有機電界発光素子
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- しょうじ のたけ
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1 rganic Electroluminescent Device Shizuo Tokito, Yasunori Taga EL EL EL IT Mg Al EL Electroluminescent (EL) the devices based on organic materials have the potential to realize the full-color flatpanel display. Some materials have now demonstrated adequate efficiency and durability for practical applications. However, the factors that govern the efficiency and durability are poorly understood. In this report, we provide a brief review of the organic EL devices on the basis of the information obtained from literatures and the results of our study. Firstly, the basic mechanism of light emission and a relationship between the device structure and the emission efficiency are reviewed. Secondly, the developments of materials such as hole transport materials, electron transport materials and emission materials are shown, and the stability, emission color and efficiency of EL devices using such materials are then discussed considering molecular structures of the organic materials. The electrode materials for high injection of electron and hole are also shown. Finally, the recent progress in the practical applications is shown and the future prospects are discussed.
2 ( CRT ) ( LCD ) ( EL ) ( FED ) 100nm V 1A/cm 2 EL EL 12 X 12 3mm 6V EL (1) (2) (3) (4) (5) (6) rganic EL devices for green and yellow emission EL10V 1000cd/m 2 2 EL EL EL EL1980 EL EL1994 EL
3 EL 2 EL3 EL 4 EL P EL 100nm EL EL ( LUM ) ( HM ) ( SCLC ) SCLC(1) J = µεε 0 V d 3 εµ 3 2 ( ) (1) V anode J hole injection metal cathode (a) LUM recombination emission HM (b) organic layer ( 100nm ) transparent anode glass substrate vacuum level electron injection cathode (a) Schematic cross section and (b) energy diagram of a typical sigle-layer organic EL device.
4 Log I ( TPD ) SCLC SCLC ( TCL ) 2 EL TPDAl ( Alq ) EL AlqTCL J V /cm 3 EL SCLC - SCLC ( ) ( ) ( ) V hm's law d Log V SCLC Space-charge-limited current (SCLC) conduction for a organic film with ohmic contact. TPD 10-3 cm 2 /Vs Alq10-5 cm 2 /Vs Si GaAs SCLC EL 1 ( lm/w ) ( /electron ) ηφη(ext) ηext (2) η(ext) ηφ ηext 20% 80% ( ) γ ηr φf ηφ γ ηr φf (3) EL γ = 1Herflich ηr =0.25 φf = 1 η(ext) = 5
5 EL ηext = GaAs GaLED γ 1 EL EML (HTL) EML ( ETL ) EML 2 HTL EML ETL3 32 γ = 1 2 ETLHTL ( ) IT γ = 1 cathode cathode cathode cathode ( EML ) EML EML ETL EML (ETL) (ETL) 1 EML ETL, EML ( HTL) HTL (HTL) HTL anode anode anode anode (a) SL (b) DL-A (c) DL-B (d) TL Typical single and multilayer-devices. SL, DL and TL are single-layer, double layer and triple-layer devices. γ Vacuum level η ext φφφ f η r Anode IT 4.9eV HTL LUM HM EML ETL Cathode MgAg 3.7eV Recombination region A schematic representation of the elementary process for external emission. Energy diagram of a typical double-layer device.
6 Alq10-6 cm 2 /Vs 10-8 cm 2 /Vs LUM γ 1 Alq 5nm 2 3 Alq20nm 20nm φf 1 ( Tg ) ( 60 ) EL Tg ( ) ( m-mtdata ) Tg Tg TPD 2 ( α-pb ) 98Tg m- MTDATA α-pb 3 HTM1 Tg TPD m-mtdata m-tadata EL ( TA ) 2 TPD -PB spiro-tpd HTM-1 Molecular structures of hole-tansport materials.
7 110 (1) (2) (3) (1) (2) IT ( eV ) (3) EL Tg Tg Tg Tg (Ip) Tg Alq Tg 167 EL TPTEEL Tg ( ) Tg TPTR Tg s-tpte Alq2 TPTE Tg TPPE Alq 5 m-tpte ( TPPE ) 4 ( TPTE ) Molecular structures of novel hole-transport materials based on triphenylamine.
