CN105968126B - One kind is containing bipyridyl/ferrosin salt water/Alcohol-soluble conjugate small molecule and the preparation method and application thereof - Google Patents
One kind is containing bipyridyl/ferrosin salt water/Alcohol-soluble conjugate small molecule and the preparation method and application thereof Download PDFInfo
- Publication number
- CN105968126B CN105968126B CN201610202829.9A CN201610202829A CN105968126B CN 105968126 B CN105968126 B CN 105968126B CN 201610202829 A CN201610202829 A CN 201610202829A CN 105968126 B CN105968126 B CN 105968126B
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- Prior art keywords
- small molecule
- ferrosin
- layer
- alcohol
- bipyridyl
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- 150000003384 small molecules Chemical class 0.000 title claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000021615 conjugation Effects 0.000 claims abstract description 5
- 230000004048 modification Effects 0.000 claims description 26
- 238000012986 modification Methods 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 13
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000011630 iodine Substances 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000004528 spin coating Methods 0.000 claims description 5
- WKYQOSNHIPTONH-UHFFFAOYSA-N 9H-fluorene 1H-indole Chemical class C1=CC=CC=2C3=CC=CC=C3CC12.N1C=CC2=CC=CC=C12 WKYQOSNHIPTONH-UHFFFAOYSA-N 0.000 claims description 4
- QJTQKPNNQVLHHO-UHFFFAOYSA-N 9h-carbazole;1h-indole Chemical class C1=CC=C2NC=CC2=C1.C1=CC=C2C3=CC=CC=C3NC2=C1 QJTQKPNNQVLHHO-UHFFFAOYSA-N 0.000 claims description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 150000001716 carbazoles Chemical class 0.000 claims description 4
- 150000002220 fluorenes Chemical class 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 125000003003 spiro group Chemical group 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000010129 solution processing Methods 0.000 claims description 3
- BFRDBSBKJUVSNP-UHFFFAOYSA-N 9h-fluorene;silicon Chemical compound [Si].C1=CC=C2CC3=CC=CC=C3C2=C1 BFRDBSBKJUVSNP-UHFFFAOYSA-N 0.000 claims description 2
- IGIIERRCOSRSLT-UHFFFAOYSA-N C1=CC=CC=2OC3=C(C21)C=CC=C3.[S] Chemical compound C1=CC=CC=2OC3=C(C21)C=CC=C3.[S] IGIIERRCOSRSLT-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 238000006619 Stille reaction Methods 0.000 claims description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 2
- 150000001555 benzenes Chemical class 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 238000010276 construction Methods 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000007641 inkjet printing Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000003475 lamination Methods 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000007761 roller coating Methods 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 230000001680 brushing effect Effects 0.000 claims 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims 1
- 238000010020 roller printing Methods 0.000 claims 1
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 claims 1
- 238000007592 spray painting technique Methods 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- DBGVGMSCBYYSLD-UHFFFAOYSA-N tributylstannane Chemical compound CCCC[SnH](CCCC)CCCC DBGVGMSCBYYSLD-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 238000000605 extraction Methods 0.000 abstract description 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- 230000031700 light absorption Effects 0.000 abstract 1
- 230000001151 other effect Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000007787 solid Substances 0.000 description 11
- 238000000502 dialysis Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000012528 membrane Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229920000144 PEDOT:PSS Polymers 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- -1 hydroxyl carbon Chemical compound 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 3
- 238000013086 organic photovoltaic Methods 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 150000005181 nitrobenzenes Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 description 1
- PIXVSOVKPMTWOF-UHFFFAOYSA-N CC(N)=[S+](C(C12)=CC(C)=CC1=C)(c1c2ccc(C)c1)I Chemical compound CC(N)=[S+](C(C12)=CC(C)=CC1=C)(c1c2ccc(C)c1)I PIXVSOVKPMTWOF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241001126918 Sycon Species 0.000 description 1
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 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 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 208000018875 hypoxemia Diseases 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003557 small molecule preparation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- KXCAEQNNTZANTK-UHFFFAOYSA-N stannane Chemical compound [SnH4] KXCAEQNNTZANTK-UHFFFAOYSA-N 0.000 description 1
- 229910000080 stannane Inorganic materials 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed 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
- H10K30/80—Constructional details
- H10K30/81—Electrodes
-
- 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
- H10K85/649—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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention discloses one kind containing bipyridyl/ferrosin salt water/Alcohol-soluble conjugate small molecule and preparation method thereof with as embellishing cathode interface layer, just set, be inverted and laminated photovoltaic devices in application.When the embellishing cathode interface layer containing bipyridyl/ferrosin salt water/Alcohol-soluble conjugate small molecule as photovoltaic cell of the invention, interface dipole effect can be formed between light absorption active layer and cathode, cathode effective work function and other effects is reduced, to promote the transmission and extraction of electronics.In methanol, n,N-Dimethylformamide, dimethyl sulfoxide, water isopolarity solvent, therefore when constructing multilayer device Intermixing of interface phenomenon will not occur for conjugation small soluble molecules solution of the invention between electron transfer layer and active layer.
