Investigation of carrier injection mechanism in small molecular organic light emitting device with a mixed single organic layer

Injection properties of electrons and holes in a mixed single layer organic light emitting device with mixed small molecules tris-(8-hydroxy-quinoline) aluminum (Alq₃), 2,5-bis(6′-(2′,2″-bipyridyl))-1,1-dimethyl-3,4-diphenylsilole (PyPySPyPy), 4′-bis[N-(1-napthyl)-N-phenyl-amino]biphenyl (α-NPD), and 5,6,11,12-tetraphenylnaphthacene (rubrene) were investigated using Au/MoO₃ as hole and Al alloy as electron injection electrodes. On the basis of measuring the temperature dependence of currents through the interface between the electrodes and the mixed single organic layer, the carrier injection mechanism was primarily ascribed to the Schottky thermionic emission with the barrier height of 0.25 eV for holes and 0.67 eV for electrons. By adding the dopant material rubrene and the electron transport material PyPySPyPy into the mixed single layer, the barrier height of electrons could be reduced. The interfacial state analysis demonstrated that the electron barrier height was also dependent on the interfacial conditions of the device.     

Affect of the electrical characteristics depending on the hole and electron injection materials of red organic light-emitting diodes

This study examined the electrical and optical properties of red OLEDs (organic light-emitting diodes) with a four-layer structure, ITO/amorphous fluoropolymer (AF)/N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1-biphenyl-4,4′-diamine (TPD)/R-H:R-D/lithium fluoride (LiF)/Al, containing a hole injection material, AF (amorphous fluoropolymer) and an electron injection layer material, LiF. Compared to the basic structure (two-layer structure), the brightness and luminous efficiency of the four-layer structure, ITO/TPD/R-H:R-D/Al, increased approximately 100 times (30,000 lm/m²) and 150 times (51 lm/W), respectively, with an applied voltage. The excellent efficiency of the external proton was also increased 150 times (0.51%). That is, the hole and electron injection layers improved the surface roughness of ITO and Al, and the interfacial physical properties. In addition, these layers allowed the smooth injection of holes and electrons. The luminance, luminous efficiency and external quantum efficiency were attributed to an increase in the recombination rates.     

Highly efficient and stable organic light-emitting diode by balancing drift current of charge

Highly efficient and stable OLED device in which hole-drift current and electron-drift current are balanced was fabricated. Drift current characteristics according to the thickness of organic layer were examined using the device with ITO/m-MTDATA/NPB/Al structure that can only move the hole and the device with Al/LiF/Alq₃/LiF/Al structure that can only move the electron. Using the result of such examination, green device with balanced drift current was produced. Device with the structure of m-MTDATA (80 nm)/NPB (20 nm)/C-545T (3%) doped Alq₃ (5 nm)/Alq₃ (59 nm)/LiF (1 nm)/Al (200 nm) showed color purity of (0.309, 0.643) and high efficiency of 7.0 lm/W (14.4 cd/A). Most of light emission was observed inside the green emitting layer. Through the result of EL spectrum for the device also including red emitting layer, same result could be obtained. The device with balanced drift current also showed half life-time of 175 h for initial luminance of 3000 cd/m², which is more stable in comparison to the device without balanced drift current.     

多层结构的阴极修饰层对有机电致发光器件的性能改善

为提高有机电致发光器件（OLEDs）的阴极电子注入效率,我们设计了新型的阴极杂化修饰层,其结构为Bphen∶LiF/Al/MoO₃,将其应用到器件ITO/NPB/Alq₃/Al中,参考器件的电子注入层选用传统材料LiF。实验研究表明,与传统的阴极修饰层LiF相比,基于这种杂化结构的阴极修饰层非常有效。测试了器件的电致发光光谱（EL谱）,其峰值位于534 nm,发光来自于Alq₃,实验中我们可以观察到明亮的绿色发光。将其与传统参考器件的EL谱进行对比,在电流密度40 mA·cm-2下,两个器件的电致发光光谱是一致的。在0～100 mA·cm-2范围内,对器件的EL谱进行了测试。实验结果表明,随着电流密度的增加,器件的发光增强,但是EL谱的形状和谱峰的位置是固定不变的。与参考器件对比,基于杂化修饰层的器件的发光性能更好。研究表明,杂化修饰层的最佳参数为Bphen∶LiF(5 nm; 6%)/Al(1 nm)/MoO₃(5 nm),在测试范围内,器件的最大电流效率和最大功率效率分别为4.28 cd·A-1和2.19 lm·W-1,相比参考器件提高了25.5%和23.7%。器件的电流密度-电压特性曲线表明阴极杂化修饰层可以增强电子的注入,使器件中的载流子更加平衡,从而提高了器件的发光性能。从两个角度对器件效率的增强进行了理论方面的论证。一方面利用阴极杂化修饰层的作用机制来解释。在HML中,LiF能填充Bphen的电子陷阱,增强电流的注入,同时HML也能限制空穴的传输,减小空穴电流。另一方面从电荷平衡因子的角度,HML增强了电子的注入,使得器件的电荷平衡因子增大,空穴和电子的平衡性更好。实验研究表明,阴极杂化修饰层很好地增强了器件的效率。     

