Design of red, green, blue transparent electrodes for flexible optical devices.

Controlling the wavelength of electrodes within a desirable region is important in most optoelectronic devices for enhancing their efficiencies. Here, we investigated a full-color flexible transparent electrode using a wavelength matching layer (WML). The WMLs were able to adjust the optical-phase thickness of the entire electrode by controlling refractive indices and were capable of producing desirable colors in the visible band from 470 to 610 nm. Electrodes with tungsten oxide (WO(3)) having a refractive index of 1.9 showed high transmittance (T = 90.5%) at 460 nm and low sheet resistance (R(s) = 11.08 Ω/sq), comparable with those of indium tin oxide (ITO, T = 86.4%, R(s) = 12 Ω/sq). The optimum structure of electrodes determined by optical simulation based on the characteristic matrix method agrees well with that based on the experimental method. Replacing the ITO electrode with the WO(3) electrode, the luminance of blue organic light-emitting diodes (λ = 460 nm) at 222 mA/cm(2) increased from 7020 to 7200 cd/m(2).

LEGO-like Assembly of Fibrous Modules for Display Textiles.

Due to their promising advantages over classical rigid devices, the development of display textiles has exciting potential for various fields, including sensor technology, healthcare, and communication. To realize display textiles, it is necessary to prepare light-emitting building blocks at the fiber level and then weave or knit them to form the desired textile structures. However, from a practical viewpoint, it is difficult to continuously weave functional fibers containing light-emitting devices using conventional textile technologies. To address this issue, we introduced fibrous modules that can be assembled like LEGO blocks to realize textile displays. A unique feature of this work is that the light-emitting pixels are generated through a simple contact between modular electrochemiluminescent (ECL) fibers. Each fiber is composed of a single metallic wire coated with a gel-type ECL electrolyte that is formed by using a simple dip-coating method in ambient air. The sticky nature of the gel electrolyte enables the construction of light-emitting pixels through the simple physical contact of two or more fiber modules without the need for external pressure or heating. The diversity of this technology offers in terms of fibrous module arrangements and assembly can provide various options for designing the geometries of light-emitting pixels. We have implemented this technique to demonstrate not only a 1 × 1 pixel but also 3 × 3 pixels with an irregular shape. These results demonstrate that the unique strategy for display devices developed in this work provides a feasible approach for various electronic and optical textile applications.

MgO nano-facet embedded silver-based dielectric/metal/dielectric transparent electrode.

We replace Indium Tin Oxide (ITO) with an MgO nano-facet Embedded WO(3)/Ag/WO(3)(WAW) multilayer for electrodes of high efficiency OLEDs. WAW shows higher values for transmittance (93%) and conductivity (1.3×10(5) S/cm) than those of ITO. Moreover, WAW shows higher transmittance (92.5%) than that of ITO (86.4%) in the blue region (<500 nm). However, due to the large difference in refractive indices (n) of glass (n=1.55) and WO(3) (n=1.95), the incident light has a small critical angle (52°). Thus, the generated light is confined by the glass/WAW interface, resulting in low light outcoupling efficiency (~20%). This can be enhanced by using a nano-facet structured MgO (n=1.73) layer and a ZrO(2) (n=1.84) layer as a graded index layer. Using these optimized electrodes, ITO-free, OLEDs with various emission wavelengths have been produced. The luminance of OLEDs using MgO/ZrO(2)/WAW layers is enhanced by 24% compared to that of devices with ITO.

Tuning Threshold Voltage of Electrolyte-Gated Transistors by Binary Ion Doping.

Electrolyte-gated transistors (EGTs) operating at low voltages have attracted significant attention in widespread applications, including neuromorphic devices, nonvolatile memories, chemical/biosensors, and printed electronics. To increase the practicality of the EGTs in electronic circuits, systematic control of threshold voltage (Vth), which determines the power consumption and noise margin of the circuits, is essential. In this study, we present a simple strategy for systematically tuning Vth to almost half of the operating potential range of the EGT by controlling the electrochemical doping of electrolyte ions into organic p-type semiconductors. The type of anion in the ionogel determines Vth as well as other transistor characteristics, such as the subthreshold swing and mobility, because the positive hole carriers are the majority carriers. More importantly, Vth can be finely controlled by binary anion doping using ionogels with two anions with varying molar fractions at a fixed cation. In addition, the binary anion doping successfully controls the inversion characteristics of ion-gated inverters. As unlimited combinations of ion pairs are possible for ionogels, this study opens a route for controlling the device characteristics to expand the practicality and applicability of ionogel-based EGTs for next-generation ionic/electronic devices.