Description
Technical field
The present invention relates to water/Alcohol-soluble conjugate small molecule fields, and in particular to one kind is containing bipyridyl/ferrosin salt
Water/Alcohol-soluble conjugate small molecule and the preparation method and application thereof.
Background technique
In recent years to water/Alcohol-soluble conjugate small molecule the study found that using such material to body heterojunction sun electricity
The cathode in pond is modified, and can achieve the effect for increasing substantially device performance.What this kind of highly polar small molecule was played
Effect includes: the pollution that can prevent the metallic cathode of vapor deposition to active layer；Optimize contact of the active layer with metal electrode, improves
The parallel resistance of device reduces series resistance；The effective Built-in potential etc. for improving device.
It is total that " materials chemistry magazine " (J.Mater.Chem.) 1 (2013) 3387 reports water/alcohol-soluble containing pyridiniujm
Yoke electrolyte can be used as boundary layer for positive polymer solar cells.Using PCDTBT:PC71BM is as the poly- of active layer
Closing object efficiency of solar cell can reach 6.56%, and relative to pure Al cathode device, performance improves 52%, shows pyridine
Salt is used for the great potential of solar cell cathodic modification layer.
The present invention has developed small point of a series of water/Alcohol-soluble conjugate using bipyridyl/ferrosin salt as basic unit
Son.Such molecule not only has excellent solubility property in environmentally friendly solvent, simultaneously because electron transporting groups bipyridyl/
The introducing of ferrosin can be further improved electronic transmission performance, and in addition free-moving anion can be in active layer
PCBM carries out n-type doping, reduces the transmission loss of electronics, improves the efficiency of transmission of electronics, as cathode interface material organic
Very big application potential will be had in terms of solar cell.
Summary of the invention
The present invention is ionized by will contain bipyridyl/ferrosin neutral conjugation small molecule, synthesized it is a series of
With the salt of good solubility in water or alcoholic solvent, and using the series salt as cathode interface material applied to just setting,
In inversion and lamination organic photovoltaic devices.
The purpose of the present invention is to provide one kind containing bipyridyl/ferrosin salt water/Alcohol-soluble conjugate small molecule and its
Preparation method.
Another object of the present invention is by described containing small point of water/Alcohol-soluble conjugate of bipyridyl/ferrosin salt
Son is used as cathodic modification layer, is applied in organic photovoltaic devices.
The purpose of the present invention is realized at least through one of following technical solution.
