CN103025737B - 硅芴金属卟啉-苯有机半导体材料及其制备方法和应用 - Google Patents
硅芴金属卟啉-苯有机半导体材料及其制备方法和应用 Download PDFInfo
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- CN103025737B CN103025737B CN201080068186.4A CN201080068186A CN103025737B CN 103025737 B CN103025737 B CN 103025737B CN 201080068186 A CN201080068186 A CN 201080068186A CN 103025737 B CN103025737 B CN 103025737B
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- porphyrin
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- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 211
- 239000000463 material Substances 0.000 title claims abstract description 104
- 239000004065 semiconductor Substances 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title abstract description 6
- UTUZBCDXWYMYGA-UHFFFAOYSA-N silafluorene Chemical compound C12=CC=CC=C2CC2=C1C=CC=[Si]2 UTUZBCDXWYMYGA-UHFFFAOYSA-N 0.000 title abstract 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 22
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 120
- 229910052710 silicon Inorganic materials 0.000 claims description 76
- 239000010703 silicon Substances 0.000 claims description 76
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 70
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 66
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 57
- 239000001301 oxygen Substances 0.000 claims description 57
- 229910052760 oxygen Inorganic materials 0.000 claims description 57
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 37
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 36
- 239000003960 organic solvent Substances 0.000 claims description 36
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 32
- AIGRXSNSLVJMEA-FQEVSTJZSA-N ethoxy-(4-nitrophenoxy)-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound O([P@@](=S)(OCC)C=1C=CC=CC=1)C1=CC=C([N+]([O-])=O)C=C1 AIGRXSNSLVJMEA-FQEVSTJZSA-N 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 150000004032 porphyrins Chemical class 0.000 claims description 27
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- BFRDBSBKJUVSNP-UHFFFAOYSA-N 9h-fluorene;silicon Chemical class [Si].C1=CC=C2CC3=CC=CC=C3C2=C1 BFRDBSBKJUVSNP-UHFFFAOYSA-N 0.000 claims description 19
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical group BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 18
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 18
- 229960001701 chloroform Drugs 0.000 claims description 16
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 230000005669 field effect Effects 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000005401 electroluminescence Methods 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 6
- 150000004033 porphyrin derivatives Chemical class 0.000 claims description 6
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical group O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 3
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- 230000003287 optical effect Effects 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims 1
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- 150000005224 alkoxybenzenes Chemical class 0.000 abstract 1
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- -1 metals porphyrin compound Chemical class 0.000 description 64
- 230000015572 biosynthetic process Effects 0.000 description 31
- 238000003786 synthesis reaction Methods 0.000 description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 19
- 239000000047 product Substances 0.000 description 19
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- 239000000243 solution Substances 0.000 description 16
- 0 CC(CC(CC=C)/C1=C(/C=CC2C3)\C3=C\C(C3)C(CCCC45)*6=C1C=CC6=C(C(C)(C)C)C4=CC=C5C(C(CC1)=CC(C)=C1C(CCC=C1)=C1N)=C(CC1)*3=C1C2c1ccc(C(C)(C)C)cc1)C(C)CC=CC=C Chemical compound CC(CC(CC=C)/C1=C(/C=CC2C3)\C3=C\C(C3)C(CCCC45)*6=C1C=CC6=C(C(C)(C)C)C4=CC=C5C(C(CC1)=CC(C)=C1C(CCC=C1)=C1N)=C(CC1)*3=C1C2c1ccc(C(C)(C)C)cc1)C(C)CC=CC=C 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000000376 reactant Substances 0.000 description 12
