CN114133376B - Organic solar cell receptor material, preparation method thereof and organic solar cell - Google Patents

Organic solar cell receptor material, preparation method thereof and organic solar cell Download PDF

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CN114133376B
CN114133376B CN202111335192.8A CN202111335192A CN114133376B CN 114133376 B CN114133376 B CN 114133376B CN 202111335192 A CN202111335192 A CN 202111335192A CN 114133376 B CN114133376 B CN 114133376B
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CN114133376A (en
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李翠红
张雅雅
王丽雯
黄浩
高燕
王毅锴
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Beijing Normal University
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Abstract

The application provides an organic solar cell receptor material, a preparation method thereof and an organic solar cell, wherein the organic solar cell receptor material is a compound with the following chemical structural general formula (I), wherein R is as follows 1 One selected from C6-C12 aryl, C6-C12 aryl heteroaryl, C6-C24 straight-chain alkyl, C6-C24 branched-chain alkyl, C6-C24 straight-chain alkoxy and C6-C24 branched-chain alkoxy; r is R 2 One selected from hydrogen atom, C6-C12 aryl hetero group, C6-C24 straight-chain alkyl, C6-C24 branched-chain alkyl, C6-C24 straight-chain alkoxy and C6-C24 branched-chain alkoxy; r is R 1 、R 2 The same or different. The organic solar cell receptor material provided by the application has the advantages of wider absorption range, narrower optical band gap and capability of improving electron mobility.
Figure DDA0003350255470000011

Description

Organic solar cell receptor material, preparation method thereof and organic solar cell
Technical Field
The invention belongs to the technical field of organic solar cell materials, and particularly relates to an organic solar cell receptor material, a preparation method thereof and an organic solar cell.
Background
An organic solar cell (Organic Photovoltaics, abbreviated as OPV) is a novel photovoltaic device which is developed in the 80 th century and is based on an organic semiconductor light absorption material to realize a photoelectric conversion effect. Research shows that compared with the traditional inorganic silicon solar cell, the OPV has the advantages of adjustable molecular structure, low price, light weight, portability, capability of realizing rapid large-area processing of flexible devices by utilizing roll-to-roll and spray printing technologies, and the like, and is widely focused and gradually moves towards industrialization.
The acceptor materials of the organic solar cell are mainly classified into fullerene-based acceptor and non-fullerene-based acceptor materials. Due to some defects of fullerene acceptor materials, such as narrow absorption spectrum, difficult energy level regulation, limited structural flexibility and the like, the further improvement of the efficiency of the organic solar cell is limited. The non-fullerene acceptor material overcomes the defect of the fullerene acceptor material, and is widely studied in the application of organic solar cells. In 2015, the small molecular ITIC of non-fullerene condensed ring acceptor is reported by the zodiac et al for the first time, and researches show that compared with fullerene acceptor materials, the material is absorbed in redshift, the structure is easy to modify, and the battery efficiency is equivalent to the efficiency of devices based on fullerene materials at the moment, so that the material is widely paid attention to by researchers in the industry. In 2019, the small molecule Y6 developed by the Yingping subject group again pushed the non-fullerene fused ring acceptor material to climax. The material mainly adopts an A-D-A type structure, namely, a larger conjugated condensed ring plane structure is used as a D unit, and an electron withdrawing group is used as an A unit for end capping. Numerous studies have been conducted around this structure by researchers, including enlarging the central conjugated backbone, modifying side groups of the central conjugated backbone, modulating electron withdrawing properties of the end groups, and modulating using non-covalent conformational locking strategies.
However, the existing non-fullerene condensed ring electron acceptor material still has the problems of narrow absorption range, wide optical band gap, low mobility and the like.
Disclosure of Invention
In view of the above, the present application provides an organic solar cell acceptor material, a method for preparing the same, and an organic solar cell, wherein the acceptor material can have a wider absorption range, a narrower optical band gap, and can improve electron mobility.
In a first aspect, the present application provides an organic solar cell receptor material, a compound having the following chemical structural formula (I):
Figure GDA0004150269210000021
wherein R is 1 Selected from the group consisting of C6-C12 aryl, C6-C12 aryl heteroaryl, C6-C24 straight chain alkyl, C6-C24 branched chain alkylOne of C6-C24 straight-chain alkoxy and C6-C24 branched-chain alkoxy;
R 2 one selected from hydrogen atom, C6-C12 aryl hetero group, C6-C24 straight-chain alkyl, C6-C24 branched-chain alkyl, C6-C24 straight-chain alkoxy and C6-C24 branched-chain alkoxy; r is R 1 、R 2 The same or different.
With reference to the first aspect, in one possible embodiment, the compound has a structure represented by formula (I-1) or (I-2):
Figure GDA0004150269210000022
with reference to the first aspect, in one possible embodiment, the compound has a structure represented by formula (I-3):
Figure GDA0004150269210000031
With reference to the first aspect, in one possible embodiment, the compound has a structure represented by formula (I-4):
Figure GDA0004150269210000032
in a second aspect, the present application provides a method for preparing an organic solar cell receptor material, comprising the steps of:
(1) Synthesis of Compound 2: dropwise adding tetrahydrofuran solution containing a compound 1 into tetrahydrofuran solution containing NaH under the protection of inert atmosphere, wherein the compound 1 is 6-methoxy-1-indenone, cooling to room temperature after the reaction is finished, and purifying to obtain a compound 2;
(2) Synthesis of Compound 3: mixing the compound 2, the Lawson reagent and toluene, heating and refluxing, cooling to room temperature after the reaction is finished, and purifying to obtain a compound 3;
(3) Synthesis of Compound 4: mixing the compound 3, bromo-n-octane, tetrahydrofuran and potassium tert-butoxide under the protection of inert atmosphere at the temperature of below 0 ℃, and purifying after the reaction is finished to obtain a compound 4;
(4) Synthesis of Compound 5: mixing the compound 4, N-dimethylformamide and N-bromosuccinimide under the protection of inert atmosphere at the temperature of below 0 ℃, and purifying after the reaction is finished to obtain a compound 5;
(5) Synthesis of compound 6 a: under the protection of inert atmosphere, mixing the compound 5, an organotin reagent, toluene and a palladium catalyst, heating and refluxing, and purifying after the reaction is finished to obtain a compound 6a;
(6) Synthesis of compound 7 a: under the protection of ice water bath and inert atmosphere, 6a, N-dimethylformamide, 1, 2-dichloroethane and POCl are taken as the compounds 3 Mixing, heating and refluxing, and purifying after the reaction is finished to obtain a compound 7a;
(7) Synthesis of Compound of formula (I-1): and (3) mixing the compound 7a, 5, 6-difluoro-3- (dicyanomethylene) indigonone, chloroform and a catalyst under the protection of inert atmosphere, refluxing at normal temperature, and purifying after the reaction is finished to obtain the compound shown in the formula (I-1).