One kind containing bipyridyl/ferrosin salt water/Alcohol-soluble conjugate small molecule, each bipyridyl or ferrosin unit
With ethylene bridging between two nitrogen-atoms, the chemical structural formula of the small molecule is as follows:
Wherein, X Cl, Br, I, CF3SO3、OrStructural unit Ar is such as
One of lower conjugation or non-conjugated structure:
2,7- substituted fluorene；
3,6- substituted fluorene；
2,8- replaces dibenzothiophen
2,8- replaces sulphur dibenzofuran
2,7- replaces spiro fluorene；
2,2 '-replace spiro fluorene
2,7- replaces silicon fluorene；
2,7- substituted carbazole；
3,6- substituted carbazole；
3,9- substituted indole carbazole；2,8- substituted indole carbazole；
3,8- replaces triphenylamine
3,9- substituted indole fluorenes；
2,8- substituted indole fluorenes；
1,4- substituted benzene；
Wherein,
(1)R1The linear or branched alkyl group for being 1-30 for carbon atom number, or for end be that phosphate-based, hydroxyl carbon is former
Subnumber is the linear or branched alkyl group of 1-30, and one or more of carbon atoms can be replaced by oxygen atom, one or more hydrogen
Atom can be replaced by fluorine atoms；
(2)R2For H or carbon atom number be 1-30 linear or branched alkyl group or end be that phosphate-based, hydroxyl carbon is former
Subnumber is the linear or branched alkyl group of 1-30, and one or more of carbon atoms can be replaced by oxygen atom, one or more hydrogen
Atom can be replaced by fluorine atoms；
(3)R3For H, F；
(4) Y is O, S, Se.
It is described above a kind of containing bipyridyl/ferrosin salt water/Alcohol-soluble conjugate small molecule preparation method, including such as
Lower step:
(1) under inert gas protection, triphenylphosphine palladium chtalyst, the bromo- 2- iodine pyridine of 5- and 2- (three normal-butyls are closed by four
Stannane base) pyridine progress Stille coupling, prepare bromo- [2, the 2 '] bipyridyl of 5-；
(2) ferrosin is dissolved in nitrobenzene, is heated to 130-140 DEG C, the nitrobenzene solution of bromine is slowly added dropwise, continued anti-
It answers 2-6 hours, obtains bromo- [1, the 10] ferrosin of 3-；
(3) under inert gas protection, by four close triphenylphosphine palladium chtalysts, will (1) or (2) preparation 5- it is bromo- [2,
2 '] bipyridyl or bromo- [1, the 10] ferrosin of 3- carry out Suzuki coupling from the structural unit of different boracic acid esters active groups,
Prepare water/Alcohol-soluble conjugate small molecule forerunner's neutrals；
(4) under inert gas protection, forerunner's neutrals prepared by (3) is dissolved in 1,2- dihalo- (chlorine, bromine or iodine) Dai Yi
Alkane carries out ion reaction at 50-130 DEG C, obtain anion be bromine, chlorine or iodine containing bipyridyl/ferrosin salt water/
Alcohol-soluble conjugate small molecule；
(5) under inert gas protection, by the water/Alcohol-soluble conjugate small molecule of bromine (or chlorine, iodine) anion of (4) preparation
It is dissolved in methanol, NaX (X CF is added3SO3、BIm4Or BArF 4), 8-48 hours progress ion exchanges are stirred at room temperature, obtain
Anion is CF3SO3、BIm4Or BArF 4Containing bipyridyl/ferrosin salt water/Alcohol-soluble conjugate small molecule.
Above-described one kind is containing bipyridyl/ferrosin salt water/Alcohol-soluble conjugate small molecule as cathode interface material
Material is applied in solar cell device, in the solar cell device of multilayered structure, by way of water/alcoholic solution processing,
It is small that one layer of water/Alcohol-soluble conjugate containing bipyridyl/ferrosin salt is inserted between the active layer and cathode layer of solar cell device
Molecular film；The solar cell device includes organic/polymer solar cells and Ca-Ti ore type solar cell.
Further, the film with a thickness of 1-200 nanometers.
Further, the structure of the solar cell device, which is positive, sets, is inverted or is laminated；Wherein just setting structure includes successively
Substrate, anode layer, anode modification layer, active layer, cathodic modification layer and the cathode layer of stacking；Inverted structure includes stacking gradually
Substrate, cathode layer, cathodic modification layer, active layer, anode modification layer and anode layer；Laminated construction include the substrate stacked gradually,
Anode layer, anode modification layer, active layer 1, articulamentum, active layer 2, cathodic modification layer and cathode layer.
Further, the cathodic modification layer is by environmental-friendly alcoholic solution processing method realization, including spin coating, brush
Painting, spraying, dip-coating, roller coating, silk-screen printing, printing or inkjet printing methods.