- 239000000741 silica gel Substances 0.000 description 12
- 229910002027 silica gel Inorganic materials 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- PNNXBWWSFIVKQW-UHFFFAOYSA-N [O].CCCCCCCCCCCCCCCC Chemical compound [O].CCCCCCCCCCCCCCCC PNNXBWWSFIVKQW-UHFFFAOYSA-N 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
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- 238000004440 column chromatography Methods 0.000 description 6
- 238000006392 deoxygenation reaction Methods 0.000 description 6
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 6
- 229950004394 ditiocarb Drugs 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
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- 229910052786 argon Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 230000006837 decompression Effects 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- RVJMVUORBCKNBX-UHFFFAOYSA-N C1=CC=CC=2C3=CC=CC=C3CC12.[Si].C1=CC=CC=C1 Chemical class C1=CC=CC=2C3=CC=CC=C3CC12.[Si].C1=CC=CC=C1 RVJMVUORBCKNBX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920000144 PEDOT:PSS Polymers 0.000 description 3
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 3
- 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 3
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
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- 239000010931 gold Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
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- 238000007738 vacuum evaporation Methods 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 2
- 229950003776 protoporphyrin Drugs 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
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- JKWKFBUUNGGYBP-UHFFFAOYSA-N C(C1)C1NC1CC1 Chemical compound C(C1)C1NC1CC1 JKWKFBUUNGGYBP-UHFFFAOYSA-N 0.000 description 1
- PBTPREHATAFBEN-UHFFFAOYSA-N C(c1ccc[nH]1)c1ccc[nH]1 Chemical compound C(c1ccc[nH]1)c1ccc[nH]1 PBTPREHATAFBEN-UHFFFAOYSA-N 0.000 description 1
- VUEHZXCETJEBKX-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Sn].[Si] Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Sn].[Si] VUEHZXCETJEBKX-UHFFFAOYSA-N 0.000 description 1
- DOOQSSKFMIJAOH-RUDMXATFSA-N Cc1ccc(/C=C2/C(Br)=C2)cn1 Chemical compound Cc1ccc(/C=C2/C(Br)=C2)cn1 DOOQSSKFMIJAOH-RUDMXATFSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- UQXKXGWGFRWILX-UHFFFAOYSA-N ethylene glycol dinitrate Chemical compound O=N(=O)OCCON(=O)=O UQXKXGWGFRWILX-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical group N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
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Classifications
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0816—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring comprising Si as a ring atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
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Abstract
提供了一种硅芴金属卟啉-苯有机半导体材料及其制备方法和应用。硅芴金属卟啉-苯有机半导体材料的结构由结构式(I)定义;其中:n为1到100之间的整数,R1、R2、R3、R4为H、C1-C32的烷基、苯基、含有一个或多个C1-C32的烷基苯或烷氧基苯;M为金属离子。所述硅芴金属卟啉-苯有机半导体材料的溶解性能好、载流子迁移率高、吸光度强、对光吸收范围宽,提高了其对太阳光的利用率。此外,制备方法的工艺简单,易于操作和控制。
Description
技术领域
本发明涉及一种有机半导体材料,更具体的涉及一种硅芴基金属卟啉-苯有机半导体材料。
本发明还涉及硅芴基金属卟啉-苯有机半导体材料的制备方法及其应用。
背景技术
利用廉价材料制备低成本、高效能的太阳能电池一直是光伏领域的研究热点和难点。目前用于地面的硅晶电池由于生产工艺复杂、成本高,使其应用受到限制。为了降低电池成本,拓展应用范围,长期以来人们一直在寻找新型的太阳能电池材料。有机半导体材料以其原料易得、廉价、制备工艺简单、环境稳定性好、有良好的光伏效应等优点备受关注。自1992年N.S.Sariciftci等在SCIENCE(N.S Sariciftci,L.Smilowitz,A.J.Heeger,etal.Science,1992,258,1474)上报道共轭聚合物与C60之间的光诱导电子转移现象后,人们在聚合物太阳能电池方面投入了大量研究,并取得了飞速的发展,但是仍比无机太阳能电池的转换效率低得多。限制性能提高的主要制约因素有:有机半导体材料的光谱响应与太阳辐射光谱不匹配,有机半导体相对较低的载流子迁移率以及较低的载流子的电极收集效率等。为了使聚合物太阳能电池得到实际的应用,开发新型的材料,大幅度提高其能量转换效率仍是这一研究领域的首要任务。
卟啉分子是在卟吩环上连有取代基的一类大环化合物的总称,卟吩是由四个吡咯环和四个次甲基桥联起来的单双键交替的平面结构大环离域π电子共轭体系。它们电荷转移和能量转移反应的量子效率较高,具有良好的电子缓冲性和光电磁性,良好的刚柔性和较好热稳定性和环境稳定性。因此,卟啉类有机半导体材料是一类很有前途的材料,其在光伏领域的应用已得到广泛研究。元素周期表中几乎所有的金属和一些非金属元素都可以与卟啉作用形成配合物。在这些化合物中,包括了大部分的主族和副族金属元素,一些镧系金属(Pr,Eu,Yb等)也己经合成。由于卟啉是具有18个π电子的大共轨体系,其环内电子流动性非常好,因此,大多数金属卟啉化合物都有较好的光电性质。
