CN114716460B - Conjugated organic small molecule and preparation method and application thereof - Google Patents
Conjugated organic small molecule and preparation method and application thereof Download PDFInfo
- Publication number
- CN114716460B CN114716460B CN202210301802.0A CN202210301802A CN114716460B CN 114716460 B CN114716460 B CN 114716460B CN 202210301802 A CN202210301802 A CN 202210301802A CN 114716460 B CN114716460 B CN 114716460B
- Authority
- CN
- China
- Prior art keywords
- conjugated
- compound
- organic
- bdf
- solar cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 150000003384 small molecules Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 54
- 150000001875 compounds Chemical class 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 230000005540 biological transmission Effects 0.000 claims description 18
- 239000012043 crude product Substances 0.000 claims description 15
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 14
- 238000004440 column chromatography Methods 0.000 claims description 13
- 239000013067 intermediate product Substances 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- 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 claims description 8
- 229910003472 fullerene Inorganic materials 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 238000004528 spin coating Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 4
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims description 4
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000000862 absorption spectrum Methods 0.000 abstract description 9
- MLIREBYILWEBDM-UHFFFAOYSA-M 2-cyanoacetate Chemical compound [O-]C(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-M 0.000 abstract description 8
- 238000010494 dissociation reaction Methods 0.000 abstract description 5
- 230000005593 dissociations Effects 0.000 abstract description 5
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 5
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000295 complement effect Effects 0.000 abstract 1
- 239000000370 acceptor Substances 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 9
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 9
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 8
- 238000004770 highest occupied molecular orbital Methods 0.000 description 8
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000000137 annealing Methods 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 3
- KXSFECAJUBPPFE-UHFFFAOYSA-N 2,2':5',2''-terthiophene Chemical compound C1=CSC(C=2SC(=CC=2)C=2SC=CC=2)=C1 KXSFECAJUBPPFE-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- CRUIOQJBPNKOJG-UHFFFAOYSA-N thieno[3,2-e][1]benzothiole Chemical compound C1=C2SC=CC2=C2C=CSC2=C1 CRUIOQJBPNKOJG-UHFFFAOYSA-N 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000009878 intermolecular interaction Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000010129 solution processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
-
- 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
- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
-
- 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
- H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
-
- 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
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention provides a conjugated organic small molecule, a preparation method and application thereof, and relates to the technical field of photoelectric materials. The conjugated organic small molecules take benzodifuran as a central electron (D) donating unit, tertiarythiophene or thienothiophene as pi bridge and rhodamine or cyanoacetate as a terminal electron (A) withdrawing unit, so that conjugated organic small molecules with A-pi-D-pi-A type structures are constructed. Compared with the prior art, the conjugated organic micromolecule can have enough voltage with the receptor to drive exciton dissociation, and is complementary with the absorption spectrum of the receptor, so that the energy conversion efficiency of the organic solar cell is improved, and the conjugated organic micromolecule has higher thermal stability.
Description
Technical Field
The invention relates to the technical field of photoelectric materials, in particular to a conjugated organic small molecule and a preparation method and application thereof.
Background
With the continuous development of economy and society, people have higher and higher demands for energy, and traditional fossil energy cannot be regenerated in a short time, so that new energy development is imperative. Among the existing solar cells, organic Solar Cells (OSC) are one of the most promising technologies for producing low-cost energy sources, and have the advantages of light weight, wide material sources, strong energy level and absorption spectrum adjustability, translucency, and the like. Because of these excellent characteristics, a great deal of researchers have been attracted to study how to improve the energy conversion efficiency (PCE) of an organic solar cell device in the last several decades. In recent years, with the rapid development of non-fullerene acceptor (NFA) materials, the energy conversion efficiency of organic solar cells has been greatly improved. To date, PCEs of organic solar cells certified by the national renewable energy laboratory have reached 18.2% and even single junction OSC efficiencies reported in the literature have reached nearly 19%.
The donor materials used for high efficiency OSCs are mostly polymeric materials, the polymers being generally determined in molecular weight by molecular weight distribution, which makes the polymeric OSCs prone to batch-to-batch variation in production and preparation. The organic small molecules have definite chemical structures, the molecular weight is also definite, the separation and purification are easier and more thorough, the controllability in mass preparation is stronger, meanwhile, the small molecules can avoid certain characteristics of the high molecules, such as defects of chain links and chain ends, and the defects can lead to structural disorder and low-level trap states. Although organic small molecule materials are simpler in structure and easier to prepare, modify and optimize than polymeric donor materials, the development of small molecule donor materials lags behind the development of polymeric donors, and the efficiency of all small molecule organic solar cells (ASM-OSC) reported to date is 16.28%, so developing an all small molecule OSC with a high PCE is one of the important challenges facing today.
