CN103080183B - 含芴有机半导体材料,其制备方法和应用 - Google Patents
含芴有机半导体材料,其制备方法和应用 Download PDFInfo
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- CN103080183B CN103080183B CN201080068946.1A CN201080068946A CN103080183B CN 103080183 B CN103080183 B CN 103080183B CN 201080068946 A CN201080068946 A CN 201080068946A CN 103080183 B CN103080183 B CN 103080183B
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- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 239000000463 material Substances 0.000 title claims abstract description 123
- 239000004065 semiconductor Substances 0.000 title claims abstract description 107
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 38
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 33
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 30
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical compound CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 229960001701 chloroform Drugs 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 10
- 230000005669 field effect Effects 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- MRWWWZLJWNIEEJ-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-propan-2-yloxy-1,3,2-dioxaborolane Chemical compound CC(C)OB1OC(C)(C)C(C)(C)O1 MRWWWZLJWNIEEJ-UHFFFAOYSA-N 0.000 claims description 6
- BRUOAURMAFDGLP-UHFFFAOYSA-N 9,10-dibromoanthracene Chemical compound C1=CC=C2C(Br)=C(C=CC=C3)C3=C(Br)C2=C1 BRUOAURMAFDGLP-UHFFFAOYSA-N 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000006539 C12 alkyl 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])C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- GMQUEDBQYNHEEM-UHFFFAOYSA-N [B].[B].CC(C)(O)C(C)(C)O.CC(C)(O)C(C)(C)O Chemical compound [B].[B].CC(C)(O)C(C)(C)O.CC(C)(O)C(C)(C)O GMQUEDBQYNHEEM-UHFFFAOYSA-N 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 150000002220 fluorenes Chemical class 0.000 claims description 3
- 230000003287 optical effect Effects 0.000 claims description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 13
- 229910052763 palladium Inorganic materials 0.000 claims 5
- 239000003446 ligand Substances 0.000 claims 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 3
- 229910052698 phosphorus Inorganic materials 0.000 claims 3
- 239000011574 phosphorus Substances 0.000 claims 3
- DKYVUZCAWAPRHD-UHFFFAOYSA-N 1,3-bis(5-bromothiophen-2-yl)thieno[3,4-c]pyrrole-4,6-dione Chemical compound S1C(Br)=CC=C1C1=C2C(=O)NC(=O)C2=C(C=2SC(Br)=CC=2)S1 DKYVUZCAWAPRHD-UHFFFAOYSA-N 0.000 claims 1
