TW201638366A - 用於真空熱蒸鍍經取代之1,2,3-三亞基三(氰甲基亞基)環丙烷與使用它們之電子裝置及半導體材料 - Google Patents
用於真空熱蒸鍍經取代之1,2,3-三亞基三(氰甲基亞基)環丙烷與使用它們之電子裝置及半導體材料 Download PDFInfo
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- TW201638366A TW201638366A TW104142042A TW104142042A TW201638366A TW 201638366 A TW201638366 A TW 201638366A TW 104142042 A TW104142042 A TW 104142042A TW 104142042 A TW104142042 A TW 104142042A TW 201638366 A TW201638366 A TW 201638366A
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- Prior art keywords
- trifluoromethyl
- trifluorophenyl
- compound
- cyano
- bis
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- -1 cyanomethanylylidene Chemical group 0.000 title claims abstract description 144
- 239000004065 semiconductor Substances 0.000 title claims abstract description 22
- 150000001942 cyclopropanes Chemical class 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 80
- 125000003118 aryl group Chemical group 0.000 claims abstract description 30
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000002019 doping agent Substances 0.000 claims abstract description 19
- 238000001704 evaporation Methods 0.000 claims abstract description 15
- 230000008020 evaporation Effects 0.000 claims abstract description 14
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 44
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- 239000000758 substrate Substances 0.000 claims description 24
- 229920006395 saturated elastomer Polymers 0.000 claims description 18
- 230000005525 hole transport Effects 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 238000002484 cyclic voltammetry Methods 0.000 claims description 5
- 238000007740 vapor deposition Methods 0.000 claims description 5
- 230000033116 oxidation-reduction process Effects 0.000 claims description 4
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 3
- 230000002441 reversible effect Effects 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims 1
- UPWZWQGQRNPKTE-UHFFFAOYSA-N 1,2,3-trimethylidenecyclopropane Chemical compound C=C1C(=C)C1=C UPWZWQGQRNPKTE-UHFFFAOYSA-N 0.000 abstract 6
- 238000002360 preparation method Methods 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 31
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 28
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 13
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- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 10
- 229960003237 betaine Drugs 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- 238000009834 vaporization Methods 0.000 description 9
- 230000008016 vaporization Effects 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 7
- YMMPLJAAWKZWBD-UHFFFAOYSA-N 2-[2,3,5,6-tetrafluoro-4-(trifluoromethyl)phenyl]acetonitrile Chemical compound FC1=C(F)C(C(F)(F)F)=C(F)C(F)=C1CC#N YMMPLJAAWKZWBD-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000012267 brine Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000004770 highest occupied molecular orbital Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 3
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
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- 239000007788 liquid Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 238000002207 thermal evaporation Methods 0.000 description 3
- BLZOHTXDDOAASQ-UHFFFAOYSA-N 1,2,3,3-tetrachlorocyclopropene Chemical compound ClC1=C(Cl)C1(Cl)Cl BLZOHTXDDOAASQ-UHFFFAOYSA-N 0.000 description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 2
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- SWKIFLYKQXAHMD-UHFFFAOYSA-N 2-(2,5,6-trifluoropyrimidin-4-yl)acetonitrile Chemical compound FC1=NC(=C(C(=N1)CC#N)F)F SWKIFLYKQXAHMD-UHFFFAOYSA-N 0.000 description 2
- AVQDQANPLBWAEW-UHFFFAOYSA-N 2-[2,3,5-trifluoro-4,6-bis(trifluoromethyl)phenyl]acetonitrile Chemical compound FC1=C(C(=C(C(=C1F)C(F)(F)F)F)C(F)(F)F)CC#N AVQDQANPLBWAEW-UHFFFAOYSA-N 0.000 description 2
- UUZLADCDKJUECN-UHFFFAOYSA-N 4-(cyanomethyl)-2,3,5,6-tetrafluorobenzonitrile Chemical compound FC1=C(F)C(C#N)=C(F)C(F)=C1CC#N UUZLADCDKJUECN-UHFFFAOYSA-N 0.000 description 2
