CN113372365A - Benzothiadiazole-based receptor material and preparation method and application thereof - Google Patents
Benzothiadiazole-based receptor material and preparation method and application thereof Download PDFInfo
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- 239000012467 final product Substances 0.000 claims description 6
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- 239000012312 sodium hydride Substances 0.000 claims description 6
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- 239000007787 solid Substances 0.000 claims description 4
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 abstract description 4
- 229910003472 fullerene Inorganic materials 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
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- 239000010408 film Substances 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
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- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains four or more hetero rings
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- 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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- 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
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Abstract
The invention discloses a benzothiadiazole-based acceptor material and a preparation method and application thereof. The polymer solar cell receptor material has a proper energy level orbit and excellent carrier transmission performance, is a potential substitute of a fullerene electron receptor, and can be widely applied to preparation of high-performance polymer solar cell devices.
Description
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to a diazosulfide-based receptor material and a preparation method and application thereof.
Background
Polymer Solar Cells (PSCs) have become one of the research hotspots in academia and industry due to their advantages of being light, cheap, and easy to implement large-area and flexible devices. With the rapid development of A-DA' D-A type micromolecule acceptor materials in recent years, the energy conversion efficiency of the polymer solar cell is enabled to break through 18%. Most of the receptor materials mainly concentrate on 500-900 nm in light absorption and have low absorption and utilization on light in a near infrared region in a solar spectrum, so that development of the ultra-narrow bandgap small molecule receptor material with near infrared absorption is important for breaking through the bottleneck in the field of polymer solar cells, and has important guiding significance for realizing the commercial development of the performance of the polymer solar cells.
Disclosure of Invention
Aiming at the problems of limited absorption range of receptor materials, unsatisfactory short-circuit current and the like in the active layer of the current polymer solar cell, the invention provides a molecular design strategy for introducing one or three vinyl pi bridges at the tail end of a seven-membered benzothiadiazole condensed ring core, so that the increase of conjugation length and the widening of electron delocalization range are realized, and the spectral absorption of molecules in a near-infrared region is remarkably enhanced.
The invention provides a technical scheme of a novel non-fullerene electron acceptor material, which has important scientific significance and practical value for constructing a high-efficiency and low-cost polymer solar cell device.
The purpose of the invention is realized by the following technical scheme.
A benzothiadiazole-based acceptor material having the following chemical structure:
the invention also provides a preparation method of the benzothiadiazole-based receptor material, which comprises the following steps: the hydroformylation of seven-membered diazosulfide fused ring nucleus is reacted with tributyl (1, 3-dioxane-2-ylmethyl) phosphonium bromide to obtain an asymmetric intermediate 1, then the asymmetric intermediate 1 is reacted with tributyl (1, 3-dioxane-2-ylmethyl) phosphonium bromide to obtain an asymmetric intermediate 2, and finally the intermediate 1 and the intermediate 2 are subjected to Knoevenagel reaction with different electron-withdrawing end groups to obtain a final product.
More specifically, the method comprises the steps of:
step 1: dissolving the hydroformylation seven-membered diazosulfide fused ring nucleus in anhydrous tetrahydrofuran, adding 1 equivalent of tributyl (1, 3-dioxane-2-ylmethyl) phosphonium bromide and sodium hydride of the hydroformylation seven-membered diazosulfide fused ring nucleus, stirring for 8 hours at room temperature under the protection of nitrogen, extracting, washing, drying, and purifying by column chromatography to obtain an intermediate 1.
Step 2: dissolving the intermediate 1 in anhydrous tetrahydrofuran, adding 2 equivalents of tributyl (1, 3-dioxane-2-ylmethyl) phosphonium bromide and sodium hydride of the intermediate 1, stirring at room temperature for 8h under the protection of nitrogen, extracting, washing, drying, and purifying by column chromatography to obtain an intermediate 2.
And step 3: dissolving the intermediate 1 or the intermediate 2 in a chloroform solution, adding 4 equivalents of the electron-withdrawing end group of the intermediate 1 or the intermediate 2, adding 1ml of anhydrous pyridine, and reacting for 10 hours at 65 ℃ under the protection of nitrogen. And after the reaction is finished, pouring the solution into methanol, dissolving, extracting and drying the separated solid, and purifying by column chromatography to obtain the final product.
