Electric‐Field‐Assisted Charge Generation and Separation Process in Transition Metal Oxide‐Based Interconnectors for Tandem Organic Light‐Emitting Diodes

The charge generation and separation process in transition metal oxide (TMO)‐based interconnectors for tandem organic light‐emitting diodes (OLEDs) is explored using data on electrical and spectral emission properties, interface energetics, and capacitance characteristics. The TMO‐based interconnector is composed of MoO₃ and cesium azide (CsN₃)‐doped 4,7‐diphenyl‐1,10‐phenanthroline (BPhen) layers, where CsN₃ is employed to replace the reactive metals as an n‐dopant due to its air stability and low deposition temperature. Experimental evidences identify that spontaneous electron transfer occurs in a vacuum‐deposited MoO₃ layer from various defect states to the conduction band via thermal diffusion. The external electric‐field induces the charge separation through tunneling of generated electrons and holes from MoO₃ into the neighboring CsN₃‐doped BPhen and hole‐transporting layers, respectively. Moreover, the impacts of constituent materials on the functional effectiveness of TMO‐based interconnectors and their influences on carrier recombination processes for light emission have also been addressed.     

Enhanced Hole Injection into Amorphous Hole‐Transport Layers of Organic Light‐Emitting Diodes Using Controlled p‐Type Doping

We demonstrate enhanced hole injection and lowered driving voltage in vacuum‐deposited organic light‐emitting diodes (OLEDs) with a hole‐transport layer using the starburst amine 4,4′,4″‐tris(N,N‐diphenyl‐amino)triphenylamine (TDATA) p‐doped with a very strong acceptor, tetrafluoro‐tetracyano‐quinodimethane (F₄‐TCNQ) by controlled coevaporation. The doping leads to high conductivity of doped TDATA layers and a high density of equilibrium charge carriers, which facilitates hole injection and transport. Moreover, multilayer OLEDs consisting of double hole‐transport layers of thick p‐doped TDATA and a thin triphenyl‐diamine (TPD) interlayer exhibit very low operating voltages.     

Reduction of Tungsten Oxide: A Path Towards Dual Functionality Utilization for Efficient Anode and Cathode Interfacial Layers in Organic Light‐Emitting Diodes

Here, we report on the dual functionality of tungsten oxide for application as an efficient electron and hole injection/transport layer in organic light‐emitting diodes (OLEDs). We demonstrate hybrid polymer light‐emitting diodes (Hy‐PLEDs), based on a polyfluorene copolymer, by inserting a very thin layer of a partially reduced tungsten oxide, WO_2.5, at the polymer/Al cathode interface to serve as an electron injection and transport layer. Significantly improved current densities, luminances, and luminous efficiencies were achieved, primarily as a result of improved electron injection at the interface with Al and transport to the lowest unoccupied molecular orbital (LUMO) of the polymer, with a corresponding lowering of the device driving voltage. Using a combination of optical absorption, ultraviolet spectoscopy, X‐ray photoelectron spectroscopy, and photovoltaic open circuit voltage measurements, we demonstrate that partial reduction of the WO₃ to WO_2.5 results in the appearance of new gap states just below the conduction band edge in the previously forbidden gap. The new gap states are proposed to act as a reservoir of donor electrons for enhanced injection and transport to the polymer LUMO and decrease the effective cathode workfunction. Moreover, when a thin tungsten oxide film in its fully oxidized state (WO₃) is inserted at the ITO anode/polymer interface, further improvement in device characteristics was achieved. Since both fully oxidized and partially reduced tungsten oxide layers can be deposited in the same chamber with well controlled morphology, this work paves the way for the facile fabrication of efficient and stable Hy‐OLEDs with excellent reproducibility.     