In a third aspect, the present application provides a method for preparing an organic solar cell receptor material, comprising the steps of:
(1) Synthesis of Compound 2: dropwise adding tetrahydrofuran solution containing a compound 1 into tetrahydrofuran solution containing NaH under the protection of inert atmosphere, wherein the compound 1 is 6-methoxy-1-indenone, cooling to room temperature after the reaction is finished, and purifying to obtain a compound 2;
(2) Synthesis of Compound 3: mixing the compound 2, lawson reagent and toluene, heating and refluxing, cooling to room temperature after the reaction is finished, and performing reduced pressure distillation and silica gel column chromatography purification on the reaction solution to obtain a compound 3;
(3) Synthesis of Compound 4: mixing the compound 3, bromo-n-octane, tetrahydrofuran and potassium tert-butoxide under the protection of inert atmosphere at the temperature of below 0 ℃, and purifying after the reaction is finished to obtain a compound 4;
(4) Synthesis of Compound 5: mixing the compound 4, N-dimethylformamide and N-bromosuccinimide under the protection of inert atmosphere at the temperature of below 0 ℃, and purifying after the reaction is finished to obtain a compound 5;
(5) Synthesis of compound 6 b: under the protection of inert atmosphere, mixing the compound 5, an organotin reagent, toluene and a palladium catalyst, heating and refluxing, and purifying after the reaction is finished to obtain a compound 6b;
(6) Synthesis of compound 7 b: under the protection of ice water bath and inert atmosphere, 6b, N-dimethylformamide, 1, 2-dichloroethane and POCl 3 Mixing, heating and refluxing, and purifying after the reaction is finished to obtain a compound 7b;
(7) Synthesis of Compound of formula (I-2): and (3) mixing the compound 7b, 5, 6-dichloro-3- (dicyanomethylene) indigoketone, chloroform and a catalyst under the protection of inert atmosphere, refluxing at normal temperature, and purifying after the reaction is finished to obtain the compound shown in the formula (I-2).
In a fourth aspect, the present application provides an organic solar cell comprising an active layer comprising an acceptor material and a donor material, the acceptor material comprising the organic solar cell acceptor material described above.
With reference to the fourth aspect, in a possible embodiment, the donor material is PBDB-T; the mass ratio of the donor material to the acceptor material is 1: (1-1.5).
With reference to the fourth aspect, in a possible embodiment, the annealing temperature of the organic solar cell is 100 ℃ to 140 ℃; preferably, the annealing temperature of the organic solar cell is 120 ℃;
with reference to the fourth aspect, in a possible embodiment, the additive in the active layer is 0.3% to 1.5%; preferably, the additive in the active layer is 0.5% -1%;
with reference to the fourth aspect, in a possible embodiment, the additive includes at least one of 1, 8-diiodooctane, 1, 8-dibromooctane, chloronaphthalene.
In a fifth aspect, the present application provides an electronic device comprising the organic solar cell described above.
According to the organic solar cell receptor material, the preparation method thereof and the organic solar cell, the receptor material utilizes a non-covalent conformation locking strategy, methoxy is introduced into a middle core (IDIDIDT-C8, the structural formula is shown as follows) unit, so that O atoms of the methoxy and S atoms on a thiophene bridge form a 'conformation lock' through S.cndot.O non-covalent interaction to lock the conformation of molecules, the planarity of the molecules is enhanced, meanwhile, the pi conjugated length of a central unit is enlarged, the absorption range of compound molecules shown as the formula I is widened, the optical band gap is narrowed, and the mobility of carriers of the organic solar cell can be further improved.
In addition, the preparation method of the organic solar cell receptor material has the advantages of simple molecular structure, small molecular weight, few and simple preparation steps, cheap and easily available synthetic raw materials, and good visible light absorption range and absorption intensity; greatly reduces the synthesis cost.
Drawings
Fig. 1 is a schematic flow chart of a preparation method of an organic solar cell receptor material according to an embodiment of the present application.
FIG. 2a is a schematic illustration of an organic solar cell acceptor material of formula I-1 provided in example 1 of the present application 1 H NMR spectrum.
FIG. 2b is a schematic illustration of an organic solar cell acceptor material of formula I-1 provided in example 1 of the present application 13 C NMR spectrum.
FIG. 3a is a schematic illustration of an organic solar cell acceptor material of formula I-2 provided in example 2 of the present application 1 H NMR spectrum.
FIG. 3b is a schematic illustration of an organic solar cell acceptor material of formula I-2 provided in example 2 of the present application 13 C NMR spectrum.
FIG. 4a is a graph showing normalized ultraviolet absorption spectra of the acceptor materials of formula I-1 and formula I-2 prepared in example 1 in chloroform solution, respectively.
FIG. 4b is a graph showing normalized ultraviolet absorption spectra of the acceptor materials of formula I-1 and formula I-2 prepared in example 1 in a thin film state, respectively.
FIG. 4c is a graph of electrochemical cyclic voltammograms of two acceptor materials of formulas I-1 and I-2 provided in the examples of the present application.
FIG. 4d is an energy level diagram of two acceptor materials of formula I-1 and formula I-2 provided in the examples of the present application.
FIG. 5a is a graph of current versus voltage for an organic solar cell made from two acceptor materials, formulas I-1 and I-2, provided in an embodiment of the present application.
FIG. 5b is a graph of external quantum efficiency of an organic solar cell made from two acceptor materials of formulas I-1 and I-2 according to an embodiment of the present application.
Detailed Description
The following description is of the preferred embodiments of the present invention, and it should be noted that, for those skilled in the art, it is possible to make several improvements and modifications without departing from the principle of the embodiments of the present invention, and these improvements and modifications are also considered as the protection scope of the embodiments of the present invention.
In a first aspect, the present application provides an organic solar cell receptor material, a compound having the following chemical structural formula (I):
Figure GDA0004150269210000061
wherein R is 1 One selected from C6-C12 aryl, C6-C12 aryl heteroaryl, C6-C24 straight-chain alkyl, C6-C24 branched-chain alkyl, C6-C24 straight-chain alkoxy and C6-C24 branched-chain alkoxy;
R 2 one selected from hydrogen atom, C6-C12 aryl hetero group, C6-C24 straight-chain alkyl, C6-C24 branched-chain alkyl, C6-C24 straight-chain alkoxy and C6-C24 branched-chain alkoxy; r is R 1 、R 2 The same or different.
In the scheme, a non-covalent conformation locking strategy is utilized for the acceptor material, methoxy is introduced into a middle core (IDIDIDT-C8, the structural formula is shown as follows) unit, so that O atoms of the methoxy and S atoms on a thiophene bridge form a 'conformation lock' through S.O non-covalent interaction to lock the conformation of the molecule, the planarity of the molecule is enhanced, meanwhile, the pi conjugation length of a central unit is enlarged, the absorption range of a compound molecule shown as the formula I is widened, the optical band gap is narrowed, and the mobility of a carrier of an organic solar cell is further improved.
Figure GDA0004150269210000062
As an alternative solution of the present application, the compound has a structure represented by chemical formula (I-1) or (I-2):
Figure GDA0004150269210000063
compared with the traditional IDIDT-C8, the compound shown in the formula (I-1) has wider absorption spectrum, narrower optical band gap and improved efficiency of the optimized battery device, and the battery device based on PBDB-T and shown in the formula (I-1) has the efficiency as high as 10.38%.
Figure GDA0004150269210000071
Compared with the compound shown in the formula (I-2), the compound shown in the formula (I-1) adopts a strategy of side chain modification, the solubility of molecules is improved through the introduction of alkyl side chains, and the stacking behavior among the molecules is further regulated, so that the result shows that the battery device based on the PBDB-T and shown in the formula (I-2) achieves the efficiency of up to 11.34%. This is because too high a degree of planarization of the molecule increases its aggregation, so that solubility is reduced, and the introduction of side chains can increase the solubility of the molecule.
In other embodiments, the compound may also be of the structure of formula (I-3) or formula (I-4):
Figure GDA0004150269210000072
in other embodiments, R 1 Is a side chain connected to the intermediate structure of the small molecule, R 1 Can also be C6H5,
Figure GDA0004150269210000073
Alkyl chains, mainly to increase the solubility of the molecule. R is R 2 Is a side chain bridged on a small molecule thiophene bridge, is mainly used for regulating and controlling the planeness of a small molecule structure and improving the electron donating ability of an intermediate nucleus, R 2 Can be C6H5,/or>
Figure GDA0004150269210000074
An alkyl chain or other long chain alkyl, aryl or alkoxy group, R 2 Typically of symmetrical construction. In summary, by introducing R 1 、R 2 The solubility and planarity of the molecules can be improved, and the stacking behavior between the molecules can be further regulated.
