CN114507232A

CN114507232A - Perylene bisimide quaternary ammonium salt solar cell electron transport layer material and preparation and application thereof

Info

Publication number: CN114507232A
Application number: CN202210048119.0A
Authority: CN
Inventors: 方洁; 赵朝委; 夏冬冬; 张月凤; 游胜勇; 李韦伟
Original assignee: Institute of Applied Chemistry Jiangxi Academy of Sciences
Current assignee: Institute of Applied Chemistry Jiangxi Academy of Sciences
Priority date: 2022-01-17
Filing date: 2022-01-17
Publication date: 2022-05-17
Anticipated expiration: 2042-01-17
Also published as: CN114507232B

Abstract

The invention relates to the technical field of organic semiconductor materials, in particular to an electron transport layer material of a perylene bisimide quaternary ammonium salt solar cell, and preparation and application thereof, wherein the structure general formula is shown as formula I:

wherein, the R group is selected from any one of alkyl, aryl, carbonyl and amide. The invention takes perylene imide as a core structure, and the perylene imide is reacted with simple halohydrocarbon to synthesize a quaternary ammonium salt product with good water-soluble property, the visible light absorption range of the perylene imide structure can be well complemented with the active layer of the solar cell, and the perylene imide can be used as a material to improve the LUMO energy level of an electron transmission layer and further improve the open-circuit voltage and the short-circuit voltage of a deviceCurrent density, and finally high photoelectric conversion efficiency is realized; the synthetic method is simple and efficient, good in stability and repeatability, low in cost, universal and easy for large-scale production.

Description

Perylene bisimide quaternary ammonium salt solar cell electron transport layer material and preparation and application thereof

Technical Field

The invention relates to the technical field of organic semiconductor materials, in particular to a perylene bisimide quaternary ammonium salt type solar cell electron transport layer material and preparation and application thereof.

Background

The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.

The organic solar cell has the advantages of low price, light weight, solution-soluble processing and the like, and has great application potential in the fields of intelligent glass, wearable equipment, Internet of things and the like. In recent years, with the continuous enrichment of organic semiconductor materials and the optimization of device processes, the photoelectric conversion efficiency of organic solar cells has broken through 18%. The interface material is used as an important component of the organic solar cell and mainly comprises an electron transport material and a hole transport material, and the main functions of the interface material comprise: 1) optimizing the contact between the light absorption layer and the electrodes and reducing charge injection potential barriers;

2) the selectivity to single charges is improved, and the carrier recombination is reduced; 3) the morphology of the active layer is improved, and the carrier transmission efficiency is improved; 4) the diffusion and mutual reaction between the polymer active layer and the electrodes are inhibited, external water and oxygen are isolated, and the stability of the device is improved; 5) as an optical spacer layer, the reflection or absorption of incident light is regulated. The electron transport layer material is used as a buffer layer between the cathode and the light absorption layer, and needs to have good electron extraction and transport capacity and hole blocking capacity, and plays an important role in improving the efficiency and stability of the organic solar cell.

At present, electron transport layer materials are in a wide variety of types, and can be classified into two major types, i.e., inorganic materials and organic materials. The inorganic electron transport layer material comprises metal or metal salt with low work function, transition metal oxide (such as zinc oxide, titanium oxide, tin oxide, etc.) and doping product (such as aluminum-doped zinc oxide), etc.; the organic electron transport layer material mainly comprises conjugated n-type organic semiconductors (such as fullerene derivatives, perylene bisimide derivatives and the like), polyelectrolytes (polyfluorene electrolytes, polythiophene electrolytes and the like), certain non-conjugated neutral polymers (polyethyleneimine and the like) and the like. Among them, organic materials such as PFNBr and PDINO have become star molecules in electron transport materials of organic solar cells and are commercially available. However, the inventors have found that these materials are cumbersome and expensive in synthesis or procedure; or use hazardous oxidizing agents. Therefore, the development of an electron transport layer material which is simple to synthesize, cheap and easy to obtain and excellent in performance still has important significance, and contributes to the promotion of the commercialization process of the organic solar cell.

Disclosure of Invention

Aiming at the problems in the prior art, the invention aims to provide a perylene bisimide quaternary ammonium salt type solar cell electron transport layer material and preparation and application thereof, in particular to synthesis of a water-alcohol soluble quaternary ammonium salt type organic micromolecule material taking perylene bisimide as a core structure and application thereof in an organic solar cell device, wherein the quaternary ammonium salt type organic micromolecule material can be used as the electron transport layer material to improve the open-circuit voltage and the short-circuit current density of the device and finally realize high photoelectric conversion efficiency; and the synthesis method is simple and efficient, has good stability and repeatability, low cost and universality, and is easy for large-scale production.

