Organic Light‐Emitting Transistors Containing a Laterally Arranged Heterojunction

An approach to produce organic light‐emitting transistors (OLETs) containing a laterally arranged heterojunction structure, which minimizes exciton quenching at the metal electrodes, is described. This device configuration provides an organic light‐emitting diode (OLED) structure where the anode (source) electrode, hole‐transport material (field‐effect material), light‐emitting material, and cathode (drain) electrode are laterally arranged, thus offering a chance to control the electroluminescent intensity by changing the gate bias. Pentacene and tris(8‐quinolinolato)aluminum (Alq₃) are employed as the field‐effect and light‐emitting materials, respectively. The laterally arranged heterojunction structures are achieved by successively inclined deposition of the field‐effect and light‐emitting materials. After deposition of pentacene, a narrow gap of about 10–20 nm between the drain electrode and pentacene was obtained, thereby creating an opportunity to fabricate a laterally arranged heterojunction. In the OLETs, unsymmetrical source and drain electrodes, that is, Au and LiF/Al ones, are used to ensure efficient injection of holes and electrons. Visible‐light emission from OLETs is observed under ambient atmosphere. This result is ascribed to efficient carrier injection and transport, formation of a heterojunction, as well as good luminescence from the organic emissive layer. The device structure serves as an excellent model system for OLETs and demonstrates a general concept of adjusting the charge‐carrier injection and transport, as well as the electroluminescent properties, by forming laterally arranged heterojunctions.     

Solution‐Processed Zinc Oxide as High‐Performance Air‐Stable Electron Injector in Organic Ambipolar Light‐Emitting Field‐Effect Transistors

Electron injection from the source–drain electrodes limits the performance of many n‐type organic field‐effect transistors (OFETs), particularly those based on organic semiconductors with electron affinities less than 3.5 eV. Here, it is shown that modification of gold source–drain electrodes with an overlying solution‐deposited, patterned layer of an n‐type metal oxide such as zinc oxide (ZnO) provides an efficient electron‐injecting contact, which avoids the use of unstable low‐work‐function metals and is compatible with high‐resolution patterning techniques such as photolithography. Ambipolar light‐emitting field‐effect transistors (LEFETs) based on green‐light‐emitting poly(9,9‐dioctylfluorene‐alt‐benzothiadiazole) (F8BT) and blue‐light‐emitting poly(9,9‐dioctylfluorene) (F8) with electron‐injecting gold/ZnO and hole‐injecting gold electrodes show significantly lower electron threshold voltages and several orders of magnitude higher ambipolar currents, and hence light emission intensities, than devices with bare gold electrodes. Moreover, different solution‐deposited metal oxide injection layers are compared. By spin‐coating ZnO from a low‐temperature precursor, processing temperatures could be reduced to 150 °C. Ultraviolet photoemission spectroscopy (UPS) shows that the improvement in transistor performance is due to reduction of the electron injection barrier at the interface between the organic semiconductor and ZnO/Au compared to bare gold electrodes.     

Variations in Hole Injection due to Fast and Slow Interfacial Traps in Polymer Light‐Emitting Diodes with Interlayers

Detailed studies on the effect of placing a thin (10 nm) solution‐processable interlayer between a light‐emitting polymer (LEP) layer and a poly(3,4‐ethylenedioxythiophene)/poly(styrenesulfonic)‐acid‐coated indium tin oxide anode is reported; particular attention is directed at the effects on the hole injection into three different LEPs. All three different interlayer polymers have low ionization potentials, which are similar to those of the LEPs, so the observed changes in hole injection are not due to variations in injection barrier height. It is instead shown that changes are due to variations in hole trapping at the injecting interface, which is responsible for varying the hole current by up to two orders of magnitude. Transient measurements show the presence of very fast interfacial traps, which fill the moment charge is injected from the anode. These can be considered as injection pathway dead‐ends, effectively reducing the active contact surface area. This is followed by slower interfacial traps, which fill on timescales longer than the carrier transit time across the device, further reducing the total current. The interlayers may increase or decrease the trap densities depending on the particular LEP involved, indicating the dominant role of interfacial chain morphology in injection. Penetration of the interlayer into the LEP layer can also occur, resulting in additional changes in the bulk LEP transport properties.     

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.     

