CN114478583B - Application of n-type A-DA' D-A micromolecule receptor containing thiophene conjugated side chain in high-efficiency organic solar cell - Google Patents

Application of n-type A-DA' D-A micromolecule receptor containing thiophene conjugated side chain in high-efficiency organic solar cell Download PDF

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CN114478583B
CN114478583B CN202210161726.8A CN202210161726A CN114478583B CN 114478583 B CN114478583 B CN 114478583B CN 202210161726 A CN202210161726 A CN 202210161726A CN 114478583 B CN114478583 B CN 114478583B
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孔晓磊
孟磊
李永舫
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Abstract

The invention discloses application of an n-type A-DA' D-A micromolecule receptor containing a thiophene conjugated side chain in a high-efficiency organic solar cell. The structural formula of the organic micromolecule receptor photovoltaic material provided by the invention is shown as a formula I and a formula II. The thiophene unit has excellent conductive property and excellent chemical modification property, is introduced into a side chain of an A-DA' D-A type micromolecule receptor through a simple synthesis means, can further expand the pi conjugation length of a main chain while obtaining a rigid plane structure, and is beneficial to delocalization of polarons and transmission of carriers. In addition, a larger pi-conjugated area is also beneficial to enhance pi-pi interaction between chains, enhance interaction between donor and acceptor, and improve molecular orientation of the interface. Therefore, thiophene is introduced into the A-DA' D-A type micromolecule receptor as a conjugated side chain, so that the energy conversion efficiency of the corresponding organic solar cell can be remarkably improved, and the organic solar cell has a wide application prospect.

Description

Application of n-type A-DA' D-A micromolecule receptor containing thiophene conjugated side chain in high-efficiency organic solar cell
Technical Field
The invention relates to application of an n-type A-DA' D-A micromolecule receptor containing a thiophene conjugated side chain in a high-efficiency organic solar cell.
Background
Energy is used as an important material basis and continuously pushes the development of world economy and human society. In recent years, with the continuous increase in energy demand and the increasing severity of environmental problems such as greenhouse effect, clean renewable energy sources such as: solar energy, wind energy, water energy, biomass energy and the like become important measures for promoting energy structure transformation and coping with climate change in countries in the world. Among various renewable energy technologies, a solar cell that directly converts solar energy into electric energy has attracted attention due to its advantages such as wide application range, safety, convenience, and the like, and has been developed for a long time in the past few decades. Organic Solar Cells (OSCs) have received much attention due to their advantages such as simple device structures, low-cost processing techniques, versatile and controllable materials, and the ability to fabricate lightweight, flexible, translucent devices. [ Y.Li, acc.chem.Res.2012,45, 723.J.Yuan, Y.Zhang, L.Zhou, G.Zhang, H.L.YIp, T.K.Lau, X.Lu, C.Zhu, H.Peng, P.A.Johnson, M.Leclerc, Y.Cao, J.Ulanski, Y.Li, Y.Zou, joule 2019,3,1140 ]. In common OSCs, the active layer materials are divided into p-type conjugated polymer donors and n-type small molecule acceptors. In the past few years, due to the breakthrough of wide-bandgap polymer donor materials and narrow-bandgap small-molecule acceptor materials, especially the rapid development of A-DA' D-A type n-type small-molecule acceptor materials, the energy conversion efficiency (PCE) of OSCs is breakthrough by 18%, which makes the commercial application of organic solar cells further forward.
Thiophene is a five-membered heterocyclic compound containing a sulfur heteroatom, has aromaticity, and is more likely to undergo electrophilic substitution than benzene, and the substitution mainly occurs at the alpha-position (2-position or 5-position). The thiophene can be used for producing various dyes, perfumes, rapid cooling and heating resistant plastics, high-activity solvents, stimulants, insecticides, brightening agents, cosmetics, biological active substances, vitamins, anesthetics, antibiotics and other medicines. As thiophene has excellent conductive characteristics, polythiophene synthesized by a chemical method or an electrochemical method is a conductive polymer material with potential application prospect. Meanwhile, thiophene can be introduced into polymer materials and small molecule materials by simple chemical means, which is often used as a conjugated unit for electron donation in organic solar cells, and thus is also gaining wide attention [ y.lin, f.zhao, q.he, l.huo, y.wu, t.c.parker, w.ma, y.sun, c.wang, d.zhu, a.j.heeger, s.r.marder, x.zhan, j.am.chem.soc.2016,138,4955; cui, y.li, energy environ.sci.2019,12,3225.
