一种多层白色磷光有机电致发光器件的制备及性能研究

制备了一种结构为ITO/NPB/NPB:Ir(piq)₂(acac)/CBP:TBPe/BAlq:rubrene/BAlq/Alq₃/Mg:Ag的白色磷光有机电致发光器件.其中空穴传输型主体NPB掺杂磷光染料Ir(piq)₂(acac)作为红色发光层,双载流子传输型主体4,4′-N,N′-dicarbazole-biphenyl (CBP)掺杂TBPe作为蓝色发光层,电子传输型主体材料BAlq掺杂rubrene作为绿色发光层.以上发光层夹于 关键词： 电致发光 磷光染料 异质结 白光     

不同主体双发光层白色有机电致发光器件的性能研究

制备了结构为ITO/NPB/CBP:TBPe:rubrene/BAlq:Ir(piq)₂(acac)/BAlq/Alq₃/Mg:Ag的白色磷光有机电致发光器件.利用两种不同的主体材料,即用双载流子传输型主体材料CBP掺杂荧光染料TBPe及rubrene作为蓝光和橙黄光发光层;用电子传输型主体材料BAlq掺杂磷光染料Ir(piq)₂(acac)作为红色发光层.以上双发光层夹于空穴传输层NPB与具有电子传输性的阻挡层BALq之间.讨论了如何控制 关键词： 有机电致发光 磷光染料 掺杂 白光     

同时掺杂磷光和荧光染料的白色有机电致发光器件性能研究

以磷光染料Ir(piq)₂(acac)作为发光掺杂剂,掺入空穴传输性主体材料NPB中得到红色发光层,荧光材料TBP掺入到主体CBP中作为蓝色发光层,制备了结构为ITO/NPB/NPB：Ir(piq)₂(acac)/CBP/CBP：TBPe/BCP/ALq/Mg：Ag的双发光层白色有机电致发光器件.其中ALq₃、未掺杂的NPB和CBP及BCP层分别作为电子传输层、空穴传输层和激子阻挡层.实验中通过调节发光层厚度及Ir(piq)_{2关键词： 磷光 激子阻挡层 有机电致发光}     

一种改善红光顶发射OLED色纯度及角度依赖特性的方法研究

在Si/SiO₂衬底上生长金属银作为阳极,4,4,4-tris(3-methylphenylpheny-lamino)-triphenylamine(m-MTDATA):MoOx/m-MTDATA/N,N-bis-(1-naphthyl)-N,N-diphenyl-1,1-biphenyl-4,4-diamine(NPB)作为空穴注入及传输层,发光层采用4,4-N,N-dicarbazole-biphenyl(CBP)掺杂磷光染料(1-(phenyl)isoquinoline)iridium(III) acetylanetonate(Ir(piq)₂(acac))的结构,4,7-di-phenyl-1,10-phenanthroline(BPhen)作为空穴阻挡层及电子传输层,阴极为LiF(1 nm)/Al(2 nm)/Ag(20 nm)复合阴极结构.通过在光取出的复合阴极上方生长一层CBP光学覆盖层,有效地改善了复合阴极膜系的透射率,从而改善了顶发射结构的光学耦合输出特性,在提高器件的正向发光效率的同时还使色坐标往深红光区移动.并且生长光学覆盖层结构的器件角度依赖特性明显得到改善,这对于制作高显示质量的显示器件具有重要意义.在原有结构的基础上增加20 nm的NPB掺杂磷光染料Ir(piq)₂(acac)作发光层,从而得到双发光层结构为NPB:Ir(piq)₂(acac)(1%,20 nm)/CBP:Ir(piq)₂(acac)(1%, 20 nm).由于NPB具有较高的空穴迁移率,避免了由于光学厚度的增加而引起器件工作电压的大幅升高,而双发光层的结构有利于增大激子复合区域,提高辐射复合几率,减少非辐射损耗,实现主客体之间高效的三线态能量传递,相对单发光层顶发射结构,双发光层结构不仅提高了器件的发光效率,而且改善了器件的色坐标.     

