具有新型双空穴注入层的有机发光二极管

采用新型双空穴注入层N, N, N', N'-tetrakis(4-Methoxy-phenyl)benzidine/Copper phthalocyanine(MeO-TPD/CuPc)及器件结构:ITO/MeO-TPD(15 nm)/CuPc(15 nm)/ N, N'-Bis(naphthalen-1-yl)-N, N'-bis(phenyl)benzidine (NPB, 15 nm)/8-hydroxyquinoline (Alq₃, 50 nm)/LiF(1 nm)/Al(120 nm), 研制出高效有机发光二极管(器件D), 与其他器件(器件A, 没有空穴注入层的器件; 器件B, MeO-TPD单空穴注入层; 器件C, CuPc单空穴注入层)相比, 其性能得到明显改善. 器件D的起亮电压降至3.2 V, 比器件A, B, C的起亮电压分别降低了2, 0.3, 0.1 V. 器件D在10 V时, 其最大亮度为23893 cd/m², 最大功率效率为1.91 lm/W, 与器件A, B, C的最大功率效率相比, 分别提高了43% (1.34 lm/W), 22% (1.57 lm/W), 7% (1.79 lm/W). 性能改善的主要原因是由于空穴注入和传输性能得到了改善, 通过单空穴型器件的J-V 曲线对这一现象进行了分析. 关键词： 有机发光二极管 空穴注入层 功率效率 势垒     

高效率的有机电致发光器件

有机电致发光器件 (OL EDs)的发光机理包括电子和空穴从电极的注入、激子的形成及复合发光 ,其中 ,空穴和电子的注入平衡是非常重要的。为了平衡载流子的注入以得到高效率和稳定性好的器件 ,人们不仅使用了电子注入更为有效的 L i F/ Al[1] 和 Cs F/ Al[2 ] 等复合电极 ,同时也使用了空穴缓冲层 ,如 S.A.Van Slyke等 [3]在ITO和 NPB之间使用 Cu Pc,使得器件的稳定性得到了明显的提高 ;A.Gyoutoku等[4 ] 用碳膜使器件的半寿命超过 3 5 0 0小时 ;最近 ,Y.Kurosaka等 [5]和 Z.B.Deng[6 ]分别在 ITO和空穴传输层之间插入一薄层 Al…     

利用C_(60)和CuPc形成的有机半导体异质结作为阳极修饰层实现高效的磷光有机发光二极管

利用C_(60)和Cu Pc形成有机半导体异质结作为阳极ITO修饰层,制备了高效绿色磷光有机发光二极管(OLEDs)。与常规MoO_3阳极修饰层相比,C_(60)(5 nm)/Cu Pc(25 nm)面异质结修饰器件的最大电流效率和外量子效率(EQE)提高了12%和11%,分别为60 cd/A和16.8%;而Cu Pc∶C_(60)(30 nm,50%)体异质结修饰器件则提高了26%和27%,分别为67 cd/A和19.3%。高的器件效率一方面归因于C_(60)与Cu Pc异质结界面处积累的电荷会在电压的作用下形成高效的电荷分离和空穴注入,另一方面归因于异质结具有吸收绿光光子形成光生载流子的光伏效应。利用Cu Pc∶C_(60)体异质结修饰阳极的器件由于具有更高效的电荷积累、更合适的空穴传输性、更平衡的载流子复合和更好的光伏特性,器件效率要比C_(60)/Cu Pc更优。研究表明,这种基于C_(60)与Cu Pc的有机半导体异质结可作为优越的ITO阳极修饰层。     

Reduction of driving voltage in organic light-emitting diodes with molybdenum trioxide in CuPc/NPB interface

A novel structure of organic light-emitting diode was fabricated by inserting a molybdenum trioxide (MoO₃) layer into the interface of hole injection layer copper phthalocyanine (CuPc) and hole transport layer N,N′-diphenyl-N,N′-bis(1-napthyl-phenyl)-1,1′-biphenyl-4,4′-diamine (NPB). It has the configuration of ITO/CuPc(10 nm)/MoO₃(3 nm)/NPB(30 nm)/ tris-(8-hydroxyquinoline) aluminum (Alq₃)(60 nm)/LiF(0.5 nm)/Al. The current density-voltage-luminance (J-V-L) performances show that this structure is beneficial to the reduction of driving voltage and the enhancement of luminance. The highest luminance increased by more than 40% compared to the device without hole injection layer. And the driving voltage was decreased obviously. The improvement is ascribed to the step barrier theory, which comes from the tunnel theory. The power efficiency was also enhanced with this novel device structure. Finally, “hole-only” devices were fabricated to verify the enhancement of hole injection and transport properties of this structure.     

