CN109293693B - Novel dithieno-silicon heterocyclic cyclopentadiene organic solar cell receptor material and preparation method and application thereof - Google Patents

Novel dithieno-silicon heterocyclic cyclopentadiene organic solar cell receptor material and preparation method and application thereof Download PDF

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CN109293693B
CN109293693B CN201811375619.5A CN201811375619A CN109293693B CN 109293693 B CN109293693 B CN 109293693B CN 201811375619 A CN201811375619 A CN 201811375619A CN 109293693 B CN109293693 B CN 109293693B
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陆仕荣
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Chongqing Institute of Green and Intelligent Technology of CAS
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Abstract

The invention provides a novel dithieno-silacyclopentadiene organic solar cell receptor material, a preparation method and application thereof, wherein the dithieno-silacyclopentadiene organic solar cell receptor material is a linear non-fullerene organic solar cell receptor material with an A-D-A structure, and the structural general formula is as follows:
Figure DDA0001870656500000011
wherein m is a natural number, and the value of m is 2 or 3; r1And R2Is a straight or branched chain alkyl group containing from 1 to 20 carbon atoms; b is1And B2Is terminated for pulling electrons. The novel dithiophene silicon heterocyclic cyclopentadiene organic solar cell receptor material overcomes the defects that the existing non-fullerene micromolecule receptor material is simple in molecular structure, small in molecular weight, simple in preparation method, cheap and easily available in synthetic raw materials, and is beneficial to the early commercial application of organic solar cells.

Description

Novel dithieno-silicon heterocyclic cyclopentadiene organic solar cell receptor material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of solar cell materials, and particularly relates to a novel dithieno-silacyclopentadiene organic solar cell receptor material and a preparation method and application thereof.
Background
Solar photovoltaic technology has been developed for the past few decades, and it has been shown from the related data that the efficiency of thin-film solar cells with GaAs as the core has reached 28.8%, approaching its theoretical maximum 30%. Meanwhile, the development of organic solar cells is ongoing, the efficiency of the organic solar cells is improved from less than 1% at the beginning to 17.3% today, but at present, the organic solar cells are in the initial stage of theoretical research and industrial development, and the photoelectric conversion efficiency and the stability of devices still have a huge improvement space. The organic solar cell takes an organic photoelectric material as a semiconductor layer and generates current through a photovoltaic effect. The working principle is as follows: under the condition of illumination, the organic semiconductor layer absorbs photons to form excitons (electron-hole bound pairs), when the excitons diffuse to the donor-acceptor contact surface, the excitons are dissociated into free electrons and free holes under the action of the energy level difference of the donor-acceptor, and the free electrons and the free holes respectively move to the positive electrode and the negative electrode and are collected to form current. The organic solar cell has the characteristics of easy processing, wide material source, capability of using flexible materials as substrates and the like.
Organic Solar Cells can be classified into four types, i.e., all-Polymer organic Solar Cells, all-small-molecule organic Solar Cells, Polymer Donor-small-molecule acceptor organic Solar Cells, and small-molecule Donor-Polymer acceptor organic Solar Cells, according to the difference of the Materials of the active layers, wherein the Polymer Donor-small-molecule acceptor organic Solar Cells have the highest Efficiency and are most studied, and the single-junction Efficiency reaches 14.4% (Zhang S, QinY, Zhu J, et al.over 14% Efficiency in Polymer Solar Cells Enabled by a Chlorinated Polymer Donor J. Advanced Materials,2018,30(20): e1800868.), and the lamination Efficiency reaches 17.3% (Meng L, Zhang Y, Wan X, et al.organic and solution-treated Cells of Solar Cells 17.3% effect, J. 8).
In recent years, polymer donor-small molecule acceptor organic solar cells are developed rapidly, but the main research is focused on small molecule acceptors, but the high-efficiency small molecule acceptor materials have single structures and complicated synthesis so far, such as penta (IDT) and hepta-thiophene fused ring (IDTT) as cores and introduction of strong electron groups. Although the photoelectric conversion efficiency of the material is high, the material has a complex structure and a large molecular weight, and the material required in the synthesis process is expensive and difficult to prepare, so that the material is not suitable for commercial application. Therefore, it is necessary to develop a small molecule receptor material with easy preparation and high efficiency.