- 125000002877 alkyl aryl group Chemical group 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims 1
- 230000031700 light absorption Effects 0.000 abstract description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 62
- 238000006243 chemical reaction Methods 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000007787 solid Substances 0.000 description 16
- -1 5-bromothienyl Chemical group 0.000 description 14
- 239000000126 substance Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000001704 evaporation Methods 0.000 description 10
- 239000000499 gel Substances 0.000 description 10
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 239000012528 membrane Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000003643 water by type Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 8
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 125000005577 anthracene group Chemical group 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 0 CC(C)*(C)*1c[b]1B1OC(C)(C)C(C)(C)O1 Chemical compound CC(C)*(C)*1c[b]1B1OC(C)(C)C(C)(C)O1 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 229920000547 conjugated polymer Polymers 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- PYJJCSYBSYXGQQ-UHFFFAOYSA-N trichloro(octadecyl)silane Chemical compound CCCCCCCCCCCCCCCCCC[Si](Cl)(Cl)Cl PYJJCSYBSYXGQQ-UHFFFAOYSA-N 0.000 description 3
- ICMWJLGQHVDYNU-UHFFFAOYSA-N 1,3-bis(5-bromothiophen-2-yl)-5-(2-ethylhexyl)thieno[3,4-c]pyrrole-4,6-dione Chemical compound C=12C(=O)N(CC(CC)CCCC)C(=O)C2=C(C=2SC(Br)=CC=2)SC=1C1=CC=C(Br)S1 ICMWJLGQHVDYNU-UHFFFAOYSA-N 0.000 description 2
- VLXLDDMOTRSMIK-UHFFFAOYSA-N 9,10-dibromo-1,4-dimethoxyanthracene Chemical compound C1=CC=C2C(Br)=C3C(OC)=CC=C(OC)C3=C(Br)C2=C1 VLXLDDMOTRSMIK-UHFFFAOYSA-N 0.000 description 2
- ZOTTUTXRNZTIRX-UHFFFAOYSA-N 9,10-dibromo-2,6-bis(2-octyldecyl)anthracene Chemical compound C1=C(CC(CCCCCCCC)CCCCCCCC)C=CC2=C(Br)C3=CC(CC(CCCCCCCC)CCCCCCCC)=CC=C3C(Br)=C21 ZOTTUTXRNZTIRX-UHFFFAOYSA-N 0.000 description 2
- RWOOWSACFPOUJD-UHFFFAOYSA-N 9,10-dibromo-2-fluoroanthracene Chemical compound C1=CC=CC2=C(Br)C3=CC(F)=CC=C3C(Br)=C21 RWOOWSACFPOUJD-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- GDLVZVSBCXPZND-UHFFFAOYSA-N 1,3-bis(5-bromothiophen-2-yl)-5-methylthieno[3,4-c]pyrrole-4,6-dione Chemical compound C=12C(=O)N(C)C(=O)C2=C(C=2SC(Br)=CC=2)SC=1C1=CC=C(Br)S1 GDLVZVSBCXPZND-UHFFFAOYSA-N 0.000 description 1
