CN114790180A

CN114790180A - Hole interface material and preparation method and application thereof

Info

Publication number: CN114790180A
Application number: CN202210352116.6A
Authority: CN
Inventors: 王漾
Original assignee: Fujian Normal University
Current assignee: Fujian Normal University
Priority date: 2022-04-03
Filing date: 2022-04-03
Publication date: 2022-07-26
Anticipated expiration: 2042-04-03
Also published as: CN114790180B

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, some hole interface materials can be dissolved and processed even in a green solvent, and the hole interface material can obtain better film morphology and interface characteristics and has adjustable photoelectric properties, 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 taking organic-inorganic hybrid perovskite materials as "light capture agents" have been developed rapidly, and the recent verification efficiency of the perovskite solar cells is 25% higher than that of silicon-based solar cells. Besides the perovskite of the active layer in the perovskite solar cell, the hole interface material is also very critical; the method can enhance the extraction and transfer of holes through interface modification, and is very important for improving the performance of the device.

Currently, in trans-perovskite cells, the most commonly used hole interface material is PTAA. However, PTAA is expensive in manufacturing cost, and too strong in surface hydrophobicity to facilitate spreading of the perovskite precursor solution, resulting in poor uniformity of perovskite film formation and low device reproducibility. Therefore, designing and developing the hole interface material with low cost and high efficiency 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, some hole interface materials can be dissolved and processed even in a green solvent, better film morphology and interface characteristics can be obtained, and the hole interface material has adjustable photoelectric properties and can be applied to perovskite solar cells.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a hole transport material having a structure as shown in formula i:

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 is independently selected from any one of hydrogen, fluorine or methyl;

y is selected from any one of oxygen or sulfur.

Preferably, the D group is selected from any one of the donor unit groups shown below:

；

wherein, R groups are independently selected from any one of hydrogen, methyl, methoxy, 2-methoxyethoxy, 2- (2-methoxyethoxy) ethoxy, methylthio, tert-butyl or vinyl, and the dotted line represents the position of the group connection.

Preferably, the hole interface material includes any one of the following compounds:

。

in a second aspect, the present invention provides a method for preparing a hole interface material as described in the first aspect, the method comprising the steps of:

(1) carrying out coupling reaction on the compound A and the compound B to obtain a compound C, wherein the reaction formula is as follows:

；

(2) and (3) carrying out hydrolysis reaction on the compound C to obtain a compound shown in the 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-methyl)Oxyethoxy) ethoxy;

y is selected from any one of oxygen or sulfur.

Preferably, the catalyst for the coupling reaction of 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), and 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 in step (1) comprises any one of tetrahydrofuran, water or toluene or a combination of at least two of them.

Preferably, the temperature of the coupling reaction in step (1) is 100 ℃ to 120 ℃, and can be 100 ℃, 105 ℃, 110 ℃, 115 ℃ and 120 ℃.

Preferably, the coupling reaction time in step (1) is 20-28 h, for example 20 h, 21 h, 22 h, 23 h, 24 h, 25 h, 26 h, 27 h, 28 h.

Preferably, the solvents for the hydrolysis reaction in step (2) are methanol and tetrahydrofuran;

preferably, the hydrolysis reaction in step (2) is carried out at a temperature of 30 to 60 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃.

Preferably, the hydrolysis reaction time in step (2) is 10-20 h, such as 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) carrying out coupling reaction on a donor compound containing a D group and a halogenated reagent shown in a formula II to obtain a compound shown in a formula III, wherein the reaction formula is as follows:

；

(B) reacting the compound shown as the formula III with pinacol diboron to obtain a compound A, wherein the reaction formula is as follows:

；

preferably, the catalyst for the coupling reaction of step (a) is a palladium catalyst.

Preferably, the palladium catalyst is Pd ₂ (dba) ₃ (tris (dibenzylacetone) dipalladium (0)).

Preferably, the solvent for the coupling reaction of step (a) comprises any one of tetrahydrofuran, water or toluene or a combination of at least two thereof.