然而含有硅芴基的金属卟啉-苯的有机半导体材料至今仍没有文献和专利报道,这就大大限制了有机半导体材料的应用范围。因此,本发明开发了一种硅芴基金属卟啉-苯的有机半导体材料。该类材料通过引入硅芴基团到卟啉架构上,并通过金属离子的配位作用,调整了卟啉聚合物的带隙,进而获得更好的稳定性和良好的成膜性,拓宽了可见光谱吸收范围,使其吸收范围延伸至近红外区,提高其对太阳光的利用率,同时提高了载流子迁移率,扩大了它们在有机太阳能电池等领域的应用范围。
发明内容
本发明的目的在于提供一种硅芴基金属卟啉-苯有机半导体材料,其可以解决上述问题。
本发明的目的还在于提供一种硅芴基金属卟啉-苯有机半导体材料的制备方法及其应用。
本发明所涉及的硅芴基金属卟啉-苯有机半导体材料,具有以下结构(I):
式中:n为1-100间的整数,R1,R2,R3,R4为相同或不相同的H、C1-C32的烷基、苯基、含有一个或多个相同或不相同的C1-C32的烷基苯基或烷氧基苯基;M为金属离子,可以但不限于Zn2+、Cu2+、Fe2+、Co2+、Cd2+、Pt2+、Zr2+、Mn2+、Ni2+、Pb2+、Sn2+等金属离子。
本发明所设计的硅芴基金属卟啉-苯有机半导体材料的制备方法,步骤如下:
步骤S1、氧化剂、第一催化剂存在条件下,将结构式为的二吡咯甲烷、结构式为的第一硅芴衍生物以及结构式为的第二硅芴衍生物溶于第一有机溶剂,于20-100℃温度下,反应1-24小时,得到结构式为的硅芴基卟啉衍生物;式中,R1,R2,R3,R4分别为H、C1-C32的烷基、苯基、含有一个或多个C1-C32的烷基苯基或烷氧基苯基;反应式如下:
步骤S2、将步骤S1中得到的硅芴基卟啉衍生物和溴化剂加入到第二有机溶剂中,于0~120℃下反应1~72小时,得到结构式为的二溴硅芴基卟啉衍生物;反应式如下;
步骤S3、将步骤S2中得到的二溴硅芴基卟啉衍生物溶于第三有机溶剂中,接着加入含M金属离子的溶液,于0-30℃下搅拌0.5-24小时,得到结构式为的二溴硅芴基金属卟啉衍生物;反应式如下:
步骤S4、无氧环境中,第二催化剂和第四有机溶剂存在条件下,将步骤S3中得到的二溴硅芴基金属卟啉衍生物和结构式为的1,4-对二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)苯按摩尔比1:2~2:1,于50-120℃中进行Suzuki耦合反应12~72小时,得到结构式为的所述硅芴基金属卟啉-苯有机半导体材料,式中,n为1-100间的整数;反应式如下:
上述硅芴基金属卟啉-苯有机半导体材料的制备方法中,优选:
所述步骤S1中,
二吡咯甲烷、第一硅芴衍生物、第二硅芴衍生物的摩尔比为a:b:c=1:1~100:1~100,其中a=b+c,且a≥b>0;所述第一催化剂为丙酸、三氟乙酸;所述氧化剂为二氯二氰基苯醌;所述第一有机溶剂为三氯甲烷、二氯甲烷中的一种或两种;
所述步骤S2中,
所述硅芴基卟啉衍生物和溴化剂的用量摩尔比为1:2~1:5;所述溴化剂为N-溴代丁二酰亚胺;所述第二有机溶剂为四氢呋喃、氯仿、二甲基酰胺或邻二氯苯中的至少一种;
所述步骤S3中,
所述二溴硅芴基卟啉衍生物和M金属离子的摩尔比为1:1~1:5;所述第三有机溶剂为三氯甲烷、四氢呋喃、苯、甲苯或二氯甲烷中的至少一种;所述含M金属离子的溶液中,M金属离子选自Zn2+、Cu2+、Fe2+、Co2+、Cd2+、Pt2+、Zr2+、Mn2+、Ni2+、Pb2+或Sn2+中的一种,溶剂为甲醇、乙醇或水中的至少一种;
所述步骤S4中,
所述第二催化剂为有机钯或有机钯与有机磷配体的混合物;
所述有机钯为Pd2(dba)3、Pd(PPh3)4、Pd(OAc)2或Pd(PPh3)2Cl2;
所述有机磷配体为P(o-Tol)3、三环己基膦;
所述第四有机溶剂为四氢呋喃、二氯甲烷、氯仿、二氧六环、二甲基酰胺、乙二醇二甲醚、二甲基亚砜、苯、氯苯或甲苯中的至少一种;
另,步骤S4中,还包括1,4-对二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)苯的制备,其制备步骤如下:
将结构式为对二溴苯加入第五有机溶剂中,用液氮/异丙醇降温至-78℃,滴加正丁基锂(n-BuLi,下同),然后在-78℃反应1-3小时,再加入结构式为的2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷,并在-78℃下反应0.5-2小时,然后自然升温至室温,反应6-36小时,得到所述1,4-对二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)苯;其中,所述第五有机溶剂中为四氢呋喃、乙醚或者二氧六环中的至少一种;所述对二溴苯与2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷的摩尔比1:2~5;反应式如下:
上述硅芴基金属卟啉-苯有机半导体材料在聚合物太阳能电池,有机电致发光,有机场效应晶体管,有机光存储,有机非线性器件和有机激光器件等领域中的应用。
与现有技术相比,本发明具有如下优点:
1.本发明中的有机半导体材料分子中含有的硅芴单元,具有良好的热稳定性,以及较高的电子亲和力和较高的电子注入和传输能力;
2.同时还含有卟啉单元,具有平面结构的大环离域π电子共轭体系,电荷转移和能量转移反应的量子效率较高,具有良好的电子缓冲性和光电磁性,以及良好的刚柔性和较好热稳定性和环境稳定性。
3.本发明的有机半导体材料由于同时包含了硅芴结构单元和卟啉单元,兼顾了它们的性能优势,并扩展了该有机半导体材料对太阳光的吸收范围,增加了与太阳辐射光谱的匹配度,从而有效扩展了该有机半导体材料在聚合物太阳能电池、有机电致发光器件、有机场效应晶体管、有机光存储器件或/和有机激光器件中的应用;
4.所述有机半导体材料的制备工艺简单,易于操作和控制。
附图说明
图1为以以本发明中的有机半导体材料作为活性层的有机太阳能电池器件的结构示意图。
图2为以本发明中的有机半导体材料作为发光层的有机电致发光器件的结构示意图。
图3为以本发明中的有机半导体材料作为有机半导体层的有机场效应晶体管器件的结构示意图。
具体实施方式
本发明所涉及的硅芴基金属卟啉-苯有机半导体材料,具有以下结构(I):
式中:n为1-100间的整数,R1,R2,R3,R4分别为相同或不相同的H、C1-C32的烷基、苯基、含有一个或多个相同或不相同的C1-C32的烷基苯基或烷氧基苯基;M为金属离子,可以但不限于Zn2+、Cu2+、Fe2+、Co2+、Cd2+、Pt2+、Zr2+、Mn2+、Ni2+、Pb2+、Sn2+等金属离子。
本发明所设计的硅芴基金属卟啉-苯有机半导体材料的制备方法,步骤如下:
步骤S1、氧化剂、第一催化剂存在条件下,将结构式为的二吡咯甲烷、结构式为的第一硅芴衍生物以及结构式为的第二硅芴衍生物溶于第一有机溶剂,于20-100℃温度下,反应1-24小时,得到结构式为的硅芴基卟啉衍生物;式中,R1,R2,R3,R4分别为H、C1-C32的烷基、苯基、含有一个或多个C1-C32的烷基苯基或烷氧基苯基;反应式如下:
步骤S2、将步骤S1中得到的硅芴基卟啉衍生物和溴化剂加入到第二有机溶剂中,于0~120℃下反应1~72小时,得到结构式为的二溴硅芴基卟啉衍生物;反应式如下;
步骤S3、将步骤S2中得到的二溴硅芴基卟啉衍生物溶于第三有机溶剂中,接着加入含M金属离子的溶液,于0-30℃下搅拌0.5-24小时,得到结构式为的二溴硅芴基金属卟啉衍生物;反应式如下:
步骤S4、无氧环境中,第二催化剂和第四有机溶剂存在条件下,将步骤S3中得到的二溴硅芴基金属卟啉衍生物和结构式为的1,4-对二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)苯按摩尔比1:2~2:1,于50-120℃中进行Suzuki耦合反应12~72小时,得到结构式为的所述硅芴基金属卟啉-苯有机半导体材料,式中,n为1-100间的整数;反应式如下:
上述硅芴基金属卟啉-苯有机半导体材料的制备方法中,优选:
所述步骤S1中,
二吡咯甲烷、第一硅芴衍生物、第二硅芴衍生物的摩尔比为a:b:c=1:1~100:1~100,其中a=b+c,且a≥b>0;所述第一催化剂为丙酸、三氟乙酸;所述氧化剂为二氯二氰基苯醌;所述第一有机溶剂为三氯甲烷、二氯甲烷中的一种或两种;
所述步骤S2中,
所述硅芴基卟啉衍生物和溴化剂的用量摩尔比为1:2~1:5;所述溴化剂为N-溴代丁二酰亚胺;所述第二有机溶剂为四氢呋喃、氯仿、二甲基酰胺或邻二氯苯中的至少一种;
所述步骤S3中,
所述二溴硅芴基卟啉衍生物和M金属离子的摩尔比为1:1~1:5;所述第三有机溶剂为三氯甲烷、四氢呋喃、苯、甲苯或二氯甲烷中的至少一种;所述含M金属离子的溶液中,M金属离子选自Zn2+、Cu2+、Fe2+、Co2+、Cd2+、Pt2+、Zr2+、Mn2+、Ni2+、Pb2+或Sn2+中的一种,溶剂为甲醇、乙醇或水中的至少一种;
所述步骤S4中,
所述第二催化剂为有机钯或有机钯与有机磷配体的混合物;
所述有机钯为Pd2(dba)3、Pd(PPh3)4、Pd(OAc)2或Pd(PPh3)2Cl2;
所述有机磷配体为P(o-Tol)3、三环己基膦;
所述第四有机溶剂为四氢呋喃、二氯甲烷、氯仿、二氧六环、二甲基酰胺、乙二醇二甲醚、二甲基亚砜、苯、氯苯或甲苯中的至少一种;