Disclosure of Invention
In view of the above, the primary object of the present invention is to provide a novel dithienosilene heterocyclic cyclopentadiene organic solar cell acceptor material, which has the advantages of simple structure, small molecular weight and high efficiency.
In order to achieve the purpose, the scheme adopted by the invention is as follows:
the novel dithieno-silacyclopentadiene organic solar cell receptor material is a linear non-fullerene organic solar cell receptor material with an A-D-A structure, and has a structural general formula as follows:
Figure GDA0002943714650000031
wherein m is a natural number, and the value of m is 2 or 3;
R1and R2Is a straight or branched chain alkyl group containing from 1 to 20 carbon atoms;
B1and B2For the purpose of pulling an electron end cap, the structure is selected from the following structures:
Figure GDA0002943714650000032
further, when m is 3, R1And R2Are all C8H17，B1And B2Are all made of
Figure GDA0002943714650000033
When the dithiophene silicon heterocyclic cyclopentadiene organic solar cell acceptor material is A1, the structural formula of A1 is as follows:
Figure GDA0002943714650000034
further, when m is 2, R1And R2Is C8H17，B1And B2Is composed of
Figure GDA0002943714650000035
The dithienosilene heterocyclic cyclopentadiene organic solar energyThe battery acceptor material is A2, and the structural formula of A2 is as follows:
Figure GDA0002943714650000041
the second purpose of the invention is to provide a preparation method of the novel dithieno-silacyclopentadiene organic solar cell receptor material, which is simple and easy to prepare, cheap and easily available in synthetic raw materials, and beneficial to the early commercial application of organic solar cells.
In order to achieve the purpose, the invention adopts the following technical scheme:
a novel preparation method of a dithieno-silacyclopentadiene organic solar cell receptor material is disclosed, wherein the novel dithieno-silacyclopentadiene organic solar cell receptor material is A1, and the structural formula of A1 is as follows:
Figure GDA0002943714650000042
the preparation method of A1 comprises the following steps:
taking a double-mouth round-bottom flask, carrying out anhydrous and anaerobic treatment, sequentially adding a compound 4, 5, 6-difluoro-3- (dicyanomethylene) indene-1-ketone, pyridine and chloroform as solvents under the protection of nitrogen, heating, reacting overnight, monitoring by TLC, transferring a reaction solution into a separating funnel after the reaction is finished, extracting by dichloromethane, washing an organic phase by saturated saline, drying the organic phase by anhydrous sodium sulfate, concentrating, and carrying out column chromatography by using chloroform as an eluent to obtain a bluish black solid A1.
Preferably, the millimolar ratio of the compound 4, 5, 6-difluoro-3- (dicyanomethylene) indene-1-ketone, pyridine and chloroform before reaction is 0.1: 0.3: 2.5: 373.
further, the preparation method of the compound 4 comprises the following steps:
1) synthesis of Compound 1: taking a double-opening round-bottom flask, carrying out anhydrous anaerobic treatment, taking N' N-dimethylformamide as a solvent, sequentially adding dithieno-silacyclopentadiene and phosphorus oxychloride, stirring at room temperature, reacting overnight, monitoring by TLC, adding a dilute sodium hydroxide solution after the reaction is finished, quenching, transferring the reaction solution to a separating funnel, extracting with ethyl acetate, washing an organic phase with saturated saline solution, drying the organic phase with anhydrous sodium sulfate, concentrating, and then using petroleum ether: passing dichloromethane as eluent through column to obtain light yellow oily compound 1;
2) synthesis of Compound 2: taking a double-neck round-bottom flask, adding chloroform as a solvent, adding a compound 1, adding NBS at 0 ℃, returning to room temperature, stirring, reacting overnight, monitoring by TLC, transferring a reaction solution to a separating funnel after the reaction is finished, extracting by dichloromethane, washing an organic phase by saturated saline solution, drying the organic phase by anhydrous sodium sulfate, concentrating, and then using petroleum ether: passing dichloromethane as eluent through the column to obtain a yellow oily compound 2;
3) synthesis of Compound 3: taking a double-mouth round-bottom flask, carrying out anhydrous and anaerobic treatment, taking anhydrous tetrahydrofuran as a solvent, adding dithieno-silacyclopentadiene under the protection of nitrogen, adding n-butyl lithium at the temperature of-78 ℃, stirring for one hour at the temperature of-78 ℃, then adding trimethyl tin chloride, returning to room temperature, stirring, reacting overnight, monitoring by TLC, after the reaction is finished, adding a potassium fluoride solution into a reaction solution to quench the reaction, transferring the reaction solution into a separating funnel, extracting by using dichloromethane, washing an organic phase by using saturated saline solution, drying the organic phase by using anhydrous sodium sulfate, and concentrating under reduced pressure to obtain a yellow oily compound 3.
