CN115109071B - Preparation method and application of conjugated macromolecule based on benzodithiophene - Google Patents

Preparation method and application of conjugated macromolecule based on benzodithiophene Download PDF

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CN115109071B
CN115109071B CN202211036490.1A CN202211036490A CN115109071B CN 115109071 B CN115109071 B CN 115109071B CN 202211036490 A CN202211036490 A CN 202211036490A CN 115109071 B CN115109071 B CN 115109071B
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张仕明
蒋欣
王凯峰
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Nanjing Lehui Optoelectronics Technology Co ltd
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Abstract

The invention relates to an organic photovoltaic receptor material, in particular to a preparation method and application of conjugated macromolecules based on benzodithiophene, belonging to the technical field of organic semiconductor material preparation. The benzodithiophene-based conjugated macromolecule provided by the invention has a special molecular structure, the main body of the benzodithiophene-based conjugated macromolecule comprises benzodithiophene and a thiophene group of a necklace, a conjugated bridging unit is connected with thiophene, electron-withdrawing end groups are connected at two ends of the bridging units at two sides, and an alkane chain or an alkane alkoxy chain is modified. The electron cloud density of a conjugated system is increased through the benzodithiophene, and the electron-donating capability of a central core is improved. Meanwhile, alkyl chains are introduced to the bridging unit and the thiophene, so that the regional flatness of the central core can be increased, the charge mobility is potentially improved, and the material solubility can be further improved.

Description

Preparation method and application of conjugated macromolecule based on benzodithiophene
Technical Field
The invention relates to an organic photovoltaic receptor material, in particular to a preparation method and application of a conjugated macromolecule based on benzodithiophene, belonging to the technical field of organic semiconductor material preparation.
Background
Energy and environmental problems have become two major challenges facing global sustainable development in the 21 st century, and the development of clean renewable energy to replace fossil fuels (coal, petroleum and natural gas) is one of the major measures for energy and environmental problems in all countries of the world. Solar energy is used as inexhaustible clean energy, and the utilization of sustainable and clean solar energy is one of the most effective methods for relieving the current energy crisis and strengthening environmental protection. Photovoltaic technology provides the ability to generate electricity directly from sunlight. As a representative of the third generation solar cell, the organic solar cell attracts people's attention due to its advantages of wide raw material source, light weight, easy processing and preparation, small environmental impact, good film forming property, large-area preparation and the like.
Organic solar cells are typically based on bulk heterojunction structures comprising a mixture of electron donors and electron acceptors, with fullerene derivatives being the most commonly used electron acceptor material. However, the performance of organic solar cells with fullerenes as the acceptor material also has some significant drawbacks, such as: low absorbance in the solar spectral range, limited photoelectric tunability and thermal instability. To solve these problems, researchers have sought a new acceptor material that can replace fullerenes. In recent years, the field of organic solar cells based on non-fullerene receptors has been developed unprecedentedly, and new efficiency records are constantly updated. Non-fullerene materials are considered to have significant advantages over fullerene acceptors in terms of long-term stability, light absorption, bandgap tunability, and front-edge orbital levels, providing higher open-circuit voltages and short-circuit current densities-thus, non-fullerene organic solar cells are considered to achieve much higher power conversion efficiencies than conventional fullerene devices.
Currently, single-junction polymer donors: the PCE of the non-fullerene acceptor solar cell reaches over 14 percent and is superior to the highest PCE (11.7 percent) of the fullerene organic solar cell. In addition to the innovation of non-fullerene acceptor materials, the development of polymer donor materials is one of the main driving forces for enhancing PCE of non-fullerene organic solar cells. Since both donor and acceptor components in the bulk heterojunction system determine the photovoltaic performance of the corresponding organic solar cell, selecting an appropriate electron donor to match the non-fullerene acceptor is critical to achieving a high efficiency non-fullerene organic solar cell. In this regard, the large number of polymer donors originally developed for fullerene matching provides a rich choice for immediate use in non-fullerene organic solar cells.
Disclosure of Invention
The invention aims to provide a preparation method and application of a benzodithiophene-based conjugated macromolecule with good film forming property and high photoelectric conversion efficiency, so as to solve the problems of low photoelectric conversion efficiency and the like of an organic receptor material in the existing organic solar cell.
