利用石墨烯掺杂在NPB中的OLED性能研究

采用NPB掺杂石墨烯作为空穴传输层,制备有机电致发光器件(OLED),器件结构为ITO/NPB:Graphene(20wt.%)(50nm)/Alq3(80nm)/LiF(0.5nm)/Al(120nm)。将其与标准器件ITO/NPB(50nm)/Alq3(80nm)/LiF(0.5nm)/Al(120nm)作性能比较,研究石墨烯对OLED性能的影响。结果表明,在NPB中掺杂石墨烯薄层的器件,在同等条件下性能最佳,当电流密度为90mA/cm2时器件电流效率达到最大值3.40cd/A,与标准器件最高效率相比增大1.49倍;亮度在15V时达到最大值10 070cd/m2,比标准器件最大亮度增大5.16倍。     

High‐Purity‐Blue and High‐Efficiency Electroluminescent Devices Based on Anthracene

Novel blue‐light‐emitting materials, 9,10‐bis(1,2‐diphenyl styryl)anthracene (BDSA) and 9,10‐bis(4′‐triphenylsilylphenyl)anthracene (BTSA), which are composed of an anthracene molecule as the main unit and a rigid and bulky 1,2‐diphenylstyryl or triphenylsilylphenyl side unit, have been designed and synthesized. Theoretical calculations on the three‐dimensional structures of BDSA and BTSA show that they have a non‐coplanar structure and inhibited intermolecular interactions, resulting in a high luminescence efficiency and good color purity. By incorporating these new, non‐doped, blue‐light‐emitting materials into a multilayer device structure, it is possible to achieve luminance efficiencies of 1.43 lm W^–1 (3.0 cd A^–1 at 6.6 V) for BDSA and 0.61 lm W^–1 (1.3 cd A^–1 at 6.7 V) for BTSA at 10 mA cm^–2. The electroluminescence spectrum of the indium tin oxide (ITO)/copper phthalocyanine (CuPc)/1,4‐bis[(1‐naphthylphenyl)‐amino]biphenyl (α‐NPD)/BDSA/tris(9‐hydroxyquinolinato)aluminum (Alq₃)/LiF/Al device shows a narrow emission band with a full width at half maximum (FWHM) of 55 nm and a λ_max = 453 nm. The FWHM of the ITO/CuPc/α‐NPD/BTSA/Alq₃/LiF/Al device is 53 nm, with a λ_max = 436 nm. Regarding color, the devices showed highly pure blue emission ((x,y) = (0.15,0.09) for BTSA, (x,y) = (0.14,0.10) for BDSA) at 10 mA cm^–2 in Commission Internationale de l'Eclairage (CIE) chromaticity coordinates.     

Molecular Engineering of Blue Fluorescent Molecules Based on Silicon End‐Capped Diphenylaminofluorene Derivatives for Efficient Organic Light‐Emitting Materials

Blue fluorescent materials based on silicone end‐capped 2‐diphenylaminofluorene derivatives are synthesized and characterized. These materials are doped into a 2‐methyl‐9,10‐di‐[2‐naphthyl]anthracene host as blue dopant materials in the emitting layer of organic light‐emitting diode devices bearing a structure of ITO/DNTPD (60 nm)/NPB (30 nm)/emitting layer (30 nm)/Alq₃ (20 nm)/LiF (1.0 nm)/Al (200 nm). All devices exhibit highly efficient blue electroluminescence with high external quantum efficiencies (3.47%–7.34% at 20 mA cm^?2). The best luminous efficiency of 11.2 cd A^?1 and highest quantum efficiency of 7.34% at 20 mA cm^?2 are obtained in a device with CIE coordinates (0.15, 0.25). A deep‐blue OLED with CIE coordinates (0.15, 0.14) exhibits a luminous efficiency of 3.70 cd A^?1 and quantum efficiency of 3.47% at 20 mA cm^?2.     

