CN108530466A - A kind of polycyclic aromatic hydrocarbon organic semiconducting materials and its preparation method and application - Google Patents
A kind of polycyclic aromatic hydrocarbon organic semiconducting materials and its preparation method and application Download PDFInfo
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- CN108530466A CN108530466A CN201810299053.6A CN201810299053A CN108530466A CN 108530466 A CN108530466 A CN 108530466A CN 201810299053 A CN201810299053 A CN 201810299053A CN 108530466 A CN108530466 A CN 108530466A
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- polycyclic aromatic
- semiconducting materials
- aromatic hydrocarbon
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 55
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 58
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 dibromo alkyl carbazoles Chemical class 0.000 claims abstract description 7
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 7
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 7
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims abstract description 6
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940126062 Compound A Drugs 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000003934 aromatic aldehydes Chemical class 0.000 claims abstract description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000002378 acidificating effect Effects 0.000 claims abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000022244 formylation Effects 0.000 claims abstract description 3
- 238000006170 formylation reaction Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- 230000005669 field effect Effects 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical group [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 claims description 3
- XCMISAPCWHTVNG-UHFFFAOYSA-N 3-bromothiophene Chemical group BrC=1C=CSC=1 XCMISAPCWHTVNG-UHFFFAOYSA-N 0.000 claims description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims description 2
- USLMRHXOAXBGCS-UHFFFAOYSA-N 2-bromo-5-octylthiophene Chemical class CCCCCCCCC1=CC=C(Br)S1 USLMRHXOAXBGCS-UHFFFAOYSA-N 0.000 claims description 2
- 241000254173 Coleoptera Species 0.000 claims description 2
- SWGXDLRCJNEEGZ-UHFFFAOYSA-N N-cyclohexylformamide Chemical class O=CNC1CCCCC1 SWGXDLRCJNEEGZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 150000004996 alkyl benzenes Chemical class 0.000 claims 1
- 230000001681 protective effect Effects 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 36
- 239000010408 film Substances 0.000 description 25
- 239000000203 mixture Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 14
- 239000012074 organic phase Substances 0.000 description 13
- 239000011541 reaction mixture Substances 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 238000004528 spin coating Methods 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- 238000004440 column chromatography Methods 0.000 description 9
- 239000003480 eluent Substances 0.000 description 9
- 229940126214 compound 3 Drugs 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 239000000741 silica gel Substances 0.000 description 8
- 229910002027 silica gel Inorganic materials 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 150000003384 small molecules Chemical class 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920001429 chelating resin Polymers 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- QPTWWBLGJZWRAV-UHFFFAOYSA-N 2,7-dibromo-9-H-carbazole Natural products BrC1=CC=C2C3=CC=C(Br)C=C3NC2=C1 QPTWWBLGJZWRAV-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical class C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- DNGRSVWAENAWJR-UHFFFAOYSA-N dianthra[2,3-b:2',3'-f]thieno[3,2-b]thiophene Chemical compound C1=CC=C2C=C(C=C3C(C=4SC=5C(C=4S3)=CC3=CC4=CC=CC=C4C=C3C=5)=C3)C3=CC2=C1 DNGRSVWAENAWJR-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003518 tetracenes Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D495/14—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The present invention relates to a kind of preparation methods of polycyclic aromatic hydrocarbon organic semiconducting materials, include the following steps：3,6 dibromo alkyl carbazoles are dissolved in anhydrous ether or tetrahydrofuran, and lithium reagent is added dropwise and stirs, and continue dropwise addition aromatic aldehyde solution and obtain compound A；Compound A is dissolved in toluene or dimethylbenzene, and zinc iodide, sodium cyanoborohydride is added, stirs to get compound B；Compound B is dissolved in absolute ethyl alcohol or tetrahydrofuran, and lithium reagent is added dropwise and stirs, anhydrous formylation reagent is then added, stirs to get compound C；Compound C is dissolved in toluene or dimethylbenzene, and macroreticular acidic ion exchange resin is added, and stirs to get the angle-style polycyclic aromatic hydrocarbon organic semiconducting materials that carbazole is core.The organic semiconducting materials of the present invention have high stability and preferable dissolubility, applied to the hole migration characteristic that FET device shows not rely on film thickness, easily repeat, are conducive to industrialized production.
Description
Technical field
The present invention relates to a kind of polycyclic aromatic hydrocarbon organic semiconducting materials and its preparation method and application, belong to polycrystalline organic thin film
Body Manifold technology field.
Background technology
Organic semiconducting materials have the structure property of can relate to strong, solution processable and can process on flexible substrates etc. excellent
Point, it has also become the main body of electronic information material of new generation.Researching and developing a kind of new and effective organic conjugate semi-conducting material must
Vast market prospect will be generated in electronic industry.Polycyclic aromatic hydrocarbon (Acenes) class material is in photovoltaic cell (OPVs) and organic
Application in field-effect transistor (OFETs) is relatively broad.In all OFET materials, one-dimensional or two-dimentional condensed ring (1D/2D
Fusedaceneorheteroacene) material all shows high device mobility.For example, pentacene
(Pentacene), rubrene (Rubrene), aphthacene (Tetracene) derivative and acid imide (PDI) class material all have
There is high mobility, general transfer rate is more than 5cm2/V·s.However, the polycyclic aromatic hydrocarbon of full benzene structure is mainly linear junction
Structure feature, usually have the shortcomings that stability is poor, be not easy functionalization, dissolubility it is poor, the preparation generally uses of OFET devices vapor deposition,
Process costs are high.