The conjugated macromolecule based on the benzodithiophene has complementary absorption with a donor material, has an energy level matched with the donor material and has high and balanced carrier mobility, and can be used for preparing an organic solar cell with high short-circuit current and energy conversion efficiency.
The structural formula of the conjugated macromolecule based on the benzodithiophene provided by the invention is shown as a formula F,
Figure DEST_PATH_IMAGE001
formula F
In the formula, R 1 Selected from C1-C30 alkyl, C1-C30 haloalkyl, C1-C30 alkoxy, C1-C30 alkylthio and C4-C30 aryl; r is 2 Selected from H, halogen substituent, cyano, C1-C30 alkyl, C1-C30 haloalkyl, C1-C30 alkoxy, C1-C30 alkylthio and C4-C30 aryl;
preferably, R 1 Selected from C1-C20 alkyl, C1-C20 haloalkyl, C1-C20 alkoxy, C1-C20 alkylthio and C4-C20 aryl; r 2 Selected from H, halogen substituent, cyano, C1-C20 alkyl, C1-C20 haloalkyl, C1-C20 alkoxy, C1-C20 alkylthio and C4-C20 aryl;
further, R 1 Selected from C1-C12 alkyl, C1-C12 haloalkyl, C1-C12 alkoxy, C1-C12 alkylthio and C4-C12 aryl; r 2 Selected from H, halogen substituent, trifluoromethyl, cyano, C1-C12 alkyl, C1-C12 halogenated alkyl, C1-C12 alkoxy, C1-C12 alkylthio and C4-C12 aryl;
ar is selected from the group consisting of a thiophene group, a thiophene derivative group, a bithiophene derivative group, a pyrrolodithienyl group, a pyrrolobithiophene derivative group, a pyrrolodiphenyl derivative group, a pentanediodithienyl group, a pentanediodithiophene derivative group, a pentanediodiphenyl group, and a pentanediodiphenyl derivative group;
when Ar is selected from thiophene derivative groups, the thiophene ring contains some common substituent groups, such as C1-C20 alkyl, C1-C20 alkoxy, carbonyl, ester groups (such as C1-C20 alkoxyacyl), phenyl, substituted phenyl (mainly containing C1-C20 alkyl or C1-C20 alkoxy on a benzene ring), thienyl or substituted thienyl (mainly containing C1-C20 alkyl or C1-C20 alkoxy on the thiophene ring); likewise, when Ar is selected from the group consisting of a benzodithiophene derivative group, a pyrrolodithiophene derivative group, a pyrrolobiphenyl derivative group, a pentanedithiophene derivative group, or a pentanedibenzene derivative group, it is meant that the benzodithiophene, pyrrolodithiophene, pyrrolobiphenyl, pentanedithiophene, or pentanedibenzene also contains a common substituent group similar to that on the thiophene derivative group.
The invention provides a preparation method of the benzodithiophene-based conjugated macromolecule, which comprises the following steps:
1) Carrying out substitution reaction on the compound A to obtain a compound B;
Figure DEST_PATH_IMAGE002
in the formula, R 1 Selected from C1-C30 alkyl, C1-C30 haloalkyl, C1-C30 alkoxy, C1-C30 alkylthio and C4-C30 aryl;
R 2 selected from H, halogen substituent, cyano, C1-C30 alkyl, C1-C30 haloalkyl, C1-C30 alkoxy, C1-C30 alkylthio and C4-C30 aryl;
2) Performing Stille coupling reaction on the compound B and the compound C to obtain a compound D;
Figure DEST_PATH_IMAGE003
wherein Ar is selected from the group consisting of a thiophene group, a thiophene derivative group, a bithiophene derivative group, a benzodithiophene derivative group, a pyrrolodithienyl group, a pyrrolobithiophene derivative group, a pyrrolodiphenyl group, a pyrrolodithienyl group, a pentanedithiophene derivative group, a pentanedithiophene group, and a pentanedibenzene derivative group;
3) Carrying out Vilsmeier-Haack reaction on the compound D to obtain a compound E;
Figure DEST_PATH_IMAGE004
4) Reacting the compound E with EG through Knoevenagel to obtain a benzodithiophene-based conjugated macromolecule shown in a formula F;
Figure DEST_PATH_IMAGE005
EG is any one of the following structures, and the dotted line is a connecting position:
Figure DEST_PATH_IMAGE006
wherein R is 4 Is hydrogen atom, halogen substituent (the halogen substituent is fluorine, chlorine, bromine or iodine), C1-C20 alkyl, C1-C20 alkoxy, C1-C20 carbonyl, C1-C20 ester group (such as C1-C20 alkoxy acyl) or cyano.