Disclosure of Invention
The invention solves the problem of how to improve the energy conversion efficiency of an organic solar cell device using small organic molecules as donor materials.
In order to solve the above problems, the first aspect of the present invention provides a conjugated organic small molecule, which has a structural formula shown in formula (i) or formula (ii):
wherein R is 1 -R 10 Is the same or different hydrogen atoms, straight-chain or branched-chain alkyl groups with 2-20 carbon atoms or straight-chain or branched-chain alkoxy groups with 2-20 carbon atoms;
ar represents an electron withdrawing unit comprising a group 1 or a group 2, the group 1 having the following structural formula:
the structural formula of the group 2 is as follows:
wherein R is 11 And R is 12 Including straight or branched alkyl groups of 2 to 20 carbon atoms, which may be the same or different.
Compared with the prior art, the invention has the advantages that:
(1) The invention constructs a conjugated organic small molecule with an A-pi-D-pi-A type structure, wherein, the benzodifuran is taken as a central electron donating (D) unit, on one hand, a large plane conjugated center is provided, which is beneficial to molecule accumulation, and on the other hand, the BDF unit also serves as an electron donating center to regulate energy level and absorption; the terthiophene or the thienothiophene bithiophene is used as pi bridge, so that the photovoltaic performance of the organic solar cell can be improved, and the miscibility with an acceptor can be effectively improved by an alkyl side chain on the introduced thiophene, thereby being beneficial to exciton dissociation; the rhodanine or cyanoacetate is used as a terminal electron-withdrawing (A) unit, and the electron-withdrawing group on the rhodanine or cyanoacetate can reduce the HOMO and LUMO energy levels of molecules, so that stronger intramolecular charge transfer is realized, a narrow band gap is realized, and intermolecular interaction is induced, so that high electron mobility is realized. Therefore, when the conjugated organic small molecule is used as a donor material for an organic solar cell, the conjugated organic small molecule can have enough voltage with an acceptor to drive exciton dissociation, so that the energy conversion efficiency of the organic solar cell is improved.
(2) According to the conjugated organic micromolecule, the fluorine-containing side chain is introduced into the BDF core, so that on one hand, the solubility required by solution processing is ensured, and the introduced side chain can cause certain twisting of the molecule due to steric hindrance, so that excessive aggregation of the molecule is inhibited, a good film form is formed, the conjugated organic micromolecule has good solubility and film forming property in common organic solvents, and the preparation of an organic solar cell with high energy conversion efficiency is facilitated; on the other hand, the thiophene side chain with monofluoride can effectively reduce the energy level of the highest occupied orbit (HOMO) and the lowest unoccupied orbit (LUMO) of the material, so that the material has better energy level matching with the receptor.
(3) The conjugated organic micromolecule has good absorption in the visible light spectrum range of 400-700nm, can form complementation with the absorption spectrum of the low band gap non-fullerene acceptor material Y6, and the mixed film has good absorption in the solar spectrum range, thereby being beneficial to improving the energy conversion efficiency of the organic solar cell.
(4) The conjugated small organic molecule can still keep the high voltage level at the high thermal annealing temperature, so that the conjugated small organic molecule has better thermal stability.
The second aspect of the present invention provides a method for preparing a conjugated small organic molecule, comprising:
dissolving a first compound, a second compound and tetraphenylphosphine palladium in a solvent, and reacting for 12 hours at 110 ℃ under the protection of inert gas and in the dark to obtain an intermediate product;
dissolving the intermediate product, a third compound and piperidine in chloroform, and reacting for 8 hours at 65 ℃ under the protection of inert gas to obtain conjugated small organic molecules;
wherein the structural formula of the first compound is as follows:
the structural formula of the second compound is as follows:
the structural formula of the third compound is as follows:
preferably, the intermediate product is obtained by column chromatography of a crude product, and the crude product is obtained by extracting a reaction solution obtained after the first compound and the second compound react with each other with chloroform, washing with deionized water, drying with anhydrous sodium sulfate, and concentrating under reduced pressure to dryness.
Preferably, the ratio of the eluent used in the column chromatography is petroleum ether to dichloromethane is 1:1-2.
Preferably, the conjugated small organic molecule is obtained by concentrating the reaction solution obtained by reacting the intermediate product with the third compound under reduced pressure, then settling the reaction solution in excessive methanol, and obtaining a solid crude product after column chromatography.
Preferably, the eluent used in the column chromatography is petroleum ether in the following proportion: the ratio of the chloroform is 1-1.5:1.
The third aspect of the invention provides an application of conjugated organic molecules in an organic solar cell.