Organic light emitting diodes using magnesium doped organic acceptor as electron injection layer and silver as cathode

Organic light emitting diodes employing magnesium doped electron acceptor 3, 4, 9, 10 perylenetetracarboxylic dianhydride (Mg:PTCDA) as electron injection layer and silver as cathode were demonstrated. As compared to Mg:Ag cathode, the combination of the Mg:PTCDA layer and silver provided enhanced electron injection into tris (8-quinolinolato) aluminium. The device with 1:2 Mg:PTCDA and Ag showed an increase of about 12% in the maximum current efficiency, mainly due to the improved hole-electron balance, and an increase of about 28% in the maximum power efficiency, as compared to the control device using Mg:Ag cathode. The properties of Mg:PTCDA composites were studied as well.     

Modification of electronic properties during adsorption of conjugate organic molecules on the surface of polycrystalline SnO<Subscript>2</Subscript>

The modification of the electronic structure during adsorption of ultrathin copper phthalocyanine (CuPc) and 3, 4, 9, 10 perylene-tetracarboxylic-dianhydride (PTCDA) coatings on the surface of polycrystalline tin dioxide is traced. Auger electron spectroscopy is employed to find changes in the atomic composition of the surface. It is found with the help of low-energy electron total current spectroscopy using a testing beam of electrons with energies up to 30 eV that the total current spectra typical of organic films are formed when the thickness of the coating being deposited is 2–7 nm. The formation of an interface layer 1.5–2.0 nm in thickness is detected, in which the intensity of the structure of the total current spectra decreases and the effect of interaction of PTCDA molecules with the SnO₂ surface is manifested.     

Modification of the electronic properties of the TiO2 (1 1 0) surface upon deposition of the ultrathin conjugated organic layers

A few nm thick 3,4,9,10-perylenetetracarboxylic acid dianhydride (PTCDA) and Cu-phthalocyanine (CuPc) overlayers were thermally deposited in situ in UHV onto TiO₂ (1 1 0) surface. Atomic composition of the surfaces under study was monitored using Auger electron spectroscopy (AES). The formation of the interfacial potential barrier and the structure of the unoccupied electronic states located 5-25 eV above the Fermi level (E_F) was monitored using a probing beam of low-energy electrons according to the total current electron spectroscopy (TCS) method. The work function values upon the overlayer deposition changed from 4.6 to 4.9 eV at the PTCDA/TiO₂ (1 1 0) interface and from 4.6 to 4.3 eV at the CuPc/TiO₂ (1 1 0) interface. Band bending in the TiO₂ substrate, molecular polarization in the organic film and changes in the work function due to the change in the surface composition were found to contribute to the formation of the interfacial potential barriers. Oxygen admixture related peaks were observed in the AES and in the TCS spectra of the CuPc overlayers. A mechanism of the transformations in the PTCDA and CuPc overlayers on the TiO₂ (1 1 0) upon elevating temperature from 25 to 400 °C was suggested.     

空穴注入层对蓝色有机电致发光器件性能的影响

以DPVBi为发光层,NPB为空穴传输层,在阳极ITO和NPB之间分别插入不同的空穴注入层CuPc和PEDOT:PSS,制备了两种结构的蓝色有机电致发光器件(OLEDs):ITO/CuPc/NPB/DPVBi/BCP/Alq3/Al和ITO/PEDOT:PSS/NPB/DPVBi/BCP/Alq3/Al,研究了不同空穴注入材料对蓝色OLEDs发光性能的影响,并与没有空穴注入层的器件进行了比较.其中CuPc分别采用旋涂和真空蒸镀两种丁艺,比较了不同成膜工艺对器件发光特性的影响.结果表明:加入空穴注入层的器件比没有空穴注入层器件性能要好,其中插入水溶性CuPc的器件,其发光亮度和效率虽然比蒸镀CuPc器件要低,但比插入PEDOT:PSS 器件发光性能要好.又由于水溶性CuPc采用旋涂工艺成膜,与传统CuPc相比,制备工艺简单,所以为一种不错的空穴注入材料.     

The performance enhancement in organic light-emitting diode using a semicrystalline composite for hole injection

A semicrystalline composite, 3, 4, 9, 10 perylenetetracarboxylic dianhydride （PTCDA） doped N,N＇-di（1-naphthyl）- N,N＇-diphenylbenzidine （NPB）, has been fabricated and characterized. An organic light-emitting diode using such a composite in hole injection exhibits the improved performance as compared with the reference device using neat NPB in hole injection. For example, at a luminance of 2000 cd/m2, the former device gives a current efficiency of 2.0cd/A, higher than 1.6cd/A obtained from the latter device. Furthermore, the semicrystalline composite has been shown thermally to be more stable than the neat NPB thin film, which is useful for making organic light emitting diodes with a prolonged lifetime.     