4) Taking a double-mouth round-bottom flask, carrying out anhydrous anaerobic treatment, sequentially adding a compound 2, a compound 3 and tetratriphenylphosphine palladium, replacing nitrogen for 3 times, adding toluene under the protection of nitrogen, heating until a reaction solution flows back, reacting overnight, monitoring by TLC, stopping heating after the reaction is finished, cooling the reaction solution to room temperature, transferring the reaction solution to a separating funnel, extracting with dichloromethane, washing an organic phase with saturated saline solution, drying the organic phase with anhydrous sodium sulfate, concentrating, and then using petroleum ether: dichloromethane was used as eluent to pass through the column to obtain compound 4 as red oil.
Preferably, the millimolar ratio of the dithienosilylcyclopentadiene, the phosphorus oxychloride and the DMF in the step 1) before the reaction is 10:10: 388; the mmol ratio of the compound 1, NBS, chloroform before reaction in step 2) is 3: 3: 249; the millimolar ratio of the dithienosilene hetero cyclopentadiene, the n-butyl lithium, the trimethyl tin chloride and the tetrahydrofuran before reaction in the step 3) is 1: 2.2: 2.4: 494; the millimolar ratio of the compound 2, the compound 3, the palladium tetratriphenylphosphine and the anhydrous toluene before the reaction in the step 4) is 2.1: 0.95: 0.1: 376.
the invention also aims to provide a preparation method of the novel dithieno-silicon heterocyclic cyclopentadiene organic solar cell receptor material, which is simple and feasible, and the raw materials are cheap and easy to obtain.
In order to achieve the purpose, the invention adopts the following scheme:
a novel preparation method of a dithieno-silacyclopentadiene organic solar cell receptor material is disclosed, wherein the novel dithieno-silacyclopentadiene organic solar cell receptor material is A2, and the structural formula of A2 is as follows:
Figure GDA0002943714650000061
the preparation method of A2 comprises the following steps:
taking a double-mouth round-bottom flask, carrying out anhydrous and anaerobic treatment, sequentially adding a compound 6, 5, 6-difluoro-3- (dicyanomethylene) indene-1-ketone, pyridine and chloroform as solvents under the protection of nitrogen, heating, reacting overnight, monitoring by TLC, transferring a reaction solution into a separating funnel after the reaction is finished, extracting by dichloromethane, washing an organic phase by saturated saline, drying the organic phase by anhydrous sodium sulfate, concentrating, and carrying out column chromatography by using chloroform as an eluent to obtain a bluish black solid A2.
Preferably, the millimolar ratio of the compound 6, 5, 6-difluoro-3- (dicyanomethylene) indene-1-one, pyridine and chloroform before reaction is 0.1: 0.3: 2.5: 373.
further, the preparation method of the compound 6 comprises the following steps:
taking a double-mouth round-bottom flask, carrying out anhydrous anaerobic treatment, and sequentially adding PdCl under the protection of nitrogen2(PhCN)2、KF，DMSO as solvent, heating, reacting overnight, monitoring by TLC, cooling the reaction solution to room temperature after the reaction is finished, transferring the reaction solution to a cold night funnel, extracting with dichloromethane, washing the organic phase with saturated saline solution, drying the organic phase with anhydrous sodium sulfate, concentrating the organic phase, and adding petroleum ether: dichloromethane was passed through the column to give compound 6 as an orange oil.