Highly Efficient p‐i‐n and Tandem Organic Light‐Emitting Devices Using an Air‐Stable and Low‐Temperature‐Evaporable Metal Azide as an n‐Dopant

Cesium azide (CsN₃) is employed as a novel n‐dopant because of its air stability and low deposition temperature. CsN₃ is easily co‐deposited with the electron transporting materials in an organic molecular beam deposition chamber so that it works well as an n‐dopant in the electron transport layer because its evaporation temperature is similar to that of common organic materials. The driving voltage of the p‐i‐n device with the CsN₃‐doped n‐type layer and a MoO₃‐doped p‐type layer is greatly reduced, and this device exhibits a very high power efficiency (57 lm W^?1). Additionally, an n‐doping mechanism study reveals that CsN₃ was decomposed into Cs and N₂ during the evaporation. The charge injection mechanism was investigated using transient electroluminescence and capacitance–voltage measurements. A very highly efficient tandem organic light‐emitting diodes (OLED; 84 cd A^?1) is also created using an n–p junction that is composed of the CsN₃‐doped n‐type organic layer/MoO₃ p‐type inorganic layer as the interconnecting unit. This work demonstrates that an air‐stable and low‐temperature‐evaporable inorganic n‐dopant can very effectively enhance the device performance in p‐i‐n and tandem OLEDs, as well as simplify the material handling for the vacuum deposition process.     

n‐Doping of a Low‐Electron‐Affinity Polymer Used as an Electron‐Transport Layer in Organic Light‐Emitting Diodes

n‐Doping electron‐transport layers (ETLs) increases their conductivity and improves electron injection into organic light‐emitting diodes (OLEDs). Because of the low electron affinity and large bandgaps of ETLs used in green and blue OLEDs, n‐doping has been notoriously more difficult for these materials. In this work, n‐doping of the polymer poly[(9,9‐dioctylfluorene‐2,7‐diyl)‐alt‐(benzo[2,1,3]thiadiazol‐4,7‐diyl)] (F8BT) is demonstrated via solution processing, using the air‐stable n‐dopant (pentamethylcyclopentadienyl)(1,3,5‐trimethylbenzene)ruthenium dimer [RuCp*Mes]₂. Undoped and doped F8BT films are characterized using ultraviolet and inverse photoelectron spectroscopy. The ionization energy and electron affinity of the undoped F8BT are found to be 5.8 and 2.8 eV, respectively. Upon doping F8BT with [RuCp*Mes]₂, the Fermi level shifts to within 0.25 eV of the F8BT lowest unoccupied molecular orbital, which is indicative of n‐doping. Conductivity measurements reveal a four orders of magnitude increase in the conductivity upon doping and irradiation with ultraviolet light. The [RuCp*Mes]₂‐doped F8BT films are incorporated as an ETL into phosphorescent green OLEDs, and the luminance is improved by three orders of magnitude when compared to identical devices with an undoped F8BT ETL.     

The Mechanism of Charge Generation in Charge‐Generation Units Composed of p‐Doped Hole‐Transporting Layer/HATCN/n‐Doped Electron‐Transporting Layers

The rate‐limiting step of charge generation in charge‐generation units (CGUs) composed of a p‐doped hole‐transporting layer (p‐HTL), 1,4,5,8,9,11‐hexaazatriphenylene hexacarbonitrile (HATCN) and n‐doped electron‐transporting layer (n‐ETL), where 1,1‐bis‐(4‐bis(4‐methyl‐phenyl)‐amino‐phenyl)‐cyclohexane (TAPC) was used as the HTL is reported. Energy level alignment determined by the capacitance–voltage (C–V) measurements and the current density–voltage characteristics of the structure clearly show that the electron injection at the HATCN/n‐ETL junction limits the charge generation in the CGUs rather than charge generation itself at the p‐HTL/HATCN junction. Consequently, the CGUs with 30 mol% Rb₂CO₃‐doped 4,7‐diphenyl‐1,10‐phenanthroline (BPhen) formed with the HATCN layer generates charges very efficiently and the excess voltage required to generate the current density of ±10 mA cm^?2 is around 0.17 V, which is extremely small compared with the literature values reported to date.     

