Enhancement of Frster energy transfer from thermally activated delayed fluorophores layer to ultrathin phosphor layer for high color stability in non-doped hybrid white organic light-emitting devices

Fluorescence/phosphorescence hybrid white organic light-emitting devices(WOLEDs) based on double emitting layers(EMLs) with high color stability are fabricated.The simplified EMLs consist of a non-doped blue thermally activated delayed fluorescence(TADF) layer using 9,9-dimethyl-9,10-dihydroacridine-diphenylsulfone(DMAC-DPS) and an ultrathin non-doped yellow phosphorescence layer employing bis[2-(4-tertbutylphenyl)benzothiazolato-N,C2']iridium(acetylacetonate)((tbt)_2Ir(acac)).Two kinds of materials of 4,7-diphenyl-1,10-phenanthroline(Bphen) and 1,3,5-tris(2-Nphenylbenzimidazolyl) benzene(TPBi) are selected as the electron transporting layer(ETL),and the thickness of yellow EML is adjusted to optimize device performance.The device based on a 0.3-nm-thick yellow EML and Bphen exhibits high color stability with a slight Commission International de l'Eclairage(CIE) coordinates variation of(0.017,0.009) at a luminance ranging from 52 cd/m~2 to 6998 cd/m~2.The TPBi-based device yields a high efficiency with a maximum external quantum efficiency(EQE),current efficiency,and power efficiency of 10%,21.1 cd/A,and 21.3 lm/W,respectively.The ultrathin yellow EML suppresses hole trapping and short-radius Dexter energy transfer,so that Forster energy transfer(FRET)from DMAC-DPS to(tbt)_2Ir(acac) is dominant,which is beneficial to keep the color stable.The employment of TPBi with higher triplet excited state effectively alleviates the triplet exciton quenching by ETL to improve device efficiency.     

间隔层对双发光层白色有机电致发光器件性能的影响

采用蓝色bis (FIrpic)和黄色bis iridium(acetylacetonate) 两种磷光染料,制备了双发光层结构的白色有机电致发光器件,器件结构为ITO/TAPC (30 nm)/host: (t-bt)₂Ir(acac) /spacer (x nm)/host: FIrpic (15 nm, 8%)/Bphen (40 nm)/Mg∶Ag (200 nm)。分别选用p型1,1-bis cyclohexane (TAPC)和n型tris borane (3TPYMB)作为主体材料制备了两种类型的器件,通过在两个发光层之间加入一层较薄的间隔层进行器件优化。结果表明,加入间隔层之后,器件性能得到提高,获得了色稳定性较好的白光器件。当主体为TAPC时,使用间隔层后器件取得最大亮度为19 550 cd/m²,最大电流效率为8.3 cd/A;当主体为3TPYMB时,使用间隔层后器件的最大亮度为1 950 cd/m²,最大电流效率为30.7 cd/A。实验结果表明,器件性能的提高,是由于加入了间隔层之后载流子复合区域拓宽,促进了发光层中电子和空穴的平衡。     

新型高色纯度弱电流猝灭性蓝色有机发光器件

以ADN为基质,分别以不同掺杂剂制备了四种蓝色有机发光器件,器件结构为:CuPc(12 nm)/NPB(40 nm)/AND∶Dopant(50 nm)/Alq(12 nm)/LiF(4 nm)/Al。掺杂剂有:BCzVB(amino-substituted distyrylarylenederivatives)、TBPe、BCzVBi和DSA-ph四种。研究了最佳掺杂浓度以及器件的亮度、电流密度、效率和色坐标等电学特性和光学特性。其中掺杂BCzVB制备了色纯度高、低电流猝灭性的蓝色有机发光器件,色坐标达到x=0.146,y=0.162,最大亮度为11600 cd/m2(15 V),电流效率为2.8 cd/A,流明效率为1.79 lm/W;以ADN为基质,分别以TBPe、BCzVBi和DSA-ph为掺杂剂,制备了另外三种对比器件。器件ADN∶TBPe色坐标为x=0.162,y=0.222(蓝绿光),效率随电流的增加而降低很快;器件ADN∶BczVBi有较好的色纯度(色坐标:x=0.164,y=0.146),但电流效率较低:2.03 cd/A,效率随电流的增加降低幅度也较快。器件ADN∶DSA-ph效率较高为8 cd/A,效率随电流增加变化幅度不大,但色纯度比较差(x=0.153,y=0.306),适合于做白色有机发光器件。     