- KGNNFMJUDQDWPU-UHFFFAOYSA-N 1,3-bis(5-bromothiophen-2-yl)-5-octylthieno[3,4-c]pyrrole-4,6-dione Chemical compound C=12C(=O)N(CCCCCCCC)C(=O)C2=C(C=2SC(Br)=CC=2)SC=1C1=CC=C(Br)S1 KGNNFMJUDQDWPU-UHFFFAOYSA-N 0.000 description 1
- CYKLQIOPIMZZBZ-UHFFFAOYSA-N 2,7-dibromo-9,9-dioctylfluorene Chemical compound C1=C(Br)C=C2C(CCCCCCCC)(CCCCCCCC)C3=CC(Br)=CC=C3C2=C1 CYKLQIOPIMZZBZ-UHFFFAOYSA-N 0.000 description 1
- QOCAIMMQZQRZFJ-UHFFFAOYSA-N BC(C=CC1C(C=C2)=C3CC2Br)=CC1C3(C)N Chemical compound BC(C=CC1C(C=C2)=C3CC2Br)=CC1C3(C)N QOCAIMMQZQRZFJ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N Methyl butyrate Chemical class CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 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
- 238000002835 absorbance Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- 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
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/115—Polyfluorene; Derivatives thereof
-
- 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
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/12—Copolymers
- C08G2261/124—Copolymers alternating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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Abstract
提供一种含芴有机半导体材料,其制备方法和应用。所述含芴有机半导体材料具有以下通式(P);式中,n为1~100之间的整数;m为1~20的整数;x、y为正实数值,且x+y=1;R1、R2分别为氢原子、氟原子、氰基、C1~C40的直链或带支链的烷基或烷氧基、芳基、或杂芳基;R3为氢原子、C1~C20的烷基。该含芴有机半导体材料载流子迁移率高,吸光度强,对光吸收范围宽,提高了其对太阳光的利用率。
Description
技术领域
本发明涉及一种共聚物有机半导体材料,更具体的涉及一类含芴有机半导体材料。
本发明还涉及一类含芴有机半导体材料的制备方法及其应用。
背景技术
高效率太阳能电池通常是以无机半导体为原料,但目前市场上主要的硅晶太阳能电池由于生产过程工艺复杂,污染严重,耗能大,成本高,抑制了其商业化应用的发展。因此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。而有机半导体材料一方面由于有机材料的环境稳定性好、制备成本低、功能易于调制、柔韧性及成膜性都较好;另一方面由于有机太阳能电池加工过程相对简单,可低温操作,器件制作成本也较低等优点而备受关注,成为廉价和有吸引力的太阳能电池材料。除此之外,有机太阳能电池的潜在优势还包括:可实现大面积制造、可使用柔性衬底、环境友好、轻便易携等。
虽然有机太阳能电池得到了较快的发展,但是仍比无机太阳能电池的转换效率低得多,限制其性能提高的主要制约因素有:有机半导体器件相对较低的载流子迁移率,器件的光谱响应与太阳辐射光谱不匹配,高光子通量的红光区没有被有效利用以及载流子的电极收集效率低等。为了使有机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。
芴由于具有平面分子特性,结构较为刚性,因此化学性质稳定;并且可通过化学反应在9位上引入其它支链,2、7位上易进行过渡金属交叉偶联,因此具有很好的化学可修饰性;另外它还具有相对较宽的带隙和较低的HOMO能级,优良的量子效率、空穴传输性能和成膜性,因此芴及其衍生物被广泛应用于光电材料的研究。
蒽及其衍生物具有很好的稳定性和较好的成膜性;其紫外可见光谱呈现出较宽的手指峰吸收,有利于提高对太阳光的吸收覆盖范围;并且它具有适当的载流子传输特性,其晶体室温下空穴迁移率可达3cm2/V·s,是一类优异的有机半导体材料。虽然蒽及其衍生物作为有机电致发光材料的报道已有很多,但作为有机光伏材料的研究却鲜有报道,这就大大限制了它的应用范围。
而噻吩并[3,4-c]吡咯-4,6-二酮的结构简单,分子中原子位置相对紧凑,且结构具有对称性,当作为含芴有机半导体材料共轭聚合物单元时,也有很强的吸电子作用。通过在吡咯环上增加烷烃链,也能很好地增加含芴有机半导体材料共轭聚合物的溶解性和加工性。目前,它在有机光电研究领域具有广泛的应用前景。