In view of the above-mentioned problems, improve its stability by the way of to full benzene structure polycyclic aromatic hydrocarbon system introducing hetero-atoms,
Hetero atom can be sulphur, nitrogen, selenium, boron etc..It is reported that Niimi, K. et al. have been found that in 2011 and two benzene among eight benzene
Ring is replaced by bithiophene ring, can obtain DATT that is stable, can be used for hot evaporation and prepare transistor device.However, either
Which kind of linear polycyclic aromatic hydrocarbon be using high temperature or it is transition metal-catalyzed by the way of realize, synthesis step is longer, operation
It is cumbersome, yield is relatively low, be not easy from commercialized base stock, controllable, the simple synthesis in regioselectivity highland.
Invention content
It is an object of the invention to：In view of the defects existing in the prior art, a kind of polycyclic aromatic hydrocarbon organic semiconductor material is proposed
Material, while preparation method and application are given, it can get one kind with commercialized carbazole derivates and simple reaction step
The ingenious combination of aryl aldehyde, and then the angle-style polycyclic aromatic hydrocarbon organic semiconducting materials that a kind of carbazole is core have been synthesized, correspondingly draw
Flexible alkyl chains appropriate are entered, have improved the stability and dissolubility of material, it is special to obtain the field-effect transistor haveing excellent performance
Property.
In order to reach object above, the present invention provides a kind of polycyclic aromatic hydrocarbon organic semiconducting materials, structural formula is as follows：
Wherein, R1For the linear or branched alkyl group with 1~24 carbon atom；R2For H, alkyl chain (CnH2n+1), alkylbenzeneAlkylthropheneOr alkyl benzothiophenesN takes
It is 1,6,8 or 10 that value, which is 1~24, m values,；Ar is thiopheneOr bithiophene
For deficiency existing for existing field-effect transistor, the present invention provides a kind of for the more of organic field effect tube
Cyclophane hydro carbons p-type organic semiconducting materials, the material can be prepared active layer using solwution method and can be in 40~220nm thickness
Stable high mobility is realized in range.Meanwhile the present invention can be held very much by the linear structure of the linear polycyclic aromatic hydrocarbon of destruction
Changing places improves the dissolubility of corresponding polycyclic aromatic hydrocarbon, while can adjust its energy level, realizes the electrode energy level with field-effect transistor
Match.
The present invention also provides a kind of preparation methods of polycyclic aromatic hydrocarbon organic semiconducting materials, include the following steps：
3,6- dibromos alkyl carbazole (10mmol, 1eq) is dissolved in anhydrous ether or tetrahydrofuran (70mL) by the first step,
Under the conditions of -30~-78 DEG C and inert gas shielding, after lithium reagent (8mL, 2.5M, 2eq) is added dropwise and stirs 1~4h, continue
Aromatic aldehyde (22mmol~26mmol, 2.2eq~2.6eq) is added dropwise, obtains compound A；
Second step after compound A (4.7mmol, 1eq) is dissolved in toluene, dichloromethane or dimethylbenzene (20mL), is added
Zinc iodide (11.75mmol~14.1mmol, 2.6eq~3.0eq), sodium cyanoborohydride (23.5mmol~28.2mmol, 5eq
~6eq), and 5 ± 1h is stirred under the conditions of 15~35 DEG C, obtain compound B；
Compound B (3.5mmol, 1eq) is dissolved in absolute ethyl alcohol or tetrahydrofuran (20mL) by third step, -30~-
Under the conditions of 78 DEG C and inert gas shielding, lithium reagent (4.4mL, 1.6M, 2eq) is added dropwise and simultaneously stirs 0.5~2h, nothing is then added
Water beetle acylating reagent (14mmol, 4eq) stirs 5~12h, obtains compound C；
Compound C (1.43mmol, 1eq) is dissolved in toluene, dichloromethane or dimethylbenzene (20mL) by the 4th step, is added
Macroreticular acidic ion exchange resin (0.715mmol~1.43mmol, 0.5eq~1eq), under the conditions of 25~90 DEG C stir 2~
12h obtains the angle-style polycyclic aromatic hydrocarbon organic semiconducting materials that carbazole is core.
The preparation method of polycyclic aromatic hydrocarbon organic semiconducting materials of the present invention can be carried out according to following circuit：
In above formula, the alkyl R of 3,6- dibromo alkyl carbazoles 11Be C1~C24 linear or branched alkyl group in one kind.
In summary, the present invention is by selecting different aryl aldehyde and 3,6- dibromo carbazole derivates reaction, by continuous four
Step synthesis, obtains the angle-style polycyclic aromatic hydrocarbon organic semiconducting materials using carbazole as core.