The material is used as an electron acceptor material for a single-section binary polymer solar cell device.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the photoelectric property is adjustable, namely different numbers of vinyl pi bridges are inserted, and the photoelectric property of the receptor material can be simply regulated and controlled;
(2) the benzothiadiazole-based acceptor material has a longer conjugated structure, and is beneficial to improving the short-circuit current and the photoelectric conversion efficiency of a polymer solar cell device.
(3) The material can be used as an electron acceptor material in a polymer solar cell and can also be used as an additive material of a ternary blended polymer solar cell.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of intermediate 1;
FIG. 2 is a nuclear magnetic resonance spectrum of intermediate 2;
FIG. 3 is a nuclear magnetic resonance spectrum of the receptor material 1V-2F;
FIG. 4 is a graph of the UV-VISIBLE-NIR absorption curves for receptor materials 1V-2F;
FIG. 5 is a graph of the 1V-2F electrochemical profile of the receptor material;
FIG. 6 is a voltage-current curve of a single-section binary photovoltaic device applied with the receptor material 1V-2F
Detailed description of the invention
The invention is further described with reference to the following figures and examples.
Example 1
Synthesis of ultra-narrow bandgap receptor material 1V-2F
Synthesis of preparation of intermediate 1: the hydroformylation of seven-membered benzothiadiazole fused ring nucleus (560mg,0.5mmol) (purchased from nakai, su) was dissolved in 30mL of anhydrous tetrahydrofuran, 1 equivalent of tributyl (1, 3-dioxan-2-ylmethyl) phosphonium bromide (180mg, 0.5mmol) and sodium hydride (24mg, 0.5mmol) of the hydroformylation of seven-membered benzothiadiazole fused ring nucleus was added, stirred at room temperature for 8 hours under nitrogen protection, 10mL of dilute hydrochloric acid was added, extracted with dichloromethane, washed with deionized water, dried over anhydrous sodium sulfate and spin-dried, and purified by column chromatography to give intermediate 1.1H NMR(400MHz,CDCl3)δ10.14(s,1H),9.71(d,J＝7.6Hz,1H),7.78(d,J＝15.3Hz,1H),6.77-6.28(m,1H),4.61(t,J＝7.7Hz,4H),3.20(t,J＝7.5Hz,2H),2.99(t,J＝7.5Hz,2H),2.04(s,2H),1.99-1.83(m,4H),1.39-1.24(m,40H),0.91-0.83(m,24H),0.78-0.55(m,18H).(MALDI-TOF)m/z calcd.for(C94H110N8O2S5):1164.6450.Found:1164.6444.
Synthesis of preparation of intermediate 2: dissolving intermediate 1(595mg, 0.5mmol) in 30mL of anhydrous tetrahydrofuran, adding 1 equivalent of hydroformylated tributyl (1, 3-dioxan-2-ylmethyl) phosphonium bromide (360mg, 1.0mmol) and sodium hydride (48mg, 1.0mmol) of a fused ring nucleus of hepta-benzothiadiazole, stirring at room temperature for 8h under nitrogen protection, adding 10mL of dilute hydrochloric acid, extracting with dichloromethane, washing with deionized water, drying over anhydrous sodium sulfate and spin-drying, and purifying by column chromatography to obtain intermediate 2.1H NMR(400MHz,CDCl3)δ9.70(d,J＝7.6Hz,1H),9.63(d,J＝7.9Hz,1H),7.78(d,J＝15.3Hz,1H),7.32(dt,J＝15.0,5.5Hz,2H),6.80(dd,J＝14.7,11.1Hz,1H),6.52(dd,J＝15.3,7.6Hz,1H),6.27(dd,J＝15.0,7.9Hz,1H),4.59(d,J＝7.2Hz,4H),2.99(t,J＝7.7Hz,2H),2.92(t,J＝7.6Hz,2H),2.04(s,2H),1.83(dd,J＝13.6,7.3Hz,4H),1.50-1.21(m,34H),1.13-0.84(m,30H),0.82-0.48(m,18H).(MALDI-TOF)m/z calcd.for(C94H110N8O2S5):1216.6763.Found:1216.6759.
The NMR spectrum of intermediate 1 is shown in FIG. 1, and the NMR spectrum of intermediate 2 is shown in FIG. 2.