Effect of Al:Ag alloy cathode on the performance of transparent organic light-emitting devices

Transparent organic light-emitting devices (TOLEDs) based on a stacked alloy cathode of LiF/Al:Ag are investigated. The devices have a structure of indium-tin-oxide (ITO)/4,4′,4′′-Tris[2-naphthyl(phenyl)amino]triphenylamine (2T-NATA) (25 nm)/N,N''-Di-[(1-naphthyl)-N,N''-diphenyl]-1,1''-biphenyl-4,4''-diamine (NPB) (40 nm)/tris-(8-hydroxyquinoline) aluminum (Alq3) (50 nm)/LiF (1 nm)/Al:Ag (1:3) (x), where the thicknesses of cathode metal layers (Al:Ag) are adjusted, respectively, from 70 nm to 100 nm. In the experiment, it is found that the LiF (1 nm)/Al:Ag (1:3) (75 nm) has good electron injection efficiency. Compared with an Al-only cathode, the turn-on voltage is lowered. At the voltage of 10 V, the luminances for bottom emission from ITO anode side and top emission from metal cathode side are 2 459 cd/m2 and 1 729 cd/m2, respectively. Thanks to electron injection enhancement by using Al:Ag cathode, we can obtain a better energy level matching between the cathode and the organic layer, thus the devices have lower turn-on voltage and higher luminance. The total transmittance of the devices can achieve about 40% at the wavelength of 550 nm.     

Improved property in organic light-emitting diode utilizing two Al/Alq3 layers

We reported on the fabrication of organic light-emitting devices (OLEDs) utilizing the two Al/Alq₃ layers and two electrodes. This novel green device with structure of Al(110 nm)/tris(8-hydroxyquinoline) aluminum (Alq₃)(65 nm)/Al(110 nm)/Alq₃(50 nm)/N,N′-dipheny1-N, N′-bis-(3-methy1phyeny1)-1, 1′-bipheny1-4, 4′-diamine (TPD)(60 nm)/ITO(60 nm)/Glass. TPD were used as holes transporting layer (HTL), and Alq₃ was used as electron transporting layer (ETL), at the same time, Alq₃ was also used as emitting layer (EL), Al and ITO were used as cathode and anode, respectively. The results showed that the device containing the two Al/Alq₃ layers and two electrodes had a higher brightness and electroluminescent efficiency than the device without this layer. At current density of 14 mA/cm², the brightness of the device with the two Al/Alq₃ layers reach 3693 cd/m², which is higher than the 2537 cd/m² of the Al/Alq₃/TPD:Alq₃/ITO/Glass device and the 1504.0 cd/m² of the Al/Alq₃/TPD/ITO/Glass. Turn-on voltage of the device with two Al/Alq₃ layers was 7 V, which is lower than the others.     

基于DOPPP的高效白光OLED器件

采用真空热蒸镀的方法,以荧光染料1-(2,5-d imethoxy-4-(1-pyrenyl)-phenyl)pyrene (DOPPP)为蓝发光 层,5,6,11,2-Tetraphenylnaphthacene (Rubrene)为黄发光层,制备了结构为ITO/m-M TDATA(10nm)/NPB(30nm)/ Rubrene (0.2nm)/ DOPPP (x nm)/TAZ(10nm)/Alq₃(30nm)/LiF(0.5nm)/Al的双发光层的高效白色有机电 致发光器件(OLED)。通过调整DOPPP层的厚度,研究器件的发光性能。当DOPPP层厚小 于25nm时,器件以 黄光发射为主;当DOPPP层厚为25nm时器件的性能最佳,在电流密度为209.18mA/cm²时,获得最 大亮度为9232cd/m²,在电流密度为103.712mA/cm²时获得最大电流效率4.68cd/A, 并随着驱动电压 的升高,器件的色坐标从(0.366,0.365)变化到(0.384,0.399),都在白光的范围之内;当DOPPP层厚度超过25nm时,器件的效率和亮度 都开始下降。     

White organic light-emitting diodes based on emission from DPVBi-doped 4,48-bis (2,28-diphenylvinyl)-1, 18-biphenyl