发明内容
本发明的目的在于提供一类含芴有机半导体材料,用于解决上述问题。
本发明的目的还在于提供一类含芴有机半导体材料的制备方法,以及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,有机非线性器件和有机激光器件等领域中的应用。
本发明所述的一类含芴有机半导体材料具有以下通式(P):
式中,n为1~100之间的整数;m为1~20的整数;优选m的取值范围为:6~12的整数;
x、y为正实数值,且x+y=1;且x+y=1;x、y的数值由三种单元体的投料比决定;
R1、R2出现时可相同或不同,彼此独立地表示单取代或多取代的官能团,选自氢原子、氟原子、氰基、C1~C40的直链或带支链的烷基或烷氧基、芳基、或杂芳基;优选R1、R2分别为具有C1~C18的直链或带支链的烷基或烷氧基;
R3为氢原子、C1~C20的烷基;优选,R3为C1~C12的烷基。
本发明所设计的一类含芴有机半导体材料,其制备方案如下:
步骤一:在无水无氧反应条件下,将2,7-二溴-9,9-二烷基芴和正丁基锂(n-BuLi,下同)或叔丁基里(t-BuLi)在-70℃~-85℃下以摩尔比1∶2~4加入至第二溶剂中,然后加入2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷或双频哪醇合二硼,进行缩合反应12~48小时,得到产物,即2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二烷基芴;其中,第二溶剂为四氢呋喃、***、二氯甲烷、三氯甲烷或乙酸乙酯中的至少一种;2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷或双频哪醇合二硼的摩尔用量为2,7-二溴-9,9-二烷基芴的2~4倍;缩合反应式如下:
步骤二:在无氧环境中,将结构式为的2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二烷基芴、结构式为的9,10-二溴蒽或其衍生物、结构式为的1,3-二(5-溴噻吩基)-噻吩并[3,4-c]吡咯-4,6-二酮或其衍生物按摩尔比i∶j∶k混合,且i=j+k,i,j,k为正实数,在70~100℃、催化剂、碱液和第一溶剂存在下,进行Suzuki反应24~72小时,得到结构式为的所述含芴有机半导体材料;其中,催化剂为Pd(PPh3)4、Pd(OAc)2、三环己基膦、Pd2(dba)3/P(o-Tol)3或Pd(PPh3)2Cl2;碱液为NaOH水溶液、Na2CO3水溶液、NaHCO3水溶液或四乙基氢氧化铵水溶液,第一溶剂为甲苯、乙二醇二甲醚、四氢呋喃、***、二氯甲烷、三氯甲烷或乙酸乙酯等,催化剂的用量为2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二烷基芴摩尔量的0.01%~20%,碱的用量为2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二烷基芴摩尔量的2~20倍;Suzuki反应式如下:
本发明与现有技术相比至少具备以下优点:
1.本发明的有机半导体材料分子中引入了蒽以及1,3-二(5-溴噻吩基)-噻吩并[3,4-c]吡咯-4,6-二酮基团,明显改善了其载流子迁移性能和光吸收范围;
2.本发明的有机半导体材料分子中含有蒽单元,由于其良好的平面度和共轭度,从而提高了其载流子迁移率,同时,1,3-二(5-溴噻吩基)-噻吩并[3,4-c]吡咯-4,6-二酮上的5位引入了烷基等修饰,提高了其溶解性,从而提高了其加工性能;
3.1,3-二(5-溴噻吩基)-噻吩并[3,4-c]吡咯-4,6-二酮的结构简单,分子中原子位置相对紧凑,且结构具有对称性,当作为含芴有机半导体材料共轭聚合物单元时,具有很强的吸电子作用。采用1,3-二(5-溴噻吩基)-噻吩并[3,4-c]吡咯-4,6-二酮单元以及蒽单元与芴单元共聚,有效调节该有机半导体材料的带隙,并将其吸收带边推向红外及近红外区,使其吸光度强,对光吸收范围宽,提高了其对太阳光的利用率,同时,使得该有机半导体材料溶解性能和电荷传输性能优异;
4.该有机半导体材料制备方法工艺简单,产率高,反应条件温和,易于操作和控制,适合于工业化生产。
附图说明
图1为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的结构示意图。
具体实施方式
本发明提供的一类含芴有机半导体材料,具有以下通式(P):
式中,n为1~100之间的整数;m为1~20的整数;优选m的取值范围为:6~12的整数
x、y为正实数值,且x+y=1;且x+y=1;x、y的数值由2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二烷基芴,9,10-二溴蒽,1,3-二(5-溴噻吩基)-噻吩并[3,4-c]吡咯-4,6-二酮三种单元体的投料比决定;
R1、R2出现时可相同或不同,彼此独立地表示单取代或多取代的官能团,选自氢原子、氟原子、氰基、C1~C40的直链或带支链的烷基或烷氧基、芳基、或杂芳基;优选R1、R2分别为具有C1~C18的直链或带支链的烷基或烷氧基;
R3为氢原子、C1~C20的烷基;优选,R3为C1~C12的烷基。
一类含芴有机半导体材料,其制备方案如下:
步骤S1:在无水无氧反应条件下,将2,7-二溴-9,9-二烷基芴和正丁基锂在-70℃~-85℃下以摩尔比1∶2~4加入至第二溶剂中,然后加入2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷或双频哪醇合二硼(其摩尔用量为2,7-二溴-9,9-二烷基芴的2~4倍),反应12~48小时,得到产物,即2,7-双(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷基)-9,9-二烷基芴;其中,第二溶剂为四氢呋喃、***、二氯甲烷、三氯甲烷或乙酸乙酯中的至少一种,其反应式如下:
步骤S2:在无氧环境中,将2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二烷基芴、9,10-二溴蒽或其衍生物、1,3-二(5-溴噻吩基)-噻吩并[3,4-c]吡咯-4,6-二酮或其衍生物按摩尔比i∶j∶k混合,且满足i=j+k,i,j,k为正实数,在70~100℃、催化剂、碱液和第一溶剂下进行Suzuki反应24~72小时,得到含芴有机半导体材料聚合物;其中,催化剂为Pd(PPh3)4、Pd(OAc)2、三环己基膦、Pd2(dba)3/P(o-Tol)3或Pd(PPh3)2Cl2;碱液为NaOH水溶液、Na2CO3水溶液、NaHCO3水溶液或四乙基氢氧化铵水溶液,第一溶剂为甲苯、乙二醇二甲醚、四氢呋喃、***、二氯甲烷、三氯甲烷或乙酸乙酯等,催化剂的用量为2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二烷基芴摩尔量的0.01%~20%,碱的用量为2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二烷基芴摩尔量的2~20倍;其反应式如下:
本发明的无氧环境是由氮气(N2)和/或惰性气体混合构成。
本发明开发了一种含芴的有机半导体材料,并将其应用于有机太阳能电池等领域。该材料具有较低的能隙,较高的迁移率,光谱的吸收范围宽,并且这种材料有利于载流子在活性层材料内部更为有效地传递。将本发明中的材料作为活性材料制备的有机太阳能电池,经过高温退火后,能有效增加分子内各基团和分子链段间排列的有序性和规整度,提高载流子迁移率的传输速度和效率,进而提高光电转换效率。
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
本实施例公开结构如下的含芴有机半导体材料聚合物P1、P2:
P1、P2的制备步骤如下:
步骤一、2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二辛基芴的制备:
搭好无水无氧反应装置,在不断搅拌和N2的保护下,往三口瓶中加入白色的2,7-二溴-9,9-二辛基芴9.0mmol,用注射器注入150ml精制的四氢呋喃溶剂,在-78℃条件下再用注射器慢慢注入27.0mmol n-BuLi,搅拌反应2小时。反应2小时后,在-78℃条件下用注射器注入30.6mmol2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷,升温到室温反应过夜。
反应结束后,加入饱和NaCl水溶液,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(v/v=15∶1)为淋洗液进行硅胶柱层析分离,得到粉末状固体2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二辛基芴,产率65%。GC-MS(EI-m/z):642(M+)。
步骤二、P1、P2的制备:
在反应器中加入2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二辛基芴1mmol、9,10-二溴蒽0.1mmol、1,3-二(5-溴噻吩基)-噻吩并[3,4-c]吡咯-4,6-二酮0.9mmol、Pd2(dba)30.025mmol、P(o-Tol)30.050mmol、2mol/L的Na2CO3水溶液5ml和甲苯溶剂30ml,通过反复进行通N2和抽真空使反应体系处于无氧状态,在70℃条件下反应70h。
反应70h后,往产物的反应瓶中加入去离子水和甲苯进行萃取,取有机相,用减压蒸馏的方法将含芴有机半导体材料聚合物/甲苯溶液蒸干至约5ml左右,将其滴入到300ml无水甲醇中不断搅拌,并有固体沉淀析出,经过抽滤、烘干后得到固体粉末。再将固体粉末用氯仿溶解,用中性氧化铝过层析柱,除去催化剂Pd2(dba)3/P(o-Tol)3,最后将含芴有机半导体材料聚合物/氯仿溶液旋蒸至剩5ml左右,将其滴入甲醇溶剂中并搅拌数小时,最后将含芴有机半导体材料聚合物P1收集烘干。用索氏抽提器将含芴有机半导体材料聚合物抽提,从而提高含芴有机半导体材料聚合物分子量的单分散性。
采用Waters Breeze凝胶色谱仪,将提纯后的含芴有机半导体材料聚合物P1溶于精制后的四氢呋喃配成1mg/1mL溶液,用仪器专用配套滤膜滤掉不溶物后以10微升量,1ml/min的进样速度进行GPC测试,数均分子量Mn≈69000,含芴有机半导体材料聚合物单分散性为1.31,n为100。
在反应器中加入2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二辛基芴1mmol、9,10-二溴蒽0.5mmol、1,3-二(5-溴噻吩基)-噻吩并[3,4-c]吡咯-4,6-二酮0.5mmol,其它物体投料量、反应条件和后处理方法均不变,则最终得到含芴有机半导体材料聚合物P2。采用Waters Breeze凝胶色谱仪,将提纯后的含芴有机半导体材料聚合物P2溶于精制后的四氢呋喃配成1mg/1mL溶液,用仪器专用配套滤膜滤掉不溶物后以10微升量,1ml/min的进样速度进行GPC测试,数均分子量Mn≈41200,含芴有机半导体材料聚合物单分散性为1.46,n为65。
实施例2
