1. A hole transport material containing an isoindigo compound, characterized in that: the hole transport material has a structure shown as a formula I, and two ends of the hole transport material are connected and respectively connected with an amino derivative:

r is selected from alkyl of less than C31, acyl of less than C31, aryl of less than C18 and heteroaryl of less than C18;

AR is selected fromOne of (1);

Y₁、Y₂each independently selected from hydrogen, deuterium, tritium, cyano, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, L¹NAr¹Ar²、L²NAr³Ar⁴One of (1);

L¹，L²each independently selected from a single bond, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; ar (Ar)¹～Ar⁴Each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; ar (Ar)¹、Ar²、Ar³、Ar⁴Are not linked to each other, or Ar¹And Ar²、Ar³And Ar⁴Two by two paired warp sheetsA bond, -O-, -S-, -C (CH)₃)₂-，-C(C₆H₅)₂-linking to larger conjugated units; m and n are respectively and independently selected from 0, 1 and 2.

2. The hole transport material containing an isoindigo compound according to claim 1, wherein: the alkyl, the substituted alkenyl, the substituted alkoxy, the substituted aryl and the substituted heteroaryl are respectively and independently selected from deuterium, halogen, cyano-unsubstituted or R ' substituted C1-C4 straight chain or straight chain alkyl, unsubstituted or R ' substituted C6-C18 aryl, unsubstituted or R ' substituted C3-C30 heteroaryl and C6-C30 arylamine; r is selected from one or more of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C4 alkyl, C6-C12 aryl, C3-C12 heteroaryl, and the halogen is selected from fluorine, chlorine, bromine or iodine.

3. The hole transport material containing an isoindigo compound according to claim 1, wherein: ar is selected from any one of the following groups:

wherein the dotted line represents the attachment site of the group;

Y¹¹、Y¹²、Y¹³、Y¹⁴、Y¹⁵、Y¹⁶、Y¹⁷、Y¹⁸、Y¹⁹、Y¹¹⁰、Y¹¹¹、Y¹¹²each independently selected from N or C-R^Y；T¹Selected from O, S, N-R^T1、CR^T2R^T3、SiR^T2R^T3；R^Y、R^T1、R^T2、R^T3Each independently selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C4 linear or branched alkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C3-C18 heteroaryl, and C6-C18 arylamine; substituent R^YAt least not connected or adjacent to each otherThe 2 substituents are linked by chemical bonds to form a ring.

4. The hole transport material containing an isoindigo compound according to claim 1, wherein: the Ar is selected from any one of the following groups, or any one of the following groups substituted by substituent groups:

the substituent is selected from deuterium, fluorine, chlorine, bromine, iodine, cyano, unsubstituted or R ' substituted C1-C4 straight chain or branched chain alkyl, unsubstituted or R ' substituted C6-C18 aryl, unsubstituted or R ' substituted C3-C18 heteroaryl, and C6-C18 arylamine; r' is selected from deuterium, fluoro, chloro, bromo, iodo and cyano, said L¹、L²Each independently selected from the group consisting of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted pyridylene group, and a substituted or unsubstituted fluorenyl group; the substituted substituent is selected from deuterium, fluorine, chlorine, bromine, iodine, cyano, C1-C4 straight chain or branched chain alkyl.

5. The hole transport material containing an isoindigo compound according to claim 1, wherein: the hole transport material includes any one of the following compounds, but is not limited to all of the structures listed.

R is selected from alkyl of less than C31, acyl of less than C31, aryl of less than C18 and heteroaryl of less than C18.

6. A method for preparing a hole transport material containing isoindigo compound is characterized in that: the intermediate F-1 and the intermediate F-2 are subjected to coupling reaction to obtain an intermediate F-3, the intermediate F-3 is subjected to alkylation reaction to obtain an intermediate F-4, the intermediate F-4 is subjected to C-C coupling reaction or C-N coupling reaction to obtain F-5, and the F-5 is the hole transport material shown in the formula I.

Wherein: z, L each independently represents one of chlorine, bromine or iodine; m and n are respectively and independently selected from 0, 1 and 2.

7. The application of a hole transport material containing isoindigo compound is characterized in that: the hole transport material is applied to the preparation of solar cell materials, and the solar cell is a perovskite solar cell.

8. The hole transport material containing an isoindigo compound according to claim 7, wherein: the perovskite solar cell comprises the following components in sequence from top to bottom: an anode electrode layer, a hole transport layer, 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 nm; the thickness of the hole transport layer is 1-10 nm; the thickness of the perovskite active layer is 400-600 nm; the electron transmission layer is a PCB modified carbon 60 electron transmission layer; the thickness of the electron transmission layer is 20-30 nm; the cathode electrode is a silver electrode; the thickness of the cathode electrode is 100-150 nm.

Background

As Perovskite Solar Cells (PSCs) have been developed to date, they have attracted much attention in solar cells and other photoelectric fields due to their advantages of high extinction coefficient, suitably adjustable band gap, long charge diffusion range, excellent bipolar carrier transport property, wide spectral absorption range, simple preparation process, mild preparation conditions, etc. Since 2009, the Miyasaka group introduced methylamine lead iodine (MAPbI3) as a light absorbing material into a dye-sensitized solar cell for the first time, achieving an energy conversion efficiency (PCE) of 3.8%.

