Origin of improvement in device performance via the modification role of cesium hydroxide doped tris(8-hydroxyquinoline) aluminum interfacial layer on ITO cathode in inverted bottom-emission organic light-emitting diodes

It has been found that cesium hydroxide (CsOH) doped tris(8-hydroxyquinoline) aluminum (Alq₃) as an interfacial modification layer on indium-tin-oxide (ITO) is an effective cathode structure in inverted bottom-emission organic light-emitting diodes (IBOLEDs). The efficiency and high temperature stability of IBOLEDs with CsOH:Alq₃ interfacial layer are greatly improved with respect to the IBOLEDs with the case of Cs₂CO₃:Alq₃. Herein, we have studied the origin of the improvement in efficiency and high temperature stability via the modification role of CsOH:Alq₃ interfacial layer on ITO cathode in IBOLEDs by various characterization methods, including atomic force microscopy (AFM), ultraviolet photoemission spectroscopy (UPS), X-ray photoemission spectroscopy (XPS) and capacitance versus voltage (C–V). The results clearly demonstrate that the CsOH:Alq₃ interfacial modification layer on ITO cathode not only enhances the stability of the cathode interface and electron-transporting layer above it, which are in favor of the improvement in device stability, but also reduces the electron injection barrier and increases the carrier density for current conduction, leading to higher efficiency.     

Thermal stability of devices with molybdenum oxide doped organic semiconductors

We demonstrate the thermal stability of transition-metal-oxide (molybdenum oxide; MoO₃)-doped organic semiconductors. Impedance spectroscopy analysis indicated that thermal deformation of the intrinsic 1,4-bis[N-(1-naphthyl)-N′-phenylamino]-4,4′-diamine (NPB) layer is facilitated when the MoO₃-doped NPB layer is deposited on the intrinsic NPB layer. The resistance of the intrinsic NPB layer is reduced from 300 kΩ to 3 kΩ after thermal annealing at 100 °C for 30 min. Temperature-dependent conductance/angular frequency–frequency (G/w-f-T) analysis revealed that the doping efficiency of MoO₃, which is represented by the activation energy (E_a), is reduced after the annealing process.     

Hybrid intermediate connector for tandem OLEDs with the combination of MoO3-based interlayer and p-type doping

We report on a high-quality hybrid intermediate connector (IC) used in tandem organic light-emitting diodes (OLEDs), which is composed of an ultrathin MoO₃ interlayer sandwiched between a n-type Cs₂CO₃-doped 4,7-diphenyl-1,10-phenanthroline (BPhen) layer and a p-type MoO₃-doped N,N′-diphenyl-N,N′-bis(1-naphthyl)-(1,1′-biphenyl)-4,4′-diamine (NPB) layer. The charge generation characteristics for light emission in tandem OLEDs have been identified by studying the interfaces and the corresponding devices. The hybrid IC structure exhibits superior charge generation capability, and its interfacial electronic structures are beneficial to the generation and injection of electrons and holes into bottom and top emission units, respectively. Compared to the organic-TMO bilayer and doped p–n junction structures, the hybrid IC structure combining MoO₃-based interlayer and p-type doping can effectively decrease the driving voltage and improve the current efficiency of tandem devices due to the increased bulk heterojunction-like charge generation interfaces. Our results indicate that the TMO-based hybrid IC structure can be a good structure in the fabrication of high-efficiency tandem OLEDs.     

Bulk and interface properties of molybdenum trioxide-doped hole transporting layer in organic light-emitting diodes

Effects of doping molybdenum trioxide (MoO₃) in N,N′-diphenyl-N,N′-bis(1,1′-biphenyl)-4,4′-diamine (NPB) are studied at various thicknesses of doped layer (25–500 Å) by measuring the current–voltage characteristics, the capacitance–voltage characteristics and the operating lifetime. We formed charge transfer complex of NPB and MoO₃ by co-evaporation of both materials to achieve higher charge density, lower operating voltage, and better reliability of devices. These improved performances may be attributed to both bulk and interface properties of the doped layer. The authors demonstrated that the interface effects play more important role in lowering the operating voltage and increasing the lifetime.     

