz)：δ8.44(d，J＝7.8Hz，1H)，7.52(t，J＝8.4Hz，2H)，7.46(d，J＝7.8Hz，1H)，7.42(d，J＝8.4Hz，2H)，7.35-7.38(m，1H)，7.10(d，J＝8.4Hz，2H)，7.05(d，J＝8.4Hz，2H)，6.96(t，J＝7.2Hz，1H)，6.51(d，J＝7.8Hz，1H)，4.91(t，J＝8.4Hz，2H)，3.71(t，J＝8.4Hz，2H)，2.23(m，2H)，1.59(m，2H)，1.41-1.46(m，4H)，1.36-1.40(m，2H)，1.20-1.26(m，2H)，1.07-1.12(m，2H)，0.94(t，J＝7.2Hz，3H)，0.87-0.89(m，5H).13C NMR(CDCl3，600MHz)：δ141.31，141.11，139.18，138.21，137.79，136.55，134.41，133.54，132.16，131.44，130.85，124.60，124.24，124.03，122.60，121.25，121.16，121.12，119.54，119.52，116.74，114.99，109.77，109.33，107.87，46.67，44.92，31.72，31.53，30.98，28.85，26.64，26.47，22.73，22.70，14.13.HR-MS：(ESI)m/z：C42H42Br2N2Calculated value 732.1715; found 732.1706.
(2) Intermediate 1b, 100mg (0.0682mmol) was dissolved in 1, 4-bisDimethoxy triphenylamine borate, 88mg (0.2044mmol), aqueous potassium carbonate (2mol/L), tetrakis (triphenylphosphine) palladium, and 30mg (0.026mmol) were added to the oxygen hexacyclic ring, and the mixture was stirred uniformly at room temperature under nitrogen, then heated, and reacted overnight. After the reaction is finished, cooling to room temperature. After toluene as a solvent was dried by spinning, water was added to the residue, followed by extraction with dichloromethane, washing with saturated brine, collecting the organic phase, drying with anhydrous sodium sulfate, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and drying under vacuum to obtain 106mg (yield: 66.0%) of an organic hole transporting material LGY-4 having a benzindole core structure.1H NMR(CDCl3，600MHz)：δ8.44(d，J＝8.4Hz，1H)，7.49-7.51(m，5H)，7.45-7.47(m，2H)，7.41-7.44(m，4H)，7.30-7.33(m，4H)，7.25-7.26(m，2H)，7.06-7.08(m，8H)，6.99(dd，J1＝9.0Hz，J2＝15.6Hz，4H)，6.83-6.87(m，9H)，6.59(d，J＝7.8Hz，1H)，4.92(t，J＝8.4Hz，2H)，3.80(s，12H)，3.75-3.78(m，2H)，2.21-2.26(m，2H)，1.58-1.62(m，2H)，1.42-1.48(m，4H)，1.36-1.37(m，2H)，1.11-1.17(m，2H)，1.04-1.09(m，2H)，0.92(t，J＝7.8Hz，2H)，0.81-0.85(m，2H)，0.76(t，J＝7.2Hz，2H).13C NMR(CDCl3，600MHz)：δ155.93，155.89，148.20，148.16，141.32，141.17，141.14，141.12，138.84，138.79，138.65，138.47，137.19，136.43，135.91，132.96，132.81，132.34，130.86，127.41，127.40，126.55，126.50，125.80，125.32，124.67，124.27，123.70，122.53，121.48，121.37，121.20，119.30，119.26，118.16，115.34，114.82，109.70，109.12，107.56，55.63，46.69，44.87，31.76，31.58，31.55，30.33，30.28，26.69，26.45，22.75，22.66，14.15，14.10.HR-MS：(ESI)m/z：C82H78N4O4Calculated value 1182.6023; found 1182.6006.
The hole-transporting materials LGY-1, LGY-2, LGY-3 and LGY-4 synthesized by the method are applied to perovskite solar cells, and the preparation process comprises the following steps:
ITO (indium tin oxide) conductive glass with the size of 20mm x 15mm is used as a transparent conductive electrodeVery much, etching is done using zinc powder and hydrochloric acid chemistry. And washing the etched conductive glass by using a detergent, sequentially carrying out ultrasonic cleaning for 15min by using deionized water, acetone and ethanol, and then treating for 15min in an ultraviolet ozone machine. The hole-transporting material solutions (20mg each of LGY-1, LGY-2, LGY-3, LGY-4 was dissolved in 1mL of chlorobenzene) were spin-coated onto an ITO conductive glass substrate by a spin coating method with the number of revolutions controlled at 3000rpm for 30s and sintered at 70 ℃ for 10 min. Mixing lead iodide (PbI)2) Methyl Ammonium Iodide (MAI) (molar ratio of 1: 1) was dissolved in N, N-dimethylformamide and dimethyl sulfoxide (concentration of 1mol/L), and stirred at 50 ℃ for 2h to prepare a perovskite material precursor solution. 50 μ L of the perovskite precursor solution was spin-coated on a hole transport material thin film at room temperature with the rotation speed controlled at 1000rpm for 10s, followed by the rotation speed controlled at 4000rpm for 30s, during which 200 μ L of chlorobenzene was dropped on the film, and the perovskite thin film was annealed and calcined at 100 ℃ for 30 min. After cooling to room temperature, a chlorobenzene solution (20mg/mL) of the electron transport material PCBM was spin-coated on the surface of the perovskite thin film by a spin coating method with the rotation speed controlled at 1200rpm for 30 s. Then the device is transferred to a vacuum evaporation chamber, the area of the battery is set to be 5mm multiplied by 5mm by adopting a mask plate, and 5nm lithium fluoride and 100nm Au are sequentially deposited on the device film by a vacuum evaporation method.