Study of different roles phosphorescent material played in different positions of organic light emitting diodes

Phosphorescent materials are crucial to improve the luminescence and efficiency of organic light emitting diodes (OLED), because its internal quantum efficiency can reach 100%. So the studying of optical and electrical properties of phosphorescent materials is propitious for the further development of phosphorescent OLED. Phosphorescent materials were generally doped into different host materials as emitting components, not only played an important role in emitting light but also had a profound influence on carrier transport properties. We studied the optical and electrical properties of the blue 4,4′-bis(2,2-diphenylvinyl)-1,1′-biphenyl (DPVBi)-based devices, adding a common yellow phosphorescent material bis[2-(4-tert-butylphenyl)benzothiazolato-N,C2′] iridium(acetylacetonate) [(t-bt)₂Ir(acac)] in different positions. The results showed (t-bt)₂Ir(acac) has remarkable hole-trapping ability. Especially the ultrathin structure device, compared to the device without (t-bt)₂Ir(acac), had increased the luminance by about 60%, and the efficiency by about 97%. Then introduced thin 4,4′-bis(carbazol-9-yl)biphenyl (CBP) host layer between DPVBi and (t-bt)₂Ir(acac), and got devices with stable white color.     

基于量子阱结构的高效磷光有机电致发光器件

采用多重量子阱结构制作了高效红色磷光有机电致发光器件。以4,4'-bis(N-carbazolyl)-1,10-biphenyl (CBP)掺杂bis(1-phenyl-isoquinoline)(Acetylacetonato) iridium(Ⅲ) (Ir(piq)₂(acac))为发光层,4,4'-bis(N-carbazolyl)-1,10-biphenyl(Bphen)为电荷控制层,形成了Ⅱ型双量子阱结构,器件的最大亮度为15 000 cd/m²,最大电流效率为7.4 cd/A,相对于参考器件提高了21%。研究结果表明:以Bphen为电荷控制层形成的Ⅱ型多重量子阱结构能有效地将载流子和激子限制在势阱中,并且使空穴和电子的注入更加平衡,从而提高了载流子复合的几率和器件的效率。     

不同主体材料对红色磷光OLED器件性能的影响

制作了结构为ITO/2T-NATA (20 nm)/NPB(60 nm)/Zn(BTZ)₂ : Ir(DBQ)₂(acac) (80 nm)/Alq₃(70 nm)/LiF(1 nm)/Al(200 nm)的红光器件,其中2T-NATA是4,4',4″-tris(N-(2-naphthyl)-N-phenyl-amino)-triphenylamine,NPB是N,N'-di(naphthalen-1-yl)-N,N'-diphenyl-benzidine, Zn(BTZ)₂是Bis-(2-(2-hydroxyphenyl) benzothiazole)zinc,Ir(DBQ)₂(acac)是iridium complex,Alq₃ 是tris(8-hydroxyquinolato)aluminum。基于Ir(DBQ)₂(acac) 掺杂的Zn(BTZ)₂体系的器件给出最高电致发光(EL)性能。结果显示:10％Ir(DBQ)₂-(acac) 掺杂Zn(BTZ)₂器件的亮度和效率分别为25 000 cd/m²和12 cd/A,其相应的EL峰位于620 nm,色坐标(x=0.63,y=0.37)。由于未使用激子阻挡层,所以,比通常磷光器件的制作工艺简单并且操作过程容易控制。     