Organiclight-emitting diodes (OLEDs) have beenin-vestigated for many years on account of their highlumi-nance,low driven voltages ,wide visual range,flexiblesubstratesinflat-panel ,full color displays and backlightapplications .For high brightness and eff…     

MoO3修饰氧化石墨烯作为空穴注入层影响研究

研究了MoO₃修饰氧化石墨烯(GO)作为空穴注入层的影响。采用旋涂的方法制备了GO, 再真空蒸镀修饰层MoO₃,得到了空穴注入能力强和透过率高的复合薄膜。MoO₃的厚分 别采用0、3、5和8nm。通过优化MoO₃的厚度发现,当MoO₃的厚为5nm时,复合薄膜 的透过率达到最大值,在 550nm的光波长下透光率为88%,且此时采用 复合薄膜作为空穴注入层制备的结构为 ITO/GO/MoO₃(5nm)/NPB(40nm)/Alq₃(40nm)/LiF(1nm)/Al(100nm)的有机电致发光器件(OLED)性能 最佳。通过对OLED进一步的优化,改变Alq₃的厚度,分别取50、60和70nm,测量其电压 、电流、亮度、色坐标和电致发光(EL)光谱等参数发现,当Alq₃的厚为50nm时器件性能最 佳。最终制备了结构为ITO/GO/MoO₃(5nm)/NPB(50nm)/Alq₃(50nm)/LiF(1nm)/Al(100 nm)的OLED,在电压为10V时,最大电流效率达到5.87cd/A,与GO单独作为空穴注入层制备的器件相比,提高了50%。     

MgF2缓冲层对蓝光OLED性能的影响

为了提高蓝光有机电致发光器件(OLED)的发光性能,将MgF2缓冲层插入ITO阳极与空穴传输层NPB之间,通过优化MgF2的厚度,制备了结构为ITO/MgF2(x nm)/NPB(50nm)/DPVBi:DSA-ph(30nm)/Alq3(30nm)/LiF(0.6nm)/Al(100nm)的高性能蓝光器件。实验结果表明,MgF2厚为1.0nm时,器件性能最佳,对应的器件最大电流效率达到5.51cd/A,最大亮度为23 290cd/m2(10.5V),与没有MgF2缓冲层的标准器件相比,分别提高47.3%和25.2%。对ITO表面的功函数测量结果表明,MgF2缓冲层可以有效修饰ITO表面,降低ITO与NPB之间的势垒高度差,改善空穴的注入效率,从而导致电子和空穴的注入更加平衡,激发机制更高效,实现了高性能的蓝光发射,为实现高效而稳定的全彩显示和白光照明奠定了基础。     

Enhancement of electron injection in inverted bottom-emitting organic light-emitting diodes using Al/LiF compound thin film

The inverted bottom-emitting organic light-emitting devices (IBOLEDs) were prepared, with the structure of ITO/Al (x nm)/LiF (1 nm)/Bphen (40 nm)/CBP: GIr1 (14%):R-4b (2%) (10 nm)/BCP (3 nm)/CBP:GIr1 (14%):R-4b (2%) (20 nm)/TCTA (10 nm)/NPB (40 nm)/MoO3 (40 nm)/Al (100 nm), where the thickness of electron injection layer Al (x) are 0 nm, 2 nm, 3 nm, 4 nm and 5 nm, respectively. In this paper, the electron injection condition and luminance properties of inverted devices were investigated by changing the thickness of Al layer in Al/LiF compound thin film. It turns out that the introduction of Al layer can improve electron injection of the devices dramatically. Furthermore, the device exerts lower driving voltage and higher current efficiency when the thickness of electron injection Al layer is 3 nm. For example, the current efficiency of the device with 3-nm-thick Al layer reaches 19.75 cd·A^-1 when driving voltage is 7 V, which is 1.24, 1.17 and 17.03 times larger than those of the devices with 2 nm, 4 nm and 5 nm Al layer, respectively. The device property reaches up to the level of corresponding conventional device. In addition, all inverted devices with electron injection Al layer show superior stability of color coordinate due to the adoption of co-evaporation emitting layer and BCP spacer-layer, and the color coordinate of the inverted device with 3-nm-thick Al layer only changes from (0.580 6, 0.405 6) to (0.532 8, 0.436 3) when driving voltage increases from 6 V to 10 V.     