A-DA 'D-A type small molecule acceptor in the organic solar cell generally refers to a molecule formed by connecting two electron-deficient (A) terminal groups through an intermediate DA' D condensed ring nuclear structure. Such structures typically consist of three active modules: DA' D fused ring core structure, side chains on the fused ring, and electron-deficient A terminus. The side chain not only is helpful for improving the molecular solubility, but also can effectively prevent the self-aggregation of the coplanar condensed ring nuclear structure and prevent the serious phase separation formed after the acceptor molecule and the donor are blended.
The group of the forever ship subjects of the institute of chemistry of the chinese academy of sciences, introduced the conjugated side chain into the molecular design of the polymer donor photovoltaic material at the earliest [ j.hou, z.tan, y.yan, y.he, c.yang, y.f.li, j.am.chem.soc.,2006,128: 4911-4916 ], and later, the benzodithiophene unit with the thiophene conjugated side chain became the star electron (D) structural unit of the high-efficiency D-a copolymer donor photovoltaic material [ l.huo, s.zhang, x.guo, f.xu, y.f.li, j.hou, angelw.chem.int.ed., 2011,50,9697-9702 ]; cui, y.li, energy environ.sci.2019,12,3225], because introduction of thiophene side chains can further expand the pi conjugation length of the main chain while obtaining a rigid planar structure, which is beneficial to delocalization of polarons and transmission of carriers. In addition, a larger pi conjugation area is also beneficial to enhance pi-pi interaction between chains, enhance interaction between donor and acceptor, and improve molecular orientation of the interface. Therefore, the thiophene conjugated side chain is introduced to the DA 'D condensed ring unit of the A-DA' D-A type micromolecule receptor, the photovoltaic performance of the receptor is expected to be improved, the energy conversion efficiency of a corresponding organic photovoltaic device is improved, and the application prospect is wide.
Disclosure of Invention
The invention synthesizes an n-type A-DA' D-A narrow band gap micromolecule receptor containing thiophene conjugated side chains and application of the micromolecule receptor in a high-efficiency organic solar cell through a side chain engineering method.
The structural formula of the micromolecule material containing the thiophene conjugated side chain is shown as a formula I and a formula II,
Figure SMS_1
r in the formula I and the formula II 1 Any one selected from the following groups: alkyl, alkoxy, alkylthio and silyl groups. The alkyl group contained in each of the above groups is a linear or branched alkyl group having 1 to 12 carbon atoms.
R in the formula I and the formula II 2 Any one selected from the following groups: alkyl, alkoxy, alkylthio and silyl groups. The alkyl group contained in each of the above groups is a linear or branched alkyl group having 1 to 12 carbon atoms.
In the formula I and the formula II, ar groups are connected with a central core in a condensation mode, ar is a conjugated aromatic ring or a condensed ring constructed by the conjugated aromatic ring, and can be any one of the following groups: a bithiophene group, a thienoselenophene group; the details are as follows:
Figure SMS_2
in the formula I and the formula II, the group A is selected from any one of the following structural formulas:
Figure SMS_3
wherein R is 3 Any one selected from the following groups: H. f, cl, br and I.
The n-type A-DA' D-A micromolecule receptor containing the thiophene conjugated side chain can be specifically, but not limited to, the structure shown as follows:
Figure SMS_4
the invention also provides a preparation method of the n-type A-DA' D-A micromolecule receptor containing thiophene conjugated side chains shown in the formula I and the formula II.