Enhanced efficiency and brightness in organic light- emitting devices with MoO3 as hole-injection layer

The organic light-emitting devices (OLEDs) using 4,4’,4’’-tris{N-(3-methylphenyl)-N-phenylamin}triphenylamine (m-MTDATA) and MoO3 or 1,3,5-triazo-2,4,6-triphosphorine-2,2,4,4,6,6-tetrachloride (TAPC) and MoO3 as the hole-injection layer (HIL) were fabricated. MoO3 can be expected to be a good injection layer material and thus enhance the emission performance of OLED. The highest occupied molecular (HOMO) of MoO3 is between those of m-MTDATA or TAPC and N,N’-bis-(1-naphthyl)-N,N’-diphenyl-1,1’-biphenyl-4,4’-diamine (NPB), which reduces the hole-injection barrier and improves the luminance of the OLEDs. The current efficiency is improved compared with that of the device without the MoO3 layer. The highest luminous efficiency of the device with 2-nm-thick MoO3 as HIL is achieved as 5.27 cd/A at 10 V, which is nearly 1.2 times larger than that of the device without it. Moreover, the highest current efficiency and power efficiency of the device with the structure indium-tin oxide (ITO)/TAPC (40 nm)/MoO3 (2 nm)/TcTa:Ir(ppy)3 (10%, 10 nm)/ tris-(8-hydroxyquinoline) aluminium (Alq) (60 nm)/LiF (1 nm)/Al are achieved as 37.15 cd/A and 41.23 lm/W at 3.2 V and 2.8 V, respectively.     

Aqueous solution-processed MoO3 as an effective interfacial layer in polymer/fullerene based organic solar cells

The authors demonstrate an effective anode interfacial layer based on aqueous solution-processed MoO₃ (sMoO₃) in poly (3-hexylthiophene) (P3HT) and indene-C60 bisadduct (ICBA) based bulk-heterojunction organic solar cells (PSCs). Various sMoO₃ concentration (0.03–0.25 wt%) was obtained by dissolving MoO₃ powder into deionized water directly with weak solubility. The characteristics of sMoO₃ films evaluated by atomic force microscope (AFM) and scanning electron microscope (SEM) suggest that the sMoO₃ films continuously cover the entire indium tin oxide (ITO) surface. The sMoO₃ based PSCs exhibit comparable power conversion efficiency with poly (3,4-ethylenedioxythiophene)–polystyrenesulfonic acid (PEDOT:PSS) based devices. However, even more importantly, the stability of sMoO₃ based devices have been greatly improved in air under continual light-illumination at 52 mW/cm². Further evaluations on Mo valence states and work function of sMoO₃ films by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) demonstrate that the aqueous solution-processed MoO₃ could act as an better anode interfacial layer than the conventional PEDOT:PSS.     

Role of hole injection layer in intermediate connector of tandem organic light-emitting devices

In this work, we demonstrate three kinds of intermediate connectors (ICs) having a general configuration of “LiNH₂-doped 4,7-diphenyl-1,10-phenanthroline (BPhen)/hole injection layer (HIL)/N,N′-diphenyl-N,N′-bis(1-naphthyl)-1,1′-biphenyl-4,4′-diamine (NPB)”, in which the HIL is 1,4,5,8,9,11-hexaazatriphenylene hexacarbonitrile (HAT-CN), MoO₃ or MoO₃-doped NPB, respectively. Tandem organic light-emitting devices (OLEDs), vertically stacking two electroluminescence units, are fabricated using these intermediate connectors in between. The results show that, higher power efficiency is achievable in the cases of utilizing HAT-CN and MoO₃-doped NPB as HILs in the intermediate connectors versus MoO₃, whereas higher current efficiency can be obtained in the cases of using MoO₃ and MoO₃-doped NPB versus HAT-CN. We use the current density–voltage and low frequency differential capacitance–voltage measurements and find that the HILs primarily influence the voltage drop and the charge generation capability of intermediate connectors. The correlation between the effectiveness of intermediate connectors and the performances of tandem OLEDs is established, which can shed light on choosing suitable component materials to optimize the intermediate connectors.     