Described can be used for preparing organic/polymer light containing bipyridyl/ferrosin salt water/Alcohol-soluble conjugate small molecule
The cathodic modification layer of device and perovskite solar cell device is lied prostrate, so that Ohmic contact is realized between active layer and cathodic metal,
Be conducive to effective collection of the carrier near electrode, to improve the short circuit current of device to improve photoelectric conversion efficiency.Together
When, it is described effectively to inhibit conjugated polymer/fowler containing bipyridyl/ferrosin salt water/Alcohol-soluble conjugate small molecule
The dark current of alkene bulk heterojunction solar cell device can further improve the photoelectricity of device to improve the open-circuit voltage of device
Transformation efficiency.
Compared with prior art, the present invention has the advantage that
(1) of the invention organic/polymer is just being set containing bipyridyl/ferrosin salt water/Alcohol-soluble conjugate small molecule,
Inversion and laminated photovoltaic devices can realize excellent electron-transport and extraction.
(2) small soluble molecules solution of the invention is molten in methanol, N,N-dimethylformamide, dimethyl sulfoxide, water isopolarity
In agent, therefore intermixing phenomenon will not occur between cathodic modification layer and active layer when constructing multilayer device.
(3) small molecule of the invention can be by solution spin coating, and the modes such as printing form a film, and is not necessarily to long-time heating or ultraviolet light
According to change its dissolubility, device preparation technology is simple and easy.
(4) since the metals such as aluminium have excellent air and steam stability, with small numerator modified high work content of the invention
Number metallic cathode interface, the aerial good processing stability of the composite cathode of composition, the stability of device are greatly improved.
Detailed description of the invention
Fig. 1 is the thermal gravimetric analysis curve figure of small molecule 3；
Fig. 2 is the UV-visible absorption spectrum of small molecule 3；
Fig. 3 is the cyclic voltammetry curve figure of small molecule 3；
Fig. 4 is just to set solar cell device current density-voltage diagram based on donor polymer PCDTBT.
Specific embodiment
Following embodiment be to proposed by the present invention containing bipyridyl/ferrosin salt water/Alcohol-soluble conjugate small molecule and
The explanation of its precursor preparation, but the present invention is not limited to listed example.
Bromo- [the 2,2 '] bipyridyl of embodiment 1:5-
Under protection of argon gas, by the bromo- 2- iodine pyridine of 5- (1 gram, 3.5 mMs) and 2- (tri-n-butyl tin alkyl) pyridine
(1.3 grams, 3.5 mMs) are dissolved in 15 milliliters of dry toluenes, and four conjunctions triphenylphosphine palladium (0.2 gram) are added and are heated to 120 DEG C instead
It answers 24 hours.It is cooled to room temperature, decompression is spin-dried for solvent, bromo- [2, the 2 '] bipyridyl of the isolated white solid 5- of silica gel column chromatography.
Its chemical equation is as follows:
Embodiment 2: water/Alcohol-soluble conjugate small molecule presoma 2
Under protection of argon gas, by bromo- [2, the 2 '] bipyridyl of 5- (0.5 gram, 2.1 mMs) and 2,7- bis- (4,4,5,5- tetra-
Methyl-1,3,2- dioxaborinates) -9,9- dioctyl fluorene (0.54 gram, 0.84 mM) is dissolved in 10 milliliters of toluene, carbon is added
Sour aqueous solutions of potassium (2 moles every liter, 3 milliliters), tetrabutylammonium bromide (80 milligrams) and four close triphenylphosphine palladium (0.1 gram), heating
It is reacted 12 hours to 85 DEG C.It is cooled to room temperature, 20 milliliters of distilled water stirrings is added, are extracted with dichloromethane 3 times, dichloromethane layer
With distillation washing 2 times, decompression is spin-dried for solvent, the isolated white solid presoma 2 of silica gel column chromatography.Its chemical equation
It is as follows:
Embodiment 3: water/Alcohol-soluble conjugate small molecule 3
Under protection of argon gas, by presoma 2 (0.21 gram, 0.3 mM) be dissolved in 1,2- Bromofume (1.3 milliliters, 15 milli