Solution‐Processed,Alkali Metal‐Salt‐Doped,Electron‐Transport Layers for High‐Performance Phosphorescent Organic Light‐Emitting Diodes

High‐performance, blue, phosphorescent organic light‐emitting diodes (PhOLEDs) are achieved by orthogonal solution‐processing of small‐molecule electron‐transport material doped with an alkali metal salt, including cesium carbonate (Cs₂CO₃) or lithium carbonate (Li₂CO₃). Blue PhOLEDs with solution‐processed 4,7‐diphenyl‐1,10‐phenanthroline (BPhen) electron‐transport layer (ETL) doped with Cs₂CO₃ show a luminous efficiency (LE) of 35.1 cd A^?1 with an external quantum efficiency (EQE) of 17.9%, which are two‐fold higher efficiency than a BPhen ETL without a dopant. These solution‐processed blue PhOLEDs are much superior compared to devices with vacuum‐deposited BPhen ETL/alkali metal salt cathode interfacial layer. Blue PhOLEDs with solution‐processed 1,3,5‐tris(m‐pyrid‐3‐yl‐phenyl)benzene (TmPyPB) ETL doped with Cs₂CO₃ have a luminous efficiency of 37.7 cd A^?1 with an EQE of 19.0%, which is the best performance observed to date in all‐solution‐processed blue PhOLEDs. The results show that a small‐molecule ETL doped with alkali metal salt can be realized by solution‐processing to enhance overall device performance. The solution‐processed metal salt‐doped ETLs exhibit a unique rough surface morphology that facilitates enhanced charge‐injection and transport in the devices. These results demonstrate that orthogonal solution‐processing of metal salt‐doped electron‐transport materials is a promising strategy for applications in various solution‐processed multilayered organic electronic devices.     

The structural composite effect of Au–WO3–Al interconnecting electrode on performance of each unit in stacked OLEDs

In this article, we report the effects of the thickness of metal and oxide layers of the Al/WO₃/Au interconnecting structure on the electrical and optical characteristics of the upper and bottom units of the two-unit stacked organic-light-emitting-devices (OLEDs). It is found that light emission performance of the upper unit is sensitive to the transmittance of semitransparent Al/WO₃/Au structure, which can be improved by changing the thickness of each layer of the Al/WO₃/Au structure. It is important to note that the introduction of WO₃ between Al and Au significantly enhances the current efficiency of both the upper and bottom units with respect to that of the corresponding Al/Au structure without WO₃. In addition, the emission spectra of both the upper and bottom units are narrower than that of the control device due to microcavity effect. Our results indicate that the Al/WO₃/Au interconnecting structure is a good candidate for fabricating independently controllable high efficiency stacked OLEDs.     

Control of Solid‐State Dye‐Sensitized Solar Cell Performance by Block‐Copolymer‐Directed TiO2 Synthesis

Hybrid dye‐sensitized solar cells are typically composed of mesoporous titania (TiO₂), light‐harvesting dyes, and organic molecular hole‐transporters. Correctly matching the electronic properties of the materials is critical to ensure efficient device operation. In this study, TiO₂ is synthesized in a well‐defined morphological confinement that arises from the self‐assembly of a diblock copolymer—poly(isoprene‐b‐ethylene oxide) (PI‐b‐PEO). The crystallization environment, tuned by the inorganic (TiO₂ mass) to organic (polymer) ratio, is shown to be a decisive factor in determining the distribution of sub‐bandgap electronic states and the associated electronic function in solid‐state dye‐sensitized solar cells. Interestingly, the tuning of the sub‐bandgap states does not appear to strongly influence the charge transport and recombination in the devices. However, increasing the depth and breadth of the density of sub‐bandgap states correlates well with an increase in photocurrent generation, suggesting that a high density of these sub‐bandgap states is critical for efficient photo‐induced electron transfer and charge separation.     

The doping effect of cesium-based compounds on carrier transport and operational stability in organic light-emitting diodes

The doping effect of cesium compounds (i.e., Cs₂CO₃, CsN₃ and CsF) doped electron injection layer (EIL) on charge transport properties and operational stability of organic light-emitting diodes (OLEDs) was systematically investigated in this work. It has been found that device characteristics and lifetime are highly dependent on the doping constituent materials. The doping of cesium compounds in EIL can improve the charge injection and transport of OLEDs, due to the increase in conductivity and reduction in electron injection barrier. Apart from the difference in electrical characteristics, the operational stability of OLEDs is strongly influenced by the doping mechanism of different cesium compounds in the EILs. The OLED device using Cs₂CO₃ as the n-type dopant for the EIL shows a superiority in both electrical property and operational lifetime.     