The fourth aspect of the present invention provides an organic solar cell, comprising a first electrode, a first transmission layer, a photoactive layer, a second transmission layer and a second electrode sequentially arranged, wherein the first electrode comprises ITO glass, the first transmission layer comprises PEDOT: PSS, the photoactive layer is a blend film comprising a conjugated small organic molecule donor material and a low band gap non-fullerene acceptor material Y6, and the second transmission layer comprises MoO 3 Or PDINO, the second electrode comprising Al or Ag.
Preferably, the thickness of the first transmission layer is 20-40nm, the thickness of the photoactive layer is 80-120nm, the thickness of the second transmission layer is 5-10nm, and the thickness of the second electrode is 80-100nm.
In a fifth aspect, the present invention provides a method for preparing an organic solar cell, comprising: mixing the conjugated organic micromolecules with the Y6, adding chloroform for dissolution, preparing the photoactive layer on the ITO glass substrate modified by the first transmission layer in a spin coating mode, spin-coating the second transmission layer after the photoactive layer is thermally annealed at 120 ℃ for 10min, and finally evaporating Al or Ag to prepare the second electrode.
The organic solar cell obtained by adopting the conjugated organic micromolecule as the donor material has high short-circuit current and can realize the improvement of the efficiency of the device.
Drawings
FIG. 1 is a flow chart of a method for preparing conjugated small organic molecules in the embodiment of the invention;
fig. 2 is a schematic structural diagram of an organic solar cell device according to an embodiment of the present invention;
FIG. 3 is a cyclic voltammogram of conjugated organic molecules BDF-1, BDF-2, and BDF-3 in an example of the invention;
FIG. 4 is a thermogravimetric analysis (TGA) curve of conjugated organic molecules BDF-1, BDF-2 and BDF-3 in the examples of the invention;
FIG. 5 is an ultraviolet-visible absorption spectrum of conjugated organic molecules BDF-1, BDF-2 and BDF-3 in chloroform solution in examples 1-3 of the invention;
FIG. 6 UV-visible absorption spectra of conjugated organic molecules BDF-1, BDF-2 and BDF-3 under a film in examples 1-3 of the invention;
FIG. 7 is an ultraviolet-visible light absorption spectrum under a film in which conjugated organic molecules BDF-1, BDF-2 and BDF-3 were blended with Y6 in examples 4-6 of the invention;
FIG. 8 is a graph showing the current-voltage curves of the organic solar cell devices of conjugated organic molecules BDF-1, BDF-2 and BDF-3 in examples 4-6.
Reference numerals illustrate:
1-ITO glass; 2-PEDOT, PSS or ZnO; a blend film of 3-conjugated small organic molecules and Y6; 4-MoO 3 Or PDINO;5-Al or Ag electrode.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
The structural formula of the conjugated organic small molecule provided by the embodiment of the invention is shown as formula (I) or formula (II):
wherein R is 1 -R 10 Is the same or different hydrogen atoms, straight-chain or branched-chain alkyl groups with 2-20 carbon atoms or straight-chain or branched-chain alkoxy groups with 2-20 carbon atoms;
ar represents an electron withdrawing unit comprising a group 1 or a group 2, the group 1 having the following structural formula:
the structural formula of the group 2 is as follows:
wherein R is 11 And R is 12 Including straight or branched alkyl groups of 2 to 20 carbon atoms, which may be the same or different.
The conjugated organic small molecules in the embodiment take benzodifuran as a central electron-donating (D) unit, tertiarythiophene or thienothiophene as pi-bridge and rhodamine or cyanoacetate as a terminal electron-withdrawing (A) unit, so that conjugated organic small molecules with A-pi-D-pi-A type structures are constructed.
Wherein, a large plane conjugate center is provided by taking a Benzodifuran (BDF) unit as a core, which is favorable for molecular accumulation; in addition, the BDF unit also acts as an electron donating center to regulate energy levels and absorption; the solubility required by solution processing is ensured by introducing the side chain on the BDF core, and the introduced side chain can cause certain distortion of the molecule itself due to steric hindrance, so that the excessive aggregation of the molecule itself is inhibited, and a good film form is formed. In addition, the energy levels of HOMO and LUMO of the material can be effectively reduced by adopting a thiophene side chain with monofluorine, so that the material and an acceptor have better energy level matching; introducing cyanoacetate or rhodamine as a terminal group, wherein electron withdrawing groups on the cyanoacetate or rhodamine can reduce HOMO and LUMO energy levels of molecules, realize stronger intramolecular charge transfer, thereby realizing narrow band gap and inducing intermolecular interaction, and further realizing high electron mobility; the terthiophene or thienothiophene bithiophene is inserted between the central core BDF and the end group as pi bridge to improve the photovoltaic performance of the organic solar cell, and the alkyl side chain on the introduced thiophene can effectively improve the miscibility with the acceptor, thereby being beneficial to exciton dissociation.