Mole), it is heated to 125 DEG C of reactions overnight.It is cooled to room temperature, filters, filter residue is dissolved in 1 ml methanol, instills in methylene chloride and sinks
Analysis, filtering, filter residue are washed repeatedly with acetone, dry to obtain red solid 3.Its chemical equation is as follows:
Fig. 1 is the thermal gravimetric analysis curve figure of small molecule 3；It will be seen from figure 1 that the temperature of 3 weightlessness 5% of small molecule is 295
Degree Celsius.Fig. 2 is the UV-visible absorption spectrum of small molecule 3；Figure it is seen that the absorption of small molecule 3 in the solution
Peak is 311 nanometers and 440 nanometers, and absorption peak in the film is 309 nanometers and 434 nanometers.It is calculated from film absorption side
Its optical band gap is 2.46 electron-volts.Fig. 3 is the cyclic voltammetry curve figure of small molecule 3, wherein illustration is the circulation of ferrocene
Volt-ampere curve；From figure 3, it can be seen that the reduction potential of small molecule 3 is -0.30 volt, so as to calculate its lumo energy
It is -4.08 electron-volts；According further to the optical band gap that Fig. 2 is obtained, can calculate its HOMO energy level is -6.54 electron volts
It is special.Fig. 4 is just to set solar cell device current density-voltage diagram, device architecture: ITO/ based on donor polymer PCDTBT
PEDOT:PSS/PCDTBT:PC71BM/ cathodic modification layer/Al.From fig. 4, it can be seen that compared to the light for not adding cathodic modification layer
Lie prostrate device, using small molecule 3 as cathodic modification layer preparation photovoltaic device short circuit current it is almost unchanged, but open-circuit voltage from
0.88 volt is increased to 0.93 volt, and fill factor is increased to 64.4% from 57.9%, final energy conversion efficiency from
5.47% is increased to 6.47%.
Bromo- [1,10] ferrosin of embodiment 4:3-
1,10- ferrosin (5 grams, 22 mMs) is dissolved in 8 milliliters of nitrobenzenes, is heated to 135 DEG C.By bromine (1.7 millis
Rise, 32 mMs) 5 milliliters of nitrobenzenes are dissolved in, reaction system is slowly instilled, the reaction was continued 4 hours after dripping.It is cooled to room
100 milliliters of concentrated ammonia liquors are added in temperature.Methylene chloride extraction, anhydrous magnesium sulfate is dry, is spin-dried for solvent.It is bromo- that column chromatography for separation obtains 3-
[1,10] ferrosin.1H NMR、13C NMR and elemental analysis are the result shows that obtained is target product.Its chemical reaction equation
Formula is as follows:
Embodiment 5: water/Alcohol-soluble conjugate small molecule presoma 5
Under protection of argon gas, by bromo- [1, the 10] ferrosin 4 (0.8 gram, 3.1 mMs) of 3- and 2,7- bis- (4,4,5,5- tetra-
Methyl-1,3,2- dioxaborinates) -9,9- bis- (6- hydroxyl hexyl) fluorenes (0.7 gram, 1.2 mMs) is dissolved in 20 milliliters of toluene,
Wet chemical (2 moles every liter, 5 milliliters) is added, tetrabutylammonium bromide (70 milligrams) and four closes triphenylphosphine palladium (0.1
Gram), it is heated to 90 DEG C and reacts 14 hours.It is cooled to room temperature, the stirring of 30 milliliters of distilled water is added, be extracted with dichloromethane 3 times, two
The distillation washing 2 times of chloromethanes layer, decompression is spin-dried for solvent, the isolated white solid presoma 5 of silica gel column chromatography.1H NMR、13C NMR and elemental analysis are the result shows that obtained is target product.Its chemical equation is as follows:
Embodiment 6: water/Alcohol-soluble conjugate small molecule 6
Under protection of argon gas, by presoma 5 (0.15 gram, 0.2 mM) be dissolved in 1,2- ethylidene periodide (1 milliliter, 7.6 milli
Mole), it is heated to 100 DEG C of reactions overnight.It is cooled to room temperature, filters, filter residue is dissolved in 1 ml methanol, instills in methylene chloride and sinks
Analysis, filtering, filter residue are washed repeatedly with acetone, dry to obtain red solid 6.1H NMR、13C NMR and elemental analysis are the result shows that gained
Arriving is target product.Its chemical equation is as follows:
Embodiment 7: water/Alcohol-soluble conjugate small molecule 8
