Donor compounds containing multiple side chain substitutions and methods, polymer materials and methods, membrane materials, components, batteries and devices

Abstract

The present invention discloses donor compounds and methods containing multiple side chain substitutions, polymer materials and methods, membrane materials, components, batteries and devices, wherein the donor compound has the following general structural formula: The present invention can obtain donor materials by optimizing the coordination with different electron-withdrawing units, and can obtain polymer donor materials, which have good solution processing properties, and the photoelectric properties, aggregation behavior, molecular orientation, film morphology, charge transfer ability, etc. of the material are easy to control.

Description

Technical Field

[0001] The present invention relates to organic solar energy technology, in particular to a donor compound containing multiple side chain substitutions and a method, a polymer material and a method, a film material, a component, a battery and a device. Background Art

[0002] As an emerging clean energy technology, polymer solar energy conversion devices such as organic solar cells have the advantages of light weight, flexibility, and low-temperature solution processing, and have attracted widespread attention from academia and industry. Among them, the active layer prepared by blending polymer donor materials and small molecule acceptor materials is the core part of polymer solar cells. The donor and acceptor materials in the active layer undertake important tasks such as exciton generation, exciton dissociation, and charge transfer. In recent years, with the continuous development and optimization of high-performance polymer donors and small molecule acceptor materials, the photoelectric conversion efficiency of organic solar cells has made breakthrough progress. The photoelectric conversion efficiency of polymer solar cells based on the blending of polymer donor: small molecule acceptor materials has exceeded 19% (Adv. Mater. 2021, 33, 2102420). However, most of the current high-efficiency devices (over 16%) are based on a few wide bandgap polymers such as PM6 and D18 as donor materials. The lack of high-performance polymer donor materials limits the further development of organic solar cells. Therefore, the development of new and efficient polymer donor materials is of great significance to further improve the photoelectric conversion efficiency of polymer solar cells.

[0003] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention and should not be regarded as an acknowledgment or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art. Summary of the invention

[0004] The object of the present invention is to provide a donor compound and method containing multiple side chain substitutions, a polymer material and method, a membrane material, a component, a battery and a device. The obtained compound can be copolymerized with different electron-withdrawing units according to product requirements to obtain a series of high-performance polymer donor materials. On the one hand, the photoelectric properties, aggregation behavior, molecular orientation, film morphology and final device performance of the target polymer donor material can be effectively modulated by changing the carbon chain length, branching position, substitution position, functional group type and conjugation length on the side chain. On the other hand, by introducing functional groups such as halogen and cyano groups on the side chain of the electron-donating unit, it is expected to form intramolecular non-covalent interactions, thereby achieving the regulation of molecular planarity, thereby changing the charge transfer characteristics of the target polymer donor, and finally achieving the purpose of optimizing device performance. Thus, a series of p-type polymer donor materials are obtained by copolymerizing with different electron-withdrawing units using electron-donating units containing multiple side chain substitutions as building blocks. This type of polymer donor material has good solution processing performance, and the photoelectric properties, aggregation behavior, molecular orientation, film morphology, charge transfer capacity and the like of the material are easy to regulate.

[0005] To achieve the above objectives, the embodiments of the present invention provide a donor compound containing multiple side chain substitutions, which is applied to organic solar materials, and the general structural formula thereof is as follows:

[0006]

[0007] Wherein, R1, R2, and R3 are each independently selected from a hydrogen atom, a halogen atom, a C1-C28 alkyl group, a C1-C28 fluorinated alkyl group, a C1-C28 partially fluorinated alkyl group, a C1-C20 alkoxy group, a C1-C20 alkylthio group, a cyano group, an ester group, and a carbonyl group;

[0008] X is selected from O, S, Se;

[0009] A is selected from

[0010]

[0011] In one or more embodiments of the present invention, the method for preparing a donor compound containing multiple side chain substitutions comprises the following steps:

[0012] A. Preparation of intermediate I based on bromination of benzodithiophene substituted by benzene ring: Bromine substitution of raw material I, wherein raw material I is R1 is selected from: C1-C28 alkyl, C1-C28 alkoxy, C1-C28 alkylthio, C1-C28 fluorinated alkyl;

[0013] B. The preparation of intermediate II based on substitution of thiophene α in benzodithiophene is as follows: under the catalysis of PddppfCl2, thiophene zinc reagent and intermediate I undergo substitution reaction at the α position;

