TWI503313B - 含卡唑及苯胺之不對稱苯乙烯衍生物及其有機發光二極體 - Google Patents
含卡唑及苯胺之不對稱苯乙烯衍生物及其有機發光二極體 Download PDFInfo
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- TWI503313B TWI503313B TW103109352A TW103109352A TWI503313B TW I503313 B TWI503313 B TW I503313B TW 103109352 A TW103109352 A TW 103109352A TW 103109352 A TW103109352 A TW 103109352A TW I503313 B TWI503313 B TW I503313B
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims description 32
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims description 12
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 title 1
- 125000003118 aryl group Chemical group 0.000 claims description 55
- 125000001072 heteroaryl group Chemical group 0.000 claims description 41
- 239000000463 material Substances 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 150000003440 styrenes Chemical class 0.000 claims description 18
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 2
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 239000010410 layer Substances 0.000 description 37
- RAPHUPWIHDYTKU-WXUKJITCSA-N 9-ethyl-3-[(e)-2-[4-[4-[(e)-2-(9-ethylcarbazol-3-yl)ethenyl]phenyl]phenyl]ethenyl]carbazole Chemical compound C1=CC=C2C3=CC(/C=C/C4=CC=C(C=C4)C4=CC=C(C=C4)/C=C/C=4C=C5C6=CC=CC=C6N(C5=CC=4)CC)=CC=C3N(CC)C2=C1 RAPHUPWIHDYTKU-WXUKJITCSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 11
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 6
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 5
- -1 furylene Chemical group 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 4
- 125000000392 cycloalkenyl group Chemical group 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 125000004366 heterocycloalkenyl group Chemical group 0.000 description 4
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- ZGUYPJJFHYFLBV-UHFFFAOYSA-N methyl n-(5-tert-butyl-1,2-oxazol-3-yl)carbamate Chemical compound COC(=O)NC=1C=C(C(C)(C)C)ON=1 ZGUYPJJFHYFLBV-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000005561 phenanthryl group Chemical group 0.000 description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- QBFQLEVWHCQDIR-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)-2-pyrrolidin-1-ylpropan-1-one Chemical compound CC1=C(C=CC(=C1)C)C(C(C)N1CCCC1)=O QBFQLEVWHCQDIR-UHFFFAOYSA-N 0.000 description 1
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 1