In order to achieve the above object, the technical solution of the present invention is as follows:

in the first aspect of the invention, the perylene imide quaternary ammonium salt type solar cell electron transport layer material PDINS is provided, and the structural general formula is shown as formula I:

wherein, the R group is selected from any one of alkyl, aryl, carbonyl and amide.

In a second aspect of the present invention, there is provided a method for preparing a PDINSs as an electron transport layer material for a perylene imide quaternary ammonium salt type solar cell in the first aspect, including the following steps:

1) reacting 3,4,9, 10-perylene tetracarboxylic dianhydride with 3-dimethylaminopropylamine to obtain PDIN, wherein the structure of the PDIN is shown as a formula II;

2) reacting PDIN with bromohydrocarbon to obtain PDINS;

the synthetic reaction formula is shown as follows:

in a third aspect of the invention, the invention provides an application of the material for the electron transport layer of the perylene imide quaternary ammonium salt type solar cell in a solar cell.

The specific embodiment of the invention has the following beneficial effects:

the invention takes perylene bisimide as a core structure, and the perylene bisimide is reacted with simple halogenated hydrocarbon to synthesize a quaternary ammonium salt product with good water-soluble property, thereby providing guarantee for the core application of the product as the electron transport layer material of the solar cell. Meanwhile, the visible light absorption range of the perylene bisimide structure can be well complemented with an active layer of the solar cell, and the perylene bisimide structure can be used as a material to improve the LUMO energy level of an electron transport layer, further improve the open-circuit voltage and the short-circuit current density of a device, and finally realize high photoelectric conversion efficiency.

The synthetic method disclosed by the invention is simple and efficient, good in stability and repeatability, low in cost, universal and easy for large-scale production.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.

FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of PDINS-Et prepared in example 1 of the present invention;

FIG. 2 is an infrared spectrum of PDINS-Et prepared in example 1 of the present invention;

FIG. 3 is a NMR spectrum of PDINS-iso prepared in example 2 of the present invention;

FIG. 4 is an infrared spectrum of PDINS-iso prepared in example 2 of the present invention;

FIG. 5 is a NMR chart of PDINS-TEMPO prepared in example 3 of the present invention;

FIG. 6 is an infrared spectrum of PDINS-TEMPO prepared in example 3 of the present invention;

FIG. 7 shows the energy conversion efficiency of an organic solar cell device in which PDINS-Et prepared in example 1 of the present invention is used as an electron transport layer material when the acceptor material is BTP-4 Cl;

FIG. 8 shows the energy conversion efficiency of an organic solar cell device in which PDINS-Et prepared in example 1 of the present invention is used as an electron transport layer material when the acceptor material is IT 4F;

FIG. 9 is an Atomic Force Microscope (AFM) profile of PDINS-Et prepared in example 1 of the present invention as an electron transport layer spin-coated on an active layer;

FIG. 10 shows the energy conversion efficiency of an organic solar cell device using PDIN-iso prepared in example 2 of the present invention as an electron transport layer material when the acceptor material is BTP-4 Cl;

FIG. 11 shows the energy conversion efficiency of an organic solar cell device using PDIN-iso prepared in example 2 of the present invention as an electron transport layer material when the acceptor material is IT 4F;

FIG. 12 is a topographic map of an atomic force microscope after the PDIN-iso prepared in example 2 of the present invention is spin-coated on an active layer as an electron transport layer;

FIG. 13 shows the energy conversion efficiency of an organic solar cell device using PDINS-TEMPO as an electron transport layer material prepared in example 3 of the present invention when the acceptor material is BTP-4 Cl;

FIG. 14 shows the energy conversion efficiency of an organic solar cell device using PDINS-TEMPO prepared in example 3 of the present invention as an electron transport layer material when the acceptor material is IT 4F;

FIG. 15 is an Atomic Force Microscope (AFM) morphology of PDINS-TEMPO prepared in example 3 of the present invention after being spin-coated on the active layer as an electron transport layer.

Detailed Description

It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.

It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.