Preferably, the inert gas is nitrogen or argon gas.
Preferably, the aromatic aldehyde is 3 bromo thiophene -2- formaldehyde, the bromo- 2- formaldehyde-bithiophenes of 3- or the bromo- 5- octyls thiophenes of 3-
Pheno -2- formaldehyde.The structural formula of aromatic aldehyde is：
Wherein, R2For H, CnH2n+1、 N takes
It is 1,6,8 or 10 that value, which is 1~24, m values,.
Preferably, the anhydrous formylation reagent is n,N-Dimethylformamide or N, N- cyclohexyl formamides；The lithium
Reagent is butyl lithium.
Preferably, the macroreticular acidic ion exchange resin be Amberlyst15, Amberlyst35 or
Amberlyst70。
General formula of the present invention provides a kind of application of polycyclic aromatic hydrocarbon organic semiconducting materials, specifically, the polycyclic aromatic hydrocarbon
Organic semiconducting materials are used in FET device.
Preferably, the FET device includes substrate, adheres to gate electrode on substrate, is affixed with gate electrode
The organic semiconductor active layer of conjunction, the source electrode to fit with organic semiconductor active layer, drain electrode, the organic semiconductor are lived
Property layer is the angle-style polycyclic aromatic hydrocarbon organic semiconducting materials that carbazole is core.
It is further preferred that organic semiconductor active layer is spun on gate electrode by solution, organic semiconductor active layer
Thickness is 40~220nm.
It can be through simple solution spin coating method by the angle-style polycyclic aromatic hydrocarbon organic semiconducting materials of core of carbazole in the present invention
For realizing its high mobility in organic field effect tube；Significantly when the thickness of organic semiconductor active layer from
When 40nm to 220nm wide fluctuations, the organic field effect tube device obtained can show stable high mobility.
It is an advantage of the invention that：Carbazole provided by the invention, which is the angle-style polycyclic aromatic hydrocarbon organic semiconducting materials of core, to be passed through
The organic reaction of three step nontransition metal catalysis is prepared, easy to operate, by-product is few, is easily isolated；Use carbazole for original
Material, not only raw material is cheap and easy to get, and can provide very high regioselectivity for chemical synthesis process；Meanwhile acquisition
Polycyclic aromatic hydrocarbon structure has larger pi-conjugated, is conducive to packing of molecules；The introducing of alkyl chain improves the stability, molten of material
Xie Xing, to obtain the field-effect transistor performance haveing excellent performance.In short, organic semiconducting materials are with high stability and preferably
Dissolubility, and the hole migration for showing not rely on film thickness in FET device prepared by solwution method is special
Property, it is easy to repeat, is conducive to instruments industriesization batch production.
Description of the drawings
The present invention will be further described below with reference to the drawings.
Fig. 1 is in the present invention using carbazole as the structural schematic diagram of the organic field effect tube of the angle-style molecule of core.
Fig. 2 is the synthetic route chart of 1 small molecular DTBCz of the embodiment of the present invention.
Fig. 3 is the synthetic route chart of 2 small molecular TDTBCz of the embodiment of the present invention.
Fig. 4 is the synthetic route chart of 3 small molecular DTBCzC8 of the embodiment of the present invention.
Fig. 5 is turn of organic field effect tube when organic semiconductor active layer film thickness is 82nm in the embodiment of the present invention 4
Move performance diagram.
Fig. 6 is the defeated of organic field effect tube when organic semiconductor active layer film thickness is 82nm in the embodiment of the present invention 4
Go out performance diagram.
Fig. 7 is turn of organic field effect tube when organic semiconductor active layer film thickness is 118nm in the embodiment of the present invention 5
Move performance diagram.
Fig. 8 is the defeated of organic field effect tube when organic semiconductor active layer film thickness is 118nm in the embodiment of the present invention 5
Go out performance diagram.
Fig. 9 is turn of organic field effect tube when organic semiconductor active layer film thickness is 181nm in the embodiment of the present invention 6
Move performance diagram.
Figure 10 is organic field effect tube when organic semiconductor active layer film thickness is 181nm in the embodiment of the present invention 6
Output characteristic curve figure.
Figure 11 is in the embodiment of the present invention 1 using carbazole as the hydrogen spectrogram of the angle-style molecule of core.
Specific implementation mode
The raw materials used in the present invention is known compound, is commercially available, or can be synthesized with means known in the art.
Embodiment 1
Present embodiments provide a kind of using carbazole as the preparation method of the angular molecular compound DTBCz of core, synthesis road
Line is as shown in Fig. 2, what is finally obtained is as follows as the angular molecular structural formula of core using carbazole：
The first step takes compound 1 (i.e. 3,6- dibromos alkyl carbazole) 14.9g (10mmol), under nitrogen protection by chemical combination
1 azoles of object is dissolved in 70mL anhydrous tetrahydro furans, a concentration of using syringe dropwise addition under -78 DEG C of low temperature and nitrogen protection
The butyl lithium 8mL (20mmol) of 2.5mol/L, and low temperature is kept to stir 1h, 3 bromo thiophene -2- formaldehyde 4.8g is then added dropwise
(25mmol) the reaction was continued.Reaction mixture is stirred at room temperature after 8h, organic phase is obtained by extraction using dichloromethane, will closed
And organic phase using sodium sulphate drying after, remove solvent, obtain the crude product 3.6g of compound 2, the crude product of compound 2 is without pure
Change can be used to react in next step.
