CN114507232B

CN114507232B - Perylene imide quaternary ammonium salt type solar cell electron transport layer material and preparation and application thereof

Info

Publication number: CN114507232B
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: 2023-05-09
Anticipated expiration: 2042-01-17
Also published as: CN114507232A

Abstract

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, wherein the structural general formula of the material is shown in formula I:

wherein the R group is selected from any one of alkyl, aryl, carbonyl and amide. According to the invention, perylene imide is taken as a core structure, and is reacted with simple halohydrocarbon to synthesize a quaternary ammonium salt product with good water-alcohol solubility, the visible light absorption range of the perylene imide structure is well complementary with an active layer of a solar cell, the perylene imide can be used as a material to improve the LUMO energy level of an electron transport layer, the open-circuit voltage and the short-circuit current density of a device are further improved, and finally high photoelectric conversion efficiency is realized; the synthesis method is simple and efficient, has good stability and repeatability, low cost and universality, and is easy for large-scale production.

Description

Perylene imide quaternary ammonium salt type 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 disclosure of this background section is only intended to increase the 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 already known to those of ordinary skill in the art.

The organic solar cell has the advantages of low cost, light weight, solution 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 abundance of organic semiconductor materials and 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 is mainly divided into an electron transport material and a hole transport material, and the main functions of the interface material include: 1) Optimizing contact between the light absorption layer and the electrodes, and reducing a charge injection potential barrier;

2) The selectivity to single charges is improved, and the carrier recombination is reduced; 3) The appearance of the active layer is improved, and the carrier transmission efficiency is improved; 4) Inhibiting diffusion and interaction between the polymer active layer and the electrode, isolating external water and oxygen, and improving the stability of the device; 5) As an optical spacer layer, the reflection or absorption of incident light is modulated. 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 capability and hole blocking capability, and plays an important role in improving the efficiency, stability and the like of the organic solar cell.

Up to now, the electron transport layer materials are various, and can be classified into inorganic materials and organic materials. The inorganic electron transport layer material comprises low work function metal or metal salt, transition metal oxide (such as zinc oxide, titanium oxide, tin oxide, etc.), doped product (such as aluminum doped zinc oxide), etc.; the organic electronic transmission layer material mainly comprises conjugated n-type organic semiconductors (such as fullerene derivatives, perylene imide derivatives and the like), polyelectrolytes (polyfluorene electrolytes, polythiophene electrolytes and the like) and certain non-conjugated neutral polymers (polyethyleneimine and the like). Among them, organic materials such as PFNBr and PDINO have become star molecules in the electron transport material of organic solar cells and are commercially available. However, the inventors have found that these materials are expensive during the synthesis process or steps; or dangerous oxidants may be used. Therefore, the development of an electron transport layer material which is simple to synthesize, low in cost, easy to obtain and excellent in performance is still of great significance, and helps to promote the commercialization process of the organic solar cell.

Disclosure of Invention

Aiming at the problems existing in the prior art, the invention aims to provide a perylene imide 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 small molecule material taking perylene imide as a core structure and application thereof in an organic solar cell device, and the material can be used as the electron transport layer material to improve the open-circuit voltage and short-circuit current density of the device and finally realize high photoelectric conversion efficiency; the synthesis method is simple and efficient, good in stability and repeatability, low in cost, universal and easy for large-scale production.

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

in a first aspect of the invention, a perylene bisimide quaternary ammonium salt type solar cell electron transport layer material PDINS is provided, and the structural general formula of the PDINS 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 perylene bisimide quaternary ammonium salt type solar cell electron transport layer material PDINS according to the first aspect, comprising the steps of:

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

2) Reacting PDIN with bromohydrocarbon to obtain PDINS;

the synthesis reaction formula is as follows:

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

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

the invention takes perylene imide as a core structure, and synthesizes the quaternary ammonium salt product with good water-soluble and alcohol-soluble properties through reaction with simple halohydrocarbon, thereby providing guarantee for core application of the quaternary ammonium salt product as a material of an electron transport layer of a solar cell. Meanwhile, the visible light absorption range of the perylene imide structure and the active layer of the solar cell can be well complemented, and as a material, the LUMO energy level of the electron transport layer can be improved, the open-circuit voltage and the short-circuit current density of the device are further improved, and finally high photoelectric conversion efficiency is realized.

