CN114790180B - Hole interface material and preparation method and application thereof - Google Patents

Hole interface material and preparation method and application thereof Download PDF

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CN114790180B
CN114790180B CN202210352116.6A CN202210352116A CN114790180B CN 114790180 B CN114790180 B CN 114790180B CN 202210352116 A CN202210352116 A CN 202210352116A CN 114790180 B CN114790180 B CN 114790180B
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hole interface
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CN114790180A (en
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王漾
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Fujian Normal University
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    • C07D285/14—Thiadiazoles; Hydrogenated thiadiazoles condensed with carbocyclic rings or ring systems
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    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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Abstract

The invention discloses a hole interface material and a preparation method and application thereof. The cavity interface material has a structure shown in a formula I. The hole interface material provided by the invention has lower preparation cost and excellent solubility, can be dissolved in a green solvent to prepare a few, can obtain better film morphology and interface characteristics, has adjustable photoelectric property, and can be applied to perovskite solar cells.

Description

Hole interface material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a hole interface material and a preparation method and application thereof.
Background
In recent years, perovskite solar cells using organic-inorganic hybrid perovskite materials as 'light capturing agents' have been rapidly developed, and the recent verification efficiency has broken through 25%, which is comparable to silicon-based solar cells. In addition to the active layer perovskite in perovskite solar cells, hole interface materials are also very critical; the extraction and transfer of holes can be enhanced through interface modification, which is important for improving the performance of the device.
Currently, in trans perovskite cells, the most common hole interface material is PTAA. However, PTAA has high cost, and the surface hydrophobicity is too strong to be beneficial to the spreading of perovskite precursor liquid, resulting in poor uniformity of perovskite film formation and low device reproducibility. Therefore, the design and development of the low-cost and high-efficiency hole interface material has important significance for improving the stability of the perovskite solar cell and reducing the manufacturing cost of the cell.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a hole interface material, a preparation method and application thereof, wherein the hole interface material has lower preparation cost and excellent solubility, can be dissolved and processed in a green solvent, can obtain better film morphology and interface characteristic, has adjustable photoelectric property, and can be applied to perovskite solar cells.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a hole transport material having a structure according to formula i:
a formula I;
wherein the D group is a donor unit group;
A 1 、A 2 、A 3 each independently selected from carbon or nitrogen;
X 1 、X 2 each independently selected from any one of hydrogen, fluorine, cyano, methoxy, 2-methoxyethoxy or 2- (2-methoxyethoxy) ethoxy;
E 1 、E 2 each independently selected from any one of hydrogen, fluorine or methyl;
y is selected from any one of oxygen and sulfur.
Preferably, the D group is selected from any one of the donor unit groups shown below:
；
wherein the R groups are independently selected from any one of hydrogen, methyl, methoxy, 2-methoxyethoxy, 2- (2-methoxyethoxy) ethoxy, methylthio, t-butyl or vinyl, and the dotted line represents the position of the group attachment.
Preferably, the hole interface material comprises any one of the following compounds:
。
in a second aspect, the present invention provides a method for preparing a hole interface material according to the first aspect, the method comprising the steps of:
(1) The compound A and the compound B undergo a coupling reaction to obtain a compound C, wherein the reaction formula is as follows:
；
(2) The compound C is subjected to hydrolysis reaction to obtain a compound shown in a formula I, wherein the reaction formula is as follows:
；
wherein the D group is a donor unit group;
A 1 、A 2 、A 3 each independently selected from carbon or nitrogen;
X 1 、X 2 each independently selected from any one of hydrogen, fluorine, cyano, methoxy, 2-methoxyethoxy or 2- (2-methoxyethoxy) ethoxy;
E 1 、E 2 each independently selected from any one of hydrogen, fluorine or methyl;
y is selected from any one of oxygen and sulfur.
Preferably, the catalyst of the coupling reaction in step (1) is a palladium catalyst.
Preferably, the palladium catalyst is Pd (PPh 3 ) 4 (tetrakis (triphenylphosphine) palladium).
Preferably, the molar mass ratio of compound A to compound B in step (1) is 1 (2.4-3.0), which may be, for example, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3.0.
Preferably, the solvent for the coupling reaction of step (1) comprises any one or a combination of at least two of tetrahydrofuran, water or toluene.
Preferably, the coupling reaction in step (1) is carried out at a temperature of 100-120℃and may be carried out, for example, at 100℃105℃110℃115℃120 ℃.