- YDQUBLDWKDOELD-UHFFFAOYSA-N 4-(cyanomethyl)-3,5,6-trifluoropyridine-2-carbonitrile Chemical compound C(#N)CC1=C(C(=NC(=C1F)F)C#N)F YDQUBLDWKDOELD-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- LALVQFXNRXDTGV-UHFFFAOYSA-N 1,2,3,5-tetrafluoro-4,6-bis(trifluoromethyl)benzene Chemical group FC1=C(F)C(C(F)(F)F)=C(F)C(C(F)(F)F)=C1F LALVQFXNRXDTGV-UHFFFAOYSA-N 0.000 description 1
- IOQMWOBRUDNEOA-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzonitrile Chemical compound FC1=CC(F)=C(F)C(C#N)=C1F IOQMWOBRUDNEOA-UHFFFAOYSA-N 0.000 description 1
- KZMWBUVUQLGBBP-UHFFFAOYSA-N 2,4,5,6-tetrafluoropyrimidine Chemical compound FC1=NC(F)=C(F)C(F)=N1 KZMWBUVUQLGBBP-UHFFFAOYSA-N 0.000 description 1
- XYFHRSUUAGJYOZ-UHFFFAOYSA-N 3,4,5,6-tetrafluoropyridine-2-carbonitrile Chemical compound FC1=NC(C#N)=C(F)C(F)=C1F XYFHRSUUAGJYOZ-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 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 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- IJWKASPTWOUPND-UHFFFAOYSA-N [K].CCOC(=O)C(C#N)c1c(F)c(F)c(c(F)c1C(F)(F)F)C(F)(F)F Chemical compound [K].CCOC(=O)C(C#N)c1c(F)c(F)c(c(F)c1C(F)(F)F)C(F)(F)F IJWKASPTWOUPND-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 238000000668 atmospheric pressure chemical ionisation mass spectrometry Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000013058 crude material Substances 0.000 description 1
- 125000004802 cyanophenyl group Chemical group 0.000 description 1
- DEZRYPDIMOWBDS-UHFFFAOYSA-N dcm dichloromethane Chemical compound ClCCl.ClCCl DEZRYPDIMOWBDS-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000000132 electrospray ionisation Methods 0.000 description 1
- OJCSPXHYDFONPU-UHFFFAOYSA-N etoac etoac Chemical compound CCOC(C)=O.CCOC(C)=O OJCSPXHYDFONPU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- OLMNIZJJAAWPAB-NBTZWHCOSA-M lithium;(9z,12z)-octadeca-9,12-dienoate Chemical compound [Li+].CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O OLMNIZJJAAWPAB-NBTZWHCOSA-M 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- COTNUBDHGSIOTA-UHFFFAOYSA-N meoh methanol Chemical compound OC.OC COTNUBDHGSIOTA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- BFNYNEMRWHFIMR-UHFFFAOYSA-N tert-butyl 2-cyanoacetate Chemical compound CC(C)(C)OC(=O)CC#N BFNYNEMRWHFIMR-UHFFFAOYSA-N 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/35—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms, or by nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/50—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings
- C07C255/51—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton to carbon atoms of non-condensed six-membered aromatic rings containing at least two cyano groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
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Abstract
本發明是關於一種用於製備包括一[3]-軸烯p-摻質之電性摻雜半導體材料的製程、或是用於製備含有一[3]-軸烯p-摻質之層之電子裝置的製程、分別的[3]-軸烯化合物、及半導體與層、及包括該化合物的電子裝置,該製程包括步驟: (i) 以該[3]-軸烯p-摻質加載一蒸鍍源;及 (ii) 在一升高溫度與一降低壓力下蒸鍍該[3]-軸烯p-摻質, 其中該[3]-軸烯p-摻質係選自具有根據式(I)之結構的化合物:□(I), 其中A1
及A2
獨立是芳基或雜芳基取代的氰亞甲基, 該芳基及/或雜芳基係獨立地選自4-氰-2,3,5,6-四氟苯基、2,3,5,6-四氟砒啶-4-基、4-三氟甲基-2,3,5,6-四氟苯基、2,4-二(三氟苯基)-3,5,6-三氟苯基、2,5-二(三氟甲基)-3,4,6-三氟苯基、2,4,6-三(三氟甲基)-1,3-二吖嗪-5-基、3,4-二氰-2,5,6-三氟苯基、2-氰-3,5,6-三氟砒啶-4-基、2-三氟甲基-3,5,6-三氟砒啶-4-基、2,5,6-三氟-1,3-二吖嗪-4-基及3-三氟甲基-4-氰-2,5,6-三氟苯基的A1
及A2
, 以及至少一個芳基或雜芳基是2,3,5,6-四氟砒啶-4-基、2,4-二(三氟甲基)-3,5,6-三氟苯基、2,5-二(三氟甲基)-3,4,6-三氟苯基、2,4,6-三(三氟甲基)-1,3-二吖嗪-5-基、3,4-二氰-2,5,6-三氟苯基、2-氰-3,5,6-三氟砒啶-4-基、2-三氟甲基-3,5,6-三氟砒啶-4-基、2,5,6-三氟-1,3-二吖嗪-4-基或3-三氟甲基-4-氰-2,5,6-三氟苯基,限制條件是在A1
及A2
中的雜芳基不能同時是 2,3,5,6-四氟砒啶-4-基。
Description
本發明關於以芳基或雜芳基取代之1,2,3-三亞基三(氫甲基亞基)環丙烷、其作為半導體電子裝置中之p-摻質或電洞注入材料之使用、以及用於製造此類裝置之穩健真空熱蒸鍍(VTE)製程。
已經發現以吸引電子的芳基或雜芳基取代了[3]-軸烯化合物之氰甲基亞基的化合物特別有用於作為一般有機發光二極體(OLED)電洞傳輸材料(HTM)之p-摻質,請見US 8,057,712 B2,其係併入本文作為參照。就使用這些化合物的電子裝置和半導體材料而言,大部分是使用真空熱蒸鍍(VTE)製程。在現有的蒸鍍源中和低於10-4
Pa之壓力下,目前使用的材料大部分是在介於150和300°C的溫度下氣化。為求有效,較佳是以材料加載一次的蒸鍍源可盡可能工作地長久。目前OLED中所使用之電洞傳輸基材化合物經常對其蒸發溫度維持其暴露達一或兩個星期,而在其不純物特性中沒有經歷明顯變化。在包含電性摻質的有機電子裝置的量產中,現有技術領域中摻質的不足長期熱穩定性,確實是極常成為生產歷時的關鍵限制。