基于CBP:BCzVB:Btp2Ir(acac)体系的白色有机电致发光器件色度飘移研究

以苯乙烯类化合物BCzVB为蓝色荧光染料,以铱配合物Btp_2Ir(acac)为红色磷光染料,共掺杂到CBP基质中作为发光层,制备了白色有机电致发光器件,研究了该体系发光色度漂移的原因。器件在掺杂CBP:6?zVB: 0．2%Btp_2Ir(acac),在．驱动电流从4～200 mA/cm~2变化范围内,发光色坐标从(0．340,0．273)飘移到(0．308, 0．273),色坐标轻微蓝移。对器件发光光谱和亮度-电流密度曲线等分析表明:器件色度的轻微蓝移是由于CBP基质向Btp_2Ir(acac)掺杂剂完全的能量传递、荧光染料BCzVB向磷光染料Btp_2Ir(acac)不完全的能量传递等内在物理过程和磷光染料Btp_2Ir(acac)自身发光饱和等特性共同决定的。     

Low voltage red phosphorescent organic light-emitting devices with triphenylphosphine oxide and 4,4′-bis(2,2′-diphenylvinyl)-1,1′-biphenyl electron transport layers

We have developed red phosphorescent organic light-emitting devices operating at low voltages by using triphenylphosphine oxide (Ph₃PO) and 4,4′-bis(2,2′-diphenylvinyl)-1,1′-biphenyl (DPVBi) electron transport layers. 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP) and tris-(1-phenylisoquinolinolato-C²,N) iridium(III) [Ir(piq)₃] were used as host and guest materials, respectively. Small voltage drops across the electron transport layers and direct injection of holes from 4,4′,4″-tris[N-(2-naphthyl)-N-phenyl-amino]-triphenylamine (2-TNATA) hole transport layer into the Ir(piq)₃ guests are responsible for the high current density at low voltage, resulting in a high luminance of 1000 cd/m² at low voltages of 2.8–3.0 V in devices with a structure of ITO/2-TNATA/CBP:Ir(piq)₃/DPVBi/Ph₃PO/LiF/Al.     

Organic Light-Emitting Diodes with Magnesium Doped CuPc as an Efficient Electron Injection Layer

Bright organic electroluminescent devices are developed using a metal-doped organic layer intervening between the cathode and the emitting layer. The typical device structure is a glass substrate/indium-tin oxide （ITO）/copper phthalocyanine （CuPc）/N,N＇-bis-（1-naphthl）-diphenyl-1,1＇-biphenyl-4,4＇-diamine （NPB）/Tris（8-quinolinolato） aluminum（Alq3）/Mg-doped CuPc/Ag. At a driving voltage of 11 V, the device with a layer of Mg-doped CuPc （1：2 in weight） shows a brightness of 4312cd/m^2 and a current efficiency of 2.52cd/A, while the reference device exhibits 514 cd/m^2 and 1.25 cd/A.     

White organic light-emitting device with\ both phosphorescent and fluorescent emissive layers

This paper reports the fabrication of novel white organic light-emitting device（WOLED） by using a high efficiency blue fluorescent dye N-（4-（（E）-2-（6-（（E）-4-（diphenylamino）styryl）naphthalen-2-yl）vinyl）phenyl）oN- phenylbenzenamine （N-BDAVBi） and a red phosphoresecent dye bis （1-（phenyl） isoquinoline） iridium （III） acetylanetonate （Ir（piq）2（acac））. The configuration of the device was ITO/PVK：TPD/CBP： N-BDAVBi /CBP/ BALq： Ir（piq）2（acac）/BCP/Alq3/LiF：AL. By adjusting the proportion of the dopants （N-BDAVBi, Ir（piq）2（acac）） in the light-emitting layer, white light with Commission Internationale de l＇Eclairage （CIE） coordinates of （0.35, 0.35） and a maximum luminance of 25350cd/m2 were obtained external quantum and current efficiency of 6.78% and between the two light-emitting layers and using BCP at an applied voltage of 22V. The WOLED exhibits maximum 12cd/A respectively. By placing an undoped spacer CBP layer as hole blocking layer, the colour stabilization slightly changed when the driving voltage increased from 6 to 22 V.     