The highest reported efficiency of perovskite solar cells today has reached 25.2%, comparable to that of polycrystalline silicon thin film cells, and although perovskite materials can conduct holes themselves, their efficiency is relatively low. In high performance perovskite solar cells, Hole Transport Materials (HTM) play a key role in the extraction and transport of holes in the perovskite light absorbing layer. The organic micromolecule hole transport material has the advantages of low-temperature solution processing, determined molecular structure, easy cutting of chemical structure, high hole mobility and the like. Therefore, the development of novel small molecule hole transport materials is of great significance.

Disclosure of Invention

The invention aims to solve the problems in the prior art and provides a hole transport material containing isoindigo compound, and a preparation method and application thereof.

The purpose of the invention is realized by the following technical scheme: a hole transport material containing isoindigo compound has a structure shown as formula I, and two ends of the hole transport material are connected and respectively connected with an amino derivative:

r is selected from alkyl of less than C31, acyl of less than C31, aryl of less than C18 and heteroaryl of less than C18;

AR is selected fromOne of (1);

Y₁、Y₂each independently selected from hydrogen, deuterium, tritium, cyano, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, L¹NAr¹Ar²、L²NAr³Ar⁴One of (1);

L¹，L²each independently selected from a single bond, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; ar (Ar)¹～Ar⁴Each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; ar (Ar)¹、Ar²、Ar³、Ar⁴Are not linked to each other, or Ar¹And Ar²、Ar³And Ar⁴Pairwise by a single bond, -O-, -S-, -C (CH)₃)₂-，-C(C₆H₅)₂-linking to larger conjugated units; m and n are respectively and independently selected from 0, 1 and 2.

Preferably, the substituted alkyl, substituted alkenyl, substituted alkoxy, substituted aryl, substituted heteroaryl are each independently selected from deuterium, halogen, C1-C4 straight or linear alkyl unsubstituted with cyano or substituted with R ', C6-C18 aryl unsubstituted or substituted with R ', C3-C30 heteroaryl unsubstituted or substituted with R ', C6-C30 arylamine. R' is independently selected from one or more of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C4 alkyl, C6-C12 aryl, C3-C12 heteroaryl, and the halogen is selected from fluorine, chlorine, bromine or iodine.

Preferably, Ar is selected from any one of the following groups:

wherein the dotted line represents the attachment site of the group;

Y¹¹、Y¹²、Y¹³、Y¹⁴、Y¹⁵、Y¹⁶、Y¹⁷、Y¹⁸、Y¹⁹、Y¹¹⁰、Y¹¹¹、Y¹¹²each independently selected from N or C-R^Y；T¹Selected from O, S, N-R^T1、CR^T2R^T3、SiR^T2R^T3；R^Y、R^T1、R^T2、R^T3Each independently selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C4 linear or branched alkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C3-C18 heteroaryl, and C6-C18 arylamine; substituent R^YAt least 2 substituents which are not linked or adjacent to each other are linked by a chemical bond to form a ring.

Preferably, the Ar is selected from any one of the following groups, or any one of the following groups substituted with a substituent group:

the substituent is selected from deuterium, fluorine, chlorine, bromine, iodine, cyano, unsubstituted or R ' substituted C1-C4 straight chain or branched chain alkyl, unsubstituted or R ' substituted C6-C18 aryl, unsubstituted or R ' substituted C3-C18 heteroaryl, and C6-C18 arylamine; r' is selected from deuterium, fluoro, chloro, bromo, iodo and cyano, said L¹、L²Each independently selected from the group consisting of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted pyridylene group, and a substituted or unsubstituted fluorenyl group; the substituted substituent is selected from deuterium, fluorine, chlorine, bromine, iodine, cyano, C1-C4 straight chain or branched chain alkyl.

Preferably, the hole transport material comprises any one of the following compounds, but is not limited to all of the structures listed.

R is selected from alkyl of less than C31, acyl of less than C31, aryl of less than C18 and heteroaryl of less than C18.

The invention also discloses a preparation method of the hole transport material containing the isoindigo compound, wherein the intermediate F-1 and the intermediate F-2 are subjected to coupling reaction to obtain an intermediate F-3, the intermediate F-3 is subjected to alkylation reaction to obtain an intermediate F-4, the intermediate F-4 is subjected to C-C coupling reaction or C-N coupling reaction to obtain F-5, and the F-5 is the hole transport material shown in the formula I.

Wherein: z, L each independently represents one of chlorine, bromine or iodine; m and n are respectively and independently selected from 0, 1 and 2.

The invention also discloses an application of the hole transport material containing the isoindigo compound, wherein the hole transport material is applied to the preparation of solar cell materials, and the solar cell is a perovskite solar cell.