因此,本發明之目的在於提供一種用以製造包含軸烯p-摻質之電子裝置的改良製程,以及可由該改良製程所製備之改良的半導體材料、層及/或電子裝置。本發明的另一目的在於為該改良製程提供改良之軸烯p-摻質。本發明的又一目的在於提供一種改良製程,以供製備該改良的軸烯p-摻質。
本發明的第一目的可藉由用於製備包含一[3]-軸烯p-摻質之一電性摻雜半導體材料、或用於製備含有包含一[3]軸烯p-摻質之層之一電子裝置的製程而實現,該製程包括步驟: (i) 以該[3]-軸烯p-摻質加載一蒸鍍源;及 (ii) 在一升高溫度與一降低壓力下蒸鍍該[3]-軸烯p-摻質, 其中該[3]-軸烯p-摻質係選自具有根據式(I)之結構的化合物:(I), 其中A1
及A2
是獨立地芳基或雜芳基取代的氰亞甲基,該芳基及/或雜芳基係獨立地在A1
及A2
中選自4-氰-2,3,5,6-四氟苯基、2,3,5,6-四氟砒啶-4-基、4-三氟甲基-2,3,5,6-四氟苯基、2,4-二(三氟苯基)-3,5,6-三氟苯基、2,5-二(三氟甲基)-3,4,6-三氟苯基、2,4,6-三(三氟甲基)-1,3-二吖嗪-5-基、3,4-二氰-2,5,6-三氟苯基、2-氰-3,5,6-三氟砒啶-4-基、2-三氟甲基-3,5,6-三氟砒啶-4-基、2,5,6-三氟-1,3-二吖嗪-4-基及3-三氟甲基-4-氰-2,5,6-三氟苯基,以及至少一個芳基或雜芳基是2,3,5,6-四氟砒啶-4-基、2,4-二(三氟甲基)-3,5,6-三氟苯基、2,5-二(三氟甲基)-3,4,6-三氟苯基、2,4,6-三(三氟甲基)-1,3-二吖嗪-5-基、3,4-二氰-2,5,6-三氟苯基、2-氰-3,5,6-三氟砒啶-4-基、2-三氟甲基-3,5,6-三氟砒啶-4-基、2,5,6-三氟-1,3-二吖嗪-4-基或3-三氟甲基-4-氰-2,5,6-三氟苯基,限制條件是在A1
及A2
中的雜芳基不能同時是 2,3,5,6-四氟砒啶-4-基。
氣化的化合物(I)接著是以齊層(neat layer)的形式沉積、或是與適當的基材材料共同沉積。化合物(I)之齊層係有利地被使用作為電洞注入或電荷產生層,其較佳是與包含基材材料之層相鄰。該基材材料較佳為包括至少一電洞傳輸基材化合物之一電洞傳輸基材材料。可以軸烯p-摻質進行電性摻雜之電洞傳輸基材化合物的實例從較早的Novaled應用而為人所知,包括本文所引用的應用。
較佳為,步驟(ii)中的蒸鍍溫度是在100至300°C的範圍內,更佳的是在125至275°C的範圍內,甚至更佳的是在150至250°C的範圍內。
步驟(ii)中的壓力較佳是低於10-1
Pa,更佳的是低於10-2
Pa,甚至更佳的是低於10-3
Pa,最佳的是低於10-4
Pa。
蒸鍍步驟(ii)的歷時較佳為比100小時久,更佳的是比150小時久,甚至更佳的是比200小時久。
為達到足夠的摻雜強度,[3]-軸烯p-摻質的氧化還原電位(藉由作為標準之循環伏安法(CV)於乙腈(ACN)中對二茂鐵/二茂鐵離子參考系統(Fc/Fc+
)所測得)較佳是在+0.10 V至+0.50 V的範圍內,更佳是在+0.20 V至+0.40 V的範圍內,甚至更佳的是在+0.25 V至+0.35 V的範圍內。
該第一目的可藉由使用從具有根據式(I)之結構的化合物中選出的[3]-軸烯化合物而實現:(I), 其中A1
及A2
是獨立地芳基或雜芳基取代的氰亞甲基,該芳基及/或雜芳基係獨立地在A1
及A2
中選自4-氰-2,3,5,6-四氟苯基、2,3,5,6-四氟砒啶-4-基、4-三氟甲基-2,3,5,6-四氟苯基、2,4-二(三氟苯基)-3,5,6-三氟苯基、2,5-二(三氟甲基)-3,4,6-三氟苯基、2,4,6-三(三氟甲基)-1,3-二吖嗪-5-基、3,4-二氰-2,5,6-三氟苯基、2-氰-3,5,6-三氟砒啶-4-基、2-三氟甲基-3,5,6-三氟砒啶-4-基、2,5,6-三氟-1,3-二吖嗪-4-基及3-三氟甲基-4-氰-2,5,6-三氟苯基, 以及至少一個芳基或雜芳基是2,3,5,6-四氟砒啶-4-基、2,4-二(三氟甲基)-3,5,6-三氟苯基、2,5-二(三氟甲基)-3,4,6-三氟苯基、2,4,6-三(三氟甲基)-1,3-二吖嗪-5-基、3,4-二氰-2,5,6-三氟苯基、2-氰-3,5,6-三氟砒啶-4-基、2-三氟甲基-3,5,6-三氟砒啶-4-基、2,5,6-三氟-1,3-二吖嗪-4-基或3-三氟甲基-4-氰-2,5,6-三氟苯基,限制條件是在A1
及A2
中的雜芳基不能同時是 2,3,5,6-四氟砒啶-4-基。
該第一目的可進一步藉由包括具有式(I)之軸烯化合物的一種半導體材料、半導體層及/或電子裝置而實現,其中,可排除建置在設有ITO陽極的玻璃基板上的實驗性OLED、由摻有8重量%之測試化合物的市售聯苯-4-基(9,9-二苯基-9H-芴-2-基)-[4-9苯基-9H-咔唑-3-基]苯基]-胺(CAS號1242056-42-3)所構成的10 nm厚電洞注入傳輸層(HIL)、由與HIL相同的基材化合物所製成之130奈米厚的電洞傳輸層、由市售帶有3 wt%之射極NUBD370的主體化合物ABH113(兩者皆來自相同供應商:韓國Sun Fine Chemicals)所製成之20nm厚發光層、由(3-(二苯並[c,h]吖啶-7-基)苯基)二苯基膦氧化物和8-亞油酸鋰(LiQ,1:1 w/w)所製成之36奈米厚電子傳輸層、及30奈米厚銀陰極,如下文裝置實例中所說明,同時可排除由以選自下文所列之化合物A1、A2、A3、A4、A5、A6、A7、A8及化合物B1、B2、B3、B4、B5、B6、B7任一種化合物的8重量%摻雜之聯苯-4-基(9,9-二苯基-9H-芴-2-基)-[4-9苯基-9H-咔唑-3-基]苯基]-胺所組成之摻雜材料,及/或這種摻雜材料之10奈米厚層。
較佳為,包括具式(I)之化合物的半導體材料或半導體層是包含在第一電極與第二電極之間。同樣較佳為,第一電極是陽極,且第二電極是陰極。在較佳具體實施例的其中之一中,包括式(I)化合物之該層與陽極相鄰。在另一較佳具體實施例中,包括式(I)化合物之該層是作為電荷產生層。同樣較佳地,該電子裝置係一OLED,在一個較佳具體實施例中為串聯OLED。
該第二目的可藉由具有根據式(I)之結構的[3]-軸烯化合物來實現:(I), 其中A1
及A2
是獨立地芳基或雜芳基取代的氰亞甲基,該芳基及/或雜芳基係獨立地在A1
及A2
中選自4-氰-2,3,5,6-四氟苯基、2,3,5,6-四氟砒啶-4-基、4-三氟甲基-2,3,5,6-四氟苯基、2,4-二(三氟苯基)-3,5,6-三氟苯基、2,5-二(三氟甲基)-3,4,6-三氟苯基、2,4,6-三(三氟甲基)-1,3-二吖嗪-5-基、3,4-二氰-2,5,6-三氟苯基、2-氰-3,5,6-三氟砒啶-4-基、2-三氟甲基-3,5,6-三氟砒啶-4-基、2,5,6-三氟-1,3-二吖嗪-4-基及3-三氟甲基-4-氰-2,5,6-三氟苯基, 以及至少一個芳基或雜芳基是2,3,5,6-四氟砒啶-4-基、2,4-二(三氟甲基)-3,5,6-三氟苯基、2,5-二(三氟甲基)-3,4,6-三氟苯基、2,4,6-三(三氟甲基)-1,3-二吖嗪-5-基、3,4-二氰-2,5,6-三氟苯基、2-氰-3,5,6-三氟砒啶-4-基、2-三氟甲基-3,5,6-三氟砒啶-4-基、2,5,6-三氟-1,3-二吖嗪-4-基或3-三氟甲基-4-氰-2,5,6-三氟苯基,限制條件是在A1
及A2
中的雜芳基不能同時是 2,3,5,6-四氟砒啶-4-基。
本發明之化合物(I)在本發明製程的具體實施例中(其中對於汽化溫度在攝氏100至300℃範圍內、且於乙腈中對於Fc+
/Fc參考氧化還原對之在0.00至0.50 V範圍內的氧化還原電位之任何電洞傳輸基材化合物而言,化合物(I)係與電洞傳輸基材材料共同蒸鍍、然後共同沉積)可選擇具有足夠p-摻雜強度且汽化溫度相比所選電洞傳輸基材化合物的汽化溫度差異低於50°C的熱穩健化合物(I)。
第三目的可藉由具有如式(I)之結構的[3]-軸烯化合物之合成製程來實現:(I), 其中A1
及A2
是獨立地芳基或雜芳基取代的氰亞甲基,該芳基及/或雜芳基係獨立地在A1
及A2
中選自4-氰-2,3,5,6-四氟苯基、2,3,5,6-四氟砒啶-4-基、4-三氟甲基-2,3,5,6-四氟苯基、2,4-二(三氟苯基)-3,5,6-三氟苯基、2,5-二(三氟甲基)-3,4,6-三氟苯基、2,4,6-三(三氟甲基)-1,3-二吖嗪-5-基、3,4-二氰-2,5,6-三氟苯基、2-氰-3,5,6-三氟砒啶-4-基、2-三氟甲基-3,5,6-三氟砒啶-4-基、2,5,6-三氟-1,3-二吖嗪-4-基及3-三氟甲基-4-氰-2,5,6-三氟苯基, 以及至少一個芳基或雜芳基是2,3,5,6-四氟砒啶-4-基、2,4-二(三氟甲基)-3,5,6-三氟苯基、2,5-二(三氟甲基)-3,4,6-三氟苯基、2,4,6-三(三氟甲基)-1,3-二吖嗪-5-基、3,4-二氰-2,5,6-三氟苯基、2-氰-3,5,6-三氟砒啶-4-基、2-三氟甲基-3,5,6-三氟砒啶-4-基、2,5,6-三氟-1,3-二吖嗪-4-基或3-三氟甲基-4-氰-2,5,6-三氟苯基,限制條件是在A1