[0014] C. The preparation of intermediate III based on β-substitution of thiophene in benzodithiophene is as follows: under the catalysis of Pd(PPh3)4, a tin reagent containing a side chain substitution and a five-membered heterocyclic ring undergo a substitution reaction with intermediate II at the β-position, wherein the tin reagent containing a side chain substitution and a five-membered heterocyclic ring is R2 and R3 are independently selected from the group consisting of a hydrogen atom, a halogen atom, a C1-C28 alkyl group, a C1-C28 fluorinated alkyl group, a C1-C28 partially fluorinated alkyl group, a C1-C20 alkoxy group, a C1-C20 alkylthio group, a cyano group, an ester group, and a carbonyl group;

[0015] D. Monomer preparation: Under the action of NBS, the intermediate III undergoes bromination reaction at the α position of the thiophene bridge connecting benzodithiophene to obtain an electron-donating unit containing multiple side chain substitutions.

[0016] In one or more embodiments of the present invention, a DA-type polymer donor material containing multiple side chain substitutions is applied to an organic solar material, and its general structural formula is as follows:

[0017] It is obtained by polymerizing the donor compound containing multiple side chain substitutions as mentioned above, wherein n is a positive integer of 10-1000.

[0018] In one or more embodiments of the present invention, the method for preparing a DA-type polymer donor material containing multiple side chain substitutions comprises the following steps:

[0019] A. Preparation of intermediate I based on bromination of benzodithiophene substituted by benzene ring: Bromine substitution of raw material I, wherein raw material I is R1 is selected from: C1-C28 alkyl, C1-C28 alkoxy, C1-C28 alkylthio, C1-C28 fluorinated alkyl;

[0020] B. The preparation of intermediate II based on substitution of thiophene α in benzodithiophene is as follows: under the catalysis of PddppfCl2, thiophene zinc reagent and intermediate I undergo substitution reaction at the α position;

[0021] C. The preparation of intermediate III based on β-substitution of thiophene in benzodithiophene is as follows: under the catalysis of Pd(PPh3)4, a tin reagent containing a side chain substitution and a five-membered heterocyclic ring undergo a substitution reaction with intermediate II at the β-position, wherein the tin reagent containing a side chain substitution and a five-membered heterocyclic ring is R2 and R3 are independently selected from the group consisting of a hydrogen atom, a halogen atom, a C1-C28 alkyl group, a C1-C28 fluorinated alkyl group, a C1-C28 partially fluorinated alkyl group, a C1-C20 alkoxy group, a C1-C20 alkylthio group, a cyano group, an ester group, and a carbonyl group;

[0022] D. Monomer preparation: Under the action of NBS, the intermediate III undergoes bromination reaction at the α position of the thiophene bridge connecting benzodithiophene to obtain a dibrominated electron-donating unit containing multiple side chain substitutions;

[0023] E. Synthesis of polymer donor materials: The monomers are subjected to Stille polymerization reaction with monomers containing ditrimethyltinyl or ditributyltinyl.

[0024] In one or more embodiments of the present invention, the membrane material comprises at least several donor thin layers mainly formed by the aforementioned DA type polymer donor material containing multiple side chain substitutions.

[0025] In one or more embodiments of the present invention, the film material further comprises a substrate, and the donor film is formed at least on a surface of the substrate.

[0026] In one or more embodiments of the present invention, a solar energy component includes a light energy conversion structure, and the light energy conversion structure includes a main body and the aforementioned film material supported on the main body.

[0027] In one or more embodiments of the present invention, a solar cell comprises at least the aforementioned solar cell component and a conductive structure electrically connected to the film material.

[0028] In one or more embodiments of the present invention, the solar energy device at least includes an energy storage and transportation device and a solar energy component as described above and / or a solar cell as described above, and the energy storage and transportation device is used to store and transfer the energy generated by the solar energy component as described above or to store and transfer the electrical energy generated by the solar cell as described above.

[0029] In one or more embodiments of the present invention, the energy is selected from electrical energy, thermal energy, light energy, microwave energy, and mechanical energy.