The conventional small molecule donor uses Benzodithiophene (BDT) as a central unit core, the conjugated organic small molecule of the embodiment uses Benzodifuran (BDF) as the central unit core of the small molecule donor, and compared with a donor material containing a BDT unit, the battery device prepared by matching the material with the structure of the embodiment with a non-fullerene acceptor (NFA) material is easier to obtain higher open circuit voltage, and the heat stability performance of the battery device is more excellent.
Referring to fig. 1, another embodiment of the present invention provides a method for preparing a conjugated small organic molecule, which includes:
dissolving a first compound, a second compound and tetraphenylphosphine palladium in a solvent, and reacting for 12 hours at 110 ℃ under the protection of inert gas and in the dark to obtain an intermediate product;
dissolving the intermediate product, a third compound and piperidine in chloroform, and reacting for 8 hours at 65 ℃ under the protection of inert gas to obtain conjugated small organic molecules;
wherein the structural formula of the first compound is as follows:
the structural formula of the second compound is as follows:
the structural formula of the third compound is as follows:
in the specific embodiment, a first compound, a second compound and tetraphenylphosphine palladium are added into a reaction vessel, toluene is used as a solvent, argon is used for protection, the reaction vessel is heated at 110 ℃ for reflux for about 12 hours under the dark condition, after the reaction is finished, reaction liquid is poured into water, crude products are obtained after extraction, washing, drying and concentration to dryness, and the crude products are subjected to column chromatography to obtain intermediate products; adding the intermediate product, a third compound, chloroform and a few drops of piperidine into a reaction vessel, heating to 65 ℃ for refluxing for about 8 hours under the protection of argon, concentrating the reaction liquid under reduced pressure after the reaction is finished, and settling the reaction liquid in a large amount of methanol to obtain a solid crude product, wherein the black solid obtained after column chromatography is the conjugated small organic molecule.
In this embodiment, the specific type of the reaction solvent is not limited, and toluene, chloroform, etc. are preferable, and the solvent is good in solubility, and the material is easy to obtain and low in cost.
The conjugated organic micromolecule containing the benzodifuran unit prepared by the method has good absorption in the visible spectrum range of 400-700nm, can form complementation with the absorption spectrum of the low band gap non-fullerene acceptor material Y6, and the mixed film has good absorption in the solar spectrum range.
Another embodiment of the invention provides an application of conjugated organic molecules in an organic solar cell.
In a specific embodiment, as shown in fig. 2, the organic solar cell includes a first electrode, a first transmission layer, a photoactive layer, a second transmission layer and a second electrode that are sequentially disposed, where the photoactive layer is a blend film including a conjugated small organic molecule and a low band gap non-fullerene acceptor material Y6. As shown in fig. 2, in the structure of the organic solar cell device, the first electrode is ITO glass 1, and the first transmission layer is mainly PEDOT: PSS or ZnO2, and the thickness thereof is about 20-40nm; the main component of the photoactive layer 3 is a blend film formed by spin coating or knife coating after the conjugated organic micromolecule containing a benzodifuran unit and Y6 are dissolved in chloroform and other solutions, and the thickness of the blend film is about 80-120nm; the second transmission layer is mainly MoO 3 Or PDINO4 with a thickness of 5-10nm; the second electrode is typically Al or Ag and has a thickness of 80-100nm.
Wherein PEDOT and PSS are aqueous solutions of high molecular polymers, the aqueous solutions consist of two substances of PEDOT and PSS, the PEDOT is a polymer of EDOT (3, 4-ethylenedioxythiophene monomer), and the PSS is polystyrene sulfonate. The structural formulas of PEDOT and PSS are respectively as follows:
the structural formula of Y6 is:
the structural formula of PDINO is:
the embodiment of the invention adopts benzodifuran as a central unit, respectively adopts two pi bridges of terthiophene and thiophene bithiophene, adopts rhodamine or cyanoacetate as a terminal unit, and the constructed conjugated organic micromolecules have a better absorption range in a visible light region and can form good absorption complementation with a non-fullerene acceptor material Y6. In addition, the material has a good plane conjugated framework, which is very beneficial to the transmission of carriers. Therefore, the conjugated organic micromolecule containing the benzodifuran unit is suitable for the field of organic solar cells, and the structural material and the cell device prepared by the NFA are easier to obtain higher open circuit voltage, and the thermal stability is more excellent.
The technical scheme of the invention is further described below with reference to specific embodiments, and the purposes and advantages of the invention are clear.
