CN116375732A - Non-fullerene acceptor material and preparation method and application thereof - Google Patents
Non-fullerene acceptor material and preparation method and application thereof Download PDFInfo
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- CN116375732A CN116375732A CN202310282263.5A CN202310282263A CN116375732A CN 116375732 A CN116375732 A CN 116375732A CN 202310282263 A CN202310282263 A CN 202310282263A CN 116375732 A CN116375732 A CN 116375732A
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- fullerene acceptor
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- 239000000463 material Substances 0.000 title claims abstract description 63
- 229910003472 fullerene Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 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 abstract description 37
- 229910002056 binary alloy Inorganic materials 0.000 claims abstract description 10
- 230000005669 field effect Effects 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 47
- 229940126214 compound 3 Drugs 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000004973 liquid crystal related substance Substances 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 10
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical group ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000013067 intermediate product Substances 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 229940125904 compound 1 Drugs 0.000 claims description 6
- 238000007363 ring formation reaction Methods 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
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- 229940125782 compound 2 Drugs 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- 238000005874 Vilsmeier-Haack formylation reaction Methods 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 238000006722 reduction reaction Methods 0.000 claims description 4
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- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 claims description 4
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims description 3
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims description 2
- WGFNXLQURMLAGC-UHFFFAOYSA-N diethyl 2,3-di(propan-2-yl)butanedioate Chemical compound CCOC(=O)C(C(C)C)C(C(C)C)C(=O)OCC WGFNXLQURMLAGC-UHFFFAOYSA-N 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 125000006413 ring segment Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 40
- 150000003384 small molecules Chemical class 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 230000021615 conjugation Effects 0.000 abstract description 3
- 125000004185 ester group Chemical group 0.000 abstract description 3
- 230000031700 light absorption Effects 0.000 abstract description 3
- 239000000370 acceptor Substances 0.000 description 47
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 46
- 239000010410 layer Substances 0.000 description 28
- 239000002904 solvent Substances 0.000 description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000000605 extraction Methods 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 229920000144 PEDOT:PSS Polymers 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000004770 highest occupied molecular orbital Methods 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000006619 Stille reaction Methods 0.000 description 3
- -1 fullerene small molecule Chemical class 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
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- 239000000758 substrate Substances 0.000 description 3
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 2
- POXIZPBFFUKMEQ-UHFFFAOYSA-N 2-cyanoethenylideneazanide Chemical group [N-]=C=[C+]C#N POXIZPBFFUKMEQ-UHFFFAOYSA-N 0.000 description 2
- NZWIYPLSXWYKLH-UHFFFAOYSA-N 3-(bromomethyl)heptane Chemical compound CCCCC(CC)CBr NZWIYPLSXWYKLH-UHFFFAOYSA-N 0.000 description 2
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
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- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000004224 UV/Vis absorption spectrophotometry Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- FXORZKOZOQWVMQ-UHFFFAOYSA-L dichloropalladium;triphenylphosphane Chemical compound Cl[Pd]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FXORZKOZOQWVMQ-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
-
- 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
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
-
- 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
- H10K30/50—Photovoltaic [PV] devices
-
- 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
- H10K30/50—Photovoltaic [PV] devices
- H10K30/53—Photovoltaic [PV] devices in the form of fibres or tubes, e.g. photovoltaic fibres
-
- 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
-
- 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
-
- 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
-
- 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 belongs to the technical field of photoelectric materials, and particularly relates to a non-fullerene acceptor material, and a preparation method and application thereof. The invention introduces ester group into the condensed ring skeleton of small molecule and prolongs the conjugation length, and designs and synthesizes a series of A-DA' D-A small molecule acceptor materials. The small molecule receptor material has good planeness, excellent film forming property and strong light absorption capacity, has stronger absorption in an ultraviolet-visible light region, and is similar to the existing common PM6: the binary system such as L8-BO has more matched energy levels, and can obtain higher open-circuit voltage and photoelectric conversion efficiency. The method has good application prospect in the fields of preparing large-area organic solar cells, organic photodetectors, organic field effect transistors, organic light-emitting diodes and the like with high open-circuit voltage and high energy conversion efficiency.
Description
Technical Field
The invention relates to the technical field of photoelectric materials, in particular to a non-fullerene acceptor material, a preparation method and application thereof.
Background
Energy is an important factor in promoting economic development in the world today. Along with the increasing severity of energy problems, the development of new energy is urgent, and solar energy has the advantages of cleanness, no pollution, inexhaustible use and the like, thus having great development prospect. The organic solar cell is a technical means for converting solar energy, namely clean energy, into electric energy, has the advantages of light weight, adjustable color, flexibility, low cost, high efficiency and the like, and can be prepared in a large area, is a target pursued by people all the time, and is widely focused in global academia and industry.
The organic solar cell has wide application prospect in the future energy field. In recent years, bulk heterojunction organic solar cells of polymer donors and non-fullerene small molecule acceptors have also evolved rapidly due to intensive research into efficient photovoltaic materials, device optimization, and interface engineering. Although organic solar cells have great potential, there are several key issues to overcome to achieve their large-scale commercial application. Among the several factors affecting the Photoelectric Conversion Efficiency (PCE) of polymer solar cells, the open circuit voltage (Open circuit voltage, voc) effect of the cell device is particularly pronounced. Therefore, it is an important research direction to achieve a breakthrough in efficiency by preparing an organic solar cell having high Voc.
In the prior art, a bulk heterojunction type organic solar cell formed by combining a polymer donor and a small molecule acceptor has low open-circuit voltage of a binary system device, and the energy conversion efficiency of the device cannot be further improved. Therefore, the development of a small molecule condensed ring skeleton with a better planar structure, and further the preparation of a non-fullerene acceptor material with excellent solubility, has important significance for improving the Voc of an organic solar cell to obtain a higher PCE, and has important significance for preparing a low-cost and large-area organic solar cell and promoting the commercialization process of the organic solar cell.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a non-fullerene acceptor material, a preparation method and application thereof, and the invention adopts a small molecule acceptor material with good planeness, excellent film forming property and strong light absorption capacity, and is characterized in that ester groups are introduced into a small molecule condensed ring framework and the conjugation length is prolonged. The small molecule acceptor material has stronger absorption in the ultraviolet-visible region (600-900 nm), higher photoelectric conversion efficiency and is compared with the existing common PM6: the binary system such as L8-BO has more matched energy levels and obtains higher open circuit voltage. The method has good application prospect in the fields of preparing large-area organic solar cells, organic photodetectors, organic field effect transistors, organic light-emitting diodes and the like with high open-circuit voltage and high energy conversion efficiency.
In a first aspect of the present invention, there is provided a non-fullerene acceptor material having a structure represented by formula (I):
wherein, the liquid crystal display device comprises a liquid crystal display device,
R 1 、R 2 each independently selected from the group consisting of straight or branched alkyl, alkoxy, or thioalkyl groups having from 1 to 30C atoms;
Ar 1 、Ar 2 each independently selected from aryl, heteroaryl, fused ring groups having 5 to 30 ring atoms, wherein the aryl, heteroaryl, fused ring groups are unsubstituted or optionally substituted with one or more S1;
said S1 is independently selected from H, F, cl, br, cyano, trifluoromethyl, or two of said S1 together form =o,
According to some embodiments of the invention, R 1 、R 2 Each independently selected from the group consisting of straight or branched alkyl, alkoxy, or thioalkyl groups having 5 to 20C atoms.
Preferably, R 1 Is a linear alkyl group having 10 to 15C atoms;
the linear alkyl group having 10 to 15C atoms may be selected from the following groups:
preferably, R 2 Is a branched alkyl group having 5 to 10C atoms;
the branched alkyl group having 5 to 10C atoms may be selected from the group consisting of:
the dashed line is the connection location.
More preferably, R 1 Is a linear alkyl group having 10 to 12C atoms, R 2 Is a branched alkyl group having 7 to 9C atoms.
According to some embodiments of the invention, ar 1 、Ar 2 Each independently selected from the following groups:
wherein, the liquid crystal display device comprises a liquid crystal display device,
X 1 、X 2 each independently selected from H, F, cl, br, cyano, trifluoromethyl;
the dashed line is the connection location.
Preferably Ar 1 、Ar 2 Is that
Wherein, the liquid crystal display device comprises a liquid crystal display device,
X 1 、X 2 each independently selected from F, cl, br, trifluoromethyl.
The invention adopts a small molecule acceptor material with good planeness, excellent film forming property and strong light absorption capability, and is characterized in that ester groups are introduced into a small molecule condensed ring framework, the conjugation length is prolonged, and a series of A-DA' D-A small molecule acceptor materials are designed and synthesized. The non-fullerene acceptor material has stronger absorption in the ultraviolet-visible region (600-900 nm) and higher photoelectric conversion efficiency.
In a second aspect of the present invention, there is provided a method for preparing the above non-fullerene acceptor material, comprising the steps of:
s1, carrying out Stille coupling reaction on a compound 1 and a compound 2 in the presence of a catalyst to obtain a compound 3;
s2, carrying out condensation ring-closure reaction on the compound 3 and triethyl phosphite, and then carrying out condensation ring-closure reaction on the compound and halogenated alkane X-R 2 Carrying out substitution reaction to obtain a compound 4;
s3, combining compound 4 with LiAlH 4 Carrying out reduction reaction to obtain an intermediate product 5;
s4, reacting the intermediate product 5 with diethyl 2, 3-diisopropyl succinate to obtain a compound 6;
s5, carrying out Vilsmeier-Haack reaction on the compound 6 and a formylating reagent to obtain a compound 7;
s6, combining Compound 7 with
Carrying out Knoevenagel reaction on the acid binding agent to obtain a non-fullerene acceptor material shown in a formula (I);
R 1 、R 2 、X 1 、X 2 is defined as before.
According to some embodiments of the invention, in the step S1: the catalyst is at least one of tetra (triphenylphosphine) palladium, palladium acetate, bis (triphenylphosphine) palladium dichloride, tris (dibenzylideneacetone) dipalladium, tris (o-tolyl) phosphine or cuprous iodide; bis triphenylphosphine palladium dichloride is preferred.
According to some embodiments of the invention, in the step S1: the Stille coupling reaction is carried out in the presence of a solvent and under the protection of inert gas or nitrogen; preferably, the solvent is at least one selected from toluene, tetrahydrofuran, N-dimethylformamide, dichloromethane, 1, 4-dioxane, dimethyl sulfoxide.
According to some embodiments of the invention, in the step S1: the molar ratio of the compound 2 to the compound 1 is 1-4: 1, a step of; the molar volume ratio of compound 1 to solvent was 1mmol: 10-30 mL; the ratio of the molar amount of the catalyst to the total molar amount of the compounds 1 and 2 was 1:60 to 80 percent.
According to some embodiments of the invention, in the step S1: the reaction temperature of the Stille coupling reaction is 60-100 ℃ and the reaction time is 12-36 h.
According to some embodiments of the invention, in the step S1: also included is the purification of compound 3, which includes spin distillation, extraction and column chromatography.
According to some embodiments of the invention, in the step S2: the condensation ring-closure reaction is carried out in the presence of a solvent and under the protection of inert gas or nitrogen, preferably the solvent is at least one selected from o-dichlorobenzene, toluene and chlorobenzene.
According to some embodiments of the invention, in the step S2: the molar ratio of the compound 3 to the triethyl phosphite is 1:4 to 15, the molar volume ratio of the compound 3 to the solvent is 1mmol: 10-20 mL.
According to some embodiments of the invention, in the step S2: the reaction temperature of the condensation ring-closure reaction is 160-200 ℃ and the reaction time is 6-18 h.
According to some embodiments of the invention, in the step S2: the substitution reaction is carried out in the presence of a solvent and under the protection of inert gas or nitrogen; preferably, the solvent is at least one selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, and 1, 4-dioxane.
According to some embodiments of the invention, in the step S2: wherein, halogenated alkane R 2 The molar ratio of X to the compound 3 is 10-20: 1.
according to some embodiments of the invention, in the step S2: the reaction raw materials of the substitution reaction also comprise potassium iodide and potassium hydroxide; preferably, the molar ratio of potassium iodide to compound 3 is 1 to 2:1, the mole ratio of potassium hydroxide to compound 3 is 30-40: 1.
according to some embodiments of the invention, in the step S2: the reaction temperature of the substitution reaction is 60-120 ℃ and the reaction time is 6-18 h.
According to some embodiments of the invention, in the step S2: also included is the purification of compound 4, which includes extraction, rotary evaporation and column chromatography.
According to some embodiments of the invention, in the step S3: the reduction reaction is carried out in the presence of a solvent and under the protection of inert gas or nitrogen; preferably, the solvent is selected from at least one of tetrahydrofuran and toluene.
According to some embodiments of the invention, in the step S3: compound 4 and LiAlH 4 The molar ratio of (2) is 1:15 to 25, the molar volume ratio of the compound 4 to the solvent is 1mmol: 10-20 mL.
According to some embodiments of the invention, in the step S3: the reaction temperature of the reduction reaction is 60-90 ℃ and the reaction time is 6-18 h.
According to some embodiments of the invention, in the step S4: the reaction is carried out in the presence of a solvent, preferably at least one selected from ethanol, methanol, isopropanol.
According to some embodiments of the invention, in the step S4: the molar ratio of the compound 4 to the diisopropyl 2, 3-dioxysuccinate is 1:2 to 4.
According to some embodiments of the invention, in the step S4: the reaction temperature of the reaction is 60-90 ℃ and the reaction time is 6-18 h.
According to some embodiments of the invention, in the step S4: also included is the purification of compound 6, which includes extraction, rotary evaporation and column chromatography.
According to some embodiments of the invention, in the step S5: the formylating reagent is phosphorus oxychloride.
According to some embodiments of the invention, in the step S5: the Vilsmeier-Haack reaction is carried out in the presence of a solvent; preferably, the solvent is at least one selected from the group consisting of N, N-dimethylformamide, dimethyl sulfoxide, and 1, 4-dioxane.
According to some embodiments of the invention, in the step S5: the mass ratio of the compound 6 to the formylating agent is 1:2 to 6; the molar volume ratio of compound 6 to solvent was 1mmol: 20-60 mL.
According to some embodiments of the invention, in the step S5: the Vilsmeier-Haack reaction is carried out for 0.5 to 2 hours at the temperature of between-4 and 10 ℃ and then carried out for 6 to 18 hours at the temperature of between 60 and 120 ℃.
According to some embodiments of the invention, in the step S5: also included is the purification of compound 7, which includes extraction, rotary evaporation and column chromatography.
According to some embodiments of the invention, in the step S6: the acid binding agent is at least one selected from pyridine and piperidine.
According to some embodiments of the invention, in the step S6: the Knoevenagel reaction is carried out in the presence of a solvent and under the protection of inert gas or nitrogen; preferably, the solvent is at least one selected from chloroform, toluene, and dichloromethane.
According to some embodiments of the invention, in the step S6: compound 7 molar amount
The molar ratio of (2) is 1:3 to 6, the molar volume ratio of the compound 7 to the solvent is 1mmol: 150-300 mL, the mol volume ratio of the compound 7 to the acid binding agent is 1mmol: 5-15 mL.
According to some embodiments of the invention, in the step S6: the reaction temperature of the Knoevenagel reaction is 50-90 ℃ and the reaction time is 6-18 h.
According to some embodiments of the invention, in the step S6: also included is the purification of non-fullerene acceptor materials of formula (I), which includes separation by methanol crystallization and column chromatography.
The non-fullerene acceptor material has the advantages of mild synthesis reaction condition, simple operation, easy realization of expanded production and high yield.
In a third aspect of the invention, there is provided the use of the non-fullerene acceptor material described above in the preparation of organic/polymer solar cells, perovskite solar cells, organic photodetectors, organic field effect transistors and organic light emitting diodes.
The non-fullerene acceptor material is applied to a ternary organic solar cell system as a third component to improve the open-circuit voltage of a device, and is applied to a large-area solar cell device.
In a fourth aspect of the invention, there is provided an organic solar cell comprising an active layer comprising a non-fullerene acceptor material as described above.
Further, the organic solar cell comprises, in order from bottom to top: a transparent substrate, a hole transport layer, the active layer, an electron transport layer, and a metal electrode.
According to some embodiments of the invention, the active layer further comprises an organic solar cell binary system;
preferably, the polymer donor of the binary system of the organic solar cell is selected from at least one of PM6, PBTB-T-2F, PBDB-T, D and PTQ-10, and the acceptor is selected from at least one of Y6, L8-BO and BTP-eC 9.
The non-fullerene acceptor material of the invention is compared with the existing common PM6: the binary system such as L8-BO has more matched energy levels and obtains higher open circuit voltage. Has good application prospect in the field of preparing large-area organic solar cells with high open-circuit voltage and high energy conversion efficiency.
The beneficial effects are that:
(1) The non-fullerene acceptor material of the invention is soluble in common solvents such as chloroform, chlorobenzene and the like, and is easy to process;
(2) The non-fullerene acceptor material adopts a small molecular structure with good planeness, good film forming property and low exciton binding energy, and is characterized in that a quinoxaline ring is connected with a small molecular acceptor of isopropoxycarbonyl, and the non-fullerene acceptor material has deeper HOMO energy level due to stronger electronegativity of the isopropoxycarbonyl (stronger electronegativity than an imide structure), so that the non-fullerene acceptor material can be used as a third component in a ternary solar cell system to improve the open circuit voltage of a device; meanwhile, the non-fullerene acceptor material has wide absorption spectrum range, and the device can obtain higher short-circuit current;
(3) The non-fullerene acceptor material is added into the existing binary system, so that the charge separation and transmission efficiency of the device is greatly improved, the open-circuit voltage is obviously improved, and the organic solar cell with the efficiency exceeding 15% is realized, and has important significance for preparing low-cost, large-area and high-efficiency cell devices;
(4) The invention obtains a ternary material system of the organic solar cell with high open-circuit voltage so as to develop the organic solar cell with high efficiency and large area, thereby promoting the device to obtain higher device efficiency.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 shows compound 6 prepared according to the example of the present invention 1 H-NMR characterization;
FIG. 2 shows the non-fullerene acceptor material DOXCT-4F prepared in the example 1 H-NMR characterization;
FIG. 3 shows the non-fullerene acceptor material DOXCT-4Cl prepared in the example 1 H-NMR characterization;
FIG. 4 is an ultraviolet-visible absorption spectrum of a non-fullerene acceptor material film prepared in the example;
FIG. 5 is a schematic view of the organic solar cell device structure of the present invention;
FIG. 6 is a J-V plot of the non-fullerene acceptor material prepared in the example applied to an organic solar cell.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention.
The synthetic method of the non-fullerene acceptor material has the following reaction process formula:
example 1
The preparation of the non-fullerene small organic molecule acceptor material DOXCT-4F comprises the following reaction processes:
synthesis of Compound 3: in a 250mL round bottom flask, compound 1 (2 g,5.2 mmol) and Compound 2 (7.59 g,13.02 mmol) were weighed into 100mL toluene, the gas was replaced, argon was purged, and ditriphenylphosphine palladium dichloride (0.3 g,0.25 mmol) was added to the reaction system under argon protection. The reaction was refluxed at 80 ℃ for 24 hours. Cooling to room temperature, spin-drying tetrahydrofuran, extracting with dichloromethane, spin-drying solvent to obtain crude product, and separating and purifying with silica gel column chromatography to obtain solid product, namely compound 3 (2.92 g, 78%); HRMS (m/z, MALDI): calc.for C 40 H 52 N 2 S 5 ，[M+H] + ：721.17，found:720.27。
Synthesis of Compound 4: compound 3 (2 g,2.8 mmol) was dissolved in a three-necked flask containing o-dichlorobenzene (o-DCB, 50 mL) under Ar protection, and after heating to 180℃triethyl phosphite (4.2 g,25.0 mmol) was slowly added dropwise to the reaction system, stirred under reflux for 12h, cooled to room temperature, distilled under reduced pressure at 100℃without passing through the column, and the next step was carried out to give an intermediate product, which was dissolved in a one-necked flask containing N, N-dimethylformamide (DMF, 90 mL), 1-bromo-2-ethylhexane (7.5 g,38.5 mmol), potassium iodide (0.56 g,3.4 mmol) and potassium hydroxide (4.8 g,91.6 mmol) under Ar protectionReflux reaction at 90 ℃ overnight, cooling the reaction to room temperature, extracting with dichloromethane and water, finally combining the organic layers, spin-drying the solvent, purifying the crude product with a silica gel column, and spin-drying the eluent DCM/PE (1/5, v/v) to obtain pale yellow solid compound 4 (1.07 g, 41%); HRMS (m/z, MALDI): calc.for C 56 H 82 N 4 S 5 ,[M+H] + ：971.60，found:970.50。
Synthesis of Compound 6: under nitrogen, compound 4 (2.0 g,2.06 mmol), liAlH 4 (1.56 g,41.17 mmol) and 30mL THF were added to a 100mL flask. The mixed solution was stirred at 75℃for 12h, cooled to room temperature, extracted with dichloromethane, and dried over anhydrous Na 2 SO 4 Drying, filtering under reduced pressure, and concentrating. Intermediate 5 was obtained and used directly in the synthesis of compound 6. Subsequently, compound 5 was subjected to a condensation coupling reaction with diisopropyl 2, 3-dioxysuccinate (1.46 g,6.36 mmol) in ethanol (30 mL) at 80 ℃. After 12h, the organic phase is separated by extraction with dichloromethane and then taken up in Na 2 SO 4 Drying. Finally, the dichloromethane was removed under reduced pressure to give a red solid which was further purified by column chromatography (petroleum ether/dichloromethane, v/v=2:1). (1.62 g, 70%). The nuclear magnetic resonance hydrogen spectrum is shown in FIG. 1, MALDI-TOF-MS: M/z= 1136.730 (M + )。
Synthesis of Compound 7: in a 100mL three-necked flask, compound 6 (0.50 g,0.44 mmol) and anhydrous N, N-dimethylformamide (25 mL) were added, and after stirring at 0℃for several minutes, phosphorus oxychloride (1.5 mL) was added. The reaction solution was stirred at 0℃for 1 hour, then the temperature was raised to 90℃and stirred overnight, cooled to room temperature, extracted with methylene chloride, and the solvent was spin-dried, and purified by column chromatography on silica gel to give Compound 7 (0.45 g, 86%), HRMS (m/z, MALDI): calc.for: C 68 H 96 N 4 O 6 S 4 ,[M+H] + ：1193.78，found:1193.62。
Synthesis of acceptor material DOXCT-4F: in a 100mL round bottom flask, compound 7 (300 mg,0.25 mmol) and 5, 6-difluoro-3- (dicyanomethylene) indidone (389.2 mg,1.01 mmol) were dissolved in 50mL chloroform, the gas was replaced 3 times, argon shielded, and 2.5 was slowly added with stirringReflux-reacting the mixed solution for 12h under the protection of argon, cooling to room temperature, pouring into 300mL of anhydrous methanol, carrying out suction filtration to obtain a crude product, and separating and purifying by silica gel column chromatography to obtain a dark blue solid, namely a receptor material DOXCT-4F (304.7 mg, 75%); the nuclear magnetic resonance hydrogen spectrum is shown in FIG. 2, HRMS (m/z, MALDI): calc.for: C 92 H 100 F 4 N 8 O 6 S 4 ,[M+H] + ：1618.10，found:1616.66。
Example 2
The preparation of the non-fullerene small organic molecule acceptor DOXCT-4Cl comprises the following reaction processes:
synthesis of Compound 3: in a 250mL round bottom flask, compound 1 (2 g,5.2 mmol) and Compound 2 (7.59 g,13.02 mmol) were weighed into a 100mL tetrahydrofuran, the gas was replaced, argon was purged for 15 minutes, and ditriphenylphosphine palladium dichloride (0.3 g,0.25 mmol) was added to the reaction system under argon. The reaction was refluxed at 80 ℃ for 24 hours. Cooling to room temperature, spin-drying tetrahydrofuran, extracting with dichloromethane, spin-drying solvent to obtain crude product, and separating and purifying with silica gel column chromatography to obtain solid product, namely compound 3 (2.92 g, 78%); HRMS (m/z, MALDI): calc.for C 40 H 52 N 2 S 5 ，[M+H] + ：721.17，found:720.27。
Synthesis of Compound 4: compound 3 (2 g,2.8 mmol) was dissolved in a three-necked flask containing o-dichlorobenzene (o-DCB, 50 mL) under Ar protection, after heating to 180℃triethyl phosphite (4.2 g,25.0 mmol) was slowly dropped into the reaction system, stirred under reflux for 12 hours, cooled to room temperature, distilled under reduced pressure at 100℃without passing through the column, and the next step was carried out to obtain an intermediate product, the intermediate product, 1-bromo-2-ethylhexane (7.5 g,38.5 mmol), potassium iodide (0.56 g,3.4 mmol) and potassium hydroxide (4.8 g,91.6 mmol) were dissolved in a one-necked flask containing N, N-dimethylformamide (DMF, 90 mL), refluxed at 90℃under Ar protection overnight, and then the reactant was cooled to room temperature, and the mixture was cooled with dichloroExtracting methane and water, finally, merging organic layers, spin-drying a solvent, purifying a crude product by using a silica gel column, and spin-drying the solvent by using DCM/PE (1/5, v/v) as an eluent to obtain a pale yellow solid compound 4 (1.07 g, 41%); HRMS (m/z, MALDI): calc.for C 56 H 82 N 4 S 5 ,[M+H] + ：971.60，found:970.50。
Synthesis of Compound 6: under nitrogen, compound 4 (2.0 g,2.06 mmol), liAlH 4 (1.56 g,41.17 mmol) and 30mL THF were added to a 100mL flask. The mixed solution was stirred at 75℃for 12h, cooled to room temperature, extracted with dichloromethane, and dried over anhydrous Na 2 SO 4 Drying, filtering under reduced pressure, and concentrating. Intermediate 5 was obtained and used directly in the synthesis of compound 6. Subsequently, compound 5 was subjected to a condensation coupling reaction with diisopropyl 2, 3-dioxysuccinate (1.46 g,6.36 mmol) in ethanol (30 mL) at 80 ℃. After 12h, the organic phase is separated by extraction with dichloromethane and then taken up in Na 2 SO 4 Drying. Finally, the dichloromethane was removed under reduced pressure to give a red solid which was further purified by column chromatography (petroleum ether/dichloromethane, v/v=2:1). (1.62 g, 70%).
1 H NMR(400MHz,CDCl 3 ),δ(ppm):7.03(s,2H),5.50–5.44(m,2H),4.70–4.61(m,4H),2.87–2.83(t,4H),2.09–2.06(t,2H),1.89–1.85(t,4H),1.55–1.54(d,6H),1.38–1.11(m,36H),1.10–0.86(m,24H),0.64–0.60(m,12H)。
13 C NMR(100MHz,CDCl 3 ),δ(ppm):165.32,143.79,140.86,137.88,136.97,134.77,131.73,123.26,122.44,119.44,117.37,69.93,55.00,39.91,31.92,29.70,29.67,29.64,29.63,29.51,29.50,29.37,28.84,27.73,27.70,23.05,22.99,22.75,22.70,21.86,14.12,13.76,S-4 10.05,10.00。
MALDI-TOF-MS:m/z＝1136.730(M + )。
Synthesis of Compound 7: in a 100mL three-necked flask, compound 6 (0.50 g,0.44 mmol) and anhydrous N, N-carboxamide (25 mL) were added, and after stirring at 0deg.C for several minutes, phosphorus oxychloride (1.5 mL) was added. The reaction solution was stirred at 0℃for 1 hour, then the temperature was raised to 90℃and stirred overnight, and cooled to room temperature, dichloromethaneAlkane extraction, spin drying of the solvent, and separation and purification by silica gel column chromatography to obtain compound 7 (0.45 g, 86%); HRMS (m/z, MALDI): calc.for: C 68 H 96 N 4 O 6 S 4 ,[M+H] + ：1193.78，found:1193.62。
Synthesis of acceptor material DOXCT-4 Cl: in a 100mL round bottom flask, compound 7 (300 mg,0.25 mmol) and 5, 6-difluoro-3- (dicyanomethylene) indidone (389.2 mg,1.01 mmol) are dissolved in 50mL chloroform, the gas is replaced for 3 times, 2.5mL pyridine is slowly added under stirring and argon protection, the mixed solution is refluxed under argon protection for 12h, cooled to room temperature, poured into 300mL anhydrous methanol, suction filtered to obtain a crude product, and separated and purified by silica gel column chromatography to obtain a dark blue solid which is an acceptor material DOXCT-4Cl (296.2 mg, 70%), and a nuclear magnetic resonance hydrogen spectrum is shown in figure 3; HRMS (m/z, MALDI): calc.for: C 92 H 100 C l4 N 8 O 6 S 4 ,[M+H]+：1683.90，found:1682.54。
Test example 1
UV-vis absorption spectroscopy was performed on the acceptor materials DOXCT-4F and DOXCT-4Cl in examples 1 and 2, and thin films of acceptor materials were prepared: a chloroform solution (20 mg/mL) of the acceptor material was spin-coated on quartz glass. The prepared receptor film was used for testing. The results are shown in FIG. 4: the absorption curve in the ultraviolet-visible region (600-900 nm) is obviously red-shifted compared with DOXCT-4Cl in the small-molecule DOXCT-4F film state, which shows that the interaction between the molecular main frame in the film state and pi-pi bonds causes stronger accumulation, which increases the interaction of electrons in the molecule, which shows that DOXCT-4F has stronger electron accepting capability, and the asymmetric structure makes the molecule generate polarity to generate dipole moment, which is favorable for charge transmission to improve Jsc.
Electrochemical performance tests were performed on the acceptor materials DOXCT-4F and DOXCT-4Cl, and the electrochemical performance of the compounds was determined by Cyclic Voltammetry (CV). First, 0.1M tetrabutylammonium hexafluorophosphate (Bu 4 NPF 6 ) Dissolved in 25mL of anhydrous acetonitrile (CH 3 CN) solution, wherein the compound was dissolved in chloroform solution using Ag/AgCl as reference electrode and platinum electrode as counter electrodeThen uniformly coating the mixture on a glassy carbon electrode which is used as a working electrode, and applying ferrocene/ferrocene (Fc/Fc) + ) As an internal redox standard. Oxidation potential E of DOXCT-4F measured onset ox Oxidation potential E of 1.23V DOXCT-4Cl onset ox Is 1.26V. According to the equation: e (E) HOMO ＝-(4.80-E1/2，Fc/Fc + +E onset ox ) (eV), the HOMO level of DOXCT-4F was calculated to be-5.67 eV, and the HOMO level of DOXCT-4Cl was calculated to be-5.64 eV. Has good energy level matching with the donor material, and simultaneously, the lower HOMO can enable the device to obtain higher Voc.
Test example 2
The non-fullerene acceptor material prepared by the invention can be used for preparing an organic solar cell, and the organic solar cell sequentially comprises the following components from bottom to top: a transparent substrate, a hole transport layer, an active layer, an electron transport layer, and a metal electrode, as shown in fig. 5.
The preparation and characterization of small area OPV devices are specifically as follows:
commercially available Indium Tin Oxide (ITO) glass is firstly rubbed with acetone, then sequentially ultrasonically cleaned with a detergent, water, deionized water, acetone and isopropanol, and after drying, a layer of 30nm thick PEDOT: PSS is spin-coated as an anode modification layer for later use. A chloroform blend solution (10-30 mg/mL) of polymer donor materials PM6, L8-BO and acceptor materials prepared in the examples (weight ratio of 1:0.9:0.3) and an additive chloronaphthalene (0.25% -3%) are spin-coated on the PEDOT: PSS anode modification layer to form an active layer of the device. And finally spin-coating a PNDIT-F3N layer with the thickness of about 10nm as a cathode modification layer and Ag (100 nm) as a device cathode to obtain a solar cell device cell structure: ITO/PEDOT: PSS/active layer/PNDIT-F3N/Ag).
Wherein the structure of the polymer donor material PM6, the acceptor L8-BO electron transport layer PNDIT-F3N used in the organic solar cell device is as follows:
energy conversion of solar cellThe conversion efficiency is 100mW/cm by using Lanyan SS-F5-3A as solar simulator 2 Performing photovoltaic performance test on the device under the light intensity, wherein the light intensity is calibrated through a standard monocrystalline silicon solar cell (SRC-00019); the J-V curve was measured using Keithley 2400. And testing the three parameters of the open-circuit voltage, the short-circuit current and the filling factor of the solar cell device, and calculating the corresponding photoelectric conversion efficiency.
The J-V curve of the solar cell device is shown in FIG. 6, and it can be seen from Table 1 that the organic solar cell device of the PM6:L8-BO system has an open circuit voltage V OC =0.85V, short-circuit current J SC ＝23.53mA/cm 2 Fill factor ff=78%, conversion efficiency pce=15.83%. Open circuit voltage V of solar cell device with DOXCT-4F as third component of PM6:L8-BO active layer OC =0.90V, short-circuit current J SC ＝23.93mA/cm 2 Fill factor ff=75%, conversion efficiency pce=16.35%. Open circuit voltage V of solar cell device with DOXCT-4Cl as third component of PM6:L8-BO active layer OC =0.90V, short-circuit current J SC =23.63 mA/cm2, fill factor ff=75%, conversion efficiency pce= 16.19%. It can be seen that the acceptor material in the present invention can obtain higher Voc than the binary system as the third component.
TABLE 1
| Device and method for manufacturing the same | J SC (mA cm -2 ) | V OC (V) | FF | PCE(％) |
| PM6:L8-BO | 23.53 | 0.85 | 0.78 | 15.83 |
| PM6:L8-BO:DOXCT-4F | 23.93 | 0.90 | 0.75 | 16.35 |
| PM6:L8-BO:DOXCT-4Cl | 23.63 | 0.90 | 0.75 | 16.19 |
Test example 3
The preparation and characterization of large area printed OPV devices are specifically as follows:
will be 20cm 2 Sequentially ultrasonically cleaning IT0 conductive glass by using acetone, ethanol and deionized water for 10-20 minutes, drying by using nitrogen, and then treating by using ultraviolet ozone for 10 minutes; a30 nm thick PEDOT: PSS layer is spin-coated on the substrate as a hole transport layer for later use. A chloroform blend solution (10-30 mg/mL) of polymer donor materials PM6, L8-BO and acceptor materials prepared in the examples (weight ratio of 1:0.9:0.3) and chloronaphthalene (0.25% -3%) as an additive was printed on the PEDOT: PSS layer to form an active layer thickness of the device of 300nm. PNDIT-F3N is dissolved in methanol solution and added with 0.5% acetic acid to prepare 1moL/mL solution, the solution is spin-coated on the surface of the active layer at the rotating speed of 4000 revolutions per second, and then the active layer is annealed at 100 ℃ for 10min to prepare the electron transport layer with the thickness of 8 nm. Finally, a printing technology is adopted to prepare an Ag electrode, and silver paste is adopted as a raw material. Directly brushing a silver paste layer on the surface of the prepared electron transport layer to serve as an electrode, and the electrodeThe thickness of the layer was 100nm.
And (3) testing the performance of the large-area device, selecting one point of the large-area battery for testing, and under the standard test condition: AM1.5, 100mW/cm 2 The open circuit voltage (V) OC ) =0.7v, short-circuit current (J SC )＝17.80mA/cm 2 Fill Factor (FF) =0.74, photoelectric Conversion Efficiency (PCE) =10.02%.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the embodiments described above, and various changes can be made within the knowledge of one of ordinary skill in the art without departing from the spirit of the present invention.
Claims (10)
1. A non-fullerene acceptor material characterized by having a structure represented by formula (I):
wherein, the liquid crystal display device comprises a liquid crystal display device,
R 1 、R 2 each independently selected from the group consisting of straight or branched alkyl, alkoxy, or thioalkyl groups having from 1 to 30C atoms;
Ar 1 、Ar 2 each independently selected from aryl, heteroaryl, fused ring groups having 5 to 30 ring atoms, wherein the aryl, heteroaryl, fused ring groups are unsubstituted or optionally substituted with one or more S1;
said S1 is independently selected from H, F, cl, br, cyano, trifluoromethyl, or two of said S1 together form =o,
2. The non-fullerene acceptor material according to claim 1, wherein R 1 、R 2 Each independently selected from the group consisting of linear or branched alkyl, alkoxy or thioalkyl groups having 5 to 20C atoms。
3. The non-fullerene acceptor material according to claim 2, wherein R 1 Is a linear alkyl group having 10 to 15C atoms, and/or R 2 Is a branched alkyl group having 5 to 10C atoms.
4. The non-fullerene acceptor material according to claim 1, wherein Ar 1 、Ar 2 Each independently selected from the group consisting of
Wherein, the liquid crystal display device comprises a liquid crystal display device,
X 1 、X 2 each independently selected from H, F, cl, br, cyano, trifluoromethyl.
5. The non-fullerene acceptor material according to claim 4, wherein Ar 1 、Ar 2 Is that
Wherein, the liquid crystal display device comprises a liquid crystal display device,
X 1 、X 2 each independently selected from F, cl, br, trifluoromethyl.
6. The method for producing a non-fullerene acceptor material according to any one of claims 1 to 5, comprising the steps of:
s1, performing the compound 1 and the compound 2 in the presence of a catalyst to obtain a compound 3;
s2, carrying out condensation ring-closure reaction on the compound 3 and triethyl phosphite, and then carrying out condensation ring-closure reaction on the compound and halogenated alkane X-R 2 Carrying out substitution reaction to obtain a compound 4;
s3, combining compound 4 with LiAlH 4 Carrying out reduction reaction to obtain an intermediate product 5;
s4, reacting the intermediate product 5 with diethyl 2, 3-diisopropyl succinate to obtain a compound 6;
s5, carrying out Vilsmeier-Haack reaction on the compound 6 and a formylating reagent to obtain a compound 7;
s6, combining Compound 7 with
Carrying out Knoevenagel reaction on the acid binding agent to obtain a non-fullerene acceptor material shown in a formula (I);
R 1 、R 2 、X 1 、X 2 is defined as before.
7. The preparation method according to claim 6, wherein in the step S1, the catalyst is at least one selected from the group consisting of tetrakis (triphenylphosphine) palladium, palladium acetate, bis (triphenylphosphine) palladium dichloride, tris (dibenzylideneacetone) dipalladium, tris (o-tolyl) phosphine and cuprous iodide;
and/or, in the step S5, the formylating agent is phosphorus oxychloride;
and/or, in the step S6, the acid binding agent is selected from at least one of pyridine and piperidine.
8. Use of a non-fullerene acceptor material according to any one of claims 1 to 5 for the preparation of organic/polymer solar cells, perovskite solar cells, organic photodetectors, organic field effect transistors and organic light emitting diodes.
9. An organic solar cell comprising an active layer, wherein the active layer comprises the non-fullerene acceptor material of any one of claims 1 to 5.
10. The organic solar cell of claim 9, wherein the active layer further comprises an organic solar cell binary system;
preferably, the polymer donor of the binary system of the organic solar cell is selected from at least one of PM6, PBTB-T-2F, PBDB-T, D and PTQ-10, and the acceptor is selected from at least one of Y6, L8-BO and BTP-eC 9.
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| CN117580380B (en) * | 2024-01-17 | 2024-03-19 | 湖南大学 | Organic heterojunction vertical phototransistor and preparation method thereof |
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