及A2
中的雜芳基不能同時是 2,3,5,6-四氟砒啶-4-基, 其中,形成式(I)化合物的最後一個合成步驟是在一溶劑中實施,該溶劑包括至少一飽和性鹵化羧酸。應理解的是,飽和性鹵化羧酸並不包括僅單(sigma)碳-碳鍵。飽和性鹵化羧酸可為脂族或脂環。更佳的是,在20°C下為液體的飽和性鹵化羧酸,甚至更佳的是,在0°C下為液體的飽和性鹵化羧酸。在一個具體實施例中,飽和性鹵化羧酸是一飽和性全鹵化羧酸。在一較佳具體實施例中,該飽和性全鹵化羧酸為三氟乙酸。
較佳為,飽和性鹵化羧酸的濃度在5-95 wt%的範圍內,更佳是在10-90 wt%的範圍內,且甚至更佳的是在15-85 wt%的範圍內,最佳的是在20-80 wt%的範圍內。
溶劑可進一步包括飽和性羧酸及/或無機酸。飽和性羧酸可為醋酸,無機酸可為硝酸。
較佳為,在形成化合物(I)之最後合成步驟中存在有氧化劑,同樣較佳地是,硝酸也是作為氧化劑。同樣較佳地,硝酸包括水。同樣較佳地,形成化合物(I)之最後合成步驟實質上不含自由鹵素,如WO2015/007729中所述。同樣較佳地,在最後合成步驟中的反應溫度是在0-100°C的範圍內,更佳地是在10-90°C的範圍內,甚至更佳是在15-85°C的範圍內,最佳的是在20-80°C的範圍內。在使用這種製程時,能夠實現特別高產率及/或純度。
US 8,057,712 B2中所述之[3]-軸烯p-摻質被證明為一種非常成功的p-摻雜概念,特別是針對OLED顯示器,如WO2010/075836、WO2010/132236、WO2011/134458、WO2014/009310、US2012/223296、WO2013/135237、WO2014/037512、WO2014/060526等其他文件中所述。
根據裝置設計以及被選擇作為電洞傳輸、電子阻擋及/或p-摻質被使用所在或相鄰的發光層基材之特定化合物而定,摻質的最低未佔據分子軌道(LUMO)的能階、以及其為與所選電洞傳輸基材和所選用於相鄰層之材料特性進行最佳匹配所需要的最佳蒸鍍溫度會在相當大的範圍中加以變化。
此變化性是要進一步開發新型化合物的主要誘因,目標是要提供大範圍光譜之[3]-軸烯p-摻質,這能夠針對每一個特別情況提供與所選基材的最高佔據分子軌道(HOMO)能階以及與在業界蒸鍍源中這種基材的蒸鍍溫度都良好匹配的摻質。
適用結構之選擇的共同點為對於所提供之p-摻質的高長期熱穩定性的需求,這允許以化合物加載的蒸鍍源的合理長久生產活動。
在候選的化合物中,已經藉由特別設計的「壺腹測試(ampulla tests)」來檢驗是否符合此需求。被分至石英安瓶中並且在真空下予以密封的每一種特定化合物的樣品被保持在各種溫度的恆溫器中達100至350小時的時間。樣品不純度輪廓的變化是由特別針對[3]-軸烯p-摻質而設計的光譜方法與色譜方法進行檢驗。最後,鑑別出能在化合物的蒸鍍溫度下具有穩定純度達至少100小時之處理時間的特定結構性基序。
新的結構性基序在新的取代模式中含有在式(I)中之芳基或雜芳基取代基。其他的研究顯示,在一軸烯分子中一起結合新鑑別的有利結構特徵、或將它們與先前技術中已經習知之選擇取代模式結合,能夠得到所需要的廣泛系列之具有各種強度和揮發性的熱穩健p-摻質。
關於式(I),所有的A1’
都是相同的,但是A1
和A2
可為彼此相同或彼此不同。
應理解的是,為求簡潔,在本案中,具有相同結構性官能基A1
和A2
中取代模式的所有式(I)化合物都被指定為「對稱型」。類似地,具有不同結構性官能基A1
和A2
中之取代模式的所有軸烯化合物被指定為「非對稱型」。這種指定並不涵蓋藉由在環外雙鍵上E-和Z-取代基的各種組合所產生的可能的幾何性同分異構物。推測儘管以說明用於本發明和比較例之軸烯化合物的示例性結構為準,但由該方法合成的材料尚可包括所有可能的幾何性同分異構物。
同樣地,為求簡潔,僅以示例性結構來簡化酯中間物、甜菜鹼中間物和軸烯前驅物的所有可能互變異構形式和幾何性同分異構物(所需之軸烯化合物的被還原形式),然而事實上,這些示例性結構代表了在各種個別情況中可能的所有同分異構物與互變異構物。
發現到對於包含結構性官能基A1
和A2
中兩種不同芳基及/或雜芳取代基的任何式(I)測試結構而言,以藉由在標準條件下於乙腈溶液中對Fc/Fc+
參考氧化還原電位對以循環伏安法測得之化合物氧化還原電位所表示的摻質強度可落在從母體對稱性軸烯化合物的氧化還原電位得到的10%之精確性內,該母體對稱性軸烯化合物包括結合於所產生之不對稱結構中之芳基/雜芳基取代模式。
發現到在[3]-軸烯分子中的每一個(雜)芳基取代之氰基亞甲基結構單元是作為以一固定增量對整體氧化還原電位有貢獻的一獨立官能基(moiety),其與接附至[3]-軸烯核心的剩餘兩個角部的(雜)芳基取代基的取代模式無關。此事實能夠以針對包括對應取代模式的「母體」對稱性結構所測得之氧化還原電位為基礎,輕易預測出非對稱性結構的氧化還原電位。
換言之,在式(I)內之任何非對稱性結構的氧化還原電位都可被估算為來自對應對稱性結構的結構官能基之增量的線性組合。
藉由比較本發明之化合物與從上述引用的先前技術文件中所知或可基於其組合教示而得知的比較例化合物的性質,即可說明該目的之實現。
本發明的技術效果可歸結為三點:根據本發明之改良的軸烯p-摻質保留了如OLED顯示器之電子裝置中以及它們的半導體材料中的已知化合物的良好性能,並且能允許穩健的VTE製程以製造包含軸烯p-摻質的有機電子裝置,其可在工業規模上應用。
具體而言,本發明允許獨立地調整摻雜強度以及摻質的揮發度為一選擇基材的摻雜度與揮發度(在其充分廣泛數值範圍中)。此外,用於製造本發明之p-摻質之本發明製程能夠進行其工業規模產製造,其具有比現有技術更穩健的品質和更高的產率。
此外,式(I)之新化合物無論是在何處被用來取代現有技術中具有較小氧化還原電位的p-摻質,都可於較低濃度中使用較強的p-摻質。相較於現有技術中的p-摻質,它提供了電子裝置設計者額外的自由度,例如就可使用本發明之材料來提供的摻雜層的較低光學吸收而言。
比較例化合物的示例結構為:C1C2C3C4C5C6.
本發明之示例結構如下:
對稱型結構:A1A2 A3 A4A5A6A7A8
非對稱型結構:B1B2B3B4B5B6B7B8B9B10
表1
表格說明:
熔點(mp)溫度是藉由DSC於加熱速率10 K/min下所測得,所報告的數值與DSC曲線上所觀察到的熔化吸熱尖峰溫度對應。Tdec
表示TGA/DSC曲線上的分解峰的尖峰溫度。兩個實驗測量參數被用於估算在用於OLED顯示器量產的工業VTE源中所能預期的汽化溫度。第一個(Ttc
)是化合物在高真空測試腔室中的汽化溫度,該高真空測試腔室設有一溫度偵測器,用以測量在填有標準量測試化合物的蒸鍍坩鍋底部的溫度。與放置在坩鍋上方的偵測器測得之蒸發起始對應的溫度係於表中報告。第二個參數T99.5%
是對應於TGA曲線顯示在正常壓力與10K/min的加熱速率下之測試化合物的0.5%重量損失處的溫度,且其係對應於在正常壓力下化合物汽化的開始。E0
表示在測試化合物之乙腈溶液中從所測量循環伏安法曲線得到的電化學氧化還原電位數值(針對作為標準的參考氧化還原對Fc/Fc+
)。所有的測試化合物在這些條件下都顯示可逆的氧化還原行為。
發現到從一特定材料之數值Ttc
和T99.5%
所計算出的算術平均值會與此材料在量產蒸鍍源中被觀察到的汽化溫度良好匹配。對於Ttc
和T99.5%
兩個數值都可得的化合物而言,表格中所提出的業界蒸鍍源汽化溫度估算值Test
係與此算術平均值相對應。
對於僅有T99.5%
為可得的化合物而言,Test
仍以同樣方式計算,只有於計算中所使用的Ttc
為從觀察之T99.5%
數值使用線性關係y=0.7326* T99.5%
-50.084所計算出的數值y,該線性關係式是得自第1圖中所示之T99.5%
與Ttc
之間的相關性。
表1說明了新的化合物的性質滿足本發明的目的,其提供了可用氧化還原電位和蒸發溫度的廣泛範圍。對於測試之化合物而言,合理的長期熱穩定性在業界VTE源中預期的蒸發溫度下被証實。
當然不排除本發明在作為VTE替代方式而開發的製程中也是有利的,特別是在溶液加工中。已證明新的化合物不僅提供了大範圍的揮發性,也提供了在各種溶劑中之大範圍可溶性。
實例
合成實例
對稱型化合物的合成是根據專利US 8,057,712和申請案EP 13176542中所述之程序。
非對稱型取代之衍生物的合成是根據專利US 3,963,769和文獻J. Am. Chem. Soc. 1976, 卷98, 第610-611頁中所述之程序。
甜菜鹼前驅物
甜菜鹼C2-B
於500毫升之Schlenk燒瓶中加入四氯環丙烯(8.30克,46.7 mmol)與2-(4-氰基-2,3,5,6-四氟苯基)乙腈(C2-A,20.0克,93.4 mmol)和乾燥的二氯甲烷(DCM,160毫升)。混合物被攪拌,並且被冷卻至-30°C,然後逐滴加入三乙基胺(30.7克,304 mmol)達30分鐘。混合物允許被加熱至室溫超過1小時。逐滴加入水(24毫升),並過濾混合物。固體利用DCM(3x50毫升)、MeOH(2x50毫升)和水(4x50毫升)清洗,並在真空中進行乾燥,以取得28克之粗產物。用乙腈重新結晶得到之產物為黃色固體(19克,34 mmol)。 TGA-DSC(篩選):0.5%之質量損失=215°C,Tdec.