White organic light-emitting diodes based on benzothiazole derivative

This paper describes the white organic light-emitting diodes (WOLEDs) made from a benzothiazole derivative, N-(4-(benzo[d]thiazol-2-yl)phenyl)-N-phenylnaphthalen-1-amine (BPNA). The bright yellowish-white emission was obtained from a non-doped triple-layer device: ITO/NPB (40 nm)/BPNA (50 nm)/Alq₃ (40 nm)/LiF/Al. The Commission Internationale de L’Eclairage (CIE) coordinates of the device were (0.24, 0.36) at 10 V. The maximum brightness of the device was 9225 cd/m² at 14.4 V. A current efficiency of 3.08 cd/A, a power efficiency of 1.21 lm/W and an external quantum efficiency of 1.18% at a driving current density of 20 mA/cm² were achieved. WOLED with a DCJTB-doped structure of ITO/TcTa/BPNA/BPNA: DCJTB (0.5%)/BPNA/BCP/Alq₃/LiF/Al was fabricated in comparison with the non-doped device. The device emitted bright white light with the CIE coordinates of (0.33, 0.29) at 10 V and a maximum luminance of 7723 cd/m² at 14.8 V.     

High-efficiency organic light-emitting diodes (OLEDs) with a mixed layer structure

Improved performance of organic light-emitting diodes (OLEDs) as obtained by a mixed layer was investigated. The OLEDs with a mixed layer which were composed of N,N′-diphenyl-N,N′-bis(1-napthyl-phenyl)-1,1′-biphenyl-4,4′-diamine (NPB), tris-(8-hydroxyquinolato) aluminum (Alq₃) and 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) showed the highest brightness and efficiency, which reached 19048 cd/m² at 17 V and 4.3 cd/A at 10 mA/cm², respectively. The turn-on voltage of the device is 2.6 V. Its Commission Internationale del’Eclairage (CIE) coordinate is (0.497, 0.456) at 17 V, and the CIE coordinates of the device are largely insensitive to the driving voltages, which depicts stabilized yellow color.     

High efficiency small molecule white organic light-emitting devices with a multilayer structure

In this paper, a new white organic light-emitting device (WOLED) with multilayer structure has been fabricated. The structure of devices is ITO/N, N-bis-(1-naphthyl)-N, N^′-diphenyl-1, 1′-biphenyl-4, 4′-diamine (NPB) (40 nm)/NPB: QAD (1%): DCJTB (1%) (10 nm) /DPVBi (10 nm) /2, 9-dimethyl, 4, 7-diphenyl, 1, 10-phenanthroline (BCP) (d nm)/tris-(8-hydroxyquinoline) aluminium (Alq₃)(50-d nm)/LiF (1 nm)/Al (200 nm). In our devices, a red dye 4-(dicyanomethylene)-2-t-butyl-6 (1, 1, 7, 7-tetramethyl julolidyl-9-enyl)-4H-pyran (DCJTB) and a green dye quinacridone (QAD) were co-doped into NPB. The device with 8 nm BCP shows maximum luminance of 12 852 cd/m² at 20 V. The current efficiency and power efficiency reach 9.37 cd/A at 9 V and 3.60 lm/W at 8 V, respectively. The thickness of the blocking layer permit the tuning of the device spectrum to achieve a balanced white emission with Commission International de’Eclairage (CIE) chromaticity coordinates of (0.33,0.33). The CIE coordinates of device change from (0.3278, 0.3043) at 5 V to (0.3251, 0.2967) at 20 V that are well in the white region, which is largely insensitive to the applied bias.     

Non-Doped Deep Blue and Doped White Electroluminescence Devices Based on Phenanthroimidazole Derivative

A novel deep-blue emitter PhImPOTD based on phenathroimidazole was synthesized, which is incorporated by an electron-donating dibenzothiophene unit and electron-withdrawing phenanthroimidazole and diphenylphosphine oxide moieties. Furthermore, the weak π–π stacking and intermolecular aggregation render the photoluminescence quantum yield is as high as 0.34 in the solid state. Non-doped organic light emitting diodes (OLEDs) based on PhImPOTD emitter exhibits a low turn-on voltage of 3.6 V, a favorable efficiency of 1.13 cd A^?1 and a deep blue emission with Commission Internationale de l’Eclairage (CIE) coordinates of (0.15, 0.08). The CIE is very close to the NTSC (National Television Standards Committe) blue standard (CIE: 0.14, 0.08). PhImPOTD is also utilized as blue emitter and the host for a yellow emitter (PO-01) to fabricate white organic light-emitting diodes (WOLEDs). This gives a forward-viewing maximum CE of 4.83 cd A^?1 and CIE coordinates of (0.32, 0.32) at the luminance of 1000 cd m^?2. Moreover, the single-carrier devices unambiguously demonstrate that typical bipolar-dominant characteristics of PhImPOTD. This work demonstrates not only that the phenanthroimidazole unit is an excellent building block to construct deep blue emission materials, but also the introduction of a diphenylphosphine oxide deprotonation substituent is an efficient tactic for harvesting deep-blue emitting devices.     