Claims (7)
1. An arylamine substituted benzodiindole organic hole transport material is characterized by having the following chemical general formula:
formula (II), R1Is C1～C6Any one of an alkane chain;
R2is an electron donating group such as triphenylamine, dimethoxy triphenylamine, phenyl carbazole and the like, and is specifically one of the following structures:
2. the method for synthesizing the arylamine substituted benzodiindole organic hole transport material according to claim 1, wherein the method comprises the following steps:
(1) benzodiindole intermediate 1 can be prepared according to the literature (org.biomol.chem., 2008, 6, 1738-;
(2) dissolving the intermediate 1 in 1, 4-dioxane, adding arylamine borate, potassium carbonate water solution and tetrakis (triphenylphosphine) palladium, uniformly stirring at room temperature under the protection of nitrogen, heating, and reacting overnight. After the reaction is finished, cooling to room temperature. And (2) after solvent toluene is dried, adding water into the reaction solution, extracting with dichloromethane, washing with saturated saline solution, collecting an organic phase, adding anhydrous sodium sulfate, drying, removing the organic solvent under reduced pressure, separating and purifying the obtained solid, and drying in vacuum to obtain the arylamine substituted benzodiindole organic hole transport materials LGY-1, LGY-2, LGY-3 and LGY-4.
3. The arylamine substituted benzodiindole organic hole transport material according to claim 2, wherein in the synthesis method: in the step (1), the molar ratio of 4, 4' -dibromobenzil, N-alkyl indole and p-methylbenzenesulfonic acid is 1: 2.5: 0.2, the reaction temperature is 110 ℃, and the reaction time is 10-24 h.
4. The arylamine substituted benzodiindole organic hole transport material according to claim 2, wherein in the synthesis method: in the step (2), the molar ratio of the intermediate 1 to the arylamine borate is 1: 2-4, the reaction temperature is 70-110 ℃, and the reaction time is 10-24 hours.
5. The arylamine substituted benzodiindole organic hole transport material is applied to a trans-planar perovskite solar cell as a hole transport layer.
6. The application of claim 5, wherein the trans-planar perovskite solar cell is composed of a transparent conductive substrate, a hole transport layer, a perovskite absorption layer, an electron transport layer, an electron buffer layer and a metal electrode, and the method comprises the following specific steps:
(1) cutting a transparent conductive substrate into a fixed size, carrying out etching treatment, respectively carrying out ultrasonic cleaning on the etched conductive substrate in different solvents, and then carrying out ultraviolet ozone treatment on the substrate;
(2) preparing a hole transport layer from the aromatic amine substituted benzodiindole organic hole transport material on the treated transparent conductive substrate by a spin-coating method;
(3) the conductive substrate coated with the hole transport layer is moved into a glove box, and the perovskite precursor liquid is coated on the hole transport layer in a rotary coating mode to form a perovskite absorption layer;
(4) coating the solution of the electron transport material on the perovskite absorption layer by a spin coating method to form an electron transport layer;
(5) depositing an electron buffer material on the electron transport layer by a vacuum evaporation method;
(6) and depositing a metal electrode on the hole transport layer by a vacuum evaporation method.
7. The use according to claim 6,
(1) the transparent conductive substrate is one of FTO conductive glass, ITO conductive glass or a flexible substrate;
(2) the hole transport material solution is prepared by dissolving 20mg of hole transport material in 1mL of chlorobenzene;
(3) the perovskite precursor liquid is prepared by the following steps: will CH3NH3I and PbI2Mixing and dissolving in dimethyl sulfoxide according to the molar ratio of 1: 1, and stirring for 1-3 hours at 50 ℃ to obtain CH3NH3PbI3Is a mixture ofA sulfone solution;
(4) the electron transport material solution is prepared by dissolving 20mg of electron transport material PCBM ([6, 6] -phenyl-C61-butyl acid methyl ester) in 1mL of chlorobenzene;
(5) the electron buffer material is lithium fluoride.
(6) The metal electrode is one of gold and silver.
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