CN115466270B - Electron acceptor material based on dicyanoindenothiazole terminal and application thereof - Google Patents

Electron acceptor material based on dicyanoindenothiazole terminal and application thereof Download PDF

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CN115466270B
CN115466270B CN202211150157.3A CN202211150157A CN115466270B CN 115466270 B CN115466270 B CN 115466270B CN 202211150157 A CN202211150157 A CN 202211150157A CN 115466270 B CN115466270 B CN 115466270B
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CN115466270A (en
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李昌治
张倩倩
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Zhejiang University ZJU
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains four or more hetero rings
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Abstract

The invention discloses an electron acceptor material based on a dicyanoindenothiazole terminal and application thereof. The electron acceptor material is prepared by coupling the dicyanoindenothiazole end and the electron-rich fragment through a metal catalytic single bond, and can be used for constructing an organic solar cell. The organic solar cell comprises a substrate, a cathode, an electron transport layer, an active layer, an anode modification layer and an anode, wherein the active layer is a blend film of a polymer electron donor and an electron acceptor based on a dicyanoindenothiazole terminal. The spectrum response range of the organic solar cell prepared by the invention is 350-900nm, and the open circuit voltage (V) oc ) Is 0.73-0.89V, short-circuit current (J sc ) Is 7.20-20.15mA cm ‑2 The energy conversion efficiency (PCE) is 5.67-11.03%, which indicates that the electron acceptor material can improve the photoelectric conversion efficiency of the organic solar cell acceptor.

Description

Electron acceptor material based on dicyanoindenothiazole terminal and application thereof
Technical Field
The invention belongs to the field of energy materials, and particularly relates to an electron acceptor material based on a dicyanoindenothiazole terminal and application thereof.
Background
In recent years, development of novel organic semiconductor materials has been rapid, and the Photoelectric Conversion Efficiency (PCE) of Organic Solar Cells (OSCs) has exceeded 19%. The traditional electron donor unit-electron acceptor unit-electron donor unit (A-D-A) has higher efficiency, but is synthesized by a Knoevenagel Condensation Reaction (KCR), an exocyclic double bond is inevitably introduced into a molecule, and in a photoaging test, the exocyclic double bond is photoisomerized, so that the molecule is degraded. In order to solve the stability problem of OSCs from the source, it is necessary to develop an organic semiconductor material having intrinsic photostability, and therefore, a receptor coupled to an electron-donating fragment and an electron-withdrawing fragment by a single bond is constructed through Stille coupling reaction (KCR), instead of an unstable exocyclic double bond brought by KCRs, while maintaining the advantages of a-D-a strategy in adjusting the optoelectronic properties of NFAs.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides an electron acceptor based on a dicyanoindenothiazole terminal and application thereof, so as to improve the photoelectric conversion efficiency of an organic solar cell acceptor. The material A has the electron fragment of dicyanoindenothiazole terminal, has stronger electron withdrawing property, and can keep better photoelectric conversion efficiency when optimizing the acceptor structure and the reaction route.
The specific technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides an electron acceptor material based on a dicyanoindenothiazole terminal, wherein the electron acceptor material takes an electron donating unit D as a core, and both ends of the electron acceptor material are coupled with an electron withdrawing unit A through single bonds to form an A-D-A structure;
the A is one of the following chemical structural formulas, and is taken as an acceptor group:
the D is one of the following chemical structural formulas, and is taken as a donor group:
wherein R is 1 R is R 2 Are modification groups, and X is a halogen atom.
Preferably, the modifying group R 1 H, C of a shape of H, C 1 -C 17 Straight chain alkyl, C 3 -C 17 Branched alkyl or C 6 -C 12 Is one of the phenyl groups of (a).
Further, the solubilizing group R is modified 1 Is one of the following chemical structural formulas:
preferably, the modifying group R 2 Is C 1 -C 17 Straight chain alkyl, C 1 -C 17 Straight-chain alkoxy, C 3 -C 17 Branched alkyl, C 3 -C 17 Branched alkoxy, C 3 -C 6 Cycloalkyl, C 3 -C 6 Is C or C 6 -C 12 Is one of the phenyl groups of (a).
Further, a modifying group R 2 Is one of the following chemical structural formulas:
preferably, the electron acceptor material has one of the chemical formulas:
in a second aspect, the present invention provides an active layer of an organic solar cell, the active layer comprising a blended film of an electron donor material and an electron acceptor material according to any of the first aspects.
Preferably, the electron donor material in the active layer is one of the following chemical formulas:
preferably, the mass ratio of the electron donor material to the electron acceptor material in the active layer is (1 to 5): (5-1), preferably, the thickness of the active layer is 10-1000 nm.
Further, the active layer is annealed at 20-250 ℃ for 1-60 min.
In a third aspect, the present invention provides an organic solar cell constructed with the active layer according to any one of the second aspects.
Preferably, the organic solar cell has a multilayer layered structure, including a substrate, a cathode, an electron transport layer, an active layer, a hole transport layer, and an anode, from bottom to top.
Preferably, the organic solar cell has a multilayer layered structure, including a substrate, an anode, a hole transport layer, an active layer, an electron transport layer, and a cathode, from bottom to top.
In a fourth aspect, the present invention also provides a method for preparing an electron acceptor material having an a-D-a structure according to the first aspect, including the steps of:
1) Using substituent substituted indan-1, 3-dione and N-bromosuccinimide as raw materials, preparing a compound containing a ketone carbonyl group and a bromine atom in a structure through bromination reaction, and directly carrying out Hantzsch reaction with thiourea without separation to obtain a second compound;
2) Taking the second compound as a raw material, and carrying out Sandmayer reaction to obtain a third compound;
3) The third compound and malononitrile are used as raw materials, chloroform is used as a solvent, ethanol is used as an initiator, and a fourth compound is obtained through Knoevenagel reaction;
4) The electron acceptor material based on the thiazole tail end is prepared by using a fourth compound, indacenodithiophene and derivatives thereof as raw materials and using tetraphenylphosphine palladium as a catalyst through Stille coupling reaction.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a novel indenothiazole electron-deficient acceptor (namely an electron acceptor material based on thiazole tail ends), which can be used for preparing a novel organic solar cell acceptor material through coupling a bromoindenothiazole derivative and IDT through single bonds. The electron acceptor provided by the invention has better illumination stability and thermal stability than the electron acceptor IT-4F condensed by the traditional double bond, however, the electron acceptor is limited by higher energy level and lower electron mobility, and the material shows lower photovoltaic parameters and has wide commercialized potential. The spectrum response range of the organic solar cell prepared by the invention is 350-900nm, and the open circuit voltage (V) oc ) Is 0.73-0.89V, short-circuit current (J sc ) Is 7.20-20.15mA cm -2 The energy conversion efficiency (PCE) is 5.67-11.03%.