(起始)=217°C。 ESI/APCI-MS:m/z=532(M-C2
H5
)。 IR [cm-1
]: 2987 (w), 2243 (m), 2196 (m), 1851 (m), 1642 (s), 1479 (s), 1422 (s), 1368 (s), 1313 (s), 1200 (m), 1139 (m), 975 (s), 894 (m), 812 (m)。19
F NMR (471 MHz, CD3CN) δ = -136.53, -141.77。1
H NMR (500 MHz, CD3CN) δ = 3.90 (q, 2H), 1.42 (t, 3H)。
甜菜鹼C4-B
於250毫升之Schlenk燒瓶中加入四氯環丙烯(4.15克,23.3 mmol)與2-(2,3,5,6-四氟-4-(三氟甲基)苯基)乙腈(C4-A,12.0克,46.7 mmol)和乾燥的DCM(80毫升)。混合物被攪拌,並且被冷卻至-30°C,然後逐滴加入三乙基胺(15.4克,152 mmol)達30分鐘。混合物允許被加熱至室溫超過1小時。逐滴加入水(12毫升),並過濾混合物。固體利用水(2x140毫升)清洗,並在真空中進行乾燥,以取得6克之粗產物。使濾液濃縮至30毫升而形成沉澱。過濾提供了第二批次的粗產物(6克)。每一批次都在室溫下以乙醚(25毫升)予以攪拌達1小時、經過濾,並於真空中使固體乾燥。
得到無色固體為產物(5.49克和5.81克,等於11.3克,17.5 mmol)。
ESI-MS:pos. 436, 648 (M)+
, 686;neg 618 (M-Et-H)- 19
F NMR (471 MHz, CD3CN) δ = -57.05, -142.79, -144.39。1
H NMR (500 MHz, CD3CN) δ = 3.89 (q, 2H), 1.43 (t, 3H)。 IR [cm-1
]: 2996 (w), 2185 (m), 1862 (w), 1652 (m), 1654 (s), 1461 (s), 1419 (s), 1397 (m), 1335 (s), 1316 (m), 1254 (s), 1170 (m), 1150 (m), 1124 (s), 1043 (m), 977 (s), 812 (m)。
類似的甜菜鹼中間物C3-8、A1-B、A2-B、A3-B、A4-B、A5-B、A6-B、A7-B及A8-B(其對應於它們的對稱型軸烯之取代基C3、A1、A2、A3、A4、A5、A6、A7與A8)係可類似於C2-B和C4-B而製備。
比較例化合物C5
軸烯前驅物(還原型)C5-P
於氬氣下,在500毫升Schlenk燒瓶中加入甜菜鹼C2-B(5.61克,10.0 mmol)、無水磷酸鉀(4.46克,21.0 mmol)以及4-二甲氨基吡啶(1.22克,10.0 mmol)。燒瓶被置於冰塊上冷卻,並加入乾燥的DMF(185毫升)。混合物被置於並冰塊上攪拌達10分鐘,並加入2-(2,3,5,6-四氟-4-(三氟甲基)苯基)乙腈C4-A(2.70克,10.5 mmol)之DMF(15毫升)溶液超過10分鐘。在冰塊上進行4小時攪拌之後,移除冷浴並使混合物加熱至室溫。在總反應時間27小時之後,將黑紅色混合物加入食鹽水(150毫升)和EtOAc(400毫升)中。使各相分離,並以半濃縮食鹽水(2x150毫升)、2M HCl水溶液(3x150毫升)(溶液轉為深綠色)及飽和的NaHCO3
水溶液(3x100毫升)(溶液轉為黑色/紅色)清洗有機層。有機相在MgSO4
中乾燥並加以濃縮。含DCM/MeOH之色柱色譜(矽膠)提供了一種深紅色溶液,其經濃縮以提供黑色固體產物(4.88克)。
中間產物並未進一步純化,其被直接被使用於最後步驟中。
軸烯C5
將前驅物C5-P(4.82克)溶解於冰醋酸(67毫升)中,並在室溫下逐滴加入硝酸水溶液(65% w/w,67毫升)。溶液從黑色/綠色轉為紅色/橘色。在攪拌16小時之後,有橘色沉澱物形成,使混合物於冰塊上冷卻。逐滴加入水(70毫升),並攪拌該混合物15分鐘。過濾得到橘色固體,其以冷水(10x40毫升)清洗,直到濾液呈中性為止。於空氣中、以及於油泵真空中乾燥,得到3.25克固體,其係溶解於熱的1-氯丁烷(100°C,400毫升)中。溶液被冷卻至室溫,並透過玻璃料進行過濾。濾液被濃縮至約50毫升而得到包含橘色固體之懸浮液。在過濾、並於空氣中和於油泵真空中乾燥之後,即可得到橘色粉末(2.62克)之產物,該產物在高度真空中藉由昇華而進一步純化。
ESI-MS:m/z = 715 (neg)。 UV-Vis(乙腈(ACN)):lmax
=457 nm。 IR [cm-1
]:2249 (w), 1662 (w), 1563 (m), 1486 (s), 1415 (m), 1343 (m), 1328 (m), 1257 (m), 1194 (m), 1155 (m), 1069 (m), 978 (s), 909 (m), 813 (m), 717 (m)。 TGA-DSC(揮發性):在281°C下有0.5%質量損失,Tdec.
(起始)=325°C。19
F NMR (471 MHz, CH3CN):δ = -57.43, -77.04, -132.42, -134.43, -135.08, -139.98。
比較例化合物C6
軸烯前驅物(還原型)C6-P
於250毫升之Schlenk燒瓶中加入Cs2
CO3
(3.42克,10.5 mmol)和DMF(90毫升)。於冰上攪拌混合物達10分鐘,並且加入甜菜鹼C4-B(3.24克,5.0 mmol)。在十分鐘之後,加入DMF(10毫升)中之2-(4-氰基-2,3,5,6-四氟苯基)乙腈的C2-A(1.09克,5.1 mmol)之溶液。混合物於冰上攪拌,並在19個小時以後移去冷浴。在總反應時間達1天又19個小時之後,將黑-紅色混合物加至食鹽水(80毫升)與EtOA(200毫升)中。分離各相,並以半濃縮食鹽水(2x80毫升)清洗有機層,有機層在MgSO4
中乾燥並加以濃縮,以得到含一些殘餘DMF之黑-紅色油質產物(6.29克)。
此中間物並未被進一步純化,其直接被使用於最後步驟中。
軸烯C6
前驅物C6-P(6.29克)被溶解於83毫升的冰醋酸中,並在室溫下逐滴加入83毫升的硝酸水溶液(65% w/w)。溶液從黑-綠色轉為紅-橘色。在攪拌16小時之後,已形成橘色沉澱物,並使混合物於冰上冷卻。逐滴加入100毫升的水,並且攪拌混合物15分鐘。過濾得到橘色固體,其以冷水(8x30毫升)清洗直到濾液呈中性為止。在於空氣中以及於油泵真空中乾燥之後,得到橘色粉末產物(3.07克),其藉由於高度真空中昇華而進一步純化。
ESI-MS:m/z = 758 (neg)。 UV-Vis(ACN):lmax
=454 nm。 IR [cm-1
]:2248 (w), 1662 (w), 1565 (m), 1483 (s), 1416 (m), 1339 (s), 1252 (m), 1198 (m), 1148 (s), 1060 (m), 984 (s), 907 (m), 812 (m), 785 (w), 715 (m)。 TGA-DSC(揮發性):在252°C下有0.5%質量損失,Tdec.