Preferably, the perovskite solar cell comprises, in order from top to bottom: an anode electrode layer, a hole transport layer, 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 nm; the thickness of the hole transport layer is 1-10 nm; the thickness of the perovskite active layer is 400-600 nm; the electron transmission layer is a PCB modified carbon 60 electron transmission layer; the thickness of the electron transmission layer is 20-30 nm; the cathode electrode is a silver electrode; the thickness of the cathode electrode is 100-150 nm.

Compared with the prior art, the invention adopting the technical scheme has the following technical effects: the hole transport material takes a compound containing isoindigo as a core, alkyl chains are introduced into the core to improve solubility, and different donor groups are introduced to regulate energy level and improve hole transport capacity. The synthesized hole transport material has low cost and good hole transport capacity, and has high application value in the field of solar cells. The hole transport material has good hole transport performance and good solubility, and is applied to perovskite solar cells as a hole transport layer, so that the photoelectric conversion efficiency of the solar cells is improved. The material has the advantages of simple synthesis, high hole mobility, high electrical conductivity, high thermal stability, high chemical stability and the like, and has high photoelectric conversion efficiency when being applied to perovskite solar cells, so that the hole transport material containing the isoindigo compound has a good application prospect.

Drawings

FIG. 1 is a diagram showing an ultraviolet absorption spectrum of a hole transporting material solution containing an isoindigo compound according to the present invention.

FIG. 2 is a diagram showing an ultraviolet absorption spectrum of a hole transporting material solution containing an isoindigo compound according to the present invention.

Fig. 3 is a structural view of the perovskite solar cell of the present invention.

Detailed Description

Objects, advantages and features of the present invention will be illustrated and explained by the following non-limiting description of preferred embodiments. The embodiments are merely exemplary for applying the technical solutions of the present invention, and any technical solution formed by replacing or converting the equivalent thereof falls within the scope of the present invention claimed.

The invention discloses a hole transport material containing isoindigo compound and a preparation method and application thereof, wherein the hole transport material has a structure shown as a formula I, and two ends of the hole transport material are respectively connected with an amino derivative:

r is selected from alkyl of less than C31, acyl of less than C31, aryl of less than C18 and heteroaryl of less than C18;

AR is selected fromOne kind of (1).

Y₁、Y₂Each independently selected from hydrogen, deuterium, tritium, cyano, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, L¹NAr¹Ar²、L²NAr³Ar⁴One kind of (1). L is¹，L²Each independently selected from a single bond, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; ar (Ar)¹～Ar⁴Each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; ar (Ar)¹、Ar²、Ar³、Ar⁴Are not linked to each other, or Ar¹And Ar²、Ar³And Ar⁴Pairwise by a single bond, -O-, -S-, -C (CH)₃)₂-，-C(C₆H₅)₂-linking to larger conjugated units; m and n are respectively and independently selected from 0, 1 and 2.

The substituted straight chain or branched alkyl, substituted alkylene, substituted alkoxy, substituted aryloxy, substituted aryl and substituted heteroaryl are respectively and independently selected from deuterium, halogen, cyano-unsubstituted or R ' substituted C1-C4 straight chain or straight chain alkyl, unsubstituted or R ' substituted C6-C18 aryl, unsubstituted or R ' substituted C3-C30 heteroaryl and C6-C30 arylamine. R' is independently selected from one or more of hydrogen, deuterium, halogen and cyano, and is substituted or unsubstituted C1-C4 alkyl, C6-C12 aryl and C3-C12 heteroaryl. The halogen is selected from fluorine, chlorine, bromine or iodine.

Ar is selected from any one of the following groups:

wherein the dotted line represents the attachment site of the group; y is¹¹、Y¹²、Y¹³、Y¹⁴、Y¹⁵、Y¹⁶、Y¹⁷、Y¹⁸、Y¹⁹、Y¹¹⁰、Y¹¹¹、Y¹¹²Each independently selected from N or C-R^Y；T¹Selected from O, S, N-R^T1、CR^T2R^T3、SiR^T2R^T3；R^Y、R^T1、R^T2、R^T3Each independently selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C4 linear or branched alkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted C3-C18 heteroaryl, and C6-C18 arylamine; substituent R^YAt least 2 substituents which are not linked or adjacent to each other are linked by a chemical bond to form a ring.

The Ar is selected from any one of the following groups, or any one of the following groups substituted by substituent groups:

the substituent is selected from deuterium, fluorine, chlorine, bromine, iodine, cyano, unsubstituted or R ' substituted C1-C4 straight chain or branched chain alkyl, unsubstituted or R ' substituted C6-C18 aryl, unsubstituted or R ' substituted C3-C18 heteroaryl, and C6-C18 arylamine; r' is selected from deuterium, fluoro, chloro, bromo, iodo and cyano.

The hole transport material includes any one of the following 144 compounds, but is not limited to all of the structures listed below:

r is selected from alkyl of less than C31, acyl of less than C31, aryl of less than C18 and heteroaryl of less than C18.