- WAKRVBPGNMSWJF-NBRVCOCJSA-N 4-methyl-N-(4-methylphenyl)-N-[4-[(E)-2-[4-[4-[(E)-2-(9-phenylcarbazol-3-yl)ethenyl]phenyl]phenyl]ethenyl]phenyl]aniline Chemical compound CC1=CC=C(C=C1)N(C1=CC=C(C=C1)\C=C\C1=CC=C(C=C1)C1=CC=C(C=C1)\C=C\C=1C=CC=2N(C3=CC=CC=C3C=2C=1)C1=CC=CC=C1)C1=CC=C(C=C1)C WAKRVBPGNMSWJF-NBRVCOCJSA-N 0.000 description 1
- XNCOSPRUTUOJCJ-UHFFFAOYSA-N Biguanide Chemical compound NC(N)=NC(N)=N XNCOSPRUTUOJCJ-UHFFFAOYSA-N 0.000 description 1
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 1
- 125000005865 C2-C10alkynyl group Chemical group 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- KMYNXIZBABUXEV-AQASXUMVSA-N N,N-bis(4-fluorophenyl)-4-[(E)-2-[4-[4-[(E)-2-(9-phenylcarbazol-3-yl)ethenyl]phenyl]phenyl]ethenyl]aniline Chemical compound FC1=CC=C(C=C1)N(C1=CC=C(C=C1)\C=C\C1=CC=C(C=C1)C1=CC=C(C=C1)\C=C\C=1C=CC=2N(C3=CC=CC=C3C=2C=1)C1=CC=CC=C1)C1=CC=C(C=C1)F KMYNXIZBABUXEV-AQASXUMVSA-N 0.000 description 1
- KWTQFIGBIXZMAM-UHFFFAOYSA-N N,N-diphenyl-4-[(E)-2-[4-[4-[(E)-2-(9-phenylcarbazol-3-yl)ethenyl]phenyl]phenyl]ethenyl]aniline Chemical compound C1(=CC=CC=C1)N(C1=CC=C(C=C1)C=CC1=CC=C(C=C1)C1=CC=C(C=C1)C=CC=1C=CC=2N(C3=CC=CC=C3C2C1)C1=CC=CC=C1)C1=CC=CC=C1 KWTQFIGBIXZMAM-UHFFFAOYSA-N 0.000 description 1
- TVTCBJUGPZGYQA-UHFFFAOYSA-N N-phenyl-N-[4-[(E)-2-[4-[4-[(E)-2-(9-phenylcarbazol-3-yl)ethenyl]phenyl]phenyl]ethenyl]phenyl]naphthalen-1-amine Chemical compound C1(=CC=CC=C1)N(C1=CC=CC2=CC=CC=C12)C1=CC=C(C=C1)C=CC1=CC=C(C=C1)C1=CC=C(C=C1)C=CC=1C=CC=2N(C3=CC=CC=C3C2C1)C1=CC=CC=C1 TVTCBJUGPZGYQA-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000005277 alkyl imino group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000004422 alkyl sulphonamide group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000000266 alpha-aminoacyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 125000004467 aryl imino group Chemical group 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 1
- 125000004421 aryl sulphonamide group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 125000004986 diarylamino group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000004438 haloalkoxy group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000005553 heteroaryloxy group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/30—Devices specially adapted for multicolour light emission
- H10K59/35—Devices specially adapted for multicolour light emission comprising red-green-blue [RGB] subpixels
-
- 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