In the above preparation method, in step 1), the substitution reaction conditions are as follows: the catalyst is n-butyllithium, and the addition amount of the catalyst is 2-4 times of the molar amount of the compound A;
in the step 2), the conditions of the Stille coupling reaction are as follows: the catalyst is tetrakis (triphenylphosphine) palladium, and the addition amount of the catalyst is 0.01-10% of the molar amount of the compound B; the molar ratio of the compound B to the compound C is 1:2.2 to 3.5; reflux reaction is carried out for 24 to 48 hours at the temperature of 80 to 110 ℃;
in the step 3), the conditions of the Vilsmeier-Haack reaction are as follows: the formylation reagent is phosphorus oxychloride, and the molar ratio of the compound D to the formylation reagent is 1:15 to 25; reflux reaction is carried out for 8 to 12 hours at the temperature of 80 to 105 ℃;
in the step 4), the conditions of the Knoevenagel reaction are as follows: the acid-binding agent is pyridine, and the molar ratio of the compound E to the EG is 1:5 to 12; reflux reaction is carried out for 12 to 16 hours at the temperature of between 60 and 70 ℃.
The conjugated macromolecule based on the benzodithiophene provided by the invention can be used as an electron acceptor material to prepare an organic solar cell;
compounding the conjugated macromolecules of the benzodithiophene with an electron donor material to prepare a light-trapping active layer of the organic solar cell;
the electron donor material can be at least one of PM6, D18, PBDB-T, PTB-Th and other organic electron donor materials;
wherein the structural formula of the PBDB-T is shown as a formula a:
Figure DEST_PATH_IMAGE007
formula a
The mass ratio of the electron donor material to the conjugated macromolecule of the benzodithiophene is 1:1~2.
The invention also provides an organic solar cell, wherein the materials of the light-capturing active layer of the organic solar cell are an electron donor material and an electron acceptor material, and the electron acceptor material is the conjugated macromolecule based on the benzodithiophene.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
the benzodithiophene-based conjugated macromolecule provided by the invention has a special molecular structure, the main body of the benzodithiophene-based conjugated macromolecule comprises benzodithiophene and a connected thiophene group, a conjugated bridging unit is connected with thiophene, an electron-withdrawing end group is connected with two ends of the two sides of the bridging unit, and an alkyl chain or an alkoxy chain is modified. According to the invention, the electron cloud density of a conjugated system is increased by the benzodithiophene, and the electron-donating capability of a central core is improved. Meanwhile, alkyl chains are introduced to the bridging unit and the thiophene, so that the regional flatness of the central core can be increased, the charge mobility can be potentially improved, and the solubility of the material can be further improved.
The benzodithiophene-based conjugated macromolecule provided by the invention has good solubility, is easy to process into a film, has strong visible near infrared absorption, can be used for preparing solar cell materials with high short-circuit current and energy conversion efficiency, and is a potential receptor material.
Compared with the previous fullerene and derivative materials thereof, the benzodithiophene-based conjugated macromolecule provided by the invention can regulate and control energy level, has good film forming property and higher photoelectric conversion efficiency, and the finished product can be made into a flexible solar cell panel.
The benzodithiophene-based conjugated macromolecule provided by the invention has mild synthesis conditions and low price, and is beneficial to realizing large-scale production.
Drawings
FIG. 1 is a scheme showing the synthesis scheme of BDTF-TT-IC, an acceptor material prepared in example 1.
FIG. 2 shows the receptor material BDTF-TT-IC prepared in example 1 1 H NMR。
FIG. 3 is an absorption spectrum of the receptor material BDTF-TT-IC prepared in example 1 in chloroform solution and in a thin film state.
FIG. 4 is the BDTF-TT-IC cyclic voltammogram of the receptor material prepared in example 1.