The synthesis method is simple and efficient, has good stability and repeatability, low cost and universality, and is easy for large-scale production.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain 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 hydrogen nuclear magnetic resonance 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 hydrogen nuclear magnetic resonance spectrum 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 using PDINS-Et prepared in example 1 of the present invention as the 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 using PDINS-Et prepared in example 1 of the present invention as the electron transport layer material when the acceptor material is IT 4F;

FIG. 9 is an atomic force microscope topography of PDINS-Et prepared in example 1 of the present invention after spin coating as an electron transport layer on an active layer;

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

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

FIG. 12 is a morphology diagram of an atomic force microscope after spin coating the PDIN-ispp prepared in example 2 of the present invention as an electron transport layer on an active layer;

FIG. 13 is a graph showing 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 as the electron transport layer material prepared in example 3 of the present invention, when the acceptor material is IT 4F;

FIG. 15 is an atomic force microscope topography of the PDINS-TEMPO prepared in example 3 of the present invention after spin coating as an electron transport layer on an active layer.

Detailed Description

It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the present application. 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 in accordance with the present application. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.

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

according to the invention, perylene imide is used as a core structure, and a quaternary ammonium salt product with good water-alcohol solubility is synthesized by reacting with simple halohydrocarbon, so that the visible light absorption range of the perylene imide structure is well complementary with an active layer of a solar cell, the perylene imide can be used as a material to improve the LUMO energy level of an electron transport layer, the open-circuit voltage and the short-circuit current density of a device are further improved, and finally high photoelectric conversion efficiency is realized.

In one embodiment of the invention, a preparation method of the perylene bisimide quaternary ammonium salt type solar cell electron transport layer material PDINS 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 step (1), the reaction temperature is 120 to 140 ℃ and the reaction time is 5 to 7 hours;

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, and after washing multiple times with tetrahydrofuran, the solid product is collected and finally dried in vacuo to yield the product PDIN.

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-trifluoroethanol and methanol;

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

in one or more embodiments, in the step (2), after the reaction is finished, evaporating the solvent, adding a proper amount of chloroform, stirring, filtering, washing three times by using chloroform and dichloromethane respectively, and drying in vacuum to obtain the product PDINS.

The synthesis reaction formula is as follows:

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

The invention is further illustrated and described below in connection with specific examples.

Example 1

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

the specific synthesis steps are as follows:

(1) 3,4,9, 10-perylenetetracarboxylic dianhydride (2 g,5 mmol) 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 (35 mmol) 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, cooling to room temperature, adding 150mL of Tetrahydrofuran (THF), precipitating dark red solid in the system, filtering, washing with tetrahydrofuran three times (50 mLx 3), collecting the solid, and drying in a vacuum drying oven for 12h to obtain the product PDIN as dark red solid with the yield of about 90%.

(2) PDIN (1.12 g,2 mmol) was weighed into a 100mL round bottom flask, 50mL of a mixed solvent of 2, 2-trifluoroethanol and chloroform (volume ratio: 1:1) was added, then bromoethane 2a (8 mmol,6 equiv.) was measured and added into a reaction flask, the reaction flask was transferred into a constant temperature oil bath at 85 ℃ and was equipped with a condenser tube, the reaction was carried out for 24 hours, the solvent was evaporated by rotating after the reaction was completed, a proper amount of chloroform was added and stirred for 30 minutes, suction filtration and washing with chloroform and methylene chloride were carried out three times, respectively, and the product PDINS-Et was obtained as a dark red solid after vacuum drying, the yield was about 80%.

The nuclear magnetic resonance hydrogen spectrum of PDINS-Et is shown in figure 1, and the infrared spectrum is shown in figure 2.

Example 2

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

the specific synthesis steps are as follows:

(1) 3,4,9, 10-perylenetetracarboxylic dianhydride (2 g,5 mmol) 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 (20 mmol) 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, cooling to room temperature, adding 150mL of Tetrahydrofuran (THF), precipitating dark red solid in the system, filtering, washing with tetrahydrofuran three times (50 mLx 3), collecting the solid, and drying in a vacuum drying oven for 12h to obtain the product PDIN as dark red solid with the yield of about 85%.

(2) PDIN (1.12 g,2 mmol) was weighed into a 100mL round bottom flask, 50mL of a mixed solvent of methanol and chloroform (volume ratio 1:1) was added, then 2-bromo-N-isopropylacetamide 2b (10 mmol,5 equiv.) was measured and added into a reaction flask, the reaction flask was transferred to a constant temperature oil bath at 85 ℃ and was equipped with a condenser tube, the reaction was carried out for 24 hours, after the reaction was completed, the solvent was evaporated by rotating, a proper amount of chloroform was added and stirred for 30 minutes, suction filtration was carried out, and chloroform and methylene chloride were used for washing three times, respectively, and after vacuum drying, the product PDINS-iso was obtained as a dark red solid with a yield of about 82%.