In a second aspect, the present application further provides a method for preparing an organic solar cell receptor material, as shown in fig. 1, including the following steps:
(1) Synthesis of Compound 2: and under the protection of inert atmosphere, dropwise adding tetrahydrofuran solution containing the compound 1 into tetrahydrofuran solution containing NaH, cooling to room temperature after the reaction is finished, distilling the reaction solution under reduced pressure, extracting, drying, filtering, and purifying by using silica gel column chromatography to obtain the compound 2.
As an alternative technical scheme, in the synthesis process of the compound 2, the reaction temperature is controlled at-78 ℃, and a proper amount of CuCl can be added 2 The tetrahydrofuran solution may be any solvent having a relatively high polarity, as long as it has good solubility in the raw material, is favorable for the reaction, and has a suitable melting point. The solvent may also be dioxane, for example.
(2) Synthesis of Compound 3: and (3) mixing the compound 2, the Lawson reagent and toluene, heating and refluxing, cooling to room temperature after the reaction is finished, and carrying out reduced pressure distillation and silica gel column chromatography purification on the reaction solution to obtain the compound 3.
As an alternative technical scheme, the toluene solvent can also be chlorobenzene, anisole and other solvents.
(3) Synthesis of Compound 4: and (3) mixing the compound 3, the bromo-n-octane, the tetrahydrofuran and the potassium tert-butoxide under the protection of inert atmosphere at the temperature of below 0 ℃, extracting, drying, filtering, distilling under reduced pressure the reaction liquid after the reaction is finished, and purifying by silica gel column chromatography to obtain the compound 4.
As an alternative technical scheme, bromon-octane can be replaced by bromobenzene, bromoisooctane and other bromocompounds. The potassium tert-butoxide can be replaced by weak base salts such as potassium acetate, potassium carbonate and the like.
(4) Synthesis of Compound 5: and (3) mixing the compound 4, N-dimethylformamide and N-bromosuccinimide under the protection of inert atmosphere at the temperature of below 0 ℃, extracting, drying, filtering, distilling under reduced pressure the reaction liquid after the reaction is finished, and purifying by silica gel column chromatography to obtain the compound 5.
As an alternative technical scheme, the N, N-dimethylformamide can be replaced by solvents such as chloroform, dichloromethane, tetrahydrofuran and the like, and the N-bromosuccinimide can be replaced by organic brominating reagents such as liquid bromine, carbon tetrabromide and the like.
(5) Synthesis of compound 6 a: and under the protection of inert atmosphere, mixing the compound 5, an organotin reagent, toluene and a palladium catalyst, heating and refluxing, extracting a reaction liquid after the reaction is finished, drying, filtering, distilling under reduced pressure, and purifying by silica gel column chromatography to obtain the compound 6a.
As an alternative technical scheme, the organotin reagent can be specifically compounds such as 2-tributylstannylthiophene, 2-trimethylstannylthiophene and the like; the toluene solvent can be other small polar solvents, and Pd (PPh 3 ) 4 、Pd(dba) 2 、[PdCl 2 (PPh 3 ) 2 ]Etc.
(6) Synthesis of compound 7 a: under the protection of ice water bath and inert atmosphere, 6a, N-dimethylformamide, 1, 2-dichloroethane and POCl are taken as the compounds 3 Mixing, heating and refluxing, extracting the reaction liquid after the reaction is finished, distilling under reduced pressure, and purifying by silica gel column chromatography to obtain the compound 7a.
As an alternative to the present application, N, N-Dimethylformamide (DMF) may be used N-methyl-N-benzene Substituted by formamide; the solvent 1, 2-dichloroethane can be replaced by DMF or other solvents with lower activity. Catalyst POCl 3 ZnCl can be used 2 Instead of this.
(7) Synthesis of Compound of formula (I-1): under the protection of inert atmosphere, the compound 7a, 5, 6-difluoro-3- (dicyanomethylene) indigoketone, chloroform and a catalyst are mixed, reflux is carried out at normal temperature, and after the reaction is finished, the reaction solution is purified by silica gel column chromatography, thus obtaining the compound shown in the formula (I-1).
As an alternative technical scheme of the application, the solvent chloroform can be replaced by methylene dichloride, 1, 2-dichloroethane and other solvents; 5, 6-difluoro-3- (dicyanomethylene) indigoid (IC-2F) may be replaced with IC-1F, IC-1Cl, IC325, etc.; the catalyst can be replaced by compounds such as piperidine, triethylamine, trimethylchlorosilane and the like.
In a third aspect, the present application further provides a method for preparing an organic solar cell receptor material, as shown in fig. 1, including the following steps:
(1) Synthesis of Compound 2: dropwise adding tetrahydrofuran solution containing a compound 1 into tetrahydrofuran solution containing NaH under the protection of inert atmosphere, cooling to room temperature after the reaction is finished, distilling the reaction solution under reduced pressure, extracting, drying, filtering, and purifying by silica gel column chromatography to obtain a compound 2;
As an alternative solution of the present application, the tetrahydrofuran solution may be any solvent having a relatively high polarity, as long as it has a good solubility in the raw material, is favorable for the reaction, and has a suitable melting point. Illustratively, the solvent may be dioxane.
(2) Synthesis of Compound 3: and (3) mixing the compound 2, the Lawson reagent and toluene, heating and refluxing, cooling to room temperature after the reaction is finished, and carrying out reduced pressure distillation and silica gel column chromatography purification on the reaction solution to obtain the compound 3.
As an alternative technical scheme, the toluene solvent can also be chlorobenzene, anisole and other solvents.
(3) Synthesis of Compound 4: and (3) mixing the compound 3, the bromo-n-octane, the tetrahydrofuran and the potassium tert-butoxide under the protection of inert atmosphere at the temperature of below 0 ℃, extracting, drying, filtering, distilling under reduced pressure the reaction liquid after the reaction is finished, and purifying by silica gel column chromatography to obtain the compound 4.
As an alternative technical scheme, bromon-octane can be replaced by bromobenzene, bromoisooctane and other bromocompounds. The potassium tert-butoxide can be replaced by weak base salts such as potassium acetate, potassium carbonate and the like.
(4) Synthesis of Compound 5: and (3) mixing the compound 4, N-dimethylformamide and N-bromosuccinimide under the protection of inert atmosphere at the temperature of below 0 ℃, extracting, drying, filtering, distilling under reduced pressure the reaction liquid after the reaction is finished, and purifying by silica gel column chromatography to obtain the compound 5.
As an alternative technical scheme, the N, N-dimethylformamide can be replaced by solvents such as chloroform, dichloromethane, tetrahydrofuran and the like, and the N-bromosuccinimide can be replaced by organic brominating reagents such as liquid bromine, carbon tetrabromide and the like.
(5) Synthesis of compound 6 b: and under the protection of inert atmosphere, mixing the compound 5, an organotin reagent, toluene and a palladium catalyst, heating and refluxing, extracting a reaction liquid after the reaction is finished, drying, filtering, distilling under reduced pressure, and purifying by silica gel column chromatography to obtain the compound 6b.
As an alternative technical scheme, the organotin reagent can be specifically compounds such as 2-tributylstannylthiophene, 2-trimethylstannylthiophene and the like; the toluene solvent can be other small polar solvents, and Pd (PPh 3 ) 4 、Pd(dba) 2 、[PdCl 2 (PPh 3 ) 2 ]Etc.