8 Critical temperature ( C) Ip Ip Ip 4 ( m-tpte, Fig. 8 ) 5.25eVTPTE 0.2eVAlq 2 30% Tg 92 2 EL2 m-mtdata TPD ( CuPc ) α-pb TPD m-mtdata CuPc Ip 5.0eV IT TPD α-pb 5.4eV Ip TPTE/Alq TPD/Alq ( TF ) EL ( PBD, BD ) ( TAZ ) Alq TPPE TPTE TPTE(S) S-TPTE TPTR TPD 50 EML Alq Tg ( C) Relationship between glass transition temperature and critical temperature for the TPA oligomer / Alq devices. Temperature dependences of luminous efficiency and turn-on voltage in a TPTE/Alq device.
9 ( SySPy ) Alq Be ( Be(5Fla) 2 ) PBD BD ( 50wt% ) 10-5 cm 2 /Vs Alq 10-6 cm 2 /Vs (1) (2) (3) (2)LUM Tg t-bu EL XD1 EL XD1 Alq EL Alq Alq Alq EL Alq Alq PBD TAZ tbu t-bu Me 2 Me 2 XD-6 BD XD-7 t-bu tbu tbu ( Tg=137) XD1 tbu tbu tbu tbu ( Tg=162) XD2 tbu tbu Si PySPy XD3 Al Alq tbu ( Tg=154) tbu ( Tg=121) XD3 XD4 Molecular structures of electron-transport materials. Molecular structures of novel electrontransport materials based on oxadiazole.
10 ( DPVBi ) TPD Alq 3 470nm 0.8lm/W ( PZ10 ) 480nm 1.84lm/W ( EM2 ) 3 490nm3.75lm/W ( BMA-nT ) 13300cd/m 2 1.1m/W 2 2PSP PySPy 3 ( 580nm ) 5lm/W ( tbu-ptc ) 610nm 500cd/m 2 Alq EL Zn ( Zn(BX)2 ) BAlq1 470nm 490nm 2000cd/m 2 Be (Bebq2) ( 516nm ) 19000cd/m 2 3.5lm/WAlq Alq ( Almq3 ) 26000cd/m EL 8-Zn4 ( Znq2 ) 16200cd/m 2 Alq Wavelength (nm) C CH CH C DPVBi EM2 P1 Si Si 2PSP t-bu t-bu tbu-ptc t-bu t-bu t-bu PZ10 DSA S n BMA-nT spiro-8φ Zn Zn(BX)2 Al BAlq1 BAlq2 Al Almq3 S Zn S Zn(BTZ)2 Be BeBq2 Bebq2 Al Alq Be Be(5Fla)2 Zn Al Znq2 Alph3 Molecular structures of emitting materials.
11 Al6 ( Alph3 ) 13000cd/m 2 Zn(BX)2 S Zn Zn(BTZ)2 150nm 10000cd/m 2 Be(5Fla)2 Tb Eu Dy nm Zn ( EM3 ) 5300cd/m 2 EM1 AlqEM5 Alq 20nm 1.1lm/W20000cd/m 2 Alq EL 3 ( ) EM1 XD lm/W5000cd/m 2 nm S Zn Zn Zn S Al (1) Al (2) Zn Al Molecular structures of novel emitting-materials based on a metal-chelate complex. EL Characteristics of the bouble-layer EL devices using novel emittingmaterials. Materials PL peak EL peak Emission Luminous Emission Maximum (nm) (nm) color efficiency efficiency luminance (1m/W) (cd/a) (cd/m 2 ) 2 EM Blue Zn ( EM1 ) 460nm 0.45lm/W EM2 EM3 EM4 EM5 EM6 Alq Green Blue Blue Greenish yellow Blue Green * cd/m 2 * LiF/Al
12 2 ( TPTE/EM1 ) ( ) Luminance-current characteristics of TPTE/EM1/XD1 and TPTE/EM1 devices. 100% ( ) (a) DCMAlq Coumarin 6 DCM1 510nm 600nm 2 Alq 2 DCM Coumarin DCM1DCM2 630nm 2.3 Mg ( MgPC ) ( TPP ) ( Qd-3 ) Alq 10 cd/m 2 10lm/W4 EL1 Wavelength (nm) H C C Perylene C CH CH C Et Et BCzVBi H Qd-3 Qd-2 Qd-1 H H (Et) 2 S Coumarin 6 Rubrene C C Mg DCM1 DCM2 Me Me H H MgPc TPP Molecular structures of dopants.