Preferably, the temperature of the coupling reaction in step (A) is 100 ℃ to 120 ℃, and may be, for example, 10 ℃, 15 ℃, 20 ℃, 25 ℃ and 30 ℃.

Preferably, the coupling reaction time in step (a) is 20-28 h, for example 20 h, 21 h, 22 h, 23 h, 24 h, 25 h, 26 h, 27 h, 28 h.

Preferably, the catalyst for 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 temperature of the coupling reaction in step (B) is 100 ℃ to 120 ℃, and may be, for example, 10 ℃, 15 ℃, 20 ℃, 25 ℃ and 30 ℃.

Preferably, the reaction time of step (B) is 20-28 h, 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 in 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 a hole interface material as described in 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 thickness of the anode electrode layer is 150-180 nm, such as 150 nm, 160 nm, 170 nm, 180 nm.

Preferably, the hole transport layer has a thickness of 1 to 10 nm, and may be, for example, 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm.

Preferably, the thickness of the perovskite active layer is 400-600 nm, and may be, for example, 400 nm, 420 nm, 440 nm, 460 nm, 480 nm, 500 nm, 520 nm, 540 nm, 560 nm, 580 nm, 600 nm.

Preferably, the electron transport layer is a PCB-decorated carbon 60 electron transport layer.

Preferably, the thickness of the electron transport layer is 20-30 nm, and may be, for example, 20 nm, 22 nm, 24 nm, 26 nm, 28 nm, 30 nm.

Preferably, the cathode electrode is a silver electrode.

Preferably, the thickness of the cathode electrode is 100-150 nm, such as 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm.

Compared with the prior art, the invention has the following beneficial effects:

the hole transport material has low preparation cost and excellent solubility, some hole transport materials can be dissolved and processed even in a green solvent, a good film appearance can be obtained, and the hole transport material also has excellent interface characteristics and adjustable photoelectric properties and can be applied to perovskite solar cells.

Drawings

FIG. 1 is an ultraviolet absorption spectrum of a hole interface material solution provided in examples 1 to 3.

FIG. 2 is a graph showing the electrochemical properties of the hole interface materials provided in examples 1 to 3.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Example 1

This example provides a hole transport material having a structure as shown in formula I-1:

formula I-1

The synthesis route of the hole interface material I-1 is as follows:

(1) synthesis of intermediate Compound 1

4- (4-Methoxyphenylamino) phenylboronic acid pinacol ester (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 two-necked bottle; after argon is pumped and flushed for three times, 7 mL of tetrahydrofuran and 1 mL of water are added; the reaction is carried out under the protection of argon; after the reaction is carried out for 24 h at 100 ℃, after the reaction is finished, the reaction system is cooled to room temperature, the solvent is spun out, and the primary product is purified by a column, so that the intermediate compound 1 with the mass of 60 mg and the yield of 54 percent can be obtained.

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 transporting Material I-1

The intermediate compound 1 (60 mg, 0.1 mmol) obtained in step (1), potassium hydroxide (56 mg, 1 mmol), THF (6 mL) and methanol (1 mL) were refluxed for 12 hours. All solvents were removed by rotary evaporation, water and 2M dilute hydrochloric acid were added and a solid precipitated. Filtering, drying the filter cake in vacuum, and collecting the compound I-1 with the mass of 30 mg and the 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 ₃₃ H ₂₅ N ₃ O ₄ S calculated value: 559.1566, found: 560.1630 [ M + H].

Calculated value of elemental analysis: c, 70.82, H, 4.50, N, 7.51, S, 5.73, found: c, 71.23, H, 4.40, N, 7.65 and S, 5.90.

Example 2

This example provides a hole interface material having a structure as shown in formula i-2:

formula 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), in a two-necked flask; after argon is pumped and flushed for three times, 25 mL of anhydrous toluene 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 spun out, and the primary product is further purified by passing through a column, so that the compound 2 with the mass of 1.5 g and the yield of 89 percent 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: putting the compound 2 (800 mg, 2 mmol) prepared in the step (1), bis (pinacolato) diboron (762 g, 3 mmol), Pd (dppf) Cl2 (73 mg, 0.1 mmol) and potassium acetate (588 mg, 6 mmol) in a double-mouth bottle; after argon is pumped and flushed for three times, 40 mL of anhydrous 1, 4-dioxane is added; the reaction is carried out under the protection of argon; after heating and refluxing for 24 hours, the reaction system is cooled to room temperature, filtered, the solvent is spun out, and the primary product is further purified by a column to obtain the compound 3 with the mass of 640 mg and the yield of 71%.