[0030] In the scheme of the present invention, by utilizing specific donor compounds and polymer materials prepared therefrom, while integrating the advantages of production, processing and molding, it is also possible to achieve efficient conversion of solar energy, a clean energy source, thereby achieving the convenience and flexibility of solar energy utilization and promoting industrialization. For example, solar energy can be converted into electrical energy, thermal energy, etc. according to the specific and application requirements of the construction site, specifically depending on the storage, transportation, transmission and application requirements. The components, devices, etc. of the present invention can all be coordinated with other existing functional components. For example, when used for solar power generation, inverters, transformers, etc. are required to be coordinated, and no additional restrictions are made here for content that is not relevant to the innovation of the present invention.

[0031] Compared with the prior art, the donor compound containing multiple side chain substitutions and methods, polymer materials and methods, membrane materials, components, batteries and devices according to the embodiments of the present invention are

[0032] The electron donating unit of the polymer donor material containing multiple side chain substitutions is a type of structure with a planar rigid conjugated skeleton. Introducing this unit into the polymer main chain can promote the close stacking between polymer molecular chains, thereby giving the material excellent hole transport properties; at the same time, the donor unit contains multiple side chain substitutions, and the synthesized polymer has good solubility, which can meet the needs of solution processing; in addition, by regulating the carbon chain length, branching position, substitution position, functional group type, conjugation length, etc. of the side chain, the photoelectric properties, aggregation behavior, molecular orientation, intermolecular interaction strength, etc. of the target polymer donor material can be effectively modulated; finally, the active layer based on this type of polymer donor can form appropriate phase separation, thereby promoting the efficient dissociation of excitons. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 is a compound 2 according to one embodiment of the present invention 1 HNMR spectrum;

[0034] Figure 2 is a compound 4 according to one embodiment of the present invention 1 HNMR spectrum;

[0035] Figure 3 is a compound 5 according to one embodiment of the present invention 1 HNMR spectrum;

[0036] Figure 4 is a polymer PL4 according to one embodiment of the present invention 1 HNMR spectrum;

[0037] Figure 5 is a polymer PL5 according to one embodiment of the present invention 1 HNMR spectrum;

[0038] Figure 6 is a compound 11 according to one embodiment of the present invention 1 HNMR spectrum;

[0039] Figure 7 is a compound 12 according to one embodiment of the present invention 1 HNMR spectrum. DETAILED DESCRIPTION

[0040] The specific implementation modes of the present invention are described in detail below in conjunction with the accompanying drawings, but it should be understood that the protection scope of the present invention is not limited by the specific implementation modes.

[0041] Unless explicitly stated otherwise, throughout the specification and claims, the term “comprise” or variations such as “include” or “comprising”, etc., will be understood to include the stated elements or components but not to exclude other elements or components.

[0042] The present invention adopts the following method to prepare a donor compound containing multiple side chain substitutions, which is a DA type polymer donor material containing multiple side chain substitutions:

[0043] 1. Preparation of benzodithiophene bromide intermediates based on benzene ring substitution

[0044]

[0045] The benzodithiophene bromide intermediate based on benzene ring substitution can be prepared according to the method in the literature (Natl. Sci. Rev., 2020, 7, 1886-1895), where R1 can be independently selected from C1-C28 alkyl, C1-C28 alkoxy, C1-C28 alkylthio, and C1-C28 fluorinated alkyl.

[0046] 2. Preparation of intermediates based on substitution of thiophene α in benzodithiophene

[0047]

[0048] The thiophene zinc reagent can react with the brominated intermediate of benzodithiophene under the catalysis of PddppfCl2, and the reaction site is at the thiophene α position of benzodithiophene.

[0049] 3. Preparation of intermediates based on β-substitution of thiophene in benzodithiophene

[0050]

[0051] A tin reagent containing a side chain substitution and a five-membered heterocyclic ring can react with bromine at the β position of the thiophene of benzodithiophene under the catalysis of Pd(PPh3)4, wherein X can be selected from O, S, and Se. R2 and R3 can be independently selected from hydrogen atoms, halogen atoms, C1-C28 alkyl groups, C1-C28 fluorinated alkyl groups, C1-C28 partially fluorinated alkyl groups, C1-C20 alkoxy groups, C1-C20 alkylthio groups, cyano groups, ester groups, and carbonyl groups;

[0052] 4. Preparation of polymer monomers containing multiple side chain substitutions

[0053]

[0054] Under the action of NBS, the α-position of the thiophene bridge connecting benzodithiophene can undergo bromination reaction to obtain an electron-donating unit containing multiple side chain substitutions.