The invention provides a preparation method of an n-type A-DA' D-A micromolecule receptor containing thiophene conjugated side chains, which is shown in a formula I and a formula II, and comprises the following steps:
Figure SMS_5
Figure SMS_6
1) Starting substrates organotin reagent, ar-Br haloalkane and Pd (PPh) 3 ) 4 Dissolved in anhydrous toluene and stirred at 110 ℃ under argon atmosphere overnight. After the reaction was complete, the mixture was cooled to room temperature, the residue was washed with water and extracted with dichloromethane, and the organic layer was washed with Na 2 SO 4 Drying, carrying out reduced pressure rotary evaporation to remove the solvent to obtain a crude product, and directly using the crude product for a subsequent reaction without further purification;
2) At-78 deg.C under argon atmosphere, 2.0M lithium diisopropylamide is dropped into the anhydrous tetrahydrofuran solution of the crude product in the previous step, after stirring for 3.5 hours, 1.0M trimethyl chloride is droppedTin, gradually heating to room temperature. After stirring overnight, the mixture was quenched with saturated aqueous KF and extracted with hexane, and the organic layer was Na 2 SO 4 Drying, carrying out reduced pressure rotary evaporation to remove the solvent to obtain a crude product, and directly putting the crude product into the next reaction without further purification.
4) The crude product obtained in the last step, 4, 7-dibromo-5, 6-dinitrobenzo [ c ]][1,2,5]Thiadiazole and Pd (PPh) 3 ) 4 Dissolved in anhydrous toluene and stirred at 110 ℃ under argon atmosphere overnight. The reaction mixture was then cooled and poured into saturated aqueous KF solution, the mixture was extracted 3 times with ether and the organic phase was washed with brine. The organic phase is then treated with Na 2 SO 4 Drying and rotary evaporation under reduced pressure to remove the solvent to give the crude product. The crude product was purified by column chromatography on silica eluting with petroleum ether/dichloromethane to give a powder solid.
5) The solid powder obtained in the previous step and triethyl phosphite were dissolved in anhydrous 1, 2-dichlorobenzene under an argon atmosphere, and the mixture was stirred at 180 ℃ overnight. After the reaction was completed and cooled to room temperature, the solvent was distilled off under reduced pressure to obtain an intermediate. Subsequently, the intermediate is reacted with K 2 CO 3 、KI、Br-R 1 The haloalkane and anhydrous DMF were mixed and stirred overnight at 100 ℃ under an argon atmosphere. After completion of the reaction, the reaction mixture was extracted 3 times with ethyl acetate and the organic phase was washed with brine. Then the organic phase is treated with Na 2 SO 4 Drying and rotary evaporation under reduced pressure gave an oil. Then, a solid was obtained by silica gel column chromatography using petroleum ether/dichloromethane as an eluent.
6) The solid product obtained in the previous step was dissolved in chloroform under an argon atmosphere, and then fresh Vilsmeier reagent (POCl) was added dropwise at 0 deg.C 3 Mixed in DMF). After stirring at 0 ℃ for 20 minutes, the mixture was heated to 65 ℃ and reacted for 24 hours. Then saturated NaHCO 3 The solution was quenched and stirred at room temperature for 24 hours. After completion of the reaction, the reaction mixture was extracted with dichloromethane, the organic layer was separated and washed with brine, na 2 SO 4 After drying, filtration and rotary evaporation under reduced pressure gave an orange oil. The crude product is purified by silica gel column chromatography in conjunction with petroleum etherDichloromethane was used as eluent to obtain solid product.
7) The solid product obtained in the previous step, compound a, pyridine was dissolved in chloroform under an argon atmosphere, the mixture was stirred at room temperature overnight, then the mixture was poured into methanol and filtered off with suction to give the crude product. The crude product was then purified by column chromatography on silica gel using dichloromethane/petroleum ether as eluent to give the final solid product.
It is yet another object of the present invention to provide an organic solar cell active layer.
The active layer of the organic solar cell comprises an n-type A-DA' D-A micromolecule acceptor containing thiophene conjugated side chains and a donor material shown in a formula I and/or a formula II; wherein the mass ratio of the donor material to the small molecule acceptor is 1 (0.8-2.0) (specifically 1.
The donor material can be a polymer donor material (e.g., PBQ6, PM7, PTQ10, etc.) or a small molecule donor material (e.g., BTR-Cl, B1, M-PhS, etc.).