Under protection of argon gas, water/alcohol-soluble small molecule 7 (0.1 gram, 0.07 mM) is dissolved in 2 ml methanols, is added three
Fluorine methanesulfonic sodium (1.2 grams, 7 mMs), is stirred at room temperature 24 hours.Then it is spin-dried for solvent, solid fills after being dissolved with 2 ml methanols
Enter dialysis membrane, seals mouth and be placed on stirring dialysis in the beaker equipped with deionized water, during which change water 3 times.It is spin-dried in dialysis membrane
Solvent dries to obtain red solid 8.X-ray photoelectron spectroscopy is the result shows that be more than 95% ion exchange.It reacts following institute
Show:
Embodiment 8: water/Alcohol-soluble conjugate small molecule 10
Under protection of argon gas, water/alcohol-soluble small molecule 9 (0.12 gram, 0.14 mM) is dissolved in 2.5 ml methanols, added
Enter NaBIm4(2.1 grams, 7 mMs), are stirred at room temperature 28 hours.Then it is spin-dried for solvent, solid is packed into after being dissolved with 2 ml methanols
Dialysis membrane seals mouth and is placed on stirring dialysis in the beaker equipped with deionized water, during which changes water 3 times.It is spin-dried for molten in dialysis membrane
Red solid 10 is dried to obtain in agent.X-ray photoelectron spectroscopy is the result shows that be more than 95% ion exchange.It reacts as follows:
Embodiment 9: water/Alcohol-soluble conjugate small molecule 12
Under protection of argon gas, water/alcohol-soluble small molecule 11 (0.15 gram, 0.13 mM) is dissolved in 3.5 ml methanols, added
Enter NaBArF 4(5.3 grams, 6 mMs), are stirred at room temperature 20 hours.Then it is spin-dried for solvent, solid is packed into after being dissolved with 3 ml methanols
Dialysis membrane seals mouth and is placed on stirring dialysis in the beaker equipped with deionized water, during which changes water 3 times.It is spin-dried for molten in dialysis membrane
Red solid 12 is dried to obtain in agent.X-ray photoelectron spectroscopy is the result shows that be more than 95% ion exchange.It reacts as follows:
Illustrate small molecule of the invention as yin by taking the water containing bipyridine salt/Alcohol-soluble conjugate small molecule 3 as an example below
Application of the pole decorative layer in organic photovoltaic devices.
The preparation and representation of 10 polymer solar cells device of embodiment
By ITO electro-conductive glass, square resistance~20 Ω/ is precut into 15 millimeters × 15 millimeters square pieces.Successively with third
Ketone, micron level semiconductor special purpose detergent, deionized water, isopropanol ultrasonic cleaning, it is spare that nitrogen purging is placed on constant temperature oven.
Before use, the net piece of ITO is in oxygen plasma etch instrument with plasma bombardment 10 minutes.Select PVK public purchased from Aldrich
Solution is prepared with tetrachloroethanes by department.PEDOT:PSS aqueous dispersions (1wt%) are purchased from Bayer company, and buffer layer is with sol evenning machine
(KW-4A) high speed spin coating is determined with a thickness of 40 nanometers by solution concentration and revolving speed, with surface profiler (Tritek company
Alpha-Tencor500 type) actual measurement monitoring.After film forming, drive away solvent residues, post bake in constant-temperature vacuum baking oven.By polymer
Solar cell material PCDTBT (PC71BM is as receptor) it is placed in weighing in clean sample bottle, then continue at the hand of nitrogen protection
In casing, the state to maintain hypoxemia low humidity is protected for high pure nitrogen in glove box.With solvent appropriate (such as toluene, chlorobenzene, two
Chlorobenzene etc.) polymer and PC of active layer will be used to prepare71BM mixing, which is placed on mixing platform to be stirred, keeps material completely molten
Solution.The ITO substrate for being coated with anode buffer layer being dried in vacuo is moved into glove box to the spin coating for carrying out polymer active layers, rotation
The process of painting is identical as anode buffer layer.Keep ITO layer exposed with the side that sharp instrument scrapes group diaphragm, the conduct after electrode is deposited
The anode of device.Dry and remove remaining organic solvent.Polymer solar battery active layer optimum thickness is 70~90 nanometers.