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 in step (1) of example 1): compound 4 was synthesized according to the procedure for compound 1 in example 1, in 90% yield.

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-transporting Material I-2 (same as in step (2) of example 1): i-2 was synthesized according to the method for synthesizing the hole transport material I-1 in example 1 in a yield of 86%.

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 ₃₃ H ₂₄ N ₃ O ₄ S calculated value: 577.1472, found: 577.1474 [ M + H].

Calculated value of elemental analysis: c, 68.62, H, 4.19, N, 7.27, S, 5.55, found: c, 68.50, H, 4.08, N, 7.36 and S, 5.75.

Example 3

This example provides a hole interface material having a structure as shown in formula i-3:

formula I-3

Synthetic route of hole interface material I-3:

(1) synthesis of Compound 5: compound 5 was synthesized in 80% yield according to the procedure for the synthesis of compound 2 in 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 according to the procedure for the synthesis of compound 3 in example 2, in 70% yield.

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 according to the method for synthesizing compound 1 in example 1, with a yield of 57%.

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 a yield of 91% according to the procedure for synthesizing the hole transporting material I-1 in 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 ₃₃ H ₂₃ F ₂ N ₃ O ₄ S calculated value: 595.1377, found: 595.1367 [ M + H].

Calculated values of elemental analysis: c, 66.55, H, 3.89, N, 7.05, S, 5.38, found: c, 66.30, H, 3.70, N, 7.11 and S, 5.60.

Example 4

This example provides a hole interface material having a structure as shown in formula I-4:

formula I-4

Synthetic route of hole interface material I-4:

(1) synthesis of Compound 1: compound 1 was synthesized with a yield of 80% according to the procedure for synthesizing compound 2 in 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 according to the procedure for synthesizing the hole transporting material I-1 in 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

This example provides a hole interface material having a structure as shown in formula I-5:

formula I-5

The synthesis route of the hole interface material I-5 is as follows:

(1) synthesis of Compound 1: compound 1 was synthesized with a yield of 96% according to the procedure for synthesizing compound 2 in 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 according to the method for synthesizing the hole interface material I-1 in 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

This example provides a hole interface material having a structure as shown in formula i-6:

formula I-6

The synthesis route of the hole interface material I-6 is as follows:

(1) synthesis of Compound 1: compound 1 was synthesized in 58% yield according to the procedure for the synthesis of compound 1 in 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 according to the method for synthesizing the hole interface material I-1 in 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

This example provides a hole interface material having a structure as shown in formula I-7:

formula I-7

The synthesis route of the hole interface material I-7 is as follows:

(1) synthesis of Compound 1: compound 1 was synthesized according to the method for synthesizing compound 1 in example 1, with a yield of 82%.

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 according to the procedure for synthesizing the hole transporting material I-1 in 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 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 a sample by using a Shimadzu UV-3600 spectrometer;

FIG. 1 shows the UV absorption spectra of the solutions of hole interface materials provided in examples 1-3, and it can be seen from FIG. 1 that the absorption peaks of the hole interface material I-1 are at 320 and 466 nm, the absorption peaks of the hole interface material I-2 are at 313 and 441 nm, and the absorption peaks of the hole interface material I-3 are at 317 and 430 nm.

(2) Electrochemical testing: testing electrochemical performance by CHI760 electrochemical workstation;

fig. 2 is an electrochemical performance test chart of the hole interface materials provided in examples 1 to 3, the hole interface materials of the present invention all exhibit significant redox peaks, the HOMO energy level and the LUMO energy level of each hole transport material are calculated from the redox initiation peak position, and the specific test results are shown in table 1:

TABLE 1

Sample (I)	HOMO energy level (eV)	LUMO energy level (eV)
			Example 1	-5.27	-3.01
Example 2	-5.36	-2.95
			Example 3	-5.42	-2.97

From the above test data, the HOMO energy levels of the hole interface materials provided in examples 1 to 3 are from-5.27 to-5.50 eV, and the LUMO energy levels are from-2.95 to-3.10 eV, which shows that the hole interface material of the present invention has good hole extracting performance.