Bismuth Trifluoride as a low-temperature-evaporable insulating dopant for efficient and stable organic light-emitting diodes

Bismuth Trifluoride (BiF₃), with a high thermal stability and a low deposition temperature, has been studied as a novel dopant for the conventional hole transporting material of N,N′-di(naphthalene-1-yl)-N,N′-diphenyl-benzidine (NPB). The efficiency and lifetime of organic light-emitting diodes (OLEDs) have been remarkably improved by using BiF₃ doped NPB. For an optimized green device, a current efficiency of 21.6 cd/A is reached, 40% higher than the control device without BiF₃. And the lifetime is increased from 115 h to 222 h at room temperature. The enhanced efficiency and lifetime are attributed to the improved balance of holes and electrons in the emissive layer. Most importantly, the thermal stability at an elevated temperature of the OLEDs with BiF₃ doped NPB is largely improved, showing an order of magnitude longer lifetime than the control device at 80 °C.     

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。     

Low and small resistance hole-injection barrier for NPB realized by wide-gap p-type degenerate semiconductor,LaCuOSe:Mg

LaCuOSe:Mg is a wide-gap p-type semiconductor with a high conductivity and a large work function. Potential of LaCuOSe:Mg as a transparent hole-injection electrode of organic light-emitting diodes (OLEDs) was examined by employing N,N′-diphenyl-N,N′-bis (1,1′-biphenyl)-4,4′-diamine (NPB) for a hole transport layer. Photoemission spectroscopy revealed that an oxygen plasma treated surface of LaCuOSe:Mg formed a hole-injection barrier as low as 0.3 eV, which is approximately a half of a conventional ITO/NPB interface. Hole-only devices composed of a LaCuOSe:Mg/NPB/Al structure showed a low threshold voltage ∼0.2 V and high-density current drivability of 250 mA cm⁻² at 2 V, which is larger by two orders of magnitude than that of ITO/NPB/Al devices. These results demonstrate that LaCuOSe:Mg has great potential as an efficient transparent anode for OLEDs and other organic electronic devices.     

Origin of Enhanced Hole Injection in Inverted Organic Devices with Electron Accepting Interlayer

Conventional organic light emitting devices have a bottom buffer interlayer placed underneath the hole transporting layer (HTL) to improve hole injection from the indium tin oxide (ITO) electrode. In this work, a substantial enhancement in hole injection efficiency is demonstrated when an electron accepting interlayer is evaporated on top of the HTL in an inverted device along with a top hole injection anode compared with the conventional device with a bottom hole injection anode. Current–voltage and space‐charge‐limited dark injection (DI‐SCLC) measurements were used to characterize the conventional and inverted N,N′‐diphenyl‐N,N′‐bis(1‐naphthyl)(1,1′biphenyl)‐4,4′diamine (NPB) hole‐only devices with either molybdenum trioxide (MoO₃) or 1,4,5,8,9,11‐hexaazatriphenylene hexacarbonitrile (HAT‐CN) as the interlayer. Both normal and inverted devices with HAT‐CN showed significantly higher injection efficiencies compared to similar devices with MoO₃, with the inverted device with HAT‐CN as the interlayer showing a hole injection efficiency close to 100%. The results from doping NPB with MoO₃ or HAT‐CN confirmed that the injection efficiency enhancements in the inverted devices were due to the enhanced charge transfer at the electron acceptor/NPB interface.     

Solution-processed aqueous composite hole injection layer of PEDOT:PSS+MoOx for efficient ultraviolet organic light-emitting diode

Hole injection layer (HIL) plays a crucial role in governing external quantum efficiency (EQE) of ultraviolet organic light-emitting diodes (UV OLEDs). We develop a solution-processed aqueous composite HIL of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) incorporated MoO_x (PEDOT:PSS+MoO_x) and cast successful application to UV OLEDs. PEDOT:PSS+MoO_x is characterized in detail with scanning electron microscopy, atomic force microscopy, UV–visible absorption spectra, X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy and impedance spectroscopy measurements. The results show that PEDOT:PSS+MoO_x features superior film morphology and exceptional electronic properties such as enhanced surface work function and promoted hole injection capacity. With PEDOT:PSS+MoO_x as HIL, the UV OLED gives maximum EQE of 4.4% and radiance of 12.2 mW/cm² as well as improved durability. The electroluminescence peaks at 376 nm with full width at half maximum of 34 nm and stable voltage-dependent spectra. Our results pave a way for exploring efficient UV OLEDs with solution-processable techniques.     