[0055] On this basis, further polymerization reaction can be carried out (implementation step 5) to obtain a polymer donor material (i.e., a polymer material obtained by the polymerization reaction of the above monomers):

[0056] 5. Synthesis of polymer donor materials

[0057] The dibrominated monomers containing multiple side-chain substituted electron-donating units can undergo Stille polymerization with monomers containing bistrimethylstannyl or bistributylstannyl.

[0058] The advantages of the scheme of the present invention are explained below by the preparation and application of two polymers of the scheme of the present invention, but it should be made clear that this description does not limit the protection scope of the scheme of the present invention.

[0059] Step 1. Preparation of Compound 2

[0060]

[0061] Under an inert atmosphere, 2-bromothiophene (0.75 g, 4.57 mmol) and 15 mL of anhydrous ether were added to a 50 mL two-necked flask in sequence, and the solution was purged with nitrogen for 5 minutes; then, the system was cooled to -78 °C, and n-butyllithium solution (2.1 mL, 5.03 mmol) was slowly injected, and the temperature was maintained for 1 hour, and then ZnCl2 solution (5.1 mL, 5.03 mmol) was injected into the flask, and the temperature was slowly raised to 0 °C and kept warm for 1 hour; finally, compound 1 (0.5 g, 0.57 mmol) ( The reaction mixture was stirred at 4 ℃ for 2 h. The mixture was stirred at 4 ℃ for 30 min. (synthesized according to the method reported in Natl. Sci. Rev., 2020, 7, 1886-1895) and the catalyst PddppfCl2 (0.042 g, 0.057 mmol) were added to the reaction flask, the temperature was raised to reflux, and the reaction was carried out for 12 hours. After the reaction, the reaction was quenched with saturated aqueous ammonium chloride solution, the organic layer was extracted with ether, the organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure, and then separated and purified by column chromatography (petroleum ether as eluent) to obtain a yellow solid (0.37 g, 73%). 1 H NMR (400MHz, CDCl3): δ7.68-7.63(m,2H),7.55–7.49(m,2H),7.21–7.17(m,2H),4 .10(d,J=6.4Hz,4H),1.68-1.63(m,2H),1.55–1.24(m,32H),1.00–0.89(m,12H).

[0062] Step 2, preparation of compound 4

[0063]

[0064] Synthesis of compound 4: Take a dry 25mL two-necked flask, add compound 3 (0.57g, 1.36mmol) (synthesized according to the method reported in J.Mater.Chem.C, 2016, 4, 3809-3814), compound 2 (0.3g, 0.34mmol) and 10mL toluene, and blow nitrogen gas for 15 minutes. Then, add catalyst Pd(PPh3)4 (0.04g, 0.034mmol) to the bottle, continue blowing nitrogen gas for 5 minutes, heat to reflux, and react for 12 hours. After the reaction is completed, the crude product is extracted with dichloromethane, the organic phase is dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and then separated and purified by column chromatography (dichloromethane: petroleum ether = 1:30 as eluent) to obtain a yellow solid (0.41g, 98%). 1 H NMR (400MHz, CDCl3): δ7.25-7.20(m,4H),6.99-6.94(m,4H),6.81(d,J=3.6Hz,2H),3.67(d,J= 6.3Hz,4H),2.84(d,J=6.6Hz,4H),1.75-1.66(m,2H),1.44–1.17(m,66H),0.99–0.87(m,24H).

[0065] Step 3, preparation of compound 5

[0066]

[0067] Synthesis of compound 5: Take a dry 25mL single-mouth round-bottom flask, add compound 4 (0.1g, 0.082mmol) and 10mL tetrahydrofuran to the flask in sequence, and bubbling nitrogen gas for 15 minutes. Then, the flask is protected from light, and N-bromosuccinimide (0.1g, 0.56mmol) is added, and the reaction is carried out at room temperature for 12 hours. After the reaction is completed, saturated sodium sulfite aqueous solution is added to quench, and dichloromethane is extracted. The organic phase is dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a yellow oil, which is then separated and purified by column chromatography (dichloromethane: petroleum ether = 1:50 as eluent) to obtain a yellow solid (0.08g, 71%). 1 HNMR (400MHz, CDCl3): δ7.02(m,2H),6.96(m,2H),6.93(m,2H),6.83(d,J=3.1Hz,2H),3.66(d,J =5.82Hz,4H),2.87(d,J=6.5Hz,4H),1.78-1.66(m,2H),1.56–1.07(m,66H)1.04–0.76(m,24H).