Example 1
The aim of this example is to prepare a conjugated small organic molecule comprising the following steps:
in a 100mL three-necked flask, compound 1 (454 mg,0.5 mmol), compound 2 (622 mg,1.25 mmol), and Tetratriphenylphosphine palladium (Pd (PPh) 3 ) 4 58mg,0.05 mmol) and 30mL of Toluene (tolene) were taken as solvent and heated to 110℃under reflux for about 12 hours in the absence of argon. Pouring the reaction solution after the reaction is finished into water, extracting by chloroform, washing by deionized waterDrying by anhydrous sodium sulfate, and concentrating under reduced pressure to obtain a crude product. The crude product was chromatographed on a column (petroleum ether: chloroform=1:2) to give P1 (472.2 mg) as a black solid in 67% yield. The resulting P1 (191 mg,0.135 mmol), compound 3 (272 mg,1.35 mmol), 20mL of chloroform (CHCl) 3 ) And a few drops of piperidine (piprolins) were sequentially added to a 100mL three-necked round bottom flask and heated to 65 ℃ reflux (reflux) for about 8 hours under argon protection. After the reaction was completed, the reaction mixture was concentrated under reduced pressure, and then settled in a large amount of methanol, and the obtained solid crude product was subjected to column chromatography (petroleum ether: chloroform=1:1) to obtain black solid BDF-1 (158 mg), with a yield of 66%.
The synthetic route of the preparation method of the conjugated small organic molecule BDF-1 is as follows:
example 2
The aim of this example is to prepare a conjugated small organic molecule comprising the following steps:
p1 (283 mg,0.2 mmol), compound 4 (435 mg,2.0 mmol), 30mL of chloroform and a few drops of piperidine obtained in example 1 were successively charged into a 100mL three-necked round bottom flask, and heated at 65℃under argon protection for about 8 hours. After the reaction was completed, the reaction mixture was concentrated under reduced pressure, and then settled in a large amount of methanol, and the obtained solid crude product was subjected to column chromatography (petroleum ether: chloroform=1.5:1) to obtain black solid BDF-2 (313 mg), with a yield of 86%.
The synthetic route of the preparation method of the conjugated small organic molecule BDF-2 is as follows:
example 3
The aim of this example is to prepare a conjugated small organic molecule comprising the following steps:
in a 100mL three-necked flask, the following is adoptedCompound 1 (318 mg,0.35 mmol), compound 5 (460 mg,0.88 mmol), tetraphenylpalladium phosphate (Pd (PPh) 3 ) 4 40mg,0.035 mmol) and 20mL toluene as solvent were heated to 110℃under reflux for about 12 hours in the absence of argon. Pouring the reaction liquid after the reaction is finished into water, extracting by chloroform, washing by deionized water, drying by anhydrous sodium sulfate, and concentrating under reduced pressure until the reaction liquid is dried to obtain a crude product. The crude product was chromatographed (petroleum ether: dichloromethane=1:1.5) to give P2 (290 mg) as a black solid in 60% yield. The resulting P2 (290 mg,0.2 mmol), compound 3 (435 mg,2.0 mmol), 30mL of chloroform and a few drops of piperidine were successively added to a 100mL three-necked round-bottomed flask, and heated at 65℃under argon atmosphere to reflux for about 8 hours. After the reaction was completed, the reaction mixture was concentrated under reduced pressure, and then settled in a large amount of methanol, and the obtained solid crude product was subjected to column chromatography (petroleum ether: chloroform=1:1) to obtain black solid BDF-3 (195 mg), with a yield of 53%.
The synthetic route of the preparation method of the conjugated small organic molecule BDF-3 is as follows:
example 4
This example is directed to the preparation of an organic solar cell comprising conjugated small organic molecules BDF-1 containing benzodifuran units comprising the steps of:
10mgBDF-1 was mixed with 10mgY6, 1mL chloroform was added for dissolution, and the mixture was spun onto PEDOT: and preparing a photoactive layer on the ITO glass substrate modified by the PSS. The photoactive layer was thermally annealed at 120℃for 10min and then spin-coated with PDINO (concentration: 1.5 mgmL) -1 Ethanol solution of (c) and finally evaporating Al to prepare the cathode.
BDF-1 based photovoltaic device performance: in white light 1.5G (100 mWcm) -2 ) Under irradiation, open circuit voltage (V OC ) =0.879v, short-circuit current (J SC )＝19.57mAcm -2 Fill Factor (FF) =53.77%, photoelectric Conversion Efficiency (PCE) =9.24%.
In this embodiment, BDF-1 is used as a donor material, and the photoactive layer prepared by mixing BDF-1 with an acceptor material Y6 can maintain high open-circuit voltage and short-circuit current at a thermal annealing temperature of 120 ℃ so as to obtain higher photoelectric conversion efficiency.