Preferably, the compound 2, PdCl2(PhCN)2The millimolar ratio of KF to DMSO before reaction was 3: 0.09: 6: 352.
the fourth purpose of the invention is to provide an application of the novel dithieno-silicon heterocyclic cyclopentadiene organic solar cell receptor material.
In order to achieve the purpose, the invention adopts the following scheme:
the novel dithiophene silicon heterocyclic cyclopentadiene organic solar cell receptor material is applied to the preparation of organic solar cells.
The fifth object of the present invention is to provide an organic solar cell.
In order to achieve the purpose, the invention adopts the following scheme:
an organic solar cell comprises a donor material and an acceptor material, wherein the acceptor material is the novel dithieno-silacyclopentadiene organic solar cell acceptor material, the donor material is PBDB-T, and the PBDB-T has a structural formula as follows:
Figure GDA0002943714650000081
the invention has the beneficial effects that: 1) the invention provides a novel dithieno-silacyclopentadiene organic solar cell receptor material, wherein the dithieno-silacyclopentadiene organic solar cell receptor materials A1 and A2 are simple linear structures, have simple molecular structures and small molecular weights, and have good visible light absorption range and absorption intensity;
2) compared with the prior art that a stille method is adopted to prepare the product, a bromination reactant and a tin reagent are adopted as reaction raw materials, the method adopts a direct oxidative coupling method, so that the preparation methods of the dithieno-silacyclopentadiene organic solar cell receptor materials A1 and A2 are simple, and the synthesis raw materials are cheap and easy to obtain;
3) the dithieno-silicon heterocyclic cyclopentadiene organic solar cell receptor material is applied to an organic solar cell photovoltaic device, so that the manufacturing cost of the device is greatly reduced on the basis of ensuring that the device obtains a good absorption range and absorption strength, and the early commercial application of the organic solar cell is facilitated;
in conclusion, the novel dithieno-silacyclopentadiene organic solar cell receptor material provided by the invention overcomes the defects that the existing non-fullerene micromolecule receptor material is complex in molecular structure, large in molecular weight, difficult in preparation process, expensive in synthesis raw materials, not beneficial to commercial application and the like, and is an ideal organic solar cell receptor material.
Drawings
FIG. 1 is a synthetic scheme of an acceptor material A1 prepared in example 1.
FIG. 2 is a synthetic scheme of the acceptor material A2 prepared in example 2.
FIG. 3 is a normalized UV-VIS absorption spectrum of the receptor material A1 prepared in example 1 in dilute solution and thin film states, respectively.
FIG. 4 is a normalized UV-VIS absorption spectrum of the receptor material A2 prepared in example 2 in dilute solution and thin film states, respectively.
FIG. 5 is a graph of electrochemical cyclic voltammetry for two acceptor materials, A1 and A2.
FIG. 6 is a current-voltage graph of a polymer solar cell photovoltaic device having the structure ITO/PEDOT: PSS/polymer PBDB-T/(A1/A2)/DPO/Ag.
Detailed Description
The examples are given for the purpose of better illustration of the invention, but the invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.
Petroleum ether, DMSO, methylene chloride, ethyl acetate, chloroform, toluene, sodium hydroxide, and silica gel for chromatography used in the following examples were purchased from Tokyo chemical Co., Ltd; anhydrous N, N-dimethylformamide, anhydrous tetrahydrofuran, N-butyllithium, palladium tetratriphenylphosphine, pyridine were purchased from shanghai taitan limited; dithienosilacyclopentadiene, 5, 6-difluoro-3- (dicyanomethylene) inden-1-one, was purchased from Jiangsu Giara Biotech, Inc. Except that the toluene in the purchased reagents needs to be subjected to anhydrous treatment by a solvent purification system, other reagents are directly used.