效率增强的新型蓝色有机发光器件

使用一种新型空穴传输材料J003制备了不同结构、不同发光层厚度的两组蓝色发光器件,其结构为:ITO/CuPc/J003/JBEM:perylene/Al_q3/LiF/Al和ITO/CuPc/J003/JBEM:perylene/TPBi/Al_q3/LiF/Al,这里CuPc(Copper phthalocyanine)和LiF分别为空穴注入层(HIL)和电子注入层(EIL),J003为空穴传输层(HTL),JBEM(9,10-bis(3,5'-diaryl)phenylylanthracene)为发光层(EML),TPBj(1,3,5-tri(phenyl-2-benzimidazole)-benzene)为空穴阻挡层(HBL),Al_q3(tris(8-quinolinolato)aluminium complex)为电子传输层(ETL).两种结构中前者为无阻挡层的普通型结构,后者在发光层和电子传输层中加入了空穴阻挡层,是新型阻挡层结构.研究了空穴阻挡层的引入在不同厚度发光层时对器件发光性能的影响,结果表明,新型阻挡层结构能明显提高器件的亮度和效率,但依赖于发光层厚度,利用能级图分析了其中的原因.     

超薄EuF3电极修饰层对有机场效应晶体管性能的提升

采用EuF₃薄层修饰低功函数金属Ag源、漏电极,制备了CuPc有机场效应晶体管,研究了不同厚度EuF₃对器件性能的影响。结果表明,EuF₃的厚度由0 nm增至0.6 nm时,接触电阻由23.65×10⁵ Ω·cm减 至3.86×10⁵ Ω·cm,使得器件载流子迁移率由1.5×10^-3 cm²·V^-1·s^-1提高到4.65×10^-3 cm²·V^-1·s^-1。 UPS测试结果表明,薄层EuF₃在Ag与有机半导体间形成了界面偶极势垒,使源漏电极表面功函数增大,空穴注入势垒降低,Ag电极与有机半导体层界面的接触电阻减小,进而提升了空穴的注入效率。     

采用复合空穴注入层提高有机电致发光器件的性能

制备了以Ag/SAM/m-MTDATA为复合空穴注入层的NPB/Alq₃双层异质结发光器件,研究了器件的性能并与传统的器件进行了对比。考察了银膜厚度的变化对器件性能的影响。研究了光谱窄化以及微腔效应对器件的影响。研究结果表明:在ITO表面制备4-FTP自组装单分子膜修饰的5 nm厚的金属银膜,可以在保持阳极透明性的基础上,增强空穴的注入,改善界面的形貌,进而提高器件性能。制备的ITO/Ag/SAM/m-MTDATA/NPB/Alq₃/LiF/Al器件的启亮电压为4 V,最 大电流效率为6.9 cd/A, 最大亮度为34 680 cd/m²(12 V);优于以ITO为阳极的对比器件(25 300 cd/m² @12 V)。     

n型掺杂PTCDA复合材料对有机发光二极管性能的提高

采用碳酸锂(Li2CO3)为n型掺杂剂,苝四甲酸二酐(3,4,9,10 perylenetetracarboxylic dianhydride,PTCDA)为母体材料,通过真空热蒸发方式制备了n型掺杂的PTCDA复合材料,将其作为电子注入材料应用到NPB/Alq3异质结有机电致发光器件中.研究发现,同LI2CO3:BC...     

MoO_3阳极缓冲层对有机太阳电池性能的影响

研究了MoO3阳极缓冲层对基于CuPc/C60异质结的有机小分子太阳电池器件性能的影响。发现:MoO3阳极缓冲层略微降低了器件的短路电流、开路电压及能量转换效率;MoO3阳极缓冲层提高了器件的整流比;具有MoO3阳极缓冲层的器件在持续光照条件下连续工作20min,其主要性能参数(如短路电流、开路电压、填充因子及能量转换效率)无明显衰减,而没有MoO3阳极缓冲层的对比器件在相同条件下连续工作20min,其能量转换效率衰减了大约45%。研究结果表明:MoO3阳极缓冲层明显提高了基于CuPc/C60异质结的有机小分子太阳电池器件的稳定性,可能的原因主要是MoO3阳极缓冲层改善了ITO阳极和CuPc界面,抑制了因持续光照连续工作引起的界面老化,从而提高了器件的稳定性。     