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/10—Triplet emission
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/82—Cathodes
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- 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
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
Description
本發明是關於一種含卡唑及苯胺之不對稱苯乙烯衍生物及其有機發光二極體,尤其是一種維持BCzVBi的主體結構,並破壞BCzVBi的對稱性之不對稱苯乙烯衍生物及其有機發光二極體。
有機發光二極體(organic light-emitting diode;OLED),通常稱作有機電致發光裝置(organic electroluminescent device),是以有機層作為主動層的一種發光二極體(LED)。由於有機電致發光裝置具有自發光、廣視角(>170°)、反應時間短(~μs)、高對比、高效率、省電、高亮度、低操作電壓(3-10V)、更輕薄(<2mm)、可撓曲性等優點,近年來已漸漸使用於平面面板顯示器(flat panel display)上。與液晶顯示器不同,有機電激發光顯示器所包含之有機發光二極體畫素陣列係具有自發光的特性,因此不需外加背光源;為了應用作為全彩顯示器,開發具適當色度(chromaticity)與高放光效率紅色、綠色與藍色的發光材料是必須且重要的。
電洞和電子之再結合而產生的激子可具有三重態(triplet state)或單重態(singlet state)之自旋態(spin state)。由單重態激子(singlet exciton)所產生的發光為螢光(fluorescence),而由三重態激子(triplet exciton)所產生的發光為磷光(phosphorescence)。磷光的發光效率是螢光的三倍,藉
由引入重金屬在發光體結構中,造成強烈的自旋軌道耦合(spin-orbital coupling),進而使得單重態及三重態激發狀態之間的混合,以致於原件的內部量子效率(internal quantum efficiency,IQE)可大幅提升至100%,因此近年來有機發光二極體多採用發磷光的金屬錯合物做為發光層中的磷光摻雜劑。此外,在發光層中通常會以掺雜技術的製程,將發光材料掺雜在主體發光材料中,以抑制發光材料自我淬息的發生,因此,主體發光材料的開發為相當重要的一個課題,主體發光材料必須具備易捕捉載子、能量轉移特性佳、高玻璃轉換溫度、高熱穩定性、合適的單重態及三重態能隙。然而,由於上述條件相當難以完全符合,因此有機發光二極體在主體發光材料的開發上仍有很大改善的空間。
特別是尋找有效率的藍光電致發光材料,因為其為將OLED實現為顯示及照明用途的重要元件。目前已有許多研究團隊成功地製備有效率的藍光螢光團(fluorophore)及其OLED。然而,到目前為止,色度y座標(Commission Internationale d’nclairage y coordinate value,CIEy
))0.15的有效率材料非常稀少。目前仍缺乏良好的有機電致發光化合物以符合上述需求。
在已知材料中,BCzVBi是相當有效率的藍光摻雜材料。但是BCzVBi的缺點之一在於溶解度過低(<0.5%wt),因此無法應用於濕式製程,使得用途受到侷限。因此,開發新穎、有效率的藍光電致發光材料是目前亟需努力的目標。
本發明目的之一是提供一種新穎的含卡唑及苯胺之不對稱苯乙烯衍生物,其維持BCzVBi的主體結構,並破壞BCzVBi的對稱性,以增加摻雜物材料的溶解度,以使用於OLED濕式製程。
依據本發明之一實施例,一種含卡唑及苯胺之不對稱苯乙烯衍生物,其具有代表式(I):
其中R1係選自氫、取代或非取代的C1
-C20
烷基、取代或非取代的芳基及取代或非取代的雜芳基,R2、R3係選自取代或非取代的C1
-C20
烷基、取代或非取代的芳基及取代或非取代的雜芳基。
本發明之另一目的為提供具有高效率元件表現的有機發光二極體。
依據本發明另一實施例,一種有機發光二極體,包括一陰極、一陽極以及設置於陰極及陽極之間的一發光層,其中發光層包含上述的不對稱苯乙烯衍生物。
本發明之不對稱苯乙烯衍生物可具有藍光發光性質,用以作為一客體發光材料。
以下藉由具體實施例配合所附的圖式詳加說明,當更容易瞭解本發明之目的、技術內容、特點及其所達成之功效。
1‧‧‧陽極
2‧‧‧陰極
3‧‧‧發光層
4‧‧‧電洞傳輸層
5‧‧‧電子傳輸層
6‧‧‧電洞阻擋層
7‧‧‧電洞注入層
8‧‧‧電子注入層
9‧‧‧電子阻擋層
圖1為示意圖顯示具有不對稱苯乙烯衍生物的發光元件結構。
圖2為示意圖顯示依據本發明一實施例之具有不對稱苯乙烯衍生物的發光元件結構。
本發明目的之一是提供一種新穎的含卡唑及苯胺之不對稱苯乙烯衍生物,其維持BCzVBi的主體結構,並破壞BCzVBi的對稱性,以增加摻雜物材料的溶解度,以使用於OLED濕式製程。
依據本發明之一種含卡唑及苯胺之不對稱苯乙烯衍生物,其具有代表式(I):
R1係選自氫、取代或非取代的C1
-C20
烷基、取代或非取代的芳基及取代或非取代的雜芳基。R2、R3係獨立選自取代或非取代的C1
-C20
烷基、取代或非取代的芳基及取代或非取代的雜芳基。其中R2、R3可為相同或相異。
依據本發明之一種含卡唑及苯胺之不對稱苯乙烯衍生物,其具有代表式(II):
R4係選自氫、取代或非取代的鹵素、取代或非取代的C1
-C20