Example 5
This example is directed to the preparation of an organic solar cell comprising conjugated small organic molecules BDF-2 containing benzodifuran units comprising the steps of:
10mgBDF-2 was mixed with 10mgY6, dissolved in 1mL chloroform, and purified by spin coating on PEDOT: and preparing a photoactive layer on the ITO glass substrate modified by the PSS. The photoactive layer was thermally annealed at 120℃for 10min and then spin-coated with PDINO (concentration: 1.5 mgmL) -1 Ethanol solution of (c) and finally evaporating Al to prepare the cathode.
BDF-2 based photovoltaic device performance: in white light 1.5G (100 mWcm) -2 ) Under irradiation V OC ＝0.898V，J SC ＝16.28mAcm -2 ，FF＝37.09％，PCE＝5.42％。
In the embodiment, BDF-2 is adopted as a donor material, and the photoactive layer prepared by mixing BDF-2 with an acceptor material Y6 can keep high open-circuit voltage and short-circuit current at the thermal annealing temperature of 120 ℃ and obtain higher photoelectric conversion efficiency.
Example 6
This example is directed to the preparation of an organic solar cell comprising conjugated small organic molecules BDF-3 containing benzodifuran units comprising the steps of:
10mgBDF-3 was mixed with 10mgY6, dissolved in 1mL chloroform, and purified by spin coating on PEDOT: and preparing a photoactive layer on the ITO glass substrate modified by the PSS. The photoactive layer was thermally annealed at 120℃for 10min and then spin-coated with PDINO (concentration: 1.5 mgmL) -1 Ethanol solution of (c) and finally evaporating Al to prepare the cathode.
BDF-3 based photovoltaic device performance: in white light 1.5G (100 mWcm) -2 ) Under irradiation V OC ＝0.848V，J SC ＝16.77mAcm -2 Fill Factor (FF) =48.69%, pce=6.92%.
In the embodiment, BDF-3 is adopted as a donor material, and the photoactive layer prepared by mixing BDF-3 with an acceptor material Y6 can keep high open-circuit voltage and short-circuit current at the thermal annealing temperature of 120 ℃ and obtain higher photoelectric conversion efficiency.
Example 7
As shown in FIG. 3, the highest occupied orbitals (HOMO) levels of BDF-1, BDF-2, BDF-3, respectively, -5.50eV, -5.52eV, -5.42eV, and the lowest unoccupied orbitals (LUMO) levels of-3.58 eV, -3.54eV, -3.52eV, respectively, as measured by Cyclic Voltammetry (CV), while the reported HOMO and LUMO levels of Y6 are-5.65 eV and-4.10 eV, respectively, indicating that there is sufficient voltage between the acceptors to drive exciton dissociation. Wherein Fc/Fc in FIG. 3 + Indicating the potential of the reference electrode.
Therefore, since the conjugated organic small molecules adopted in the embodiment of the invention take BDF units as cores, BDF can serve as electron donating centers to regulate energy level and absorption; in addition, the thiophene side chain in the conjugated organic micromolecule structure contains fluorine, so that the energy level of the highest occupied orbit (HOMO) and the lowest unoccupied orbit (LUMO) of the material can be effectively reduced, and the material and an acceptor have better energy level matching; in addition, the electron withdrawing groups on the cyanoacetate or the rhodanine as end groups may also lower the HOMO and LUMO energy levels of the molecule. Therefore, BDF-1, BDF-2 and BDF-3 prepared by the embodiment of the invention are used as donor materials, can form good complementation with the absorption of a low band gap acceptor material when being applied to an organic solar cell, are beneficial to obtaining high short circuit current and high open circuit voltage, and realize improvement of device efficiency (for example, embodiment 4-embodiment 6).
As shown in FIG. 4, BDF-1, BDF-2 and BDF-3 are obtained through Thermal Gravimetric Analysis (TGA) at the temperature of 355.8 ℃ and 350.8 ℃ and 385.5 ℃ respectively at the temperature of 5% thermal gravimetric analysis, which shows that all three materials have good thermal stability, so that the materials can still keep the high voltage level at the high thermal annealing temperature (120 ℃).
As shown in FIGS. 5-7, it can be seen that three conjugated small organic molecules BDF-1, BDF-2 and BDF-3 have good solubility and film forming property in common organic solvents (such as chloroform, chlorobenzene and o-dichlorobenzene) by ultraviolet-visible light absorption spectra of conjugated organic molecules BDF-1, BDF-2 and BDF-3 in examples 1-3 under chloroform solution and film and ultraviolet-visible light absorption spectra of conjugated organic molecules BDF-1, BDF-2 and BDF-3 under film after being respectively blended with Y6 in examples 4-6.