In one embodiment of the invention, the perylene imide quaternary ammonium salt type solar cell electron transport layer material PDINS is provided, and the structural general formula of the material PDINS is shown as formula I:

wherein, the R group is selected from any one of alkyl, aryl, carbonyl and amide;

in one or more embodiments, the R group is selected from

Specifically, the structure of the perylene bisimide quaternary ammonium salt solar cell electron transport layer material PDINS is as follows:

according to the invention, perylene bisimide is taken as a core structure, and reacts with simple halogenated hydrocarbon to synthesize a quaternary ammonium salt product with good water-soluble property, the visible light absorption range of the perylene bisimide structure can be well complemented with an active layer of a solar cell, and the perylene bisimide structure can be used as a material to improve the LUMO energy level of an electron transmission layer, further improve the open-circuit voltage and short-circuit current density of a device, and finally realize high photoelectric conversion efficiency.

In an embodiment of the invention, a preparation method of the electron transport layer material PDINSs of the perylene bisimide quaternary ammonium salt solar cell is provided, which comprises the following steps:

2) reacting PDIN with bromohydrocarbon to obtain PDINS;

In one or more embodiments, in step (1), the molar ratio of 3,4,9, 10-perylenetetracarboxylic dianhydride to 3-dimethylaminopropylamine is from 1:4 to 1: 10;

in one or more embodiments, in the step (1), the reaction temperature is 120-140 ℃ and the reaction time is 5-7 h;

in one or more embodiments, in step (1), the reaction solvent is N, N-Dimethylformamide (DMF);

in one or more embodiments, in step (1), after the reaction is completed, the system is cooled to room temperature, excess Tetrahydrofuran (THF) is added to precipitate the product from the solution system, the solid product is collected after washing with tetrahydrofuran for multiple times, and finally, the product PDIN is obtained by vacuum drying.

In one or more embodiments, in step (2), the molar ratio of PDIN to brominated hydrocarbon is from 1:3 to 1: 6;

in one or more embodiments, in step (2), the reaction solvent is a mixed solvent of alcohol and chloroform in a ratio of 1: 1;

preferably, the alcohol is any one of 2,2, 2-trifluoroethanol and methanol;

in one or more embodiments, in the step (2), the reaction temperature is 80-90 ℃ and the reaction time is 23-25 h;

in one or more embodiments, in step (2), after the reaction is completed, the solvent is evaporated to dryness, an appropriate amount of chloroform is added, stirring and suction filtration are performed, chloroform and dichloromethane are used for washing three times respectively, and the product PDINS is obtained after vacuum drying.

The synthetic reaction formula is shown as follows:

in an embodiment of the invention, an application of the electron transport layer material of the perylene bisimide quaternary ammonium salt type solar cell in a solar cell is provided.

The invention will be further explained and illustrated with reference to specific examples.

Example 1

The synthesis method of the perylene bisimide quaternary ammonium salt PDINS-Et is as follows:

the specific synthetic steps are as follows:

(1) 3,4,9, 10-perylenetetracarboxylic dianhydride (2g,5mmol) was weighed into a 100mL dry single-neck round-bottom flask, 40mL of N, N-Dimethylformamide (DMF) was added as a solvent, 3-dimethylaminopropylamine (35mmol) was then weighed into a reaction flask, and the flask was transferred to a constant temperature oil bath at 130 ℃ for reaction for 6 hours. After the reaction is finished, the reaction product is cooled to room temperature, 150mL of Tetrahydrofuran (THF) is added, a dark red solid is precipitated in the system, the suction filtration is carried out, the reaction product is washed three times with the THF (50mLx 3), the solid is collected and placed in a vacuum drying oven to be dried for 12 hours, and the product PDIN is the dark red solid, and the yield is about 90%.

(2) Weighing PDIN (1.12g, 2mmol) in a 100mL round bottom flask, adding 50mL of a mixed solvent (volume ratio is 1:1) of 2,2, 2-trifluoroethanol and chloroform, then weighing bromoethane 2a (8mmol, 6equiv.) in a reaction bottle, transferring the reaction bottle to a constant temperature oil bath at 85 ℃, installing a condenser tube, reacting for 24 hours, evaporating the solvent in a rotary manner after the reaction is finished, adding an appropriate amount of chloroform, stirring for 30 minutes, performing suction filtration, washing for three times by using chloroform and dichloromethane respectively, and drying in vacuum to obtain a product PDINS-Et which is a dark red solid with the yield of about 80%.

The NMR spectrum of PDINS-Et is shown in FIG. 1, and the IR spectrum is shown in FIG. 2.