(6) Synthesis of compound 7 b: under the protection of ice water bath and inert atmosphere, 6b, N-dimethylformamide, 1, 2-dichloroethane and POCl 3 Mixing, heating and refluxing, extracting reaction liquid after the reaction is finished, distilling under reduced pressure, and purifying by silica gel column chromatography to obtain a compound 7b;
as an alternative to the present application, N-Dimethylformamide (DMF) may be replaced with N-methyl-N-phenylformamide; the solvent 1, 2-dichloroethane may be DM F and other solvents with lower activity are replaced. Catalyst POCl 3 ZnCl can be used 2 Instead of this.
(7) Synthesis of Compound of formula (I-2): under the protection of inert atmosphere, mixing the compound 7b, 5, 6-dichloro-3- (dicyanomethylene) indigoketone, chloroform and a catalyst, refluxing at normal temperature, and purifying the reaction liquid by silica gel column chromatography after the reaction is finished to obtain the compound shown in the formula (I-2).
As an alternative technical scheme, the solvent chloroform can be replaced by methylene dichloride, 1, 2-dichloroethane and other solvents, and the 5, 6-difluoro-3- (dicyanomethylene) indigonone (IC-2F) can be replaced by IC-1F, IC-1Cl, IC325 and the like; the catalyst can be replaced by compounds such as piperidine, triethylamine, trimethylchlorosilane and the like.
In a fourth aspect, the present application also provides an organic solar cell comprising an active layer comprising an acceptor material and a donor material, the acceptor material comprising the organic solar cell acceptor material described above.
As an alternative embodiment of the present application, the donor material includes, but is not limited to, at least one of the following: poly (p-phenylene vinylenes), poly (arylene vinylenes), poly (p-phenylene) s, poly (arylene) s, polythiophenes, polyquinolines, leaf-lins, porphyrins, phthalocyanines, and oligomeric small molecules.
In a specific embodiment, the donor material is PBDB-T.
Figure GDA0004150269210000101
As an alternative technical solution of the present application, the mass ratio of the donor material to the acceptor material is 1: (1 to 1.5), specifically, 1:1, 1:1.05, 1:1.1, 1:1.15, 1:1.2, 1:1.3, 1:1.5, etc., are not limited herein.
As an optional technical scheme of the application, the annealing temperature of the organic solar cell is 100-140 ℃; specifically, the temperature may be 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, or the like, and other values within the above range may be used. Preferably, the annealing temperature is 120 ℃.
As an alternative technical solution of the application, the active layer includes an additive, and the additive is at least one of 1, 8-diiodooctane (abbreviated as DIO), 1, 8-dibromooctane (abbreviated as DBrO) and chloronaphthalene (abbreviated as CN).
As an alternative solution of the present application, the mass content of the additive in the active layer is 0.3% -1.5%, specifically, may be 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.7%, 0.8%, 0.9%, 1.0%, 1.2%, 1.4% or 1.5%, etc., and is not limited herein. Preferably, the mass content of the additive in the active layer is 0.5% -1%.
In a fifth aspect, the present application further provides an electronic device, including the above organic solar cell.
The following examples are provided to further illustrate embodiments of the invention. The embodiments of the present invention are not limited to the following specific embodiments. The modification can be appropriately performed within the scope of the main claim.
Example 1
The preparation method of the compound shown in the formula (I-1) in the embodiment comprises the following steps:
(1) Synthesis of Compound 2:
6-methoxy-1-indenone was selected as compound 1, and purchased from saen chemical technologies (Shanghai) limited.
Compound 1 (5 g,0.031 mol) dissolved in ultra-dry reagent tetrahydrofuran (100 mL) was added to a 125mL constant pressure dropping funnel, naH (1.85 g, 60% silicone oil) dissolved in the ultra-dry reagent tetrahydrofuran was added to a 500mL three-necked flask, the system was purged with nitrogen several times at room temperature, and then the solution containing compound 1 was dropwise added to the tetrahydrofuran solution containing NaH under nitrogen-protected atmosphere, and stirring was carried out at room temperature until H was no longer generated 2 Until that point. After the reaction was completed, deionized water was slowly added to quench, the tetrahydrofuran solvent was dried by spinning, then extracted three times with dichloromethane, the organic phases were combined, and dried over anhydrous MgSO 4 Drying, filtering, and distilling under reduced pressureThe solvent is spin-dried to obtain a crude product. The crude product was purified by column chromatography on silica gel eluting with a volume ratio of 5:1 petroleum ether/ethyl acetate to give a yellow solid (2.37 g, 47.7% yield).
Compound 2 1 H NMR spectrum, 1H NMR (400 mhz, cdcl 3) δ (ppm): 7.29 (s, 2H), 7.23-7.22 (d, j=2.36 hz, 1.96H), 7.20-7.19 (d, j=2.56 hz, 1.87H), 3.85 (s, 6H), 3.37 (s, 1.88H), 3.13-3.10 (d, j=10.04 hz, 2H), 2.40-2.37 (d, j=13.8 hz, 2H).
(2) Synthesis of Compound 3:
in a 250mL single flask was added compound 2 (2.4 g,7.5 mmol), lawson's reagent (3.63 g,8.9 mmol), dried toluene (50 mL), and the mixture was dehydrated several times and heated under reflux for 2.5h under nitrogen atmosphere. After the reaction is completed, cooling to room temperature, spin-drying the Lawson solvent by a reduced pressure distillation method, purifying by a silica gel column chromatography, wherein the eluent is petroleum ether/dichloromethane with the volume ratio of 2:1, and obtaining a crude product. The crude product was recrystallized from methylene chloride to give a beige solid (1.3 g, yield 55%).
Compound 3 1 H NMR spectrum, 1H NMR (400 mhz, cdcl 3) δ (ppm): 7.38-7.36 (d, j=8.2 hz, 2.20H), 7.04 (s, 2H), 6.75-6.74 (d, j=5.88 hz, 2H), 3.88 (s, 6H), 3.64 (s, 4.20H).
(3) Synthesis of Compound 4:
compound 3 (750 mg,2.75 mmol), n-octyl bromide (2.13 mL,12.37 mmol) and the treated tetrahydrofuran solution (30 mL) were dried in a 100mL shutter flask, and the mixture was dehydrated in an ice-water bath at 0℃for several times, and the system was stirred for 2 hours under nitrogen atmosphere in the absence of light, followed by addition of potassium t-butoxide (1.23 g). After the reaction was completed, the mixture was extracted three times with dichloromethane, and the organic phases were combined and dried over anhydrous MgSO 4 After drying, the mixture was filtered, and the solvent was dried by distillation under reduced pressure to give a crude product. The crude product was purified by column chromatography on silica gel eluting with petroleum ether/dichloromethane in a volume ratio of 3:1 to give a yellow solid (1.34 g, 54% yield).
Compound 4 1 H NMR spectrum, 1H NMR (600 mhz, cdcl 3) δ (ppm): 7.09-7.07 (d, j=8).04Hz,1.83H),6.91(s,1.81H),6.72-7.10(d,J＝8.28Hz,1.82H),3.87(s,6H),2.03-2.00(t,8.36H),1.59-1.56(m,20.65H),1.10-1.06(m,26.12H),0.82-0.79(m,14.42H)。
(4) Synthesis of Compound 5:
compound 4 (566 mg,0.74 mmol), ultra-dry N, N-dimethylformamide (DMF, 30 mL) was added to a 100mL shutter flask, the system was purged several times, nitrogen was filled into the system, N-bromosuccinimide (NBS, 217mg,1.84 mmol) was added in portions under a dark condition in an ice-water bath at 0℃and stirred for 5h. After completion of the reaction, the reaction mixture was extracted three times with dichloromethane, and the organic phases were combined and dried over anhydrous MgSO 4 Drying, filtration and removal of solvent DMF by distillation under reduced pressure gave the crude product. The crude product was purified by column chromatography on silica gel eluting with petroleum ether/dichloromethane in a volume ratio of 4:1 to give a yellow solid (681 mg, 91% yield).