Influence of connecting units’ thicknesses on tandem organic devices’ performances

The present work investigates the influence of the Alq₃:Mg and MoO₃ thicknesses in the connecting unit on the performance of tandem organic light-emitting devices (OLEDs). By systematically varying the Alq₃:Mg and MoO₃ thicknesses, we obtained a higher current efficiency of 37.3 cd/A for a device with 30 nm Alq₃:Mg and 3 nm MoO₃ layer as connecting units. The optimal device performance is enhanced by at least 14%, compared with those of devices we fabricated in this paper. It suggests that appropriate Alq₃:Mg and MoO₃ thicknesses can enhance the charge generating ability for connecting units. On the other hand, it was found that the charge transporting layer would decrease strongly because of much thicker or thinner MoO₃ thicknesses. The results demonstrate that it is an effective method to improve the performance of OLEDs by using a optimal thickness for Alq₃:Mg and MoO₃ layers.     

Sulfate‐Assisted Interfacial Engineering for High Yield and Efficiency of Triple Cation Perovskite Solar Cells with Alkali‐Doped TiO2 Electron‐Transporting Layers

Facile electron injection and extraction are two key attributes desired in electron transporting layers to enhance the efficiency of planar perovskite solar cells. Herein it is demonstrated that the incorporation of alkali metal dopants in mesoporous TiO₂ can effectively modulate electronic conductivity and improve the charge extraction process by counterbalancing oxygen vacancies acting as nonradiative recombination centers. Moreover, sulfate bridges (SO₄^2?) grafted on the surface of K‐doped mesoporous titania provide a seamless integration of absorber and electron‐transporting layers that accelerate overall transport kinetics. Potassium doping markedly influences the nucleation of the perovskite layer to produce highly dense films with facetted crystallites. Solar cells made from K:TiO₂ electrodes exhibit power conversion efficiencies up to 21.1% with small hysteresis despite all solution coating processes conducted under ambient air conditions (controlled humidity: 25–35%). The higher device efficiencies are attributed to intrinsically tuned electronic conductivity and chemical modification of grain boundaries enabling uniform coverage of perovskite films with large grain size.     

Cover Picture: An Organic Light‐Emitting Diode with Field‐Effect Electron Transport (Adv. Funct. Mater. 1/2008)

The cover shows an organic light‐emitting diode with remote metallic cathode, reported by Sarah Schols and co‐workers on p. 136. The metallic cathode is displaced from the light‐emission zone by one to several micrometers. The injected electrons accumulate at an organic heterojunction and are transported to the light‐emission zone by field‐effect. The achieved charge‐carrier mobility and in combination with reduced optical absorption losses because of the remoteness of the cathode may lead to applications as waveguide OLEDs and possibly a laser structure. (The result was obtained in the EU‐funded project “OLAS” IST‐ FP6‐015034.) We describe an organic light‐emitting diode (OLED) using field‐effect to transport electrons. The device is a hybrid between a diode and a field‐effect transistor. Compared to conventional OLEDs, the metallic cathode is displaced by one to several micrometers from the light‐emitting zone. This micrometer‐sized distance can be bridged by electrons with enhanced field‐effect mobility. The device is fabricated using poly(triarylamine) (PTAA) as the hole‐transport material, tris(8‐hydroxyquinoline) aluminum (Alq₃) doped with 4‐(dicyanomethylene)‐2‐methyl‐6‐(julolindin‐4‐yl‐vinyl)‐4H‐pyran (DCM₂) as the active light‐emitting layer, and N,N′‐ditridecylperylene‐3,4,9,10‐tetracarboxylic diimide (PTCDI‐C₁₃H₂₇), as the electron‐transport material. The obtained external quantum efficiencies are as high as for conventional OLEDs comprising the same materials. The quantum efficiencies of the new devices are remarkably independent of the current, up to current densities of more than 10 A cm^–2. In addition, the absence of a metallic cathode covering the light‐emission zone permits top‐emission and could reduce optical absorption losses in waveguide structures. These properties may be useful in the future for the fabrication of solid‐state high‐brightness organic light sources.     