The donor materials are preferably PBQ6 and PTQ10 of the formula.
Figure SMS_7
The organic solar cell active layer can be mixed by adopting at least one of trichloromethane, chlorobenzene, o-dichlorobenzene, toluene and tetrahydrofuran solvents; in the obtained mixed solution, the mass volume ratio of the donor material to the solvent is 6-7 mg/mL; the mass-volume ratio of the micromolecular acceptor solvent is 4.8-14 mg/mL.
The organic solar cell active layer further includes an additive (e.g., chloronaphthalene). The additive is used in an amount of 0.3 to 2.0% (specifically, 0.4%) of the total volume of the small molecule acceptor, the donor material and the solvent.
The invention also provides an application of the small molecule receptor material shown in the formula I or the formula II or the active layer in preparing the following functional photoelectric devices: thin film semiconductor devices, photodetection devices, single junction and stacked organic/polymer solar cell devices, and other related optoelectronic devices.
The invention also provides an organic solar cell device.
The organic solar cell device sequentially comprises a transparent conductive electrode containing an interface layer, the organic solar cell active layer, the interface layer and a metal electrode.
The preparation method of the organic solar cell device comprises the following steps: the micromolecule receptor material and a proper donor material are dissolved in a solvent (containing or not containing additives), after being uniformly mixed, the micromolecule receptor material and the proper donor material are coated on the transparent conductive electrode containing the interface layer in a spinning or scraping mode to prepare a film active layer, then the interface layer is prepared on the film active layer, and finally the metal electrode is evaporated on the interface layer to obtain the organic solar cell device.
The invention has the following beneficial effects:
the thiophene unit has excellent conductive property and excellent chemical modification property, and different types of thiophene conjugated side chains are introduced into an intermediate condensed ring structure of a traditional A-DA' D-A micromolecule receptor:
1) The planarity of molecules is changed, the electron energy level of the material is adjusted, the LUMO energy level of a small molecule acceptor is improved, and the organic solar cell is provided with an open-circuit voltage (V) oc ) Plays a key role in improving;
2) The pi conjugate length of the main chain can be further expanded while a rigid planar structure is obtained, which is beneficial to the delocalization of polarons and the transmission of carriers, thereby improving the mobility of the donor-acceptor blend membrane and realizing the short-circuit current (J) of the organic solar cell sc ) Make a contribution to improvement of;
3) The larger pi conjugated area is also beneficial to enhancing the pi-pi interaction between chains, enhancing the interaction between donor and acceptor, improving the molecular orientation of an interface, optimizing the molecular accumulation and the morphology of an active layer after the material is formed into a film, and further improving the Filling Factor (FF) of the organic solar cell;
4) Thiophene is introduced into an A-DA' D-A small molecular receptor as a conjugated side chain, so that the energy conversion efficiency of a corresponding device can be remarkably improved, and particularly after the thiophene is matched with a quinoxaline p-type conjugated polymer donor PBQ6, the energy conversion efficiency of the obtained binary organic solar cell is greatly improved and exceeds 18.5 percent, so that the binary organic solar cell is the highest energy conversion efficiency in the currently known binary system.
Drawings
FIG. 1 is the preparation of the small molecule receptor m-TEH of example 1 1 H NMR spectrum;
FIG. 2 is the preparation of the small molecule receptor m-TEH of example 1 13 C NMR spectrogram;
FIG. 3 is the preparation of the small molecule receptor o-TEH of example 2 1 H NMR spectrum;
FIG. 4 is a diagram of the small molecule receptor o-TEH prepared in example 2 13 C NMR spectrum;
FIG. 5 is a diagram showing UV-VIS absorption spectra of the small molecule receptors m-TEH and o-TEH prepared in examples 1 and 2 in chloroform solution and thin film state;
FIG. 6 is a cyclic voltammogram of the small molecule acceptors m-TEH and o-TEH prepared in examples 1 and 2;
FIG. 7 is a J-V curve of organic solar cell devices prepared by blending the small molecule receptors m-TEH and o-TEH prepared in examples 1 and 2 with PBQ6, respectively;
FIG. 8 is a graph of external quantum conversion efficiency (EQE) of organic solar cell devices made by blending the small molecule acceptors m-TEH and o-TEH prepared in examples 1 and 2 with PBQ6, respectively.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. 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.