Second step takes a 50mL reaction tubes, and 20mL dichloromethane is added into reaction tube, and 3.4g (4.7mmol) is changed
The crude product for closing object 2 is dissolved in dichloromethane, and 4g (12.5mmol) zinc iodide is then added, and 1.6g is added after waiting for 30min
(25mmol) sodium cyanoborohydride is adopted and mixture is extracted with ethyl acetate after stirring 5h at room temperature, mixture is directly used true
Empty evaporator removes solvent, and reaction mixing is purified finally by column chromatography (silica gel, PE/DCM=5/1, v/v is as eluent)
Object obtains compound 3, weighs compound 3, the yield of weight 2.6g, the reaction are 81%.The hydrogen of compound 3 is composed：1H
NMR(400MHz,CDCl3) δ 10.16 (s, 2H), 7.43 (d, J=5.4Hz, 2H), 7.34 (s, 4H), 7.10 (d, J=5.3Hz,
2H), 4.69 (s, 4H), 4.25 (t, J=7.2Hz, 2H), 1.87-1.81 (m, 2H), 1.32-1.20 (m, 18H), 0.86 (d, J
=7.0Hz, 3H)13C NMR(100MHz,CDCl3)δ184.9,157.9,139.9,136.6,129.7,127.6,126.7,
123.7,122.8,120.5,109.1,43.3,34.2,32.0,29.7,29.6,29.5,29.4,29.4,29.1,27.4,
22.8,14.2.
Third step, -78 DEG C and argon gas protection under, by syringe by 2.4g (3.5mmol) compound 3 be dissolved in 20mL without
In water tetrahydrofuran, the butyl lithium solution 4.4mL (7mmol) of a concentration of 1.6mol/L is taken to be injected into compound 3 using syringe
Tetrahydrofuran solution in, obtain mixture.Mixture is kept stirring 10min at -78 DEG C, 1mL is then added
(14mmol) anhydrous n,N-Dimethylformamide, is obtained by the reaction reaction mixture.Reaction mixture is kept into 8h at room temperature, so
After adopt mixture be extracted with ethyl acetate, take organic phase.After combined organic phase is dried using sodium sulphate, remove under vacuum
Solvent purifies reaction mixture finally by column chromatography (silica gel, PE/EA=10/1, v/v is as eluant, eluent), obtains chemical combination
Object 4 weighs compound 4, and the yield of weight 1.06g, the reaction are 52%, and compound 4 is white solid.Compound 4
Hydrogen spectrum is as follows：1H NMR(400MHz,CDCl3) δ 10.07 (s, 2H), 7.90 (s, 2H), 7.45 (d, J=5.4Hz, 2H), 7.34
(s, 4H), 7.10 (d, J=5.3Hz, 2H), 4.69 (s, 4H), 4.25 (t, J=7.2Hz, 2H), 1.87-1.81 (m, 2H),
1.32-1.20 (m, 18H), 0.86 (d, J=7.0Hz, 3H)13C NMR(100MHz,CDCl3)δ184.9,157.9,139.9,
136.6,129.7,127.6,126.7,123.7,122.8,120.5,109.1,43.3,34.2,32.0,29.7,29.6,
29.5,29.4,29.4,29.1,27.4,22.8,14.2.
4th step takes a 50mL reaction tubes, the toluene of the fresh distillations of 20mL is added into reaction tube, by 1.00g
(1.71mmol) compound 4 is dissolved in toluene, and 1.0g macroporous ion exchange resins (Amberlyst) are added, obtain mixture.It will
It after mixture stirs 12h under the conditions of 90 DEG C, is cooled to room temperature, mixture is extracted using chloroform, is then detached through column chromatography
(silica gel, PE/DCM=8/1, v/v is as eluent) purified mixture obtains compound DTBCz0.16g, the yield of the reaction
It is 17%.The hydrogen spectrum of compound DTBCz is as follows：1H NMR(400MHz,CDCl3)δ9.34(s,1H),9.17(s,1H),8.75
(s, 1H), 8.54 (s, 1H), 8.51 (s, 1H), 8.06 (d, J=9.0Hz, 1H), 7.96 (s, 1H), 7.67 (dd, J=9.0,
5.7Hz, 2H), 7.63 (d, J=5.5Hz, 1H), 7.51 (d, J=5.6Hz, 1H), 7.46 (d, J=5.7Hz, 1H), 4.48 (t,
J=7.2Hz, 2H), 2.04-1.96 (m, 2H), 1.24 (m, 18H), 0.86 (t, J=6.8Hz, 3H)13C NMR(100MHz,
CDCl3)δ139.9,127.9,125.1,136.5,130.0,123.5,128.8,122.6,120.5,111.1,111.0,
58.3,29.6,29.4,29.3,27.3,22.7,14.1.Calcd for C36H37NS2, molecular weight:547.24, mass spectrum MS (m/
z):547.22. nuclear-magnetism is as shown in figure 11.