Electronic structures of CuI interlayers in organic electronic devices: An interfacial studies of N,N′-diphenyl-N,N′-bis(1-naphthyl)-1,1′-biphenyl-4,4′-diamine/CuI and tris-(8-hydroxyquinolinato)aluminum/CuI

Electronic structures with the copper iodide (CuI) interlayer in organic electronic devices were measured and its strong electron-withdrawing properties were revealed. In situ ultraviolet and X-ray photoelectron spectroscopy showed the interfacial electronic structures of N,N′-diphenyl-N,N′-bis(1-naphthyl)-1,1′-biphenyl-4,4′-diamine (NPB)/CuI/indium–tin-oxide (ITO) and tris-(8-hydroxyquinolinato)aluminum (Alq₃)/CuI/ITO as a representative hole- and electron-transport material. The large work function of the CuI interlayer induces electron transfer from both molecules and ITO to CuI. As a result, CuI dramatically reduces the hole injection barrier (HIB) from ITO to NPB and Alq₃ layers. Notably, CuI assists molecular ordering of the NPB layer, which would increase the intermolecular interaction, so would enhance the charge transport properties. Simultaneous enhancement in HIB and molecular ordering with the CuI interlayer would improve the device performance.     

Molybdenum oxide anode buffer layers for solution processed,blue phosphorescent small molecule organic light emitting diodes

In this work we present solution processed organic light emitting diodes (OLEDs) comprising small molecule, blue phosphorescent emitter layers from bis(4,6-difluorophenylpyridinato-N,C2)picolinatoiridium doped 4,4′,4″-tris(carbazol-9-yl)-triphenylamine and molybdenum trioxide (MoO₃) anode buffer layers. The latter were applied from a molybdenium(V)ethoxide precursor solution that was thermally converted to MoO₃ at moderate temperatures. The high work function MoO₃ facilitated hole injection into the emission layer. The MoO₃ layer properties were investigated by means of energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy and Kelvin probe force microscopy. MoO₃ buffer layers performed superior to the commonly used poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) and enabled an enhanced OLED device efficiency.     

Reducing the driving voltage of organic light-emitting diodes by inserting a transparent ultrathin layer of oxidized silver as a hole-injecting layer

Organic light-emitting diodes (OLEDs) containing a transparent ultrathin layer of oxidized silver as a hole-injecting layer, placed between a indium–tin-oxide (ITO) electrode and the hole-transporting layer, were fabricated, and their electrical and luminescent properties were investigated. The OLEDs had a structure that consisted of an ITO layer; followed by an ultrathin Ag layer oxidized by a ultraviolet (UV)–ozone surface treatment; a N,N′-di-[(1-naphthyl)-N,N′-diphenyl]-1,1′-biphenyl)-4,4′-diamine (α-NPD) layer; a 5,6,11,12-tetraphenylnaphthacene (rubrene)-doped 9,10-diphenylanthracene (DPA) layer; a tris-(8-hydroxyquinoline) aluminum (Alq₃) layer; a lithium fluoride (LiF) layer; and a Al layer. The operating voltages of the OLEDs with the oxidized Ag (i.e., AgO_x) layer were drastically lower than those of the layer-free OLEDs, because the AgO_x layer, which had high oxidizability, contributed to hole injection as it oxidized the surface of the α-NPD layer. However, the external quantum efficiency of the OLEDs with the AgO_x layer was lower than that of the AgO_x layer-free OLEDs, suggesting that the carrier balance (i.e., the balance between the holes and electrons) became uneven in the emission layer, owing to the insertion of the AgO_x layer. It was assumed that this imbalance resulted from the number of holes in the emission layer being higher because of the increase in hole injection in the AgO_x layer.     