Preferably, the coupling reaction in step (1) is carried out for a period of time ranging from 20 to 28 h, and may be, for example, 20 h, 21 h, 22 h, 23 h, 24 h, 25 h, 26 h, 27 h, 28 h.
Preferably, the solvent for the hydrolysis reaction in step (2) is methanol and tetrahydrofuran;
preferably, the hydrolysis reaction in step (2) is carried out at a temperature of 30-60℃and may be carried out at 30℃40℃50℃60 ℃.
Preferably, the hydrolysis reaction in step (2) is performed for a period of time ranging from 10 to 20 h, and may be, for example, 10 h, 11 h, 12 h, 13 h, 14 h, 15 h, 16 h, 17 h, 18 h.
Preferably, the preparation method of the compound A specifically comprises the following steps:
(A) The donor compound containing the D group and the halogenating reagent shown in the formula II undergo a coupling reaction to obtain a compound shown in the formula III, wherein the reaction formula is shown as follows:
；
(B) The compound shown in the formula III reacts with the pinacol diboronate to obtain a compound A, wherein the reaction formula is shown as follows:
；
preferably, the catalyst of the coupling reaction in step (a) is a palladium catalyst.
Preferably, the palladium catalyst is Pd 2 (dba) 3 (tris (dibenzyl acetone) dipalladium (0)).
Preferably, the solvent for the coupling reaction of step (a) comprises any one or a combination of at least two of tetrahydrofuran, water or toluene.
Preferably, the coupling reaction in step (A) is carried out at a temperature of 100-120deg.C, for example 10, 15, 20, 25, 30 ℃.
Preferably, the coupling reaction in step (A) is carried out for a period of time ranging from 20 to 28 h, and may be, for example, 20 h, 21 h, 22 h, 23 h, 24 h, 25 h, 26 h, 27 h, 28 h.
Preferably, the catalyst of the reaction of step (B) is a palladium catalyst.
Preferably, the palladium catalyst is Pd (dppf) Cl 2 ([ 1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride).
Preferably, the solvent for the reaction of step (B) is 1, 4-dioxane.
Preferably, the coupling reaction in step (B) is carried out at a temperature of 100-120deg.C, for example 10, 15, 20, 25, 30 ℃.
Preferably, the reaction in step (B) is carried out for a period of time ranging from 20 to 28 h, and may be, for example, 20 h, 21 h, 22 h, 23 h, 24 h, 25 h, 26 h, 27 h, 28 h.
In a third aspect, the present invention provides a use of a hole interface material as described in the first aspect for the preparation of a solar cell material.
Preferably, the solar cell is a perovskite solar cell.
In a fourth aspect, the present invention provides a hole interface layer comprising the hole interface material according to the first aspect.
In a fifth aspect, the present invention provides a perovskite solar cell comprising a hole interface layer as described in the fourth aspect.
Preferably, the perovskite solar cell comprises, in order from top to bottom: an anode electrode layer, a hole interface layer, a perovskite active layer, an electron transport layer, and a cathode electrode layer.
Preferably, the anode electrode layer is ITO conductive glass.
Preferably, the anode electrode layer has a thickness of 150-180 a nm a, for example 150 nm a, 160 a nm a, 170 a nm a, 180 a nm a.
Preferably, the hole transport layer has a thickness of 1-10 a nm a, for example 1 nm a, 2 a nm a 3 a nm a 4 a nm a 5 a nm a 6 a nm a 7 a nm a 8 a nm a 9 a nm a 10 a nm a.
Preferably, the perovskite active layer has a thickness of 400-600 nm, which may be 400 nm, 420 nm, 440 nm, 460 nm, 480 nm, 500 nm, 520 nm, 540 nm, 560 nm, 580 nm, 600 nm, for example.
Preferably, the electron transport layer is a PCB-modified carbon 60 electron transport layer.
Preferably, the electron transport layer has a thickness of 20-30 a nm a, for example 20 a nm a 22 a nm a 24 a nm a 26 a nm a 28 a nm a 30 a nm a.
Preferably, the cathode electrode is a silver electrode.
Preferably, the thickness of the cathode electrode is 100-150 a nm a, for example 100 a nm a, 110 a nm a 120 a nm a 130 a nm a 140 a nm a 150 a nm a.
Compared with the prior art, the invention has the following beneficial effects:
the hole transport material has lower preparation cost, excellent solubility, better film morphology and excellent interface characteristic and adjustable photoelectric property, can be dissolved and processed in a green solvent, and can be applied to perovskite solar cells.