Compound 5 1 H NMR spectrum, 1H NMR (600 mhz, cdcl 3) δ (ppm): 7.34 (s, 1.92H), 6.91 (s, 1.92H), 3.98 (s, 6H), 2.02-1.97 (t, 8.16H), 1.54 (s, 10.19H), 1.21-1.18 (m, 9.76H), 1.11-1.06 (m, 26.19H), 0.83-0.80 (m, 14.12H).
(5) Synthesis of compound 6 a:
in a 100mL single flask, compound 5 (220 mg,0.24 mmol), 2-tributylstannylthiophene (222.6 mg,0.59 mmol), toluene (30 mL) were added, the air was removed several times, the system was purged with nitrogen, and Pd (PPh) 3 ) 4 (27.5 mg,0.02 mmol) was refluxed for 36h. After the reaction was completed, the reaction mixture was repeatedly extracted three times with dichloromethane and dried over MgSO 4 Drying, and removing the solvent by distillation under reduced pressure to obtain a crude product. The crude product was purified by column chromatography on silica gel eluting with petroleum ether/dichloromethane in a volume ratio of 6:1 to give a yellow solid (100 mg, 45.1% yield).
Compound 6a 1 H NMR spectrum, 1H NMR (600 mhz, cdcl 3) δ (ppm): 7.52 (s, 2H), 7.46 (s, 1.76H), 7.34-7.32 (d, j=6.96 hz, 2.28H), 7.13-7.12 (d, j=5.52 hz, 1.96H), 6.99-6.98 (d, j=7.5 hz, 2H), 4.03 (s, 6H), 2.09-2.06 (t, 8.60H), 1.49 (s, 20.34H), 1.19-1.08 (m, 24.19H), 0.81-0.77 (m, 16.21H).
(6) Synthesis of compound 7 a:
in a 250mL double flask, compound 6a (100 mg,0.11 mmol), DMF (4 mL), 1, 2-dichloroethane (40 mL) was added, the reaction system was purged several times with nitrogen, and POCl was added at 0℃in an ice-water bath 3 (0.1 mL) was stirred for 40min, and then the ice-water bath was changed to an oil bath, and the mixture was heated under reflux for 15h. After the reaction was completed, a proper amount of saturated sodium bicarbonate solution was added to quench, extraction was repeated 3 times with ethyl acetate, and the solvent was removed by distillation under reduced pressure to obtain a crude product. The crude product was purified by column chromatography on silica gel eluting with petroleum ether/ethyl acetate in a volume ratio of 8:1 to give an orange oil (85 mg, 80% yield).
Compound 7a 1 H NMR spectrum, 1H NMR (600 mhz, cdcl 3) δ (ppm): 9.93 (s, 2H), 7.35 (d, j=3.96 hz, 2.05H), 6.64 (s, 1.77H), 7.55 (s, 2.16H), 7.02 (s, 1.88H), 4.08 (s, 6H), 2.11-2.07 (t, 8.22H), 1.17-1.15 (m, 8H), 1.10-1.07 (m, 29.86H), 0.79-0.77 (m, 4.37H).
(7) Synthesis of Compound formula I-1:
to a 100mL shutter flask was added compound 7a (85 mg,0.086 mmol), 5, 6-difluoro-3- (dicyanomethylene) indidone (IC-2F) (40 mg), chloroform (30 mL), and the mixture was degassed several times to fill the reaction system with nitrogen, pyridine (1 mL) was added, and the mixture was stirred at room temperature overnight. After the reaction was completed, it was directly purified by silica gel column chromatography with petroleum ether/dichloromethane in a volume ratio of 3:1 as eluent to give a blue solid (85 mg, 79% yield).
FIG. 2a is a schematic illustration of an organic solar cell acceptor material of formula I-1 provided in example 1 of the present application 1 H NMR spectrum; as shown in fig. 2a, 1H NMR (600 mhz, cdcl 3) δ (ppm): 8.86 (s, 2.01H), 8.54-8.51 (q, 2.06H), 8.03-8.02 (d, j=5.16 hz, 2H), 7.81 (s, 1.93H), 7.72-7.69 (t, 2.10H), 7.66 (s, 1.78H), 7.07 (s, 2H), 4.19 (s, 6H), 2.17-2.13 (t, 8.09H), 1.17-1.10 (m, 32.36H), 0.79-0.76 (m, 20.07H).
FIG. 2b is a schematic illustration of an organic solar cell acceptor material of formula I-1 provided in example 1 of the present application 13 C NMR spectrum. As shown in FIG. 2b, 13C NMR (125 MHz, CDCl 3) delta 185.70,158.82,155.36,155.29,153.33,153.23,152.78,142.21,136.85,134.59,127.03,120.95,114.79,114.37,112.47,101.91,77.28,77.03,76.77,69.14,56.14,55.48,40.23,30.20,29.45,24.19,22.61,14.04。MS(MALDI-TOF):Calcd for C 86 H 88 F 4 N 4 O 4 S 3 (M+):1412.59,Found:1413.09。
Example 2
The preparation method of the compound shown in the formula (I-2) in the embodiment comprises the following steps:
(1) Synthesis of Compound 2:
6-methoxy-1-indenone was selected as compound 1, and purchased from saen chemical technologies (Shanghai) limited.
Compound 1 (5 g,0.031 mol) dissolved in ultra-dry reagent tetrahydrofuran (100 mL) was added to a 125mL constant pressure dropping funnel, naH (1.85 g, 60% silicone oil) dissolved in the ultra-dry reagent tetrahydrofuran was added to a 500mL three-necked flask, the system was purged with nitrogen several times at room temperature, and then the solution containing compound 1 was dropwise added to the tetrahydrofuran solution containing NaH under nitrogen-protected atmosphere, and stirring was carried out at room temperature until H was no longer generated 2 Until that point. After the reaction was completed, deionized water was slowly added to quench, the tetrahydrofuran solvent was dried by spinning, then extracted three times with dichloromethane, the organic phases were combined, and dried over anhydrous MgSO 4 Drying, filtering, and spin-drying the solvent by vacuum distillation to obtain a crude product. The crude product was purified by column chromatography on silica gel eluting with a volume ratio of 5:1 petroleum ether/ethyl acetate to give a yellow solid (2.37 g, 47.7% yield).
Compound 2 1 H NMR spectrum, 1H NMR (400 mhz, cdcl 3) δ (ppm): 7.29 (s, 2H), 7.23-7.22 (d, j=2.36 hz, 1.96H), 7.20-7.19 (d, j=2.56 hz, 1.87H), 3.85 (s, 6H), 3.37 (s, 1.88H), 3.13-3.10 (d, j=10.04 hz, 2H), 2.40-2.37 (d, j=13.8 hz, 2H).
(2) Synthesis of Compound 3:
in a 250mL single flask was added compound 2 (2.4 g,7.5 mmol), lawson's reagent (3.63 g,8.9 mmol), dried toluene (50 mL), and the mixture was dehydrated several times and heated under reflux for 2.5h under nitrogen atmosphere. After the reaction is completed, cooling to room temperature, spin-drying the Lawson solvent by a reduced pressure distillation method, purifying by a silica gel column chromatography, wherein the eluent is petroleum ether/dichloromethane with the volume ratio of 2:1, and obtaining a crude product. The crude product was recrystallized from methylene chloride to give a beige solid (1.3 g, yield 55%).
Compound 3 1 H NMR spectrum, 1H NMR (400 mhz, cdcl 3) δ (ppm): 7.38-7.36 (d, j=8.2 hz, 2.20H), 7.04 (s, 2H), 6.75-6.74 (d, j=5.88 hz, 2H), 3.88 (s, 6H), 3.64 (s, 4.20H).