The invention also discloses a preparation method of the hole transport material containing the isoindigo compound, which comprises the following steps of carrying out coupling reaction on the intermediate F-1 and the intermediate F-2 to obtain an intermediate F-3, carrying out alkylation reaction on the intermediate F-3 to obtain an intermediate F-4, carrying out C-C coupling reaction or C-N coupling reaction on the intermediate F-4 to obtain F-5, wherein the F-5 is the hole transport material shown in the formula I.

Wherein: z, L each independently represents one of chlorine, bromine or iodine; m and n are respectively and independently selected from 0, 1 and 2.

The invention also discloses an application of the isoindigo compound-containing hole transport material in preparation of a solar cell material, wherein the solar cell is a perovskite solar cell.

The perovskite solar cell comprises a hole transport layer, and the perovskite solar cell comprises the following components in sequence from top to bottom: an anode electrode layer, a hole transport layer, a perovskite active layer, an electron transport layer and a cathode electrode layer. In the technical scheme, the anode electrode layer is made of ITO conductive glass. The thickness of the anode electrode layer is 150-180nm, such as 150nm, 160nm, 170nm, 180 nm. The thickness of the hole transport layer is 1 to 10nm, and may be, for example, 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, or 10 nm. The thickness of the perovskite active layer is 400-600nm, and can be 400nm, 420nm, 440nm, 460nm, 480nm, 500nm, 520nm, 540nm, 560nm, 580nm and 600 nm. The electron transmission layer is a PCB modified carbon 60 electron transmission layer. The thickness of the electron transport layer is 20 to 30nm, and may be, for example, 20nm, 22nm, 24nm, 26nm, 28nm, or 30 nm. The cathode electrode is a silver electrode. The thickness of the cathode electrode is 100-150nm, and can be, for example, 100nm, 110nm, 120nm, 130nm, 140nm, 150 nm.

The invention also provides a hole transport layer which comprises the hole transport material.

Unless otherwise indicated, reagents and materials used in the following examples are commercially available

Example 1:

the present embodiment provides a structure shown in the following formula M1:

synthetic route of hole transport material M1:

synthesis of Compound 1: 5, 6-dibromoindol-2-one (3g, 10.3mmol), 5, 6-dibromoisatin (3.14g, 10.3mmol), p-toluenesulfonic acid monohydrate (0.29g, 1.5mmol) were placed in a two-necked flask, 20mL of glacial acetic acid was added, after reaction at 115 ℃ for 20 hours, cooling to room temperature was performed, and the reaction mixture was filtered and washed with methanol to give 3.4g of crude compound 1 in 60% yield.

Synthesis of Compound 2: putting the compound 1(3g, 5.4mmol), 1-bromooctane (2.5g, 13mmol) and anhydrous potassium carbonate (3.7g, 27mmol) in a double-mouth bottle, pumping nitrogen for three times, adding 30mL of tetrahydrofuran, reacting under the protection of nitrogen, reacting at 70 ℃ for 10 hours, cooling the reaction system to room temperature, extracting with water/dichloromethane, drying an organic layer with anhydrous sodium sulfate, spinning out the solvent, and performing column chromatography on a crude product to obtain the compound 2, wherein the mass of the compound 2 is 3.3g, and the yield is 76%.

Synthesis of Compound 3: 4, 4' -dimethoxydiphenylamine (5g, 21.8mmol), p-bromoiodobenzene (6.5g, 22.9mmol) and Pd₂(dba)₃(200mg), dppf (110mg), potassium tert-butoxide (4.9g, 43.6mmol), in a two-necked flask; after nitrogen is pumped and exchanged for three times, 40mL of anhydrous toluene is added; the reaction is carried out under the protection of nitrogen; after 8 hours of reaction at 105 ℃, the reaction is cooled to room temperature, water/dichloromethane extraction is carried out, the organic layer is dried by anhydrous sodium sulfate, the solvent is spun out, and the crude product is subjected to column chromatography to obtain the compound 3 with the mass of 5.45g and the yield of 65%.

Synthesis of Compound 4: compound 3(4g, 10.4mmol) was placed in a two-necked flask at-78 ℃ under a nitrogen atmosphere; vacuumizing and ventilating for three times, and adding 40mL of anhydrous tetrahydrofuran; the reaction is carried out under the protection of nitrogen; 2.5mol/L n-butyllithium (4.6mL, 11.4mmol) was added dropwise, and after the mixture was reacted for 2 hours, tributyltin chloride (4.06g, 12.5mmol) was added; heating to 25 ℃, continuing to react for 8 hours, finishing the reaction, extracting with water/petroleum ether, drying the organic layer with anhydrous sodium sulfate, and spinning out the solvent to obtain a crude product of the compound 4, wherein the crude product is directly used for synthesizing M1 without further treatment.

Synthesis of hole transport material M1: placing a crude product of the compound 4 and a compound 2(1g, 13mmol) in a double-mouth bottle, adding 30ml of anhydrous toluene for dissolving, flushing the mixture for 10 minutes by using nitrogen, adding tetrakis (triphenylphosphine) palladium (30mg), reacting under the protection of nitrogen, cooling a reaction system to room temperature after reacting for 18 hours at 110 ℃, adding an ethyl acetate spin-drying solvent, and performing column chromatography on the crude product to obtain a hole transport material M1, wherein the mass of the hole transport material M1 is 1.4g, and the yield of the hole transport material M is 65%.