发光层和空穴传输层对白色电致发光器件性能的影响

利用电子传输性能良好的苯并噻唑螯合锌(Zn(BTZ)₂)作为蓝光层，通过设计不同类型的空穴传输层并试验不同厚度的发光层后，制作了一种最佳厚度的双发光层白色电致发光器件：氧化铟锡(ITO)/N-N′-双(3-甲基苯基)-N-N′-二苯基-1-1′-二苯基-4-4′-二胺(TPD)∶N,N′-二(1-萘基)-N,N′-二苯基-1,1′-联苯-4-4′-二胺(NPB)(1∶0.0 关键词： 厚度 空穴传输层 白光 载流子     

Efficient Solution-Processed Blue Electrophosphorescent Devices Based on a Novel Small-Molecule Host

Efficient blue small molecular phosphorescent fight-emitting diodes with a blue phosphorescent dye bis（3,5- difluoro-2-（2-pyridyl）-phenyl-（2-carboxypride） iridium （Ⅲ） （Flrpic） doped into a novel small-molecule host 9,9- bis[4-（3,6-di-tert-butylcarbazol-9-yl）phenyl] fluorene （TBCPF） as the light-emitting layer have been fabricated by spin-coating. The host TBCPF can form homogeneous amorphous films by spin-coating and has triplet energy higher than that of the blue phosphorescent dye Flrpic. All the devices with different Flrpic concentration in the emitting layer give emission from Flrpic indicating complete energy transfer from TBCPF to Flrpic. The device shows the best performance with a peak brightness of 8050 cd/m^2 at 10.2 V and the maximum current efficiency up to 3.52 cd/A, when the Flrpic doped concentration is as high as 16%.     

Hole transport characteristics in phosphorescent dye-doped NPB films by admittance spectroscopy

Admittance spectroscopy is a powerful tool to determine the carrier mobility. The carrier mobility is a significant parameter to understand the behavior or to optimize the organic light-emitting diode or other organic semiconductor devices. Hole transport in phosphorescent dye, bis[2-(9,9-diethyl-9H-fluoren-2-yl)-1-phenyl-1Hbenzoimidazol-N,C3] iridium(acetylacetonate [(fbi)₂Ir(acac)]) doped into N,N-diphenyl-N,N-bis(1-naphthylphenyl)-1,1-biphenyl-4,4-diamine (NPB) films was investigated by admittance spectroscopy. The results show that doped (fbi)₂Ir(acac) molecules behave as hole traps in NPB, and lower the hole mobility. For thicker films(?300 nm), the electric field dependence of hole mobility is as expected positive, i.e., the mobility increases exponentially with the electric field. However, for thinner films (?300 nm), the electric field dependence of hole mobility is negative, i.e., the hole mobility decreases exponentially with the electric field. Physical mechanisms behind the negative field dependence of hole mobility are discussed. In addition, three frequency regions were divided to analyze the behaviors of the capacitance in the hole-only device and the physical mechanism was explained by trap theory and the parasitic capacitance effect.     

发光层厚度变化的高效红色有机电致磷光器件

以铱配合物红色磷光体为掺杂剂，制备了基于TPBi材料的红色电致磷光器件,其结构为ITO/CuPc/NPB/TPBi:Btp₂Ir(acac)/ TPBi/Alq/LiF/Al.取得了在x=0.62，y=0.35的色度下，效率最高达2.43cd/A；电流密度为20mA/cm²时，亮度431cd/m²；电流密度为400mA/cm²时，亮度4798 cd/m²的结果.讨论了不同的发光层厚度影响器件色度和 关键词： 三线态 红光掺杂剂 有机电致磷光 T-T湮没     