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

Example 3

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

the specific synthesis steps are as follows:

(1) 3,4,9, 10-perylenetetracarboxylic dianhydride (2 g,5 mmol) 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 (50 mmol) 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, cooling to room temperature, adding 150mL of Tetrahydrofuran (THF), precipitating dark red solid in the system, filtering, washing with tetrahydrofuran three times (50 mLx 3), collecting the solid, and drying in a vacuum drying oven for 12h to obtain the product PDIN as dark red solid with the yield of about 91%.

(2) PDIN (1.12 g,2 mmol) was weighed into a 100mL round bottom flask, 50mL of a mixed solvent of 2, 2-trifluoroethanol and chloroform (volume ratio: 1:1) was added, then brominated TEMPO derivative 2c (6 mmol,3 equiv.) was measured and added into the reaction flask, the reaction flask was transferred into a constant temperature oil bath at 85 ℃ and was equipped with a condenser tube, the reaction was carried out for 24 hours, the solvent was evaporated by rotating after the reaction was completed, a proper amount of chloroform was added and stirred for 30 minutes, suction filtration was carried out, chloroform and methylene chloride were respectively used for washing three times, and the product PDINS-TEMPO was obtained as a dark red solid after vacuum drying, the yield was about 75%.

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

Example 4

Organic solar cell device with perylene imide quaternary ammonium salt PDINS-Et as electron transport layer material:

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

(1) The cleaned and dried ITO glass substrate was treated with Plasma for 15 minutes, and after the PEODT: PSS aqueous solution was filtered with a water-soluble filter head, it was spin-coated on an ITO substrate at 6000 rpm and annealed at 150℃for 15 minutes to form a uniform film. PM6 was then: BTP-4cl=1:1.2%12mg/mL, PM6 as a basis) was spin-coated uniformly on top of PEDOT: PSS and annealed at 80℃for 10 min (thickness about 90 nm), then 3500 rpm spin-coated with PDINS-Et in 2, 2-trifluoroethanol (1 mg/mL-3 mg/mL) as electron transport layer, and finally evaporated to 100nm of Ag electrode. Under the optimal conditions of the device (test area of 0.04 cm) ² ) The energy conversion efficiency pce=17.25% was obtained, wherein the short-circuit current density (Jsc) was 26.16ma·cm ^-2 The open circuit voltage (Voc) was 0.840V and the Fill Factor (FF) was 78.52, demonstrating the potential application of this material in organic solar cells (as shown in fig. 7).

(2) The cleaned and dried ITO glass substrate was treated with Plasma for 15 minutes, and after the PEODT: PSS aqueous solution was filtered with a water-soluble filter head, it was spin-coated on an ITO substrate at 6000 rpm and annealed at 150℃for 15 minutes to form a uniform film. PM6 was then: a solution of IT4 f=1:1.2 (10 mg/mL, PM6 basis) in chlorobenzene was spin-coated uniformly on top of PEDOT: PSS and annealed at 100 ℃ for 10 minutes (thickness around 90 nm), then a solution of 3500 rpm spin-coated PDINS-Et in 2, 2-trifluoroethanol (1 mg/mL to 3 mg/mL) was used as electron transport layer, finally 100nm Ag electrodes were evaporated. Under the optimal 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 20.27 mA.cm ^-2 The 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 the aspect of organic solar cells (as shown in fig. 8).

The morphology of the material PDINS-Et as an electron transport layer after spin-coating on the active layer can be observed by an atomic force microscope, as shown in FIG. 9.

Example 5

(1) The cleaned and dried ITO glass substrate was treated with Plasma for 15 minutes, and after the PEODT: PSS aqueous solution was filtered with a water-soluble filter head, it was spin-coated on an ITO substrate at 6000 rpm and annealed at 150℃for 15 minutes to form a uniform film. PM6 was then: a solution of BTP-4Cl=1:1.2 (12 mg/mL, PM6 basis) in chlorobenzene was spin-coated uniformly on top of PEDOT: PSS and annealed at 80℃for 10 minClock (thickness about 90 nm), then take 3500 r/min spin coating PDINS-iso 2, 2-trifluoro ethanol (1 mg/mL-3 mg/mL) solution as electron transport layer, finally vapor plating 100nm Ag electrode. Under the optimal conditions of the device (test area of 0.04 cm) ² ) The energy conversion efficiency pce=17.46% was obtained, wherein the short-circuit current density (Jsc) was 26.21ma·cm ^-2 The open circuit voltage (Voc) was 0.856V and the Fill Factor (FF) was 77.79, demonstrating the potential application of this material in organic solar cells (as shown in fig. 10).