(起始)=320°C。19
F NMR (471 MHz, CD3CN) δ = -57.46, -132.46, -134.50, -135.15, -140.04。
本發明之化合物B5
步驟1:1-氰基-1-(2-氰基-2,3,6-三氟吡啶-4-基)-2-乙氧基-2-氧乙醇-1-化物鉀酯(酯中間體A3-EE)
在250毫升的燒瓶中對7.2克(142 mmol)的2-氰基-3,4,5,6-四氟吡啶、60毫升的乙腈以及6.78克(170.4 mmol)的碳酸鉀加入4.6克(142 mmol)氰乙酸乙酯(溶解於10毫升之ACN中)。在室溫下攪拌三天之後,所形成的沉澱物被過濾,並以2x20毫升之ACN進行清洗。有機溶劑被蒸散,剩餘的橘色固體在真空(10-3
mbar)下進行乾燥,並且不進行任何進一步純化即被使用於下一個步驟中。
產率:10.4克(83%)。 ESI-MS:M(neg)=268。 HPLC-MS m/z=268(neg)。
步驟2:4-(氰基甲基)-3,5,6-三氟氰基吡啶 (丁腈中間體A3-A)
在250毫升圓底燒瓶中,10.39克(33.8 mmol)的酯中間體A3-eE被溶解於86毫升醋酸水溶液(50% w/w)中。加入1.3毫升之硫酸(濃縮)並且在迴流下加熱混合物2小時。在冷卻至室溫之後,混合物與200毫升冰水一起被倒入1升燒杯中。在加入200毫升乙酸乙酯之後,在室溫下攪拌混合物達30分鐘。有機層被分離,並且以2x200毫升的乙酸乙酯萃取水溶液層。利用200毫升的水、200毫升的飽和碳酸氫鈉水溶液、以及200毫升的水清洗組合之有機層。經硫酸鈉乾燥後,於真空中移除溶液中之溶劑,得到黃色油狀物。在真空中進行蒸餾而得到淺黃色油狀物(在4*10-3
mbar下,Tbath
為190 °C;bp為110°C)。 產率:4.5克(68%)。 TLC(SiO2
, DCM):Rf
=0.65 GC-MS: tR
= 9.02分,m/z = 197.95%;tR
= 8.86分,m/z = 197.5%。1
H-NMR (600 MHz, CD3CN):δ = 4.03 (s, 2H)。19
F-NMR (282 MHz, CD3CN):δ = -81.11 (t, J = 25.4, 1F), -114.21 (dd, J = 8.1, 26.5, 1F), -122.46 (dd, J = 8.0, 24.3, 1F)。
步驟3:(Z)-4-(氰基(2-(氰基(2,3,5,6-四氟-4-(三氟甲基)-苯基)甲基)-3-(氰基(2,3,5,6-四氟-4-(三氟甲基)苯基)-亞甲基)環丙基-1-烯-1-基)甲基)-3,5,6-三氟丙二腈 (軸烯前驅物B5-P)
於250毫升之Schlenk燒瓶中,在氬氣下使3.3克Cs2
CO3
懸浮於90毫升DMF中。懸浮液被冷卻至0°C,並且加入3.1克(4.8 mmol)之甜菜鹼中間體C4-B而形成橘色懸浮物。在0°C下於10毫升的乾燥DMF中加入1.0克4-(氰基甲基)-3,5,6-三氟氰基吡啶(A3-A,5.0 mmol)之後,移除冷浴,並持續攪拌過夜。在室溫下另外攪拌棕色懸浮液24小時,並將混合物倒入100毫升的飽和NaCl溶液中。以100毫升之乙酸乙酯進行萃取,以50毫升NaCl水溶液清洗兩次,以Na2
SO4
進行乾燥,並移除溶劑而產出紅色油狀物,其於真空中被乾燥。
粗產率:6.89克(191%) HPLC-MS:m/z = 371 ((m/z)/2),742 (m/z – H, C29
H1
F17
N5 2-
), tR
= 7.8分,m/z = 741 (m/z – H, C29
F17
N5 -
),tR
= 13.9分。 步驟4:(2Z,2’E)-2,2’-((E)-3-(氰基(2-氰基-3,5,6-三氟吡啶-4-基)亞甲基)環丙烷-1,2-亞乙基)雙(2-(2,3,5,6-四氟-4-(三氟甲基)-苯基)乙腈) (軸烯化合物B5)
將3.3克(1.0 mmol)軸烯前驅物B5-P溶解於44毫升冰醋酸中,並在室溫下以44毫升硝酸水溶液(65% w/w)逐滴處理。所產生的紅色溶液經攪拌過夜,然後被倒入80毫升冷水中。在室溫下攪拌1小時,過濾出所產生的橘色沉澱物,並以水進行清洗直到pH呈中性為止,並於真空中乾燥。
產率:1.26克(39%)。
粗產物係從環己烷與氯己烷之混合物重新結晶而得。
本發明之化合物B6
步驟1:乙基2-氰基-2-(2,3,5-三氟-4,6-雙(三氟甲基)苯基)乙酸乙酯鉀鹽 (酯中間體A2-eE)
在250毫升燒瓶中,混合10克全氟-間-二甲苯、65毫升DMF以及5.8克無水碳酸鉀。攪拌5分鐘之後,將3.75毫升氰乙酸乙酯逐滴加入至持續攪拌的黃色懸浮液中。在室溫下經過48小時之後,根據TLC分析可知反應已完成。在反應期間所形成的沉澱物藉由過濾移除,並以乙腈加以清洗。使濾液旋轉蒸發至乾,並將所產生的油狀物溶解於40毫升甲苯中,並且再次蒸發至乾以去除殘留的DMF。
粗產率:18.8克(129%) ESI-MS:m/z = 378 (m/z – K, C13
H5
F9
NO2 -
;neg)。 IR (ATR):3443, 2161, 1662, 1599, 1469, 1352, 1262, 1215, 1125, 1062, 936, 879, 732 cm-1
。
步驟2:2-(2,3,5-三氟-4,6-雙(三氟甲基)苯基)乙腈 (丁腈中間體A2-A)
在250毫升燒瓶中,使18.0克粗2-氰基-2-(2,3,5-三氟-4,6-雙(三氟甲基)苯基)乙酸乙酯鉀鹽(先前步驟中之A2-eE)與4.6毫升濃縮硫酸溶解於醋酸水溶液(50% v/v)中。混合物在迴流下加熱48小時。在冷卻至室溫之後,混合物與100毫升冰水一起被倒入至500毫升燒杯中並且攪拌5分鐘。以3x50毫升乙酸乙酯萃取該混合物。以2x50毫升飽和碳酸氫鈉水溶液和100毫升水清洗組合之有機層。在以硫酸鈉乾燥該有機層之後,於真空中移除溶劑,以得棕色油狀物。於真空中蒸餾可得到無色液體(bp為75-80°C (在10-2
mbar下;主要部分))。
產率:8.45克(64%)。 GC-MS:m/z=307。 IR(ATR):1650, 1608, 1495, 1469, 1354, 1243, 1142, 1081, 1033, 963, 894, 733, 655 cm-1
。
步驟3:4-(氰基(2-(氰基(2,3,5-三氟-4,6-雙(三氟甲基)苯基)-甲基)-3-(氰基(4-氰基-2,3,5,6-四氟苯基)甲基)環丙-2-烯-1-亞基)-甲基)-2,3,5,6-四氟苯甲腈 (軸烯前驅物B6-P)
在氬氣下之100毫升Schlenk燒瓶中,2.12克碳酸銫懸浮於45毫升乾燥二甲基甲醯胺中,並且冷卻至0°C。將在5毫升乾燥二甲基甲醯胺中1.0克之2-(2,3,5-三氟-4,6-雙(三氟甲基)苯基)乙腈溶液緩慢加到懸浮液中。攪拌混合物達5分鐘,並加入1.74克甜菜鹼中間體C2-B成為固體。攪拌持續達24小時,讓反應達到環境溫度。反應混合物被倒入內含100毫升水與80毫升乙酸乙酯之250毫升分液漏斗中。有機層被分離、以80毫升的半飽和NaCl水溶液清洗兩次,以80毫升的2M HCL水溶液清洗兩次,並以80毫升的飽和碳酸氫鈉水溶液清洗兩次。
最後以硫酸鎂使有機層乾燥,並且藉由真空蒸發來小心移除溶劑,得到深紫色固體。
粗產率:2.8克(115%)。 ESI-MS: m/z = 766, 382 (neg)。 IR (ATR): 2233, 2165, 1639, 1475, 1370, 1339, 1257, 1214, 1134, 969, 815, 732 cm-1
。
步驟4:(4,4’-((1Z, 1’E)-((E)-3-(氰基(3,5,6-三氟-2,4-雙(三氟甲基)苯基)亞甲基)環丙烷-1,2-亞基)雙(氰亞基))雙(2,3,5,6-四氟芐腈) (軸烯化合物B6)
在配有滴濾漏斗之100毫升燒瓶中,使1.44克(1.88 mmol)軸烯前驅物B6-P溶解於19毫升的冰醋酸中。在劇烈攪拌下,逐滴加入19毫升之濃縮硝酸(65%,w/w)。在加入硝酸期間,溶液的顏色從黃綠色轉為暗紅色。持續攪拌過夜。然後將溶液冷卻至0°C並且逐滴加入40毫升的水,以產生亮橘色產物沉澱。於燒結之玻璃料上收集粗固體產物,並以3x15毫升水進行清洗。使潮濕生料在真空下於乾燥爐中以40°C乾燥3小時,然後在高度真空(10-2
mbar)下以環境溫度予以乾燥。乾燥的材料接著從3:2(v/v)的1-氯丁烷和環己烷之混合物重新結晶。 產率:333毫克(23%)
本發明之化合物B7
步驟1:鉀2-(叔丁氧基)-1-氰基-2-氧代-1-(2,5,6-三氟吡啶-4-基)乙-1-化物鉀酯(酯中間體A7-tbE)