空穴传输层对有机电致发光器件性能的影响

制备了结构为ITO/MoO₃(40 nm)/空穴传输层/CBP:Ir(ppy)₂acac(8%)(30 nm)/BCP(10 nm)/Alq₃(40 nm)/LiF(1 nm)/Al(100 nm)的器件,其中Ir(ppy)₂acac为绿色磷光染料,空穴传输层分别为TAPC(50 nm)、TAPC(40 nm)/TCTA(10 nm)、NPB(50 nm)、NPB(40 nm)/TCTA(10 nm)。通过使用4种不同结构的空穴传输层,对器件的发光性能进行了研究。结果表明,空穴传输层对器件的发光性能有较大影响。在电压为6 V、电流密度为2 mA/cm²的条件下,4种结构的器件的电流效率分别为52.5,67.8,35.6,56.6 cd/A。其原因是TAPC/TCTA及NPB/TCTA能级结构更有利于空穴对发光层的注入而且TAPC拥有较高的空穴迁移率;另外,TAPC及TCTA拥有较高的LUMO和三线态能量,可以有效地将电子和三线态激子束缚在发光层内,增加绿光染料的复合发光几率。所制备的器件均表现出良好的色坐标稳定性。     

Enhancement of electroluminescent properties of organic optoelectronic integrated device by doping phosphorescent dye

Organic optoelectronic integrated devices(OIDs) with ultraviolet(UV) photodetectivity and different color emitting were constructed by using a thermally activated delayed fluorescence(TADF) material 4, 5-bis(carbazol-9-yl)-1, 2-dicyanobenzene(2 CzPN) as host. The OIDs doping with typical red phosphorescent dye [tris(1-phenylisoquinoline)iridium(Ⅲ), Ir(piq)_3], orange phosphorescent dye {bis[2-(4-tertbutylphenyl)benzothiazolato-N,C~(2')]iridium(acetylacetonate),(tbt)_2 Ir(acac)}, and blue phosphorescent dye [bis(2, 4-di-fluorophenylpyridinato)-tetrakis(1-pyrazolyl)borate iridium(Ⅲ), FIr6] were investigated and compared. The(tbt)_2 Ir(acac)-doped orange device showed better performance than those of red and blue devices, which was ascribed to more effective energy transfer. Meanwhile, at a low dopant concentration of 3 wt.%, the(tbt)_2 Ir(acac)-doped OIDs showed the maximum luminance, current efficiency, power efficiency of 70786 cd/m~2, 39.55 cd/A, and 23.92 lm/W, respectively, and a decent detectivity of 1.07 × 10~(11) Jones at a bias of -2 V under the UV-350 nm illumination. This work may arouse widespread interest in constructing high efficiency and luminance OIDs based on doping phosphorescent dye.     

以BAlq为主体的高效高色纯度的红色有机电致磷光器件

以铱配合物红色磷光体Ir(piq)₂(acac)为掺杂剂,制备了基于BAlq材料的红色电致磷光器件,其结构为ITO/NPB(30nm)/Ir(piq)₂(acac):BAlq(25nm)/BCP(13nm)/Alq₃(35nm)/LiF(1nm)/Al(1000nm),当掺杂浓度为8%的时候,器件发光的色坐标为(x=0.67,y=0.32),基本满足了全色显示对红色发光的要求。在电压为16V时,器件达到最高亮度9380cd/m²。在电流密度为5.45mA/cm²时,外量子效率达到最大5.7%。由于磷光体Ir(piq)₂(acac)的磷光寿命较短,所以器件在高电流密度下,仍然保持较高的外量子效率。电流密度为100mA/cm²时,外量子效率仍然维持在4.7%。进一步研究表明在器件中短程的Dexter能量传递以及红光染料对空穴的直接捕获两种机制同时存在。     

A study on the characteristics of OLEDs using Ir complex for blue phosphorescence

Several iridium-based complexes were investigated as phosphorescent dopants. They achieved about 100% internal quantum efficiency, due to utilization of both singlet and triplet excitons in the radiative processes. We have fabricated phosphorescent OLEDs with 8% Ir(ppz)₃ as a triplet emissive dopant in various host materials. CBP, which has an efficiency of 0.20 cd/A, is the best host material. Furthermore, we synthesized metal-organic phosphor complexes based on Ir with different ligands as to (Im)₂Ir(acac), (Im-R)₂Ir(acac), and Ir(ppz)₂(acac).     