As shown in fig. 8, the current-voltage curves of the organic solar cell devices using the conjugated organic molecules BDF-1, BDF-2 and BDF-3 in examples 4 to 6 show that the organic solar cell fabricated using the conjugated organic small molecules having a-pi-D-pi-a type structure according to the embodiment of the present invention can generate a higher short circuit current.
Although the present disclosure is described above, the scope of protection of the present disclosure is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the disclosure, and these changes and modifications will fall within the scope of the invention.
Claims (10)
1. A conjugated organic small molecule is characterized in that the conjugated organic small molecule has the structural formula of
2. A method of preparing the conjugated small organic molecule of claim 1, comprising:
dissolving a first compound, a second compound and tetraphenylphosphine palladium in a solvent, and reacting for 12 hours at 110 ℃ under the protection of inert gas and in the dark to obtain an intermediate product, wherein the structure of the intermediate product is as follows:
dissolving the intermediate product, a third compound and piperidine in chloroform, and reacting for 8 hours at 65 ℃ under the protection of inert gas to obtain conjugated small organic molecules;
wherein the structural formula of the first compound is as follows:
the structural formulas of the second compound and the third compound are respectively as follows:
alternatively, the structural formulas of the second compound and the third compound are respectively:
3. the method for preparing a conjugated small organic molecule according to claim 2, wherein the intermediate product is obtained by column chromatography of a crude product obtained by extracting a reaction solution obtained after the reaction of the first compound and the second compound with chloroform, washing with deionized water, drying with anhydrous sodium sulfate, and concentrating under reduced pressure to dryness.
4. The method for preparing a conjugated small organic molecule according to claim 3, wherein the ratio of the eluent used in the column chromatography is petroleum ether to dichloromethane is 1:1-2.
5. The method for producing a conjugated small organic molecule according to claim 2, wherein the conjugated small organic molecule is obtained by concentrating a reaction solution obtained by reacting the intermediate product with the third compound under reduced pressure, and then precipitating the concentrated reaction solution in an excessive amount of methanol, and the obtained solid crude product is subjected to column chromatography.
6. The method for preparing conjugated small organic molecules according to claim 5, wherein the ratio of the eluent used in the column chromatography is petroleum ether to chloroform 1-1.5:1.
7. Use of the conjugated organic molecule according to claim 1 in an organic solar cell.
8. An organic solar cell, comprising a first electrode, a first transmission layer, a photoactive layer, a second transmission layer and a second electrode which are sequentially arranged, wherein the first electrode comprises ITO glass, and the first transmission layer comprises PEDOT: PSS, the photoactive layer being a blended film comprising a donor material and a low band gap non-fullerene acceptor material Y6, the donor material being the conjugated small organic molecule of claim 1, the second transport layer comprising MoO 3 Or PDINO, the second electrode comprising Al or Ag.
9. The organic solar cell according to claim 8, wherein the thickness of the first transport layer is 20-40nm, the thickness of the photoactive layer is 80-120nm, the thickness of the second transport layer is 5-10nm, and the thickness of the second electrode is 80-100nm.
10. A method of manufacturing an organic solar cell according to claim 8 or 9, comprising: mixing the conjugated organic micromolecules with the Y6, adding chloroform for dissolution, preparing the photoactive layer on the ITO glass substrate modified by the first transmission layer in a spin coating mode, spin-coating the second transmission layer after the photoactive layer is thermally annealed at 120 ℃ for 10min, and finally evaporating Al or Ag to prepare the second electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210301802.0A CN114716460B (en) | 2022-03-25 | 2022-03-25 | Conjugated organic small molecule and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210301802.0A CN114716460B (en) | 2022-03-25 | 2022-03-25 | Conjugated organic small molecule and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114716460A CN114716460A (en) | 2022-07-08 |
| CN114716460B true CN114716460B (en) | 2023-11-07 |
Family
ID=82240622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210301802.0A Active CN114716460B (en) | 2022-03-25 | 2022-03-25 | Conjugated organic small molecule and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114716460B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115109071B (en) * | 2022-08-29 | 2022-12-09 | 南京乐汇光电科技有限公司 | Preparation method and application of conjugated macromolecule based on benzodithiophene |