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.     

Improving efficiency of organic light-emitting devices by optimizing the LiF interlayer in the hole transport layer

The efficiency of organic light-emitting devices (OLEDs) based on N,N'-bis(1-naphthyl)-N,N'-diphenyl-N,1'-biphenyl-4,4'-diamine (NPB) (the hole transport layer) and tris(8-hydroxyquinoline) aluminum (Alq₃) (both emission and electron transport layers) is improved remarkably by inserting a LiF interlayer into the hole transport layer. This thin LiF interlayer can effectively influence electrical performance and significantly improve the current efficiency of the device. A device with an optimum LiF layer thickness at the optimum position in NPB exhibits a maximum current efficiency of 5.96 cd/A at 215.79 mA/cm², which is about 86% higher than that of an ordinary device (without a LiF interlayer, 3.2 cd/A). An explanation can be put forward that LiF in the NPB layer can block holes and balance the recombination of holes and electrons. The results may provide some valuable references for improving OLED current efficiency.     

新型稀土铕配合物Eu(o-BBA)3(phen)电致发光研究

研究了一种新的稀土配合物邻苯甲酰苯甲酸-1,10-菲咯啉-铕(Eu(o-BBA)3(phen))的电致发光特性.采用不同的电子传输层材料,制备了多种结构的有机电致发光器件及有机无机复合器件.比较了单层电致发光器件A:ITO/PVK:Eu/Al与有机无机复合器件B:ITO/PVK:Eu/ZnS/Al发光性能的不同.分析了采用无机半导体材料ZnS作为电子传输层的优点.研究结果表明采用无机的电子传输层,能有效地避免激基复合物的形成,提高器件的亮度同时保持稀土离子发光的色纯性.     

Significant improvement of OLED efficiency and stability by doping both HTL and ETL with different dopant in heterojunction of polymer/small-molecules

This paper reports that the polymer/organic heterojunction doped light-emitting diodes using a novel poly-TPD as hole transport material and doping both hole transport layer and emitter layer with the highly fluorescent rubrene and DCJTB has been successfully fabricated. The basic structure of the heterostructure is PTPD/Alq₃. When hole transport layer and electron transport layer are doped simultaneously with different dopant, the electroluminescence quantum efficiencies are about 3 times greater than that of the undoped device. Compared with undoped device and conventional TPD/Alq₃ diode, the stability of the doping device is significantly improved. The process of emission for doped device may include carrier trapping as well as F\"{o}rster energy transfer.     

Efficient organic light-emitting diodes with zinc acetate as an effective electron injection layer

We report on the fabrication of organic light-emitting diodes (OLEDs) using a zinc acetate ((CH₃COO)₂Zn) layer as the cathode buffer layer. The results show that the device containing a (CH₃COO)₂Zn interlayer shows improved luminance and efficiency due to the Zn–N bond formation resulting in the occurrence of Alq₃ anion and also due to the band bending at the Alq₃/Al interface, which is beneficial to electron injection by lowering electron injection barrier. And the devices with structured cathodes (CH₃COO)₂Zn/LiF/Al and LiF/(CH₃COO)₂Zn/Al have a higher luminance and efficiency than the LiF/Al cathode-based device.     

Enhanced performance of the OLED with plasma treated ITO and plasma polymerized thiophene buffer layer

In this work, indium-tin-oxide (ITO) electrode in organic light emitting device (OLED) was modified by using an O₂ plasma treatment and plasma polymerized thiophene buffer layers were inserted between ITO (anode) and organic layer in order to improve the hole injection efficiency. Furthermore, electron injection to cathode (Al) in the test OLED seemed to be improved due to introduction of quantum well in the cathode. The plasma-polymerized thiophene buffer layer on the O₂ plasma-treated transparent ITO electrode seemed to result in formation of a stable interface and consequently, reduction the hole mobility, which in turn caused enhanced recombination of hole and electron in the emitting layer. Compared with the test device without buffer layer, the turn-on voltage of the test device with the buffer layer was lowered by 1.0 V.     