深陷阱对有机磷光双掺杂体系电致发光器件效率衰退的影响

研究利用溶液法制备的有机磷光双重掺杂体系电致发光器件的光致发光特性与电致发光特性,并研究了在这种体系中深能级陷阱导致的器件效率衰退现象。首先利用紫外光谱仪和光致瞬态寿命测试系统对基于旋涂法制备的以宽带隙材料4,4’-bis(N-carbazolyl)-1,1’-biphenyl（CBP）为主体,绿色磷光材料tris(2-phenylpyridine) iridium(Ⅲ)（Ir(ppy)₃）和红色磷光材料tris(1-phenylisoquinolinato-C2,N)iridium(Ⅲ)（Ir(piq)₃）为客体材料的薄膜进行了光致发射光谱测试和薄膜在Ir(ppy)₃发光峰516 nm处的光致发光寿命测试,实验发现在Ir(ppy)₃掺杂比例保持定值时,随着深能级掺杂材料Ir(piq)₃的引入,其光致发光光谱中Ir(ppy)₃的相对发光强度减弱且发光寿命变短,当Ir(piq)₃掺杂浓度继续提高时,薄膜光致发光光谱基本保持不变且Ir(ppy)₃的发光寿命基本不变。实验说明在低浓度掺杂下两者的三线态能级之间存在着能量传递,但当掺杂浓度达到高浓度时,能量传递主要来自于主客体之间的传递,两者作为独立的发光中心发光。然后利用溶液法制备了发光层分别为CBP∶Ir(ppy)₃,CBP∶Ir(ppy)₃∶Ir(piq)₃和CBP∶Ir(ppy)₃∶PTB7的三组器件,器件结构为ITO/PEDOT∶PSS/Poly-TPD/EML/TPBi（15 nm）/Alq₃（25 nm）/LiF（0.6 nm）/Al（80 nm）。在Ir(ppy)₃和Ir(piq)₃共掺杂器件和Ir(ppy)₃单掺杂器件的对比实验中发现,加入一定比例的深能级材料后,器件的电致发光光谱发生改变,Ir(piq)₃的相对发光强度增强,器件发光效率下降且效率滚降现象明显。通过对器件进行J-V测试,发现在Ir(ppy)₃单掺杂器件中陷阱填充电流随着掺杂材料浓度的提高而提高,但在加入等浓度深能级材料Ir(piq)₃后,陷阱填充电流基本保持一致。瞬态电致发光测试表明,随着Ir(ppy)₃掺杂比例的提高,器件内由于陷阱载流子释放而产生的瞬时发光强度降低,这是由于Ir(ppy)₃具有一定的传导电荷作用,会减少器件中的陷阱载流子,这进一步说明了具有较深能级的Ir(piq)₃是限制载流子的主要能级陷阱。同时发现随反向偏压的增大,瞬态发光强度增大且发光衰减加速,这是因为位于深能级陷阱的载流子在高电压下被释放,重新复合发光,说明深能级陷阱的确限制住了大量载流子,而由于主体三线态激子具有较长的寿命,激子间相互作用产生的单线态激子在高反压下解离,从而引起三线态激子-极化子相互作用的加剧,导致发光衰减加速。在窄带隙聚合物材料PTB7与Ir(ppy)₃共掺杂器件实验中发现,随着PTB7掺杂浓度提高,陷阱浓度变大且器件效率降低,具有较深能级的PTB7成为了限制载流子的深能级陷阱。因此说明在双掺杂有机磷光电致发光器件中,深能级材料会成为限制载流子的能级陷阱,引起载流子大量堆积,从而导致三线态激子与极化子相互作用加剧,使器件的发光效率衰退。