Drawings
Fig. 1 is a basic structure of an organic solar cell;
FIG. 2 is a photo stability comparison of single bond coupled A-D-A electron acceptors Q3-4F (e), Q3-4Cl (F) and conventional A-D-A electron acceptors IT-4F (a), IT-IC (b), IT-M (c), IT-CC (D) in example 11 and comparative example 1;
FIG. 3 is a comparison of thermal stability of single bond coupled A-D-A electron acceptors and conventional A-D-A electron acceptors in example 12 and comparative example 2;
fig. 4 is a graph showing current and voltage curves of the organic solar cell devices of examples 13 and 14;
fig. 5 is a graph showing current and voltage curves of the organic solar cell devices of examples 15 and 16;
in the figure: anode 1, hole transport layer 2, active layer 3, electron transport layer 4, cathode 5, substrate 6.
Detailed Description
The invention is further illustrated and described below with reference to the drawings and detailed description. The technical features of the embodiments of the invention can be combined correspondingly on the premise of no mutual conflict.
In the invention, an electron acceptor material based on dicyanoindenothiazole is provided, wherein the electron acceptor material takes an electron donating unit D as a core, and both ends of the electron acceptor material are coupled with an electron withdrawing unit A through single bonds to form an electron withdrawing unit (A) -electron donating unit (D) -electron withdrawing unit (A) structure. Wherein the chemical structural formulas of the core (D) and the tail end (A) are shown in the summary of the invention.
The electron acceptor material can be used for preparing an active layer of an organic solar cell, wherein the active layer is a blend film of an electron donor material and the A-D-A electron acceptor material. The electron donor materials can be selected according to the requirements, such as PTB7, P3HT, PTQ10, PBTB-T, PM6, J51, J71 and the like, and the specific structural formulas are also shown in the summary of the invention. In practical application, the mass ratio of the electron donor material to the electron acceptor material in the active layer is preferably selected from (1:5) - (5:1), and the thickness of the active layer is 10-1000 nm.
The invention also provides an organic solar cell constructed based on the active layer, as shown in fig. 1, wherein the organic solar cell has a multi-layer laminated structure, and the specific structure can be adjusted according to the requirement. The organic solar cell may have a positive structure, i.e., a substrate 6, an anode 5, a hole transport layer 4, an active layer 3, an electron transport layer 2, and a cathode 1 from bottom to top, and the structure is shown in fig. 1. Of course, the organic solar cell may also have an inversion structure, i.e., a substrate, a cathode, an electron transport layer, an active layer, a hole transport layer, and an anode from bottom to top, respectively. The materials of the other layers except the active layer of the present invention are not limited, and in practical application, the following materials may be used: the substrate 6 is glass, the anode 5 is ITO, the hole transport layer 4 is PEDOT: PSS, the electron transport layer is Bis-FIMG, and the cathode is Ag.
The following describes the implementation and technical effects of the present invention by means of specific examples. The reagents and materials used in the examples below may be commercially available materials unless otherwise specified. In addition, some compounds in the synthetic route equation of each example are numbered, and in the following description, the compounds will be denoted by numbers at some positions for convenience of description. The electron donor materials used in the examples have the structural formulae described in the summary of the invention.
Example 1
The embodiment provides a method for preparing single bond coupled A-D-A electron acceptor Q3-4F by using 2-bromo-methyl benzoate as an initial raw material, which comprises the following steps:
the reaction equation is:
the synthesis steps of the intermediate and Q3-4F are as follows:
5, 6-difluoroindan-1, 3-dione (1 g,5.49 mmol) was placed in 50mL of ethanol at 0deg.C, and N-bromosuccinimide (1.95 g,10.98 mmol) was added. The reaction was stirred for 1 hour, thiourea (0.84 g,10.98 mmol) was added and DMF (0.43 mL,5.49 mmol) was added to catalyze the reaction and the reaction was refluxed for 4-5 hours. Adding the reaction product into ice water for quenching to obtain a suspension containing brick red precipitate, and filtering to obtain a red powdery second intermediate.
CuBr (1.45 g,10.1 mmol) was added to a MeCN (25 mL) solution at 60℃and t BuONO (1.49 mL,12.6 mmol) and stirred for 10 min. To the reaction was added the second intermediate (1 g,4.20 mmol) and the reaction mixture was stirred at 60℃for 1 hour. After the reaction, the reaction mixture was poured into 1N HCl solution and treated with CH 2 Cl 2 Extracting with water for three times, collecting organic layer, concentrating, purifying with silica gel chromatographic column, eluting with n-hexane/CH 2 Cl 2 (6:1, v/v) to give a yellow third intermediate solid (1.16 g, 70%).
The third intermediate (200 mg,0.66 mmol) and CH 3 COONa (65.17 mg,0.79 mmol) was added to CHCl 3 To a solution (10 mL) was added malononitrile (43.74 mg,0.66 mmol). The mixed solution was stirred at 60℃for 2 hours. The excess reaction solution was removed and purified by silica gel chromatography column using n-hexane/CH 2 Cl 2 (3:1, v/v) as eluent, yielding the fourth intermediate at the electron acceptor terminus (148 mg, 64%) as a purple solid.
Under the protection of argon, a fourth intermediate (60 mg,0.171 mmol) and indacenothiotin salt (96 mg,0.078 mmol) and toluene (20 mL) are placed in a Schlenk vacuum sealed bottle, after liquid nitrogen is frozen, three cycles of vacuumizing and argon filling are carried out, and a catalyst Pd (PPh) is rapidly added 3 ) 4 (11 mg,0.02 mmol) was frozen and drawn three times. The reaction was heated at 110℃for 24h under reflux. And (3) removing redundant solvent by rotary evaporation, adding a few drops of chloroform into a eggplant-shaped bottle until the product can be completely dissolved, dropwise adding the dissolved system into a methanol solution by using a dropper to generate green precipitate, performing vacuum suction filtration, washing the precipitate on filter paper for two to three times by using methanol, and drying the precipitate on filter paper to obtain a crude product. The product was isolated using a silica gel column with a mixed solution of n-hexane and dichloromethane as eluent and dried thoroughly in a vacuum oven to give 105mg of product Q3-4F (green solid, 96% yield).
Example 2
The embodiment provides a method for preparing single bond coupled A-D-A electron acceptor Q4-4F by using 2-bromo-methyl benzoate as an initial raw material, which comprises the following steps:
the reaction equation is as follows:
the synthesis steps of the intermediate and Q4-4F are as follows:
5, 6-difluoroindan-1, 3-dione (1 g,5.49 mmol) was placed in 50mL of ethanol at 0deg.C, and N-bromosuccinimide (1.95 g,10.98 mmol) was added. The reaction was stirred for 1 hour, thiourea (0.84 g,10.98 mmol) was added and DMF (0.43 mL,5.49 mmol) was added to catalyze the reaction and the reaction was refluxed for 4-5 hours. Adding the reaction product into ice water for quenching to obtain a suspension containing brick red precipitate, and filtering to obtain a red powdery second intermediate.