一种新型结构的黄光有机电致发光器件

用有机荧光染料罗丹明B(Rhodamine B)作为掺杂剂, 采用双量子阱结构制备了一种新型的黄光有机电致发光器件,器件结构及各层厚度为：ITO/CuPc(6 nm)/NPB(20 nm)/Alq₃(3 nm)/Alq₃：Rhodamine B(3 nm)/Alq₃(3 nm)/Alq₃：Rhodamine B(3 nm)/Alq₃(30 nm)/Liq(5 nm)/Al(30 nm)。研究发现Rhodamine B的掺杂浓度对该器件的发光亮度和发光效率有较大影响。当Rhodamine B的掺杂浓度为1.5 wt％时, 得到了最大电流效率1.526 cd·A-1,最大发光亮度1 309 cd·m-2的黄光有机电致发光器件。由器件的电致光谱曲线,可以看到在发光层之间存在着Alq₃向RhB传递能量的过程。由于量子阱的斯托克斯效应与RhB染料分子间的自极化作用,随着掺杂浓度的增加,λ_max出现明显红移。     

F16CuPc作为阳极缓冲层对有机太阳能电池性能的显著改善

采用F₁₆CuPc作为有机太阳能电池的阳极缓冲层可使器件的性能得到显著提高。F₁₆CuPc的引入,一方面可以实现CuPc分子的定向生长,从而改善CuPc薄膜的结晶度,提高其空穴迁移率;另一方面在F₁₆CuPc/CuPc界面处可形成偶极层,改善空穴的输出效率。以上两个作用有效提高了器件的载流子收集效率,降低了器件的串联电阻和光生载流子复合几率,从而提高了器件的短路电流和填充因子。同时,F₁₆CuPc的引入使器件的内建电场增大,提高了器件的开路电压。     

互混型有机电致发光器件

通过共蒸镀空穴传输材料TPD和电子传输材料Alq₃,在普通双层器件的异质结界面引入了均匀互混层,并研究了互混层的厚度变化对器件光电性能的影响。互混层的引入在一定程度上改善了普通双层器件的异质结界面由于高浓度载流子积聚导致的高电场和界面缺陷对器件主要性能(效率和寿命)的负面影响。我们发现一定厚度的互混层使器件的性能有所提高。     

CuPc/ITO结构的表面和界面电子态的XPS研究

覆盖有Indium tin oxide(ITO)膜的透明导电玻璃广泛地用作有机发光器件 (OLEDs)的空穴注入电极 ,但是ITO膜的功函数通常与空穴传输材料的最高被占据分子轨道 (HOMO)不匹配。铜酞菁 (CuPc)作为缓冲层可以提高空穴从ITO向空穴传输材料的注入效率。对CuPc ITO样品的XPS表面分析表明 ,在CuPc分子中 ,铜原子显 2价 ,通过配位键和氮原子相互作用。CuPc分子中有两类碳原子 :8个C原子与 2个N原子成键 ;其余 2 4个C原子具有芳香烃性质。N原子也处在两种化学环境中 :有 4个N原子只与 2个C原子形成CNC键 ;另外 4个N原子不仅与 2个C原子成键 ,还通过配位键与Cu原子成键。用氩离子束对样品表面进行了溅射剥蚀 ,当溅射时间分别为 2 ,5 ,10min时进行XPS采谱分析 ,结果表明 ,随着氩离子束溅射时间增长 ,C 1s,N 1s峰变弱 ,Cu 2p ,O 1s,In 3d,Sn 3d峰增强 ,C 1s,N 1s,O 1s,In 3d和Sn 3d峰都向高束缚能或低束缚能方向移动 ,但它们的情况却不相同。     

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.     

4,4′,4″-三(N-3-甲基苯基-N-苯基氨基)三苯胺掺杂MoOx作为空穴传输层对有机太阳电池性能的影响

通过采用4,4′,4″-三(N-3-甲基苯基-N-苯基氨基)三苯胺 (m-MTDATA)掺入MoO_x作为器件的空穴传输层来提高酞菁铜(CuPc)/C₆₀小分子 有机太阳电池的效率. 采用真空蒸镀的方法制备了一系列器件, 其中结构为铟锡氧化物 (ITO)/m-MTDATA:MoO_x(3:1)(30 nm)/CuPc(20 nm)/C₆₀(40 nm)/4,7-二苯 基-1,10-菲罗啉 (Bphen)(8 nm)/LiF(0.8 nm)/Al(100 nm)的器件, 在AM1.5 (100 mW/cm²)模拟太阳光的照射条件下, 开路电压V_oc=0.40 V, 短路电流J_sc=6.59 mA/cm², 填充因子为0.55, 光电转换效率达1.46%, 比没有空穴传输层的器件ITO/CuPc(20 nm)/C₆₀(40 nm)/Bphen(8 nm)/LiF(0.8 nm)/Al(100 nm) 光电转换效率提高了38%. 研究表明, 加入m-MTDATA:MoO_x(3:1)(30 nm)空穴传输层减小了有机层和ITO电极之间的接触电阻, 从而减小了整个器件的串联电阻, 提高了器件的光电转换效率.