另,步骤S4中,还包括1,4-对二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)苯的制备,其制备步骤如下:
将结构式为对二溴苯加入第五有机溶剂中,用液氮/异丙醇降温至-78℃,滴加正丁基锂(n-BuLi),然后在-78℃反应1-3小时,再加入结构式为的2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷,并在-78℃下反应0.5-2小时,然后自然升温至室温,反应6-36小时,得到所述1,4-对二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)苯;其中,所述第五有机溶剂中为四氢呋喃、乙醚或者二氧六环中的至少一种;所述对二溴苯与2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷的摩尔比1:2~5;反应式如下:
本发明的无氧环境由氮气或惰性气体构成。
上述硅芴基金属卟啉-苯有机半导体材料的制备方法中,2-溴-9-取代硅芴由2-溴硅芴的制得,参考文献:Macromolecules 2002,35,3474;2-醛-9-取代硅芴由2-溴-9-取代硅芴的制得,参考文献:Macromolecules 2006,39,456;二吡咯甲烷的制得,参考文献:Tetrahedron 1994,39,11427。
下面结合附图,对本发明的较佳实施例作进一步详细说明。
实施例1
本实施例公开一种结构如下的硅芴基锌卟啉-苯有机半导体材料
上式中,n=78;
上述有机半导体材料制备步骤如下:
一、1,4-对二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)苯的合成
在氮气的保护下,往三口瓶中加入对二溴苯(4.8g,0.02mol),加入100ml的四氢呋喃(THF,下同)溶剂,在-78℃条件下再用注射器慢慢注入正丁基锂(n-BuLi,16.8mL,2.5M,0.04mol),继续搅拌反应2h,在-78℃条件下用注射器注入2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷(8.7mL,0.04mol),室温下搅拌过夜。加入饱和氯化钠水溶液(30ml)终止反应,用氯仿萃取,无水硫酸钠干燥,抽虑后将滤液收集并旋蒸掉溶剂。最后将粗产物用石油醚/乙酸乙酯(15/1)为淋洗液进行硅胶柱层析分离,得到产物,产率94.6%。
GC-MS(EI-m/z):332(M+)
二、5,15-二(9’,9’-二辛基)硅芴基卟啉的合成
搭好无水无氧装置,称取中间体2-醛-9,9-二辛基硅芴(0.44g,1mmol)与二吡咯甲烷(0.15g,1mmol),溶解于250ml二氯甲烷中,通入氮气30min,注射器加入丙酸1ml,20℃下搅拌24h,然后加入二氯二氰基苯醌(DDQ)(0.91g,4mmol),继续在室温下搅拌30min,然后加入1ml三乙胺淬灭反应,浓缩溶剂,过滤,收集滤液并旋干溶剂,用二氯甲烷在硅胶柱上快速淋洗,旋干溶剂,用乙醚/甲醇重结晶到产物,产率约为85%。
GC-MS(EI-m/z):1120(M+)
三、5,15-二溴-10,20-二(9’,9’-二辛基)硅芴基卟啉的合成
搭好无水无氧装置,称取10,20-二(9’,9’-二辛基)硅芴基卟啉(0.23g,0.2mmol)溶解于80ml氯仿中,加入1ml吡啶,将反应物降到0℃,加入N-溴代丁二酰亚胺(0.07g,0.4mmol),搅拌72h后,混合物恢复到室温,然后继续搅拌4h,加入5ml丙酮终止反应,除去溶剂,用乙醚/甲醇进行重结晶得到产物,产率81%。
GC-MS(EI-m/z):1278(M+)
四、5,15-二溴-10,20-二(9’,9’-二辛基)硅芴基锌卟啉的合成
称取中间体5,15-二溴-10,20-二(9,9-二辛基芴)卟啉(0.25g,0.2mmol)溶解于50ml二氯甲烷中,加入含醋酸锌(Zn(OAc)2,0.11g,0.5mmol)的甲醇溶液(5ml),室温下搅拌5h,旋干溶剂,然后用二氯甲烷/石油醚(1/1)在硅胶柱上淋洗,收集并旋干溶剂得到产物,产率94%。
GC-MS(EI-m/z):1340(M+)
五、硅芴基锌卟啉-苯有机半导体材料的合成
在氮气保护下,加入1,4-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)苯(66mg,0.2mmol)、5,15-二溴-10,20-二(9’,9’-二辛基)硅芴基锌卟啉(268mg,0.2mmol)和甲苯溶剂50ml,抽真空除氧并充入氮气,然后加入5mg Pd(PPh3)2Cl2与2ml NaHCO3(50%)溶液,加热到100℃反应56h,得到硅芴基锌卟啉-苯有机半导体材料反应物混合液。
冷却至室温后将混合液滴加到300ml甲醇中进行沉降;抽滤,甲醇洗涤,干燥;然后用甲苯溶解,加入到二乙基二硫代氨基甲酸钠的水溶液中,然后将混合液加热到80℃搅拌过夜;将有机相通过氧化铝的柱层析,氯苯淋洗;减压除去有机溶剂,甲醇沉降,抽滤,所得固体用丙酮索氏提取器提取三天;甲醇沉降,抽滤。真空泵下抽过夜得到硅芴基锌卟啉-苯有机半导体材料固体产物,产率72%.Molecular weight(GPC,THF,R.I):Mn=98000,Mw/Mn=3.24;)
实施例2
本实施例公开一种结构如下的硅芴基铁卟啉-苯有机半导体材料
上式中,n=56;
上述有机半导体材料制备步骤如下:
一、1,4-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)苯的合成
其制备详见实施例1,只是无氧环境采用氩气作为保护气。
二、5-(9’-甲基-9’-十六烷基)硅芴基-15-(9’-三十二烷基)硅芴基卟啉的合成
搭好无水无氧装置,称取中间体2-醛-9-甲基-9-十六烷基硅芴(0.45g,1mmol)、2-醛-9-三十二烷基硅芴(0.66g,1mmol)、二吡咯甲烷(0.30g,2mmol),溶解于250ml二氯甲烷中,通入氩气30min,注射器加入三氟乙酸2ml,100℃下搅拌1h,然后加入二氯二氰基苯醌(DDQ)(1.82g,8mmol),继续在室温下搅拌30min,然后加入2ml吡啶淬灭反应,浓缩溶剂,过滤,收集滤液并旋干溶剂,用二氯甲烷在硅胶柱上快速淋洗,旋干溶剂,用乙醚/甲醇重结晶到产物,产率约为78%。
GC-MS(EI-m/z):1359(M+)
三、5,15-二溴-10-(9’-甲基-9’-十六烷基)硅芴基-20-(9’-三十二烷基)硅芴基卟啉的合成
搭好无水无氧装置,称取5-(9’-甲基-9’-十六烷基)硅芴基-15-(9’-三十二烷基)硅芴基卟啉(0.27g,0.2mmol)溶解于80ml氯仿中,加入1ml吡啶,将反应物降到0℃,加入N-溴代丁二酰亚胺(0.07g,0.4mmol),搅拌0.5h后,混合物升温至120℃,然后继续搅拌1h后,加入5ml丙酮终止反应,除去溶剂,用乙醚/甲醇进行重结晶得到产物,产率79%。
GC-MS(EI-m/z):1516(M+)
四、5,15-二溴-10-(9’-甲基-9’-十六烷基)硅芴基-20-(9’-三十二烷基)硅芴基铁卟啉的合成
氩气条件下,称取中间体5,15-二溴-10-(9’-甲基-9’-十六烷基)硅芴基-20-(9’-三十二烷基)硅芴基卟啉(0.31g,0.2mmol)溶解于50ml二氯甲烷中,加入含氯化亚铁(0.12g,1mmol)的甲醇溶液(5ml),室温下搅拌8h,旋干溶剂,然后用二氯甲烷/石油醚(1/1)在硅胶柱上淋洗,收集并旋干溶剂得到产物,产率95%。
GC-MS(EI-m/z):1569(M+)
五、硅芴基铁卟啉-苯有机半导体材料的合成
在氩气保护下,加入1,4-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)苯(66mg,0.2mmol)、5,15-二溴-10-(9’-甲基-9’-十六烷基)硅芴基-20-(9’-三十二烷基)硅芴基铁卟啉(314mg,0.2mmol)和甲苯溶剂120ml,抽真空除氧并充入氩气,然后加入Pd(OAc)2(2.5mg)/三环己基膦(6.5mg)和2ml 20%(wt)四乙基绥氢氧化物(Et4NOH,下同)溶液,加热到120℃反应24h,得到硅芴基铁卟啉-苯有机半导体材料反应物混合液。
冷却至室温后将混合液滴加到200ml甲醇中进行沉降;抽滤,甲醇洗涤,干燥;然后用甲苯溶解,加入到二乙基二硫代氨基甲酸钠的水溶液中,然后将混合液加热到80℃搅拌过夜;将有机相通过氧化铝的柱层析,氯苯淋洗;减压除去有机溶剂,甲醇沉降,抽滤,所得固体用丙酮索氏提取三天;甲醇沉降,抽滤;空泵下抽过夜得到硅芴基铁卟啉-苯有机半导体材料固体产物,产率74%.Molecular weight(GPC,THF,R.I):Mn=87000,Mw/Mn=3.63;)
实施例3
本实施例公开一种结构如下的)硅芴基铜卟啉-苯有机半导体材料
上式中,n=28;
上述有机半导体材料制备步骤如下:
一、1,4-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)苯的合成
其制备详见实施例1.