有机白光器件中CdS薄层增加电子注入的研究

为了研究光电材料CdS在有机白光器件中增加电子注入的特性,将结构为ITO/NPB/Rubrene/NPB/DPVBi/Alq3/LiF/Al的白光器件,不插入CdS薄层或将CdS薄层分别插入到NPB和ITO之间以及Alq3和LiF之间或同时将CdS薄层插入到它们之间,制作了四个元器件。通过研究得出,在Alq3和LiF之间插入CdS薄层的器件,在同等条件下性能较好。性能的改善来自于CdS薄层的引入使器件电子注入增加,激子形成的数量和比率也获得了相应的提高,从而提高了器件的亮度和效率。     

蓝绿色磷光OLED的制备及发光性能研究

以mCP为主体发光材料,蓝绿色磷光染料BGIr1作 为掺杂剂,制备了6种不同BGIr1掺杂量的蓝绿色磷光有机电致发光器件(OLED),研究了不 同掺杂量对蓝绿色磷光OLED器件发光特性的影 响。制得器件的结构为ITO/MoO₃(20nm)/NPB(40nm)/mCP:BGIr1(x%,30nm)/BCP(10nm)/Alq₃(20 nm)/LiF/Al(100nm),其中x%为发光层中磷光染料BGIr1的掺杂量(质量分数)。结果表明,BGIr1掺杂量 为18%时,获得器件的发光性能最佳。18% BGIr 1掺杂器件在488nm和 512nm处获得两个主发射峰,当电 流密度为26.5mA/cm²时,获得最大发光效率为6.2cd/A;在15V驱动电压下,获得最大亮度为6970cd/cm², CIE坐标为(0.17,0.31)。这说明,BGI r1掺杂改善了器件的发光亮度和色纯度,提高了器件的发光效率。     

A DCM‐Type Red‐Fluorescent Dopant for High‐Performance Organic Electroluminescent Devices

2‐(2‐tert‐Butyl‐6‐((E)‐2‐(2,6,6‐trimethyl‐2,4,5,6‐tetrahydro‐1H‐pyrrolo[3,2,1‐ij]quinolin‐8‐yl)vinyl)‐4H‐pyran‐4‐ylidene)malononitrile (DCQTB) is designed and synthesized in high yield for application as the red‐light‐emitting dopant in organic light‐emitting diodes (OLEDs). Compared with 4‐(dicyanomethylene)‐2‐tert‐butyl‐6‐(1,1,7,7,‐tetramethyljulolidyl‐9‐enyl)‐4H‐pyran (DCJTB), one of the most efficient red‐emitting dopants, DCQTB exhibits red‐shifted fluorescence but blue‐shifted absorption. The unique characteristics of DCQTB with respect to DCJTB are utilized to achieve a red OLED with improved color purity and luminous efficiency. As a result, the device that uses DCQTB as dopant, with the configuration: indium tin oxide (ITO)/N,N′‐bis(1‐naphthyl)‐N,N′‐diphenyl‐1,1′‐biphenyl‐4,4′‐diamine (NPB; 60 nm)/tris(8‐quinolinolato) aluminum (Alq₃):dopant (2.3 wt %) (7 nm)/2,9‐dimethyl‐4,7‐diphenyl‐1,10‐phenanthroline (BCP; 12 nm)/Alq₃(45 nm)/LiF(0.3 nm):Al (300 nm), shows a larger maximum luminance (L_max = 6021 cd m^–2 at 17 V), higher maximum efficiency (η_max = 4.41 cd A^–1 at 11.5 V (235.5 cd m^–2)), and better chromaticity coordinates (Commission Internationale de l'Eclairage, CIE, (x,y) = (0.65,0.35)) than a DCJTB‐based device with the same structure (L_max = 3453 cd m^–2 at 15.5 V, η_max = 3.01 cd A^–1 at 10 V (17.69 cd m^–2), and CIE (x,y) = (0.62,0.38)). The possible reasons for the red‐shifted emission but blue‐shifted absorption of DCQTB relative to DCJTB are also discussed.     