CuBr (1.45 g,10.1 mmol) was added to a MeCN (25 mL) solution at 60℃and t BuONO (1.49 mL,12.6 mmol) and stirred for 10 min. Intermediate 2 (1 g,4.20 mmol) was added to the reaction and the reaction mixture was stirred at 60℃for 1 hour. After the reaction, the reaction mixture was poured into 1N HCl solution and treated with CH 2 Cl 2 Extracting with water for three times, collecting organic layer, concentrating, purifying with silica gel chromatographic column, eluting with n-hexane/CH 2 Cl 2 (6:1, v/v) to afford a third intermediate (1.16 g, 70%) as a yellow solid.
Intermediate 3 (200 mg,0.66 mmol) and CH 3 COONa (65.17 mg,0.79 mmol) was added to CHCl 3 To a solution (10 mL) was added malononitrile (43.74 mg,0.66 mmol). The mixed solution was stirred at 60℃for 2 hours. The excess reaction solution was removed and purified by silica gel chromatography column using n-hexane/CH 2 Cl 2 (3:1, v/v) as eluent, yielding the fourth intermediate at the electron acceptor terminus (148 mg, 64%) as a purple solid.
Under the protection of argon, a fourth intermediate (60 mg,0.171 mmol) and 12- (2-butyloctyl) -13- (2-ethylhexyl) -12, 13-dihydro-3, 9-bisdecanyl-dithiophene [2',3': 4',5']Thiophene [2',3':4,5]Pyrrole [3,2-e:2',3' -g][2,1,3]Tin salt of benzothiadiazole (100 mg,0.071 mmol), toluene (20 mL), put in a Schlenk vacuum sealed bottle, after freezing with liquid nitrogen, three cycles of vacuum pumping and argon filling were performed, and catalyst Pd (PPh) was rapidly added 3 ) 4 (11 mg,0.02 mmol) was frozen and drawn three times. The reaction was heated at 110℃for 24h under reflux. And (3) removing redundant solvent by rotary evaporation, adding a few drops of chloroform into a eggplant-shaped bottle until the product can be completely dissolved, dropwise adding the dissolved system into a methanol solution by using a dropper to generate green precipitate, performing vacuum suction filtration, washing the precipitate on filter paper for two to three times by using methanol, and drying the precipitate on filter paper to obtain a crude product. The product was isolated by silica gel column using a mixed solution of n-hexane and dichloromethane as eluent and dried sufficiently in a vacuum oven to give 118mg of product Q4-4F (green solid, yield 93%).
Example 3
The embodiment provides a method for preparing single bond coupled A-D-A electron acceptor Q5-4F by using 2-bromo-methyl benzoate as an initial raw material, which comprises the following steps:
the reaction equation is:
the synthesis steps of the intermediate and Q5-4F are as follows:
5, 6-difluoroindan-1, 3-dione (1 g,5.49 mmol) was placed in 50mL of ethanol at 0deg.C, and N-bromosuccinimide (1.95 g,10.98 mmol) was added. The reaction was stirred for 1 hour, thiourea (0.84 g,10.98 mmol) was added and DMF (0.43 mL,5.49 mmol) was added to catalyze the reaction and the reaction was refluxed for 4-5 hours. Adding the reaction product into ice water for quenching to obtain a suspension containing brick red precipitate, and filtering to obtain a red powdery second intermediate.
CuBr (1.45 g,10.1 mmol) was added to a MeCN (25 mL) solution at 60℃and t BuONO (1.49 mL,12.6 mmol) and stirred for 10 min. To the reaction was added the second intermediate (1 g,4.20 mmol) and the reaction mixture was stirred at 60℃for 1 hour. After the reaction, the reaction mixture was poured into 1N HCl solution and treated with CH 2 Cl 2 Extracting with water for three times, collecting organic layer, concentrating, purifying with silica gel chromatographic column, eluting with n-hexane/CH 2 Cl 2 (6:1, v/v) to afford a third intermediate (1.16 g, 70%) as a yellow solid.
The third intermediate (200 mg,0.66 mmol) and CH 3 COONa (65.17 mg,0.79 mmol) was added to CHCl 3 To a solution (10 mL) was added malononitrile (43.74 mg,0.66 mmol). The mixed solution was stirred at 60℃for 2 hours. The excess reaction solution was removed and purified by silica gel chromatography column using n-hexane/CH 2 Cl 2 (3:1, v/v) as eluent, yielding the fourth intermediate at the electron acceptor terminus (148 mg, 64%) as a purple solid.
Under the protection of argon, a fourth intermediate (60 mg,0.171 mmol) and tin benzodithiophene salt (90 mg,0.085 mmol), toluene (20 mL) are placed in a Schlenk vacuum sealing bottle, after liquid nitrogen freezing, three cycles of vacuumizing and argon filling are carried out, and catalyst Pd (PPh) is rapidly added 3 ) 4 (11 mg,0.02 mmol) was frozen and drawn three times. The reaction was heated at 110℃for 24h under reflux. And (3) removing redundant solvent by rotary evaporation, adding a few drops of chloroform into a eggplant-shaped bottle until the product can be completely dissolved, dropwise adding the dissolved system into a methanol solution by using a dropper to generate green precipitate, performing vacuum suction filtration, washing the precipitate on filter paper for two to three times by using methanol, and drying the precipitate on filter paper to obtain a crude product. The product was isolated using a silica gel column with a mixed solution of n-hexane and dichloromethane as eluent and dried thoroughly in a vacuum oven to give 103mg of product Q5-4F (green solid, 92% yield).
Example 4
The embodiment provides a method for preparing single bond coupled A-D-A electron acceptor Q6-4F by using 2-bromo-methyl benzoate as an initial raw material, which comprises the following steps:
the reaction equation is:
the synthesis steps of the intermediate and Q6-4F are as follows:
5, 6-difluoroindan-1, 3-dione (1 g,5.49 mmol) was placed in 50mL of ethanol at 0deg.C, and N-bromosuccinimide (1.95 g,10.98 mmol) was added. The reaction was stirred for 1 hour, thiourea (0.84 g,10.98 mmol) was added and DMF (0.43 mL,5.49 mmol) was added to catalyze the reaction and the reaction was refluxed for 4-5 hours. Adding the reaction product into ice water for quenching to obtain a suspension containing brick red precipitate, and filtering to obtain a red powdery second intermediate.
CuBr (1.45 g,10.1 mmol) was added to a MeCN (25 mL) solution at 60℃and t BuONO (1.49 mL,12.6 mmol) and stirred for 10 min. To the reaction was added the second intermediate (1 g,4.20 mmol) and the reaction mixture was stirred at 60℃for 1 hour. After the reaction, the reaction mixture was poured into 1N HCl solution and treated with CH 2 Cl 2 Extracting with water for three times, collecting organic layer, concentrating, purifying with silica gel chromatographic column, eluting with n-hexane/CH 2 Cl 2 (6:1, v/v) to afford a third intermediate (1.16 g, 70%) as a yellow solid.