Example 1
A novel dithiophene silicon heterocyclic cyclopentadiene organic solar cell receptor material has a linear non-fullerene organic solar cell receptor material with an A-D-A structure, and the structural general formula is as follows:
Figure GDA0002943714650000101
when m is 3, R1And R2Is C8H17，B1And B2Is composed of
Figure GDA0002943714650000102
When the dithiophene silicon heterocyclic cyclopentadiene organic solar cell acceptor material is A1, the structural formula of A1 is as follows:
Figure GDA0002943714650000103
the preparation method of the A1 is as follows (the preparation route is shown in figure 1):
1) synthesis of Compound 1: taking a double-opening round-bottom flask, carrying out anhydrous anaerobic treatment, taking N' N-dimethylformamide as a solvent, sequentially adding dithieno-silacyclopentadiene and phosphorus oxychloride, stirring at room temperature, reacting overnight, monitoring by TLC, adding a dilute sodium hydroxide solution after the reaction is finished, quenching, transferring the reaction solution to a separating funnel, extracting with ethyl acetate, washing an organic phase with saturated saline solution, drying the organic phase with anhydrous sodium sulfate, concentrating, and then using petroleum ether: and (3) passing dichloromethane serving as an eluent through a column to obtain a light yellow oily compound 1, wherein the proportions of the dithienosilene heterocycle, the phosphorus oxychloride and the N' N-dimethylformamide are as follows: 10 parts of dithienosilene heterocyclic cyclopentadiene, 10 parts of phosphorus oxychloride, 30 parts of N', N-dimethylformamide by volume and 85% of yield;
2) synthesis of Compound 2: taking a double-neck round-bottom flask, adding chloroform as a solvent, adding a compound 1, adding NBS at 0 ℃, returning to room temperature, stirring, reacting overnight, monitoring by TLC, transferring a reaction solution to a separating funnel after the reaction is finished, extracting by dichloromethane, washing an organic phase by saturated saline solution, drying the organic phase by anhydrous sodium sulfate, concentrating, and then using petroleum ether: and (3) passing dichloromethane serving as an eluent through a column to obtain a yellow oily compound 2, wherein the mixture ratio of the compound 1, NBS and chloroform is as follows: 13 parts by weight of compound: NBS 3 parts by weight: chloroform volume 20, yield 76%;
3) synthesis of Compound 3: taking a double-mouth round-bottom flask, carrying out anhydrous anaerobic treatment, taking anhydrous tetrahydrofuran as a solvent, adding dithienosilene heteropentadiene under the protection of nitrogen, adding n-butyl lithium at the temperature of-78 ℃, stirring for one hour at the temperature of-78 ℃, then adding trimethyl tin chloride, returning to room temperature, stirring, reacting overnight, monitoring by TLC, after the reaction is finished, adding a potassium fluoride solution into a reaction solution to quench the reaction, transferring the reaction solution into a separating funnel, extracting by dichloromethane, washing an organic phase by saturated saline solution, drying the organic phase by anhydrous sodium sulfate, and concentrating under reduced pressure to obtain a yellow oily compound 3, wherein the ratio of the dithienosilene heteropentadiene, the n-butyl lithium, the trimethyl tin chloride and the tetrahydrofuran is as follows: 1 part by weight of dithienosilene heterocycle cyclopentadiene: 2.2 parts of n-butyl lithium: 2.4 parts of trimethyl tin chloride: tetrahydrofuran 40 volume parts, yield 95%;
4) synthesis of Compound 4: taking a double-mouth round-bottom flask, carrying out anhydrous anaerobic treatment, sequentially adding a compound 2, a compound 3 and tetratriphenylphosphine palladium, replacing nitrogen for 3 times, adding toluene under the protection of nitrogen, heating until a reaction solution flows back, reacting overnight, monitoring by TLC, stopping heating after the reaction is finished, cooling the reaction solution to room temperature, transferring the reaction solution to a separating funnel, extracting with dichloromethane, washing an organic phase with saturated saline solution, drying the organic phase with anhydrous sodium sulfate, concentrating, and then using petroleum ether: and (2) passing dichloromethane serving as an eluent through a column to obtain a red oily compound 4, wherein the mixture ratio of the compound 2 to the compound 3 to the palladium tetratriphenylphosphine to the anhydrous toluene is as follows: compound 22.1 parts by weight: compound 30.95 parts by weight: 0.1 part by weight of palladium tetratriphenylphosphine: 40 parts by volume of anhydrous toluene and 82% yield;
5) synthesis of a 1: taking a double-mouth round-bottom flask, carrying out anhydrous and anaerobic treatment, sequentially adding a compound 4, 5, 6-difluoro-3- (dicyanomethylene) indene-1-ketone and pyridine under the protection of nitrogen, heating at 70 ℃, reacting overnight, monitoring by TLC, transferring a reaction solution into a separating funnel after the reaction is finished, extracting by dichloromethane, washing an organic phase by saturated saline, drying the organic phase by anhydrous sodium sulfate, concentrating, and carrying out column chromatography by using chloroform as an eluent to obtain a bluish black solid A1, wherein the mixture ratio of the compound 2, the compound 3, the tetratriphenylphosphine palladium and the anhydrous toluene is as follows: compound 22.1 parts by weight: compound 30.95 parts by weight: 0.1 part by weight of palladium tetratriphenylphosphine: 40 parts by volume of anhydrous toluene, and the yield is 72%.