In‐Situ Switching from Barrier‐Limited to Ohmic Anodes for Efficient Organic Optoelectronics

Injection and extraction of charges through ohmic contacts are required for efficient operation of semiconductor devices. Treatment using polar non‐solvents switches polar anode surfaces, including PEDOT:PSS and ITO, from barrier‐limited hole injection and extraction to ohmic behaviour. This is caused by an in‐situ modification of the anode surface that is buried under a layer of organic semiconductor. The exposure to methanol removes polar hydroxyl groups from the buried anode interface, and permanently increases the work function by 0.2–0.3 eV. In the case of ITO/PEDOT:PSS/PBDTTT‐CT:PC71BM/Al photovoltaic devices, the higher work function promotes charge transfer, leading to p‐doping of the organic semiconductor at the interface. This results in a two‐fold increase in hole extraction rates which raises both the fill factor and the open‐circuit voltage, leading to high power conversion efficiency of 7.4%. In ITO/PEDOT:PSS/F8BT/Al polymer light‐emitting diodes, where the organic semiconductor's HOMO level lies deeper than the anode Fermi level, the increased work function enhances hole injection efficiency and luminance intensity by 3 orders of magnitude. In particular, hole injection rates from PEDOT:PSS anodes are equivalent to those achievable using MoO₃. These findings exemplify the importance of work function control as a tool for improved electrode design, and open new routes to device interfacial optimization using facile solvent processing techniques. Such simple, persistent, treatments pave the way towards low cost manufacturing of efficient organic optoelectronic devices.     

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.     

Over 1.1 eV Workfunction Tuning of Cesium Intercalated Metal Oxides for Functioning as Both Electron and Hole Transport Layers in Organic Optoelectronic Devices

In this paper, over 1.1 eV continuous tuning of metal oxides workfunction is realized by cesium intercalation, making the metal oxide function as both electron transport layer and hole transport layer in organic optoelectronic devices. The demonstrated metal oxides are commonly used molybdenum oxide and vanadium oxide. The proposed approach of synthesizing cesium intercalated metal oxides has interesting properties of room‐temperature, ambient atmosphere, water free and solution process, favoring the formation of metal oxides as carrier transport layers at different regions in multilayered devices and large scale fabrication of organic optoelectronics at low cost. Besides the wide range of controllable workfunction adjustment, band structures, and electrical properties are investigated in detail, to understand the effects of cesium intercalation on metal oxides. The device results show that, using the proposed cesium intercalation approach, each of the two investigated metal oxides can function as both ETL and HTL in organic solar cells and organic light emitting diodes with very good device performances. Consequently, with the interesting properties in film synthesis, the proposed cesium intercalated metal oxides can achieve continuously workfunction tuning over a large range and contribute to evolution of the simple route for fabricating high performance organic optoelectronic devices.     

Investigation on the Low Luminous Efficiency in a Polymer Light‐Emitting Diode with a High Work‐function Cathode by Soft Contact Lamination**

This article reports the main origin of the low luminescent efficiency in hole‐dominant polymer light‐emitting diodes by controlling the hole injection and by chemically modifying the cathode by molecular monolayers. Since molecular modification of the top electrode is impossible when one deposits the electrode using a vacuum deposition method, this study was performed using a soft contact lamination technique to form electrical contacts on top of the emissive layer. The top electrode was chemically modified with an alkane thiol self‐assembled monolayer (SAM) to act as an interfacial spacer layer between the emitting layer and the cathode. Herein, it is reported that, contrary to common belief, a high device quantum efficiency can be achieved from the dominantly hole‐transporting device with a high work‐function cathode (like Au) by facilitating more hole injection from the anode in the device with low population of exciton quenching channels near the cathode.     

Small Molecules in Light‐Emitting Electrochemical Cells: Promising Light‐Emitting Materials

Light‐emitting electrochemical cells (LECs) are solid‐state lighting devices that convert electric current to light within electroluminescent organic semiconductors, and these devices have recently attracted significant attention. Introduced in 1995, LECs are considered a great breakthrough in the field of light‐emitting devices for their applications in scalable and adaptable fabrication processes aimed at producing cost‐efficient devices. Since then, LECs have evolved through the discovery of new suitable emitters, understanding the working mechanism of devices, and the development of various fabrication methods. LECs are best known for their simple architecture and easy, low‐cost fabrication techniques. The key feature of their fabrication is the use of air stable electrodes and a single active layer consisting of mobile ions that enable efficient charge injection and transport processes within LEC devices. More importantly, LEC devices can be operated at low voltages with high efficiencies, contributing to their widespread interest. This review provides a general overview of the development of LECs and discusses how small molecules can be utilized in LEC applications by overcoming the use of traditional lighting materials like polymers and ionic transition metal complexes. The achievements of each study concerning small molecule LECs are discussed.     