在250毫升之燒瓶中,使10克(65.8 mmol)的全氟嘧啶與18.2克(132 mmol)的無水碳酸鉀溶解於/懸浮於130毫升的乙腈中。在攪拌下加入10毫升乙腈中之11.14克(78.9 mmol)氰乙酸叔丁酯之溶液,觀察到反應混合物的顏色變化轉為黃色。反應混合物在環境溫度下攪拌達3天,並過濾以移除固體。從濾液中移除溶劑,並以120毫升DCM搗碎所得之黃色固體。
產率:20.1克(98%)1
H-NMR (CD3CN, 300 MHz): 1.47 (s, 9 H)。19
F-NMR (CD3CN, 282.3 MHz): -53.2 (d, 1 F), -93.4 (d, 1 F), -163.7 (br s, 1 F)。 IR (ATR, cm-1
): 2185, 1738, 1646, 1606, 1539, 1461, 1442, 1377, 1281, 1198, 1155, 1115, 1027, 899, 840, 775。
步驟2:2-(2,5,6-三氟嘧啶-4-基)乙腈 (丁腈中間體A7-A)
於帶有螺帽蓋的壓力管中加入5.5克(17.7 mmol)之A7-tbE以及60毫升的二烷。對此混合物添加17.7毫升的4M二烷中無水HCl,並且密封此管。反應混合物被加熱4小時至100°C,然後被倒入100毫升水中。此混合物以3x50毫升的EtOAc萃取,並且以50毫升水及50毫升食鹽水清洗所收集的有機層。在以Na2
SO4
進行乾燥之後,溶劑被移除,並且藉由球對球蒸餾(bulb-to-bulb distillation)來純化粗產物(140°C @3x10-3
mbar)。
產率:2.02克(66%)19
F-NMR (CDCl3, 282.3 MHz): -45.2 (d, 1F), -72.3 (d, 1 F), -156.2 (m, 1 F)。 GC-MS: m/z = 173 (M+
, 100), 153(20), 108(20)。 IR (ATR, cm-1
): 2269, 1609, 1462, 1402, 1243, 1105, 1050, 1017, 928, 769, 725。
步驟3:(Z)-2-(2-(氰基(2,3,5,6-四氟-4-(三氟甲基)苯基)-甲基)-3-(氰基(2,3,5,6-四氟-4-(三氟甲基)苯基)亞甲基)環丙基-1-烯-1-基)-2-(2,5,6-三氟嘧啶-4-基)乙腈 (軸烯前驅物B7-P)
於氬氣下、250毫升之Schlenk燒瓶中,使3.6克Cs2
CO3
懸浮於90毫升DMF中。懸浮液被冷卻至0°C,加入甜菜鹼中間體C4-B(3.6克,5.6 mmol),此時形成橘色懸浮物。在0°C下對被攪拌的混合物加入10毫升乾燥DMF中1.0克2-(2,5,6-三氟嘧啶-4-基)乙腈(A7-A,5.7 mmol)之後,移除冷浴,並持續攪拌過夜。在室溫下再另外攪拌棕色懸浮物24小時,然後將反應混合物倒入100毫升的飽和NaCl水溶液中。以100毫升乙酸乙酯萃取,以50毫升NaCl溶液清洗兩次,以Na2
SO4
進行乾燥,並移除溶劑而得到在真空下被乾燥之紅色油狀物。
產率:6.06克(151%)。 HPLC-MS: m/z = 358 ((m/z)/2), 718 (M-H)。
步驟4:(2Z,2’E)-2,2’-((E)-3-(氰基(2,5,6-三氟吡啶-4-基)亞甲基)環丙烷-1,2-亞乙基)雙(2-(2,3,5,6-四氟-4-(三氟甲基)苯基)-乙腈) (軸烯化合物B7)
在室溫下使3.0克(4.2 mmol)之A7-P溶解於42毫升冰醋酸中,並以42毫升硝酸水溶液(65% w/w)逐滴處理。所產生的紅色溶液被攪拌過夜,然後被倒入80毫升冷水中。在室溫下攪拌1小時之後,所產生的橘色沉澱物被過濾出,並以水清洗直到pH值呈中性為止,並於真空中乾燥。
粗產率:0.9克(30%) 從環己烷和氯己烷的混合物重新結晶出粗產物。
裝置實例
在設有ITO陽極、10奈米厚之電洞注入傳輸層(HIL)、130奈米厚之電洞傳輸層、20奈米厚之發射層、36奈米厚之電子傳輸層、以及30奈米厚之銀陰極的玻璃基板上建置一實驗型OLED,其中HIL是由摻有8重量%之測試化合物的市售聯苯-4-基(9,9-二苯基-9H-芴-2-基)-[4-9苯基-9H-咔唑-3-基)苯基]-胺(CAS編號:1242056-42-3)所組成,電洞傳輸層是由與HIL相同之基材化合物製成,發射層是由帶有3 wt%射極NUBD370之市售主材化合物ABH113所製成(兩者皆得自相同供應商:韓國Sun Fine Chemicals),電子傳輸層是由(3-(二苯並[c,h]吖啶-7-基)苯基)二苯基膦氧化物和8-羥基烯醇鋰(LiQ,1:1 w/w)所製成,對於比較例和本發明之化合物而言,在電壓、效率、使用壽命與色彩座標上都觀察到類似性能。
在前述說明與申請專利範圍中所揭露之本發明特徵可獨立地被使用、以及以任意組合方式使用,以在各個具體實施例中實現本發明。
在本案中所使用的縮寫和符號包括: ACN 乙腈 bp 沸點 br 廣 CAS 化學文摘服務社 conc. 濃縮 CV 循環伏安法 DCM 二氯甲烷 DMF N,N-二甲基甲醯胺 DSC 差示掃瞄量熱法 E0
電化學氧化還原電位 EIL 電子注入層 ESI 電噴霧離子化 ETL 電子傳輸層 ETM 電子傳輸基材 EtOAc 乙酸乙酯 Fc+
/Fc 二茂鐵離子/二茂鐵參考系統 GC 氣相色層分析法 HIL 電洞注入層 HOMO 最高佔據分子軌道 HTL 電洞傳輸層 HTM 電洞傳輸基材 IR 紅外線(光、光譜) ITO 氧化銦錫 LiQ 8-羥基烯醇鋰 LUMO 最低未佔據分子軌道 mol% 莫耳百分率濃度 MeOH 甲醇 mp 熔點 MS 質譜分析法 m/z 質量/電荷比率 neg 負 OLED 有機發光二極體 Rf
滯留因子 TGA 熱重分析 THF 四氫呋喃 TLC 薄層色譜分析 tr
停留時間 UV-vis 紫外光-可見光(光、光譜) vol% 體積百分率濃度 v/v 體積對體積比(體積百分率) VTE 真空熱蒸鍍 wt% 重量(質量)百分率 w/w 重量對重量比(重量百分率)
無。
第1圖說明在正常壓力下於TGA分析中產生0.5 %重量損失之溫度T99.5
與於高真空測試腔室中測量之速率起始溫度Ttc
之間的相關性(圖中以Tsub
指示);表現為線性關係y = 0.7326*T99.5%
- 50.084的相關性於無法得到實驗數值時用以估算化合物之值Ttc
。
Claims (15)
- 用於製備一電性摻雜半導體材料或一電子裝置之製程,該電性摻雜半導體材料包括一[3]-軸烯p-摻質,該電子裝置包括一層,該層有一[3]-軸烯p-摻質,該製程包括下列步驟: (i) 以該[3]-軸烯p-摻質加載一蒸鍍源;及(ii) 在一升高溫度與一降低壓力下蒸鍍該[3]-軸烯p-摻質,其中該[3]-軸烯p-摻質係選自具有根據式(I)之一結構的化合物:(I), 其中A1 及A2 是獨立地芳基或雜芳基取代的氰亞甲基, 該芳基及/或雜芳基係獨立地選自4-氰-2,3,5,6-四氟苯基、2,3,5,6-四氟砒啶-4-基、4-三氟甲基-2,3,5,6-四氟苯基、2,4-二(三氟苯基)-3,5,6-三氟苯基、2,5-二(三氟甲基)-3,4,6-三氟苯基、2,4,6-三(三氟甲基)-1,3-二吖嗪-5-基、3,4-二氰-2,5,6-三氟苯基、2-氰-3,5,6-三氟砒啶-4-基、2-三氟甲基-3,5,6-三氟砒啶-4-基、2,5,6-三氟-1,3-二吖嗪-4-基及3-三氟甲基-4-氰-2,5,6-三氟苯基的A1 及A2 , 以及至少一個芳基或雜芳基是2,3,5,6-四氟砒啶-4-基、2,4-二(三氟甲基)-3,5,6-三氟苯基、2,5-二(三氟甲基)-3,4,6-三氟苯基、2,4,6-三(三氟甲基)-1,3-二吖嗪-5-基、3,4-二氰-2,5,6-三氟苯基、2-氰-3,5,6-三氟砒啶-4-基、2-三氟甲基-3,5,6-三氟砒啶-4-基、2,5,6-三氟-1,3-二吖嗪-4-基或3-三氟甲基-4-氰-2,5,6-三氟苯基,限制條件是在A1 及A2 中的雜芳基不能同時是 2,3,5,6-四氟砒啶-4-基。
- 如申請專利範圍第1項所述之製程,其中步驟(ii)中的該溫度是在100至300°C的該範圍內。
- 如申請專利範圍第1項或第2項所述之製程,其中該步驟(ii)的歷時是至少為100小時。
- 如申請專利範圍第1項至第3項中任一項所述之製程,其中在該步驟(ii)中,一電洞傳輸材料係與具有結構(I)之該化合物共同蒸鍍,該電洞傳輸材料包括至少一個電洞傳輸基材化合物,並且在一後續步驟(iii)中,該化合物(I)與該電洞傳輸基材化合物係共同沉積以形成一半導體材料。
- 如申請專利範圍第1項至第4項中任一項所述之製程,其中該步驟(ii)是在低於10-1 Pa的一壓力下實施。
- 如申請專利範圍第1項至第5項中任一項所述之製程,其中化合物(I)具有在+0.10至+0.50 V的該範圍中藉由循環伏安法於乙腈中對二茂鐵/二茂鐵離子參考系統測得之可逆的氧化還原電位。