The third intermediate (200 mg,0.66 mmol) and CH 3 COONa (65.17 mg,0.79 mmol) was added to CHCl 3 To a solution (10 mL) was added malononitrile (43.74 mg,0.66 mmol). The mixed solution was stirred at 60℃for 2 hours. The excess reaction solution was removed and purified by silica gel chromatography column using n-hexane/CH 2 Cl 2 (3:1, v/v) as eluent, yielding the fourth intermediate at the electron acceptor terminus (148 mg, 64%) as a purple solid.
Under the protection of argon, a fourth intermediate (60 mg,0.171 mmol) and 10, 11-bis (2-hexyldecyl) -10, 11-dihydro-dithieno [2',3':4,5]Pyrrolo [3,2-e:2',3' -g][2,1,3]Tin salt of benzothiadiazole (86 mg,0.083 mmol), toluene (20 mL), were placed in a Schlenk vacuum flask, frozen with liquid nitrogen, and then subjected to three cycles of vacuum pumping and argon filling, and catalyst Pd (PPh) was rapidly added 3 ) 4 (11 mg,0.02 mmol) was frozen and drawn three times. The reaction was heated at 110℃for 24h under reflux. And (3) removing redundant solvent by rotary evaporation, adding a few drops of chloroform into a eggplant-shaped bottle until the product can be completely dissolved, dropwise adding the dissolved system into a methanol solution by using a dropper to generate green precipitate, performing vacuum suction filtration, washing the precipitate on filter paper for two to three times by using methanol, and drying the precipitate on filter paper to obtain a crude product. Using silica gel column to make the mixtureThe product was isolated using a mixture of alkane and dichloromethane as eluent and dried thoroughly in a vacuum oven to give 105mg of product Q6-4F (green solid, 95% yield).
Example 5
The embodiment provides a method for preparing single bond coupled A-D-A electron acceptor Q7-4F by using 2-bromo-methyl benzoate as an initial raw material, which comprises the following steps:
the reaction equation is:
the synthesis steps of the intermediate and Q7-4F are as follows:
5, 6-difluoroindan-1, 3-dione (1 g,5.49 mmol) was placed in 50mL of ethanol at 0deg.C, and N-bromosuccinimide (1.95 g,10.98 mmol) was added. The reaction was stirred for 1 hour, thiourea (0.84 g,10.98 mmol) was added and DMF (0.43 mL,5.49 mmol) was added to catalyze the reaction and the reaction was refluxed for 4-5 hours. Adding the reaction product into ice water for quenching to obtain a suspension containing brick red precipitate, and filtering to obtain a red powdery second intermediate.
CuBr (1.45 g,10.1 mmol) was added to a MeCN (25 mL) solution at 60℃and t BuONO (1.49 mL,12.6 mmol) and stirred for 10 min. To the reaction was added the second intermediate (1 g,4.20 mmol) and the reaction mixture was stirred at 60℃for 1 hour. After the reaction, the reaction mixture was poured into 1N HCl solution and treated with CH 2 Cl 2 Extracting with water for three times, collecting organic layer, concentrating, purifying with silica gel chromatographic column, eluting with n-hexane/CH 2 Cl 2 (6:1, v/v) to afford a third intermediate (1.16 g, 70%) as a yellow solid.
The third intermediate (200 mg,0.66 mmol) and CH 3 COONa (65.17 mg,0.79 mmol) was added to CHCl 3 To a solution (10 mL) was added malononitrile (43.74 mg,0.66 mmol). The mixed solution was stirred at 60℃for 2 hours. The excess reaction solution was removed and purified by silica gel chromatography column using n-hexane/CH 2 Cl 2 (3:1, v/v) as eluent to give a fourth intermediate at the end of the electron acceptor (148 mg, 64%),as a violet solid.
Under the protection of argon, the fourth intermediate (60 mg,0.171 mmol) and 5, 11-bis [ (2-butyldecyl) oxy]-4, 10-dihydro-hexylthieno [3,2-b ]]Thieno [2",3":4",5 ]"]Pyrrolo [2",3":4',5 ]']Thieno [2',3':5,6][1]Benzothieno [2,3-d ]]Tin salt of pyrrole (100 mg,0.075 mmol), toluene (20 mL), put in a Schlenk vacuum sealed bottle, frozen with liquid nitrogen, and subjected to three cycles of vacuum pumping and argon filling, and catalyst Pd (PPh) was added rapidly 3 ) 4 (11 mg,0.02 mmol) was frozen and drawn three times. The reaction was heated at 110℃for 24h under reflux. And (3) removing redundant solvent by rotary evaporation, adding a few drops of chloroform into a eggplant-shaped bottle until the product can be completely dissolved, dropwise adding the dissolved system into a methanol solution by using a dropper to generate green precipitate, performing vacuum suction filtration, washing the precipitate on filter paper for two to three times by using methanol, and drying the precipitate on filter paper to obtain a crude product. The product was isolated using a silica gel column with a mixed solution of n-hexane and dichloromethane as eluent and dried thoroughly in a vacuum oven to give 108mg of product Q7-4F (green solid, 95% yield).
Example 6
This example provides a method for preparing single bond coupled A-D-A electron acceptor Q3-4Cl, comprising the following steps:
the reaction equation is as follows:
the synthesis steps of the intermediate and Q3-4Cl are as follows:
5, 6-dichloro-indan-1, 3-dione (1 g,5.49 mmol) was placed in 50mL of ethanol at 0deg.C, and N-bromosuccinimide (1.95 g,10.98 mmol) was added. The reaction was stirred for 1 hour, thiourea (0.84 g,10.98 mmol) was added and DMF (0.43 mL,5.49 mmol) was added to catalyze the reaction and the reaction was refluxed for 4-5 hours. Adding the reaction product into ice water for quenching to obtain a suspension containing brick red precipitate, and filtering to obtain a red powdery sixth intermediate.
CuBr (1.45 g,10.1 mmol) was added to a MeCN (25 mL) solution at 60℃and t BuONO (1.49 mL,12.6 mmol) and stirred for 10 minAnd (3) a clock. A sixth intermediate (1 g,4.20 mmol) was added to the reaction system and the reaction mixture was stirred at 60℃for 1 hour. After the reaction, the reaction mixture was poured into 1N HCl solution and treated with CH 2 Cl 2 Extracting with water for three times, collecting organic layer, concentrating, purifying with silica gel chromatographic column, eluting with n-hexane/CH 2 Cl 2 (6:1, v/v) to afford seventh intermediate (1.16 g, 70%) as a yellow solid.