二、10,20-二(9’-十六烷基-9’-(3”-十六烷基-4”-十六烷氧基)苯)硅芴基卟啉的合成
搭好无水无氧装置,称取中间体2-醛-9-十六烷基-9-(3’-十六烷基-4’-十六烷氧基)苯)硅芴基(1.95g,2mmol)与二吡咯甲烷(0.30g,2mmol),溶解于300ml二氯甲烷中,通入氮气30min,注射器加入三氟乙酸2ml,室温下搅拌3h,然后加入二氯二氰基苯醌(DDQ)(1.82g,8mmol),继续在室温下搅拌30min,然后加入2ml三乙胺淬灭反应,浓缩溶剂,过滤,收集滤液并旋干溶剂,用二氯甲烷在硅胶柱上快速淋洗,旋干溶剂,用乙醚/甲醇重结晶到产物,产率约为85%。
GC-MS(EI-m/z):2201(M+)
三、5,15-二溴-10,20-二(9’-十六烷基-9’-(3”-十六烷基-4”-十六烷氧基)苯)硅芴基卟啉的合成
搭好无水无氧装置,称取10,20-二(9’-十六烷基-9’-(3”-十六烷基-4”-十六烷氧基)苯)硅芴基卟啉(0.44g,0.2mmol)溶解于80ml氯仿中,加入1ml吡啶,将反应物降到0℃,加入N-溴代丁二酰亚胺(0.07g,0.4mmol),搅拌0.5h后,混合物升温至30℃,然后继续搅拌48h,加入5ml丙酮终止反应,除去溶剂,用乙醚/甲醇进行重结晶得到产物,产率76%。
GC-MS(EI-m/z):2360(M+)
四、5,15-二溴-10,20-二(9’-十六烷基-9’-(3”-十六烷基-4”-十六烷氧基)苯)硅芴基铜卟啉的合成
称取中间体5,15-二溴-10,20-二(9’-十六烷基-9’-(3”-十六烷基-4”-十六烷氧基)苯)硅芴基卟啉(0.47g,0.2mmol)溶解于50ml二氯甲烷中,加入CuSO4·5H2O(0.05g,0.2mmol)溶液(5ml),室温下搅拌5h,旋干溶剂,然后用二氯甲烷/石油醚(1/1)在硅胶柱上淋洗,收集并旋干溶剂得到产物,产率93%。
GC-MS(EI-m/z):2416(M+)
五、硅芴基铜卟啉-苯有机半导体材料的合成
在氮气保护下,加入1,4-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)苯(66mg,0.2mmol)、5,15-二溴-10,20-二(9’-十六烷基-9’-(3”-十六烷基-4”-十六烷氧基)苯)硅芴基铜卟啉(483mg,0.2mmol)和甲苯溶剂100ml,抽真空除氧并充入氮气,然后加入10mg Pd(PPh3)2Cl2与2ml KHCO3(30%)溶液,加热到50℃反应72h,得到硅芴基铜卟啉-苯有机半导体材料反应物混合液。
冷却至室温后将混合液滴加到300ml甲醇中进行沉降;抽滤,甲醇洗涤,干燥;然后用甲苯溶解,加入到二乙基二硫代氨基甲酸钠的水溶液中,然后将混合液加热到80℃搅拌过夜;将有机相通过氧化铝的柱层析,氯苯淋洗;压除去有机溶剂,甲醇沉降,抽滤,所得固体用丙酮索氏提取三天;甲醇沉降,抽滤,真空泵下抽过夜得到得到硅芴基铜卟啉-苯有机半导体材料固体产物,产率82%。Molecular weight(GPC,THF,R.I):Mn=65400,Mw/Mn=3.18;)
实施例4
本实施例公开一种结构如下的硅芴基镉卟啉-苯有机半导体材料
上式中,n=100;
上述有机半导体材料制备步骤如下:
一、1,4-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)苯的合成
其制备详见实施例1.
二、5-(9’-对二十烷基苯基-9’-(3”,5”-双十二烷氧基苯基))硅芴基-15-(9’-对十六烷氧基苯基-9’-间癸烷基苯基)硅芴基卟啉的合成
搭好无水无氧装置,称取中间体2-醛-9-对二十烷基苯基-9-(3’,5’-双十二烷氧基苯基)硅芴(1.02g,1mmol)、2-醛-9-对十六烷氧基苯基-9-间癸烷基苯基硅芴(0.74g,1mmol)与二吡咯甲烷(0.30g,2mmol),溶解于250ml二氯甲烷中,通入氮气30min,注射器加入乙酸1ml,20℃下搅拌24h,然后加入二氯二氰基苯醌(DDQ)(0.91g,4mmol),继续在室温下搅拌30min,然后加入1ml三乙胺淬灭反应,浓缩溶剂,过滤,收集滤液并旋干溶剂,用二氯甲烷在硅胶柱上快速淋洗,旋干溶剂,用乙醚/甲醇重结晶到产物,产率约为83%。
GC-MS(EI-m/z):2205(M+)
三、5,15-二溴-10-(9’-对二十烷基苯基-9’-(3”,5”-双十二烷氧基苯基))硅芴基-20-(9’-对十六烷氧基苯基-9’-间癸烷基苯基)硅芴基卟啉的合成
搭好无水无氧装置,称取5,15-二溴-10-(9’-对二十烷基苯基-9’-(3”,5”-双十二烷氧基苯基))硅芴基-20-(9’-对十六烷氧基苯基-9’-间癸烷基苯基)硅芴基卟啉(0.44g,0.2mmol)溶解于80ml二甲基酰胺(DMF)中,将反应物降到0℃,加入N-溴代丁二酰亚胺(0.07g,0.4mmol),搅拌72h后,混合物恢复到室温,然后继续搅拌4h,加入5ml丙酮终止反应,除去溶剂,用乙醚/甲醇进行重结晶得到产物,产率83%。
GC-MS(EI-m/z):2162(M+)
四、5,15-二溴-10-(9’-对二十烷基苯基-9’-(3”,5”-双十二烷氧基苯基))硅芴基-20-(9’-对十六烷氧基苯基-9’-间癸烷基苯基)硅芴基镉卟啉的合成
称取中间体5,15-二溴-10-(9’-对二十烷基苯基-9’-(3”,5”-双十二烷氧基苯基))硅芴基-20-(9’-对十六烷氧基苯基-9’-间癸烷基苯基)硅芴基卟啉(0.43g,0.2mmol)溶解于50ml二氯甲烷中,加入Cd(NO3)2·4H2O(0.31g,1mmol)的甲醇溶液(5ml),室温下搅拌5h,旋干溶剂,然后用二氯甲烷/石油醚(1/1)在硅胶柱上淋洗,收集并旋干溶剂得到产物,产率94%。
GC-MS(EI-m/z):2271(M+)
五、硅芴基镉卟啉-苯有机半导体材料的合成
在氮气保护下,加入1,4-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)苯(66mg,0.2mmol)、5,15-二溴-10-(9’-对二十烷基苯基-9’-(3”,5”-双十二烷氧基苯基))硅芴基-20-(9’-对十六烷氧基苯基-9’-间癸烷基苯基)硅芴基卟啉(454mg,0.2mmol)和二氧六环溶剂60ml,抽真空除氧并充入氮气,然后加入Pd2(dba)3(5mg)/P(o-Tol)3(8mg)与15%的Na2CO3(3ml)溶液,加热到80℃反应36h,得到硅芴基镉卟啉-苯有机半导体材料反应物混合液。
冷却至室温后将混合液滴加到250ml甲醇中进行沉降;抽滤,甲醇洗涤,干燥;然后用甲苯溶解,加入到二乙基二硫代氨基甲酸钠的水溶液中,然后将混合液加热到80℃搅拌过夜;将有机相通过氧化铝的柱层析,氯苯淋洗;减压除去有机溶剂,甲醇沉降;抽滤,所得固体用丙酮索氏提取器提取三天;醇沉降,抽滤;真空泵下抽过夜得到硅芴基镉卟啉-苯有机半导体材料固体产物,产率75%.Molecular weight(GPC,THF,R.I):Mn=219000,Mw/Mn=4.36;
实施例5
本实施例公开一种结构如下的硅芴基钴卟啉-苯有机半导体材料
上式中,n=40;
上述有机半导体材料制备步骤如下:
一、1,4-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)苯的合成
其制备详见实施例1.