白光有机电致发光器件发光稳定性研究

基于红绿/蓝双发光层,制作了结构为ITO/MoO ₃(10nm)/NPB(40nm)/TCTA(10nm)/CBP:R-4B(2%):GIR1(14%,X nm)/mCP:Firpic(8%,Y nm/BCP(10nm)/Alq₃(40nm)/LiF(1nm)/Al( 100nm)的白色全磷光有机电致发光器件(OLED),通过 调节红绿发光层的厚度X与蓝光发光层的厚度Y,研究了不同发光层厚度器件发 光性能的影响。研究发现:当X 为23nm、Y为7nm时,器件的光效和色坐标都具有 很高的稳定性,在电压分别为5、 10和15V时,色坐标分别为(0.33,0.37)、(0.33,0. 37)和(0.34,0.38);在电压为 5V时,电流密度为0.674mA,亮度为158.7cd ,最大电流效率为26.87cd/A;利用电子阻 挡材料TCTA和空穴阻挡材料BCP能够显著提高载流子的复合效率。分析认为:发光层顺序 为红绿/蓝时,更有利于蓝光的出射,从而使白光的色坐标更稳定。     

Stable,Glassy, and Versatile Binaphthalene Derivatives Capable of Efficient Hole Transport,Hosting, and Deep‐Blue Light Emission

Organic light‐emitting diodes (OLEDs) have great potential applications in display and solid‐state lighting. Stability, cost, and blue emission are key issues governing the future of OLEDs. The synthesis and photoelectronics of a series of three kinds of binaphthyl (BN) derivatives are reported. BN_1–3 are “melting‐point‐less” and highly stable materials, forming very good, amorphous, glass‐like films. They decompose at temperatures as high as 485–545 °C. At a constant current density of 25 mA cm^?2, an ITO/BN₃/Al single‐layer device has a much‐longer lifetime (>80 h) than that of an ITO/NPB/Al single‐layer device (8 h). Also, the lifetime of a multilayer device based on BN₁ is longer than a similar device based on NPB. BNs are efficient and versatile OLED materials: they can be used as a hole‐transport layer (HTL), a host, and a deep‐blue‐light‐emitting material. This versatility may cut the cost of large‐scale material manufacture. More importantly, the deep‐blue electroluminescence (emission peak at 444 nm with CIE coordinates (0.16, 0.11), 3.23 cd A^?1 at 0.21 mA cm^?2, and 25200 cd m^?2 at 9 V) remains very stable at very high current densities up to 1000 mA cm^?2.     

功能层界面制备方法对OLED性能的影响

在功能层界面处采用各功能材料共蒸的方法,制备了典型的绿光有机发光器件(OLED)。器件的结构为ITO/NPB(37nm)/(NPB:Alq3)(3nm)/Alq3(27nm):C545T(3%)/Alq3(20nm)/LiF(1nm)/Al(100nm),并与传统的制备方法进行了比较。结果发现,起亮电压从4.5V降低到2.5V,最高耐压从16V提高到21V,最大亮度从13 940cd/m2提高到24 630cd/m2,发光效率由7.0cd/A提高到11.4cd/A。结果表明,本文方法有利于载流子传输,可以有效提高激子形成概率,提高了OLED发光效率。     

Blade coating of Tris(8-hydroxyquinolinato)aluminum as the electron-transport layer for all-solution blue fluorescent organic light-emitting diodes