All-in-one-type organic light-emitting diodes for color tuning using phosphor in glasses with Pb-free silicate powders

We demonstrate all-in-one-type organic light-emitting diodes (OLEDs) that are fabricated using a color converting plate as a substrate. The color converting plate is Pb-free phosphor-in-glass (PiG), which is prepared by mixing Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce³⁺) and SiO₂–B₂O₃–RO (R = Ba, Zn) glass frit by sintering at 750 °C for 30 min. The maximum luminance, luminance efficiency, and power efficiency of blue OLEDs fabricated on commercial glass are measured as 10500 cd/m², 10.18 cd/A, and 2.95 lm/W, respectively. The Commission Internationale de l'Eclairge (CIE) coordinates of blue OLEDs is (0.167, 0.325). Our obtained results show that the luminance value decreased as the PiG thickness increased, and the glass to phosphor (GTP) ratio decreased. The OLED devices fabricated on the PiG substrate (GTP ratio = 9:1, thickness: 150 μm) showed a maximum luminance, luminance efficiency, and power efficiency of 7600 cd/m², 8.76 cd/A, and 2.85 lm/W, respectively. The CIE color coordinates changed to (0.286, 0.504) at 200 mA/cm². These results proved that color coordination can be easily adjusted by varying the GTP ratio and the thickness of the PiG.     

色彩转换膜对白色有机电致发光光谱的影响

利用蓝色有机发光二极管激发荧光色彩转换膜的方法,制备了一种新型的白色有机电致发光器件。蓝色有机发光二极管的发光层采用4,4’-Bis(carbazol-9-yl)biphenyl(CBP)主体掺杂高效蓝色荧光染料N-(4-((E)-2-(6-((E)-4-(diphenylamino)styryl)naphthalen-2-yl)vinyl)phenyl)-N-phenylbenzenamine (N-BDAVBi)来制备。有机/无机复合色彩转换膜是将有机荧光颜料VQ-D25和无机荧光粉掺铈钇铝石榴石(YAG∶Ce3+)按一定的重量比均匀分散到-[CH₃CH₂COOCH₃]_n-(PMMA)中来制备。获得了色稳定性较高的白色有机电致发光器件。当驱动电压由6升至14 V时,器件光谱非常稳定且CIE色坐标仅从(0.354,0.304)变化到(0.357,0.312),其最高电流效率约为5.8 cd·A-1(4.35 mA·cm-2),最高亮度为16 800 cd·m-2(14 V)。     

三元铱配合物磷光体系的白光有机电致发光器件光谱特性研究

将黄光磷光材料bis[2-(4-tertbutylphenyl)benzothiazolato-N,C2’]iridium (acetylacetonate) [(t-bt)₂Ir(acac)]超薄层作为黄光发光层,两个蓝光磷光染料iridium(Ⅲ) bis(4’,6’-difluorophenylpyridinato)tetrakis(1-pyrazolyl)borate (FIr6)和bis[(4,6-difluorophenyl)-pyridinato-N,C2’](picolinate) iridium (Ⅲ) (FIrpic)掺杂层作为蓝光发光层,制备了三元发光层的白光有机电致发光器件。该器件具有三元磷光染料分子协同发光特性,并且利用合适厚度的隔层,将三线态激子束缚在各自激子复合区域内,获得了稳定电致发光光谱,CIE色坐标为(0.29±0.01, 0.34±0.01),处于理想的白光区域。通过器件电学特性的测试,验证了磷光染料在三元发光层器件中电致发光作用的机理,同时结果表明,三元发光层器件由于稳定的激子复合区域而有效减弱了器件效率滚降现象。     

Enhancement of performance for blue organic light emitting devices by utilizing an adjustable chromaticity layer

An adjustable chromaticity layer was successfully applied to a TBADN-based blue organic light-emitting device (BOLED) for improving chromaticity and luminance efficiency. The device was constructed by sandwiching an ultrathin [DPVBi: BCzVB] layer between hole-transport layer and primary emission layer. The optimized device gives the Commission Internationale de I’éclairage (CIE) color coordinates of (0.166, 0.201) at the current density of 20 mA/cm² and a maximum luminance efficiency of 8.43 cd/A at the driving voltage of 11 V.     