[0068] Step 4: Preparation of polymer PL4

[0069]

[0070] Synthesis of polymer PL4: Take a dry 25mL two-necked flask, add compound 6 (0.063g, 0.0724mmol) and 9mL toluene to the flask in turn, blow nitrogen gas into the solution for 15 minutes, then add compound 5 (0.1g, 0.0724mmol), catalyst Pd2(dba)3 (0.003g, 0.004mmol) and ligand P(o-tol)3 (0.002g, 0.08mmol) to the flask, continue blowing nitrogen gas for 5 minutes, heat to reflux, and react for 78 hours. After the reaction, the crude product was extracted with methanol, acetone, and n-hexane for 24 hours respectively, and then extracted with dichloromethane and chloroform respectively, concentrated under reduced pressure, dissolved the product with a small amount of chloroform and added methanol to precipitate the solid, and filtered to obtain dark red polymer PL4 (0.111g, 76%). M n =55.1kDa,PDI=2.17.

[0071] Step 5: Preparation of polymer PL5

[0072]

[0073] Synthesis of PL5: The synthetic route of polymer PL5 is similar to that of PL4. After the reaction is completed, the crude product is extracted with methanol, acetone, and n-hexane for 24 hours respectively, and then extracted with dichloromethane, concentrated under reduced pressure, dissolved with a small amount of dichloromethane, and methanol is added to precipitate the solid, which is filtered to obtain a dark red polymer PL5 (yield 71%). n =64.3kDa,PDI=2.41.

[0074] Step 6, Preparation of Compound 9

[0075]

[0076] Under a nitrogen atmosphere, compound 8 (0.66 g, 3.08 mmol) (synthesized according to the method reported in J. Mater. Chem. A, 2019, 7, 2646–2652) and anhydrous tetrahydrofuran (10 mL) were added to a dry 50 mL two-necked flask, and nitrogen was bubbled for 10 minutes. The temperature was then lowered to -78 ° C. LDA solution (1.7 mL, 3.39 mmol) was slowly injected into the flask and kept at this temperature for 1 hour; then, a tetrahydrofuran solution of trimethyltin chloride (0.92 g, 4.62 mmol) was injected into the flask, and the temperature was slowly raised to room temperature overnight. The crude product was extracted with dichloromethane and dried over anhydrous magnesium sulfate, and then directly used in the next reaction.

[0077] Step 7, Preparation of Compound 11

[0078]

[0079] Take a dry 25mL two-necked flask, add compound 10 (0.15g, 0.195mmol), compound 9 (0.54g, 1.17mmol) and 10mL toluene into the flask in sequence, blow nitrogen into the solution for 15 minutes, then add catalyst Pd(PPh3)4 (0.03g, 0.02mmol) into the flask, continue blowing nitrogen for 5 minutes, heat to reflux, and react for 12 hours. After the reaction is completed, the crude product is extracted with dichloromethane, the organic phase is dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and then separated and purified by column chromatography (petroleum ether as eluent) to obtain a yellow solid (0.17g, 85%). 1 H NMR (400MHz, CDCl3): δ7.32-7.29(m,2H),7.26–7.23(m,2H),7.02–6.98(t,2H),6.88–6.84(s,2H),3.76–3. 68(d,J=4.0Hz,4H),2.79–2.75(d,J=6.8Hz,4H),1.65–1.62(m,2H),1.34–1.26(m,34H),0.96–0.90(m,24H).