Example 2:

the present embodiment provides a structure shown in the following formula M2:

synthetic route of hole transport material M2:

synthesis of Compound 1: 5, 6-dibromoindol-2-one (3g, 10.3mmol), 5, 6-dibromoisatin (3.14g, 10.3mmol), p-toluenesulfonic acid monohydrate (0.29g, 1.5mmol) were placed in a two-necked flask, 20mL of glacial acetic acid was added, after reaction at 115 ℃ for 20 hours, cooling to room temperature was performed, and the reaction mixture was filtered and washed with methanol to give 3.4g of crude compound 1 in 60% yield.

Synthesis of Compound 2: putting the compound 1(3g, 5.4mmol), 1-bromooctane (2.5g, 13mmol) and anhydrous potassium carbonate (3.7g, 27mmol) in a double-mouth bottle, pumping nitrogen for three times, adding 30mL of tetrahydrofuran, reacting under the protection of nitrogen, reacting at 70 ℃ for 10 hours, cooling the reaction system to room temperature, extracting with water/dichloromethane, drying an organic layer with anhydrous sodium sulfate, spinning out the solvent, and performing column chromatography on a crude product to obtain the compound 2, wherein the mass of the compound 2 is 3.3g, and the yield is 76%.

Synthesis of Compound 5: 3, 6-dimethoxy-9H-carbazole (5g, 22mmol), p-bromoiodobenzene (6.5g, 23.1mmol), Pd₂(dba)₃(200mg), dppf (110mg), potassium tert-butoxide (4.9g, 43.6mmol), in a two-necked flask; after nitrogen is pumped and exchanged for three times, 40mL of anhydrous toluene is added; the reaction is carried out under the protection of nitrogen; after 8 hours of reaction at 105 ℃, the reaction is cooled to room temperature, water/dichloromethane extraction is carried out, the organic layer is dried by anhydrous sodium sulfate, the solvent is spun off, and the compound 5 is obtained after crude column chromatography, the mass is 6.1g, and the yield is 73%.

Synthesis of Compound 6: compound 5(4g, 10.4mmol) was placed in a two-necked flask at-78 deg.C under nitrogen; vacuumizing and ventilating for three times, and adding 40mL of anhydrous tetrahydrofuran; the reaction is carried out under the protection of nitrogen; 2.5mol/L n-butyllithium (4.6mL, 11.4mmol) was added dropwise, and after the mixture was reacted for 2 hours, tributyltin chloride (4.06g, 12.5mmol) was added; heating to 25 ℃, continuing to react for 8 hours, finishing the reaction, extracting with water/petroleum ether, drying the organic layer with anhydrous sodium sulfate, and spinning out the solvent to obtain a crude product of the compound 6, wherein the crude product is directly used for synthesizing M2 without further treatment.

Synthesis of hole transport material M2: placing the crude product of the compound 6 and the compound 2(1g and 1.3mmol) in a double-mouth bottle, adding 30ml of anhydrous toluene for dissolving, flushing the mixture with nitrogen for 10 minutes, adding tetrakis (triphenylphosphine) palladium (30mg), reacting under the protection of nitrogen, cooling the reaction system to room temperature after reacting at 110 ℃ for 18 hours, adding an ethyl acetate spin-drying solvent, and carrying out column chromatography on the crude product to obtain the hole transport material M2, wherein the mass of the hole transport material M2 is 1.6g, and the yield is 74%.

Example 3:

the present embodiment provides a structure having the following formula M3:

synthetic route of hole transport material M3:

synthesis of Compound 1: 5, 6-dibromoindol-2-one (3g, 10.3mmol), 5, 6-dibromoisatin (3.14g, 10.3mmol), p-toluenesulfonic acid monohydrate (0.29g, 1.5mmol) were placed in a two-necked flask, 20mL of glacial acetic acid was added, after reaction at 115 ℃ for 20 hours, cooling to room temperature was performed, and the reaction mixture was filtered and washed with methanol to give 3.4g of crude compound 1 in 60% yield.

Synthesis of Compound 2: putting the compound 1(3g, 5.4mmol), 1-bromooctane (2.5g, 13mmol) and anhydrous potassium carbonate (3.7g, 27mmol) in a double-mouth bottle, pumping nitrogen for three times, adding 30mL of tetrahydrofuran, reacting under the protection of nitrogen, reacting at 70 ℃ for 10 hours, cooling the reaction system to room temperature, extracting with water/dichloromethane, drying an organic layer with anhydrous sodium sulfate, spinning out the solvent, and performing column chromatography on a crude product to obtain the compound 2, wherein the mass of the compound 2 is 3.3g, and the yield is 76%.