Seventh intermediate (200 mg,0.66 mmol) and CH 3 COONa (65.17 mg,0.79 mmol) was added to CHCl 3 To a solution (10 mL) was added malononitrile (43.74 mg,0.66 mmol). The mixed solution was stirred at 60℃for 2 hours. The excess reaction solution was removed and purified by silica gel chromatography column using n-hexane/CH 2 Cl 2 (3:1, v/v) as eluent, yielding the electron acceptor end eighth intermediate (148 mg, 64%) as a purple solid.
Under the protection of argon, placing an eighth intermediate (60 mg,0.171 mmol) and indacenothiotin salt (96 mg,0.078 mmol) and toluene (20 mL) in a Schlenk vacuum sealing bottle, freezing with liquid nitrogen, performing three times of vacuum pumping and argon filling cycles, and rapidly adding catalyst Pd (PPh 3 ) 4 (11 mg,0.02 mmol) was frozen and drawn three times. The reaction was heated at 110℃for 24h under reflux. And (3) removing redundant solvent by rotary evaporation, adding a few drops of chloroform into a eggplant-shaped bottle until the product can be completely dissolved, dropwise adding the dissolved system into a methanol solution by using a dropper to generate green precipitate, performing vacuum suction filtration, washing the precipitate on filter paper for two to three times by using methanol, and drying the precipitate on filter paper to obtain a crude product. The product was isolated using a silica gel column with a mixture of n-hexane and dichloromethane as eluent and dried thoroughly in a vacuum oven to give 105mg of product Q3-4Cl (green solid, 96% yield).
Example 7
This example provides a method for preparing a single bond coupled A-D-A electron acceptor Q4-4Cl, comprising the following steps:
the reaction equation is as follows:
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the synthesis steps of the intermediate and Q4-4Cl are as follows:
5, 6-dichloro-indan-1, 3-dione (1 g,5.49 mmol) was placed in 50mL of ethanol at 0deg.C, and N-bromosuccinimide (1.95 g,10.98 mmol) was added. The reaction was stirred for 1 hour, thiourea (0.84 g,10.98 mmol) was added and DMF (0.43 mL,5.49 mmol) was added to catalyze the reaction and the reaction was refluxed for 4-5 hours. Adding the reaction product into ice water for quenching to obtain a suspension containing brick red precipitate, and filtering to obtain a red powdery sixth intermediate.
CuBr (1.45 g,10.1 mmol) was added to a MeCN (25 mL) solution at 60℃and t BuONO (1.49 mL,12.6 mmol) and stirred for 10 min. A sixth intermediate (1 g,4.20 mmol) was added to the reaction system and the reaction mixture was stirred at 60℃for 1 hour. After the reaction, the reaction mixture was poured into 1N HCl solution and treated with CH 2 Cl 2 Extracting with water for three times, collecting organic layer, concentrating, purifying with silica gel chromatographic column, eluting with n-hexane/CH 2 Cl 2 (6:1, v/v) to afford seventh intermediate (1.16 g, 70%) as a yellow solid.
Seventh intermediate (200 mg,0.66 mmol) and CH 3 COONa (65.17 mg,0.79 mmol) was added to CHCl 3 To a solution (10 mL) was added malononitrile (43.74 mg,0.66 mmol). The mixed solution was stirred at 60℃for 2 hours. The excess reaction solution was removed and purified by silica gel chromatography column using n-hexane/CH 2 Cl 2 (3:1, v/v) as eluent, yielding the electron acceptor end eighth intermediate (148 mg, 64%) as a purple solid.
Eighth intermediate (60 mg,0.171 mmol) and 12- (2-butyloctyl) -13- (2-ethylhexyl) -12, 13-dihydro-3, 9-bisdecanyl-dithiophene [2',3': 4',5' -under argon ']Thiophene [2',3':4,5]Pyrrole [3,2-e:2',3' -g][2,1,3]Tin salt of benzothiadiazole (80 mg,0.065 mmol), toluene (20 mL), were placed in a Schlenk vacuum flask, frozen with liquid nitrogen, and then subjected to three cycles of vacuum pumping and argon filling, and catalyst Pd (PPh) was rapidly added 3 ) 4 (11 mg,0.02 mmol) was frozen and drawn three times. The reaction was heated at 110℃for 24h under reflux. Removing excessive solvent by rotary evaporation, adding a few drops of chloroform into eggplant-shaped bottle until the product is completely dissolved,and (3) dropwise adding the dissolved system into a methanol solution by using a dropper to generate green precipitate, performing vacuum filtration, washing twice to three times by using methanol, and drying the precipitate on filter paper to obtain a crude product. The product was isolated using a silica gel column with a mixture of n-hexane and dichloromethane as eluent and dried thoroughly in a vacuum oven to give 85mg of product Q4-4Cl (green solid, 96% yield).
Example 8
This example provides a method for preparing single bond coupled A-D-A electron acceptor Q5-4Cl, comprising the following steps:
the reaction equation is as follows:
the synthesis steps of the intermediate and Q5-4Cl are as follows:
5, 6-dichloro-indan-1, 3-dione (1 g,5.49 mmol) was placed in 50mL of ethanol at 0deg.C, and N-bromosuccinimide (1.95 g,10.98 mmol) was added. The reaction was stirred for 1 hour, thiourea (0.84 g,10.98 mmol) was added and DMF (0.43 mL,5.49 mmol) was added to catalyze the reaction and the reaction was refluxed for 4-5 hours. Adding the reaction product into ice water for quenching to obtain a suspension containing brick red precipitate, and filtering to obtain a red powdery sixth intermediate.
CuBr (1.45 g,10.1 mmol) was added to a MeCN (25 mL) solution at 60℃and t BuONO (1.49 mL,12.6 mmol) and stirred for 10 min. A sixth intermediate (1 g,4.20 mmol) was added to the reaction system and the reaction mixture was stirred at 60℃for 1 hour. After the reaction, the reaction mixture was poured into 1N HCl solution and treated with CH 2 Cl 2 Extracting with water for three times, collecting organic layer, concentrating, purifying with silica gel chromatographic column, eluting with n-hexane/CH 2 Cl 2 (6:1, v/v) to afford seventh intermediate (1.16 g, 70%) as a yellow solid.
Seventh intermediate (200 mg,0.66 mmol) and CH 3 COONa (65.17 mg,0.79 mmol) was added to CHCl 3 To a solution (10 mL) was added malononitrile (43.74 mg,0.66 mmol). The mixed solution was stirred at 60℃for 2 hours. Removing excess reactionThe solution was purified by silica gel chromatography column with n-hexane/CH 2 Cl 2 (3:1, v/v) as eluent, yielding the electron acceptor end eighth intermediate (148 mg, 64%) as a purple solid.