本实施例公开结构如下的含芴有机半导体材料聚合物P3、P4:
P3、P4的制备步骤如下:
步骤一、2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二己基芴的制备:
其制备过程参考实施例1中的步骤一,只是用氩气来构建无氧环境保护气氛。
步骤三、P3、P4的制备:
在反应器中加入2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二己基芴1mmol、9,10-二溴-2,6-二(2-辛基癸基)蒽0.8mmol(该化合物合成方法参见KlausMullen等人的Macromol.Chem.Phys.2006,207,1107-1115)、1,3-二(5-溴噻吩基)-5-甲基-噻吩并[3,4-c]吡咯-4,6-二酮0.2mmol、Pd(OAc)23mg、2mol/L的Na2CO3水溶液10ml和甲苯溶剂40ml,通过反复进行通氩气和抽真空使反应体系处于无氧状态,在100℃条件下反应24h。
反应24h后,往反应瓶中加入去离子水和甲苯进行萃取,取有机相,用减压蒸馏的方法将含芴有机半导体材料聚合物/甲苯溶液蒸干至少量,将其滴入到300ml无水甲醇中不断搅拌,有固体沉淀析出,经过抽滤、烘干后得到固体粉末。再将固体粉末用氯仿溶解,用中性氧化铝过层析柱,除去催化剂Pd(OAc)2,最后将含芴有机半导体材料聚合物/氯仿溶液旋蒸至剩5ml左右,将其滴入甲醇溶剂中并搅拌数小时,最后将含芴有机半导体材料聚合物P3收集烘干。用索氏抽提器将含芴有机半导体材料聚合物抽提,从而提高含芴有机半导体材料聚合物分子量的单分散性。
采用Waters Breeze凝胶色谱仪,将提纯后的含芴有机半导体材料聚合物P3溶于精制后的四氢呋喃配成1mg/1mL溶液,用仪器专用配套滤膜滤掉不溶物后以10微升量,1ml/min的进样速度进行GPC测试,数均分子量Mn≈35800,含芴有机半导体材料聚合物单分散性为1.87,n为38。
在反应器中加入2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二己基芴1mmol、9,10-二溴-2,6-二(2-辛基癸基)蒽0.2mmol、1,3-二(5-溴噻吩基)-5-甲基-噻吩并[3,4-c]吡咯-4,6-二酮0.8mmol,其它物体投料量、反应条件和后处理方法均不变,则最终得到含芴有机半导体材料聚合物P4。采用Waters Breeze凝胶色谱仪,将提纯后的含芴有机半导体材料聚合物P4溶于精制后的四氢呋喃配成1mg/1mL溶液,用仪器专用配套滤膜滤掉不溶物后以10微升量,1ml/min的进样速度进行GPC测试,数均分子量Mn≈31500,含芴有机半导体材料聚合物单分散性为2.03,n为43。
实施例3
本实施例公开结构如下的含芴有机半导体材料聚合物P5、P6:
P5、P6的制备步骤如下:
步骤一、2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二(十二烷基)芴的制备:
其制备过程参考实施例1中的步骤一,只是用氮气和氩气混合气构建无氧环境保护气氛。
步骤二、P5、P6的制备:
在反应器中加入2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二(十二烷基)芴1mmol、9,10-二溴-2-氟蒽0.5mmol(该化合物的合成方法参见ElimelechRochlin等人的J.Org.Chem.,2003,68,216-226)、1,3-二(5-溴噻吩基)-5-辛基-噻吩并[3,4-c]吡咯-4,6-二酮0.5mmol、Pd(PPh3)40.02mmol、2mol/L的Na2CO3水溶液10ml和甲苯溶剂40ml,通过反复进行通通氮气和氩气混合气,并抽真空使反应体系处于无氧状态,在80℃条件下反应58h。
反应58h后,往反应瓶中加入去离子水和甲苯进行萃取,取有机相,用减压蒸馏的方法将含芴有机半导体材料聚合物/甲苯溶液蒸干至少量,将其滴入到300ml无水甲醇中不断搅拌,有固体沉淀析出,经过抽滤、烘干后得到固体粉末。再将固体粉末用氯仿溶解,用中性氧化铝过层析柱,除去催化剂Pd(PPh3)4,最后将含芴有机半导体材料聚合物/氯仿溶液旋蒸至剩5ml左右,将其滴入甲醇溶剂中并搅拌数小时,最后将含芴有机半导体材料聚合物P5收集烘干。用索氏抽提器将含芴有机半导体材料聚合物抽提,从而提高含芴有机半导体材料聚合物分子量的单分散性。
采用Waters Breeze凝胶色谱仪,将提纯后的含芴有机半导体材料聚合物P5溶于精制后的四氢呋喃配成1mg/1mL溶液,用仪器专用配套滤膜滤掉不溶物后以10微升量,1ml/min的进样速度进行GPC测试,数均分子量Mn≈20300,含芴有机半导体材料聚合物单分散性为2.33,n为25。在反应器中加入2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二(十二烷基)芴1mmol、9,10-二溴-2-氟蒽0.6mmol、1,3-二(5-溴噻吩基)-5-辛基-噻吩并[3,4-c]吡咯-4,6-二酮0.4mmol,其它物体投料量、反应条件和后处理方法均不变,则最终得到含芴有机半导体材料聚合物P6。采用Waters Breeze凝胶色谱仪,将提纯后的含芴有机半导体材料聚合物P6溶于精制后的四氢呋喃配成1mg/1mL溶液,用仪器专用配套滤膜滤掉不溶物后以10微升量,1ml/min的进样速度进行GPC测试,数均分子量Mn≈21300,含芴有机半导体材料聚合物单分散性为2.16,n为27。
实施例4
本实施例公开结构如下的含芴有机半导体材料聚合物P7、P8:
P7、P8的制备步骤如下:
步骤一、2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二癸基芴的制备:
其制备过程参考实施例1中的步骤一。
步骤二、P7、P8的制备:
在反应器中加入2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二癸基芴1mmol、9,10-二溴-1,4-二甲氧基蒽0.5mmol(该化合物的合成方法参见OsmanCakmak等人的J.Org.Chem.,2006,71,1795-1801)、1,3-二(5-溴噻吩基)-5-(2-乙基己基)-噻吩并[3,4-c]吡咯-4,6-二酮0.5mmol、三环己基膦5mg、2mol/L的Na2CO3水溶液10ml和甲苯溶剂50ml,通过反复进行通N2和抽真空使反应体系处于无氧状态,在90℃条件下反应64h。
反应64h后,往反应瓶中加入去离子水和甲苯进行萃取,取有机相,用减压蒸馏的方法将含芴有机半导体材料聚合物/甲苯溶液蒸干至少量,将其滴入到300ml无水甲醇中不断搅拌,有固体沉淀析出,经过抽滤、烘干后得到固体粉末。再将固体粉末用氯仿溶解,用中性氧化铝过层析柱,除去催化剂三环己基膦,最后将含芴有机半导体材料聚合物/氯仿溶液旋蒸至剩5ml左右,将其滴入甲醇溶剂中并搅拌数小时,最后将含芴有机半导体材料聚合物P7收集烘干。用索氏抽提器将含芴有机半导体材料聚合物抽提,从而提高含芴有机半导体材料聚合物分子量的单分散性。
采用Waters Breeze凝胶色谱仪,将提纯后的含芴有机半导体材料聚合物P7溶于精制后的四氢呋喃配成1mg/1mL溶液,用仪器专用配套滤膜滤掉不溶物后以10微升量,1ml/min的进样速度进行GPC测试,数均分子量Mn≈56700,含芴有机半导体材料聚合物单分散性为1.43,n为73。
在反应器中加入2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二癸基芴1mmol、9,10-二溴-1,4-二甲氧基蒽0.4mmol、1,3-二(5-溴噻吩基)-5-(2-乙基己基)-噻吩并[3,4-c]吡咯-4,6-二酮0.6mmol,其它物体投料量、反应条件和后处理方法均不变,则最终得到含芴有机半导体材料聚合物P8。采用Waters Breeze凝胶色谱仪,将提纯后的含芴有机半导体材料聚合物P8溶于精制后的四氢呋喃配成1mg/1mL溶液,用仪器专用配套滤膜滤掉不溶物后以10微升量,1ml/min的进样速度进行GPC测试,数均分子量Mn≈47700,含芴有机半导体材料聚合物单分散性为1.31,n为60。
实施例5
本实施例公开结构如下的含芴有机半导体材料聚合物P9、P10:
P9、P10的制备步骤如下:
步骤一、2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二辛基芴的制备:
其制备过程参考实施例1中的步骤一。
步骤二、P9、P10的制备:
在反应器中加入2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二辛基芴1mmol、9,10-二溴-2-辛基-6-十八烷氧基蒽0.5mmol、1,3-二(5-溴噻吩基)-5-十二烷基-噻吩并[3,4-c]吡咯-4,6-二酮0.5mmol、Pd(PPh3)2Cl20.02mmol、2mol/L的Na2CO3水溶液10ml和甲苯溶剂50ml,通过反复进行通N2和抽真空使反应体系处于无氧状态,在75℃条件下反应40h。
反应40h后,往反应瓶中加入去离子水和甲苯进行萃取,取有机相,用减压蒸馏的方法将含芴有机半导体材料聚合物/甲苯溶液蒸干至少量,将其滴入到300ml无水甲醇中不断搅拌,有固体沉淀析出,经过抽滤、烘干后得到固体粉末。再将固体粉末用氯仿溶解,用中性氧化铝过层析柱,除去催化剂Pd(PPh3)2Cl2,最后将含芴有机半导体材料聚合物/氯仿溶液旋蒸至剩5ml左右,将其滴入甲醇溶剂中并搅拌数小时,最后将含芴有机半导体材料聚合物P9收集烘干。用索氏抽提器将含芴有机半导体材料聚合物抽提,从而提高含芴有机半导体材料聚合物分子量的单分散性。
采用Waters Breeze凝胶色谱仪,将提纯后的含芴有机半导体材料聚合物P9溶于精制后的四氢呋喃配成1mg/1mL溶液,用仪器专用配套滤膜滤掉不溶物后以10微升量,1ml/min的进样速度进行GPC测试,数均分子量Mn≈30000,含芴有机半导体材料聚合物单分散性为1.83,n为33。
在反应器中加入2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二癸基芴1mmol、9,10-二溴-2-辛基-6-十八烷氧基蒽0.1mmol、1,3-二(5-溴噻吩基)-5-(2-乙基己基)-噻吩并[3,4-c]吡咯-4,6-二酮0.9mmol,其它物体投料量、反应条件和后处理方法均不变,则最终得到含芴有机半导体材料聚合物P10。采用WatersBreeze凝胶色谱仪,将提纯后的含芴有机半导体材料聚合物P10溶于精制后的四氢呋喃配成1mg/1mL溶液,用仪器专用配套滤膜滤掉不溶物后以10微升量,1ml/min的进样速度进行GPC测试,数均分子量Mn≈26400,含芴有机半导体材料聚合物单分散性为2.01,n为30。
本发明还提供了结构式为(式中,n为1~100之间的整数;m为1~20的整数;x、y为正实数值,且x+y=1;R1、R2分别为氢原子、氟原子、氰基、C1~C40的直链或带支链的烷基或烷氧基、芳基、或杂芳基;R3为氢原子、C1~C20的烷基)的一类含芴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。