White organic electroluminescence from fluorescent bis (2-(2-hydroxyphenyl) benzoxazolate)zinc doped with phosphorescent material

Efficient white electroluminescence has been obtained by using an electroluminescent layer comprising of a blue fluorescent bis (2-(2-hydroxyphenyl) benzoxazolate)zinc [Zn(hpb)₂] doped with red phosphorescent bis (2-(2′-benzothienyl) pyridinato-N,C^3′)iridium(acetylacetonate) [Ir(btp)₂acac] molecules. The color coordinates of the white emission spectrum was controlled by optimizing the concentration of red dopant in the blue fluorescent emissive layer. Organic light-emitting diodes were fabricated in the configuration ITO/α-NPD/Zn(hpb)₂:0.01 wt%Ir(btp)₂acac/BCP/Alq₃/LiF/Al. The J-V-L characteristic of the device shows a turn on voltage of 5 V. The electroluminescence (EL) spectra of the device cover a wide range of visible region of the electromagnetic spectrum with three peaks around 450, 485 and 610 nm. A maximum white luminance of 3500 cd/m² with CIE coordinates of (x, y=0.34, 0.27) at 15 V has been achieved. The maximum current efficiency and power efficiency of the device was 5.2 cd/A and 1.43 lm/W respectively at 11.5 V.     

Simple-structure white organic light emitting diodes with high color temperature

We present high color temperature white organic light emitting diodes with a simple p-i-n structure. A sky blue phosphorescent dopant of iridium(III) bis[4,6-(difluorophenyl)-pyridinato-N,C^2’] picolinate and a red phosphorescent dopant of bis(2-phenylquinoline)(acetylacetonate)iridium(III) in the emissive layers is employed to make high color temperature devices. Very stable color variation under ?0.02 until a 5000 cd/m² brightness value is realized by efficient carrier control in a multi stacked emitting layer of blue/red/blue colors. Maximum current and power efficiencies of 23.8 cd/A and 22.9 lm/W in forward direction are obtained. With balanced emissions from the two emitters, the white light emission with very high correlated color temperature of 7308 K as well as CIE coordinates of (0.30, 0.33) is achieved.     

Angle-stable top-emitting white organic light-emitting devices employing a down-conversion layer

Angle-stable white top-emitting organic light-emitting devices (WTEOLEDs) by the combination of a blue TEOLED with a down-conversion (DC) layer are demonstrated. The DC layer is composed of red fluorescent dye doped in a host of tris (8-hydroxy-quinolinato) aluminum. The TEWOLED shows a CIE coordinates of (0.240, 0.332) and a maximum current efficiency of 3.95 cd/A. Furthermore, the WTEOLED shows excellently angle-stable characteristic, the CIE coordinates at 20 mA/cm² only shift by (0.023, −0.007) from 0° to 60°. It can be attributed to the angle-stable blue TEOLED based on the Ag/Ge/Ag transparent cathode.     

Non-doped phosphorescent white organic light-emitting devices with a quadruple-quantum-well structure

Non-doped white organic light-emitting devices (WOLEDs) with a quadruple-quantum-well structure were fabricated. An alternate layer of ultrathin blue and yellow iridium complexes was employed as the potential well layer, while potential barrier layers (PBLs) were chosen to be 2,2',2''-(1,3,5-benzenetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi) or N,N'-dicarbazolyl-3,5-benzene (mCP) combined TPBi. On adjusting the PBLs for device performance comparison, the results showed that the device with all-TPBi PBLs exhibited a yellow emission with the color coordinates of (0.50,0.47) at a luminance of 1000 cd/m², while stable white emission with the color coordinates of (0.36,0.44) was observed in the device using mCP combined TPBi as the PBLs. Meanwhile, for the WOLED, with a reduced efficiency roll-off, a maximum luminance, luminous efficiency, and external quantum efficiency of 12,610 cd/m², 10.2 cd/A, and 4.4%, respectively, were achieved. The performance improvement by the introduction of mCP PBL was ascribed to the well confined exciton and the reduced exciton quenching effect in the multiple emission regions.     