In the following examples, efforts are made to ensure accuracy with respect to numbers used (including amounts, temperature, reaction time, etc.) but some experimental errors and deviations should be accounted for. The pressure used in the following examples is at or near atmospheric pressure. All solvents used were purchased as HPLC grade and all reactions were carried out under an inert atmosphere of argon, all reagents and starting materials being commercially available unless otherwise indicated.
Example 1: preparation of n-type A-DA' D-A Small molecule receptor m-TEH containing thiophene conjugated side chain (see synthetic route below)
Figure SMS_8
1) The compounds tributyl (4- (2-ethylhexyl) thiophen-2-yl) stannane (4.00g, 8.24mmol), 3-bromothiophene [3,2-b ]]Thiophene (1.85g, 8.45mmol) and Pd (PPh) 3 ) 4 (0.35g, 0.30mmol) was dissolved in dry toluene (40.0 mL) and stirred at 110 deg.C under an argon atmosphere overnight. After the reaction was complete, the mixture was cooled to room temperature, the residue was washed with water and extracted with dichloromethane, and the organic layer was washed with Na 2 SO 4 Drying and rotary evaporation under reduced pressure to remove the solvent to obtain a crude product m-1 which is used in the subsequent reaction without further purification.
2) 2.0M lithium diisopropylamide (3.0 mL,6.0 mmol) was added dropwise to a solution of the crude product M-1 in anhydrous tetrahydrofuran (40 mL) at-78 ℃ under an argon atmosphere, and after stirring for 3.5 hours, 1.0M trimethyltin chloride (6.0 mL,6.0 mmol) was added dropwise and the temperature was gradually raised to room temperature. After stirring overnight, the mixture was quenched with saturated aqueous KF and extracted with hexane, and the organic layer was Na 2 SO 4 Drying, decompressing and rotary distilling to remove the solvent to obtain a crude product m-2, and directly putting the crude product into the next reaction without further purification.
4) The crude product m-2, 4, 7-dibromo-5, 6-dinitrobenzo [ c ] is treated][1,2,5]Thiadiazole (0.96g, 2.5mmol) and Pd (PPh) 3 ) 4 (0.20g, 0.17mmol) was dissolved in anhydrous toluene (25.0 mL) and stirred at 110 ℃ under an argon atmosphere overnight. The reaction mixture was then cooled and poured into saturated aqueous KF solution, the mixture was extracted 3 times with ether and the organic phase was washed with brine. The organic phase is then treated with Na 2 SO 4 Drying and rotary evaporation under reduced pressure to remove the solvent to obtain the crude product. The crude product was purified by column chromatography on silica eluting with petroleum ether/dichloromethane (3/1, v/v) to give m-3 as a red powder solid (1.74g, 78% yield).
5) Compound m-3 (1.74g, 1.95mmol) and triethyl phosphite (10 mL) were dissolved under an argon atmosphereIn anhydrous 1, 2-dichlorobenzene (o-DCB, 10 mL) and the mixture was stirred at 180 ℃ overnight. After the reaction was completed and cooled to room temperature, the solvent was distilled off under reduced pressure to obtain a red intermediate. Subsequently, the red intermediate is reacted with K 2 CO 3 (2.70 g, 19.5 mmol), KI (0.32g, 1.95mmol), 2-butyl-1-bromooctane (1.46g, 5.85mmol) and anhydrous DMF (25 mL) were mixed and stirred at 100 ℃ under an argon atmosphere overnight. After completion of the reaction, the reaction mixture was extracted 3 times with ethyl acetate and the organic phase was washed with brine. The organic phase is then washed with Na 2 SO 4 Dried and rotary evaporated under reduced pressure to give an orange oil. Thereafter, using petroleum ether/dichloromethane (6/1, v/v) as an eluent, m-4 (1.04g, 46% yield) was obtained as an orange solid by silica gel column chromatography.