Drawings
FIG. 1 is an ultraviolet absorption spectrum of the hole interface material solution provided in examples 1-3.
FIG. 2 is an electrochemical performance test chart of the hole interface materials provided in examples 1-3.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
This embodiment provides a hole transport material having a structure as shown in formula I-1:
i-1
The synthesis route of the hole interface material I-1 is as follows:
(1) Synthesis of intermediate Compound 1
Pinacol 4- (4-methoxyphenylamino) phenylborate (106 mg, 0.24 mmol), 7-bromo-4- (p-ethoxycarbonylphenyl) benzo [ C][1,2,5]Thiadiazole (70 mg, 0.19 mmol), pd (PPh) 3 ) 4 (6 mg, 0.0095 mmol), potassium carbonate (43 mg, 0.285 mmol) in a double-necked flask; argon is pumped three times, tetrahydrofuran 7 mL and water 1 mL are added; the reaction is carried out under the protection of argon; after the reaction is carried out at 100 ℃ for 24 h, the reaction system is cooled to room temperature after the reaction is completed, the solvent is unscrewed, and the initial product is purified by a column, so that the intermediate compound 1 can be obtained, the mass is 60 mg, and the yield is 54%.
1 H NMR (400 MHz, CDCl 3 ): δ 8.23 (d, J = 8.4 Hz, 2H), 8.08 (d, J = 8.4 Hz, 2H), 7.87-7.83 (m, 3H), 7.77 (d, J = 7.4 Hz, 1H), 7.18 (d, J = 8.9 Hz, 4H), 7.09 (d, J = 8.8 Hz, 2H), 6.90 (d, J = 9.0 Hz, 4H), 4.45 (q, J = 7.1 Hz, 2H), 3.84 (s, 6H), 1.45 (t, J = 7.1 Hz, 3H).
13 C NMR (100 MHz, CDCl 3 ): δ 166.57, 156.26, 154.10, 153.99, 149.19, 141.92, 140.37, 133.98, 130.87, 129.87, 129.82, 129.07, 128.85, 128.51, 127.16, 126.66, 119.57, 114.81, 99.98, 61.18, 55.53, 14.36。
(2) Synthesis of hole transport Material I-1
Intermediate compound 1 (60 mg, 0.1 mmol), potassium hydroxide (56 mg, 1 mmol), THF (6 mL) and methanol (1 mL) from step (1) were reacted under reflux 12 h. All solvents were removed by rotary evaporation, water and 2M diluted hydrochloric acid were added and solids precipitated. Filtering, vacuum drying filter cake, collecting the obtained compound I-1 with mass of 30 mg and yield of 55%.
1 H NMR (400 MHz, acetone-d 6 ): δ 8.22 (s, 4H), 8.03 (d, J = 7.4 Hz, 1H), 7.99-7.93 (m, 3H), 7.18 (d, J = 8.9 Hz, 4H), 7.01-6.97 (m, 6H), 3.83 (s, 6H).
13 C NMR (100 MHz, CDCl 3 ): δ 171.57, 156.26, 154.09, 153.93, 149.40, 142.79, 140.50, 134.15, 130.73, 130.48, 129.89, 129.19, 128.99, 128.45, 127.17, 126.63, 119.55, 114.81, 100.12, 55.37.
High resolution mass spectrometry: c (C) 33 H 25 N 3 O 4 S calculated value: 559.1566, found: 560.1630 [ M+H ]].
Elemental analysis calculated: c, 70.82; H, 4.50; N, 7.51; S, 5.73, found: c, 71.23, H, 4.40, N, 7.65, S, 5.90.
Example 2
The embodiment provides a hole interface material, which has a structure shown as a formula I-2:
i-2
The synthesis route of the hole interface material I-2 is as follows:
(1) Synthesis of Compound 2: 4,4' -Dimethoxydiphenylamine (960 mg,4.2 mmol), 2-bromo-5-iodofluorobenzene (1.56 g, 5.25 mmol), pd 2 (dba) 3 (193 mg, 0.21 mmol), dppf (112 mg, 0.18 mmol), sodium tert-butoxide (2 g, 21 mmol), were placed in a double-necked flask; argon is pumped three times, and then anhydrous toluene 25 mL is added; the reaction is carried out under the protection of argon; after 24 hours of reaction at 120 ℃, the reaction system is cooled to room temperature, the solvent is removed, and the initial product is further purified by a column, so that compound 2 with the mass of 1.5 g and the yield of 89% can be obtained.