Example 2

The synthesis method of the perylene bisimide quaternary ammonium salt PDINS-iso is as follows:

the specific synthetic steps are as follows:

(1) 3,4,9, 10-perylenetetracarboxylic dianhydride (2g,5mmol) was weighed into a 100mL dry single-neck round-bottom flask, 40mL of N, N-Dimethylformamide (DMF) was added as a solvent, then 3-dimethylaminopropylamine (20mmol) was weighed into a reaction flask, and the reaction flask was transferred to a constant temperature oil bath at 130 ℃ for reaction for 6 hours. After the reaction is finished, the reaction product is cooled to room temperature, 150mL of Tetrahydrofuran (THF) is added, a dark red solid is precipitated in the system, the suction filtration is carried out, the reaction product is washed three times with the THF (50mLx 3), the solid is collected and placed in a vacuum drying oven to be dried for 12 hours, and the product PDIN is the dark red solid, and the yield is about 85%.

(2) Weighing PDIN (1.12g, 2mmol) in a 100mL round bottom flask, adding 50mL of a mixed solvent of methanol and chloroform (volume ratio is 1:1), then weighing 2-bromo-N-isopropylacetamide 2b (10mmol, 5equiv.) in a reaction bottle, transferring the reaction bottle to a constant-temperature oil bath at 85 ℃, installing a condenser tube, reacting for 24 hours, evaporating the solvent in a rotary manner after the reaction is finished, adding an appropriate amount of chloroform, stirring for 30 minutes, performing suction filtration, washing for three times by using chloroform and dichloromethane respectively, and drying in vacuum to obtain a product PDINS-isop which is a dark red solid with the yield of about 82%.

The hydrogen nuclear magnetic resonance spectrum of PDINS-iso is shown in FIG. 3, and the infrared spectrum is shown in FIG. 4.

Example 3

The synthesis method of the perylene bisimide quaternary ammonium salt PDINS-TEMPO is as follows:

the specific synthetic steps are as follows:

(1) 3,4,9, 10-perylenetetracarboxylic dianhydride (2g,5mmol) was weighed into a 100mL dry single-neck round-bottom flask, 40mL of N, N-Dimethylformamide (DMF) was added as a solvent, then 3-dimethylaminopropylamine (50mmol) was weighed into a reaction flask, and the reaction flask was transferred to a constant temperature oil bath at 130 ℃ for reaction for 6 hours. After the reaction is finished, the reaction product is cooled to room temperature, 150mL of Tetrahydrofuran (THF) is added, a dark red solid is precipitated in the system, the suction filtration is carried out, the reaction product is washed three times with the THF (50mLx 3), the solid is collected and placed in a vacuum drying oven to be dried for 12 hours, and the product PDIN is the dark red solid, and the yield is about 91%.

(2) Weighing PDIN (1.12g, 2mmol) in a 100mL round bottom flask, adding 50mL of a mixed solvent (volume ratio is 1:1) of 2,2, 2-trifluoroethanol and chloroform, then weighing bromo-TEMPO derivative 2c (6mmol, 3equiv.) in a reaction bottle, transferring the reaction bottle to a constant-temperature oil bath at 85 ℃, installing a condenser tube, reacting for 24 hours, evaporating the solvent in a rotary manner to dryness after the reaction is finished, adding an appropriate amount of chloroform, stirring for 30 minutes, performing suction filtration, washing for three times by using chloroform and dichloromethane respectively, and drying in vacuum to obtain a product PDIN-TEMPO which is a dark red solid with the yield of about 75%.

The hydrogen nuclear magnetic resonance spectrum of PDINS-TEMPO is shown in FIG. 5, and the infrared spectrum is shown in FIG. 6.

Example 4

The organic solar cell device with perylene imide quaternary ammonium salt PDINS-Et as the electron transport layer material comprises:

the donor material used in the battery device is PM6, the acceptor materials are BTP-4Cl and IT4F, and the structure is shown in the following figure:

(1) the washed and dried ITO glass substrate was treated with Plasma for 15 minutes, and the aqueous solution of PEODT: PSS was filtered through a water-soluble filter, spin-coated on an ITO substrate at 6000 rpm and annealed at 150 ℃ for 15 minutes to form a uniform thin film. The PM 6: a solution of BTP-4Cl ═ 1:1.2(12mg/mL, PM6 as reference) in chlorobenzene was spin coated uniformly on top of PEDOT: PSS and annealed at 80 ℃ for 10 minutes (thickness about 90 nm), followed by spin coating at 3500 rpm of a solution of PDINS-Et in 2,2, 2-trifluoroethanol (1mg/mL to 3mg/mL) as an electron transport layer and finally evaporation of 100nm Ag electrode. Under the optimum conditions of the device (test area of 0.04 cm)²) The obtained energy conversion efficiency PCE was 17.25%, where the short-circuit current density (Jsc) was 26.16mA · cm^-2The open-circuit voltage (Voc) is 0.840V and the Fill Factor (FF) is 78.52, which proves that the material has potential application value in organic solar cells (as shown in fig. 7).