二、5-(9’-(3”,4”,5”-三癸烷氧基)苯-9’-对十六烷基苯基)硅芴基-15-(9’-(3”-十二烷基-5”-二十烷氧基)苯-9’-(3”-三十二烷基-4”-三十二烷氧基)苯)硅芴基卟啉的合成
搭好无水无氧装置,称取中间体2-醛-9-(3’,4’,5’-三癸烷氧基)苯-9-对十六烷基苯基硅芴(1.06g,1mmol)、2-醛-9-(3’-十二烷基-5’-二十烷氧基)-9-(3’-三十二烷基-4’-三十二烷氧基)苯硅芴(1.74g,1mmol)、二吡咯甲烷(0.30g,2mmol),溶解于250ml二氯甲烷中,通入氮气30min,注射器加入丙酸2ml,100℃下搅拌1h,然后加入二氯二氰基苯醌(DDQ)(1.82g,8mmol),继续在室温下搅拌30min,然后加入2ml吡啶淬灭反应,浓缩溶剂,过滤,收集滤液并旋干溶剂,用二氯甲烷在硅胶柱上快速淋洗,旋干溶剂,用乙醚/甲醇重结晶到产物,产率约为74%。
GC-MS(EI-m/z):3047(M+)
三、5,15-二溴-10-(9’-(3”,4”,5”-三癸烷氧基)苯-9’-对十六烷基苯基)硅芴基-20-(9’-(3”-十二烷基-5”-二十烷氧基)苯-9’-(3”-三十二烷基-4”-三十二烷氧基)苯)硅芴基卟啉的合成
搭好无水无氧装置,称取5-(9’-(3”,4”,5”-三癸烷氧基)苯-9’-对十六烷基苯基)硅芴基-15-(9’-(3”-十二烷基-5”-二十烷氧基)苯-9’-(3”-三十二烷基-4”-三十二烷氧基)苯)硅芴基卟啉(0.61g,0.2mmol)溶解于40ml四氢呋喃中,加入0.5ml三乙胺,将反应物降到0℃,加入N-溴代丁二酰亚胺(0.07g,0.4mmol),搅拌0.5h后,混合物升温至回流,然后继续搅拌1h后,加入5ml丙酮终止反应,除去溶剂,用乙醚/甲醇进行重结晶得到产物,产率82%。
GC-MS(EI-m/z):3204(M+)
四、5-(9’-(3”,4”,5”-三癸烷氧基)苯-9’-对十六烷基苯基)硅芴基-15-(9’-(3”-十二烷基-5”-二十烷氧基)苯-9’-(3”-三十二烷基-4”-三十二烷氧基)苯)硅芴基钴卟啉的合成
称取中间体5-(9’-(3”,4”,5”-三癸烷氧基)苯-9’-对十六烷基苯基)硅芴基-15-(9’-(3”-十二烷基-5”-二十烷氧基)苯-9’-(3”-三十二烷基-4”-三十二烷氧基)苯)硅芴基卟啉(0.64g,0.2mmol)溶解于50ml二氯甲烷中,加入CoCl2·6H2O(0.12g,0.5mmol)溶液(5ml),室温下搅拌12h,旋干溶剂,然后用二氯甲烷/石油醚(1/1)在硅胶柱上淋洗,收集并旋干溶剂得到产物,产率96%。
GC-MS(EI-m/z):3257(M+)
五、硅芴基钴卟啉-苯有机半导体材料的合成
在氮气保护下,加入1,4-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)苯(66mg,0.2mmol)、5,15-二溴-10-(9’-(3”,4”,5”-三癸烷氧基)苯-9’-对十六烷基苯基)硅芴基-20-(9’-(3”-十二烷基-5”-二十烷氧基)苯-9’-(3”-三十二烷基-4”-三十二烷氧基)苯)硅芴基钴卟啉(650mg,0.2mmol)和DMF溶剂80ml,抽真空除氧并充入氮气,然后加入Pd(OAc)2(2.5mg)/三环己基膦(6.5mg)和2ml 20%(wt)Et4NOH溶液,加热到80℃反应48h,得到硅芴基钴卟啉-苯有机半导体材料反应物混合液。
冷却至室温后将混合液滴加到250ml甲醇中进行沉降;抽滤,甲醇洗涤,干燥;然后用甲苯溶解,加入到二乙基二硫代氨基甲酸钠的水溶液中,然后将混合液加热到80℃搅拌过夜;将有机相通过氧化铝的柱层析,氯苯淋洗;减压除去有机溶剂,甲醇沉降;抽滤,所得固体用丙酮索氏提取三天;醇沉降,抽滤;真空泵下抽过夜得到硅芴基钴卟啉-苯有机半导体材料固体产物,产率83%.Molecular weight(GPC,THF,R.I):Mn=127100,Mw/Mn=3.96。
实施例6
本实施例公开一种结构如下的硅芴基锡卟啉-苯有机半导体材料
上式中,n=10;
上述有机半导体材料制备步骤如下:
一、1,4-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)苯的合成
其制备详见实施例1.
