CN111499624A - Oligothiophene photovoltaic material and preparation method and application thereof - Google Patents

Oligothiophene photovoltaic material and preparation method and application thereof Download PDF

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CN111499624A
CN111499624A CN202010317052.7A CN202010317052A CN111499624A CN 111499624 A CN111499624 A CN 111499624A CN 202010317052 A CN202010317052 A CN 202010317052A CN 111499624 A CN111499624 A CN 111499624A
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oligothiophene
energy
photovoltaic material
compound
drcn5t2cl
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向芸颉
郑绍辉
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Southwest University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • H—ELECTRICITY
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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Abstract

The invention discloses an oligothiophene photovoltaic material, and a preparation method and application thereof.A DRCN5T2Cl is obtained by substituting Cl for DRCN5T, and the theoretical calculation of L UMO/HOMO energy and energy gap, open-circuit voltage, dipole moment and exciton binding energy shows that the DRCN5T2Cl has lower HOMO energy level, larger band gap, higher open-circuit voltage and smaller dipole moment and exciton binding energy than DRCN5T, so that the DRCN5T2Cl can be used as an excellent organic solar cell electron donor material.

Description

Oligothiophene photovoltaic material and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic solar cells, in particular to an oligothiophene photovoltaic material and a preparation method and application thereof.
Background
Nowadays, energy problems and environmental problems are increasingly highlighted, and the search for new green pollution-free energy is always urgent worldwide. Solar energy has been the development direction of green energy in the present society due to the unique advantages of inexhaustible, green, environmental protection, safety and the like, and the solar cell technology for converting solar energy into electric energy is the research focus of development and application in recent years.
Organic Solar Cells (OSCs) have the advantages of wide material sources, easily-adjustable structure, simple manufacturing process, solution processing, capability of being manufactured into large-area flexible devices and the like, and are widely concerned by countries in the world. The energy conversion efficiency of Bulk Heterojunction (BHJ) single-layer OSCs taking fullerene as an acceptor material reaches 11.7%, the energy conversion efficiency of BHJ single-layer OSCs taking non-fullerene as an acceptor material reaches 18.22%, and the energy conversion efficiency of laminated OSCs exceeds 17.3%. It has been found that whether the device structure is a stack or a single layer, and whether the donor material is a fullerene or a non-fullerene, the choice of donor material in the photoactive layer is extremely important. However, the types of donor materials with good properties available in the photoactive layer are still not wide enough, and especially the types of small molecule donor materials are few. Therefore, the development of new donor materials in the active layer is the key direction for the development of organic solar cells.
Oligothiophenes are highly studied organic semiconductor materials and are widely used in organic photovoltaic devices due to their excellent charge transport properties, tunable optical/electrochemical properties, high polarizability, high stability, relatively simple synthesis and ready availability of these properties. The Chenyong group reported DRCN7T, a linear acceptor-donor-acceptor molecule with heptathiophene as the backbone and 2- (1, 1-dicyanomethylene) rhodanine as the end group, possessing a 9.3% photoelectric conversion efficiency. They reported that spatial symmetry and conjugation length have a great influence on molecular packing, phase separation, molecular orbital level and carrier mobility. They then studied a series of acceptor-donor-acceptor molecules (DRCN4T-DRCN9T) with similar backbones and identical end groups but different steric symmetries and conjugation lengths. They found that DRCN5T possessed the highest photoelectric conversion efficiency of 10.1%.
Disclosure of Invention
The invention aims to provide an oligothiophene photovoltaic material, and a preparation method and application thereof, wherein the oligothiophene photovoltaic material has a lower HOMO energy level, a larger energy gap (gap), a higher open-circuit voltage, a smaller dipole moment and exciton binding energy and better organic solar cell performance than DRCN 5T.
In order to achieve the above purpose, the invention adopts the technical scheme that:
the invention discloses an oligothiophene photovoltaic material, which has the following structural formula:
Figure BDA0002459945780000021
the invention also discloses a preparation method of the oligothiophene photovoltaic material, which comprises the following steps:
(1) compound 1, compound 2, Pd2(dba)3And tri (o-tolyl) phosphine were dissolved in degassed chlorobenzene, and the mixture was then heated to react; after the reaction, washing, extracting, drying and purifying the organic layer to obtain a compound 3;
Figure BDA0002459945780000022
(2) dissolving the mixture of the compound 3 and the compound 4 in anhydrous chloroform, and adding alkaline Al2O3Then, stirring the mixture and heating for reaction; after the reaction, filtering, washing and purifying the mixture to obtain the oligothiophene photovoltaic material;
Figure BDA0002459945780000023
the invention also discloses an application of the oligothiophene photovoltaic material in an organic solar cell, and the oligothiophene photovoltaic material is used as an electron donor material in the organic solar cell.
The invention has the beneficial effects that:
the invention substitutes DRCN5T with Cl to obtain DRCN5T2Cl, and through theoretical calculation of L UMO/HOMO energy and energy gap, open-circuit voltage, dipole moment and exciton binding energy, DRCN5T2Cl is found to have lower HOMO energy level, larger energy gap (gap), higher open-circuit voltage, smaller dipole moment and exciton binding energy than DRCN5T, so that DRCN5T2Cl can be applied as an excellent organic solar cell electron donor material.
Drawings
FIG. 1 shows that the L UMO/HOMO energy and energy gap of DRCN5T and DRCN5T2Cl are calculated in dichloromethane by using CAM-B3L YP/6-31+ g (d);
fig. 2 is a calculated value of the open circuit voltage.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described with reference to the accompanying drawings.
Example 1 Synthesis of oligothiophene photovoltaic material DRCN5T2Cl
(1) Synthesis of Compound 3:
mixing compound 1(745mg,1.50mmol), compound 2(297mg,0.62mmol), Pd2(dba)3(55mg,0.06mmol) and tri (o-tolyl) phosphine (91mg,0.30mmol) were dissolved in 20m L degassed chlorobenzene, which was placed in a dry Schlenk tube, the mixture was heated for reaction for 48 hours, after the reaction, the organic layer was washed with brine and washed with CH2Cl2(3 × 40m L) and then extracting with Na2SO4And (5) drying. After removal of the solvent, the crude product was purified by silica gel to give compound 3.
Figure BDA0002459945780000031
(2) Synthesis of product DRCN5T2 Cl:
a mixture of Compound 3(306mg, 0.31mmol) and Compound 4(608mg, 3.14mmol) was dissolved in anhydrous chloroform (40m L), and basic Al was added2O3After (excess), the mixture was stirred and heated for 24 h after cooling, the mixture was filtered and washed with chloroform (3 × 50m L) then the solvent was evaporated and the crude product was purified by silica gel column chromatography to give the product DRCN5T2 Cl.
Figure BDA0002459945780000032
Example 2 theoretical calculation
The invention utilizes Density Functional Theory (DFT) and time-dependent density functional theory (TDDFT) to calculate L UMO/HOMO energy and energy gap, open-circuit voltage, dipole moment and exciton binding energy of DRCN5T and DRCN5T2 Cl.
(1) The L UMO/HOMO energy and energy gap were calculated using the CAM-B3L YP density functional, and the results show that in FIG. 1, DRCN5T2Cl has a reduced HOMO compared to DRCN5T, and the energy gap becomes larger than DRCN 5T. the lower HOMO level further increases the open circuit voltage and improves the photovoltaic performance of the device as a whole.
(2) Open circuit voltage (Voc), one of the important factors affecting the photoelectric conversion efficiency of organic solar cells, was calculated using the empirical formula reported by Scharber et al for solar cells with PC71BM as acceptor and DRCN5T and DRCN5T2Cl as donor.
VOC＝(1/e)(|EDonorHOMO|-|EPCBMLUMO|)-0.3V
Wherein E represents an electronic charge, EDonorHOMO represents HOMO energy, EPCBML UMO shows the L UMO energy of the PC71BM receptor the CAM-B3L YP calculated the L UMO/HOMO energy and energy gap of PC71BM as-3.01 eV, -5.78eV and 2.77eV, respectively.
Fig. 2 shows calculated values of open circuit voltage, DRCN5T2Cl has a higher open circuit voltage than DRCN5T, which directly results in an increase in overall photovoltaic efficiency.
(3) The dipole moment is related to the accumulation of molecules and the separation of charges. As the dipole moment increases, the separation of charges increases. However, if the dipole moment is too large, the molecules will be clustered together and the charge will not be efficiently transferred, and therefore the value of the dipole moment should be appropriate. The dipole moment of DRCN5T was 17.33Debye and the dipole moment of DRCN5T2Cl was 13.42 Debye. Further reduced dipole moment will reduce the aggregation of donor molecules, mixing well with the donor material, improving the performance of the organic solar cell.
(4) The invention utilizes CAM-B3L YP/6-31+ G (d) to calculate the exciton binding energy of DRCN5T and DRCN5T2Cl in the thin film, the exciton binding energy of DRCN5T is 0.5191eV, and the exciton binding energy of DRCN5T2Cl is 0.4532 eV. smaller, so that the energy consumption required by the separation of electron-hole pairs is reduced, the separation is greatly promoted, and the performance of the organic solar cell is improved.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (4)