Organic light-emitting diodes (OLEDs) with a low driving voltage and efficient blue fluorescence were fabricated through blade coating. Tris(8-hydroxyquinolinato)aluminum (Alq₃) is a relatively stable electron-transporting material commonly used in evaporation. However, depositing Alq₃ through a solution process is difficult because of its extremely low solubility organic solvents, a result of its symmetrical molecular structure. In this study, Alq₃ was successfully deposited through blade coating at a very low concentration below 0.1wt%. The OLEDs contained co-dopants BUBD-1 and p-bis(p-N,N-diphenyl-aminostyryl)benzene (DSA-Ph), and a high-band-gap host 2-methyl-9,10-bis(naphthalen-2-yl)anthracene (MADN) as the emission layer with the following structure: ITO/PEDOT:PSS (40 nm)/VB-FNPD (30 nm)/MADN:2% BUBD-1:1% DSA-Ph (50 nm)/TPBI (30 nm)/LiF (0.8 nm)/Al (100 nm)or ITO/PEDOT:PSS (40 nm)/VB-FNPD (30 nm)/MADN:3% BUBD-1 (50 nm)tris(8-hydroxyquinolinato)aluminum (Alq₃; 10 nm)/LiF (0.8 nm)/Al (100 nm). 2,7-disubstituted fluorene-based triaryldiamine(VB-FNPD)is the cross-linking transporting material. The device exhibited a peak current efficiency of 5.67 cd/A for Alq₃ and 5.76 cd/A for TPBI. The device with Alq₃ has operated lifetime seven times higher than the device with TPBI.     

Interface studies of Aluminum, 8-hydroxyquinolatolithium (Liq) and Alq3 for inverted OLED application

This study examined the interfaces of Alq₃ on a thin 8-hydroxyquinolatolithium (Liq) layer deposited on aluminum using X-ray and ultraviolet photoemission spectroscopy. A thin layer of Liq reacted with the underlying aluminum surface. As a result, the molecular orbital features of Alq₃ shifted to a higher binding energy and a new gap state was created. This effect is believed to lower the barrier height for electron injection. An organic light emitting device with a structure of ITO/Al/Liq/Alq₃/NPB/WO₃/Al was fabricated.The device performance showed characteristics that were consistent with the results of the photoemission studies. It is proposed that Al/Liq can be used as an efficient electron injection layer for inverted organic light emitting devices.     

Pure‐Red Dye for Organic Electroluminescent Devices: Bis‐Condensed DCM Derivatives

In this paper, the bis‐condensed 4‐(dicyanomethylene)‐2‐methyl‐6‐[p‐(dimethylamino)styryl]‐4H‐pyran ( DCM) derivatives are introduced as a new class of red dye for organic light‐emitting devices (OLEDs). They showed more red‐shifted emission than the mono‐substituted DCM derivatives and the emission maxima increased as the electron‐donating ability of the aromatic donor group increased. On the basis of these results, red light‐emitting devices were fabricated with bis‐condensed DCM derivatives as red dopants. For a device of configuration ITO/TPD/Alq₃ + DADB (5.2 wt.‐%)/Alq₃/Al (where ITO is indium tin oxide, TPD is N,N′‐diphenyl‐N,N′‐bis(3‐methylphenyl)‐1,1′‐biphenyl‐4,4′‐diamine, Alq₃ is tris(8‐hydroxyquinoline) aluminum, and DADB is [2,6‐bis[2‐[5‐(dibutylamino)phenyl]vinyl]‐4H‐pyran‐4‐ylidene]propanedinitrile), pure red emission was observed with Commission Internationale de l’Eclairage (CIE 1931) coordinates of (0.658, 0.337) at 25 mA/cm².     

Bright green organic light-emitting devices having a composite electron transport layer

A bright green organic light-emitting device employing a co-deposited Al-Alq₃ layer has been fabricated. The device structure is glass/indium tin oxide (ITO)/ N, N′-diphenyl-N, N′- (3-methylphenyl)-1, 1′-biphenyl-4, 4′-diamine (TPD)/tris(8-quinolinolato) aluminum (Alq₃)/ Al-Alq₃/Al. In this device, Al-Alq₃ is used as electron transport layer (ETL). The device shows an operation voltage of 6.1 V at 20 mA/cm². At optimal condition, the brightness of a device at 20 mA/cm² is 2195 cd/m² achieved a luminance efficiency of 5.64lm/W. The result proves that the composite Al-Alq₃ layer is suitable for the ETL of organic light-emitting devices (OLEDs).