Water Washable and Flexible Light-Emitting Fibers Based on Electrochemiluminescent Gels.

Herein, a new concept of device architecture to fabricate fibrous light-emitting devices is demonstrated based on an electrochemiluminescence (ECL) material for an electronic textile system. A unique feature of this work is that instead of conventional semiconductor materials, such as organics, perovskites, and quantum dots for fibrous light emitting devices, a solid-state ECL electrolyte gel is employed as a light-emitting layer. The solid-state ECL gel is prepared from a precursor solution composed of matrix polymer, ionic liquid, and ECL luminophore. From this, we successfully realize light-emitting fibers through a simple and cost-effective single-step dip-coating method in ambient air, without complicated multistep vacuum processes. The resulting fiber devices reliably operated under applied AC bias of ±2.5 V and showed luminance of 47 cd m-2. More importantly, the light-emitting fibers exhibited outstanding water resistance without any passivation layers, owing to the water immiscible and hydrophobic nature of the ECL gel. In addition, because of their simple structure, the fiber devices can be easily deformed and woven together with commercial knitwear by hand. Therefore, these results suggest a promising strategy for the development of practical fiber displays and contribute to progress in electronic textile technology.

Electrochemiluminescent Transistors: A New Strategy toward Light-Emitting Switching Devices.

Light-emitting transistors (LETs) have attracted a significant amount of interest as multifunctional building blocks for next-generation electronics and optoelectronic devices. However, it is challenging to obtain LETs with a high carrier mobility and uniform light-emission because the semiconductor channel should provide both the electrical charge transport and optical light-emission, and typical emissive semiconductors have low, imbalanced carrier mobilities. In this work, a novel device platform that adapts the electrochemiluminescence (ECL) principle in LETs, referred to as an ECL transistor (ECLT) is proposed. ECL is a light-emission phenomenon from electrochemically excited luminophores generated by redox reactions. A solid-state ECL electrolyte consisting of a network-forming polymer, ionic liquid, luminophore, and co-reactant is employed as the light-emitting gate insulator of the ECLT. Based on this construction, high-performance LETs that make use of various conventional non-emissive semiconductors (e.g., poly(3-hexylthiophene), zinc oxide, and reduced graphene oxide) are successfully demonstrated. All the devices exhibit a high mobility (0.9-10 cm2 V-1 s-1 ) and a uniform light-emission. This innovative approach demonstrates a novel LET platform and provides a promising pathway to achieve significant breakthroughs to develop electronic circuits and optoelectronic applications.

Completely Hazy and Transparent Films by Embedding Air Gaps for Elimination of Angular Color Shift in Organic Light-Emitting Diodes.

Red, green, and blue top-emission organic light-emitting diodes (RGB TOLEDs) suffer from white color change with viewing angle due to the microcavity effect, called white angular dependence (WAD). Great efforts are devoted by applying various kinds of hazy films, but they suffer from poor mechanical stability and optical transmittance. Herein, we introduce an air-gap-embedded hazy film (AEHF) to solve these problems and suppress WAD in RGB TOLEDs. The AEHF is designed with optical simulation to realize high haze with transparency. By tuning geometries of the air gap inside the polymer, the AEHF realizes high haze of more than 90% in all RGB colors while maintaining high transparency. To experimentally demonstrate the AEHF, the O2 plasma is treated on a polymer film with AgCl as an etching mask to fabricate microstructures with high aspect ratios. Afterward, PDMS is coated on the patterned surface; air gaps develop spontaneously in the valleys between microstructures during the coating process. Using these processes, an air gap with 1.2 µm size and 400 nm period is formed inside the film and ∼100% haze is achieved while maintaining a high transmittance of 88%; these results agree well with rigorous coupled wave analysis results. By utilizing the AEHF into TOLEDs, the WAD can be drastically suppressed by 95.2% compared with that of a device without AEHF.

Thermostable Ion Gels for High-Temperature Operation of Electrolyte-Gated Transistors.