(2) The washed and dried ITO glass substrate was treated with Plasma for 15 minutes, and after filtering the aqueous solution of PEODT: PSS with a water-soluble filter, it was spin-coated on an ITO substrate at 6000 rpm and annealed at 150 ℃ for 15 minutes to form a uniform thin film. The PM 6: a chlorobenzene solution of IT4F ═ 1:1.2(10mg/mL, PM6 as reference) was uniformly spin-coated on top of PEDOT: PSS and annealed at 100 ℃ for 10 minutes (thickness about 90 nm), then a solution of PDINS-Et in 2,2, 2-trifluoroethanol (1mg/mL to 3mg/mL) was spin-coated at 3500 rpm as an electron transport layer, and finally a 100nm Ag electrode was vapor-deposited. Under the optimum conditions of the device (test area of 0.04 cm)²) The energy conversion efficiency was 13.80%, in which the short-circuit current density (Jsc) was 20.27mA · cm^-2The open-circuit voltage (Voc) is 0.871V and the Fill Factor (FF) is 78.10, which proves that the material has potential application value in organic solar cells (as shown in fig. 8).

Wherein, the topography of the material PDINS-Et as the electron transport layer after being coated on the active layer can be observed by an atomic force microscope, as shown in FIG. 9.

Example 5

(1) The washed and dried ITO glass substrate was treated with Plasma for 15 minutes, and after filtering the aqueous solution of PEODT: PSS with a water-soluble filter, it was spin-coated on an ITO substrate at 6000 rpm and annealed at 150 ℃ for 15 minutes to form a uniform thin film. The PM 6: a solution of BTP-4Cl ═ 1:1.2(12mg/mL, PM6 as reference) in chlorobenzene was uniformly spin-coated on top of PEDOT: PSS and annealed at 80 ℃ for 10 minutes (thickness about 90 nm), followed by spin-coating at 3500 rpm a solution of PDINS-iso in 2,2, 2-trifluoroethanol (1mg/mL to 3mg/mL) as an electron transport layer, and finally evaporation of 100nm Ag electrodes. Under the optimum conditions of the device (test area of 0.04 cm)²) The obtained energy conversion efficiency PCE was 17.46%, wherein the short-circuit current density (Jsc) was 26.21 mA-cm^-2The open-circuit voltage (Voc) is 0.856V and the Filling Factor (FF) is 77.79, which proves that the material has potential application value in the aspect of organic solar cells (as shown in figure 10).

(2) The washed and dried ITO glass substrate was treated with Plasma for 15 minutes, and after filtering the aqueous solution of PEODT: PSS with a water-soluble filter, it was spin-coated on an ITO substrate at 6000 rpm and annealed at 150 ℃ for 15 minutes to form a uniform thin film. The PM 6: a chlorobenzene solution of IT4F ═ 1:1.2(10mg/mL, PM6 as reference) was uniformly spin-coated on top of PEDOT: PSS and annealed at 100 ℃ for 10 minutes (thickness about 90 nm), then a solution of PDINS-

iso

2,2, 2-trifluoroethanol (1mg/mL to 3mg/mL) was spin-coated at 3500 rpm as an electron transport layer, and finally a 100nm Ag electrode was vapor-deposited. Under the optimum conditions of the device (test area of 0.04 cm)²) The obtained energy conversion efficiency PCE was 13.77%, where the short-circuit current density (Jsc) was 20.21mA · cm^-2The open circuit voltage (Voc) is 0.867V and the Fill Factor (FF) is 78.62, which proves the potential application value of the material in organic solar cells (as shown in fig. 11).

The topography of the material PDIN-iso as an electron transport layer spin-coated on the active layer can be observed by an atomic force microscope, as shown in FIG. 12.