Embodiment 2
Present embodiments provide a kind of using carbazole as the preparation method of the angle-style molecular compound TDTBCz of core, synthesis road
Line is as shown in figure 3, finally obtaining and being by the structural formula of the angle-style molecular compound TDTBCz of core of carbazole：
4.9g (10mmol) compound 1 is dissolved under the protection of nitrogen in 70mL anhydrous tetrahydro furans by the first step ,-
The butyl lithium solution 8mL (20mmol) of a concentration of 2.5mol/L is added under 78 DEG C of low temperature and nitrogen protection using syringe,
It keeps low temperature to stir 1h, the bromo- 2- formaldehyde-bithiophenes of 6.18g (25mmol) 3- is then added, carry out that reaction mixing is obtained by the reaction
Object.After reaction mixture keeps 8h at room temperature, mixture is extracted using dichloromethane, organic phase is taken, combined organic phase is adopted
It is dried with sodium sulphate.Then solvent is removed under vacuum, obtains the crude product of 4.6g compounds 2, the crude product of compound 2 is without purifying
It can be used to react in next step.
Second step, in 50mL reaction tubes, 3.8g (4.5mmol) compound 2 is dissolved in 20mL dichloromethane.Then plus
Enter 3.6g (11.5mmol) zinc iodide, 1.4g (23mmol) sodium cyanoborohydride is added after waiting for 30min, keeps 5h at room temperature
Afterwards, it adopts and mixture is extracted with ethyl acetate, mixture is directly removed into solvent with cold boiler.Finally by column chromatography
(silica gel, PE/DCM=5/1, v/v are pure as eluent) changes reaction mixture, obtains 2.5g compounds 3, yield 69%.Change
The hydrogen of conjunction object 3, which is composed, is：1H NMR(400MHz,CDCl3)δ10.02(s,2H),7.87(d,2H),7.30(s,4H),7.09(d,J
=5.3Hz, 2H), 4.65 (s, 4H), 4.25 (t, J=7.2Hz, 2H), 1.85-1.80 (m, 2H), 1.32-1.20 (m, 18H),
0.86 (d, J=7.0Hz, 3H)13C NMR(100MHz,CDCl3)δ185.1,165.3,161.4,158.9,157.8,139.0,
135.6,129.0,125.5,124.7,123.2,122.6,120.5,109.3,43.2,34.2,32.0,29.7,29.6,
29.5,29.4,29.4,29.0,27.3,22.7,14.3.
Third walks, at -78 DEG C, and 2.4g (3.0mmol) compound 3 is dissolved in 20mL anhydrous tetrahydro furans by syringe
In, the butyl lithium solution 3.75mL (6mmol) of a concentration of 1.6mol/L is then injected into the tetrahydrochysene of compound 3 using syringe
In tetrahydrofuran solution, mixture is obtained.Mixture is stirred into 10min at -78 DEG C, 0.86mL (12mmol) anhydrous N is then added,
Dinethylformamide obtains reaction mixture.After reaction mixture is kept 8h at room temperature, mixing is extracted with ethyl acetate
Object takes organic phase.After combined organic phase is dried with sodium sulphate, solvent is removed under vacuum, finally by column chromatography (silicon
Glue, PE/EA=10/1, v/v is as eluant, eluent) purifying obtains 1.13g compounds 4, and yield 53%, compound 4 is that white is solid
Body.The hydrogen of compound 4 is composed：1H NMR(400MHz,CDCl3) δ 10.08 (s, 2H), 7.93 (s, 2H), 7.38 (d, J=
5.4Hz, 2H), 7.30 (d, 4H), 7.06 (d, J=5.3Hz, 2H), 4.66 (s, 4H), 4.25 (t, J=7.2Hz, 2H), 1.85-
1.81 (m, 2H), 1.32-1.20 (m, 18H), 0.86 (d, J=7.0Hz, 3H)13C NMR(100MHz,CDCl3)δ184.5,
168.7,166.4,160.3,157.6,139.6,136.3,129.4,126.6,126.4,123.3,122.2,120.0,
109.1,43.4,34.2,32.0,29.7,29.6,29.5,29.4,29.4,29.1,27.4,22.8,14.3。
4th step, in 50mL reaction tubes, by 1.00g (1.43mmol) compound 4 and 1.0g macroporous ion exchange resins
(Amberlyst) it is added in the toluene of the fresh distillations of 20mL, is uniformly mixed and obtains mixture.By mixture under the conditions of 90 DEG C
After stirring 12h, it is cooled to room temperature, mixture is extracted with chloroform, takes organic phase.Combined organic phase is dried with sodium sulphate.