High-temperature durability is critical for application of organic materials in electronic devices that operate in harsh environments. In this work, thermostable physically cross-linked polymer electrolytes, or thermostable physical ion gels, were successfully developed using crystallization-induced phase separation of semicrystalline polyamides (PAs) in an ionic liquid (IL). In these ion gels, phase-separated PA crystals act as network junctions and enable the ion gels to maintain their mechanical integrity up to 180 °C. ILs and ion gels are suitable electrolyte candidates for thin-film devices operating at high temperatures because they outperform other electrolytes that use aqueous and organic solvents, owing to their superior thermal stability and nonvolatility. In addition to thermal stability, the PA gels exhibited high ionic conductivity (∼1 mS/cm) and specific capacitance (∼10 µF/cm2) at room temperature; these values increased significantly with increasing temperature, while the gel retained its solid-state mechanical integrity. These thermostable ion gels were successfully used as an electrolyte gate dielectric in organic thin-film transistors that operate at high temperatures (ca. 150 °C) and low voltages (<1 V). The transistors gated with the dielectrics had a high on/off current ratio of (3.04 ± 0.24) × 105 and a hole mobility of 2.83 ± 0.20 cm2/V·s. By contrast, conventional physical ion gels based on semicrystalline polymers of poly(vinylidene fluoride-co-hexafluoropropylene) and polyvinylidene fluoride lost their mechanical integrity and dewetted from a semiconductor channel at lower temperatures. Therefore, these results demonstrate an effective method of generating thermally stable, mechanically robust, and highly conductive solid polymer electrolytes for electronic and electrochemical devices operating in a wide temperature range.

Ultrahigh-Mobility and Solution-Processed Inorganic P-Channel Thin-Film Transistors Based on a Transition-Metal Halide Semiconductor.

The development of p-channel devices with comparable electrical performances to their n-channel counterparts has been delayed due to the lack of p-type semiconductor materials and device optimization. In this present work, we successfully demonstrated p-channel inorganic thin-film transistors (TFTs) with high hole mobilities similar to the values of n-channel devices. To boost the device performance, the solution-processed copper iodide (CuI) semiconductor was gated by a solid polymer electrolyte. The electrolyte gating could realize electrical double layer (EDL) formation and a three-dimensional carrier transport channel and thus substantially increased charge accumulation in the channel region and realized a high mobility above 90 cm2/(V s) (45.12 ± 22.19 cm2/(V s) on average). In addition, due to the high-capacitance EDL formed by electrolyte gating, the CuI TFTs exhibited a low operation voltage below 0.5 V (Vth = -0.045 V) and a high ON current level of 0.7 mA with an ON/OFF ratio of 1.52 × 103. We also evaluated the operational stabilities of CuI TFTs and the devices showed 80% retention under electrical/mechanical stress. All the active layers of the transistors were fabricated by solution processes at low temperatures (<100 °C), indicating their potential use for flexible, wearable, and high-performance electronic applications.

Flexible top-emitting organic light emitting diodes with a functional dielectric reflector on a metal foil substrate.

For flexible organic light emitting diodes (OLEDs), roll-to-roll production enables low-cost fabrication and wide-ranging applications. Choosing an appropriate substrate material is one of the critical issues in the fabrication of flexible OLEDs. We demonstrated top-emitting OLEDs with a highly reflective distributed Bragg reflector (DBR) using a metal foil substrate. The DBR, made of seven pairs of SiO2/ZrO2, was formed by electron-beam evaporation on metal foil and showed high reflectivity of 90.5% at λ = 500 nm. The DBR served not only as the optical reflector, but also the substrate insulating layer which enabled the electrical isolation and prevented crosstalk. The OLEDs showed an operation voltage of 6.5 V at a current density of J = 10 mA cm-2 and maximum luminance of 17 400 cd m-2 at J = 225 mA cm-2. The electroluminescence property of the device could be maintained under the tensile bending condition.

Extremely flat metal films implemented by surface roughness transfer for flexible electronics.

We present an innovative approach to fabricate an extremely flat (EF) metal film which was done by depositing metal on an extremely flat mother substrate, then detaching the metal from the substrate. The detached flexible metal films had a roughness that was within 2% of the roughness of the mother substrate, so EFs with R a < 1 nm could be fabricated using the surface roughness transfer method. With quantitative analysis using in situ synchrotron XPS, it was concluded that the chemical reaction of oxygen atoms with the metal film played a critical role in designing a peel-off system to get extremely flat metal films from the mother substrate. The OLED was successfully implemented on the metal film. The OLED's luminance could be increased from 15 142 to 17 100 cd m-2 at 25 mA m-2 by replacing the glass substrate with an EF copper (Cu) substrate, due to the enhanced heat dissipation during the operation. This novel method can be very useful for mass production of large scale, low-cost and high quality metal films using roll-to-roll process.

Physically Cross-Linked Homopolymer Ion Gels for High Performance Electrolyte-Gated Transistors.