- [3]-軸烯化合物,其具有根據式(I)之結構:(I), 其中A1 及A2 是獨立地芳基或雜芳基取代的氰亞甲基, 該芳基及/或雜芳基係獨立地在A1 及A2 中選自4-氰-2,3,5,6-四氟苯基、2,3,5,6-四氟砒啶-4-基、4-三氟甲基-2,3,5,6-四氟苯基、2,4-二(三氟苯基)-3,5,6-三氟苯基、2,5-二(三氟甲基)-3,4,6-三氟苯基、2,4,6-三(三氟甲基)-1,3-二吖嗪-5-基、3,4-二氰-2,5,6-三氟苯基、2-氰-3,5,6-三氟砒啶-4-基、2-三氟甲基-3,5,6-三氟砒啶-4-基、2,5,6-三氟-1,3-二吖嗪-4-基及3-三氟甲基-4-氰-2,5,6-三氟苯基, 以及至少一個芳基或雜芳基是2,3,5,6-四氟砒啶-4-基、2,4-二(三氟甲基)-3,5,6-三氟苯基、2,5-二(三氟甲基)-3,4,6-三氟苯基、2,4,6-三(三氟甲基)-1,3-二吖嗪-5-基、3,4-二氰-2,5,6-三氟苯基、氰-3,5,6-三氟砒啶-4-基、2-三氟甲基-3,5,6-三氟砒啶-4-基、2,5,6-三氟-1,3-二吖嗪-4-基或3-三氟甲基-4-氰-2,5,6-三氟苯基,限制條件是在A1 及A2 中的該雜芳基不能同時是 2,3,5,6-四氟砒啶-4-基。
- 如申請專利範圍第7項所述之化合物,其具有藉由循環伏安法於乙腈中對二茂鐵/二茂鐵離子參考系統測得在+0.10至+0.50 V的該範圍中之可逆的氧化還原電位+。
- 半導體材料,其包括如申請專利範圍第7項或第8項所述之化合物以及一基材材料,該基材材料包括至少一電洞傳輸基材化合物。
- 半導體層,其由如申請專利範圍第7項或第8項所述之化合物所組成或由如申請專利範圍第9項所述之半導體材料所組成。
- 如申請專利範圍第7項或第8項所述之化合物作為在一半導體材料中、在一半導體層中、及/或在一電子裝置中之一p-摻質的用途。
- 電子裝置,其於一第一和第二電極之間包含如申請專利範圍第9項所述之半導體材料、及/或如申請專利範圍第10項所述之半導體層。
- 如申請專利範圍第11項所述之電子裝置,其係一有機發光二極體。
- 如申請專利範圍第12項或第13項所述之電子裝置,其中具有式(I)之該化合物係含於一電洞注入層中、及/或一電洞傳輸層中、及/或一電荷產生層中。
- 用於合成如申請專利範圍第7項或第8項所述之[3]-軸烯化合物的製程,其中,形成式(I)之該化合物的最後合成步驟是在一溶劑中實施,該溶劑包括至少一飽和性鹵化羧酸。
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DE102008061843B4 (de) | 2008-12-15 | 2018-01-18 | Novaled Gmbh | Heterocyclische Verbindungen und deren Verwendung in elektronischen und optoelektronischen Bauelementen |
US8603642B2 (en) * | 2009-05-13 | 2013-12-10 | Global Oled Technology Llc | Internal connector for organic electronic devices |
WO2011134458A1 (de) | 2010-04-27 | 2011-11-03 | Novaled Ag | Organisches halbleitendes material und elektronisches bauelement |
CN102630367A (zh) | 2009-11-25 | 2012-08-08 | 夏普株式会社 | 电源电路和具有该电源电路的液晶显示装置 |
TWI526418B (zh) | 2011-03-01 | 2016-03-21 | 諾瓦發光二極體股份公司 | 有機半導體材料及有機組成物 |
TW201341347A (zh) | 2012-03-15 | 2013-10-16 | Novaled Ag | 芳香胺三聯苯化合物及其在有機半導體元件中的應用 |
EP2684932B8 (en) * | 2012-07-09 | 2016-12-21 | Hodogaya Chemical Co., Ltd. | Diarylamino matrix material doped with a mesomeric radialene compound |
EP2706584A1 (en) | 2012-09-07 | 2014-03-12 | Novaled AG | Charge transporting semi-conducting material and semi-conducting device |
EP2722908A1 (en) | 2012-10-17 | 2014-04-23 | Novaled AG | Phosphorescent OLED and hole transporting materials for phosphorescent OLEDs |
EP2826768A1 (en) | 2013-07-15 | 2015-01-21 | Novaled GmbH | Process for manufacturing 1,2,3-triylidenetris(cyanomethanylylidene)tris(2,3,5,6-tetrafluorobenzonitrile)-cyclopropane |
-
2014
- 2014-12-16 EP EP14198165.4A patent/EP3034489A1/en not_active Withdrawn
-
2015
- 2015-12-15 TW TW104142042A patent/TWI695899B/zh active
- 2015-12-16 EP EP15813358.7A patent/EP3233787B1/en active Active
- 2015-12-16 CN CN202310716552.1A patent/CN116789565A/zh active Pending
- 2015-12-16 WO PCT/EP2015/080046 patent/WO2016097017A1/en active Application Filing
- 2015-12-16 CN CN202310717101.XA patent/CN116789566A/zh active Pending
- 2015-12-16 CN CN201580069040.4A patent/CN107207420A/zh active Pending
- 2015-12-16 KR KR1020177019758A patent/KR102601563B1/ko active IP Right Grant
- 2015-12-16 JP JP2017532070A patent/JP6649952B2/ja active Active
- 2015-12-16 US US15/536,778 patent/US10128442B2/en active Active
Also Published As
Publication number | Publication date |
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CN116789565A (zh) | 2023-09-22 |
CN107207420A (zh) | 2017-09-26 |
US10128442B2 (en) | 2018-11-13 |
KR102601563B1 (ko) | 2023-11-10 |
JP2018506137A (ja) | 2018-03-01 |
KR20170097707A (ko) | 2017-08-28 |
TWI695899B (zh) | 2020-06-11 |
WO2016097017A1 (en) | 2016-06-23 |
CN116789566A (zh) | 2023-09-22 |
EP3233787B1 (en) | 2018-09-26 |
EP3233787A1 (en) | 2017-10-25 |
JP6649952B2 (ja) | 2020-02-19 |
EP3034489A1 (en) | 2016-06-22 |
US20170373251A1 (en) | 2017-12-28 |
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