烷基、取代或非取代的芳基、取代或非取代的雜芳基。
在此「芳基」指的是具有一或多個芳香環之碳氫基團。舉例而言,芳基之碳數可為6至20。芳基基團範例包括苯基(phenyl,Ph)、亞苯基(phenylene)、萘基(naphthyl)、亞萘基(naphthylene)、芘基(pyrenyl)、蒽基(anthryl)、及菲基(phenanthryl)。
「雜芳基」指的是具有一或多個芳香環之碳氫基團,且該芳香環包含至少一雜原子(例如,氮、氧或硫)。舉例而言,雜芳基基團之碳數可為2至20。雜芳基基團範例可包括呋喃基(furyl)、亞呋喃基(furylene)、茀基(fluorenyl)、吡咯基(pyrrolyl)、噻吩基(thienyl)、噁唑基(oxazolyl)、咪唑基(imidazolyl)、噻唑基(thiazolyl)、吡啶基(pyridyl)、嘧啶基(pyrimidinyl)、喹唑啉基(quinazolinyl)、喹啉基(quinolyl)、異喹啉基(isoquinolyl)及吲哚基(indolyl)。
在此應註明的是烷基、烯基、炔基、環烷基、環烯基、雜環烷基、雜環烯基、芳基、以及雜芳基可包括經取代及未經取代之基團。可能取代於環烷基、環烯基、雜環烷基、雜環烯基、芳基、以及雜芳基之取代基包含但不受限於C1
-C10
烷基、C2
-C10
烯基、C2
-C10
炔基、C3
-C20
環烷基、C3
-C20
環烯基、C1
-C20
雜環烷基、C1
-C20
雜環烯基、C1
-C10
烷氧基、芳基、芳氧基、雜芳基、雜芳氧基、胺基、C1
-C10
烷胺基、C1
-C20
二烷胺基、芳胺基、二芳胺基、C1
-C10
烷基磺胺(C1
-C10
alkylsulfonamino)、
芳基磺胺(arylsulfonamino)、C1
-C10
烷基亞胺(C1
-C10
alkylimino)、芳基亞胺(arylimino)、C1
-C10
烷基磺亞胺(C1
-C10
alkylsulfonimino)、芳基磺亞胺(arylsulfonimino)、氫氧基、鹵素、硫代基(thio)、C1
-C10
烷硫基、芳硫基、C1
-C10
烷磺醯基(alkylsulfonyl)、芳磺醯基(arylsulfonyl)、醯基胺(acylamino)、胺基醯(aminoacyl)、胺基硫醯(aminothioacyl)、醯胺基(amido)、脒基(amidino)、胍基(guanidine)、脲基(ureido)、硫脲基(thioureido)、腈基、硝基、亞硝基、疊氮基(azido)、醯基、硫醯基、醯氧基(acyloxy)、羧基、及羧酸酯等。另一方面,可能取代於烷基、烯基、或炔基之取代基包含除C1
-C10
烷基外之上述所有取代基。環烷基、環烯基、雜環烷基、雜環烯基、芳基、及雜芳基亦可互相稠合(fused)。
較佳者,R1係選自C1
-C20
烷基、雜芳基、芳基、芳基取代的芳基、具有C1
-C20
烷基取代的芳基、具有C1
-C20
鹵代烷基取代基的芳基、具有胺基取代的芳基、具有鹵素取代基的芳基、具有雜芳基取代基的芳基、具有芳基取代的雜芳基、具有C1
-C20
烷基取代的雜芳基、具有C1
-C20
鹵代烷基取代基的雜芳基、具有鹵素取代基的雜芳基及具有雜芳基取代基的雜芳基。
較佳者,R2、R3係選自C1
-C20
烷基、雜芳基、芳基、芳基取代的芳基、具有C1
-C20
烷基取代的芳基、具有C1
-C20
鹵代烷基取代基的芳基、具有胺基取代的芳基、具有鹵素取代基的芳基、具有雜芳基取代基的芳基。
較佳者,R4係選自C1
-C20
烷基、雜芳基、芳基、芳基取代的芳基、具有C1
-C20
烷基取代的芳基、具有C1
-C20
鹵代烷基取代基的芳基、具有胺基取代的芳基、具有鹵素取代基的芳基、具有雜芳基取代基的芳基、具有芳基取代的雜芳基、具有C1
-C20
烷基取代的雜芳基、具有C1
-C20
鹵代烷基取代基的雜芳基、具有鹵素取代基的雜芳基及具有雜芳基取代基的雜芳基。
以下揭示本發明化合物實施例。
合成方式
實施例:PCzDPA
以PCzDPA
(N,N-diphenyl-4-[(E)-2-(4-{4-[(E)-2-(9-phenyl-9H-carbazol-3-yl)ethenyl]phenyl}phenyl)ethenyl]aniline)為例,其合成方式如下。
其餘化合物皆以下列方式合成。
以下提供化合物之光譜資料:
PCzDPA
(N,N-diphenyl-4-[(E)-2-(4-{4-[(E)-2-(9-phenyl-9H-carbazol-3-yl)ethenyl]phenyl}phenyl)ethenyl]aniline)
1
H NMR(400MHz,CDCl3):δ 8.28(s,1H),8.17(d,J=7.6Hz,1H),7.65-7.55(m,11H),7.47(dd,J=8.4Hz,J=7.2Hz,2H),7.40-7.38(m,4H),7.35(d,J=11.2Hz,2H),7.32-7.23(m,6H),7.19(d,J=16.4Hz,2H),7.12-7.00(m,9H).
PCzNA
(N-phenyl-N-{4-[(E)-2-(4-{4-[(E)-2-(9-phenyl-9H-carbazol-3-yl)ethenyl]phenyl}phenyl)ethenyl]phenyl}naphthalen-1-amine)
1
H NMR(400MHz,CDCl3):δ 8.28(s,1H),8.17(d,J=7.6Hz,1H),7.90(dd,J=8.4Hz,2H),7.77(d,J=8.0Hz,1H),7.59-7.28(m,24H),7.22-7.18(m,4H),7.08-6.94(m,7H).