(3) Synthesis of Compound 4:
compound 3 (750 mg,2.75 mmol), n-octyl bromide (2.13 mL,12.37 mmol) and the treated tetrahydrofuran solution (30 mL) were dried in a 100mL shutter flask, and the mixture was dehydrated in an ice-water bath at 0℃for several times, and the system was stirred for 2 hours under nitrogen atmosphere in the absence of light, followed by addition of potassium t-butoxide (1.23 g). After the reaction was completed, the mixture was extracted three times with dichloromethane, and the organic phases were combined and dried over anhydrous MgSO 4 After drying, the mixture was filtered, and the solvent was dried by distillation under reduced pressure to give a crude product. The crude product was purified by column chromatography on silica gel eluting with petroleum ether/dichloromethane in a volume ratio of 3:1 to give a yellow solid (1.34 g, 54% yield).
Compound 4 1 H NMR spectrum, 1H NMR (600 mhz, cdcl 3) δ (ppm): 7.09-7.07 (d, j=8.04 hz, 1.83H), 6.91 (s, 1.81H), 6.72-7.10 (d, j=8.28 hz, 1.82H), 3.87 (s, 6H), 2.03-2.00 (t, 8.36H), 1.59-1.56 (m, 20.65H), 1.10-1.06 (m, 26.12H), 0.82-0.79 (m, 14.42H).
(4) Synthesis of Compound 5:
compound 4 (566 mg,0.74 mmol), ultra-dry N, N-dimethylformamide (DMF, 30 mL) was added to a 100mL shutter flask, the system was purged several times, nitrogen was filled into the system, N-bromosuccinimide (NBS, 217mg,1.84 mmol) was added in portions under a dark condition in an ice-water bath at 0℃and stirred for 5h. After completion of the reaction, the reaction mixture was extracted three times with dichloromethane, and the organic phases were combined and dried over anhydrous MgSO 4 Drying, filtration and removal of solvent DMF by distillation under reduced pressure gave the crude product. The crude product was purified by silica gel column chromatography,the eluent was petroleum ether/dichloromethane in a volume ratio of 4:1 to give a yellow solid (681 mg, 91% yield).
Compound 5 1 H NMR spectrum, 1H NMR (600 mhz, cdcl 3) δ (ppm): 7.34 (s, 1.92H), 6.91 (s, 1.92H), 3.98 (s, 6H), 2.02-1.97 (t, 8.16H), 1.54 (s, 10.19H), 1.21-1.18 (m, 9.76H), 1.11-1.06 (m, 26.19H), 0.83-0.80 (m, 14.12H).
(5) Synthesis of compound 6 b:
in a 100mL single flask, compound 5 (220 mg,0.24 mmol), 4-octyl-2-tributylstannylthiophene (289.3 mg,0.59 mmol), toluene (30 mL) were added, the gas was removed several times, the system was purged with nitrogen, and Pd (PPh) 3 ) 4 (27.5 mg,0.02 mmol) was refluxed for 36h. After the reaction was completed, the reaction mixture was repeatedly extracted three times with dichloromethane and dried over MgSO 4 Drying, and removing the solvent by distillation under reduced pressure to obtain a crude product. The crude product was purified by column chromatography on silica gel eluting with petroleum ether/dichloromethane in a volume ratio of 8:1 to give a yellow solid (125 mg, 45.4% yield).
Compound 6b 1 H NMR spectrum, 1H NMR (600 mhz, cdcl 3) δ (ppm): 7.42 (s, 1.81H), 7.35 (s, 1.80H), 6.97 (s, 1.71H), 6.92 (s, 1.65H), 4.01 (s, 6H), 2.67-2.63 (t, 4.15H), 2.07-2.05 (t, 8.36H), 1.73-1.65 (m, 4.38H), 1.52 (s, 10.26H), 1.15-1.07 (m, 32.36H), 0.91-0.87 (m, 6.69H), 0.81-0.77 (m, 13.83H).
(6) Synthesis of compound 7 b:
in a 250mL double flask, compound 6b (125, mg,0.11 mmol), DMF (4 mL), 1, 2-dichloroethane (40 mL) was added, the reaction system was purged several times with nitrogen, and POCl was added at 0℃in an ice-water bath 3 (0.1 mL) was stirred for 40min, and then the ice-water bath was changed to an oil bath, and the mixture was heated under reflux for 15h. After the reaction was completed, a proper amount of saturated sodium bicarbonate solution was added to quench, extraction was repeated 3 times with ethyl acetate, and the solvent was removed by distillation under reduced pressure to obtain a crude product. The crude product was purified by column chromatography on silica gel eluting with petroleum ether/ethyl acetate in a volume ratio of 8:1 to give an orange oil (124 mg, 95% yield).
Compound 7b 1 H NMR spectrum, 1H NMR (600 mhz, cdcl 3) δ (ppm): 10.05 (s, 2H), 7.51 (s, 2.16H), 7.43 (s, 1.86H), 7.00 (s, 1.90H), 4.06 (s, 6.37H), 2.99-2.97 (t, 4.02H), 2.11-2.07 (t, 8.07H), 1.76-1.72 (m, 4.42H), 1.34-1.25 (m, 17.73H), 1.10-1.07 (m, 28.27H), 0.90-0.88 (m, 8.21H), 0.80-0.78 (m, 4.11H).
(7) Synthesis of Compound formula I-2:
to a 100mL shutter flask was added compound 7b (124 mg,0.102 mmol), 5, 6-dichloro-3- (dicyanomethylene) indidone (IC-2 Cl) (45 mg), chloroform (30 mL), and the mixture was degassed several times to fill the reaction system with nitrogen, pyridine (1 mL) was added, and the mixture was stirred at room temperature overnight. After the reaction was completed, it was directly purified by silica gel column chromatography with petroleum ether/methylene chloride in a volume ratio of 4:1 as eluent to give a blue solid (110 mg, 82% yield).
FIG. 3a is a schematic illustration of an organic solar cell acceptor material of formula I-2 provided in example 2 of the present application 1 H NMR spectrum; as shown in fig. 3a, 1H NMR (600 mhz, cdcl 3) δ (ppm): 9.04 (s, 1.80H), 8.56-8.53 (q, 2.19H), 7.71-7.70 (t, 4H), 7.68 (s, 2H), 7.04 (s, 1.85H), 4.19 (s, 6H), 3.04-3.01 (t, 4.29H), 2.17-2.14 (t, 8.47H), 1.78-1.71 (m, 4.37H), 1.49-1.45 (m, 4.26H), 1.17-1.05 (m, 36.37H), 0.90-0.87 (m, 6.62H), 0.79-0.76 (m, 16.19H).
FIG. 3b is a schematic illustration of an organic solar cell acceptor material of formula I-2 provided in example 2 of the present application 13 C NMR spectrum. As shown in FIG. 3b, 13C NMR (125 MHz, CDCl 3) delta 185.78,155.28,155.21,153.22,153.11,152.24,136.54,134.61,114.87,114.70,112.44,112.30,102.02,77.28,77.03,76.77,68.06,56.19,40.22,29.26,22.62,14.13,14.04.MS (MALDI-TOF): calcd for C 102 H 120 F 4 N 4 O 4 S 3 (M+):1636.84，Found:1638.27。
Test method
(1) The compounds prepared in example 1 and example 2 were subjected to optical and electrochemical performance tests
The optical and electrochemical properties of the two acceptor materials prepared in example 1 and example 2 are shown in table 1 below and fig. 4a, fig. 4b, fig. 4d. Table 1 lists the optical and electrochemical performance parameters of the two acceptor materials and IDIDT-C8.