Film thickness is measured with TENCOR ALFA-STEP-500 surface profiler.Small molecule 3 is dissolved in methyl alcohol, is configured to 1 milligram/milli
The solution of concentration is risen, with the filtering of 0.45 micron membrane filter.With sol evenning machine respectively got rid of polymer solar battery material and
A thin layer is generated on PEDOT:PSS layers of ITO substrate, with a thickness of 5 nanometers.Aluminium electrode is vaporized on vacuum degree in vacuum coating equipment
Reach 3 × 10-4It is completed when Pa or less.The thickness of plated film rate and each layer electrode is by quartz vibrator film thickness monitor (STM-100
Type, Sycon company) real time monitoring.The region that the light emitting region of device is interacted covering by mask with ITO is determined as 0.15 square li
Rice.All preparation process carry out in the glove box for providing nitrogen inert atmosphere.Solar cell performance is in simulated solar irradiation
(AM1.5G 100mW/cm2) under measure.For the effect for showing electron transfer layer of the present invention, using not plus interface
The device of layer is as a comparison.Measurement result is as shown in Figure 4 and Table 1；Wherein, table 1 is Photovoltaic Device Performance data.
Table 1
Device architecture: ITO/PEDOT:PSS/PCDTBT:PC71BM/ cathodic modification layer/Al
As it can be seen from table 1 being prepared compared to the photovoltaic device of no boundary layer using small molecule 3 as cathodic modification layer
The short circuit current variation of photovoltaic device is little, but open-circuit voltage and fill factor increase, and the energy of final the latter converts effect
Rate tool is greatly improved；To the improvement effect of Photovoltaic Device Performance and small molecule 3 when small molecule 6-12 is as cathodic modification layer
Almost the same, numerous to list herein, water of the invention/Alcohol-soluble conjugate small molecule described above is that one kind has great potential
Photovoltaic device embellishing cathode interface material.
The above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be to the present invention
Embodiment restriction.For those of ordinary skill in the art, it can also make on the basis of the above description
Other various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all of the invention
Made any modifications, equivalent replacements, and improvements etc., should be included in the protection of the claims in the present invention within spirit and principle
Within the scope of.
Claims (3)
1. one kind is containing bipyridyl/ferrosin salt water/Alcohol-soluble conjugate small molecule, it is characterised in that: each bipyridyl or phenanthrene
With ethylene bridging between two nitrogen-atoms of hello quinoline unit, the chemical structural formula of the small molecule is as follows:
In formula, X Cl, Br, I, CF3SO3、Structural unit Ar is following conjugation or non-conjugated structure
One of:
2,7- substituted fluorene；
3,6- substituted fluorene；
2,8- replaces dibenzothiophen
2,8- replaces sulphur dibenzofuran
2,7- replaces spiro fluorene；
2,2 '-replace spiro fluorene
2,7- replaces silicon fluorene；
2,7- substituted carbazole；
3,6- substituted carbazole；
3,9- substituted indole carbazole；
2,8- substituted indole carbazole；
3,8- replaces triphenylamine
3,9- substituted indole fluorenes；
2,8- substituted indole fluorenes；
1,4- substituted benzene；
Wherein,
(1)R1For carbon atom number be 1-30 linear or branched alkyl group or end be that phosphate-based, hydroxyl carbon atom number is
The linear or branched alkyl group of 1-30, one or more of carbon atoms can be replaced by oxygen atom, and one or more hydrogen atoms can
It is replaced by fluorine atoms；
(2)R2For H or carbon atom number be 1-30 linear or branched alkyl group or end be that phosphate-based, hydroxyl carbon atom number is
The linear or branched alkyl group of 1-30, one or more of carbon atoms can be replaced by oxygen atom, and one or more hydrogen atoms can
It is replaced by fluorine atoms；
(3)R3For H or F；
(4) Y is O, S or Se.