1 H NMR (400MHz, CDCl3): δ 7.26-7.23 (m, 1H), 7.08 (d, J = 8.8 Hz, 4H), 6.87 (d, J = 8.8 Hz, 4H), 6.64 (dd, J = 11.4, 2.5 Hz, 1H), 6.56 (dd, J = 8.8, 2.5 Hz, 1H), 3.82 (s, 6H)。
(2) Synthesis of Compound 3: compound 2 (800 mg,2 mmol) produced in step (1), bis (pinacolato) diboron (762 g, 3 mmol), pd (dppf) Cl2 (73 mg, 0.1 mmol), potassium acetate (588 mg, 6 mmol) was placed in a double-necked flask; argon is pumped for three times, and then anhydrous 1, 4-dioxane 40 and mL are added; the reaction is carried out under the protection of argon; after heating and refluxing for 24 hours, the reaction system was cooled to room temperature, filtered, the solvent was removed, and the crude product was purified further by passing through a column to give compound 3, mass 640 mg, 71% yield.
1 H NMR (400MHz, CDCl3): δ 7.52-7.48 (m, 1H), 7.10 (d, J = 8.9 Hz, 4H), 6.87 (d, J = 8.9 Hz, 4H), 6.60 (dd, J = 8.3, 2.1 Hz, 1H), 6.48 (dd, J = 12.5, 2.1 Hz, 1H), 3.83 (s, 6H), 1.35 (s, 12H). 19F NMR (376MHz, CDCl3): δ -101.66。
(3) Synthesis of Compound 4 (same as example 1 step (1)): compound 4 was synthesized in 90% yield according to the procedure of compound 1 in example 1.
1 H NMR (400 MHz, CDCl 3 ): δ 8.24 (d, J = 8.1 Hz, 2H), 8.07 (d, J = 6.8 Hz, 2H), 7.84-7.78 (m, 2H), 7.64-7.59 (m, 1H), 7.20 (d, J = 8.7 Hz, 4H), 6.92 (d, J = 8.7 Hz, 4H), 6.82-6.73 (m, 2H), 4.48-4.43 (m, 2H), 3.84 (s, 6H), 1.46 (t, J = 7.8 Hz, 3H).
19 F NMR (376 MHz, CDCl 3 ): δ -113.72.
13 C NMR (100 MHz, CDCl 3 ): δ 166.41, 156.81, 154.38, 153.62, 141.79, 139.64, 132.06, 132.03, 131.83, 130.04, 129.83, 129.41, 129.38, 129.14, 129.07, 128.48, 127.69, 114.96, 113.98, 105.71, 105.50, 61.06, 55.52, 14.39。
(4) Hole transport material I-2 (same as in example 1 step (2)): i-2 was synthesized in 86% yield by the method of example 1 using cavity transfer material I-1.
1 H NMR (400 MHz, d 6 -DMSO): δ 8.14-8.09 (m, 4H), 7.99 (d, J = 7.3 Hz, 1H), 7.79 (d, J = 7.0 Hz, 1H), 7.58-7.55 (m, 1H), 7.20 (d, J = 8.8 Hz, 4H), 6.99 (d, J = 8.8 Hz, 4H), 6.61 (dd, J = 8.6, 1.9 Hz, 1H), 6.48 (dd, J = 13.4, 1.9 Hz, 1H), 3.77 (s, 6H).
19 F NMR (376 MHz, d 6 -DMSO): δ -112.94.
13 C NMR (100 MHz, d 6 -DMSO): δ 167.65, 159.16, 157.25, 154.14, 153.22, 146.34, 141.45, 139.21, 132.97, 131.36, 130.74, 129.97,129.87, 129.69, 129.24, 128.83, 128.40, 125.25, 115.69, 114.99, 113.27, 55.91.
High resolution mass spectrometry: c (C) 33 H 24 N 3 O 4 S calculated value: 577.1472, found: 577.1474 [ M+H ]].
Elemental analysis calculated: c, 68.62; H, 4.19; N, 7.27; S, 5.55, found: c, 68.50, H, 4.08, N, 7.36, S, 5.75.
Example 3
The embodiment provides a hole interface material, which has a structure shown as a formula I-3:
i-3
The synthesis route of the hole interface material I-3 is as follows:
(1) Synthesis of Compound 5: compound 5 was synthesized in 80% yield according to the procedure of compound 2 in synthesis example 2.
1 H NMR (400 MHz, CDCl 3 ): δ 7.25-7.21 (m, 1H), 6.95 (d, J = 9.0 Hz, 1H), 6.83 (d, J = 9.0 Hz, 1H), 6.81-6.77 (m, 1H), 3.81 (s, 6H).