Synthesis of acceptor materials 1V-2F: intermediate 1(127mg, 0.11mmol) and 2(5, 6-difluoro-3-oxo-2, 3-dihydro-1H-indene-1-ethylene) malononitrile (100mg, 0.43mmol) were dissolved in 30mL of chloroform solution, 1mL of anhydrous pyridine was added, and reaction was carried out at 65 ℃ for 10H under nitrogen. And after the reaction is finished, pouring the solution into methanol, dissolving, extracting and drying the separated solid, and purifying by column chromatography to obtain a final product 1V-2F.1H NMR(400MHz,CDCl3)1H NMR(400MHz,CDCl3)δ9.16(s,1H),8.7-48.32(m,4H),8.01-7.46(m,3H),4.97-4.57(m,4H),3.23(t,J＝7.6Hz,2H),3.03(t,J＝7.6Hz,2H),2.11(br,2H),1.8(br,4H),1.55-1.20(m,33H),1.18-0.83(m,33H),0.82-0.56(m,16H).MS(MALDI-TOF)m/z calcd.for(C92H104F4N8O2S5):1589.7855.Found:1589.7831.
The nuclear magnetic resonance spectrum of the acceptor material 1V-2F is shown in FIG. 3.
Example 2
Synthesis of ultra-narrow bandgap receptor material 3V-2F
Synthesis of acceptor Material 3V-2F: intermediate 2(69mg, 0.06mmol) and 2(5, 6-difluoro-3-oxo-2, 3-dihydro-1H-indene-1-ethylene) malononitrile (52mg, 0.22mmol) were dissolvedTo 20mL of chloroform solution, 1mL of anhydrous pyridine was added and the mixture was reacted at 65 ℃ for 10 hours under nitrogen. And after the reaction is finished, pouring the solution into methanol, dissolving, extracting and drying the separated solid, and purifying by column chromatography to obtain a final product 3V-2F.1H NMR(400MHz,Chloroform-d)δ8.72-8.58(m,1H),8.58-8.46(m,3H),8.53-8.39(m,1H),8.33-8.20(m,1H),7.68(m,3H),7.53-7.39(m,1H),7.42-7.30(m,1H),7.15-6.95(m,1H),4.64(s,4H),3.10-2.85(m,6H),2.10(s,1H),1.96-1.78(m,4H),1.52-1.24(m,32H),1.19-0.82(m,30H),0.69(dd,J＝16.5,6.9Hz,18H).MS(MALDI-TOF)m/z calcd.for(C96H108F4N8O2S5):1641.7168.Found:1641.7151.
Example 3
Measurement of optical band gap of acceptor material 1V-2F by absorption spectroscopy
The ultraviolet-visible absorption spectrum of the receptor material 1V-2F prepared in example 1 measured under chloroform and a thin film is shown in FIG. 4. The optical bandgap of the acceptor material can be represented by the empirical formula (E)g opt＝1240/λAbsorption edge) The calculation was 1.26 eV.
Example 4
Determination of electronic energy levels of acceptor materials 1V-2F by electrochemical cyclic voltammetry
The acceptor material 1V-2F (1mg) prepared in example 1 was dissolved in 1mL of chloroform, the solution was dropped onto a working platinum electrode, and HOMO and LUMO levels of the acceptor material were measured using an acetonitrile solution of tetrabutylammonium hexafluorophosphate as an electrolyte. The cyclic voltammograms of the receptor materials 1V-2F prepared in example 1 of the present invention are shown in FIG. 5. The HOMO and LUMO of the acceptor material 1V-2F prepared in the embodiment 1 of the invention are-5.64 eV and-3.92 eV respectively.
Example 5
Preparation and characterization of polymer solar cell based on benzothiadiazole acceptor material
The conventional structure of the BHJ-PSC device material comprises ITO/PEDOT, PSS/active layer/PNDIT-F3N/Ag, wherein ITO is a positive electrode, Ag is a negative electrode, PSS is a hole transport layer, and PNDIT-F3N is an electron transport layer.