A new type of physically cross-linked solid polymer electrolyte was demonstrated by using a poly(vinylidene fluoride) (PVDF) homopolymer in a room-temperature ionic liquid. The physical origins of gelation, specific capacitance, ionic conductivity, mechanical property, and capacitive charge modulation in organic thin-film electrochemical transistors were investigated systematically. Gelation occurs through bridging phase-separated homopolymer crystals by polymer chains in the composite electrolyte, thereby forming a rubbery network. The resulting homopolymer ion gels are able to accommodate both outstanding electrical (ionically conductive and capacitive) and mechanical (flexible and free-standing) characteristics of the component ionic liquid and the structuring polymer, respectively. These ion gels were successfully applied to organic thin-film transistors as high-capacitance gate dielectrics. Therefore, these results provide an effective route to generate a highly conductive rubbery polymer electrolyte that can be used in widespread electronic and electrochemical devices.

Area-Controllable Stamping of Semicrystalline Copolymer Ionogels for Solid-State Electrolyte-Gated Transistors and Light-Emitting Devices.

Two types of thin-film electrochemical devices (electrolyte-gated transistors and electrochemical light-emitting cells) are demonstrated using area-controllable ionogel patches generated by transfer-stamping. For the successful transfer of ionogel patches on various target substrates, thermoreversible gelation by phase-separated polymer crystals within the ionogel is essential because it allows the gel to form a conformal contact with the acceptor substrate, thereby lowering the overall Gibbs energy of the system upon transfer of the ionogel. This crystallization-mediated stamping provides a much more efficient deposition route for producing thin films of ionically conductive high-capacitance solid ionogel electrolytes. The lateral dimensions of the transferred ionogels range from 1 mm × 1 mm to 40 mm × 40 mm. These ionogel patches are incorporated in organic p-type and inorganic n-type thin-film transistors and electrochemical light-emitting devices. The resulting transistors show sub-1 V device operation with high transconductance currents, and the optoelectronic devices emit orange light through a series of electrochemical redox reactions. These results demonstrate a simple yet versatile route to employ physical ionogels for various solid-state electrochemical device applications.

Self-Supporting Ion Gels for Electrochemiluminescent Sticker-Type Optoelectronic Devices.

Nowadays, there has been an increasing demand to develop low-cost, disposable or reusable display devices to meet and maximize short-term user convenience. However, the disposable device has unfortunately not materialized yet due to the light-emitting materials and fabrication process issues. Here, we report sticker-type electrochemiluminescent (ECL) device using self-supporting, light-emitting gel electrolytes. The self-supporting ion gels were formulated by mixing a network-forming polymer, ionic liquid, and metal complex luminophore. The resulting ion gels exhibit excellent mechanical strength to form free-standing rubbery light-emitting electrolyte films, which enables the fabrication of sticker-type display by simple transfer and lamination processes on various substrates. The sticker-type ECL devices can be operated under an AC bias and exhibit a low operating voltage of 4 V (peak-to-peak voltage) with a maximum luminance of 90 cd/m(2). It is notable that the result is the first work to realize sticker displays based on electrochemical light emitting devices and can open up new possibilities for flexible or disposal display.

The effect of localized surface plasmon resonance on the emission color change in organic light emitting diodes.

Three primary colors, cyan, yellow, and green, are obtained from Ag nano-dot embedded organic light emitting diodes (OLEDs) by localized surface plasmon resonance (LSPR). By changing the thickness of the Ag film, the size and spacing of Ag nano-dots are controlled. The generated light from the emissive layer in the OLEDs interacts with the free electrons near the surface of the Ag nano-dots, which leads to LSPR absorption and scattering. The UV-visible absorption spectra of glass/ITO/Ag nano-dot samples show intense peaks from 430 nm to 520 nm with an increase of Ag nano-dot size. And also, the Rayleigh scattering spectra results show the plasmon resonance wavelength in the range of 470-550 nm. The effect of the LSPR of Ag nano-dots on the change of emission color in OLEDs is demonstrated using 2 dimensional finite-difference time-domain simulations. The intensity of the electro-magnetic field in the sample with 5 nm-thick Ag is low at the incident wavelength of 500 nm, but it increases with the incident wavelength. This provides evidence that the emission color change in OLEDs originates from LSPR at the Ag nano-dots. As a result, the emission peak wavelength of OLEDs shifted toward longer wavelengths, from cyan to yellow-green, with the increase of Ag nano-dot size.