2. prepare one kind described in claim 1 containing bipyridyl/ferrosin salt water/Alcohol-soluble conjugate small molecule method,
It is characterized in that, includes the following steps:
(1) under inert gas protection, triphenylphosphine palladium chtalyst, the bromo- 2- iodine pyridine of 5- and 2- (tri-n-butyl stannane are closed by four
Base) pyridine is dissolved in dry toluene, and Stille coupling is carried out at 110-130 DEG C, obtains bromo- [2, the 2 '] bipyridyl of 5-；
(2) ferrosin is dissolved in nitrobenzene, is heated to 130-140 DEG C, the nitrobenzene solution of bromine is added dropwise, the reaction was continued, and 2-6 is small
When, obtain bromo- [1, the 10] ferrosin of 3-；
(3) under inert gas protection, triphenylphosphine palladium chtalyst is closed by four, 5- prepared by step (1) or step (2) is bromo-
The structural unit of [2,2 '] bipyridyl or bromo- [1,10] ferrosin of 3- and boracic acid esters active group is dissolved in toluene or tetrahydrofuran
In, Suzuki coupling is carried out at 60-100 DEG C, obtains water/Alcohol-soluble conjugate small molecule forerunner's neutrals；
(4) under inert gas protection, forerunner's neutrals prepared by step (3) is dissolved in 1,2- dichloro, bromine or iodine for ethane,
Ion reaction is carried out at 50-130 DEG C, and it is molten to obtain water/alcohol containing bipyridyl/ferrosin salt that anion is bromine, chlorine or iodine
Property conjugation small molecule；
It (5) under inert gas protection, is bromine, chlorine or iodine containing bipyridyl/ferrosin salt by the anion of step (4) preparation
Water/Alcohol-soluble conjugate small molecule be dissolved in methanol, be added CF3SO3Na、NaBIm4Or NaBArF 4, it is small that 8-48 is stirred at room temperature
Shi Jinhang ion exchange, obtaining anion is CF3SO3、BIm4Or BArF 4Water/alcohol-soluble containing bipyridyl/ferrosin salt it is total
Yoke small molecule.
3. one kind described in claim 1 is containing bipyridyl/ferrosin salt water/Alcohol-soluble conjugate small molecule as cathode interface
Material is applied in solar cell device, which is characterized in that in the solar cell device of multilayered structure, passes through water/alcoholic solution
The mode of processing, between the active layer and cathode layer of solar cell device be inserted into one layer containing bipyridyl/ferrosin salt water/
Alcohol-soluble conjugate small molecule film, as cathodic modification layer；The solar cell device include organic/polymer solar cells and
Ca-Ti ore type solar cell；The film with a thickness of 1-200 nanometers；The structure of the solar cell device, which is positive, sets, is inverted
Or lamination；Wherein just setting structure includes the substrate stacked gradually, anode layer, anode modification layer, active layer, cathodic modification layer and yin
Pole layer；Inverted structure includes the substrate stacked gradually, cathode layer, cathodic modification layer, active layer, anode modification layer and anode layer；
Laminated construction includes the substrate stacked gradually, anode layer, anode modification layer, active layer 1, articulamentum, active layer 2, cathodic modification
Layer and cathode layer；The cathodic modification layer is by environmental-friendly alcoholic solution processing method realization, including spin coating, brushing, spray
Painting, dip-coating, roller coating, printing or inkjet printing methods.
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Citations (1)
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| "Pyridinium salt-based molecules as cathode interlayers for enhanced performance in polymer solar cells";Hua Ye et al.;《Journal of Materials Chemistry A》;20130109;第1卷;第3387-3394页 * |
| "Synthesis and Characterization of Platinum(II) Complexes Containing Spiro System";Woong Kyu Jo et al.;《Journal of Nanoscience and Nanotechnology》;20131231;第13卷(第6期);第4350-4354页 * |
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