The preparation of the BHJ-PSC device specifically comprises the following steps:
(1) firstly, the ITO glass is respectively cleaned by detergent, deionized water, acetone and isopropanol for 20min by ultrasonic wave, and the ITO glass is dried for 2h at 120 ℃ in an oven and then irradiated for 15min by an ultraviolet ozone cleaning instrument. Spin-coating aqueous solution of PEDOT: PSS (1:1, w/w) on the ITO glass at the rotating speed of 5000rpm, drying at 150 ℃ for 15min, and transferring the ITO/PEDOT: PSS film into a nitrogen glove box;
(2) dissolving 1V-2F and a donor material PM6 in a trichloromethane solution according to a mass ratio of 1:1.2, wherein the total concentration of a donor is 16mg/mL, preparing an active layer solution, spin-coating the active layer solution on an ITO/PEDOT: PSS film by using a spin coater, and carrying out thermal annealing at 100 ℃ for 5min to prepare an active layer;
(3) 0.5mg/mL of a methanol solution of PNID-F3N was spin-coated onto the active layer at 2000rpm, and finally placed in a vacuum evaporation chamber at a pressure of 5X 10-5And under the condition of Pa, evaporating an electron transport layer Ag to obtain the BHJ-OPV device.
The prepared BHJ-OPV device has a current-voltage (J-V) curve with Keithley 2400 stray illumination intensity of 100mW cm-2The current-voltage (J-V) curve of the BHJ-OPV device was measured and is shown in fig. 6, and it can be seen from fig. 6 that: for MP6/1V-2F single-layer binary device, the measured open-circuit voltage is V at a mass ratio of 1:1.2OC0.80V, short-circuit current Jsc＝24.75mA cm-2The fill factor FF is 0.72, and the photoelectric conversion efficiency PCE is 14.24%.
The benzothiadiazole-based acceptor material disclosed by the invention has excellent carrier mobility and good solution processability, and is a potential substitute for a fullerene derivative electron acceptor. The method is suitable for being widely applied to preparation of efficient polymer solar cell devices as a non-fullerene electron acceptor material.
The above embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention. Any replacement, modification, combination or simplification made by those skilled in the art without changing the spirit of the present invention will fall within the protection scope of the present invention.
Claims (4)
1. A benzothiadiazole-based acceptor material, comprising the following chemical structure:
2. the method for preparing benzothiadiazole-based acceptor material according to claim 1, wherein: the hydroformylation of seven-membered benzothiadiazole fused ring nucleus is reacted with tributyl (1, 3-dioxane-2-ylmethyl) phosphonium bromide to obtain an asymmetric intermediate (1), then the asymmetric intermediate (1) is reacted with the tributyl (1, 3-dioxane-2-ylmethyl) phosphonium bromide to obtain an asymmetric intermediate (2), and finally the intermediate (1) and the intermediate (2) are subjected to Knoevenagel reaction with different electron-withdrawing end groups to obtain a final product.
3. The method for preparing benzothiadiazole-based acceptor material according to claim 2, characterized in that: the method specifically comprises the following steps:
step 1: dissolving the hydroformylation seven-membered diazosulfide fused ring nucleus in anhydrous tetrahydrofuran, adding 1 equivalent of tributyl (1, 3-dioxane-2-ylmethyl) phosphonium bromide and sodium hydride of the hydroformylation seven-membered diazosulfide fused ring nucleus, stirring for 8 hours at room temperature under the protection of nitrogen, extracting, washing, drying, and purifying by column chromatography to obtain an intermediate (1);
step 2: dissolving the intermediate (1) in anhydrous tetrahydrofuran, adding 2 equivalents of tributyl (1, 3-dioxan-2-ylmethyl) phosphonium bromide and sodium hydride of the intermediate (1), stirring at room temperature for 8h under the protection of nitrogen, extracting, washing, drying, and purifying by column chromatography to obtain an intermediate (2);
and step 3: dissolving the intermediate (1) or the intermediate (2) in a chloroform solution, adding 4 equivalents of an electron-withdrawing end group of the intermediate (1) or the intermediate (2), adding 1mL of anhydrous pyridine, reacting at 65 ℃ for 10h under the protection of nitrogen, pouring the solution into methanol after the reaction is finished, dissolving, extracting and drying the separated solid, and purifying by column chromatography to obtain a final product.
4. Use of the benzothiadiazole-based acceptor material according to claim 1, characterized in that: the material is used as an electron acceptor material for a single-section binary polymer solar cell device.
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