FIG. 5 shows the current-voltage values of organic solar cells prepared in example 2J-V) Graph is shown.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The technical solution of the present invention is further illustrated by the following specific experimental means.
Methylene chloride, ethyl acetate, petroleum ether, diethyl ether, methanol, isopropanol, chloroform, tributyltin chloride used in the following examples were purchased from Tianjin Cordcord chemical reagent works; n-butyllithium, anhydrous tetrahydrofuran, tetrakis (triphenylphosphine) palladium, pyridine, toluene, aqueous sodium chloride solution, aqueous sodium carbonate solution, potassium fluoride, anhydrous N, N-dimethylformamide, phosphorus oxychloride were purchased from Beijing YinuoKai science and technology, inc.; 3- (Dicyanomethylene) indolone is available from Jiaxing Hepu optoelectronics, inc. All the reagents purchased above were used directly without further treatment.
Example 1 preparation of a benzodithiophene-based conjugated macromolecule of formula F
In formula F, the substituents are as follows:
R 1 is composed of
Figure DEST_PATH_IMAGE008
，R 2 Is composed of
Figure DEST_PATH_IMAGE009
，
EG is
Figure DEST_PATH_IMAGE010
Ar is
Figure DEST_PATH_IMAGE011
。
The synthetic scheme is shown in fig. 1:
1) Carrying out substitution reaction on the compound 1 and trimethyl tin chloride under the protection of nitrogen to obtain a compound 2:
compound 1 (331.67 mg,0.54 mmol) was dissolved in 30 mL anhydrous tetrahydrofuran and cooled to-78 ℃ under nitrogen blanket. N-butyllithium (0.65 mL,1.62 mmol) was added dropwise. The mixture was held at-78 ℃ for 1 hour, then slowly warmed to room temperature and heated for an additional 2 hours. The mixture was then cooled again to-78 ℃ and tributyltin chloride solution (1.2 mL,1.2 mmol) was added via syringe and slowly warmed to room temperature to maintain stirring for an additional 12 hours. Thereafter, the reaction was quenched with 50 mL water and extracted with ether. The organic phase was then passed over anhydrous Na 2 SO 4 Drying and rotary evaporating under reduced pressure to remove solventRecrystallization from isopropanol yielded compound 2 as a pale yellow solid (386.12 mg, 75%).
2) Performing Stille coupling reaction on the compound 2 and the compound 3 under the protection of nitrogen to obtain a compound 4:
in N 2 To compound 2 (386.12 mg,0.41 mmol), pd (PPh) under ambient conditions 3 ) 4 (34.67 mg,0.03 mmol) in toluene (10 mL) Compound 3 (373.01 mg, 0.88 mmol) was added and the reaction mixture heated with stirring to reflux 24 h (110 ℃). Then wait to cool to 25 ℃. Aqueous KF was added and stirred at ambient temperature for 1h to quench the reaction and remove excess tin reagent. Washed with water and aqueous NaCl, then with CH 2 Cl 2 Extraction was carried out three times. The combined organic phases were then passed over anhydrous Na 2 SO 4 Drying, suction filtration and rotary evaporation under reduced pressure to remove the solvent. Purification by column chromatography (eluent: petroleum ether: dichloromethane = 2:1) followed by methanol precipitation gave compound 4 as a dark red solid (161.52 mg, 30.56%).
3) The compound 4 and N, N-dimethylformamide are subjected to Vilsmeier-Haack reaction to obtain a compound 5:
in N 2 Under the ambient conditions, DMF (1.24 mL,16.01 mmol,0.945 g.mL) -1 ) Dichloromethane (DCM) (10.0 mL) was dissolved in the reaction flask. Phosphorus oxychloride (0.37g, 2.4 mmol) was slowly added dropwise with stirring 1h under ice bath conditions. Compound 4 (0.16g, 0.12 mmol) was dissolved in DCM (5.00 mL), slowly added dropwise to the system, the solution gradually turned deep red, and stirred at 80 ℃ overnight for reaction. After the reaction, na was added 2 CO 3 Fully stirring to adjust the pH of the solution to be neutral, and using CH 2 Cl 2 Extracting with NaCl aqueous solution for several times, collecting organic layer, anhydrous Na 2 SO 4 Drying, suction filtration and spin-drying, purification using column chromatography (eluent: petroleum ether: dichloromethane = 2:1) gave the product compound 5 (110.0 mg, 64.77%).