Under the protection of argon, an eighth intermediate (60 mg,0.171 mmol) and tin salt of benzodithiophene (92 mg,0.081 mmol), toluene (20 mL) are placed in a Schlenk vacuum sealing bottle, after liquid nitrogen freezing, three cycles of vacuumizing and argon filling are carried out, and catalyst Pd (PPh) is rapidly added 3 ) 4 (11 mg,0.02 mmol) was frozen and drawn three times. The reaction was heated at 110℃for 24h under reflux. And (3) removing redundant solvent by rotary evaporation, adding a few drops of chloroform into a eggplant-shaped bottle until the product can be completely dissolved, dropwise adding the dissolved system into a methanol solution by using a dropper to generate green precipitate, performing vacuum suction filtration, washing the precipitate on filter paper for two to three times by using methanol, and drying the precipitate on filter paper to obtain a crude product. The product was isolated using a silica gel column with a mixture of n-hexane and dichloromethane as eluent and dried thoroughly in a vacuum oven to give 98mg of product Q5-4Cl (green solid, 88% yield).
Example 9
This example provides a method for preparing single bond coupled A-D-A electron acceptor Q6-4Cl, comprising the following steps:
the reaction equation is as follows:
the synthesis steps of the intermediate and Q6-4Cl are as follows:
5, 6-dichloro-indan-1, 3-dione (1 g,5.49 mmol) was placed in 50mL of ethanol at 0deg.C, and N-bromosuccinimide (1.95 g,10.98 mmol) was added. The reaction was stirred for 1 hour, thiourea (0.84 g,10.98 mmol) was added and DMF (0.43 mL,5.49 mmol) was added to catalyze the reaction and the reaction was refluxed for 4-5 hours. Adding the reaction product into ice water for quenching to obtain a suspension containing brick red precipitate, and filtering to obtain a red powdery sixth intermediate.
CuBr (1.45 g,10.1 mmol) was added to a MeCN (25 mL) solution at 60℃and t BuONO (1.49 mL,12.6 mmol) and stirred for 10 minAnd (3) a clock. A sixth intermediate (1 g,4.20 mmol) was added to the reaction system and the reaction mixture was stirred at 60℃for 1 hour. After the reaction, the reaction mixture was poured into 1N HCl solution and treated with CH 2 Cl 2 Extracting with water for three times, collecting organic layer, concentrating, purifying with silica gel chromatographic column, eluting with n-hexane/CH 2 Cl 2 (6:1, v/v) to afford seventh intermediate (1.16 g, 70%) as a yellow solid.
Seventh intermediate (200 mg,0.66 mmol) and CH 3 COONa (65.17 mg,0.79 mmol) was added to CHCl 3 To a solution (10 mL) was added malononitrile (43.74 mg,0.66 mmol). The mixed solution was stirred at 60℃for 2 hours. The excess reaction solution was removed and purified by silica gel chromatography column using n-hexane/CH 2 Cl 2 (3:1, v/v) as eluent, yielding the electron acceptor end eighth intermediate (148 mg, 64%) as a purple solid.
Eighth intermediate (60 mg,0.171 mmol) and 10, 11-bis (2-hexyldecyl) -10, 11-dihydro-dithieno [2',3':4,5 were taken under argon]Pyrrolo [3,2-e:2',3' -g][2,1,3]Benzothiadiazole tin salt (90 mg,0.075 mmol), toluene (20 mL) were placed in a Schlenk vacuum sealed bottle, after freezing with liquid nitrogen, three cycles of vacuum pumping and argon filling were performed, and catalyst Pd (PPh) was rapidly added 3 ) 4 (11 mg,0.02 mmol) was frozen and drawn three times. The reaction was heated at 110℃for 24h under reflux. And (3) removing redundant solvent by rotary evaporation, adding a few drops of chloroform into a eggplant-shaped bottle until the product can be completely dissolved, dropwise adding the dissolved system into a methanol solution by using a dropper to generate green precipitate, performing vacuum suction filtration, washing the precipitate on filter paper for two to three times by using methanol, and drying the precipitate on filter paper to obtain a crude product. The product was isolated using a silica gel column with a mixture of n-hexane and dichloromethane as eluent and dried thoroughly in a vacuum oven to give 78mg of product Q6-4Cl (green solid, 90% yield).
Example 10
This example provides a method for preparing single bond coupled A-D-A electron acceptor Q7-4Cl, comprising the following steps:
the reaction equation is as follows:
the intermediate and Q7-4Cl are synthesized as follows:
5, 6-dichloro-indan-1, 3-dione (1 g,5.49 mmol) was placed in 50mL of ethanol at 0deg.C, and N-bromosuccinimide (1.95 g,10.98 mmol) was added. The reaction was stirred for 1 hour, thiourea (0.84 g,10.98 mmol) was added and DMF (0.43 mL,5.49 mmol) was added to catalyze the reaction and the reaction was refluxed for 4-5 hours. Adding the reaction product into ice water for quenching to obtain a suspension containing brick red precipitate, and filtering to obtain a red powdery sixth intermediate.
CuBr (1.45 g,10.1 mmol) was added to a MeCN (25 mL) solution at 60℃and t BuONO (1.49 mL,12.6 mmol) and stirred for 10 min. A sixth intermediate (1 g,4.20 mmol) was added to the reaction system and the reaction mixture was stirred at 60℃for 1 hour. After the reaction, the reaction mixture was poured into 1N HCl solution and treated with CH 2 Cl 2 Extracting with water for three times, collecting organic layer, concentrating, purifying with silica gel chromatographic column, eluting with n-hexane/CH 2 Cl 2 (6:1, v/v) to afford seventh intermediate (1.16 g, 70%) as a yellow solid.
Seventh intermediate (200 mg,0.66 mmol) and CH 3 COONa (65.17 mg,0.79 mmol) was added to CHCl 3 To a solution (10 mL) was added malononitrile (43.74 mg,0.66 mmol). The mixed solution was stirred at 60℃for 2 hours. The excess reaction solution was removed and purified by silica gel chromatography column using n-hexane/CH 2 Cl 2 (3:1, v/v) as eluent, yielding the electron acceptor end eighth intermediate (148 mg, 64%) as a purple solid.
Under the protection of argon, eighth intermediate (60 mg,0.171 mmol) and 5, 11-bis [ (2-butyldecyl) oxy]-4, 10-dihydro-hexylthieno [3,2-b ]]Thieno [2",3":4",5 ]"]Pyrrolo [2",3":4',5 ]']Thieno [2',3':5,6][1]Benzothieno [2,3-d ]]Tin salt of pyrrole (95 mg,0.076 mmol), toluene (20 mL), put in a Schlenk vacuum sealed bottle, frozen with liquid nitrogen, and subjected to three cycles of vacuum pumping and argon filling, and catalyst Pd (PPh) was rapidly added 3 ) 4 (11 mg,0.02 mmol) was frozen and drawn three times. Heating reflux reaction at 110 DEG C24h. And (3) removing redundant solvent by rotary evaporation, adding a few drops of chloroform into a eggplant-shaped bottle until the product can be completely dissolved, dropwise adding the dissolved system into a methanol solution by using a dropper to generate green precipitate, performing vacuum suction filtration, washing the precipitate on filter paper for two to three times by using methanol, and drying the precipitate on filter paper to obtain a crude product. The product was isolated using a silica gel column with a mixture of n-hexane and dichloromethane as eluent and dried thoroughly in a vacuum oven to give 105mg of product Q7-4Cl (green solid, 89% yield).