Charge transport across bulk heterojunction organic thin film

The transport of charges in organic photo-active film has been the focus of tremendous research in the past few decades with the view to understand the physics of the polymers. Bulk heterojunction type devices are particularly more interesting because of their high power conversion efficiency. We have fabricated organic PV cell based on sandwich type ITO/PEDOT:PSS/APFO green-6:PCBM/LiF/Al device structure. The space charge limited currents were investigated to be able to derive important transport parameters of the devices. The measured current agrees very well with trap free space charge limited transport theory. The zero field mobility and field activation factor found from the data were μ ₀=(3.39±0.2)×10⁻⁶ m²/V sec and γ=(8.3±0.3)×10⁻⁴ (m/V)^1/2, respectively.     

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.     

Enhanced electron injection in organic light-emitting devices using Al/LiF electrodes

The temperature dependence of the current-voltage-luminescence characteristics in organic light-emitting diodes (OLEDs) with varying thickness of LiF layers are studied to understand the mechanism of the enhanced electron injection by inserting a thin insulating LiF layer at the tris(8-hydroxyquinoline) aluminum (Alq₃)–Al interfaces. At room temperature, the LiF/Al cathode enhances the electron injection and the quantum efficiency (QE) of the electroluminescence (EL), implying that the LiF thin layer lowers the electron-injection barrier. However, at low temperatures it is observed that the injection-limited current dominates and the barrier height for the electron injection in the device with LiF/Al appears to be similar with the Al only device. Thus, our results suggest that at low temperatures the insertion of LiF does not cause a significant band bending of Alq₃ or reduction of the Al work function.     

Efficient and low potential operative host/guest concentration graded bilayer polymer electrophosphorescence devices

This study investigates enhanced electrophosphorescence and its mechanism in poly(N-vinyl carbazole) (PVK): N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1-biphenyl]-4,4′-diamine (TPD)/2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD): fac-tris(2-phenylpyridine)iridium [Ir(ppy)₃] concentration graded bilayer electroluminescence devices. The two layers are partially intermixed at the bilayer interface because the upper layer (composed of Ir(ppy)₃ and PBD) was spun cast from a solvent that slightly swells the bottom layer (composed of PVK and TPD). Moreover, PBD in the upper layer can act as an efficient electron transport layer as well as a hole blocking layer, resulting in greatly enhanced electron–hole recombination. An indium tin oxide (ITO)/3,4-polyethylenedioxythiophene–polystyrenesulfonate (PEDOT)/[PVK:TPD/Ir(ppy)₃:PBD] bilayer/LiF/Al device showed dramatically decreased turn-on and driving voltages, enhanced luminescence efficiency, and narrower emission spectra compared to those of conventional ITO/PEDOT:PSS/[PVK:TPD:Ir(ppy)₃:PBD] blend/LiF/Al devices.     

一种采用Li3N掺杂电子注入层的底发射倒置结构OLED的制备

采用Li3N掺杂电子注入层Alq3∶Li3N,制作了一种结构为ITO/Alq3 Alq3∶Li3N/Alq3/NPB/MoO3/Al的倒置底发射有机发光器件.其中ITO玻璃作为透明阴极,金属Al作为顶部阳极,在ITO阴极与电子传输层之间加入Li3N n型掺杂层,改善了该器件的电子注入和传输能力|在Al阳极与空穴传输层之间加入MoO3缓冲层,降低了Al阳极与NPB之间较大的空穴注入势垒,改善了空穴注入能力.实验表明:此结构的倒置底发射有机发光器件性能可达到传统结构的常用有机发光器件如ITO/NPB/Alq3/LiF/Al的性能,完全可以满足非晶硅薄膜晶体管有源有机发光器件中驱动电路的匹配及性能要求.     