Example 2
A novel dithiophene silicon heterocyclic cyclopentadiene organic solar cell receptor material has a linear non-fullerene organic solar cell receptor material with an A-D-A structure, and the structural general formula is as follows:
Figure GDA0002943714650000121
when m is 2, R1And R2Is C8H17，B1And B2Is composed of
Figure GDA0002943714650000131
When the dithiophene silicon heterocyclic cyclopentadiene organic solar cell acceptor material is A2, the structural formula of A2 is as follows:
Figure GDA0002943714650000132
the preparation method of the A2 is as follows (the preparation route is shown in figure 2):
1) the synthesis of compound 2 is shown in example 1;
2) synthesis of Compound 6: taking a 100mL double-mouth round-bottom flask, carrying out anhydrous and anaerobic treatment, and sequentially adding a compound 2(3mmol) and PdCl under the protection of nitrogen2(PhCN)2(0.09mmol), KF (6mmol) and DMSO (25mL) are used as solvents, the mixture is heated to 60 ℃, the reaction is carried out overnight, TLC monitoring is carried out, after the reaction is finished, the heating is turned off, the reaction liquid is cooled to room temperature, then the reaction liquid is transferred to a separating funnel, dichloromethane is used for extraction, saturated saline solution (100mL multiplied by 3) is used for washing an organic phase, the organic phase is dried by anhydrous sodium sulfate and then concentrated, chloroform is used for column chromatography to obtain an orange oily compound 6, and the yield is 60%;
3) synthesis of a 2: taking a 100mL double-mouth round bottom flask, carrying out anhydrous and anaerobic treatment, sequentially adding a compound 6(0.1mmol), 5, 6-difluoro-3- (dicyanomethylene) indene-1-ketone (0.3mmol), pyridine (0.2mL) and chloroform (30mL) as solvents under the protection of nitrogen, heating at 70 ℃, reacting overnight, monitoring by TLC, stopping heating after the reaction is finished, cooling the reaction liquid to room temperature, transferring the reaction liquid into a separating funnel, extracting by dichloromethane, washing an organic phase by saturated saline (100mL multiplied by 3), drying the organic phase by anhydrous sodium sulfate, concentrating, and carrying out column chromatography by using chloroform as an eluent to obtain a blue-black solid A2 with the yield of 70%.
Example 3
The optical performance and electrochemical performance parameters of the novel dithieno-silicon heterocyclic cyclopentadiene organic solar cell receptor materials A1 and A2 are researched.
Optical and electrochemical performance parameters studies of a1 and a2 as shown in table 1, the electrochemical properties of a1 and a2 were characterized by Cyclic Voltammetry (CV). Ferrocene/ferrocene (Fc/Fc +) redox couple (4.8 eV below vacuum level) was used to calibrate the potential as an internal standard. As shown in FIG. 5, the Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) levels of A1 were-5.29 eV and-3.93 eV, and A2 was-5.26 eV and-3.87 eV, respectively, as calculated from the initial oxidation and reduction potentials. FIGS. 3 and 4 are normalized UV-VIS absorption spectra of the receptor materials A1 and A2 in dilute solution and thin film states, respectively, and it can be seen from FIGS. 3 and 4 that the maximum absorption peak at the long wavelength of the receptor material A1 in the thin film state is 858nm, which is red-shifted by 72nm compared to 786nm at the solution absorption; the maximum absorption peak at a long wavelength in the state of the receptor material A2 film was 841nm, which was red-shifted by 71nm from 776nm in the absorption of the solution. This indicates that the acceptor materials A1 and A2 have relatively strong intermolecular interactions in the solid state, resulting in tighter order of pi-pi stacking in the small molecule aggregation state.