[0080] Step 8, Preparation of Compound 12

[0081]

[0082] Take a dry 25mL single-mouth round-bottom flask, add compound 11 (0.2g, 0.193mmol) and 20mL tetrahydrofuran to the flask in sequence, and bubbling nitrogen gas for 15 minutes. Then, the flask is protected from light, and N-bromosuccinimide (1.13g, 6.37mmol) is added, and the reaction is carried out at room temperature for 12 hours. After the reaction is completed, saturated sodium sulfite aqueous solution is added to quench, and dichloromethane is extracted. The organic phase is dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain a yellow oil, which is then separated and purified by column chromatography (petroleum ether as eluent) to obtain a yellow solid (0.18g, 78%). 1 H NMR (400MHz, CDCl3): δ7.04–7.02(d,J=3.6Hz,2H),6.96–6.93(d,J=3.6Hz,2H),6.86–6.83(s,2H),3.71–3.66(d,J=4.4Hz ,4H),3.71–3.66(d,J=4.4Hz,4H),2.79–2.74(d,J=6.4Hz,4H),1.65-1.61(m,2H),1.49–1.17(m,34H)1.00–0.74(m,24H).

[0083] Step 9: Preparation of polymer PL6

[0084]

[0085] The synthetic route of polymer PL6 is similar to that of PL4. After the reaction is completed, the crude product is extracted with methanol, acetone, n-hexane, and dichloromethane for 24 hours respectively, and then extracted with chloroform, concentrated under reduced pressure, dissolved with a small amount of chloroform, and methanol is added to precipitate the solid, which is then filtered to obtain a dark red polymer PL6 (yield 62%).

[0086] The DA-type polymer donor material containing multiple side chain substitutions obtained in the above steps 4, 5 and 9 is used to prepare solar cell devices and conduct tests.

[0087] In the embodiments shown below, the small molecule receptor material involved can be Y6 (CAS: 2304444-49-1), whose structural formula is as follows:

[0088]

[0089] It should be noted that the small molecule receptor material here is not limited to the above-mentioned Y6 compound. Other small molecule receptor materials, such as another small molecule receptor material CAS: 2389125-23-7 of Nanjing Zhiyan Technology Co., Ltd., do not affect the implementation of the scheme of the present invention.

[0090] Example 1. Preparation of devices using polymer donor PL4

[0091] The solar cell device adopts an upright device structure:

[0092] Glass substrate / ITO / PEDOT:PSS / photoactive layer / PDIN / Ag. Among them, the ITO layer is attached to the glass substrate. ITO and glass substrate are collectively referred to as ITO glass. The ITO glass is washed with detergent, water, acetone and isopropanol in ultrasound for thirty minutes each. Then it is dried in an oven at 90°C overnight. After the ITO glass is treated with UV ozone for 15 minutes, PEDOT:PSS is spin-coated on the ITO layer and placed in a 140°C oven for 15 minutes, and then quickly transferred to a glove box for standby use. The small molecule receptor Y6 and the polymer donor material PL4 (PL4:Y6) are dissolved in chloroform at a weight ratio of 1:1.4, and 1,8-diiodooctane is added as an additive at a volume ratio of 1%. The total concentration of the solution is 20 mg / mL, and the solution is stirred at 50°C for 4 hours, and then the solution is spin-coated on the PEDOT:PSS film as an active layer with a thickness of about 100 nm. In order to improve the electron injection efficiency, a methanol solution of PDIN (1.5 mg / mL containing 0.2% acetic acid) was spin-coated on the active layer. -5 100nm silver electrode was deposited under Pa conditions, and the device area was 5mm 2 .

[0093] Example 2: Preparation of devices using polymer donor PL5

[0094] Same as Example 1, the only difference is that the active layer is PL5:Y6.

[0095] Example 3: Preparation of devices using polymer donor PL6

[0096] Same as Example 1, the only difference is that the active layer is PL6:Y6.

[0097] The performance of the devices obtained in Examples 1-3 was tested: the devices were tested by using a SS-X50 (EnliTech) solar simulator to simulate AM 1.5G (100 mW / cm 2 ) and measured using a Keithley 2400 digital source meter tester. The parameters of the solar cell devices obtained in Examples 1-3 are summarized in Table 1.

[0098] Table 1. Parameters of solar cell devices prepared based on the donor materials

[0099]

[0100] Table 2. Hole and electron mobility of hybrid films prepared based on the donor materials

[0101]

[0102] The foregoing description of specific exemplary embodiments of the present invention is for the purpose of illustration and demonstration. These descriptions are not intended to limit the present invention to the precise form disclosed, and it is clear that many changes and variations can be made based on the above teachings. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the present invention and its practical application, so that those skilled in the art can realize and utilize various different exemplary embodiments of the present invention and various different selections and changes. The scope of the present invention is intended to be limited by the claims and their equivalents.