Then solvent is removed under vacuum, is purified and is mixed finally by column chromatography (silica gel, PE/DCM=8/1, v/v is as eluent)
Object, obtains 0.18g compound TDTBCz, yield 14%, and compound TDTBCz is yellow solid.The hydrogen of compound TDTBCz is composed
For：1H NMR(400MHz,CDCl3)δ9.30(s,1H),9.15(s,1H),8.74(s,1H),8.52(s,1H),8.51(s,
1H), 8.03 (d, J=9.0Hz, 1H), 7.95 (s, 1H), 7.82 (s, 1H) 7.66 (dd, J=9.0,5.7Hz, 2H), 7.62 (d,
J=5.5Hz, 1H), 7.51 (d, J=5.6Hz, 1H), 4.47 (t, J=7.2Hz, 2H), 2.04-1.96 (m, 2H), 1.24 (m,
18H), 0.86 (t, J=6.8Hz, 3H)13C NMR(100MHz,CDCl3)δ139.9,139.8,136.5,133.6,133.5,
131.2,128.8,126.4,125.1,123.8,122.6,121.5,120.1,117.9,111.1,58.3,31.9,29.6,
29.4,29.3,27.3 22.7,14.1.Calcd for C40H37NS4, molecular weight:659.18, mass spectrum MS (m/z):659.21.
Embodiment 3
Present embodiments provide a kind of using carbazole as the preparation method of the angle-style molecular compound DTBCzC8 of core, synthesis
Route is as shown in figure 4, finally obtaining and being by the structural formula of the angle-style molecular compound DTBCzC8 of core of carbazole：
5g (10mmol) compound 1 is dissolved under the protection of nitrogen in 70mL anhydrous tetrahydro furans by the first step, -78
DEG C low-temperature protection under using syringe the butyl lithium 8mL (20mmol) of a concentration of 2.5mol/L is added, keep low temperature to stir 1h,
Then the bromo- 5- octyl thiophenes -2- formaldehyde of 7.6g (25mmol) 3- is added, obtains reaction mixture.Reaction mixture is at room temperature
After stirring 8h, is extracted with dichloromethane, take organic phase, and combined organic phase is dried with sodium sulphate.Solvent is removed, is changed
The crude product 3.3g of object 2 is closed, crude product can be used to react in next step without purifying.
Second step, in 50mL reaction tubes, 2 crude product of 3.2g (3.4mmol) compound is dissolved in 20mL dichloromethane.So
2.72g (8.5mmol) zinc iodide is added afterwards, 1.1g (17mmol) sodium cyanoborohydride is added after waiting for 30min, stirs at room temperature
After 5h, mixture is extracted with ethyl acetate, mixture is directly removed into solvent with cold boiler.Finally by column chromatography
(silica gel, PE/DCM=5/1, v/v is as eluent) purifies reaction mixture, obtains 2.3g compounds 3, yield 75%.Chemical combination
The hydrogen of object 3 is composed：1H NMR(400MHz,CDCl3)δ10.13(s,2H),7.93(s,2H),7.34(s,4H),4.69(s,4H),
4.25 (t, J=7.2Hz, 2H), 3.50 (t, J=7.2Hz, 4H) 1.87-1.81 (m, 6H), 1.32-1.20 (m, 40H), 0.86
(d, J=7.0Hz, 9H)13C NMR(100MHz,CDCl3)δ184.7,158.0,139.6,136.8,129.5,127.3,
126.2,123.4,122.8,120.5,109.1,43.3,34.2,32.0,29.7,29.6,29.5,29.4,29.4,29.1,
27.4,22.8,14.2.
Third walks, at -78 DEG C, and 2.2g (2.4mmol) compound 3 is dissolved in 20mL anhydrous tetrahydro furans by syringe
In, then the butyl lithium solution 3mL (4.8mmol) of a concentration of 1.6mol/L is injected into using syringe in above-mentioned solution, is obtained
To mixture.Mixture is stirred into 10min at -78 DEG C, 0.68mL (9.6mmol) anhydrous n,N-Dimethylformamide is added,
It carries out that reaction mixture is obtained by the reaction.After reaction mixture is kept 8h at room temperature, mixture is extracted with ethyl acetate, has taken
Machine phase.Combined organic phase is dried with sodium sulphate.Solvent is removed under vacuum, then passes through column chromatography (silica gel, PE/EA
=10/1, v/v are as eluant, eluent) purifying, 1.08g compounds 4, yield 54% are obtained, compound 4 is white solid.Chemical combination
The hydrogen of object 4 is composed：1H NMR(400MHz,CDCl3) δ 10.16 (s, 2H), 7.94 (s, 2H), 7.43 (d, J=5.4Hz, 2H),
7.34 (s, 4H), 4.67 (s, 4H), 4.24 (t, J=7.2Hz, 2H), 3.50 (t, J=7.2Hz, 4H) 1.86-1.81 (m, 6H),
1.32-1.20 (m, 40H), 0.86 (d, J=7.0Hz, 9H)13C NMR(100MHz,CDCl3)δ184.6,157.8,139.9,
136.7,129.6,127.5,126.4,123.4,122.5,120.4,109.0,43.3,34.2,32.0,29.7,29.6,
29.5,29.4,29.4,29.1,27.4,22.8,14.3.