2D WC/WO3 Heterogeneous Hybrid for Photocatalytic Decomposition of Organic Compounds with Vis–NIR Light

Developing catalysts to improve charge‐carrier transfer and separation is critical for efficient photocatalytic applications driven by low‐energy photons. van der Waals stacking of 2D materials has opened up opportunities to engineer heteromaterials for strong interlayer excitonic transition. However, fabrication of 2D heteromaterials with clean and seamless interfaces remains challenging. Here, a 2D tungsten carbide/tungsten trioxide (WC/WO₃) heterogeneous hybrid in situ synthesized by a chemical engineering method has been reported. The hybrid comprises of layer‐by‐layer stacked WC and WO₃ monolayers. The WC and specific interfacial interfaces between the WC and WO₃ layers exhibit synergetic effects, promoting interfacial charge transfer and separation. Binderless WC performing platinum‐like behavior works as a potential substitute for noble metals and accelerates multielectron oxygen reduction, consequently speeding up the photocatalytic decomposition of organic compounds over the WO₃ catalyst. The specific interfacial interaction between WC and WO₃ layers potentially improves interfacial charge transfer from conduction band of WO₃ to WC. In the absence of noble metals, the WC/WO₃ hybrid as a catalyst exhibits distinct decomposition of organic compounds with vis–NIR light (λ = 400–800 nm). This finding provides a cost‐effective approach to capture low‐energy photons in environmental remediation applications.     

Influences of Connecting Unit Architecture on the Performance of Tandem Organic Light‐Emitting Devices

The present work investigates the influence of the n‐type layer in the connecting unit on the performance of tandem organic light‐emitting devices (OLEDs). The n‐type layer is typically an organic electron‐transporting layer doped with reactive metals. By systematically varying the metal dopants and the electron‐transporting hosts, we have identified the important factors affecting the performance of the tandem OLEDs. Contrary to common belief, device characteristics were found to be insensitive to metal work functions, as supported by the ultraviolet photoemission spectroscopy results that the lowest unoccupied molecular orbitals of all metal‐doped n‐type layers studied here have similar energy levels. It suggests that the electron injection barriers from the connecting units are not sensitive to the metal dopant used. On the other hand, it was found that performance of the n‐type layers depends on their electrical conductivities which can be improved by using an electron‐transporting host with higher electron mobility. This effect is further modulated by the optical transparency of constituent organic layers. The efficiency of tandem OLEDs would decrease as the optical transmittance decreases.     

CdS/CdTe thin‐film solar cells with Cu‐free transition metal oxide/Au back contacts

Superstrate CdS/CdTe thin‐film solar cells with Cu‐free transition metal oxide (TMO)/Au and Au‐only back contacts have been fabricated. The TMOs include MoO_3‐x, V₂O_5‐x, and WO_3‐x. The incorporation of the TMO buffer layers at the back contacts resulted in significant improvement on open‐circuit voltage (V_OC) as compared with the cells with Cu‐free Au‐only back contacts. Among the cells using TMO buffer layers, the ones with MoO_3‐x buffer layers exhibited the best performance, yielding an efficiency of 14.1% under AM1.5 illumination with V_OC of 815 mV and a fill factor of 67.9%. Though the performance is slightly behind the best reference cell with a Cu/Au back contact fabricated in our lab with V_OC of 844 mV, fill factor of 76.3%, and efficiency of 15.7%, the use of Cu‐free back contacts may lead to improved long‐term cell stability. Copyright © 2013 John Wiley & Sons, Ltd.     

Highly stable and high power efficiency tandem organic light-emitting diodes with transition metal oxide-based charge generation layers

Tandem organic light-emitting diodes (OLEDs) have been studied to improve the long-term stability of OLEDs for 10 years. The key element in a tandem OLEDs is the charge generation layer (CGL), which provides electrons and holes to the adjacent sub-OLED units. Among different types of CGLs, n-doped electron transporting layer (ETL)/transition metal oxide (TMO)/hole transporting layer (HTL) has been intensively studied. Past studies indicate that this kind of CGL can achieve the desired efficiency enhancement, however, its long-term stability was reported not good and sometime even poor than a single OLED. This issue was not well addressed over the past 10 years. Here, for the first time, we found that this is caused by the unwanted diffusion of TMO into the underlying n-doped ETL layer and can be well resolved by introducing an additional diffusion suppressing layer (DSL) between them. Our finding will fully release the potential of TMO-based CGL in tandem OLEDs.     