Claims

1. A donor compound containing multiple side chain substitutions, used for preparing organic solar energy materials, the general structural formula of which is as follows: in, R1 is selected from C1-C20 alkoxy; R2 and R3 are each independently selected from: hydrogen atom, halogen atom, C1-C28 alkyl; X is selected from S.

2. The method for preparing the donor compound containing multiple side chain substitutions as claimed in claim 1, comprising the following steps: A. Preparation of intermediate I based on bromination of benzodithiophene substituted by benzene ring: Bromine substitution of raw material I, wherein raw material I is R1 is selected from: C1-C28 alkoxy; B. The preparation of intermediate II based on substitution of thiophene α in benzodithiophene is as follows: under the catalysis of PddppfCl2, a substitution reaction occurs between the thiophene zinc reagent and the intermediate I at the α position. The raw materials of the thiophene zinc reagent include n-BuLi, ZnCl2; C. The preparation of intermediate III based on β-substitution of thiophene in benzodithiophene is as follows: under the catalysis of Pd(PPh3)4, a tin reagent containing a side chain substitution and a five-membered heterocyclic ring undergo a substitution reaction with intermediate II at the β-position, wherein the tin reagent containing a side chain substitution and a five-membered heterocyclic ring is R2 and R3 are independently selected from: hydrogen atom, halogen atom, C1-C28 alkyl; X is selected from S; D. Monomer preparation: Under the action of NBS, the intermediate III undergoes bromination reaction at the α position of the thiophene bridge connecting benzodithiophene to obtain a donor compound containing multiple side chain substitutions.

3. A DA-type polymer donor material containing multiple side chain substitutions, applied to organic solar energy materials, and its general structural formula is as follows: It is obtained by Stille polymerization of the donor compound containing multiple side chain substitutions as claimed in claim 1 and the A structure substituted with bistrimethyltin, wherein n is a positive integer of 10-1000, and A is selected from 4. The method for preparing the DA type polymer donor material containing multiple side chain substitutions as claimed in claim 3, comprising the following steps: A. Preparation of intermediate I based on bromination of benzodithiophene substituted by benzene ring: Bromine substitution of raw material I, wherein raw material I is R1 is selected from: C1-C28 alkoxy; B. The preparation of intermediate II based on substitution of thiophene α in benzodithiophene is as follows: under the catalysis of PddppfCl2, thiophene zinc reagent and intermediate I undergo substitution reaction at the α position; C. The preparation of intermediate III based on β-substitution of thiophene in benzodithiophene is as follows: under the catalysis of Pd(PPh3)4, a tin reagent containing a side chain substitution and a five-membered heterocyclic ring undergo a substitution reaction with intermediate II at the β-position, wherein the tin reagent containing a side chain substitution and a five-membered heterocyclic ring is R2 and R3 are independently selected from: hydrogen atom, F, C1-C28 alkyl; X is selected from S; D. Monomer preparation: Under the action of NBS, the intermediate III undergoes bromination reaction at the α position of the thiophene bridge connecting benzodithiophene to obtain a dibrominated donor compound containing multiple side chain substitutions; E. Synthesis of polymer donor material: The monomer of step D is subjected to Stille polymerization reaction with monomer A substituted with ditrimethyltin.

5. A membrane material comprising at least a plurality of donor thin layers formed by using the DA type polymer donor material containing multiple side chain substitutions as claimed in claim 3 as a raw material.

6. The membrane material according to claim 5, characterized in that The invention also comprises a substrate, wherein the donor film is formed at least on a surface of the substrate.

7. A solar energy component, comprising a light energy conversion structure, wherein the light energy conversion structure comprises a main body and a film material as claimed in claim 5 or 6 carried on the main body.

8. A solar cell comprising at least the solar module according to claim 7 and a conductive structure electrically connected to the film material.

9. A solar energy device, comprising at least an energy storage and transportation device and a solar energy component as described in claim 7 and / or a solar cell as described in claim 8, wherein the energy storage and transportation device is used to store and transfer the energy generated by the solar energy component as described in claim 7 or to store and transfer the electrical energy generated by the solar cell as described in claim 8.

10. The solar device according to claim 9, characterized in that: The energy is selected from electrical energy, thermal energy, and light energy.

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