Synthesis of compound 7: 2, 2' -dinaphthylamine (5g, 18.5mmol), p-bromoiodobenzene (6.5g, 19.4mmol), Pd₂(dba)₃(200mg), dppf (110mg), potassium tert-butoxide (5.2g, 46.25mmol), in a two-necked flask; after nitrogen is pumped and exchanged for three times, 40mL of anhydrous toluene is added; the reaction is carried out under the protection of nitrogen; after 8 hours of reaction at 105 ℃, the reaction is cooled to room temperature, water/dichloromethane extraction is carried out, the organic layer is dried by anhydrous sodium sulfate, the solvent is spun off, and the crude product is subjected to column chromatography to obtain the compound 7 with the mass of 5.7g and the yield of 71%.

Synthesis of compound 8: compound 7(4.4g, 10.4mmol) was placed in a two-necked flask at-78 deg.C under nitrogen; vacuumizing and ventilating for three times, and adding 40mL of anhydrous tetrahydrofuran; the reaction is carried out under the protection of nitrogen; 2..5mol/L n-butyllithium (4.6mL, 11.4mmol) was added dropwise, and after the mixture was reacted for 2 hours, tributyltin chloride (4.06g, 12.5mmol) was added; heating to 25 ℃, continuing to react for 8 hours, finishing the reaction, extracting with water/petroleum ether, drying the organic layer with anhydrous sodium sulfate, and spinning out the solvent to obtain a crude product of the compound 8, wherein the crude product is directly used for synthesizing M3 without further treatment.

Synthesis of hole transport material M3: placing the crude product of the compound 8 and the compound 2(1g and 1.3mmol) in a double-mouth bottle, adding 30ml of anhydrous toluene for dissolving, flushing the mixture with nitrogen for 10 minutes, adding tetrakis (triphenylphosphine) palladium (30mg), reacting under the protection of nitrogen, cooling the reaction system to room temperature after reacting at 110 ℃ for 18 hours, adding an ethyl acetate spin-drying solvent, and performing column chromatography on the crude product to obtain the hole transport material M3, wherein the mass of the hole transport material M3 is 1.9g, and the yield is 78%.

Example 4: the present embodiment provides a structure shown in the following formula M4:

synthetic route of hole transport material M4:

synthesis of Compound 1: 5, 6-dibromoindol-2-one (3g, 10.3mmol), 5, 6-dibromoisatin (3.14g, 10.3mmol), p-toluenesulfonic acid monohydrate (0.29g, 1.5mmol) were placed in a two-necked flask, 20mL of glacial acetic acid was added, after reaction at 115 ℃ for 20 hours, cooling to room temperature was performed, the reaction mixture was filtered and washed with methanol to give 3.8g of crude compound 1 in 64% yield.

Synthesis of Compound 2: putting the compound 1(3g, 5.4mmol), 1-bromooctane (2.5g, 13mmol) and anhydrous potassium carbonate (3.7g, 27mmol) in a double-mouth bottle, pumping nitrogen for three times, adding 30mL of tetrahydrofuran, reacting under the protection of nitrogen, reacting at 70 ℃ for 10 hours, cooling the reaction system to room temperature, extracting with water/dichloromethane, drying an organic layer with anhydrous sodium sulfate, spinning off the solvent, and performing column chromatography on a crude product to obtain the compound 2, wherein the mass of the compound 2 is 3.2g, and the yield is 75%.

Synthesis of compound 9: 4, 4' -dimethoxydiphenylamine (5g, 21.8mmol), 2-bromo-5-iodopyridine (6.5g, 22.9mmol) and Pd₂(dba)₃(200mg), dppf (110mg), potassium tert-butoxide (4.9g, 43.6mmol), in a two-necked flask; after nitrogen is pumped and exchanged for three times, 40mL of anhydrous toluene is added; the reaction is carried out under the protection of nitrogen; after 8 hours of reaction at 105 ℃, the reaction is cooled to room temperature, water/dichloromethane extraction is carried out, the organic layer is dried by anhydrous sodium sulfate, the solvent is spun off, and the crude product is subjected to column chromatography to obtain the compound 9 with the mass of 6.3g and the yield of 75%.

Synthesis of compound 10: compound 9(4g, 10.4mmol) was placed in a two-necked flask at-78 ℃ under a nitrogen atmosphere; vacuumizing and ventilating for three times, and adding 40mL of anhydrous tetrahydrofuran; the reaction is carried out under the protection of nitrogen; 2..5mol/L n-butyllithium (4.6mL, 11.4mmol) was added dropwise, and after the mixture was reacted for 2 hours, tributyltin chloride (4.06g, 12.5mmol) was added; heating to 25 ℃, continuing to react for 8 hours, finishing the reaction, extracting with water/petroleum ether, drying the organic layer with anhydrous sodium sulfate, and spinning out the solvent to obtain a crude product of the compound 10, wherein the crude product is directly used for synthesizing M4 without further treatment.

Synthesis of hole transport material M4: placing a crude product of the compound 10 and a compound 2(1g, 13mmol) in a double-mouth bottle, adding 30ml of anhydrous toluene for dissolving, flushing the mixture for 10 minutes by using nitrogen, adding tetrakis (triphenylphosphine) palladium (30mg), reacting under the protection of nitrogen, cooling a reaction system to room temperature after reacting for 18 hours at 110 ℃, adding an ethyl acetate spin-drying solvent, and carrying out column chromatography on the crude product to obtain a hole transport material M4, wherein the mass of the hole transport material M4 is 1.68g, and the yield of the hole transport material M is 76%.