Efficient and stable single-dopant white OLEDs based on 9,10-bis (2-naphthyl) anthracene

Efficient white organic light-emitting diodes (WOLEDs) are fabricated with a thin layer of 9,10-bis (2-naphthyl) anthracene (ADN) doped with Rubrene as the source of white emission. A device with the structure of ITO/NPB (70 nm)/ADN: 0.5% Rubrene (30 nm)/Alq₃ (50 nm)/MgAg shows a maximum current efficiency of 3.7 cd/A, with the CIE coordinates of x=0.33, y=0.43. The EL spectrum of the devices and the CIE coordinates remains almost the same when the voltage is increased from 10 to 15 V and the current efficiency remains quite stable with the current density increased from 20 to 250 mA/cm².     

High efficient and color stable WOLED using double white emissive layer

For the high luminance and quantum efficiency, we propose a novel structure of white organic light-emitting diode (WOLED) using two white emissive layers (EML). The host material of MADN with the blue dopant of BCzVBi and the red dopant of DCJTB was used for one EML and DPVBi as host material with those dopants for the other EML. By considering the order of the EMLs and their energy band gaps in the device structure, the charge carrier trapping can be generated. They play a role in the barrier function at the EML enhancing the recombination where the holes and electrons were trapped in the DPVBi and MADN. The quantum efficiency can be improved by the charge carrier trapping in the WOLED with the double white EMLs as obtaining 4.23% at 10 mA/cm², and it is vastly superior to that of the WOLED with a single EML. White color balance is also excellent with color coordinates of (0.36, 0.34) in the CIE 1931 (x, y) chromaticity diagram.     

Improving the color purity and efficiency of blue organic light-emitting diodes (BOLED) by adding hole-blocking layer

This work demonstrates the fabrication of a bright blue organic light-emitting diode (BOLED) with good color purity using 4,4′-bis(2,2-diphenylvinyl)-1,1′-biphenyl (DPVBi) and bathocuproine (BCP) as the emitting layer (EML) and the hole-blocking layer (HBL), respectively. Devices were prepared by vacuum deposition on indium tin oxide (ITO)-glass substrates. The thickness of DPVBi used in the OLED has an important effect on color and efficiency. The blue luminescence is maximal at 7670 cd/m² when 13 V is applied and the BCP thickness is 2 nm. The CIE coordinate at a luminance of 7670 cd/m² is (0.165, 0.173). Furthermore, the current efficiency is maximum at 4.25 cd/A when 9 V is applied.     

Blue organic light-emitting diodes with 2-methyl-9,10-bis(naphthalen-2-yl)anthracene as hole transport and emitting layer and the impedance spectroscopy analysis

2-methyl-9,10-bis(naphthalen-2-yl)anthracene (MADN) based fluorescent blue organic light-emitting diodes (OLEDs) are demonstrated. With MADN as emitting layer, experiments indicate that thick MADN (40–60 nm) is preferable for constructing efficient blue OLED. With MADN as hole-transport and emitting layer and tris(8-hydroxy-quinolinato)aluminium (Alq₃) as electron-transport layer, the OLED electroluminescent characteristics show a mixture emission of MADN and Alq₃ with Commission Internationale d'Eclairage (CIE) color coordinates of (0.25, 0.34), indicating feasible hole transporting in MADN. Using 4,7-diphenyl-1,10-phenanthroline (BPhen) replacing Alq₃ as electron-transport layer, the OLED shows deep blue emission with a maximum luminous efficiency of 4.8 cd/A and CIE color coordinates of (0.16, 0.09). The hole transport characteristics of MADN are further clarified by constructing hole-only device and performing impedance spectroscopy analysis. The results indicate that MADN shows superior hole-transport ability which is almost comparable to typical hole-transport material of N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)-benzidine (NPB), suggesting a promising application for constructing efficient blue OLED with integrated hole-transport layer and emitting layer.     

一种基于蓝色荧光与磷光敏化技术的高显色指数白光有机电致发光器件的制备

通过采用4,4'-bis(9-ethyl-3-carbazovinylene)-1,1'-biphenyl (BCzVBi)为蓝色荧光发光单元,绿色磷光材料fac tris(2-phenylpyridine) iridium 敏化红色荧光材料4-(dicyanomethylene)-2-tert-butyl-6-(1,1,7,7-tetramethyljulolidin-4-yl-vinyl)-4H-pyran (DCJTB)为混合黄色发光单元,制备了一组白光有机电致发光器件。通过对染料掺杂浓度的优化,以及引入适当厚度的4,4-N,N-dicarbazole-biphenyl (CBP)作为中间层,获得了高效率、高显色指数的白光有机电致发光器件。器件在100 cd/m²亮度下的最高显色指数达到了90,此时的色坐标为(0.32,0.32), 非常接近白光等能点。该组器件的最大电流效率达到了11.00 cd/A,相应器件的最大亮度为13 330 cd/m²。