The applicant states that the present invention is illustrated by the above examples to show the hole transport material, the preparation method and the application thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by the above examples. It will be apparent to those skilled in the art that any modifications to the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific forms, etc., are within the scope and disclosure of the present invention.

Claims

1. A hole interface material, wherein the hole interface material has a structure according to formula I:

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, fluoro or methyl;

y is selected from oxygen or sulfur.

2. The hole interface material of claim 1, wherein the donor unit group D is selected from any one of the donor unit groups represented by 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 dashed line on the N represents the position of attachment of the group.

3. The hole interface material according to any one of claims 1 to 2, wherein the hole interface material is selected from any one of the following compounds:

。

4. a method of preparing the hole interface material of any one of claims 1-3, comprising the steps of:

；

；

wherein the D group is a donor unit group;

A ₁ 、A ₂ 、A ₃ each independently selected from carbon or nitrogen;

E ₁ 、E ₂ each independently selected from hydrogen, fluoro or methyl;

y is selected from oxygen or sulfur.

5. The method according to claim 4, wherein the catalyst for the coupling reaction in step (1) is a palladium catalyst;

preferably, the palladium catalyst is Pd (PPh) ₃ ) ₄ ；

Preferably, the molar mass ratio of the compound A to the compound B in the step (1) is 1 (2.4-3.0);

preferably, the solvent for the coupling reaction in step (1) comprises any one or a combination of at least two of tetrahydrofuran, water or toluene;

preferably, the temperature of the coupling reaction in step (1) is 100-120 ℃;

preferably, the coupling reaction time of the step (1) is 20-28 h;

preferably, the solvent for the hydrolysis reaction in step (2) is methanol or tetrahydrofuran;

preferably, the temperature of the hydrolysis reaction in the step (2) is 30-60 ℃;

preferably, the hydrolysis reaction time of the step (2) is 10-20 h;

；

(B) reacting the compound shown in the formula III with pinacol diboron to obtain a compound A, wherein the reaction formula is as follows:

；

preferably, the catalyst for the coupling reaction of step (a) is a palladium catalyst;

preferably, the palladium catalyst is Pd ₂ (dba) ₃ ；

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 temperature of the coupling reaction in step (A) is 100-120 ℃;

preferably, the coupling reaction time of the step (A) is 20-28 h;

preferably, the catalyst for the reaction of step (B) is a palladium catalyst;

preferably, the palladium catalyst is Pd (dppf) Cl ₂ ；

Preferably, the solvent for the reaction of step (B) is 1, 4-dioxane;

preferably, the temperature of the coupling reaction in step (B) is 100-120 ℃;

preferably, the reaction time of step (B) is 20-28 h.

6. Use of a hole interface material as claimed in any one of claims 1 to 3 in the preparation of a solar cell material;

preferably, the solar cell is a perovskite solar cell.

7. A hole interface layer comprising the hole interface material according to any one of claims 1 to 3.

8. A perovskite solar cell, wherein the perovskite solar cell comprises the hole interfacial layer of claim 7.

9. The perovskite solar cell according to claim 8, comprising in sequence from top to bottom: an anode electrode layer, the hole interface layer of claim 7, a perovskite active layer, an electron transport layer and a cathode electrode layer;

preferably, the anode electrode layer is ITO conductive glass;

preferably, the thickness of the anode electrode layer is 150-180 nm;

preferably, the thickness of the hole interface layer is 1-10 nm;

preferably, the thickness of the perovskite active layer is 400-600 nm;

preferably, the electron transport layer is a PCB-modified carbon 60 electron transport layer;

preferably, the thickness of the electron transport layer is 20-30 nm;

preferably, the cathode electrode is a silver electrode;

preferably, the thickness of the cathode electrode is 100-150 nm.