6) Compound m-4 (1.04g, 0.90mmol) was dissolved in 20mL of chloroform under an argon atmosphere, and fresh Vilsmeier reagent (3.3 mL of POCl) was added dropwise at 0 deg.C 3 Mixed in 6.9mL DMF). After stirring at 0 ℃ for 20 minutes, the mixture was heated to 65 ℃ and reacted for 24 hours. Then saturated NaHCO 3 The solution was quenched and stirred at room temperature for 24 hours. After completion of the reaction, the reaction mixture was extracted with dichloromethane, the organic layer was separated and washed with brine, na 2 SO 4 After drying, filtration and rotary evaporation under reduced pressure gave an orange-red oil. The crude product was purified by column chromatography on silica gel eluting with petroleum ether/dichloromethane (1/1, v/v) to give m-5 as an orange solid (889.0 mg,81% yield).
7) The compound m-5 (50.0mg, 0.04mmol), 2- (5, 6-difluoro-3-oxo-2, 3-dihydro-1H-indene-1-ethylene) malononitrile (110.7mg, 0.48mmol), pyridine (1.0 mL) were dissolved in chloroform (10.0 mL) under an argon atmosphere, and the mixture was stirred at room temperature overnight, then the mixture was poured into methanol and suction-filtered to give a crude product. The crude product was then purified by column chromatography on silica gel using dichloromethane/petroleum ether (1/1, v/v) as eluent to give m-TEH (48.7mg, 74% yield) as a dark blue solid.
Example 2: preparation of n-type A-DA' D-A Small molecule receptor containing thiophene conjugated side chain o-TEH (see synthetic route below)
Figure SMS_9
1) The compounds tributyl (5- (2-ethylhexyl) thiophen-2-yl) stannane (4.00g, 8.24mmol), 3-bromothiophene [3,2-b ]]Thiophene (1.85g, 8.45mmol) and Pd (PPh) 3 ) 4 (0.35g, 0.30mmol) was dissolved in dry toluene (40.0 mL) and stirred at 110 deg.C under an argon atmosphere overnight. After the reaction was complete, the mixture was cooled to room temperature, the residue was washed with water and extracted with dichloromethane, and the organic layer was washed with Na 2 SO 4 Drying and rotary evaporation under reduced pressure to remove the solvent to obtain the crude product o-1, which is used in the subsequent reaction without further purification.
2) 2.0M lithium diisopropylamide (3.0 mL,6.0 mmol) was added dropwise to a solution of the crude product o-1 in anhydrous tetrahydrofuran (40 mL) at-78 ℃ under an argon atmosphere, and after stirring for 3.5 hours, 1.0M trimethyltin chloride (6.0 mL,6.0 mmol) was added dropwise and the temperature was gradually raised to room temperature. After stirring overnight, the mixture was quenched with saturated aqueous KF and extracted with hexane, and the organic layer was extracted with Na 2 SO 4 Drying, decompressing and rotary evaporating to remove the solvent to obtain a crude product o-2, and directly putting the crude product into the next reaction without further purification.
4) The crude product o-2, 4, 7-dibromo-5, 6-dinitrobenzo [ c ]][1,2,5]Thiadiazole (0.96g, 2.5mmol) and Pd (PPh) 3 ) 4 (0.20g, 0.17mmol) was dissolved in anhydrous toluene (25.0 mL) and stirred at 110 ℃ under an argon atmosphere overnight. The reaction mixture was then cooled and poured into saturated aqueous KF solution, the mixture was extracted 3 times with ether and the organic phase was washed with brine. The organic phase is then washed with Na 2 SO 4 Drying and rotary evaporation under reduced pressure to remove the solvent to give the crude product. The crude product was purified by column chromatography on silica eluting with petroleum ether/dichloromethane (3/1, v/v) to give o-3 as a red powder solid (1.69g, 76% yield).