Optical and electrochemical Performance parameters of tables 1, A1 and A2
Figure GDA0002943714650000141
Figure GDA0002943714650000151
Example 4
PBDB-T is used as a donor material, A1 or A2 is used as an acceptor material, and the performance of the solar cell manufactured according to ITO/PEDOT, PSS/PBDB-T (A1/A2)/B-n/DPO/Ag is researched.
The photovoltaic performance parameters of the polymer PBDB-T in the active layer of the solar cell photovoltaic device and the cells of two receptor materials B-n are shown in Table 2, and the Table 2 lists the main photovoltaic performance parameters of the polymer solar cell photovoltaic device based on the structure of ITO/PEDOT, PSS/PBDB-T (A1/A2)/B-n/DPO/Ag, such as open circuit voltage, short circuit current, filling factor, photoelectric conversion efficiency and the like; the current-voltage curve diagram of the polymer solar cell photovoltaic device is shown in fig. 6, when A1 is taken as an acceptor material, the short-circuit current and the open-circuit voltage of the device are respectively 21.4mA/cm2 and 0.64V; when A2 is used as the acceptor material, the short-circuit current and open-circuit voltage of the device are respectively 20.5mA/cm2 and 0.7V.
TABLE 2 photovoltaic Performance parameters of solar cells
Activelayer Jsc[mA/cm2] Voc[V] FF[％] PCE[％]
A1 21.4 0.64 68 9.3
A2 20.5 0.7 70.2 9.62
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.

Claims (11)

1. The novel dithieno-silacyclopentadiene organic solar cell receptor material is characterized in that the dithieno-silacyclopentadiene organic solar cell receptor material is a linear non-fullerene organic solar cell receptor material with an A-D-A structure, and the structural general formula is as follows:
Figure FDA0002943714640000011
wherein m is a natural number, and the value of m is 2 or 3;
R1and R2Is a straight chain alkyl containing 1 to 20 carbon atoms;
B1and B2For the purpose of pulling an electron end cap, the structure is selected from the following structures:
Figure FDA0002943714640000012
2. the novel dithienosilene heterocyclopentadiene organic solar cell acceptor material according to claim 1, wherein R is R when m is 31And R2Are all C8H17，B1And B2Are all made of
Figure FDA0002943714640000013
When the dithiophene silicon heterocyclic cyclopentadiene organic solar cell acceptor material is A1, the structural formula of A1 is as follows:
Figure FDA0002943714640000014
3. the novel dithienosilene heterocycle organic solar cell acceptor material of claim 1, whereinCharacterized in that when m is 2, R1And R2Are all C8H17，B1And B2Are all made of
Figure FDA0002943714640000021
When the dithiophene silicon heterocyclic cyclopentadiene organic solar cell acceptor material is A2, the structural formula of A2 is as follows:
Figure FDA0002943714640000022
4. a preparation method of a novel dithieno-silacyclopentadiene organic solar cell receptor material is characterized in that the novel dithieno-silacyclopentadiene organic solar cell receptor material is A1, and the structural formula of A1 is as follows:
Figure FDA0002943714640000023
the preparation method of A1 comprises the following steps:
sequentially adding pyridine and chloroform into the compound 4 and 5, 6-difluoro-3- (dicyanomethylene) indene-1-ketone for heating reaction, extracting by dichloromethane, washing by water, drying, concentrating, and eluting by chloroform to obtain A1;
the preparation method of the compound 4 comprises the following steps:
1) synthesis of Compound 1: adding dithieno-silacyclopentadiene and phosphorus oxychloride into N', N-dimethylformamide in sequence, stirring at room temperature for reaction, extracting by dichloromethane, washing with water, drying, concentrating, and eluting by dichloromethane to obtain a compound 1;
2) synthesis of Compound 2: adding the compound 1 in the step 1) into chloroform, adding NBS at 0 ℃, stirring at room temperature for reaction, extracting by dichloromethane, washing by water, drying, concentrating, and eluting by dichloromethane to obtain a compound 2;
3) synthesis of Compound 3: adding dithieno-silacyclopentadiene into tetrahydrofuran, adding n-butyl lithium at-78 ℃, stirring, adding trimethyl tin chloride, stirring for reaction at room temperature, quenching by potassium fluoride, extracting by dichloromethane, washing by water, drying, and concentrating to obtain a compound 3;
4) synthesis of Compound 4: and (3) adding toluene into the compounds 2 and 3, namely the palladium tetratriphenylphosphine, carrying out heating reaction, extracting by using dichloromethane, washing by using water, drying, concentrating, and eluting by using dichloromethane to obtain a compound 4.