19 F NMR (376 MHz, CDCl 3 ): δ -111.97 (d, J = 14.1 Hz, 1F), -121.97 (d, J = 14.1 Hz, 1F)。
(2) Synthesis of Compound 6: compound 6 was synthesized in 70% yield according to the procedure of compound 3 in synthesis example 2.
1 H NMR (400 MHz, CDCl 3 ): δ 7.37-7.34 (m, 1H), 6.97 (d, J = 9.0 Hz, 4H), 6.83 (d, J = 9.0 Hz, 4H), 6.64-6.60 (m, 1H), 3.81 (s, 6H), 1.36 (s, 12H).
19 F NMR (376 MHz, CDCl 3 ): δ -107.11 (d, J = 17.5 Hz, 1F), -125.35 (d, J = 17.6 Hz, 1F)。
(3) Synthesis of Compound 7: compound 7 was synthesized in 57% yield according to the procedure of compound 1 in synthesis example 1.
1 H NMR (400 MHz, CDCl 3 ): δ 8.25 (d, J = 8.4 Hz, 2H), 8.08 (d, J = 8.5 Hz, 2H), 7.85 (s, 2H), 7.61-7.57 (m, 1H), 7.08 (d, J = 9.0 Hz, 4H), 6.91-6.86 (m, 5H), 4.49-4.43 (m, 2H), 3.84 (s, 6H), 1.46 (t, J = 7.8 Hz, 3H).
19 F NMR (376 MHz, CDCl 3 ): δ -118.68 (d, J = 15.7 Hz, 1F), -123.62 (d, J = 15.7 Hz, 1F).
13 C NMR (100 MHz, CDCl 3 ): δ 166.39, 156.09, 155.32, 153.94, 153.59, 141.50, 140.47, 137.10, 132.77, 130.26, 129.96, 129.92, 129.85, 129.21, 128.28, 127.49, 125.10, 119.47, 119.29, 119.25, 114.65, 61.11, 55.52, 14.36。
(4) Synthesis of hole transport material I-3: i-3 was synthesized in 91% yield by the method of hole transport material I-1 in Synthesis example 1.
1 H NMR (400 MHz, d 6 -DMSO): δ 8.16-8.11 (m, 4H), 8.05-8.02 (m, 1H), 7.94-7.92 (m, 1H), 7.72-7.69 (m, 1H), 7.00 (d, J = 8.8 Hz, 4H), 6.93 (d, J = 8.7 Hz, 4H), 6.87-6.84 (m, 1H), 3.76 (s, 6H).
19 F NMR (376 MHz, d 6 -DMSO): δ -117.73 (d, J = 15.9 Hz, 1F), -123.97 (d, J = 15.2 Hz, 1F).
13 C NMR (100 MHz, d 6 -DMSO): δ 167.57, 156.20, 153.77, 153.17, 141.24, 140.33, 137.12, 132.26, 130.91, 130.62, 130.59, 130.27, 129.99, 129.76, 129.08, 128.84, 128.06, 127.05, 125.24, 124.83, 115.30, 55.72.
High resolution mass spectrometry: c (C) 33 H 23 F 2 N 3 O 4 S calculated value: 595.1377, found: 595.1367 [ M+H ]].
Elemental analysis calculated: c, 66.55; H, 3.89; N, 7.05; S, 5.38, found: c, 66.30, H, 3.70, N, 7.11, S, 5.60.
Example 4
The embodiment provides a hole interface material, which has a structure shown as a formula I-4:
i-4
Synthetic route of hole interface material I-4:
(1) Synthesis of Compound 1: compound 1 was synthesized in 80% yield according to the procedure of compound 2 in synthesis example 2.
1 H NMR (400 MHz, CDCl 3 ): δ 8.21 (d, J = 8.4 Hz, 2H), 7.83 (d, J = 8.4 Hz, 2H), 7.60 (d, J = 8.7 Hz, 2H), 7.16 (d, J = 8.9 Hz, 4H), 7.05 (d, J = 8.8 Hz, 2H), 6.88 (d, J = 9.0 Hz, 4H), 4.45 (q, J = 7.1 Hz, 2H), 3.77 (s, 6H), 3.75 (s, 3H), 3.76 (s, 3H), 1.45 (t, J = 7.1 Hz, 3H)。
(2) Synthesis of hole transport material I-4: i-4 was synthesized in 88% yield by the method of hole transport material I-1 in Synthesis example 1.