4th step, in 50mL reaction tubes, by 1.00g (1.23mmol) compound 4 and 1.0g macroporous ion exchange resins
(Amberlyst) it is dissolved in the toluene of the fresh distillations of 20mL, is uniformly mixed.Mixture stirs 12h under the conditions of 90 DEG C, is cooled to
Room temperature extracts mixture with chloroform, through column chromatography separation (silica gel, PE/DCM=8/1, v/v is as eluent) purifying mixing
Object obtains 0.17g compound DTBCzC8, yield 18%.The hydrogen of compound DTBCzC8 is composed：1H NMR(400MHz,
CDCl3) δ 9.34 (s, 1H), 9.17 (s, 1H), 8.75 (s, 1H), 8.54 (s, 1H), 8.51 (s, 1H), 8.06 (d, J=
9.0Hz, 1H), 7.96 (s, 1H), 7.67 (dd, J=9.0,5.7Hz, 2H), 7.63 (d, J=5.5Hz, 1H), 7.51 (d, J=
5.6Hz, 1H), 7.46 (d, J=5.7Hz, 1H), 4.48 (t, J=7.2Hz, 2H), 2.04-1.96 (m, 2H), 1.24 (m,
18H), 0.86 (t, J=6.8Hz, 3H)13C NMR(100MHz,CDCl3)δ146.1,139.9,139.1,137.1,136.5,
133.6,133.5,128.8,123.8,122.6,120.5,118.0,117.9,111.1,58.3,39.6,31.9,29.6,
29.4,29.3,29.2,27.3,22.7,14.1.Calcd for C52H69NS2, molecular weight:771.49, mass spectrum MS (m/z):
771.51。
Embodiment 4
Present embodiments provide a kind of using carbazole as the angle-style molecule organic field effect tube of core, structure such as Fig. 1 institutes
Show, including substrate, be formed in the gate electrode of the substrate, the gate insulation layer being covered on the gate electrode is formed in the grid
Having using carbazole as the small molecule film layer (i.e. porous organic semiconductor active layer) of the angle-style molecule of core, shape on insulating layer
At the source in the porous organic semiconductor active layer surface channel region both sides, drain electrode.Wherein, substrate attach most importance to doped silicon wafer,
Sheet glass or plastics PET.It is as follows as the structure of the angle-style molecule DTBCzC8 of core using carbazole：
In addition, using heavy doping silicon chip as substrate and gate electrode；A layer thickness is that the silica of 300nm is exhausted as grid
Edge layer；It is 80~90nm that spin coating, which has the small molecule film of DTBCzC8, thickness, on gate insulation layer, is had on small molecule film
Conducting channel；In conducting channel both sides, evaporation metal gold is as source, drain electrode.
Small molecule film layer with DTBCzC8 is the toluene solution by DTBCzC8, is prepared using spin-coating film technique
Film.
When actually preparing film, laboratory room temperature is maintained at 25 DEG C or so, and indoor humidity is maintained at 50% or less.
The storage implement body preparation process of the present embodiment is as follows：
(1) configuration is using carbazole as the angle-style molecular solution of core, a concentration of 10mg/mL of the solution, and solvent is without additional
The toluene of processing will be added by the angle-style molecule of core of carbazole in toluene, and stirring for 24 hours, makes it be uniformly dispersed.
(2) the heavy doping silicon chip of 300nm thick silicon dioxides uses acetone, ethyl alcohol, deionized water ultrasound successively on surface
Each 10min, supersonic frequency 100KHz are cleaned, then is dried up substrate surface liquid to ensure that substrate surface is clean with high pure nitrogen
Only, it is put into 120 DEG C of baking oven and dries later.
(3) dried substrate is put into UV ozone machine and handles 5min.
(4) under conditions of air humidity is 40%, by the ultraviolet substrate surface spin coating handled well using carbazole as the angle of core
Type molecular solution obtains small molecule film, and spin coating rotating speed is 2000r/min, spin-coating time 30s, is added dropwise when by changing spin coating
Amount of solution by plastics thickness control in 82nm or so, the good substrate of spin coating is put into 120 DEG C of baking close annealing 20min.
(5) source, drain electrode are served as in film surface vacuum evaporation metal, evaporation rate isCoordination electrode thickness
In 60~80nm；The channel width of mask plate is 2000 μm, and length is 100 μm.
After the completion of prepared by storage component part, electric property is characterized by 4200 semiconductor analysis instrument of Keithley, data
The transfer curve being depicted as is handled as shown in figure 5, mobility reaches 0.001cm2/ Vs, on-off ratio is up to 103More than.Device it is defeated
Go out indicatrix as shown in fig. 6, device field-effect is fine.
Embodiment 5
The present embodiment and embodiment 4 the difference is that：It is molten as the angle-style molecule of core using carbazole in substrate surface spin coating
Liquid obtains small molecule film, and plastics thickness control is in 118nm or so.The electric property of the present embodiment device is by Keithley 4,200 half
Conductor analyzer is characterized, and the transfer curve that data processing is depicted as is as shown in fig. 7, mobility reaches 0.004cm2/ Vs,
On-off ratio is up to 103, than film thickness be 82nm when mobility higher.The output indicatrix of device is as shown in figure 8, device field-effect ratio
Film thickness is better when being 82nm.