Example 6

(1) The washed and dried ITO glass substrate was treated with Plasma for 15 minutes, and after filtering the aqueous solution of PEODT: PSS with a water-soluble filter, it was spin-coated on an ITO substrate at 6000 rpm and annealed at 150 ℃ for 15 minutes to form a uniform thin film. The PM 6: a solution of BTP-4Cl ═ 1:1.2(12mg/mL, PM6 as reference) in chlorobenzene was uniformly spin-coated on top of PEDOT: PSS and annealed at 80 ℃ for 10 minutes (thickness about 90 nm), followed by spin-coating at 3500 rpm a solution of PDINS-TEMPO in 2,2, 2-trifluoroethanol (1mg/mL to 3mg/mL) as an electron transport layer, and finally evaporation of 100nm Ag electrodes. Under the optimum conditions of the device (test area of 0.04 cm)²) The obtained energy conversion efficiency PCE was 17.35%, where the short-circuit current density (Jsc) was 26.85mA · cm^-2The open circuit voltage (Voc) is 0.847V and the Fill Factor (FF) is 76.26, which proves that the material has potential application value in organic solar cells (as shown in fig. 13).

(2) The washed and dried ITO glass substrate was treated with Plasma for 15 minutes, and after filtering the aqueous solution of PEODT: PSS with a water-soluble filter, it was spin-coated on an ITO substrate at 6000 rpm and annealed at 150 ℃ for 15 minutes to form a uniform thin film. The PM 6: a chlorobenzene solution of IT4F ═ 1:1.2(10mg/mL, PM6 as reference) was uniformly spin-coated on top of PEDOT: PSS and annealed at 100 ℃ for 10 minutes (thickness about 90 nm), then a solution of PDINS-TEMPO in 2,2, 2-trifluoroethanol (1mg/mL to 3mg/mL) was spin-coated at 3500 rpm as an electron transport layer, and finally a 100nm Ag electrode was vapor-deposited. Under the optimum conditions of the device (test area of 0.04 cm)²) The obtained energy conversion efficiency PCE was 13.82%, where the short-circuit current density (Jsc) was 20.48mA · cm^-2The open circuit voltage (Voc) is 0.865V and the Fill Factor (FF) is 77.96, which proves the potential application value of the material in organic solar cells (as shown in fig. 14).

Wherein, the topography of the material PDINS-TEMPO as an electron transport layer after being coated on the active layer by spin coating can be observed by an atomic force microscope, as shown in FIG. 15.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. The perylene bisimide quaternary ammonium salt solar cell electron transport layer material is characterized in that the structure general formula is shown as formula I:

2. The perylene imide quaternary ammonium salt type solar cell electron transport layer material of claim 1, wherein the R group is selected from the group consisting of

3. The perylene imide quaternary ammonium salt type solar cell electron transport layer material of claim 1, wherein the structure of the perylene imide quaternary ammonium salt type solar cell electron transport layer material PDINS is as follows:

4. the preparation method of the perylene imide quaternary ammonium salt type solar cell electron transport layer material as defined in any one of claims 1 to 3, which is characterized by comprising the following steps:

2) reacting PDIN with bromohydrocarbon to obtain the compound;

5. the method according to claim 4, wherein in the step (1), the molar ratio of 3,4,9, 10-perylenetetracarboxylic dianhydride to 3-dimethylaminopropylamine is 1:4 to 1: 10;

in the step (1), the reaction temperature is 120-140 ℃ and the reaction time is 5-7 h.

6. The method according to claim 4, wherein in step (1), the reaction solvent in step (1) is N, N-Dimethylformamide (DMF);

or, in the step (1), after the reaction is finished, cooling the system to room temperature, adding excessive tetrahydrofuran to separate out a product from the solution system, washing the product with tetrahydrofuran for multiple times, collecting a solid product, and finally drying the solid product in vacuum to obtain the product PDIN.

7. The method according to claim 4, wherein in the step (2), the molar ratio of PDIN to the brominated hydrocarbon is 1:3 to 1: 6.

8. The method according to claim 4, wherein in the step (2), the reaction solvent is a mixed solvent of alcohol and chloroform in a ratio of 1: 1;

preferably, the alcohol is any one of 2,2, 2-trifluoroethanol and methanol.

9. The preparation method according to claim 4, wherein in the step (2), the reaction temperature is 80-90 ℃ and the reaction time is 23-25 h;

or, in the step (2), after the reaction is finished, evaporating the solvent to dryness, adding a proper amount of chloroform, stirring, carrying out suction filtration, washing with chloroform and dichloromethane for three times respectively, and carrying out vacuum drying to obtain the product PDINS.

10. The use of the perylene imide quaternary ammonium salt type solar cell electron transport layer material according to any one of claims 1 to 3 in solar cells.