4) Performing Knoevenagel reaction on the compound 5 and the 3- (dicyanomethylene) indone under the protection of nitrogen to obtain a compound BDTF-TT-IC:
in general N 2 To 3- (dicyanomethylene) indolone (78.00 mg,0.40 mmol) and compound 5 (110.0 mg,0.08 mmol) in the form of anhydrous CHCl 3 To the solution (8 mL), pyridine (0.5 mL) was slowly added dropwise. The reaction was heated with stirring to reflux 18 h and then cooled to 25 ℃ before the reacted mixture was poured into CH 3 OH (100 mL) and the residue remaining in the filter paper was filtered with CHCl 3 And (4) dissolving. After removal of the solvent by rotary evaporation under reduced pressure, a blue-green solid product BDTF-TT-IC (50.00 mg, 36.23%) was obtained. 1H NMR (400 MHz, CDCl3): δ = 8.92,8.69 (d, J = 7.0), 7.90,7.75,7.71,7.65,7.22 (d, J = 4.6), 2.88,1.95 (d, J = 8.3), 1.27,1.18,1.03 (t, J = 7.5), 0.82 (t, J = 6.7) Elemental Analysis (%): c,71.54; h,6.12, F,2.22; n,3.27; s,14.98.
The UV-visible absorption spectrum of BDTF-TT-IC is shown in figure 3, wherein the solution has strong absorption peak in the wavelength range of 600 to 800 nm, and the maximum molar extinction coefficient is 4.68 x 10 4 M –1 ∙cm –1 The film absorbs most strongly around 700 nm.
The cyclic voltammogram is shown in FIG. 4, the HOMO energy level is-5.30 eV, the LUMO energy level is-3.84 eV, and the band gap is 1.46 eV, which shows that the poly-fused ring conjugated macromolecule shown in formula I has better electron accepting capability and can be matched with most of the general electron donor materials in energy level.
Example 2 preparation of organic solar cell
Indium Tin Oxide (ITO) glass (purchased from shenzhen glass float glass limited) as a cathode is cleaned by a detergent, then sequentially cleaned by deionized water, acetone and isopropanol by ultrasonic cleaning, and then dried and spin-coated with a layer of PEDOT 30 nm thick: and drying the PSS anode modification layer at 150 ℃ for 15 minutes for later use.
BDTF-TT-IC molecules are used as A-D-A type micromolecule receptors of BHJ type OSC, polymer PBDB-T is used as a P type donor, and a (ITO/PEDOT: PSS/PBDB-T: acceptor/PDINN/Ag) forward structure device is prepared by changing spin coating rotation speed, annealing treatment conditions, the ratio of the receptors, the thickness of an active layer and the proportion of additives. PBDB-T BDTF-TT-IC device, optimizing the conditions (in 20 mg. ML) -1 1:1 in CF solvent, 0.5% in additive DIO, 10 min of annealing at 100 ℃) produced 3.26% PCE.
A solar light source was simulated with an AM1.5 filter (model XES-70S1, SAN-EI ELECTRIC Co., ltd.) at 100 mW/cm 2 The devices were subjected to photocurrent density measurements at light intensity calibrated by standard single crystal silicon solar cells (available from VLSI Standards Inc). The resulting I-V curve was measured using a Keithley 2450 Source-Measure Unit, computer controlled by Labview software. The resulting I-V curve is shown in FIG. 5.
Table 1 lists the performance parameters of the cell at different ratios of the two materials PBDB-T and BDTF-TT-IC in the active layer of the solar cell.