以下实施例是一类含芴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6
以实施例一中的P1作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一中的P1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一中的P1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7
以实施例一中的P1作为有机电致发光器件
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:发光层以实施例一中的P1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一中的P1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8
以含实施例一中的P1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:Si31/440nm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一中的P1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一中的P1为材质的有机半导体层34,厚度约为5030-300nm;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 (10)
1.下述通式(P)的一类含芴有机半导体材料:
式中,n为1~100之间的整数;m为1~20的整数;
x、y为正实数值,且x+y=1;
R1、R2分别为氢原子、氟原子、氰基、C1~C40的直链或带支链的烷基或烷氧基、芳基、或杂芳基;R3为氢原子、C1~C20的烷基。
2.根据权利要求1所述的一类含芴有机半导体材料,其特征在于,所述m的取值范围为:6~12的整数;所述R1、R2分别为具有C1~C18的直链或带支链的烷基或烷氧基;所述R3为C1~C12的烷基。
3.一类含芴有机半导体材料的制备方法,其特征在于,包括如下步骤:
在无氧环境中,将结构式为的2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二烷基芴、结构式为的9,10-二溴蒽或其衍生物和结构式为的1,3-二(5-溴噻吩基)-噻吩并[3,4-c]吡咯-4,6-二酮或其衍生物,按摩尔比i:j:k混合,且满足i=j+k,且i,j,k为正实数,于70~100℃、催化剂、碱液和第一溶剂条件下,进行Suzuki反应24~72小时,得到结构式为的所述含芴有机半导体材料;其中,
n为1~200的整数,m为1~20的整数;
x、y为正实数,且x+y=1;
R1、R2分别为氢原子、氟原子、氰基、C1~C40的烷基、烷氧基、芳基、或杂芳基;R3为氢原子、C1~C20的烷基。
4.根据权利要求3所述的制备方法,其特征在于,所述m的取值范围为:6~12的整数;所述R1、R2分别为具有C1~C18的直链或带支链的烷基或烷氧基;所述R3为C1~C12的烷基。
5.根据权利要求3所述的制备方法,其特征在于,还包括所述2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二烷基芴的制备过程,制备步骤如下:
在无水无氧条件中,将结构式为的2,7-二溴-9,9-二烷基芴和正丁基锂在-70℃~-85℃下,以摩尔比1:2~4加入至第二溶剂中,然后加入结构式为的双频哪醇合二硼或者结构式为的2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷,进行缩合反应12~48小时,得到结构式为的所述2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二烷基芴。
6.根据权利要求5所述的制备方法,其特征在于,所述第二溶剂为四氢呋喃、***、二氯甲烷、三氯甲烷或乙酸乙酯中的至少一种;所述2-异丙氧基-4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷或双频哪醇合二硼的摩尔量为2,7-二溴-9,9-二烷基芴的2~4倍。
7.根据权利要求3所述的制备方法,其特征在于,所述催化剂的摩尔用量为2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二烷基芴的0.01%~20%;
所述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Pd(PPh3)4、Pd(OAc)2、Pd2(dba)3或Pd(PPh3)2Cl2;
所述有机磷配体为三环己基膦或P(o-Tol)3。
8.根据权利要求7所述的制备方法,其特征在于,所述有机钯与有机磷配体的混合物中,所述有机钯与有机磷配体的摩尔比为1:1~20。
9.根据权利要求3所述的制备方法,其特征在于,所述碱液为NaOH水溶液、Na2CO3水溶液、NaHCO3水溶液或四乙基氢氧化铵水溶液;所述碱液中碱的用量为2,7-二(4,4,5,5-四甲基-1,3,2-二杂氧戊硼烷)基-9,9-二烷基芴摩尔量的2~20倍;所述第一有机溶剂为甲苯、乙二醇二甲醚、四氢呋喃、***、二氯甲烷、三氯甲烷或乙酸乙酯中的至少一种。
10.一种如权利要求1所述的一类含芴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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