5. The process according to claim 4, wherein the millimolar ratio of the compound 4, 5, 6-difluoro-3- (dicyanomethylene) inden-1-one, pyridine, chloroform before reaction is 0.1: 0.3: 2.5: 373.
6. the method according to claim 4, wherein the millimolar ratio of the dithienosilylcyclopentadiene, phosphorus oxychloride and DMF before the reaction in step 1) is 10:10: 388; the mmol ratio of the compound 1, NBS, chloroform before reaction in step 2) is 3: 3: 249; the millimolar ratio of the dithienosilene hetero cyclopentadiene, the n-butyl lithium, the trimethyl tin chloride and the tetrahydrofuran before reaction in the step 3) is 1: 2.2: 2.4: 494; the millimolar ratio of the compound 2, the compound 3, the palladium tetratriphenylphosphine and the anhydrous toluene before the reaction in the step 4) is 2.1: 0.95: 0.1: 376.
7. a preparation method of a novel dithieno-silacyclopentadiene organic solar cell receptor material is characterized in that the novel dithieno-silacyclopentadiene organic solar cell receptor material is A2, and the structural formula of A2 is as follows:
Figure FDA0002943714640000041
the preparation method of A2 comprises the following steps:
adding pyridine and chloroform into the compound 6 and 5, 6-difluoro-3- (dicyanomethylene) indene-1-ketone in sequence, heating for reaction, extracting by dichloromethane, washing by water, drying, concentrating, and eluting by chloroform to obtain A2;
the preparation method of the compound 6 comprises the following steps:
1) synthesis of Compound 1: adding dithieno-silacyclopentadiene and phosphorus oxychloride into N', N-dimethylformamide in sequence, stirring at room temperature for reaction, extracting by dichloromethane, washing with water, drying, concentrating, and eluting by dichloromethane to obtain a compound 1;
2) synthesis of Compound 2: adding the compound 1 in the step 1) into chloroform, adding NBS at 0 ℃, stirring at room temperature for reaction, extracting by dichloromethane, washing by water, drying, concentrating, and eluting by dichloromethane to obtain a compound 2;
3) and sequentially adding the compound 2, PdCl2(PhCN)2, KF and DMSO, carrying out heating reaction, extracting by using dichloromethane, washing by using water, drying, concentrating, and eluting by using dichloromethane to obtain the compound 6.
8. The process according to claim 7, wherein the millimolar ratio of the compound 6, 5, 6-difluoro-3- (dicyanomethylene) inden-1-one, pyridine, chloroform before reaction is 0.1: 0.3: 2.5: 373.
9. the preparation method according to claim 7, wherein the millimolar ratio of compound 2, PdCl2(PhCN)2, KF and DMSO before reaction is 3: 0.09: 6: 352.
10. use of a novel dithienosilene heterocyclopentadiene organic solar cell acceptor material according to any one of claims 1-3 for the preparation of organic solar cells.
11. An organic solar cell comprising a donor material and an acceptor material, wherein the acceptor material is the novel dithienosilene heterocyclopentadiene organic solar cell acceptor material of any one of claims 1-3, the donor material is PBDB-T, and the PBDB-T has the following structural formula:
Figure FDA0002943714640000051
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