Example 5:

the present embodiment provides a structure shown in the following formula M5:

synthetic route of hole transport material M5:

synthesis of Compound 1: 5, 6-dibromoindol-2-one (3g, 10.3mmol), 5, 6-dibromoisatin (3.14g, 10.3mmol), p-toluenesulfonic acid monohydrate (0.29g, 1.5mmol) were placed in a two-necked flask, 20mL of glacial acetic acid was added, after reaction at 115 ℃ for 20 hours, cooling to room temperature was performed, the reaction mixture was filtered and washed with methanol to give 3.8g of crude compound 1 in 64% yield.

Synthesis of Compound 2: putting the compound 1(3g, 5.4mmol), 1-bromooctane (2.5g, 13mmol) and anhydrous potassium carbonate (3.7g, 27mmol) in a double-mouth bottle, pumping nitrogen for three times, adding 30mL of tetrahydrofuran, reacting under the protection of nitrogen, reacting at 70 ℃ for 10 hours, cooling the reaction system to room temperature, extracting with water/dichloromethane, drying an organic layer with anhydrous sodium sulfate, spinning off the solvent, and performing column chromatography on a crude product to obtain the compound 2, wherein the mass of the compound 2 is 3.2g, and the yield is 75%.

Synthesis of compound 11: 3, 6-dimethoxy-9H-carbazole (5g, 22mmol), 2-bromo-5-iodopyridine (6.5g, 23.1mmol), Pd₂(dba)₃(200mg), dppf (110mg), potassium tert-butoxide (4.9g, 43.6mmol), in a two-necked flask; after nitrogen is pumped and exchanged for three times, 40mL of anhydrous toluene is added; the reaction is carried out under the protection of nitrogen; after 8 hours of reaction at 105 ℃, the reaction is finished and cooled to room temperature, water/dichloromethane extraction is carried out, the organic layer is dried by anhydrous sodium sulfate, the solvent is spun out, and the crude product is subjected to column chromatography to obtain the compound 11 with the mass of 63g and the yield of 75%.

Synthesis of compound 12: compound 11(4g, 10.4mmol) was placed in a two-necked flask at-78 deg.C under nitrogen; vacuumizing and ventilating for three times, and adding 40mL of anhydrous tetrahydrofuran; the reaction is carried out under the protection of nitrogen; 2..5mol/L n-butyllithium (4.6mL, 11.4mmol) was added dropwise, and after the mixture was reacted for 2 hours, tributyltin chloride (4.06g, 12.5mmol) was added; heating to 25 ℃, continuing to react for 8 hours, finishing the reaction, extracting with water/petroleum ether, drying the organic layer with anhydrous sodium sulfate, and spinning out the solvent to obtain a crude product of the compound 12, wherein the crude product is directly used for synthesizing M5 without further treatment.

Synthesis of hole transport material M5: placing the crude product of the compound 12 and the compound 2(1g and 1.3mmol) in a double-mouth bottle, adding 30ml of anhydrous toluene for dissolving, flushing the mixture with nitrogen for 10 minutes, adding tetrakis (triphenylphosphine) palladium (30mg), reacting under the protection of nitrogen, cooling the reaction system to room temperature after reacting at 110 ℃ for 18 hours, adding an ethyl acetate spin-drying solvent, and carrying out column chromatography on the crude product to obtain the hole transport material M5, wherein the mass of the hole transport material M5 is 1.59g, and the yield is 72%.

Example 6:

the present embodiment provides a structure shown in the following formula M6:

synthetic route of hole transport material M6:

synthesis of Compound 1: 5, 6-dibromoindol-2-one (3g, 10.3mmol), 5, 6-dibromoisatin (3.14g, 10.3mmol), p-toluenesulfonic acid monohydrate (0.29g, 1.5mmol) were placed in a two-necked flask, 20mL of glacial acetic acid was added, after reaction at 115 ℃ for 20 hours, cooling to room temperature was performed, the reaction mixture was filtered and washed with methanol to give 3.8g of crude compound 1 in 64% yield.

Synthesis of Compound 2: putting the compound 1(3g, 5.4mmol), 1-bromooctane (2.5g, 13mmol) and anhydrous potassium carbonate (3.7g, 27mmol) in a double-mouth bottle, pumping nitrogen for three times, adding 30mL of tetrahydrofuran, reacting under the protection of nitrogen, reacting at 70 ℃ for 10 hours, cooling the reaction system to room temperature, extracting with water/dichloromethane, drying an organic layer with anhydrous sodium sulfate, spinning off the solvent, and performing column chromatography on a crude product to obtain the compound 2, wherein the mass of the compound 2 is 3.2g, and the yield is 75%.