Example 11
This example provides a photostability test for two single bond coupled A-D-A electron acceptors Q3-4F and Q3-4Cl, as follows:
10mg of Q3-4F prepared in example 1 and Q3-4Cl prepared in example 6 were dissolved in 0.5mL of chloroform solution, respectively, and stirred for 0.5 hours to obtain a receptor solution. Spin-coating on the surface of quartz plate at 3000r/min to obtain a receptor film with a layer thickness of about 60 nm.
At an illumination intensity of 100mW/cm 2 Under the irradiation of AM1.5 simulated sunlight, a metal halide lamp without ultraviolet ray filtration is used as a light source, the light stability of the Q3-4F and Q3-4Cl films is tested under the atmosphere, and the change of the relative light absorption intensity is recorded.
Example 12
This example provides a thermal stability test of two single bond coupled A-D-A electron acceptors Q3-4F and Q3-4Cl, as follows:
10mg of Q3-4F prepared in example 1 and Q3-4Cl prepared in example 6 were taken respectively, and the degradation temperature was measured by heating at a rate of 10 ℃/min under nitrogen protection.
Example 13
The embodiment provides a preparation method of an organic solar cell device using Q1-4F as an electron acceptor, which comprises the following steps:
sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, and treating for 15 minutes by using oxygen plasma; spin-coating PEDOT (PSS) on the surface of the conductive glass, wherein the rotating speed is 3000r/min, and drying at 150 ℃ for 10 minutes; next to this, the process is carried out,spin-coating PM6 and Q1-4F mixed solution on the substrate at a rotating speed of 3000r/min, wherein the total concentration of the solution is 20mg/mL, the solvent is chloroform, the weight ratio of PM6 to Q1-4F is 1:1.5, and the spin-coating time is 40 seconds, so as to obtain a layer of PM6 and Q1-4F mixed film (active layer) with a thickness of 100 nm; annealing at 120 ℃ for 10 minutes; then spin coating a layer of Bis-FIMG on the active layer, wherein the rotating speed is 3000r/min, and the concentration of the solution is 2mg/mL; finally, at a pressure lower than 5X 10 -4 And evaporating a layer of Ag with the thickness of 100nm under Pa vacuum, thereby obtaining a complete organic solar cell device.
Example 14
The embodiment provides a preparation method of an organic solar cell device using Q3-4F as an electron acceptor, which comprises the following steps:
sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, and treating for 15 minutes by using oxygen plasma; spin-coating PEDOT (PSS) on the surface of the conductive glass, wherein the rotating speed is 3000r/min, and drying at 150 ℃ for 10 minutes; then spin-coating a mixed solution of PM6 and Q3-4F on the substrate at a rotating speed of 3000r/min, wherein the total concentration of the solution is 20mg/mL, the solvent is chloroform, the weight ratio of PM6 to Q3-4F is 1:1.5, and the spin-coating time is 40 seconds, so as to obtain a layer of PM6 and Q3-4F blend film (active layer) with a thickness of 100 nm; annealing at 120 ℃ for 10 minutes; then spin coating a layer of Bis-FIMG on the active layer, wherein the rotating speed is 3000r/min, and the concentration of the solution is 2mg/mL; finally, at a pressure lower than 5X 10 -4 And evaporating a layer of Ag with the thickness of 100nm under Pa vacuum, thereby obtaining a complete organic solar cell device.
Example 15
The embodiment provides a preparation method of an organic solar cell device using Q2-4F as an electron acceptor, which comprises the following steps:
sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, and treating for 15 minutes by using oxygen plasma; spin-coating PEDOT (PSS) on the surface of the conductive glass, wherein the rotating speed is 3000r/min, and drying at 150 ℃ for 10 minutes; next, PM6 and Q2-4F are spin-coated thereonMixing the solution at a rotating speed of 3000r/min, wherein the total concentration of the solution is 20mg/mL, the solvent is chloroform, the weight ratio of PTB7-Th to Q2-4F is 1:1.5, and the spin coating time is 40 seconds, so as to obtain a layer of PM6 and Q2-4F blend film (active layer) with a thickness of 100 nm; annealing at 120 ℃ for 10 minutes; then spin coating a layer of Bis-FIMG on the active layer, wherein the rotating speed is 3000r/min, and the concentration of the solution is 2mg/mL; finally, at a pressure lower than 5X 10 -4 And evaporating a layer of Ag with the thickness of 100nm under Pa vacuum, thereby obtaining a complete organic solar cell device.
Example 16
The embodiment provides a preparation method of an organic solar cell device using Q4-4F as an electron acceptor, which comprises the following steps:
sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, and treating for 15 minutes by using oxygen plasma; spin-coating PEDOT (PSS) on the surface of the conductive glass, wherein the rotating speed is 3000r/min, and drying at 150 ℃ for 10 minutes; then, spin-coating a mixed solution of PTB7-Th and Q4-4F on the substrate at a rotating speed of 3000r/min, wherein the total concentration of the solution is 20mg/mL, the solvent is chloroform, the weight ratio of PTB7-Th to Q4-4F is 1:1.5, and the spin-coating time is 40 seconds, so as to obtain a blend film (active layer) of PTB7-Th and Q4-4F, wherein the thickness of the blend film is 100 nm; annealing at 120 ℃ for 10 minutes; then spin coating a layer of Bis-FIMG on the active layer, wherein the rotating speed is 3000r/min, and the concentration of the solution is 2mg/mL; finally, at a pressure lower than 5X 10 -4 And evaporating a layer of Ag with the thickness of 100nm under Pa vacuum, thereby obtaining a complete organic solar cell device.
Comparative example 1
This comparative example provides light stability testing of four conventional electron acceptors IT-4F, IT-4F, IT-M and IT-CC, as follows:
10mg of IT-4F, IT-4F, IT-M and IT-CC, respectively, were dissolved in 0.5mL of chloroform solution and stirred for 0.5 hours to obtain a receptor solution. Spin-coating on the surface of quartz plate at 3000r/min to obtain a receptor film with a layer thickness of about 60 nm.
At an illumination intensity of 100mW/cm 2 AM1.5 of (c) simulated solar radiationThe light stability of IT-4F, IT-4F, IT-M and IT-CC films was tested under atmospheric conditions using a metal halide lamp without UV filtration as the light source, and the change in relative absorbance intensity was recorded.