PCzDFA
N,N-bis(4-fluorophenyl)-4-[(E)-2-(4-{4-[(E)-2-(9-phenyl-9H-carbazol-3-yl)ethenyl]phenyl}phenyl)ethenyl]aniline
1
H NMR(400MHz,CDCl3):δ 8.28(s,1H),8.17(d,J=6.8Hz,1H),7.63-7.55(m,9H),7.47(dd,J=6.8Hz,J=7.2Hz,2H),7.40-7.38(m,4H),7.35(d,J=11.6Hz,2H),7.32-7.23(m,6H),7.19(d,J=16.4Hz,2H),7.12-7.00(m,9H).
PCzDMA
N,N-bis(4-methylphenyl)-4-[(E)-2-(4-{4-[(E)-2-(9-phenyl-9H-carbazol-3-yl)ethenyl]phenyl}phenyl)ethenyl]aniline。
1
H NMR(400MHz,CDCl3):δ 8.28(s,1H),8.17(d,J=7.6Hz,1H),7.63-7.54(m,11H),7.47(dd,J=6.8Hz,J=7.2Hz,2H),7.41-7.28(m,8H),7.18(d,J=16Hz,2H),7.11-6.97(m,11H).
請參照表一,其顯示本案化合物之吸收及發射光譜,其中本案之化合物為藍色發光材料。
註:
[a]吸收與螢光光譜係於濃度為1×10-5
M之甲苯溶液中測量。
[b]螢光光譜係於薄膜(25nm)中測量。
[c]依薄膜光學發射閥值估算。
[d]依光電光譜儀(AC-II)估算。
[e]LUMO=HOMO-E g
[f]量子產率係於環己烷中測量,並以9,10-二苯基蒽(9,10-diphenylanthrecene,Q.Y.=0.90)為標準值。
此外,請參照圖1,圖1為示意圖顯示具有化合物的有機發光二極體之一實施例。有機發光二極體之發光元件結構具有設置於陽極1及陰極2之間包含化合物的發光層3。發光層3係將發光材料摻雜至主體發光材料中所構成。發光元件結構還包括從陽極1上方依序形成之電洞注入層7、電洞傳輸層4、電子阻擋層9、發光層3、電洞阻擋層6、電子傳輸層5及電子注入層8。其中,各層之實際厚度與圖中所顯示之尺寸並無關係。其中,本發光元件之電洞注入層7、電子阻擋層9、電洞阻擋層6及電子注入層8為選擇性包含。其中本發明之化合物可為發光層之一客體發光材料。
請參照圖2,依據本發明之一實施例,所形成的裝置結構之中,ITO做為基板,測試的電極材料包括LiF/Al;測試的發光材料包括P1(DMPPP,如下列化學式
);測試的電子傳輸層包括BCP(2,9-dimethyl-4,7-diphenyl-[1,10]phenanthroline)及Alq3
(tris(8-hydroxyquinoline)aluminum(III)),其可做為電洞阻擋層或者同時做為電洞阻擋層及電子傳輸層。測試的電洞傳輸層包括NPB(4,4’-bis[N-(1-naphthyl)-N-phenyl-amino]bipheny),其可做為電子阻擋層或者同時做為電子阻擋層及電洞傳輸層。
本發明的元件裝置如下:
A:NPB
(60nm)/NPB:3%PCzDFA
(10nm)/P1:3%PCzDFA
(15nm)/BAlq
(20nm)/LiF
(1nm)/Al
(100nm)
B:NPB
(60nm)/NPB:3%PCzNA
(10nm)/P1:3% PCzNA
(15nm)/BAlq
(20nm)/LiF
(1nm)/Al
(100nm)
C:NPB
(60nm)/NPB:3%PCzDPA
(10nm)/P1:3%PCzDPA
(15nm)/BAlq
(20nm)/LiF
(1nm)/Al
(100nm
D:NPB
(60nm)/NPB:3%PCzDMA
(10nm)/P1:3%PCzDMA
(15nm)/BAlq
(20nm)/LiF
(1nm)/Al
(100nm)
E:NPB
(60nm)/NPB:5%BCzVBi
(10nm)/P1:5%BCzVBi
(15nm)/BAlq
(20nm)/LiF
(1nm)/Al
(100nm)
請參照表二,其中裝置A、B、C的最大外部效能皆超過8.0,而可分別達到8.4、9.4、9.7。其中裝置B、C、D的最大發光值皆大於使用BCzVBi
的對照組E。