TABLE 1 optical Properties and electrochemical Property parameters of acceptor materials
Figure GDA0004150269210000151
Table 1 lists the maximum absorption wavelengths, optical bandgaps and E of the acceptor materials of formulas I-1 and I-2 LUMO And E is HOMO Optical performance such as energy level and electrochemical performance parameters. FIGS. 4a and 4b are normalized UV-visible absorption spectra of the acceptor materials of formula I-1 and formula I-2 in chloroform solution and film state, respectively, and it can be seen from FIGS. 4a and 4b that the maximum absorption peak at long wavelength in film state of the acceptor material of formula I-1 is at 770nm, which is red shifted by 68nm compared with 702nm in solution absorption; the maximum absorption peak of the acceptor material in the state of the film of the formula I-2 at a long wavelength is 750nm, and is red-shifted by 47nm compared with 703nm under solution absorption. This suggests that the acceptor materials of formula I-1 and formula I-2 have relatively strong intermolecular interactions in the solid state, resulting in a tighter pi-pi stacking order in the small molecule aggregation state. Compared with the acceptor material formula I-1, the acceptor material formula I-2 adopts a strategy of side chain modification, the solubility of molecules is improved through the introduction of alkyl side chains, and the steric hindrance of the acceptor material formula I-2 is smaller in an aggregation state, so that the stacking behavior among molecules is regulated.
Meanwhile, from the formula Eg, opt=1240/λonset, their optical band gaps Eg, opt being 1.42eV and 1.47eV, respectively, can be obtained.
FIG. 4c is an electrochemical cyclic voltammetry graph of two acceptor materials of formula I-1 and formula I-2, wherein the initial oxidation-reduction potential of the acceptor material relative to Ag/Ag+ is obtained by measuring the oxidation-reduction process of the acceptor material by electrochemical cyclic voltammetry, and the initial oxidation potential E of the acceptor materials of formula I-1 and formula I-2 is shown in FIG. 4c OX，onset 0.61eV and 0.58eV, respectively. According to formula E HOMO ＝-4.7-E OX，onset Thus, E of the receptor materials of formula I-1 and formula I-2 can be calculated HOMO The energy levels are respectively-5.31 eV and-5.28 eV, and then the energy levels are respectively represented by the formula E LUMO ＝E HOMO +Eg, opt can calculate itE of them LUMO The energy levels were-3.98 eV and-3.86 eV, respectively.
The performance of organic solar cells made according to ITO/PEDOT: PSS/polymer PBDB-T/formula I-1 (1:1, 1:1.5,1:2 wt/wt)/Ca/Al using PBDB-T as donor material and formula I-1 as acceptor material is shown in Table 2 and FIGS. 5a, 5b below. Table 2-1 lists the photovoltaic performance parameters exhibited by the cells at different ratios of the polymer PBDB-T and the acceptor material formula I-1 in the active layers of the solar cell photovoltaic devices.
TABLE 2-1 photovoltaic parameters of the cells of formula I-1 based on PBDB-T under different Mass ratios (D/A)
Figure GDA0004150269210000161
Wherein D/A represents the mass ratio of donor material to acceptor material.
Table 2-1 lists the major photovoltaic performance parameters of open circuit voltage, short circuit current, fill factor, and photoelectric conversion efficiency for organic solar cells based on the structure ITO/PEDOT: PSS/polymer PBDB-T/formula I-1 (1:1, 1:1.5,1:2 wt/wt)/Ca/Al.
FIG. 5a shows a current-voltage plot of the PBDB-T in the active layer for the acceptor material formula I-1 at an optimum ratio of 1:1.5 for an organic solar cell; when the compound shown in the formula I-1 is used as an acceptor material, the short-circuit current and the open-circuit voltage of the solar cell are respectively 14.82mA/cm 2 And 0.89V; the fill factor of the solar cell was 64.23%, and the photoelectric conversion efficiency of the solar cell was 8.54%.
In the preparation of organic solar cells, the effects between the annealing temperature and the main photovoltaic performance parameters such as open circuit voltage, short circuit current, fill factor and photoelectric conversion efficiency of the cells based on the formula I-1 of PBDB-T are listed in Table 2-2 by adjusting different annealing temperatures.
TABLE 2-2 photovoltaic parameters for PBDB-T based batteries of formula I-1 under different annealing temperature conditions
Figure GDA0004150269210000162
At the optimal annealing temperature of 120 ℃, the short-circuit current and the open-circuit voltage of the solar cell can reach 16.19mA/cm respectively 2 And 0.90V; the fill factor of the solar cell was 65.21%, and the photoelectric conversion efficiency of the solar cell was 9.54%.
In the preparation of the organic solar cell, the influence between the main photovoltaic performance parameters such as open-circuit voltage, short-circuit current, fill factor and photoelectric conversion efficiency of the cell based on the formula I-1 and the addition amount of the additive CN is listed in tables 2 to 3 by adjusting the addition amount of the additive CN.
TABLE 2-3 photovoltaic parameters after optimization procedure of the cell usage additive CN based on PBDB-T formula I-1
Figure GDA0004150269210000171
When the additive amount of the additive CN is 0.5%, the short-circuit current and the open-circuit voltage of the solar cell can reach 16.77mA/cm respectively 2 And 0.89V; the fill factor of the solar cell was 68.53%, and the photoelectric conversion efficiency of the solar cell was 10.24%.
Further, the performance of organic solar cells made from ITO/PEDOT: PSS/polymer PBDB-T/formula I-2 (1:1, 1:1.5,1:2 wt/wt)/Ca/Al using PBDB-T as donor material and formula I-2 as acceptor material is shown in Table 3 below and FIGS. 5a, 5b. Table 3-1 lists the photovoltaic performance parameters exhibited by the cells at different ratios of the polymer PBDB-T and the acceptor material formula I-2 in the active layers of the solar cell photovoltaic devices.
TABLE 3-1 photovoltaic parameters for PBDB-T based batteries of formula I-2 under different Mass ratio (D/A) conditions
Figure GDA0004150269210000172
Wherein D/A represents the mass ratio of donor material to acceptor material.
Table 3-1 lists the major photovoltaic performance parameters of open circuit voltage, short circuit current, fill factor, and photoelectric conversion efficiency for organic solar cells based on the structure ITO/PEDOT: PSS/polymer PBDB-T/formula I-2 (1:1, 1:1.5,1:2 wt/wt)/Ca/Al.
FIG. 5a shows a graph of current versus voltage for an organic solar cell for the PBDB-T in the active layer with an optimum 1:1 ratio of acceptor material formula I-2; when the compound shown in the formula I-2 is used as an acceptor material, the short-circuit current and the open-circuit voltage of the solar cell are respectively 13.84mA/cm 2 And 0.95V; the fill factor of the solar cell was 58.51%, and the photoelectric conversion efficiency of the solar cell was 7.73%.
In the preparation of organic solar cells, the effects between the annealing temperature and the main photovoltaic performance parameters such as open circuit voltage, short circuit current, fill factor and photoelectric conversion efficiency of the cells based on the formula I-2 of PBDB-T are listed in Table 3-2 by adjusting different annealing temperatures.
TABLE 3-2 photovoltaic parameters for PBDB-T based batteries of formula I-2 under different annealing temperature conditions
Figure GDA0004150269210000173
Figure GDA0004150269210000181
At the optimal annealing temperature of 120 ℃, the short-circuit current and the open-circuit voltage of the solar cell can reach 15.58mA/cm respectively 2 And 0.93V; the fill factor of the solar cell was 64.54%, and the photoelectric conversion efficiency of the solar cell was 9.43%.