Embodiment 6
The present embodiment and embodiment 4 the difference is that：It is molten as the angle-style molecule of core using carbazole in substrate surface spin coating
Liquid obtains small molecule film, and spin coating rotating speed is 3000r/min, preferred 181nm of film thickness or so.The electricity of the present embodiment device
Performance is characterized by 4200 semiconductor analysis instrument of Keithley, and the transfer curve that data processing is depicted as is as shown in figure 9, mobility
Reach 0.002cm2/ Vs, on-off ratio is up to 104, with film thickness be 82nm when mobility be not much different, on-off ratio is larger.Device
Export indicatrix it is as shown in Figure 10, device field-effect than film thickness be 82nm when it is better, but compared with film thickness be 118nm when slightly
Difference.
In short, the present invention will be introduced by the angle-style molecular film of core of carbazole in organic field effect tube, pass through
Simple process means can efficiently solve organic semiconducting materials synthesis complexity, rely on greatly film thickness, stability is bad, has
The problems such as field effect transistors yield is not high is commercialized organic field effect tube and promotes important in inhibiting.
In addition to the implementation, the present invention can also have other embodiment.It is all to use equivalent substitution or equivalent transformation shape
At technical solution, fall within the scope of protection required by the present invention.
Claims (9)
1. a kind of polycyclic aromatic hydrocarbon organic semiconducting materials, which is characterized in that the structure of the polycyclic aromatic hydrocarbon organic semiconducting materials
Formula is as follows：
Wherein, R1For the linear or branched alkyl group with 1~24 carbon atom；R2For H, alkyl chain, alkylbenzene, alkylthrophene or
Alkyl benzothiophenes, n values are that 1~24, m values are 1,6,8 or 10；Ar is thiophene or bithiophene.
2. a kind of preparation method of polycyclic aromatic hydrocarbon organic semiconducting materials, which is characterized in that include the following steps：
3,6- dibromo alkyl carbazoles are dissolved in anhydrous ether or tetrahydrofuran by the first step, in -30~-78 DEG C and indifferent gas
Under body protective condition, after lithium reagent is added dropwise and stirs 1~4h, continues that aromatic aldehyde is added dropwise, obtain compound A；
Second step, after compound is dissolved in toluene, dichloromethane or dimethylbenzene, be added zinc iodide, sodium cyanoborohydride, and
5 ± 1h is stirred under the conditions of 15~35 DEG C, obtains compound B；
Compound B is dissolved in absolute ethyl alcohol or tetrahydrofuran by third step, in -30~-78 DEG C and inert gas shielding condition
Under, lithium reagent is added dropwise and stirs 0.5~2h, anhydrous formylation reagent is then added, stirs 5~12h, obtains compound C；
Compound C is dissolved in toluene, dichloromethane or dimethylbenzene by the 4th step, macroreticular acidic ion exchange resin is added, 25
2~12h is stirred under the conditions of~90 DEG C, obtains the angle-style polycyclic aromatic hydrocarbon organic semiconducting materials that carbazole is core.
3. a kind of preparation method of polycyclic aromatic hydrocarbon organic semiconducting materials according to claim 2, which is characterized in that described lazy
Property gas be nitrogen or argon gas.
4. a kind of preparation method of polycyclic aromatic hydrocarbon organic semiconducting materials according to claim 2, which is characterized in that the virtue
Fragrant aldehyde is 3 bromo thiophene -2- formaldehyde, the bromo- 2- formaldehyde-bithiophenes of 3- or the bromo- 5- octyl thiophenes -2- formaldehyde of 3-.
5. a kind of preparation method of polycyclic aromatic hydrocarbon organic semiconducting materials according to claim 2, which is characterized in that the nothing
Water beetle acylating reagent is N,N-dimethylformamide or N, N- cyclohexyl formamides；The lithium reagent is butyl lithium.
6. a kind of preparation method of polycyclic aromatic hydrocarbon organic semiconducting materials according to claim 2, which is characterized in that described big
Hole acid-exchange resin is Amberlyst15, Amberlyst35 or Amberlyst70.
7. a kind of application of polycyclic aromatic hydrocarbon organic semiconducting materials, which is characterized in that the polycyclic aromatic hydrocarbon organic semiconducting materials
For in FET device.
8. a kind of application of polycyclic aromatic hydrocarbon organic semiconducting materials according to claim 7, which is characterized in that the field-effect
Transistor device includes substrate, adheres to gate electrode on substrate, the organic semiconductor active layer to fit with gate electrode, and is had
Source electrode that machine semiconductor active layer fits, drain electrode, the organic semiconductor active layer is that the angle-style that carbazole is core is polycyclic
Aromatic hydrocarbons organic semiconducting materials.
9. a kind of application of polycyclic aromatic hydrocarbon organic semiconducting materials according to claim 8, which is characterized in that described organic half
The thickness of conductor active layer is 40~220nm.
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