5) Compound o-3 (1.69g, 1.90mmol) and triethyl phosphite (10 mL) were dissolved in anhydrous 1, 2-dichlorobenzene (o-DCB, 10 mL) under an argon atmosphere, and the mixture was stirred at 180 ℃ overnight. After the reaction was completed and cooled to room temperature, the solvent was distilled off under reduced pressure to obtain a red intermediate. Subsequently, the red intermediate is reacted with K 2 CO 3 (263g,19.0 mmol), KI (0.32g, 1.90mmol), 2-butyl-1-bromooctane (1.42g, 5.70mmol) and anhydrous DMF (25 mL) were mixed and stirred at 100 ℃ under an argon atmosphere overnight. After completion of the reaction, the reaction mixture was extracted 3 times with ethyl acetate and the organic phase was washed with brine. The organic phase is then washed with Na 2 SO 4 Dried and rotary evaporated under reduced pressure to give an orange oil. Thereafter, using petroleum ether/dichloromethane (6/1,v/v) as an eluent, o-4 (1.08g, 49% yield) was obtained as an orange solid by silica gel column chromatography.
6) Compound o-4 (1.08g, 0.93mmol) was dissolved in 20mL of chloroform under an argon atmosphere, and fresh Vilsmeier reagent (3.4 mL of POCl) was added dropwise at 0 deg.C 3 Mix in 7.2mL DMF). After stirring at 0 ℃ for 20 minutes, the mixture was heated to 65 ℃ and reacted for 24 hours. Then saturated NaHCO 3 The solution was quenched and stirred at room temperature for 24 hours. After completion of the reaction, the reaction mixture was extracted with dichloromethane, the organic layer was separated and washed with brine, na 2 SO 4 After drying, filtration and rotary evaporation under reduced pressure gave an orange-red oil. The crude product was purified by silica gel column chromatography eluting with petroleum ether/dichloromethane (1/1, v/v) to give o-5 as an orange solid (907.6 mg,80% yield).
7) The compound o-5 (50.0mg, 0.04mmol), 2- (5, 6-difluoro-3-oxo-2, 3-dihydro-1H-indene-1-ethylene) malononitrile (110.7mg, 0.48mmol), pyridine (1.0 mL) were dissolved in chloroform (10.0 mL) under an argon atmosphere, and the mixture was stirred at room temperature overnight, then the mixture was poured into methanol and suction-filtered to give a crude product. The crude product was then purified by column chromatography on silica gel using dichloromethane/petroleum ether (1/1, v/v) as eluent to give o-TEH as a dark blue solid (48.7mg, 74% yield).
Example 3: measuring optical band gaps of small molecule receptors m-TEH and o-TEH by using ultraviolet visible absorption spectrum
Absorption spectra of the small molecule acceptors m-TEH and o-TEH prepared in examples 1 and 2 measured under a chloroform solution and a thin film are shown in FIG. 5. The optical band gap of the molecule can be determined by empirical formula (E) g ＝1240/λ Absorption edge ) Calculated and shown in table 1.
TABLE 1 optical absorption data for the receptors m-TEH and o-TEH
Figure SMS_10
Example 4: method for measuring electronic energy levels of small molecule receptors m-TEH and o-TEH by using electrochemical cyclic voltammetry
The small molecule acceptors m-TEH and o-TEH prepared in examples 1 and 2 (0.5 mg each) were dissolved in 1mL of chloroform, respectively, and then the solution was dropped on a working electrode such as a platinum plate and dried; using 0.1mol/L anhydrous acetonitrile solution of tetrabutylammonium hexafluorophosphate as electrolyte; taking a platinum wire as a counter electrode; the Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) of the polymer were determined using Ag/AgCl as a reference electrode. Cyclic voltammograms of the small molecule acceptors m-TEH and o-TEH prepared in examples 1 and 2 of the invention are shown in FIG. 6. The HOMO and LUMO of the small molecule receptor m-TEH prepared in the embodiment 1 are respectively-5.71eV and-3.92 eV, and the HOMO and LUMO of the small molecule receptor o-TEH prepared in the embodiment 2 are respectively-5.70eV and-3.90 eV. The appropriate molecular energy levels of the molecules m-TEH and o-TEH prepared in examples 1 and 2 of the invention ensure that the molecules can be used as receptor photovoltaic materials in organic solar cells.