(2) The cleaned and dried ITO glass substrate was treated with Plasma for 15 minutes, and after the PEODT: PSS aqueous solution was filtered with a water-soluble filter head, it was spin-coated on an ITO substrate at 6000 rpm and annealed at 150℃for 15 minutes to form a uniform film. PM6 was then: a chlorobenzene solution of IT4 f=1:1.2 (10 mg/mL, PM6 basis) was spin-coated uniformly on top of PEDOT: PSS and annealed at 100 ℃ for 10 minutes (thickness around 90 nm), then a solution of 3500 rpm spin-coated PDINS-iso in 2, 2-trifluoroethanol (1 mg/mL to 3 mg/mL) was used as the electron transport layer, finally 100nm Ag electrodes were evaporated. Under the optimal conditions of the device (test area of 0.04 cm) ² ) The energy conversion efficiency pce=13.77% was obtained, wherein the short-circuit current density (Jsc) was 20.21ma·cm ^-2 The open circuit voltage (Voc) was 0.867V and the Fill Factor (FF) was 78.62, proving the potential application value of the material in organic solar cells (as shown in fig. 11).

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

Example 6

(1) The cleaned and dried ITO glass substrate was treated with Plasma for 15 minutes, and after the PEODT: PSS aqueous solution was filtered with a water-soluble filter head, it was spin-coated on an ITO substrate at 6000 rpm and annealed at 150℃for 15 minutes to form a uniform film. PM6 was then: a solution of BTP-4Cl=1:1.2 (12 mg/mL, PM6 basis) in chlorobenzene was spin-coated uniformly on top of PEDOT: PSS and annealed at 80℃for 10 minutes (thickness around 90 nm), then spin-coated at 3500 revolutions per minute of PDINS-TEMPO in 2, 2-trifluoroethyleneAlcohol (1 mg/mL-3 mg/mL) solution is used as an electron transport layer, and finally 100nm Ag electrode is evaporated. Under the optimal conditions of the device (test area of 0.04 cm) ² ) An energy conversion efficiency pce=17.35% was obtained, in which the short-circuit current density (Jsc) was 26.85ma·cm ^-2 The open circuit voltage (Voc) was 0.847V and the Fill Factor (FF) was 76.26, demonstrating the potential application of this material in organic solar cells (as shown in fig. 13).

(2) The cleaned and dried ITO glass substrate was treated with Plasma for 15 minutes, and after the PEODT: PSS aqueous solution was filtered with a water-soluble filter head, it was spin-coated on an ITO substrate at 6000 rpm and annealed at 150℃for 15 minutes to form a uniform film. PM6 was then: a chlorobenzene solution of IT4 f=1:1.2 (10 mg/mL, PM6 basis) was spin-coated uniformly on top of PEDOT: PSS and annealed at 100 ℃ for 10 minutes (thickness around 90 nm), then a solution of 3500 rpm spin-coated PDINS-TEMPO in 2, 2-trifluoroethanol (1 mg/mL to 3 mg/mL) was used as the electron transport layer, and finally 100nm Ag electrodes were evaporated. Under the optimal conditions of the device (test area of 0.04 cm) ² ) The energy conversion efficiency pce=13.82% was obtained, wherein the short-circuit current density (Jsc) was 20.48ma·cm ^-2 The open circuit voltage (Voc) was 0.865V and the Fill Factor (FF) was 77.96, demonstrating the potential application of this material in organic solar cells (as shown in fig. 14).

The morphology of the PDINS-TEMPO material as an electron transport layer spin-coated on the active layer can be observed by an atomic force microscope, as shown in fig. 15.

The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. The preparation method of the perylene bisimide quaternary ammonium salt type solar cell electron transport layer material is characterized in that the perylene bisimide quaternary ammonium salt type solar cell electron transport layer material PDINS has the following structure:

the preparation method comprises the following steps:

2) Reacting PDIN with bromohydrocarbon to obtain the final product;

in the step (1), the molar ratio of the 3,4,9, 10-perylenetetracarboxylic dianhydride to the 3-dimethylaminopropylamine is 1: 4-1: 10;

in the step (1), the reaction solvent is N, N-Dimethylformamide (DMF);

in the step (2), the mole ratio of PDIN to bromohydrocarbon is 1:3-1:6;

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

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

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

2. The process according to claim 1, wherein in the step (1), the reaction temperature is 120 to 140℃and the reaction time is 5 to 7 hours.

3. The process according to claim 1, wherein in step (1), after the reaction, the system is cooled to room temperature, an excess of tetrahydrofuran is added to precipitate the product from the solution system, and the solid product is collected after washing with tetrahydrofuran a plurality of times, and finally the product PDIN is obtained by vacuum drying.

4. The process according to claim 1, wherein in the step (2), the reaction temperature is 80 to 90℃and the reaction time is 23 to 25 hours.

5. Use of the perylene bisimide quaternary ammonium salt type solar cell electron transport layer material as defined in any one of claims 1 to 4 in solar cells.