Versatile hole injection of VO2: Energy level alignment at N,N′-di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine/VO2/fluorine-doped tin oxide

Energy level alignments at the interface of N,N′-di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (NPB)/VO₂/fluorine-doped tin oxide (FTO) were studied by photoemission spectroscopy. The overall hole injection barrier between FTO and NPB was reduced from 1.38 to 0.59 eV with the insertion of a VO₂ hole injection layer. This could allow direct hole injection from FTO to NPB through a shallow valence band of VO₂. Surprisingly, VO₂ can also act as a charge generation layer due to its small band gap of 0.80 eV. That is, its conduction band is quite close to the Fermi level, and thus electrons can be extracted from the highest occupied molecular orbital (HOMO) of NPB, which is equivalent to hole injection into the NPB HOMO.     

Dynamic processes of charges generation in intermediate connectors for tandem organic light emitting diodes

The role of transition metal oxides (TMOs) based intermediate connectors in tandem organic light emitting diodes (OLEDs) has been studied via capacitance-voltage and current-voltage characteristics, in order to elucidate the dynamic processes of charges generation and transport within externally applied voltages. The TMO-based intermediate connectors are composed of molybdenum trioxide (MoO₃) and cesium azide (CsN₃)-doped-4, 7–diphenyl-1, 10-phenanthroline (BPhen) layers, where MoO₃ and CsN₃ are used due to low deposition temperatures. From the obtained results of capacitance and current density, charges generation in CsN₃:BPhen/MoO₃/NPB is proposed to the defect states in thermally evaporated MoO₃, which offers a minimal energy offset for charges generation. Moreover, our results clearly indicate that charges generation efficiency is not only relying on the MoO₃-NPB interface, but also influenced by CsN₃:BPhen-MoO₃ interface. CsN₃ doped BPhen layer further improves charges separation efficiency, which finally results in favorable charges transport into the adjacent layers and ensure to function efficiently for tandem OLEDs.     

Effect of oxygen plasma treatment on air exposed MoOx thin film

Oxygen plasma (OP) treatment on air exposed molybdenum oxide (MoO_x) has been investigated with ultraviolet photoemission spectroscopy (UPS) and angle resolved X-ray photoemission spectroscopy (AR-XPS). It was found that the work function (WF) reduction of MoO_x by air exposure can be recovered partially by OP treatment on the surface. The overall recovery was measured to be slightly more than 64%, which was adequate to provide a hole extraction layer to many hole-conducting organic materials. The incompleteness of the WF recovery could be attributed to the formation of a very thin layer of oxygen rich absorbents on top of the evaporated MoO_x film after OP treatment. AR-XPS showed that OP treatment shifted the core levels of oxygen and molybdenum about 0.1 eV toward the lower binding energy (BE), and confirmed the existence of oxygen deficiency in the evaporated MoO_x film. We also investigated the electronic energy level evolution of copper phthalocyanine (CuPc) on MoO_x/ITO by UPS. With the deposition of CuPc on OP treated MoO_x we observed band bending and the highest occupied molecular orbital (HOMO) level of CuPc was almost pinned to the Fermi level, which indicates the possibility of efficient hole injection with the OP treated MoO_x film.     

Analysis of charge transfer complex at the interface between organic and inorganic semiconductors

Improving the electrical performance of organic semiconductors is critical to use them for optoelectronic applications. In this study, we analyze the mechanism of charge transfer complex (CTC) formation at the interface between organic and inorganic semiconductors through extensive optical and electrical measurements. N,N′-Bis(naphthalen-1-yl)-N,N′-bis(phenyl)benzidine (NPB) and molybdenum oxide (MoO₃) were sequentially deposited to form a donor/accepter heterojunction structure. The CTC formation and conductivity of the films were determined using UV–visible spectroscopy and transmission line method, respectively. Compared with the single layer devices, the donor/accepter heterojunction exhibits significantly enhanced conductivity. In addition, the conductivity and CTC generation efficiency of the heterojunction display strong dependence on NPB layer thickness, which originates from the variation of dipole interactions at the heterojunction interface. These results provide useful insights on interfacial doping properties, which is potentially beneficial for enhancing the understanding of organic/inorganic interfaces.     

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.