| CN115785126B (en) * | 2022-12-01 | 2024-04-30 | 中国科学院宁波材料技术与工程研究所 | Conjugated organic molecule, photoactive layer material, ternary organic solar cell and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103570743A (en) * | 2012-10-26 | 2014-02-12 | 中国科学院化学研究所 | Soluble liquid machining two-dimensional conjugated organic molecular photovoltaic material as well as preparation method and application thereof |
| CN104926830A (en) * | 2015-06-11 | 2015-09-23 | 苏州大学 | Two-dimensional conjugated dibenzothiophene compound as well as preparation method and application thereof |
| CN111777622A (en) * | 2020-08-07 | 2020-10-16 | 中国科学院重庆绿色智能技术研究院 | Micromolecule donor material based on terminal alkyl chain isomerization as well as preparation and application thereof |
| CN113563374A (en) * | 2021-07-30 | 2021-10-29 | 中国科学院宁波材料技术与工程研究所 | Organic small molecule donor photovoltaic material and preparation method and application thereof |
| CN114106017A (en) * | 2020-08-31 | 2022-03-01 | 中国科学院宁波材料技术与工程研究所 | Small molecule donor material containing bithiophene, preparation method thereof and solar cell |
-
2022
- 2022-03-25 CN CN202210301802.0A patent/CN114716460B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103570743A (en) * | 2012-10-26 | 2014-02-12 | 中国科学院化学研究所 | Soluble liquid machining two-dimensional conjugated organic molecular photovoltaic material as well as preparation method and application thereof |
| CN104926830A (en) * | 2015-06-11 | 2015-09-23 | 苏州大学 | Two-dimensional conjugated dibenzothiophene compound as well as preparation method and application thereof |
| CN111777622A (en) * | 2020-08-07 | 2020-10-16 | 中国科学院重庆绿色智能技术研究院 | Micromolecule donor material based on terminal alkyl chain isomerization as well as preparation and application thereof |
| CN114106017A (en) * | 2020-08-31 | 2022-03-01 | 中国科学院宁波材料技术与工程研究所 | Small molecule donor material containing bithiophene, preparation method thereof and solar cell |
| CN113563374A (en) * | 2021-07-30 | 2021-10-29 | 中国科学院宁波材料技术与工程研究所 | Organic small molecule donor photovoltaic material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114716460A (en) | 2022-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | 15.8% efficiency binary all-small-molecule organic solar cells enabled by a selenophene substituted sematic liquid crystalline donor | |
| CN114716460B (en) | Conjugated organic small molecule and preparation method and application thereof | |
| CN108912139B (en) | Organic solar cell electron acceptor material and preparation method and application thereof | |
| US9153785B2 (en) | Semiconducting polymers | |
| Yue et al. | Synthesis and photovoltaic properties from inverted geometry cells and roll-to-roll coated large area cells from dithienopyrrole-based donor–acceptor polymers | |
| US8598301B2 (en) | Copolymer containing fluorenylporphyrin-anthracene, preparation method and application thereof | |
| CN112608309B (en) | Non-condensed ring organic small molecular material containing fluorene ring group and preparation method and application thereof | |
| CN110408010A (en) | A kind of D-A type conjugated polymer of the lactone containing condensed ring and the preparation method and application thereof | |
| CN110194778B (en) | Multi-arm structure organic photovoltaic material and preparation method and application thereof | |
| CN111808126A (en) | A-pi-D-pi-A type BODIPY micromolecule photovoltaic material and preparation method and application thereof | |
| CN114044885B (en) | Polymer electron acceptor material containing non-covalent condensed ring acceptor unit and application thereof | |
| Liu et al. | Solution processable low bandgap small molecule donors with naphthalene end-groups for organic solar cells | |
| KR101828012B1 (en) | Conjugated polymer for organic solar cell and manufacturing method thereof | |
| CN116178364A (en) | Non-condensed ring receptor micromolecular material and synthesis method and application thereof | |
| CN110028488A (en) | Using indeno [1,2-b] fluorenes as A-D-A type photovoltaic small molecule receptor of core and its preparation method and application | |
| CN111171287A (en) | Dithia-benzo-dithiophene polymer, preparation method and application thereof | |
| CN112409387B (en) | A-D-A organic micromolecule photovoltaic material taking reduction orange 1 as central core | |
| CN112592464B (en) | Two-dimensional conjugated 2-chlorophenyl fluorene copolymer photovoltaic material, preparation method and application | |
| CN111100145B (en) | Asymmetric aromatic heterocyclic thiophene diketone organic solar cell donor material, and preparation method and application thereof | |
| CN110498793B (en) | Small-molecule photovoltaic bulk phase material based on rhodanine and application thereof | |
| CN113024541A (en) | Skeleton non-condensed small molecule receptor using selenophene as pi bridge, preparation method and application thereof | |
| CN109337046B (en) | Polymer donor material containing dibenzothiophene sulfoxide unit and preparation thereof | |
| CN113387964A (en) | Cyclopentathiophene organic micromolecule photovoltaic material and preparation method and application thereof | |
| CN112159418A (en) | Conjugated organic molecule and organic solar cell | |
| Zhu et al. | Asymmetric ITIC acceptor for asymmetric benzodithiophene polymer solar cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |