CN112442034A - Novel conjugated micromolecule inner salt containing sulfonate quaternary ammonium salt and preparation method and application thereof - Google Patents
Novel conjugated micromolecule inner salt containing sulfonate quaternary ammonium salt and preparation method and application thereof Download PDFInfo
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- CN112442034A CN112442034A CN202011398826.XA CN202011398826A CN112442034A CN 112442034 A CN112442034 A CN 112442034A CN 202011398826 A CN202011398826 A CN 202011398826A CN 112442034 A CN112442034 A CN 112442034A
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- 150000003839 salts Chemical class 0.000 title claims abstract description 61
- -1 sulfonate quaternary ammonium salt Chemical class 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 230000005669 field effect Effects 0.000 claims abstract description 4
- 150000003384 small molecules Chemical class 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 5
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 4
- YHBTXTFFTYXOFV-UHFFFAOYSA-N Liquid thiophthene Chemical compound C1=CSC2=C1C=CS2 YHBTXTFFTYXOFV-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical compound C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 claims description 3
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 2
- 125000006701 (C1-C7) alkyl group Chemical group 0.000 claims description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 2
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical compound C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 claims description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 2
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000005462 imide group Chemical group 0.000 claims description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- UWMISBRPSJFHIR-UHFFFAOYSA-N naphtho[2,3-b][1]benzothiole Chemical compound C1=CC=C2C=C3C4=CC=CC=C4SC3=CC2=C1 UWMISBRPSJFHIR-UHFFFAOYSA-N 0.000 claims description 2
- 238000013086 organic photovoltaic Methods 0.000 claims description 2
- 229950000688 phenothiazine Drugs 0.000 claims description 2
- 150000004032 porphyrins Chemical class 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- PFZLGKHSYILJTH-UHFFFAOYSA-N thieno[2,3-c]thiophene Chemical compound S1C=C2SC=CC2=C1 PFZLGKHSYILJTH-UHFFFAOYSA-N 0.000 claims description 2
- URMVZUQDPPDABD-UHFFFAOYSA-N thieno[2,3-f][1]benzothiole Chemical compound C1=C2SC=CC2=CC2=C1C=CS2 URMVZUQDPPDABD-UHFFFAOYSA-N 0.000 claims description 2
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 claims description 2
- PWYVVBKROXXHEB-UHFFFAOYSA-M trimethyl-[3-(1-methyl-2,3,4,5-tetraphenylsilol-1-yl)propyl]azanium;iodide Chemical compound [I-].C[N+](C)(C)CCC[Si]1(C)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 PWYVVBKROXXHEB-UHFFFAOYSA-M 0.000 claims description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 230000005693 optoelectronics Effects 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011787 zinc oxide Substances 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- LNZDAVYFINUYOH-UHFFFAOYSA-M sodium;3-bromopropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCBr LNZDAVYFINUYOH-UHFFFAOYSA-M 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 2
- 229940105325 3-dimethylaminopropylamine Drugs 0.000 description 2
- VWEYDBUEGDKEHC-UHFFFAOYSA-N 3-methyloxathiolane 2,2-dioxide Chemical compound CC1CCOS1(=O)=O VWEYDBUEGDKEHC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- 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
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- Spectroscopy & Molecular Physics (AREA)
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- Optics & Photonics (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses a novel conjugated micromolecule inner salt containing sulfonate quaternary ammonium salt, and a preparation method and application thereof. The structural formula of the conjugated micromolecule inner salt is shown as a formula I. The conjugated micromolecule inner salt can be used as a cathode interface layer of the organic solar cell to replace zinc oxide, can improve the stability of devices, and realizes higher photoelectric conversion efficiency. The conjugated micromolecule inner salt can also be applied to photovoltaic devices such as organic light-emitting diodes, organic field effect transistors and the like. The organic conjugated micromolecule inner salt containing the sulfonate quaternary ammonium salt is an electron transmission material with excellent performance, can improve the stability of a device to a great extent, and realizes higher photoelectric conversion efficiency. The problems that the traditional organic solar cell is poor in stability and cannot operate for a long time are solved.
Description
Technical Field
The invention relates to a novel conjugated micromolecule inner salt containing sulfonate quaternary ammonium salt, a preparation method and application thereof.
Background
With the continuous development of human society, the traditional energy is gradually difficult to meet the requirements of human beings, and meanwhile, the problem of environmental pollution is also urgently solved. However, the conventional power generation methods such as hydroelectric power generation and thermal power generation are not environment-friendly and have certain destructiveness. Therefore, the vigorous development of new energy sources is becoming more urgent. The solar energy has the advantages of cleanness, greenness, no pollution, wide distribution on the earth, inexhaustibility, and the like, has the greatest development prospect, and the development and utilization of the solar energy can be a solution for effectively dealing with the energy problem. Organic solar cells have received much attention because of their light weight, low cost, solution processibility, and flexibility. With the rapid development of organic photovoltaic materials, the photoelectric conversion efficiency of organic solar cells (efficiency is increased from the first 4% to 16% (y.zou, j.yuan, y.zhang, l.zhou, g.zhang, h.l.yip, t.k.lau, x.lu, c.zhu, h.peng, p.a.johnson, m.leclerc, y.cao, j.ulanski, y.li, Joule 2019,3,1140.) exhibits excellent application potential.
However, although the above materials achieve high photoelectric conversion efficiency, the organic solar cell has a problem that is not negligible in terms of the current development, that is, the stability of the device. In a conventional forward device structure, the anode interface layer material used is usually poly 3, 4-ethylenedioxythiophene: polystyrene sulfonate, which is hygroscopic, tends to cause device instability. In the reverse device structure, the cathode interface layer material used is usually zinc oxide, which has photo-oxidation property and is easy to oxidize the active layer, thus destroying the stability of the device. The problem of stability of organic solar cells has largely limited their further commercialization. Therefore, it is desirable to provide a cathode interface layer material that can improve the stability of an organic solar cell.
Disclosure of Invention
The invention aims to provide a novel conjugated micromolecule inner salt containing sulfonate quaternary ammonium salt, which can be used as a cathode interface layer of an organic solar cell reverse device to replace zinc oxide, improve the stability of the device and realize higher photoelectric conversion efficiency; the novel conjugated micromolecule of the sulfonate quaternary ammonium salt can also be applied to photovoltaic devices such as organic light-emitting diodes, organic field effect transistors and the like.
The conjugated micromolecule inner salt containing the sulfonate quaternary ammonium salt has the structural formula shown in the formula I,
in the formula I, Ar represents a conjugated group selected from the following unsubstituted or substituted groups: benzene, thiophene, naphthalene, anthracene, perylene, fluorene, triphenylamine, phenothiazine, pyrrole, pyrazine, thiazole, pyridine, bipyridine, quinoline, furan, biphenyl, porphyrin, porphyrine, thieno [3,2-b ] thiophene, thieno [3,4-b ] thiophene, thieno [2,3-b ] thiophene, bisthio [3,2-b:2 ', 3' -d ] thiophene, carbazole, indole, 4H-cyclopropyl [2,1-b:3,4-b '] dithiophene, 4, 8-bisalkoxybenzoxazole [1,2-b:4, 5-b' ] dithiophene, 4 '-bisalkylbisthiophene [3,2-b: 2', 3 '-d ] silole, benzo [1,2-b:4, 5-b' ] dithiophene, benzo [1, 4,5-b '] bis [ thieno [2,3-b ] thiophene ], benzo [5,6-b ] naphtho [2,3-d ] thiophene, naphtho [4,5-b:8, 9-b' ] dithiophene, naphthalimide, perylene imide, benzimide; preferably a naphthalimide or perylene bisimide;
R1and R2The same or different, each is independently selected from hydrogen or C1-C20 alkyl, C1-C20 alkoxy, C1-C20 ester group, C1-C20 amine group and imide group, C6 aryl, C6-C20 aralkyl, sulfonate, quaternary ammonium salt, C2-C20 alkenyl, aryl substituted by single bond, double bond, triple bond or combination thereof;
n is a natural number between 1 and 20, and m is a natural number between 1 and 20;
x, Y and Z are independently selected from hydrogen and C1-C7 alkyl.
The conjugated micromolecule inner salt is specifically shown as a formula II:
in formula II, X, Y, Z, m and n are as defined in formula I;
further, X is preferably a C1-C3 alkyl group, more preferably a methyl group, Y is preferably a methyl C1-C3 alkyl group, more preferably a methyl group, Z is preferably H or a C1-C3 alkyl group, more preferably hydrogen or a methyl group;
m is preferably 1 to 5, more preferably 2 or 3, and n is preferably 1 to 5, more preferably 2.
The conjugated micromolecular inner salt shown in the formula II is shown in the formula II-1, the formula II-2 or the formula II-3:
the invention also provides a preparation method of the conjugated micromolecule inner salt, which comprises the following steps:
reacting a compound shown in a formula III with a compound shown in a formula IV or a formula V to obtain the compound;
in the formula III, Ar and R1、R2X, Y and n are as defined in formula I;
in the formula IV, Z is defined as in the formula I, and o is a natural number between 1 and 18;
in the formula V, W is fluorine, chlorine, bromine or iodine, and o is a natural number between 1 and 18.
In the above preparation method, the reaction is carried out in the following solvents:
tetrahydrofuran, methanol, ethanol, N-dimethylformamide, chloroform, water, toluene or a mixed solvent of the above solvents.
In the above preparation method, the reaction is carried out under an inert atmosphere;
the reaction temperature is 40-200 ℃;
the reaction time is 4-72 hours.
The invention also provides a conjugated micromolecule (NDI-N-SO) shown as a formula II-13) The preparation method comprises two steps:
one is as follows: dissolving (N, N-dimethylamino) propyl naphthalimide (formula III-1) and 1, 3-propane sultone (formula IV-1) in an organic solvent (preferably methanol), and reacting for 24-48 hours to prepare the conjugated micromolecule inner salt with the structure of formula II-1;
the specific reaction is shown as the following formula:
the reaction temperature is 40-70 ℃, and preferably 50-60 ℃;
the second step is as follows: dissolving (N, N-dimethylamino) propyl naphthalimide (formula III-1) and 3-bromopropane-1-sodium sulfonate (formula V-1) in a blending solvent (preferably ethanol: water ═ 1:1), and reacting for 24-48 hours to prepare the conjugated micromolecule inner salt with the structure of formula II-1;
the specific reaction is shown as the following formula:
wherein, the compound shown in the formula III-1 is prepared by the following method:
dissolving 1,4,5, 8-naphthalene tetracarboxylic anhydride and 3-dimethylaminopropylamine in an organic solvent (such as N, N-dimethylformamide), maintaining the reaction at 120 ℃ for preferably 24 hours, and performing column chromatography by using halogenated hydrocarbon (preferably dichloromethane) as an eluent to obtain a compound shown in a formula III-1: (N, N-dimethylamino) propylnaphthalimide;
the specific reaction formula is as follows:
according to the invention, the compound of formula V-1 is prepared by the following method:
dissolving 1, 3-dibromopropane and sodium sulfite in an organic solvent (preferably ethanol), maintaining the reaction at 45 ℃ for 18 hours, and recrystallizing the solution with a mixed solution of ethanol and water to obtain the compound shown in the formula V-1: 3-bromopropane-1-sulfonic acid sodium salt;
the specific reaction formula is as follows:
the conjugated micromolecule inner salt provided by the invention can be used as a cathode interface layer of an organic solar cell to replace zinc oxide, can improve the stability of a device, and realizes higher photoelectric conversion efficiency.
The conjugated micromolecule inner salt provided by the invention can also be applied to photovoltaic devices such as organic light-emitting diodes, organic field effect transistors and the like.
The organic conjugated micromolecule inner salt containing the sulfonate quaternary ammonium salt provided by the invention is an electron transport material with excellent performance, and can improve the stability of devices to a great extent and realize higher photoelectric conversion efficiency. The problems that the traditional organic solar cell is poor in stability and cannot operate for a long time are solved.
Drawings
FIG. 1 is a NMR chart of a conjugated small molecule inner salt of formula II-1 prepared in example 1.
FIG. 2 is a NMR chart of a conjugated small molecule inner salt of formula II-2 prepared in example 2.
FIG. 3 is a NMR chart of a conjugated small molecule inner salt of formula II-3 prepared in example 3.
FIG. 4 is an absorption spectrum of a conjugated small molecule inner salt of formula II-1 prepared in example 1.
FIG. 5 is an absorption spectrum of the conjugated small molecule inner salt of formula II-2 obtained in example 2.
FIG. 6 is an absorption spectrum of a conjugated small molecule inner salt of formula II-3 prepared in example 3.
FIG. 7 is a voltammogram of electrochemical cycles in 0.1mol/L acetonitrile solution of tetrabutylammonium hexafluorophosphate in conjugated small molecules of formulae II-1, II-2, II-3 prepared in examples 1 to 3 on a platinum electrode; wherein the curve with dots represents the electrochemical cyclic voltammogram of formula II-1, the curve with squares represents the electrochemical cyclic voltammogram of formula II-2, and the curve with triangles represents the electrochemical cyclic voltammogram of formula II-3.
FIG. 8 shows a diagram of the structure ITO/formula II-1/PBDB-TF BTP-eC11/MoO prepared based on the conjugated small molecule inner salt of formula II-1 prepared in example 13Voltage-current (I-V) curve of organic solar cell of/Al.
FIG. 9 shows a diagram of the structure ITO/formula II-2/PBDB-TF BTP-eC11/MoO prepared based on the conjugated small molecule inner salt of formula II-2 prepared in example 23Voltage-current (I-V) curve of organic solar cell of/Al.
FIG. 10 shows the structure of ITO/formula II-3/PBDB-TF BTP-eC11/MoO prepared based on the conjugated small molecule inner salt of formula II-3 prepared in example 33Voltage-current (I-V) curve of organic solar cell of/Al.
FIG. 11 shows a diagram of the structure ITO/formula II-1/PBDB-TF BTP-eC11/MoO prepared based on the conjugated small molecule inner salt of formula II-1 prepared in example 13External Quantum Efficiency (EQE) curve for organic solar cells of/Al.
FIG. 12 shows the structure of ITO/formula II-2/PBDB-TF BTP-eC11/MoO prepared based on the conjugated small molecule inner salt of formula II-2 prepared in example 23External Quantum Efficiency (EQE) curve for organic solar cells of/Al.
FIG. 13 shows a diagram of the structure ITO/formula II-3/PBDB-TF BTP-eC11/MoO prepared based on the conjugated small molecule inner salt of formula II-3 prepared in example 33External Quantum Efficiency (EQE) curve for organic solar cells of/Al.
FIG. 14 shows a diagram of the structure ITO/formula II-1/PBDB-TF BTP-eC11/MoO prepared based on the conjugated small molecule inner salt of formula II-1 prepared in example 13Energy conversion efficiency curve of the/Al organic solar cell stored in nitrogen.
FIG. 15 shows a device fabricated based on the conjugated small molecule inner salt of formula II-2 prepared in example 2Has the structure of ITO/formula II-2/PBDB-TF BTP-eC11/MoO3Energy conversion efficiency curve of the/Al organic solar cell stored in nitrogen.
FIG. 16 shows the structure of ITO/formula II-3/PBDB-TF: BTP-eC11/MoO prepared based on the conjugated small molecule inner salt of formula II-3 prepared in example 33Energy conversion efficiency curve of the/Al organic solar cell stored in nitrogen.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Conventional techniques of organic chemistry within the skill of the art can be employed in the present invention. In the following examples, efforts are made to ensure accuracy with respect to numbers used (including amounts, temperature, reaction time, etc.) but some experimental errors and deviations should be accounted for. The temperatures (in degrees centigrade) used in the following examples are expressed in degrees centigrade and the pressures are at or near atmospheric. All solvents were purchased as HPLC grade and all reactions were performed under an inert atmosphere of argon. All reagents were obtained commercially unless otherwise indicated.
EXAMPLE 1 Synthesis of (N, N, N-dimethylammoniylpropyl-1-sulfonate) propylnaphthalimide (formula II-1)
(1) Synthesis of (N, N-dimethylamino) propylnaphthalimide
Under an argon atmosphere, 2.68g (10mmol) of 1,4,5, 8-naphthalenetetracarboxylic anhydride was dissolved in 200ml of N, N-dimethylformamide, followed by addition of 4.1g (40mmol) of 3-dimethylaminopropylamine and maintenance of the reaction at 120 ℃ for 24 hours. After the reaction is finished, cooling to room temperature to precipitate a solid, and performing suction filtration to obtain a brownish black solid crude product. Column chromatography with dichloromethane as eluent gave 2.62g of a golden yellow solid, i.e. (N, N-dimethylamino) propylnaphthalimide, in 60% yield.
(2) 3-bromopropane-1-sulfonic acid sodium salt.
2.02g (10mmol) of 1, 3-dibromopropane and 2.77g (22mmol) of sodium sulfite are dissolved in 200ml of ethanol under an argon atmosphere and the reaction is maintained at 45 ℃ for 18 hours. After the reaction is finished, the reaction solution is concentrated by rotary evaporation, and is dropwise added with 300ml of acetone, and solid is precipitated by sedimentation. Filtering to obtain off-white solid. Recrystallization from a mixed solution of ethanol and water gave 1.8g of a white solid, i.e., sodium 3-bromopropane-1-sulfonate, in 80% yield.
(3) Synthesis of (N, N, N-dimethylammoniylpropyl-1-sulfonate) propylnaphthalimide
1.31g (3mmol) of (N, N-dimethylamino) propylnaphthalimide and 1.39g (6.2mmol) of sodium 3-bromopropane-1-sulfonate were dissolved in 140ml of a mixed solution of methanol and water (methanol: water ═ 6:1) under an argon atmosphere, and reacted at 60 ℃ for 48 hours. After the reaction is finished, cooling to room temperature to separate out solid, and performing suction filtration to obtain a yellow-white solid crude product. The crude product was washed with 100ml of ethanol and 100ml of acetone, respectively. The crude product was purified by methanol: dissolving in a mixed solvent of 2:1 water, passing through a reverse column, and eluting with methanol: water 2:1, 1.16g of white solid, i.e. (N, N-dimethylammoniumpropyl-1-sulfonate) propylnaphthalimide, was obtained in 57% yield.
Nuclear magnetic resonance hydrogen spectrum structural characterization:1h NMR (300MHz, D2O, delta) 8.51(s,4H),4.22(t,4H),3.54(m,8H),3.16(s,12H),2.97(t,4H),2.27(m,8H) and the spectrum is shown in FIG. 1.
Elemental analysis (%): c30H40N4O10S2Calculating the following values: c52.93, H5.92, N8.23, O23.50, S9.42; found C50.95, H5.17, N7.46, O28.56, S7.86.
EXAMPLE 2 Synthesis of (N, N, N-dimethylammolbutyl-1-sulfonate) propylnaphthalimide (formula II-2)
1.31g (3mmol) of (N, N-dimethylamino) propylnaphthalimide and 1.22g (9mmol) of 2, 4-butanesultone were dissolved in 120ml of methanol under an argon atmosphere and reacted at 60 ℃ for 48 hours. After the reaction is finished, cooling to room temperature to separate out solid, and performing suction filtration to obtain a yellow-white solid crude product. The crude product was washed with 100ml ethanol, 100ml acetone, respectively, after which the mixture was washed with ethanol: recrystallization from a mixed solvent of water 6:1 gave 0.85g of a white solid, i.e., (N, N-dimethylammonobutyl-1-sulfonate) propylnaphthalimide, in 40% yield.
Nuclear magnetic resonance hydrogen spectrum structural characterization:1h NMR (400MHz, D2O, delta) 8.47(s,4H),4.27(t,4H),3.54(m,4H),3.41(t,4H),3.16(s,12H),2.30(m,4H),1.92(m,4H),1.21(t,4H), the spectra are shown in FIG. 2.
Elemental analysis (%): c32H44N4O10S2Calculating the following values: c54.22, H6.26, N7.90, O22.57, S9.05; found C50.97, H6.44, N7.43, O27.25, S7.91.
EXAMPLE 3 Synthesis of (N, N, N-dimethylammolbutyl-2-sulfonate) propylnaphthalimide (formula II-3)
1.31g (3mmol) of (N, N-dimethylamino) propylnaphthalimide and 1.22g (9mmol) of 2, 4-butanesultone were dissolved in 120ml of methanol under an argon atmosphere and reacted at 60 ℃ for 48 hours. After the reaction is finished, cooling to room temperature to separate out solid, and performing suction filtration to obtain a yellow-white solid crude product. The crude product was washed with 100ml ethanol, 100ml acetone, respectively, after which the mixture was washed with ethanol: recrystallization from a mixed solvent of water 6:1 gave 0.94g of a white solid, i.e. (N, N-dimethylammonobutyl-2-sulfonate) propylnaphthalimide, in 44% yield.
Nuclear magnetic resonance hydrogen spectrum structural characterization:1h NMR (300MHz, D2O, delta) 8.60(s,4H),4.28(t,4H),3.58(m,8H),3.12(s,12H),3.00(m,2H),2.11(m,8H),1.37(D,6H) with the spectrum shown in FIG. 3. .
Elemental analysis (%): c32H44N4O10S2Calculating the following values: c54.22, H6.26, N7.90, O22.57, S9.05; found C48.94, H6.10, N7.49, O28.75, S8.72.
Example 4 measurement of UV-visible absorption spectra of conjugated small molecule inner salts of formulae II-1, II-2, II-3 obtained in examples 1 to 3
The conjugated micromolecule inner salts of the formulas II-1, II-2 and II-3 prepared in the examples 1 to 3 are respectively dissolved in water, respectively spin-coated on a quartz plate to prepare a solid film, and the absorption spectra measured by an ultraviolet visible absorption spectrometer are respectively shown in figures 4,5 and 6, so that the conjugated micromolecule inner salts of the formulas II-1, II-2 and II-3 have stronger absorption near 380nm wavelength and do not absorb in a visible light region, and the conjugated micromolecule inner salts of the formulas II-1, II-2 and II-3 are suitable for being used as interface layer materials in the spectrum.
Example 5 measurement of the Lowest Unoccupied Molecular Orbital (LUMO) of the conjugated small molecule inner salt of formulae II-1, II-2, II-3 prepared in examples 1 to 3 by electrochemical cyclic voltammetry. .
Dissolving the conjugated small molecule inner salts of the formulas II-1, II-2 and II-3 prepared in the examples 1 to 3 in water respectively, and then dripping the solution on a working electrode such as a platinum sheet; using acetonitrile solution of 0.1mol/L tetrabutylammonium hexafluorophosphate as electrolyte; taking a platinum wire as a counter electrode; measurements were performed in this system using electrochemical cyclic voltammetry with silver wire as reference electrode. The cyclic voltammetry data for the conjugated small molecule inner salts of formulae II-1, II-2, II-3 are shown in FIG. 7. The LUMO energy levels of the conjugated small molecule inner salts shown in the formulas II-1, II-2 and II-3 are respectively-3.53 eV, -3.41eV and-3.45 eV, which are higher than the LUMO energy level of the acceptor material BTP-eC9-4.08eV, and therefore, electrons are easily transmitted from the acceptor material BTP-eC9 to the conjugated small molecule inner salts shown in the formulas II-1, II-2 and II-3 in the organic solar cell device.
Example 6 fabrication of organic solar cell devices from the conjugated small molecule inner salts of formulae II-1, II-2, and II-3 obtained in examples 1 to 3
1mg of the conjugated small molecule inner salt of the formula II-1, II-2 or II-3 prepared in examples 1 to 3 was dissolved in 0.25ml of deionized water, and the solution was heated to 50 ℃ and dissolved for 1 hour to obtain a solution of 4 mg/ml. The solution is coated on tin oxide (ITO) conductive glass in a spin coating film forming mode to obtain an interface layer film with the thickness of about 10 nm. Then 10mg/ml of BTP-eC11 and PBDB-TF blended solution is coated on the interface layer film in a spin coating film forming mode. Then put into a high vacuum coating chamber at about 10 DEG-4Under the vacuum degree of Pa, molybdenum trioxide with the thickness of 10nm is evaporated by a vacuum evaporation mode to be used as an anode interface layer. Finally, aluminum with a thickness of 100nm is evaporated as a top electrode, and a xenon lamp is used for simulating a solar light source (AM1.5 intensity, 100 mW/cm)2) Under the irradiation of (2), measuring the voltage-current curve of the device to obtain the open-circuit voltage (V) of the deviceoc) Short-circuit current (J)sc) And a Fill Factor (FF) value, thereby obtaining the Photoelectric Conversion Efficiency (PCE) of the device. Xenon lamp solar simulator was calibrated in the National Renewable Energy Laboratory (NREL) using silicon diodes (with KG5 visible filter).
The voltage-current (I-V) curves of the polymer solar cell devices based on the conjugated small molecule inner salts of formulae II-1, II-2, and II-3 prepared in examples 1 to 3 are shown in FIGS. 8,9, and 10, respectively. Wherein, the open circuit voltage V of the conjugated small molecule inner salt of formula II-1 prepared in example 1oc0.85V, short-circuit current Jsc＝25.72mA/cm2The fill factor FF is 73.82%, and the conversion efficiency PCE is 16.20%; example 2 open Circuit Voltage V of conjugated Small molecule inner salt of formula II-2oc0.85V, short-circuit current Jsc＝25.74mA/cm2The fill factor FF is 74.60%, and the conversion efficiency PCE is 16.38%; open Circuit Voltage V of conjugated Small molecule inner salt of formula II-3 prepared in example 3oc0.85V, short-circuit current Jsc＝25.77mA/cm2The fill factor FF is 74.16%, and the conversion efficiency PCE is16.22％。
Example 7 testing of external quantum conversion efficiency of organic solar cell devices based on conjugated small molecule inner salts of formulae II-1, II-2, II-3 prepared in examples 1 to 3
The results of the test of the external quantum efficiency curves of the polymer solar cell devices prepared according to the procedure of example 6 based on the conjugated small molecule inner salts of formulae ii-1, ii-2, and ii-3 prepared in examples 1 to 3 using an external quantum efficiency tester of Enli from taiwan light edge corporation are shown in fig. 11, 12, and 13, respectively. It can be seen that the external quantum efficiency of the solar cell devices based on examples 1-3 is substantially greater than 70% over the entire spectral range. It is shown that such materials can effectively promote exciton dissociation.
Example 8 test of storage stability of organic solar cell devices based on conjugated small molecule inner salts of formulae II-1, II-2, II-3 obtained in examples 1 to 3
Polymer solar cell devices prepared according to the procedure of example 6 based on the conjugated small molecule inner salts of formulae II-1, II-2, II-3 prepared in examples 1 to 3 were stored in a N-filled cell2In a glove box, and using an AAA grade solar simulator at an AM1.5 intensity of 100mW/cm every 24 hours2The open-circuit voltage, the short-circuit current, the fill factor and the energy conversion efficiency of the prepared polymer solar cell are tested. After 60 days, the conversion efficiency of the device can still keep more than 90% of the initial value after 60 days, the stability of the device is greatly improved, and the change of the device efficiency with time is respectively shown in fig. 14, fig. 15 and fig. 16.
The invention is illustrated by the above-described embodiments. It will be understood by those skilled in the art that the following examples are not intended to limit the scope of the present invention, and that many modifications and substitutions may be made thereto based on the teachings herein without departing from the scope of the present invention as set forth in the appended claims. Any modifications and variations made on the basis of the present invention are within the scope of the present invention.
Claims (9)
1. A conjugate micromolecule inner salt containing quaternary ammonium salt of sulfonate shown in a formula I,
in the formula I, Ar represents a conjugated group selected from the following unsubstituted or substituted groups: benzene, thiophene, naphthalene, anthracene, perylene, fluorene, triphenylamine, phenothiazine, pyrrole, pyrazine, thiazole, pyridine, bipyridine, quinoline, furan, biphenyl, porphyrin, porphyrine, thieno [3,2-b ] thiophene, thieno [3,4-b ] thiophene, thieno [2,3-b ] thiophene, bisthio [3,2-b:2 ', 3' -d ] thiophene, carbazole, indole, 4H-cyclopropyl [2,1-b:3,4-b '] dithiophene, 4, 8-bisalkoxybenzoxazole [1,2-b:4, 5-b' ] dithiophene, 4 '-bisalkylbisthiophene [3,2-b: 2', 3 '-d ] silole, benzo [1,2-b:4, 5-b' ] dithiophene, benzo [1, 4,5-b '] bis [ thieno [2,3-b ] thiophene ], benzo [5,6-b ] naphtho [2,3-d ] thiophene, naphtho [4,5-b:8, 9-b' ] dithiophene, naphthalimide, perylene imide, benzimide;
R1and R2The same or different, each is independently selected from hydrogen or C1-C20 alkyl, C1-C20 alkoxy, C1-C20 ester group, C1-C20 amine group and imide group, C6 aryl, C6-C20 aralkyl, sulfonate, quaternary ammonium salt, C2-C20 alkenyl, aryl substituted by single bond, double bond, triple bond or combination thereof;
n is a natural number between 1 and 20, and m is a natural number between 1 and 20;
x, Y, Z are independently selected from hydrogen and C1-C7 alkyl.
2. The conjugated small molecule inner salt of claim 1, wherein: the conjugated micromolecule inner salt is shown as a formula II:
in formula II, X, Y, Z, m and n are as defined in formula I.
3. The conjugated small molecule inner salt of claim 2, wherein: the conjugated micromolecule inner salt is shown as a formula II-1, a formula II-3 or a formula II-3:
4. a method of preparing the conjugated small molecule inner salt of any one of claims 1-3, comprising the steps of:
reacting a compound shown in a formula III with a compound shown in a formula IV or a formula V to obtain the compound;
in the formula III, Ar and R1、R2X, Y and n are as defined in formula I;
in the formula IV, Z is defined as in the formula I, and o is a natural number between 1 and 18;
in the formula V, W is fluorine, chlorine, bromine or iodine, and o is a natural number between 1 and 18.
5. The method of claim 4, wherein: the reaction is carried out in the following solvents:
tetrahydrofuran, methanol, ethanol, N-dimethylformamide, chloroform, water, toluene or a mixed solvent of the above solvents.
6. The production method according to claim 4 or 5, characterized in that: the reaction is carried out under an inert atmosphere;
the reaction temperature is 40-200 ℃;
the reaction time is 4-72 hours.
7. An organic solar cell, wherein the cathode interface layer is made of the conjugated small molecule inner salt according to any one of claims 1 to 3.
8. Use of the conjugated small molecule inner salt of any one of claims 1-3 for the preparation of an organic solar cell.
9. Use of the conjugated small molecule inner salt of any one of claims 1-3 for the preparation of the following organic optoelectronic functional device:
organic photovoltaic devices, organic field effect transistors, and organic light emitting diodes.
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