1 H NMR (400MHz, d 6 -DMSO): δ 8.09 (d, J = 8.1 Hz, 2H), 7.78 (d, J = 8.1 Hz, 2H), 7.51 (d, J = 8.6 Hz, 2H), 7.14 (d, J = 8.8 Hz, 4H), 6.97 (d, J = 8.8 Hz, 4H), 6.87 (d, J = 8.6 Hz, 2H), 3.77 (s, 6H), 3.75 (s, 3H), 3.76 (s, 3H).
13 C NMR (100 MHz, d 6 -DMSO): δ 167.62, 156.54, 153.94, 153.09, 152.05, 151.60, 148.73, 140.25, 138.43, 131.69, 131.18, 130.59, 129.39, 127.70, 124.78, 124.49, 122.57, 118.18, 115.55, 61.90, 61.61, 55.75。
Example 5
The embodiment provides a hole interface material, which has a structure shown as a formula I-5:
i-5
The synthesis route of the hole interface material I-5 is as follows:
(1) Synthesis of Compound 1: compound 1 was synthesized in 96% yield according to the procedure of compound 2 in synthesis example 2.
1 H NMR (400 MHz, CDCl 3 ): δ 8.20 (d, J = 8.3 Hz, 2H), 7.85 (d, J = 8.3 Hz, 2H), 7.59 (d, J = 8.7 Hz, 2H), 7.15 (d, J = 8.9 Hz, 4H), 7.04 (d, J = 8.7 Hz, 2H), 6.86 (d, J = 8.9 Hz, 4H), 4.43 (q, J = 7.1 Hz, 1H), 4.09 (br, 4H), 3.57-3.56 (m, 2H), 3.47-3.45 (m, 2H), 3.30 (s, 3H), 3.19 (s, 3H), 1.43 (t, J= 7.1 Hz, 3H)。
(2) Synthesis of hole interface material I-5: i-5 was synthesized in 85% yield by the method of cavity interface material I-1 in Synthesis example 1.
1 H NMR (400MHz, d 6 -DMSO): δ 8.07 (d, J = 8.3 Hz, 2H), 7.78 (d, J = 8.3 Hz, 2H), 7.53 (d, J = 8.7 Hz, 2H), 7.12 (d, J = 8.9 Hz, 4H), 6.96 (d, J = 9.0 Hz, 4H), 6.87 (d, J = 8.7 Hz, 2H), 4.06-4.02 (m, 4H), 3.76 (s, 6H), 3.48-3.46 (m, 2H), 3.41-3.39 (m, 2H), 3.17 (s, 3H), 3.08 (s, 3H).
13 C NMR (100 MHz, d 6 -DMSO): δ 156.45, 153.13, 152.29, 152.06, 151.71, 148.06, 140.37, 131.98, 131.34, 131.31, 129.18, 127.50, 124.88, 124.83, 122.75, 118.43, 115.51, 73.38, 73.03, 71.43, 71.37, 58.39, 58.31, 55.74。
Example 6
The embodiment provides a hole interface material, which has a structure shown as a formula I-6:
i-6
Synthetic route of hole interface material I-6:
(1) Synthesis of Compound 1: compound 1 was synthesized in 58% yield according to the procedure of compound 1 in synthesis example 1.
1 H NMR (400 MHz, CDCl 3 ): δ 8.21 (d, J = 8.3 Hz, 2H), 7.85 (d, J = 8.3 Hz, 2H), 7.27-7.24 (m, 1H), 7.05 (d, J = 8.9 Hz, 4H), 6.87-6.84 (m, 5H), 4.43 (q, J = 7.1 Hz, 2H), 4.26-4.24 (m, 2H), 4.05-4.03 (m, 2H), 3.59-3.57 (m, 2H), 3.46-3.44 (m, 2H), 3.31 (s, 3H), 3.19 (s, 3H), 1.43 (t, J = 7.1 Hz, 3H).
19 F NMR (376 MHz, CDCl 3 ): δ -115.22 (d, J = 15.4 Hz, 1H), -124.23 (d, J = 15.4 Hz, 1H).
13 C NMR (100 MHz, CDCl 3 ): δ 166.44, 157.29, 156.11, 153.58, 152.61, 151.73, 151.45, 140.59, 138.04, 130.89, 130.10, 129.58, 129.27, 126.00, 125.78, 125.02, 124.46, 118.52, 114.63, 112.52, 100.04, 73.41, 73.33, 71.66, 71.47, 61.06, 58.85, 58.69, 14.38。
(2) Synthesis of hole interface material I-6: i-6 was synthesized in 50% yield by the method of the hole interface material I-1 in Synthesis example 1.