請參照表四,本發明之例示化合物之溶解度已較BczVBi
提升,其中PCzDFA、PCzDMA
溶於甲苯之溶解度可大於2wt%。
在一實施例中,本發明的例示化合物可用於濕式製程,其元件裝置如下:
A:PEDOT:PSS(300rpm 5sec,2500rpm 25sec)/PO-C 6 :3% PCzDPA
(2000rpm 30sec)/TPBI(40)
B:PEDOT:PSS(300rpm 5sec,2500rpm 25sec)/PO-C 6 :3% PCzDPA
(2500rpm 30sec)/TPBI(40)
綜合上述,本發明提供一種含卡唑及苯胺之不對稱苯乙烯衍生物,其維持BCzVBi的主體結構,並破壞BCzVBi的對稱性,以增加摻雜物材料的溶解度並使用於OLED濕式製程。
以上所述之實施例僅係為說明本發明之技術思想及特點,其目的在使熟習此項技藝之人士能夠瞭解本發明之內容並據以實施,當不能以之限定本發明之專利範圍,即大凡依本發明所揭示之精神所作之均等變化或修飾,仍應涵蓋在本發明之專利範圍內。
1‧‧‧陽極
2‧‧‧陰極
3‧‧‧發光層
4‧‧‧電洞傳輸層
5‧‧‧電子傳輸層
6‧‧‧電洞阻擋層
7‧‧‧電洞注入層
8‧‧‧電子注入層
9‧‧‧電子阻擋層
Claims (8)
- 一種含卡唑及苯胺之不對稱苯乙烯衍生物,其具有代表式(I):
- 如請求項1所述之卡唑及苯胺之不對稱苯乙烯衍生物,其中R2、R3係選自C1 -C20 烷基、雜芳基、芳基、芳基取代的芳基、具有C1 -C20 烷基取代的芳基、具有C1 -C20 鹵代烷基取代基的芳基、具有胺基取代的芳基、具有鹵素取代基的芳基、具有雜芳基取代基的芳基。
- 如請求項1所述之卡唑及苯胺之不對稱苯乙烯衍生物,其中R1係選自C1 -C20 烷基、雜芳基、芳基、芳基取代的芳基、具有C1 -C20 烷基取代的芳基、具有C1 -C20 鹵代烷基取代基的芳基、具有胺基取代的芳基、具有鹵素取代基的芳基、具有雜芳基取代基的芳基、具有芳基取代的雜芳基、具有C1 -C20 烷基取代的雜芳基、具有C1 -C20 鹵代烷基取代基的雜芳基、具有鹵素取代基的雜芳基及具有雜芳基取代基的雜芳基。
- 如請求項1所述之卡唑及苯胺之不對稱苯乙烯衍生物,其具有代表式(II),
- 如請求項4所述之卡唑及苯胺之不對稱苯乙烯衍生物,其中R4係選自C1 -C20 烷基、雜芳基、芳基、芳基取代的芳基、具有C1 -C20 烷基取代的芳基、具有C1 -C20 鹵代烷基取代基的芳基、具有胺基取代的芳基、具有鹵素取代基的芳基、具有雜芳基取代基的芳基、具有芳基取代的雜芳基、具有C1 -C20 烷基取代的雜芳基、具有C1 -C20 鹵代烷基取代基的雜芳基、具有鹵素取代基的雜芳基及具有雜芳基取代基的雜芳基。
- 一種有機發光二極體,包括:一陰極;一陽極;以及一發光層,設置於該陰極及該陽極之間,其中該發光層包含請求項1至5至少其一之卡唑及苯胺之不對稱苯乙烯衍生物。
- 如請求項6所述之有機發光二極體,其中該有機發光二極體為一藍色發光二極體。
- 如請求項6所述之有機發光二極體,其中該卡唑及苯胺之不對稱苯乙烯 衍生物為一客體發光材料。
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WO2011037209A1 (ja) * | 2009-09-25 | 2011-03-31 | パナソニック電工株式会社 | 有機電界発光素子 |
US20120228648A1 (en) * | 2011-03-09 | 2012-09-13 | Seiko Epson Corporation | Light-emitting device, light-emitting apparatus, display device and electronic apparatus |
CN102208559A (zh) * | 2011-04-18 | 2011-10-05 | 电子科技大学 | 一种柔性发光器件用基板及其制备方法 |
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US9112158B1 (en) | 2015-08-18 |
TW201534584A (zh) | 2015-09-16 |
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