二、5-(9’-十六烷基-9’-(3”-甲基-4”-三十二烷氧基)苯)硅芴基-15-(9’-(3”,5”-二癸烷基)苯-9’-(3”-辛基-4”-十二烷氧基)苯)硅芴基卟啉的合成
搭好无水无氧装置,称取中间体2-醛-9-十六烷基-9-(3’-甲基-4’-三十二烷氧基)苯硅芴(0.99g,1mmol)、2-醛-9-(3’,5’-二癸烷基)苯-9-(3’-辛基-4’-十二烷氧基)苯硅芴(0.94g,1mmol)、二吡咯甲烷(0.30g,2mmol),溶解于250ml二氯甲烷中,通入氮气30min,注射器加入三氟乙酸2ml,100℃下搅拌1h,然后加入二氯二氰基苯醌(DDQ)(1.82g,8mmol),继续在室温下搅拌30min,然后加入2ml三乙胺淬灭反应,浓缩溶剂,过滤,收集滤液并旋干溶剂,用二氯甲烷在硅胶柱上快速淋洗,旋干溶剂,用乙醚/甲醇重结晶到产物,产率约为74%。
GC-MS(EI-m/z):2179(M+)
三、5,15-二溴-10-(9’-十六烷基-9’-(3”-甲基-4”-三十二烷氧基)苯)硅芴基-20-(9’-(3”,5”-二癸烷基)苯-9’-(3”-辛基-4”-十二烷氧基)苯)硅芴基卟啉的合成
搭好无水无氧装置,称取5-(9’-十六烷基-9’-(3”-甲基-4”-三十二烷氧基)苯)硅芴基-15-(9’-(3”,5”-二癸烷基)苯-9’-(3”-辛基-4”-十二烷氧基)苯)硅芴基卟啉(0.44g,0.2mmol)溶解于80ml邻二氯苯中,加入1ml吡啶,将反应物降到0℃,加入N-溴代丁二酰亚胺(0.07g,0.4mmol),搅拌0.5h后,混合物升温至120℃,然后继续搅拌1h后,加入5ml丙酮终止反应,除去溶剂,用乙醚/甲醇进行重结晶得到产物,产率85%。
GC-MS(EI-m/z):2337(M+)
四、5,15-二溴-10-(9’-十六烷基-9’-(3”-甲基-4”-三十二烷氧基)苯)硅芴基-20-(9’-(3”,5”-二癸烷基)苯-9’-(3”-辛基-4”-十二烷氧基)苯)硅锡卟啉的合成
N2氛围下,称取中间体5,15-二溴-10-(9’-十六烷基-9’-(3”-甲基-4”-三十二烷氧基)苯)硅芴基-20-(9’-(3”,5”-二癸烷基)苯-9’-(3”-辛基-4”-十二烷氧基)苯)硅芴基卟啉(0.47g,0.2mmol)溶解于50ml二氯甲烷中,加入含SnCl2(0.11g,0.6mmol)的乙醇溶液(5ml),室温下搅拌24h,旋干溶剂,然后用二氯甲烷/石油醚(1/1)在硅胶柱上淋洗,收集并旋干溶剂得到产物,产率95%。
GC-MS(EI-m/z):2451(M+)
五、10-(9’-十六烷基-9’-(3”-甲基-4”-三十二烷氧基)苯)硅芴基-20-(9’-(3”,5”-二癸烷基)苯-9’-(3”-辛基-4”-十二烷氧基)苯)硅芴基锡卟啉-苯有机半导体材料的合成(n=10)
在氮气保护下,加入1,4-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)苯(66mg,0.2mmol)、5,15-二溴-10-(9’-十六烷基-9’-(3”-甲基-4”-三十二烷氧基)苯)硅芴基-20-(9’-(3”,5”-二癸烷基)苯-9’-(3”-辛基-4”-十二烷氧基)苯)硅芴基锡卟啉(490mg,0.2mmol)和乙二醇二甲醚溶剂80ml,抽真空除氧并充入氮气,然后加入10mg Pd(PPh3)4和4ml K2CO3(5%)溶液,加热到80℃反应24h,得到硅芴基锡卟啉-苯有机半导体材料反应物混合液。
冷却至室温后将混合液滴加到250ml甲醇中进行沉降;抽滤,甲醇洗涤,干燥;然后用甲苯溶解,加入到二乙基二硫代氨基甲酸钠的水溶液中,然后将混合液加热到80℃搅拌过夜;将有机相通过氧化铝的柱层析,氯苯淋洗;减压除去有机溶剂,甲醇沉降;抽滤,所得固体用丙酮索氏提取三天;甲醇沉降,抽滤;真空泵下抽过夜得到硅芴基锡卟啉-苯有机半导体材料固体产物,产率72%.Molecular weight(GPC,THF,R.I):Mn=23700,Mw/Mn=2.86。
本发明还提供了结构式为(式中:n为1-100间的整数,R1,R2,R3,R4为H、C1-C32的烷基、苯基、含有一个或多个C1-C32的烷基苯基或烷氧基苯基;M为金属离子)的硅芴基金属卟啉-苯有机半导体材料在聚合物太阳能电池,有机电致发光,有机场效应晶体管,有机光存储,有机非线性器件和有机激光器件等领域中的应用。
以下实施例是硅芴基金属卟啉-苯有机半导体材料在有机太阳能电池,有机场效应晶体管,有机电致发光器件中的应用。
实施例7
以实施例1中的硅芴基金属卟啉-苯有机半导体材料为活性层材料的有机太阳能电池器件
一种有机太阳能电池器件,其结构如图1所示。其中,本实施例中的衬底采用ITO玻璃,玻璃作为衬底基材,ITO作为导电层。
该有机太阳能电池器件的结构为:玻璃11/ITO层12/PEDOT:PSS层13/活性层14/Al层15;其中,活性层的材质为混合物,包括电子给体材料,PCBM为电子受体材料;电子给体材料以实施例1中的硅芴基金属卟啉-苯有机半导体材料为材质,电子受体材料为[6,6]苯基-C61-丁酸甲酯(简称PCBM);ITO是方块电阻为10-20Ω/口的氧化铟锡,PEDOT为聚(3,4-亚乙二氧基噻吩),PSS为聚(苯乙烯磺酸);优选方块电阻为18Ω/口的ITO。
该有机太阳能电池器件的制备过程为:
在玻璃基片11的一个表面沉积一层方块电阻为10-20Ω/口的氧化铟锡(ITO)层12,形成作为阳极的导电层,厚度约为50-300nm;
ITO玻璃经过超声波清洗,并用氧-Plasma处理后,在ITO表面涂上一层起修饰作用的PEDOT:PSS层13,厚度为20-300nm;
在聚(3,4-亚乙二氧基噻吩):PSS为聚(苯乙烯磺酸)层上采用旋涂技术涂覆一层活性层14,厚度为50-300nm,该活性层的材质以实施例1中的硅芴基金属卟啉-苯有机半导体材料和[6,6]苯基-C61-丁酸甲酯(简称PCBM)的混合物;
在活性层的表面真空蒸镀金属铝,形成作为阴极的金属铝层15,得到有机太阳能电池器件;
将有机太阳能电池器件用环氧树脂封装后,置于110℃密闭条件下退火1.5小时,再降到室温。由于器件经过退火后,材料的化学结构更加规整有序,提高了载流子的传输速度和效率,从而提高了器件的光电转换效率。
优选ITO、PEDOT:PSS层、活性层、Al层的厚度分别为150nm、50nm、120nm、100nm。
实施例8
以实施例1中的硅芴基金属卟啉-苯有机半导体材料为材质的机电致发光器件
一种有机电致发光器件,其结构如图2所示;本实施例中的衬底采用ITO玻璃,玻璃作为衬底基材,ITO作为导电层。