1 H NMR (400 MHz, THF-d 8 ): δ 8.13 (d, J = 8.4 Hz, 2H), 7.87 (d, J = 8.4 Hz, 2H), 7.31-7.27 (m, 1H), 7.02 (d, J = 8.9 Hz, 4H), 6.86 (d, J = 9.0 Hz, 4H), 6.83-6.80 (m, 1H), 4.24-4.23 (m, 2H), 4.05-4.03 (m, 2H), 3.76 (s, 6H), 3.53-3.51 (m, 2H), 3.43-3.41 (m, 2H), 3.24 (s, 3H), 3.14 (s, 3H).
19 F NMR (376 MHz, THF-d 8 ): δ -115.91 (d, J = 15.5 Hz, 1H), -125.73 (d, J = 15.5 Hz, 1H)。
Example 7
The embodiment provides a hole interface material, which has a structure shown as a formula I-7:
i-7
Synthetic route of hole interface material I-7:
(1) Synthesis of Compound 1: compound 1 was synthesized in 82% yield according to the procedure of compound 1 in synthesis example 1.
1 H NMR (400MHz, CDCl 3 ): δ 8.28-8.24 (m, 4H), 8.12 (d, J = 8.4 Hz, 2H), 7.96-7.91 (m, 2H), 7.80-7.78 (m, 3H), 7.45 (br, 2H), 7.19-7.17 (m, 3H), 7.02 (br, 8H), 6.81 (d, J = 7.5 Hz, 8H), 4.47 (q, J = 7.1 Hz, 2H), 1.47 (t, J = 7.2 Hz, 3H).
13 C NMR (100 MHz, CDCl 3 ): δ 166.44, 153.98, 141.56, 133.11, 132.51, 130.70, 130.26, 129.89, 129.22, 128.66, 128.14, 124.36 (br), 114.57 (br), 110.75, 61.21, 55.54, 14.41。
(2) Synthesis of hole transport material I-7: i-7 was synthesized in 68% yield by the method of hole transport material I-1 in Synthesis example 1.
1 H NMR (40H NMR, d6-DMSO): δ 8.29 (d, J = 8.4 Hz, 2H), 8.09-8.00 (m, 6H), 7.77 (d, J = 8.4 Hz, 2H), 7.70 (s, 2H), 7.41 (d, J = 8.8 Hz, 2H), 7.10 (d, J = 10.6 Hz, 2H), 6.87 (d, J = 9.0 Hz, 8H), 6.81 (d, J = 9.0 Hz, 8H), 3.69 (s, 12H).
High resolution mass spectrometry: c (C) 59 H 45 N 5 O 6 S calculated value: 951.3091, found: 951.3085 [ M+H ]]。
The hole interface materials provided in examples 1-3 were tested for performance by the following method:
(1) Ultraviolet absorption light test: carrying out ultraviolet absorption light test on the sample by using a Shimadzu UV-3600 spectrometer;
fig. 1 shows the ultraviolet absorption spectrum of the hole interface material solution provided in example 1-3, and it can be seen from fig. 1 that the absorption peaks of the hole interface material I-1 are located at 320 and 466 and nm, the absorption peaks 313 and 441 nm of the hole interface material I-2, and the absorption peaks of the hole interface material I-3 are located at 317 and 430 and nm.
(2) Electrochemical testing: testing its electrochemical performance by the CHI760 electrochemical workstation;
FIG. 2 is a graph showing the electrochemical performance test of the hole interface materials provided in examples 1-3, wherein the hole interface materials according to the present invention all exhibit distinct redox peaks, and the HOMO energy level and the LUMO energy level of each hole transport material are calculated from the redox initiation peak positions, and the specific test results are shown in Table 1:
TABLE 1
Sample of HOMO level (eV) LUMO level (eV)
Example 1 -5.27 -3.01
Example 2 -5.36 -2.95
Example 3 -5.42 -2.97
From the test data, the hole interface material provided in examples 1-3 has HOMO energy levels of-5.27 to-5.50 eV and LUMO energy levels of-2.95 to-3.10 eV, which indicates that the hole interface material has good hole extraction performance.
The applicant states that the hole transport materials, and methods of making and using them, according to the present invention are described by way of the above examples, but the invention is not limited to, i.e., it is not meant that the invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.