1. An oligothiophene photovoltaic material, characterized in that: the structural formula is as follows:
Figure FDA0002459945770000011
2. a method of preparing an oligothiophene photovoltaic material according to claim 1, wherein: the method comprises the following steps:
(1) compound 1, compound 2, Pd2(dba)3And tri (o-tolyl) phosphine were dissolved in degassed chlorobenzene, and the mixture was then heated to react; after the reaction, washing, extracting, drying and purifying the organic layer to obtain a compound 3;
Figure FDA0002459945770000012
(2) dissolving the mixture of the compound 3 and the compound 4 in anhydrous chloroform, and adding alkaline Al2O3Then, stirring the mixture and heating for reaction; after the reaction, filtering, washing and purifying the mixture to obtain the oligothiophene photovoltaic material;
Figure FDA0002459945770000013
3. use of the oligothiophene photovoltaic material of claim 1 in an organic solar cell.
4. Use of an oligothiophene photovoltaic material according to claim 3 in an organic solar cell, wherein: the oligothiophene photovoltaic material is used as an electron donor material in an organic solar cell.
CN202010317052.7A 2020-04-21 2020-04-21 Oligothiophene photovoltaic material and preparation method and application thereof Pending CN111499624A (en)

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US20230397492A1 (en) * 2022-06-07 2023-12-07 Taizhou University Small-molecule electron donor material with an electron-deficient heterocyclic core, preparation and application thereof

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230397492A1 (en) * 2022-06-07 2023-12-07 Taizhou University Small-molecule electron donor material with an electron-deficient heterocyclic core, preparation and application thereof
US11917911B2 (en) * 2022-06-07 2024-02-27 Taizhou University Small-molecule electron donor material with an electron-deficient heterocyclic core, preparation and application thereof

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