In the preparation of the organic solar cell, the influence between the main photovoltaic performance parameters such as open-circuit voltage, short-circuit current, fill factor and photoelectric conversion efficiency of the cell based on the formula I-2 and the addition amount of the additive CN is listed in tables 3-3 by adjusting the addition amount of the additive CN.
TABLE 3-3 photovoltaic parameters after optimization procedure of the cell usage additive CN based on PBDB-T formula I-2
Figure GDA0004150269210000182
When the additive amount of the additive CN is 1%, the short-circuit current and the open-circuit voltage of the solar cell can respectively reach 16.72mA/cm 2 And 0.96V; the fill factor of the solar cell was 69.85%, and the photoelectric conversion efficiency of the solar cell was 11.21%.
According to the optimal preparation parameters found in the preparation process of the organic solar cell, the D/A mass ratio is 1:1.5, and the annealing temperature is 120 ℃, so that the organic solar cell with the optimal photovoltaic performance parameters is prepared.
TABLE 4 optimal photovoltaic Performance parameters for organic solar cells
Figure GDA0004150269210000183
The average efficiency in brackets a is obtained by counting PCE values for 10 identical battery devices.
As can be seen from Table 4, under the optimal preparation process parameters, the organic solar cell prepared from the compound shown in formula I-1 as the donor material and the compound shown in formula I-1 as the acceptor material has a D/A mass ratio of 1:1.5, the additive amount of the additive CN is controlled to be 0.5%, the annealing temperature is controlled to be 120 ℃, and the short-circuit current and the open-circuit voltage of the solar cell can respectively reach 17.23mA/cm 2 And 0.92V; the fill factor of the solar cell was 65.75%, and the average photoelectric conversion efficiency of the solar cell was 10.38%.
Under the optimal preparation process parameters, the organic solar cell is prepared from the compound shown in the formula I-2, wherein the donor material is PBDB-T, the acceptor material is the compound shown in the formula I-2, the D/A mass ratio is 1:1.5, the adding amount of the additive CN is controlled to be 1%, the annealing temperature is controlled to be 120 ℃, and the short-circuit current and the open-circuit voltage of the solar cell can respectively reach 17.44mA/cm 2 And 0.93V; the fill factor of the solar cell was 70.11%, and the average photoelectric conversion efficiency of the solar cell was 11.34%.
While the preferred embodiment has been described, it is not intended to limit the scope of the claims, and any person skilled in the art can make several possible variations and modifications without departing from the spirit of the invention, so the scope of the invention shall be defined by the claims.

Claims (8)

1. An organic solar cell receptor material characterized by a compound having the following chemical structural formula (I):
Figure FDA0004106321780000011
wherein R is 1 Is a C6-C24 linear alkyl group;
R 2 is a hydrogen atom, or a C6-C24 linear alkyl group; r is R 1 、R 2 The same or different.
2. The organic solar cell acceptor material according to claim 1, wherein the compound has a structure represented by formula (I-1) or (I-2):
Figure FDA0004106321780000012
3. The method for preparing an organic solar cell receptor material according to claim 2, comprising the steps of:
(1) Synthesis of Compound 2: dropwise adding tetrahydrofuran solution containing a compound 1 into tetrahydrofuran solution containing NaH under the protection of inert atmosphere, wherein the compound 1 is 6-methoxy-1-indenone, cooling to room temperature after the reaction is finished, and purifying to obtain a compound 2;
(2) Synthesis of Compound 3: mixing the compound 2, the Lawson reagent and toluene, heating and refluxing, cooling to room temperature after the reaction is finished, and purifying to obtain a compound 3;
(3) Synthesis of Compound 4: mixing the compound 3, bromo-n-octane, tetrahydrofuran and potassium tert-butoxide under the protection of inert atmosphere at the temperature of below 0 ℃, and purifying after the reaction is finished to obtain a compound 4;
(4) Synthesis of Compound 5: mixing the compound 4, N-dimethylformamide and N-bromosuccinimide under the protection of inert atmosphere at the temperature of below 0 ℃, and purifying after the reaction is finished to obtain a compound 5;
(5) Synthesis of compound 6 a: under the protection of inert atmosphere, mixing the compound 5, an organotin reagent, toluene and a palladium catalyst, heating and refluxing, and purifying after the reaction is finished to obtain a compound 6a;
(6) Synthesis of compound 7 a: under the protection of ice water bath and inert atmosphere, 6a, N-dimethylformamide, 1, 2-dichloroethane and POCl are taken as the compounds 3 Mixing, heating and refluxing, and purifying after the reaction is finished to obtain a compound 7a;
(7) Synthesis of Compound of formula (I-1): under the protection of inert atmosphere, mixing the compound 7a, 5, 6-difluoro-3- (dicyanomethylene) indigoketone, chloroform and a catalyst, refluxing at normal temperature, purifying after the reaction is finished to obtain a compound shown as a formula (I-1), wherein the synthetic route is as follows:
Figure FDA0004106321780000021
4. the method for preparing an organic solar cell receptor material according to claim 2, comprising the steps of:
(1) Synthesis of Compound 2: dropwise adding tetrahydrofuran solution containing a compound 1 into tetrahydrofuran solution containing NaH under the protection of inert atmosphere, wherein the compound 1 is 6-methoxy-1-indenone, cooling to room temperature after the reaction is finished, and purifying to obtain a compound 2;
(2) Synthesis of Compound 3: mixing the compound 2, lawson reagent and toluene, heating and refluxing, cooling to room temperature after the reaction is finished, and performing reduced pressure distillation and silica gel column chromatography purification on the reaction solution to obtain a compound 3;
(3) Synthesis of Compound 4: mixing the compound 3, bromo-n-octane, tetrahydrofuran and potassium tert-butoxide under the protection of inert atmosphere at the temperature of below 0 ℃, and purifying after the reaction is finished to obtain a compound 4;
(4) Synthesis of Compound 5: mixing the compound 4, N-dimethylformamide and N-bromosuccinimide under the protection of inert atmosphere at the temperature of below 0 ℃, and purifying after the reaction is finished to obtain a compound 5;
(5) Synthesis of compound 6 b: under the protection of inert atmosphere, mixing the compound 5, an organotin reagent, toluene and a palladium catalyst, heating and refluxing, and purifying after the reaction is finished to obtain a compound 6b;
(6) Synthesis of compound 7 b: under the protection of ice water bath and inert atmosphere, 6b, N-dimethylformamide, 1, 2-dichloroethane and POCl 3 Mixing, heating and refluxing, and purifying after the reaction is finished to obtain a compound 7b;
(7) Synthesis of Compound of formula (I-2): under the protection of inert atmosphere, mixing the compound 7b, 5, 6-dichloro-3- (dicyanomethylene) indigoketone, chloroform and a catalyst, refluxing at normal temperature, and purifying after the reaction is finished to obtain a compound shown as a formula (I-2), wherein the synthetic route is as follows:
Figure FDA0004106321780000031
5. an organic solar cell, characterized in that the organic solar cell comprises an active layer comprising an acceptor material and a donor material, the acceptor material comprising the organic solar cell acceptor material of any one of claims 1-2.
6. The organic solar cell according to claim 5, characterized in that it satisfies at least one of the following characteristics:
(1) The donor material is PBDB-T;
(2) The mass ratio of the donor material to the acceptor material is 1: (1-1.5).
7. The organic solar cell according to claim 5, characterized in that it satisfies at least one of the following characteristics:
(3) The annealing temperature of the organic solar cell is 100-140 ℃;
(4) The annealing temperature of the organic solar cell is 120 ℃;
(5) The additive in the active layer is 0.3% -1.5%;
(6) The additive comprises at least one of 1, 8-diiodooctane, 1, 8-dibromooctane and chloronaphthalene.
8. An electronic device comprising the organic solar cell of claims 5-7.
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