该有机电致发光器件的结构为:玻璃21/ITO层22/发光层23/LiF缓冲层24/Al层25;其中:发光层以实施例1中的硅芴基金属卟啉-苯有机半导体材料为材质。
该有机电致发光器件的制备过程为:
在玻璃基片21的一个表面沉积一层方块电阻为10-20Ω/口的氧化铟锡(ITO)层22,形成作为阳极的导电层,厚度为50-300nm;优选方块电阻为10Ω/口的ITO。
通过旋涂技术在ITO表面制备一层以实施例1中的硅芴基金属卟啉-苯有机半导体材料为材质的发光层23,厚度约为50-300nm;
在发光层上真空蒸镀LiF,作为缓冲层14,厚度约为0.3-2nm;
在所述发光层上真空蒸镀金属铝,形成作为阴极的金属铝层25,得到所述有机电致发光器件。
实施例9
以含实施例一中的实施例一中的硅芴基金属卟啉-苯有机半导体材料为材质的有机场效应晶体管
一种有机场效应晶体管,其结构如图3所示;本实施例中的衬底采用掺杂硅片(Si)作为衬底。
该有机场效应晶体管的结构为:Si 31/450nm厚的SiO2绝缘层32/用于修饰SiO2的十八烷基三氯硅烷(OTS)层33/有机半导体层34/以金为材质的源电极(S)35和漏电极(D)36;其中,有机半导体层以实施例1中的硅芴基金属卟啉-苯有机半导体材料为材质;其中,源电极(S)和漏电极(D)材质也可以选用铜材。
该有机场效应晶体管的制备过程为:
首先,在清洗过后的掺杂硅片31的一个表面上涂覆一层450nm厚的SiO2绝缘层32;其次,在所述SiO2绝缘层上涂覆一层起修饰作用的十八烷基三氯硅烷层33,厚度为10-200nm;接着,在所述十八烷基三氯硅烷层上旋涂一层以实施例1中的硅芴基金属卟啉-苯有机半导体材料为材质的有机半导体层34,厚度约为30-300nm;最后,在所述有机半导体层上间隔设置有以金但不仅限于金为材质的源电极(S)35和漏电极(D)36,得到所述有机场效应晶体管。
应当理解的是,上述针对本发明较佳实施例的表述较为详细,并不能因此而认为是对本发明专利保护范围的限制,本发明的专利保护范围应以所附权利要求为准。
Claims (9)
1.具有如下通式(I)的硅芴基金属卟啉-苯有机半导体材料:
式中:n为1-100间的整数,R1,R2,R3,R4分别为H、C1-C32的烷基、苯基、含有一个或多个C1-C32的烷基苯基或烷氧基苯基;M为金属离子。
2.根据权利要求1所述的硅芴基金属卟啉-苯有机半导体材料,其特征在于,所述金属离子为Zn2+、Cu2+、Fe2+、Co2+、Cd2+、Pt2+、Zr2+、Mn2+、Ni2+、Pb2+、Sn2+。
3.一种硅芴基金属卟啉-苯有机半导体材料的制备方法,其特征在于,所述制备方法包括如下步骤:
步骤S1、氧化剂、第一催化剂存在条件下,将结构式为的二吡咯甲烷、结构式为的第一硅芴衍生物以及结构式为的第二硅芴衍生物溶于第一有机溶剂,于20-100℃温度下,反应1-24小时,得到结构式为的硅芴基卟啉衍生物;式中,R1,R2,R3,R4分别为H、C1-C32的烷基、苯基、含有一个或多个C1-C32的烷基苯基或烷氧基苯基;所述氧化剂为二氯二氰基苯醌,所述第一催化剂为丙酸或三氟乙酸,所述第一有机溶剂为三氯甲烷、二氯甲烷中的一种或两种;
步骤S2、将步骤S1中得到的硅芴基卟啉衍生物和溴化剂加入到第二有机溶剂中,于0~120℃下反应1~72小时,得到结构式为的二溴硅芴基卟啉衍生物;所述溴化剂为N-溴代丁二酰亚胺,所述第二有机溶剂为四氢呋喃、氯仿、二甲基酰胺或邻二氯苯中的至少一种;
步骤S3、将步骤S2中得到的二溴硅芴基卟啉衍生物溶于第三有机溶剂中,接着加入含M金属离子的溶液,于0-30℃下搅拌0.5-24小时,得到结构式为的二溴硅芴基金属卟啉衍生物;所述第三有机溶剂为三氯甲烷、四氢呋喃、苯、甲苯或二氯甲烷中的至少一种;
步骤S4、无氧环境中,第二催化剂和第四有机溶剂存在条件下,将步骤S3中得到的二溴硅芴基金属卟啉衍生物和结构式为的1,4-对二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)苯按摩尔比1:2~2:1,于50-120℃中进行Suzuki耦合反应12~72小时,得到结构式为的所述硅芴基金属卟啉-苯有机半导体材料,式中,n为1-100间的整数;所述第二催化剂为有机钯或有机钯与有机膦配体的混合物,所述第四有机溶剂为四氢呋喃、二氯甲烷、氯仿、二氧六环、二甲基酰胺、乙二醇二甲醚、二甲基亚砜、苯、氯苯或甲苯中的至少一种。
4.根据权利要求3所述的制备方法,其特征在于,所述步骤S2中,所述硅芴基卟啉衍生物和溴化剂的用量摩尔比为1:2~1:5。
5.根据权利要求3所述的制备方法,其特征在于,所述步骤S3中,所述二溴硅芴基卟啉衍生物和M离子的摩尔比为1:1~1:5;所述含M金属离子的溶液中,M金属离子选自Zn2+、Cu2+、Fe2+、Co2+、Cd2+、Pt2+、Zr2+、Mn2+、Ni2+、Pb2+或Sn2+中的一种,溶剂为甲醇、乙醇或水中的至少一种。
6.根据权利要求3所述的制备方法,其特征在于,所述步骤S4中;
所述有机钯为Pd2(dba)3、Pd(PPh3)4、Pd(OAc)2或Pd(PPh3)2Cl2;
所述有机膦配体为P(o-Tol)3、三环己基膦。
7.根据权利要求3所述的制备方法,其特征在于,所述步骤S4中,还包括1,4-对二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)苯的制备,其制备步骤如下:
将结构式为对二溴苯加入第五有机溶剂中,用液氮/异丙醇降温至-78℃,然后滴加正丁基锂,并在-78℃反应1-3小时,再加入结构式为的2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷,继续在-78℃下反应0.5-2小时,然后自然升温至室温,反应6-36小时,得到所述1,4-对二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)苯;所述第五有机溶剂中为四氢呋喃、乙醚或者二氧六环中的至少一种。
8.根据权利要求7所述的制备方法,其特征在于,所述对二溴苯与2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷的摩尔比1:2~5。
9.一种如权利要求1所述的硅芴基金属卟啉-苯有机半导体材料在有机太阳能电池,有机电致发光器件,有机场效应晶体管,有机光存储,有机非线性器件和有机激光器件领域中的应用。
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