Multifunctional Deep‐Blue Emitter Comprising an Anthracene Core and Terminal Triphenylphosphine Oxide Groups

A highly efficient blue‐light emitter, 2‐tert‐butyl‐9,10‐bis[4′‐(diphenyl‐phosphoryl)phenyl]anthracene (POAn) is synthesized, and comprises electron‐deficient triphenylphosphine oxide side groups appended to the 9‐ and 10‐positions of a 2‐tert‐butylanthracene core. This sophisticated anthracene compound possesses a non‐coplanar configuration that results in a decreased tendency to crystallize and weaker intermolecular interactions in the solid state, leading to its pronounced morphological stability and high quantum efficiency. In addition to serving as an electron‐transporting blue‐light‐emitting material, POAn also facilitates electron injection from the Al cathode to itself. Consequently, simple double‐layer devices incorporating POAn as the emitting, electron‐transporting, and ‐injecting material produce bright deep‐blue lights having Commission Internationale de L'Eclairage coordinates of (0.15,0.07). The peak electroluminescence performance was 4.3% (2.9 cd A^?1). For a device lacking an electron‐transport layer or alkali fluoride, this device displays the best performance of any such the deep‐blue organic light‐emitting diodes reported to date.     

Novel cationic water-soluble polyfluorene derivatives with ion-transporting side groups for efficient electron injection in PLEDs

Synthesis of cationic water-soluble polyfluorene derivatives with various side groups, which are used as electron injecting layers in polymer light emitting diodes, is described. Neutral polyfluorene derivatives containing bromo-alkyl terminal groups were synthesized by a palladium catalyzed Suzuki coupling reaction. The bromo-alkyl terminal groups in the neutral polyfluorenes were quaternized by treatment with a trimethyl amine solution. When a high work-function metal such as Ag is used as a cathode in a light emitting diode with an ITO/PEDOT:PSS/MEH-PPV/water-soluble polyfluorene/Ag configuration, effects of these water-soluble polyfluorenes on the device performance were investigated. In the case of poly[(9,9-bis((6′-(N,N,N-trimethylammonium) hexyl)-2,7-fluorene))-alt-(9,9-bis(2-(2-methoxyethoxy)ethyl)-fluorene)] Dibromide (WPF-oxy-F) containing ethylene oxide groups as the electron injecting layer, the electroluminescence efficiency of light emitting devices was significantly enhanced by about two orders of magnitude compared to that of a device without an electron injecting layer because migration of bromide ions via the ethylene oxide side groups led to large space charge. As a result, the injection barrier could be reduced between the emitting layer and Ag cathode resulting high electroluminescence efficiency.     

1‐Methyl‐2‐(anthryl)‐imidazo[4,5‐f][1,10]‐phenanthroline: A Highly Efficient Electron‐Transport Compound and a Bright Blue‐Light Emitter for Electroluminescent Devices

A new organic blue‐light emitter 1‐methyl‐2‐(anthryl)‐imidazo[4,5‐f][1,10]‐phenanthroline ( 1 ) has been synthesized and fully characterized. The utility of compound 1 as a blue‐light emitter in electroluminescent (EL) devices has been evaluated by fabricating a series of EL devices A where compound 1 functions as an emitter. The EL spectrum of device series A has the emission maximum at 481 nm with the CIE (Commission Internationale de l'Eclairage) color coordinates 0.198 and 0.284. The maximum luminance of devices in series A is 4000 cd m^–2 and the best external quantum efficiency of device series A is 1.82 %. The utility of compound 1 as an electron injection–electron transport material has been evaluated by constructing a set of EL devices B where 1 is used as either the electron‐injection layer or the electron injection–electron transport layer. The performance of device series B is compared to the standard device in which Alq₃ (tris(8‐hydroxyquinoline) aluminum) is used as the electron injection–electron transport layer. The experimental results show that the performance of 1 as an electron injection–electron transport material is considerably better than Alq₃. The stability of device series B is comparable to that of the standard Alq₃ device. The excellent performance of 1 as an electron injection/transport material may be attributed to the strong intermolecular interactions of 1 in the solid state as revealed by single‐crystal X‐ray diffraction analysis. In addition, compound 1 is a colorless material with a much larger highest occupied molecular orbital–lowest unoccupied molecular (HOMO–LUMO) gap than Alq₃, which renders it potentially useful for a wide range of applications in EL devices.     