Table 1 solar cell device parameters prepared based on acceptor materials
Figure DEST_PATH_IMAGE012
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (4)

1. A preparation method of conjugated macromolecules based on benzodithiophene is characterized by comprising the following steps:
1) Carrying out substitution reaction on the compound A to obtain a compound B;
Figure FDA0003924901750000011
in the formula, R 1 Is composed of
Figure FDA0003924901750000012
R 2 Is composed of
Figure FDA0003924901750000016
2) Performing Stille coupling reaction on the compound B and the compound C to obtain a compound D;
Figure FDA0003924901750000013
in the formula, ar is
Figure FDA0003924901750000014
3) Carrying out Vilsmeier-Haack reaction on the compound D to obtain a compound E;
Figure FDA0003924901750000015
4) Reacting the compound E with EG through Knoevenagel to obtain a benzodithiophene-based conjugated macromolecule shown in a formula F;
Figure FDA0003924901750000021
EG is
Figure FDA0003924901750000022
In the step 2), the conditions of the Stille coupling reaction are as follows: the catalyst is tetrakis (triphenylphosphine) palladium, and the addition amount of the catalyst is 0.01-10% of the molar amount of the compound B; the molar ratio of the compound B to the compound C is 1:2.2 to 3.5; reflux reaction is carried out for 24 to 48 hours at the temperature of 80 to 110 ℃;
in the step 3), the conditions of the Vilsmeier-Haack reaction are as follows: the formylation reagent is phosphorus oxychloride, and the molar ratio of the compound D to the formylation reagent is 1:15 to 25; reflux reaction is carried out for 8 to 12 hours at the temperature of 80 to 105 ℃;
in the step 4), the conditions of the Knoevenagel reaction are as follows: the acid-binding agent is pyridine, and the molar ratio of the compound E to the EG is 1:5 to 12; reflux reaction is carried out for 12 to 16 hours at the temperature of between 60 and 70 ℃.
2. Use of the benzodithiophene-based conjugated macromolecule prepared by the preparation method according to claim 1 for preparing an organic solar cell, wherein the benzodithiophene-based conjugated macromolecule serves as an electron acceptor material.
3. The use of the benzodithiophene-based conjugated macromolecule prepared by the preparation method according to claim 2 for preparing an organic solar cell,
the conjugated macromolecule of the benzodithiophene and an electron donor material are compounded to prepare a light-trapping active layer of the organic solar cell;
the electron donor material is at least one of PM6, D18, PBDB-T, PTB-Th and other organic electron donor materials;
the mass ratio of the electron donor material to the benzodithiophene-based conjugated macromolecule is 1:1 to 2.
4. An organic solar cell, characterized in that the materials of the light-trapping active layer of the organic solar cell are an electron donor material and an electron acceptor material, and the electron acceptor material is the benzodithiophene-based conjugated macromolecule prepared by the preparation method of claim 1.
CN202211036490.1A 2022-08-29 2022-08-29 Preparation method and application of conjugated macromolecule based on benzodithiophene Active CN115109071B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104086561A (en) * 2014-07-08 2014-10-08 国家纳米科学中心 Soluble organic photovoltaic micromolecule material with high fill factor, preparation method and application of material
CN104086752A (en) * 2014-05-16 2014-10-08 中国华能集团清洁能源技术研究院有限公司 Benzodithiophene polymer, its preparation method, semiconductor composition containing it, and solar cell using it
CN104119355A (en) * 2014-06-27 2014-10-29 南开大学 Organic photoelectric compounds, preparing method thereof and applications of the compounds
CN105315273A (en) * 2015-11-20 2016-02-10 国家纳米科学中心 Polyceptor-structure small molecule compound and preparing method and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110423245B (en) * 2019-08-27 2021-04-06 苏州潜寻新能源科技有限公司 A-D-A conjugated molecule, preparation method, application in organic solar cell and organic solar cell
CN114716460B (en) * 2022-03-25 2023-11-07 中国科学院宁波材料技术与工程研究所 Conjugated organic small molecule and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104086752A (en) * 2014-05-16 2014-10-08 中国华能集团清洁能源技术研究院有限公司 Benzodithiophene polymer, its preparation method, semiconductor composition containing it, and solar cell using it
CN104119355A (en) * 2014-06-27 2014-10-29 南开大学 Organic photoelectric compounds, preparing method thereof and applications of the compounds
CN104086561A (en) * 2014-07-08 2014-10-08 国家纳米科学中心 Soluble organic photovoltaic micromolecule material with high fill factor, preparation method and application of material
CN105315273A (en) * 2015-11-20 2016-02-10 国家纳米科学中心 Polyceptor-structure small molecule compound and preparing method and application thereof

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