Example 5: preparation of organic solar cell devices of conventional Structure the photovoltaic performance of the small molecule receptor photovoltaic materials m-TEH and o-TEH of the invention was tested
Respectively blending and dissolving the small molecular acceptors m-TEH and o-TEH prepared in the embodiments 1 and 2 of the invention and a polymer donor PBQ6 in chloroform according to the weight ratio of the donor to the acceptor being 1.2 to prepare a 18mg/mL blending active layer solution, and adding 0.4% of chloronaphthalene in volume ratio after fully dissolving the solution. The glass is annealed at 90 ℃ for 5 minutes by spin coating on transparent Indium Tin Oxide (ITO) conductive glass containing an anode modification layer of poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT: PSS), and then 30 microliter of a PDINN methanol solution is thrown on; and (3) preparing a sample, conveying the sample to an evaporation chamber, and plating silver with the thickness of 100nm to obtain the organic solar cell photovoltaic device with the conventional structure. AAA-grade solar simulator AM1.5G (100 mW/cm) was used in a nitrogen-atmosphere glove box 2 ) To the product at a strength ofThe open-circuit voltage, the short-circuit current, the fill factor and the energy conversion efficiency of the organic solar cell device are tested.
Current density-voltage curves based on PBQ6: m-TEH and PBQ6: o-TEH after the test are shown in FIG. 7, and external quantum efficiencies are shown in FIG. 8. The PBQ6: m-TEH-based organic solar cell device has the open-circuit voltage of 0.880V and the short-circuit current of 26.61mA/cm 2 The filling factor is 79.03 percent, the energy conversion efficiency is 18.51 percent, the open-circuit voltage of an organic solar cell device corresponding to PBQ6: o-TEH is 0.882V, and the short-circuit current is 26.10 mA/cm 2 The fill factor was 70.47% and the energy conversion efficiency was 16.22%. Both EQE response ranges are 300-1000nm, and the integrated currents are 25.92 and 25.43mA/cm respectively 2 。
TABLE 2 organic solar cell devices based on PBQ6: m-TEH and PBQ6: o-TEH at AM1.5G,100mW/cm 2 Photovoltaic performance parameters under light conditions
Figure SMS_11
The invention is described with reference to specific embodiments and examples. However, the present invention is not limited to only the above-described embodiments and examples. One of ordinary skill in the art will recognize, based on the teachings of this patent, that many substitutions and alterations can be made without departing from the scope of the invention, which is defined by the claims.

Claims (7)

1. A compound of formula m-TEH or formula o-TEH:
Figure FDA0004053423920000011
2. an organic solar cell active layer comprising a compound of formula m-TEH or formula o-TEH according to claim 1 and a donor material; wherein the mass ratio of the donor material to the compound shown by the formula m-TEH or the formula o-TEH is 1 (0.8-2.0).
3. The organic solar cell active layer according to claim 2, characterized in that: the donor material is a polymer donor material or a small molecule donor material.
4. The organic solar cell active layer according to claim 3, characterized in that: the donor materials are PBQ6 and PTQ10 of the formula:
Figure FDA0004053423920000012
5. the organic solar cell active layer according to any of claims 2-4, characterized in that:
the organic solar cell active layer is mixed by adopting at least one of trichloromethane, chlorobenzene, o-dichlorobenzene, toluene and tetrahydrofuran solvents; in the obtained mixed solution, the mass volume ratio of the donor material to the solvent is 6-7 mg/mL; the mass-volume ratio of the compound shown in the formula m-TEH or the formula o-TEH to the solvent is 4.8-14 mg/mL.
6. The organic solar cell active layer according to any one of claims 2 to 4, characterized in that: the organic solar cell active layer further comprises an additive; the dosage of the additive is 0.3-2.0% of the total volume of the compound shown by the formula m-TEH or the formula o-TEH, the donor material and the solvent.
7. Use of a compound of formula m-TEH or o-TEH according to claim 1 or an active layer of an organic solar cell according to any of claims 2 to 6 for the preparation of: thin film semiconductor devices, photodetection devices, single junction and stacked organic/polymer solar cell devices, and other related optoelectronic devices.
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