Ethoxylated polyethylenimine as an efficient electron injection layer for conventional and inverted polymer light emitting diodes

We report inverted light emitting devices using ethoxylated polyethylenimine (PEIE) as a single electron injection layer for indium tin oxide cathode, which possess comparable efficiency to those using ZnO/PEIE double electron injection layers. Implementation of a PEIE layer between light emitting polymer layer and aluminum has been shown to significantly enhance device efficiency as well. Improvement of device efficiency can be attributed to increased electron injection due to the reduced work function of PEIE modified cathode as well as the hole blocking effect of PEIE layer. Furthermore, PEIE serves as an efficient electron injector for a range of light emitting polymers with wide distribution of energy levels.     

Solution‐Processed Full‐Color Polymer Organic Light‐Emitting Diode Displays Fabricated by Direct Photolithography

The first full‐color polymer organic light‐emitting diode (OLED) display is reported, fabricated by a direct photolithography process, that is, a process that allows direct structuring of the electroluminescent layer of the OLED by exposure to UV light. The required photosensitivity is introduced by attaching oxetane side groups to the backbone of red‐, green‐, and blue‐light‐emitting polymers. This allows for the use of photolithography to selectively crosslink thin films of these polymers. Hence the solution‐based process requires neither an additional etching step, as is the case for conventional photoresist lithography, nor does it rely on the use of prestructured substrates, which are required if ink‐jet printing is used to pixilate the emissive layer. The process allows for low‐cost display fabrication without sacrificing resolution: Structures with features in the range of 2 μm are obtained by patterning the emitting polymers via UV illumination through an ultrafine shadow mask. Compared to state‐of‐the‐art fluorescent OLEDs, the display prototype (pixel size 200 μm × 600 μm) presented here shows very good efficiency as well as good color saturation for all three colors. The application in solid‐state lighting is also possible: Pure white light [Commision Internationale de l'Éclairage (CIE) values of 0.33, 0.33 and color rendering index (CRI) of 76] is obtained at an efficiency of 5 cd A^–1 by mixing the three colors in the appropriate ratio. For further enhancement of the device efficiency, an additional hole‐transport layer (HTL), which is also photo‐crosslinkable and therefore suitable to fabricate multilayer devices from solution, is embedded between the anode and the electroluminescent layer.     

Bright Blue Light—emitting Diodes Based on a Novel Fluorescent Dye Containing Heterocyclic Groups

Novel molecular material ,1-benzothiazoly-3-pheny1-pyrazoline (BTPP) was found to function as bright blue light emitting dye in organic electroluminescent device, and its optical and electric characteristics were investigated. This heterovyclic compound exhibited good characteristics of blue photoluminescence and electroluminescence,which had the emission peak at 450nm .The single layer light-emitting devices using BTPP as light -emitting material dispersed in poly(N-vinylcarbazole)(PVK) and double layer ones using PBD as hole block layer above the light-emitting layer were fabricated using conventional spin-casting and vaccum vapour deposition methods. The introduction of PBD has enhanced electron injection and luminance efficiency, compared with the single layer LEDs.     

Solution‐Processed Organic Light‐Emitting Transistors Incorporating Conjugated Polyelectrolytes

Improved performance of p‐type organic light‐emitting transistors (OLETs) is demonstrated by introducing a conjugated polyelectrolyte (CPE) layer and symmetric high work function (WF) source and drain metal electrodes. The OLET comprises a tri‐layer film consisting of a hole transporting layer, an emissive layer, and a CPE layer as an electron injection layer. The thickness of the CPE layer is critical for achieving good performance and provides an important structural handle for consideration in future optimization studies. We also demonstrate for the first time, good performance solution‐processed blue‐emitting OLETs. These results further demonstrate the simplification of device fabrication and improved performance afforded by integrating CPE interlayers into organic optoelectronic devices.     