Plasmonic Electrically Functionalized TiO2 for High‐Performance Organic Solar Cells

Optical effects of the plasmonic structures and the materials effects of the metal nanomaterials have recently been individually studied for enhancing performance of organic solar cells (OSCs). Here, the effects of plasmonically induced carrier generation and enhanced carrier extraction of the carrier transport layer (i.e., plasmonic‐electrical effects) in OSCs are investigated. Enhanced charge extraction in TiO₂ as a highly efficient electron transport layer by the incorporation of metal nanoparticles (NPs) is proposed and demonstrated. Efficient device performance is demonstrated by using Au NPs incorporated TiO₂ at a plasmonic wavelength (560–600 nm), which is far longer than the originally necessary UV light. By optimizing the concentration ratio of the Au NPs in the NP‐TiO₂ composite, the performances of OSCs with various polymer active layers are enhanced and efficiency of 8.74% is reached. An integrated optical and electrical model, which takes into account plasmonic‐induced hot carrier tunneling probability and extraction barrier between TiO₂ and the active layer, is introduced. The enhanced charge extraction under plasmonic illumination is attributed to the strong charge injection of plasmonically excited electrons from NPs into TiO₂. The mechanism favors trap filling in TiO₂, which can lower the effective energy barrier and facilitate carrier transport in OSCs.     

Polaron Transport and Thermoelectric Behavior in La‐Doped SrTiO3 Thin Films with Elemental Vacancies

The electrodynamic properties of La‐doped SrTiO₃ thin films with controlled elemental vacancies are investigated using optical spectroscopy and thermopower measurement. In particular, a correlation between the polaron formation and thermoelectric properties of the transition metal oxide (TMO) thin films is observed. With decreasing oxygen partial pressure during the film growth (P(O₂)), a systematic lattice expansion is observed along with the increased elemental vacancy and carrier density, experimentally determined using optical spectroscopy. Moreover, an absorption in the mid‐infrared photon energy range is found, which is attributed to the polaron formation in the doped SrTiO₃ system. Thermopower of the La‐doped SrTiO₃ thin films can be largely modulated from –120 to –260 μV K^?1, reflecting an enhanced polaronic mass of ≈3 < m _polron/m < ≈4. The elemental vacancies generated in the TMO films grown at various P(O₂) influences the global polaronic transport, which governs the charge transport behavior, including the thermoelectric properties.     

An Indium‐Free Anode for Large‐Area Flexible OLEDs: Defect‐Free Transparent Conductive Zinc Tin Oxide

Flexible large‐area organic light‐emitting diodes (OLEDs) require highly conductive and transparent anodes for efficient and uniform light emission. Tin‐doped indium oxide (ITO) is the standard anode in industry. However, due to the scarcity of indium, alternative anodes that eliminate its use are highly desired. Here an indium‐free anode is developed by a combinatorial study of zinc oxide (ZnO) and tin oxide (SnO₂), both composed of earth‐abundant elements. The optimized Zn–Sn–O (ZTO) films have electron mobilities of up to 21 cm² V^?1 s^?1, a conductivity of 245 S cm^?1, and <5% absorptance in the visible range of the spectrum. The high electron mobilities and low surface roughness (<0.2 nm) are achieved by producing dense and void‐free amorphous layers as confirmed by transmission electron microscopy. These ZTO layers are evaluated for OLEDs in two anode configurations: i) 10 cm² devices with ZTO/Ag/ZTO and ii) 41 cm² devices with ZTO plus a metal grid. The ZTO layers are compatible with OLED processing steps and large‐area white OLEDs fabricated with the ZTO/grid anode show better performance than those with ITO/grid anodes. These results confirm that ZTO has the potential as an In‐free and Earth‐abundant alternative to ITO for large‐area flexible OLEDs.