13 Qd-1EL Qd-1Alq d-3qd-2 BCzVBi DPVBi 470nm 5lm/W ( ) Fig. 17(b) ( Rubrene ) Alq560nm 3lm/W TPD 2 Almq3 LUM exciton energy transfer HM (a) dopant emission LUM dopant electron eleccron traping emission hole traping (b) HM Schematic diagrams of (a) energy transfer and (b) trap mechanisms for two devices with a dopant. Coumarin 6EL 7% IT MgAg EL HM IT LUM IT Sn2 In23 Zn:Al IT IT200nm 10Ω/ IT UV UV UV UV IT10 IT IT IT CuPc ( ) CuPc IT IT EL ITUV2
14 2 Sn eV Ar IT - ( ) Vx Mox 30nmIT IT IT IT300 IT AFMnm 30nm 100nm 1MV/cm IT ( ZnInxy ) EL MgAg MgIn AlLi AlLiLi (0.1 ) MgAg 9:1 2 AlLiAlLi MgAg TPD/AlqV Li Al Al LiF LiF/Al Current density (ma/cm 2 ) Current density (ma/cm 2 ) Current-voltage characteristics of the TPD/Alq devices using metal oxides as hole injectinglayer. Current-voltage characteristics of the TPTE/Alq devices with various cathodes.
15 AlLi MgAg 0.2nm0.5nm AlLi LixAl2 LUM ( ) 2 Al AlqAl Alq LUM ( LiF Al Alq0.2eV m = 4.3 ev EF m Evac = 0 ev ε F vac = 4.3 ev ε F v = 1.7 ev Evac LUM EF m Evac m = 4.3 ev ~ 1.0 ev ε F vac = 3.3 ev ε F v = 2.7 ev Evac LUM Ba ( BaF2 ) LiF MgAg Al23 LiF 2 EL SCLC ELV EL ( ) (1) Display Size : 94.7 mm x 21.1 mm HM HM Al Alq Al Alq (a) (b) Energy diagrams Al/Alq interface ; (a) vacuum level alignment case (b) directly observed alignment using the results by UPS experiments. Photograph of FM multiplex reciever with an organic EL display.
16 (2) umber of Dots : 256 x 36 (3) Dot Size : 0.32 x 0.34 mm (4) Luminance : 100 cd/m 2 (5) Contrast : > 100:1 at 500 lux EL IT 100cd/m 2 EL ( ) (1) 3 3 (2) 3 (3) ( CCM ) 3 0.1mm 0.1mm 5QVGA 3 ( CCM ) 3 10 QVGA TFT TFT Cathode ETL HTL Anode Glass substrate Cathode ETL Blue EML HTL Anode Cathode ETL White emitting layer HTL Anode Red filter CCM (B-R) Red EML Green EML Blue EML Red Green Blue ( a ) Red Green Blue ( b ) Red Green Blue ( c ) CCM (B-G) CCM (B-B) Blue filter Green filter Architectures for implementing full-color pixels: (a) side-by-side patterning of discrete R, G and B pixels, (b) downconvertion of blue light to generate green and red light, (c) filtering of a white light by color passband filters.
17 EL EL ( 100nm ) EL ( ) (1) 15nm EL EL EL( ) (2) (3) 9.5lm/W 50000cd/m 2 IT EL Schematic structure of a microcavity type organic EL device. Microcavity EL device 0 oncavity EL device EL Emission patterns of microcavity EL device and noncavity EL device.
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58 185 2016 167-171 Journal of the Combustion Society of Japan Vol.58 No.185 (2016) 167-171 ORIGINAL PAPER 火災旋風近傍の流れに関する研究 Flow Around a Fire Whirl * ONISHI, Hiroyuki and KUWANA, Kazunori 992-8510 4-3-16
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/Opinion Kawaii as an Affective Value Michiko OHKURA Abstract In the 21 st century, the affective/kansei values of industrial products are considered very important. However, since not many studies have