Highly Efficient Electroluminescence from Green‐Light‐Emitting Electrochemical Cells Based on CuI Complexes

The complexes [Cu(dnbp)(DPEphos)]⁺(X^–) (dnbp and DPEphos are 2,9‐di‐n‐butyl‐1,10‐phenanthroline and bis[2‐(diphenylphosphino)phenyl]ether, respectively, and X^– is BF₄^–, ClO₄^–, or PF₆^–) can form high‐quality films with photoluminescence quantum yields of up to 71 ± 7 %. Their electroluminescent properties are studied using the device structure indium tin oxide (ITO)/complex/metal cathode. The devices emit green light efficiently, with an emission maximum of 523 nm, and work in the mode of light‐emitting electrochemical cells. The response time of the devices greatly depends on the driving voltage, the counterions, and the thickness of the complex film. After pre‐biasing at 25 V for 40 s, the devices turn on instantly, with a turn‐on voltage of ca. 2.9 V. A current efficiency of 56 cd A^–1 and an external quantum efficiency of 16 % are realized with Al as the cathode. Using a low‐work‐function metal as the cathode can significantly enhance the brightness of the device almost without affecting the turn‐on voltage and current efficiency. With a Ca cathode, a brightness of 150 cd m^–2 at 6 V and 4100 cd m^–2 at 25 V is demonstrated. The electroluminescent performance of these types of complexes is among the best so far for transition metal complexes with counterions.     

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.     

Fundamentals of Materials Selection for Light‐Emitting Electrochemical Cells

The in situ formation of a light‐emitting p–n or p–i–n junction in light‐emitting electrochemical cells (LECs) necessitates mixed ionic–electronic conductors in the active layer. This unique characteristic requires electronic, luminescent, and ionic ingredients that work synergistically in the LECs. The material requirements that lead to promising electroluminescent properties are discussed and the important components reported so far are surveyed. Particular attention is paid to the working mechanisms behind junction formation and stabilization to create efficient and stable electroluminescence in conjugated‐polymer‐based LECs. Keeping these fundamentals in mind explains how LEC devices have evolved from classic conjugated polymer blends into highly stable crosslinked, hybrid composite, and stretchable device architectures. To conclude, a future development strategy is proposed based on a dual approach: develop new materials specifically for LEC devices and explore novel ways to efficiently process and stabilize the p–i–n junction, which will drive improvements in both LEC external quantum efficiency and operating lifetime toward truly low‐cost solid‐state lighting applications.     

Self‐assembled Electroactive Phosphonic Acids on ITO: Maximizing Hole‐Injection in Polymer Light‐Emitting Diodes

In order to fulfill the promise of organic electronic devices, performance‐limiting factors, such as the energetic discontinuity of the material interfaces, must be overcome. Here, improved performance of polymer light‐emitting diodes (PLEDs) is demonstrated using self‐assembled monolayers (SAMs) of triarylamine‐based hole‐transporting molecules with phosphonic acid‐binding groups to modify the surface of the indium tin oxide (ITO) anode. The modified ITO surfaces are used in multilayer PLEDs, in which a green‐emitting polymer, poly[2,7‐(9,9‐dihexylfluorene)‐co‐4,7‐(2,1,3‐benzothiadiazole)] (PFBT5), is sandwiched between a thermally crosslinked hole‐transporting layer (HTL) and an electron‐transporting layer (ETL). All tetraphenyl‐diamine (TPD)‐based SAMs show significantly improved hole‐injection between ITO and the HTL compared to oxygen plasma‐treated ITO and simple aromatic SAMs on ITO. The device performance is consistent with the hole‐transporting properties of triarylamine groups (measured by electrochemical measurements) and improved surface energy matching with the HTL. The turn‐on voltage of the devices using SAM‐modified anodes can be lowered by up to 3 V compared to bare ITO, yielding up to 18‐fold increases in current density and up to 17‐fold increases in brightness at 10 V. Variations in hole‐injection and turn‐on voltage between the different TPD‐based molecules are attributed to the position of alkyl‐spacers within the molecules.