Comparative example 2
This comparative example provides thermal stability testing of four conventional A-D-A electron acceptors IT-4F, IT-IC, IT-M, IT-CC, as follows:
10mg of the traditional electron acceptors IT-4F, IT-IC and IT-M, IT-CC are respectively taken, heated at a speed of 10 ℃/min under the protection of nitrogen, and the degradation temperature is tested.
In the stability test of examples 11 and 12 and comparative examples 1 and 2 described above, the structural formulas of the conventional a-D-a electron acceptor and single bond coupled a-D-a electron acceptor structures used are as follows, respectively:
wherein:
the photostability comparison of the single bond coupled A-D-A electron acceptor and the conventional A-D-A electron acceptor in example 11 and comparative example 1 is shown in FIG. 2:
as shown in FIG. 2 (a), the relative absorbance of the IT-4F film gradually decreased with increasing illumination time, and after 8 hours of the experiment, the film was nearly transparent, with an absorbance of about 28% of the initial intensity. As shown in FIG. 2 (b), the relative absorbance of the IT-IC film gradually decreased with increasing illumination time, and after 8 hours of the experiment, the film was nearly transparent, with an absorbance of about 3% of the initial intensity. As shown in FIG. 2 (c), the relative absorbance intensity of the IT-M film gradually decreased with increasing illumination time, and after 8 hours of the experiment, the film was nearly transparent, with an absorbance intensity of about 4% of the initial intensity. As shown in FIG. 2 (d), the relative absorbance of the IT-CC film gradually decreased with increasing illumination time, and after 8 hours of the experiment, the film was nearly transparent, with an absorbance of about 19% of the initial intensity.
As shown in FIG. 2 (e), the relative absorbance of the Q3-4F film did not change much, and after 8 hours of the experiment, the film color did not change significantly, and the light absorption intensity was about 91% of the initial intensity. As shown in FIG. 2 (f), the relative absorbance intensity of the Q3-4Cl film remained substantially unchanged with prolonged illumination time, and after 8 hours of the experiment, the film color did not change, and the light absorbance intensity did not change much from the initial intensity.
The thermal stability comparison of the single bond coupled A-D-A electron acceptor and the conventional A-D-A electron acceptor in example 12 and comparative example 2 is shown in FIG. 3:
as the temperature increases, thermal degradation of the material occurs at temperatures (corresponding to 5% of the relative mass degraded) of 349 ℃ (IT-4F), 359 ℃ (IT-IC), 373 ℃ (IT-M), 375 ℃ (IT-CC), 407 ℃ (Q3-4F), 409 ℃ (Q3-4 Cl), respectively.
In the photoelectric performance test of the devices of examples 13 to 16, the structural formulae of the single bond coupled a-D-a electron acceptor structures used were as follows:
in example 13: at an illumination intensity of 100mW/cm 2 The current-voltage curve based on the PM6:Q1-4F device under the AM1.5 simulated sunlight is shown in FIG. 4, from which an open circuit voltage of 0.82V and a short circuit current density of 12.99mA/cm were obtained 2 The fill factor was 0.75 and the photoelectric energy conversion efficiency was 7.98%.
In example 14: at an illumination intensity of 100mW/cm 2 The current-voltage curve based on the PM6:Q3-4F device under the AM1.5 simulated sunlight is shown in FIG. 4, from which an open circuit voltage of 0.79V and a short circuit current density of 17.68mA/cm were obtained 2 The fill factor was 0.74 and the photoelectric energy conversion efficiency was 10.43%.
In example 15: at an illumination intensity of 100mW/cm 2 The current-voltage curve based on PTB7-Th: Q2-4F device under AM1.5 simulated sunlight is shown in FIG. 5, from which an open circuit voltage of 0.78V and a short circuit current density of 13.05mA/cm were obtained 2 The filling factor is 0.65, and the photoelectric energy is convertedThe conversion efficiency is 6.79%
In example 16: at an illumination intensity of 100mW/cm 2 The current-voltage curve based on PTB7-Th: Q4-4F device under AM1.5 simulated sunlight is shown in FIG. 5, from which an open circuit voltage of 0.74V and a short circuit current density of 16.45mA/cm were obtained 2 The fill factor was 0.73 and the photoelectric energy conversion efficiency was 9.14%.
From this, it can be seen that the organic solar cell receptor material prepared by the present invention has excellent intrinsic chemical stability and thermal stability, wherein the optical stability and thermal stability of Q3-4Cl are optimal, as shown in fig. 2.
According to examples 13 to 16, as shown in fig. 4 and 5, substitution of thiophene units in the a-electron fragment with thiazole units can improve electronegativity of the terminal electron fragment, reduce energy level of acceptor molecule, obtain higher exciton dissociation energy, and obtain higher photoelectric conversion efficiency.
The above embodiment is only a preferred embodiment of the present invention, but it is not intended to limit the present invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, all the technical schemes obtained by adopting the equivalent substitution or equivalent transformation are within the protection scope of the invention.

Claims (8)

1. An electron acceptor material based on the tail end of dicyanoindenothiazole is characterized in that the electron acceptor material takes an electron donating unit D as a core, and the two ends of the electron acceptor material are coupled with an electron withdrawing unit A through single bonds to form an A-D-A structure;
the A is one of the following chemical structural formulas, and is taken as an acceptor group:
the D is one of the following chemical structural formulas, and is taken as a donor group:
wherein R is 1 R is R 2 All are modification groups, X is a halogen atom;
the modification group R 1 Is one of the following chemical structural formulas:
the modification group R 2 Is one of the following chemical structural formulas:
2. the bis-cyano-indenothiazole-terminal based electron acceptor material of claim 1, wherein the electron acceptor material has one of the chemical formulas Q3-4F, Q4-4F, Q5-4F, Q6-4F, Q7-4F, Q3-4Cl, Q4-4Cl, Q5-4Cl, Q6-4Cl, Q7-4Cl, respectively:
3. an active layer of an organic solar cell, characterized in that the active layer is a blend film of an electron donor material and an electron acceptor material according to any one of claims 1 or 2.
4. An active layer of an organic solar cell according to claim 3, wherein the electron donor material is one of the following chemical formulas:
5. an active layer of an organic solar cell according to claim 3, wherein the mass ratio of electron donor material to electron acceptor material in the active layer is 1-5: 5 to 1; the thickness of the active layer is 10-1000 nm.
6. An active layer of an organic solar cell according to claim 3, wherein the active layer is annealed at a temperature of 20-250 ℃ for a time of 1-60 min.
7. An organic solar cell constructed with the active layer of any one of claims 3 to 6.
8. The organic solar cell according to claim 7, wherein the organic solar cell has a multilayer layered structure comprising a substrate, a cathode, an electron transport layer, an active layer, a hole transport layer, and an anode, which are stacked in this order.
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