Claims (8)

1. A hole interface material, characterized in that the hole interface material has a structure as shown in formula I:
；
a formula I;
wherein the D group is a donor unit group;
A 1 、A 2 、A 3 each independently selected from carbon or nitrogen;
X 1 、X 2 each independently selected from hydrogen, fluoro, cyano, methoxy, 2-methoxyethoxy or 2- (2-methoxyethoxy) ethoxy;
E 1 、E 2 each independently selected from hydrogen, fluorine or methyl;
y is selected from oxygen or sulfur;
the donor unit group D is selected from any one of donor unit groups shown in the following structures:
；
wherein the R groups are independently selected from hydrogen, methyl, methoxy, 2-methoxyethoxy, 2- (2-methoxyethoxy) ethoxy, methylthio, t-butyl or vinyl, and the dotted line on N represents the position of attachment of the group.
2. The hole interface material according to claim 1, wherein the hole interface material is selected from any one of the following compounds:
。
3. the method for preparing a hole interface material according to any one of claims 1 to 2, comprising the steps of:
(1) The compound A and the compound B undergo a coupling reaction to obtain a compound C, wherein the reaction formula is as follows:
；
(2) The compound C is subjected to hydrolysis reaction to obtain a compound shown in a formula I, wherein the reaction formula is as follows:
；
wherein the D group is a donor unit group;
A 1 、A 2 、A 3 each independently selected from carbon or nitrogen;
X 1 、X 2 each independently selected from hydrogen, fluoro, cyano, methoxy, 2-methoxyethoxy or 2- (2-methoxyethoxy) ethoxy;
E 1 、E 2 each independently selected from hydrogen, fluorine or methyl;
y is selected from oxygen or sulfur.
4. The method according to claim 3, wherein the catalyst for the coupling reaction in the step (1) is a palladium catalyst;
the palladium catalyst is Pd (PPh) 3 ) 4 ；
The molar mass ratio of the compound A to the compound B in the step (1) is 1 (2.4-3.0);
the solvent of the coupling reaction in the step (1) comprises any one or a combination of at least two of tetrahydrofuran, water and toluene;
the temperature of the coupling reaction in the step (1) is 100-120 ℃;
the coupling reaction time of the step (1) is 20-28 h;
the solvent of the hydrolysis reaction in the step (2) is methanol or tetrahydrofuran;
the temperature of the hydrolysis reaction in the step (2) is 30-60 ℃;
the time of the hydrolysis reaction in the step (2) is 10-20 h;
the preparation method of the compound A specifically comprises the following steps:
(A) The donor compound containing the D group and the halogenating reagent shown in the formula II undergo a coupling reaction to obtain a compound shown in the formula III, wherein the reaction formula is shown as follows:
；
(B) The compound shown in the formula III reacts with the pinacol diboronate to obtain a compound A, wherein the reaction formula is shown as follows:
；
the catalyst of the coupling reaction in the step (A) is a palladium catalyst;
the palladium catalyst is Pd 2 (dba) 3 ；
The solvent of the coupling reaction in the step (A) comprises any one or a combination of at least two of tetrahydrofuran, water and toluene;
the temperature of the coupling reaction in the step (A) is 100-120 ℃;
the coupling reaction time of the step (A) is 20-28 h;
the catalyst of the reaction in the step (B) is a palladium catalyst;
the palladium catalyst is Pd (dppf) Cl 2 ；
The solvent of the reaction in the step (B) is 1, 4-dioxane;
the temperature of the coupling reaction in the step (B) is 100-120 ℃;
the reaction time in the step (B) is 20-28 h.
5. Use of the hole interface material of any of claims 1-2 for the preparation of a solar cell material;
the solar cell is a perovskite solar cell.
6. A hole interface layer, characterized in that it comprises the hole interface material according to any one of claims 1-2.
7. A perovskite solar cell comprising the hole interface layer of claim 6.
8. The perovskite solar cell of claim 7, wherein the perovskite solar cell comprises, in order from top to bottom: an anode electrode layer, the hole interface layer of claim 6, a perovskite active layer, an electron transport layer, and a cathode electrode layer;
the anode electrode layer is ITO conductive glass;
the thickness of the anode electrode layer is 150-180 and nm;
the thickness of the cavity interface layer is 1-10 nm;
the thickness of the perovskite active layer is 400-600 nm;
the electron transport layer is a carbon 60 electron transport layer modified by a PCB;
the thickness of the electron transport layer is 20-30 nm;
the cathode electrode is a silver electrode;
the thickness of the cathode electrode is 100-150 a nm a.
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