Electrospun ion gel nanofibers for flexible triboelectric nanogenerator: electrochemical effect on output power.

A simple fabrication route for ion gel nanofibers in a triboelectric nanogenerator was demonstrated. Using an electrospinning technique, we could fabricate a large-area ion gel nanofiber mat. The triboelectric nanogenerator was demonstrated by employing an ion gel nanofiber and the device exhibited an output power of 0.37 mW and good stability under continuous operation.

Correction: Electrospun ion gel nanofibers for flexible triboelectric nanogenerator: electrochemical effect on output power.

Correction for 'Electrospun ion gel nanofibers for flexible triboelectric nanogenerator: electrochemical effect on output power' by Byeong Uk Ye et al., Nanoscale, 2015, 7, 16189-16194.

Continuous 1D-Metallic Microfibers Web for Flexible Organic Solar Cells.

We report the use of a continuous 1D-metallic microfibers web (MFW) as transparent electrode for organic solar cells (OSCs). The MFW electrode can be produced with a process that involves simple electrospinning and wet etching of metal thin film. Au MFW exhibits a maximum optical transmittance of 90.8% (at 15 Ω/sq of the sheet resistance) and excellent mechanical flexibility. The MFW structure has an average width in the range from 4 to 6 µm and a junction-free structure, resulting in very smooth surface roughness. The OSCs with Au MFW electrode exhibited a higher power conversion efficiency (PCE) of 3.50% than the device with an indium tin oxide electrode (PCE = 3.20%). The optical modeling calculation showed that the Au MFW electrode induced light scattering and improved the light absorption in the active layer, resulting in an improved PCE in the OSCs.

Aerosol jet printed p- and n-type electrolyte-gated transistors with a variety of electrode materials: exploring practical routes to printed electronics.

Printing electrically functional liquid inks is a promising approach for achieving low-cost, large-area, additive manufacturing of flexible electronic circuits. To print thin-film transistors, a basic building block of thin-film electronics, it is important to have several options for printable electrode materials that exhibit high conductivity, high stability, and low-cost. Here we report completely aerosol jet printed (AJP) p- and n-type electrolyte-gated transistors (EGTs) using a variety of different electrode materials including highly conductive metal nanoparticles (Ag), conducting polymers (polystyrenesulfonate doped poly(3,4-ethylendedioxythiophene, PEDOT:PSS), transparent conducting oxides (indium tin oxide), and carbon-based materials (reduced graphene oxide). Using these source-drain electrode materials and a PEDOT:PSS/ion gel gate stack, we demonstrated all-printed p- and n-type EGTs in combination with poly(3-hexythiophene) and ZnO semiconductors. All transistor components (including electrodes, semiconductors, and gate insulators) were printed by AJP. Both kinds of devices showed typical p- and n-type transistor characteristics, and exhibited both low-threshold voltages (<2 V) and high hole and electron mobilities. Our assessment suggests Ag electrodes may be the best option in terms of overall performance for both types of EGTs.

High capacitance, photo-patternable ion gel gate insulators compatible with vapor deposition of metal gate electrodes.

A facile fabrication route to pattern high-capacitance electrolyte thin films in electrolyte-gated transistors (EGTs) was demonstrated using a photoinitiated cross-linkable ABA-triblock copolymer ion gel. The azide groups of poly(styrene-r-vinylbenzylazide) (PS-N3) end-blocks can be chemically cross-linked via UV irradiation (λ = 254 nm) in the self-assembly of poly[(styrene-r-vinylbenzylazide)-b-ethylene oxide-b-(styrene-r-vinylbenzylazide)] (SOS-N3) triblock copolymer in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMI][TFSI]). Impedance spectroscopy and small-angle X-ray scattering revealed that ion transport and microstructure of the ion gel are not affected by UV cross-linking. Using a photoinduced cross-linking strategy, photopatterning of ion gels through a patterned mask was achieved. Employing a photopatterned ion gel as the high-capacitance gate insulator in thin film transistors (TFTs), arrays of TFTs exhibited uniform and high device performance. Specifically, both p-type (poly(3-hexylthiophene)) (P3HT) and n-type (ZnO) transistors displayed high carrier mobility (hole mobility of ∼ 1.4 cm(2)/ (V s) and electron mobility of ∼ 0.7 cm(2)/ (V s) and ON/OFF current ratio (∼ 10(5)) at supply voltages below 2 V. This study suggests that photopatterning is a promising candidate to conveniently incorporate high-capacitance ion gels into TFTs in the fabrication of printed electronics.