Synthesis of compound 13: synthesis of Compound 3: 4, 4' -dimethyldiphenylamine (43g, 21.8mmol), p-bromoiodobenzene (6.5g, 22.9mmol) and Pd₂(dba)₃(200mg), dppf (110mg), potassium tert-butoxide (4).9g, 43.6mmol) in a double-mouth bottle; after nitrogen is pumped and exchanged for three times, 40mL of anhydrous toluene is added; the reaction is carried out under the protection of nitrogen; after 8 hours of reaction at 105 ℃, the reaction is cooled to room temperature, water/dichloromethane extraction is carried out, the organic layer is dried by anhydrous sodium sulfate, the solvent is spun off, and the compound 13 is obtained after crude column chromatography, the mass is 5.8g, and the yield is 78%.

Synthesis of compound 14: compound 13(3.66g, 10.4mmol) was placed in a two-necked flask at-78 deg.C under nitrogen; vacuumizing and ventilating for three times, and adding 40mL of anhydrous tetrahydrofuran; the reaction is carried out under the protection of nitrogen; 2..5mol/L n-butyllithium (4.6mL, 11.4mmol) was added dropwise, and after the mixture was reacted for 2 hours, tributyltin chloride (4.06g, 12.5mmol) was added; heating to 25 ℃, continuing to react for 8 hours, finishing the reaction, extracting with water/petroleum ether, drying the organic layer with anhydrous sodium sulfate, and spinning out the solvent to obtain a crude product of the compound 14, wherein the crude product is directly used for synthesizing M6 without further treatment.

Synthesis of hole transport material M6: placing the crude product of the compound 14 and the compound 2(1g and 13mmol) in a double-mouth bottle, adding 30ml of anhydrous toluene for dissolving, flushing the mixture for 10 minutes by using nitrogen, adding tetrakis (triphenylphosphine) palladium (30mg), reacting the mixture at 110 ℃ for 18 hours under the protection of nitrogen, cooling the reaction system to room temperature, adding an ethyl acetate spin-drying solvent, and carrying out column chromatography on the crude product to obtain the hole transport material M6, wherein the mass of the hole transport material M6 is 1.6g, and the yield of the hole transport material M is 79%.

Test example 1: the hole transport material obtained in example 1 was tested for its 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 an ultraviolet absorption spectrum of the hole transport material provided in example 1, in which the abscissa of fig. 1 represents a wavelength and the ordinate represents a normalized absorbance, and it can be seen from fig. 1 that an absorption peak of the hole transport material M1 is 512 nm.

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

FIG. 2 is a graph showing the test of the electrochemical properties of the hole transport material provided in example 1, and the horizontal line in FIG. 2The ordinate is XX and the ordinate is XX, where E (Fc/Fc)⁺The hole transport material of the present invention exhibits a distinct oxide green peak, and the HOMO level of each hole transport material M1 calculated from the oxide green original peak position is-4.98 eV and the LUMO level is-3.61 eV, and fig. 2 illustrates that the hole transport material of the present invention has good hole transport properties.

Application of example 1: the preparation method of the perovskite solar cell comprises the following steps: the ITO glass is used as a substrate material, and is subjected to ultrasonic cleaning by deionized water, acetone and isopropanol respectively, and then dried in an oven overnight. The ITO was UV-treated and transferred to a glove box, and the hole transport materials M2, M4, and M5 provided in examples 2, 4, and 5 were dissolved in chlorobenzene to form solutions, respectively, which were spin-coated on an ITO substrate, followed by annealing at 140 ℃ for 10 minutes. Will PbI₂、PbCl₂FAI (formamidine iodide) and MAI (methylamine iodide) are dissolved in a DMF (dimethyl formamide) and DMSO (dimethyl sulfoxide) mixed solvent, stirring is carried out for 2 hours at 60 ℃, the front body fluid is spin-coated on a hole transport layer, reverse solvent chlorobenzene is dropwise added at the last stage of the spin coating to carry out the spin coating, annealing is carried out for 10 minutes at 100 ℃, then a C60 electron transport layer is evaporated, a BCP (barium copper phosphate) buffer layer is spin-coated, an Ag electrode is evaporated finally, and the finally obtained perovskite solar cell sequentially comprises from top to bottom: the structure of the device is shown in figure 3, wherein the structure comprises an ITO glass anode electrode layer (the thickness is 150nm), a hole transport layer (the thickness is 10nm), a perovskite active layer (the thickness is 500nm), an electron transport layer (the thickness is 30nm) and a cathode electrode layer (the thickness is 120 nm).

AM1.5G intensity (100 mW/cm) using xenon lamp solar simulator in glove box filled with N2²) Three parameters of the prepared solar cell device, namely open-circuit voltage, short-circuit current and fill factor, are tested, and as shown in the following figure, the following figure is a perovskite solar cell device performance list.

The hole transport material takes a compound containing isoindigo as a core, alkyl chains are introduced to the core to improve solubility, and different donor groups are introduced to regulate energy level and improve hole transport capacity. The synthesized hole transport material has low cost and good hole transport capacity, and has high application value in the field of solar cells.

The invention has various embodiments, and all technical solutions formed by adopting equivalent transformation or equivalent transformation are within the protection scope of the invention.