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…     

Enhancing properties of organic light-emitting diodes with LiF inside the hole transport layer

A new device has been made by inserting thin LiF layer in N,N′-diphenyl-N,N′-bis(1-napthyl–phenyl)-1, 1′-biphenyl-4,4′-diamine (NPB), which has a configuration of ITO/NPB(20 nm)/LiF(0.5 nm)/NPB(20 nm)/Alq₃(60 nm)/LiF(0.5 nm)/Al. Compared with normal device, the device inserted LiF layer inside NPB (HTL) can improve its performance. The luminance and efficiency is about 1.4 and 1.3 folds high of the conventional structure, respectively. The suggestion mechanism is that the LiF in the NPB layer can block holes of NPB, and balance the holes and electrons. Consequently, there are more excitons formed to boost the diode’s luminance and efficiency. And it may offer some valuable references for OLED’s structure.     

Improvement of performance of tetraphenylporphyrin-based red organic light emitting diodes using WO3 and C60 buffer layers

One of the porphyrin derivatives, meso-tetraphenylporphyrin (TPP), has been synthesized and examined as an emitter material (EM) for efficient fluorescent red organic light-emitting diodes (OLEDs). By inserting a tungsten oxide (WO₃) layer into the interface of anode (ITO) and hole transport layer N,N′-Di-[(1-napthyl)-N,N′-diphenyl]-(1,1′-biphenyl)-4,4′-diamine (NPB) and by using fullerene (C₆₀) in contact with a LiF/Al cathode, the performance of devices was markedly improved. The current density–voltage–luminance (J–V–L) characterizations of the samples show that red OLEDs with both WO₃ and C₆₀ as buffer layers have a lower driving voltage and higher luminance compared with the devices without buffer layers. The red OLED with the configuration ITO/WO₃ (3 nm)/NPB (50 nm)/TPP (60 nm)/BPhen (30 nm)/C₆₀ (5 nm)/LiF (0.8 nm)/Al (100 nm) achieved the high luminance of 6359 cd/m² at the low driving voltage of 8 V. At a current density of 20 mA/cm², a pure red emission with CIE coordinates of (0.65; 0.35) is observed for this device. Moreover, a power efficiency of 2.07 lm/W and a current efficiency of 5.17 cd/A at 20 mA/cm² were obtained for the fabricated devices. The study of the energy level diagram of the devices revealed that the improvement in performance of the devices with buffer layers could be attributed to lowering of carrier-injecting barrier and more balanced charge injection and transport properties.     

体异质结有机太阳能电池性能提高的研究

制备了四种不同结构的有机太阳能电池器件,器件1 ITO/LiF/PEDOT∶PSS/MEH-PPV/C₆₀/Al、器件2 ITO/PEDOT∶PSS/MEH-PPV/C₆₀/Al、器件3 ITO/LiF/PEDOT∶PSS/MEH-PPV∶C₆₀/C₆₀/Al和器件4 ITO/PEDOT∶PSS/MEH-PPV∶C₆₀/C₆₀/Al。测量了它们的电流－电压特性,结果显示在ITO和PEDOT∶PSS之间插入一薄层LiF使得器件性能得到较大提高。其器件1的J_SC和FF比器件2的提高了74%和31%; 器件3的J_SC比器件4的提高了约40%。这主要是由于LiF层有效地抑制了空穴向阳极的传输,并且LiF层在ITO和PEDOT:PSS之间形成了良好的界面特性。因此,这种结构上的改进有效地提高了有机太阳能电池的性能。     

Co50Fe50-xSix合金的结构相变和磁性

利用实验测量和理论计算相结合的方法,研究了介于B2结构CoFe低有序合金和L2₁结构Co₂FeSi高有序合金之间的Co₅₀Fe_50-xSi_x合金的结构相变、磁相变、分子磁矩和居里温度.采用考虑Coulomb相互作用的广义梯度近似(GGA+U)方法计算了合金的能带结构.研究发现,合金出现较强的原子有序倾向,表现出较强的共价成相作用.合金的晶格常数、磁矩、居里温度随Si含量的增加而线性地降低,极限成分Co₂FeSi合金的分子磁矩和居里温度分别达到5.92μ_B和777 ℃.原子尺寸效应导致合金晶格发生变化,但并未成为居里温度和分子磁矩变化的主导因素.分子磁矩的变化符合Slater-Pauling原理,但发现原子磁矩的变化并非线性,据此提出了共价成相对磁性影响的观点.采用Stearns理论解释了居里温度的变化趋势,排除了原子间距对居里温度的主导影响作用.能带计算的结果还表明,Co₂FeSi作为半金属材料并非十分完美,可能在实际应用中会出现自旋极化率降低的问题.发现该系列合金的结构相变和磁相变随着成分的变化聚集在窄小的成分和温度范围内. 关键词： 磁性 Heusler合金 结构相变