Bio‐Inspired Stretchable,Adhesive, and Conductive Structural Color Film for Visually Flexible Electronics

The rapid progress in flexible electronic devices has attracted immense interest in many applications, such as health monitoring devices, sensory skins, and implantable apparatus. Here, inspired by the adhesion features of mussels and the color shift mechanism of chameleons, a novel stretchable, adhesive, and conductive structural color film is presented for visually flexible electronics. The film is generated by adding a conductive carbon nanotubes polydopamine (PDA) filler into an elastic polyurethane (PU) inverse opal scaffold. Owing to the brilliant flexibility and inverse opal structure of the PU layer, the film shows stable stretchability and brilliant structural color. Besides, the catechol groups on PDA impart the film with high tissue adhesiveness and self‐healing capability. Notably, because of its responsiveness, the resultant film is endowed with color‐changing ability that responds to motions, which can function as dual‐signal soft human‐motion sensors for real‐time color‐sensing and electrical signal monitoring. These features make the bio‐inspired hydrogel‐based electronics highly potential in the flexible electronics field.     

Structure and Morphology of PDI8‐CN2 for n‐Type Thin‐Film Transistors

A multiscale investigation of N,N′‐bis(n‐octyl)‐x:y, dicyanoperylene‐3,4:9,10‐bis(dicarboximide), PDI8‐CN2, shows the same molecular arrangement in the bulk and in thin films sublimated on SiO₂/Si wafers. Non‐conventional powder diffraction methods and theoretical calculations concur to provide a coherent picture of the crystalline structure. X‐ray diffraction (XRD) and atomic force microscopy (AFM) analyses of films of different thickness deposited at different substrate temperatures indicate the existence of two temperature‐dependent deposition regimes: a low‐temperature (room temperature) regime and a high‐temperature (80–120 °C) one, each characterized by different growth mechanisms. These mechanisms eventually result in different morphological and structural features of the films, which appear to be highly correlated with the trend of the electrical parameters that are measured in PDI8‐CN2‐based field‐effect transistors.     

Design of Novel Dielectric Surface Modifications for Perylene Thin‐Film Transistors

Dielectric surface modifications (DSMs) can improve the performance of organic thin‐film transistors (OTFTs) significantly. In order to gain a deeper understanding of this performance enhancement and to facilitate high‐mobility transistors, perylene based devices utilizing novel dielectric surface modifications have been produced. Novel DSMs, based on derivates of tridecyltrichlorosilane (TTS) with different functional end‐groups as well as polymeric dielectrics have been applied to tailor the adhesion energy of perylene. The resulting samples were characterized by electronic transport measurements, scanning probe microscopy, and X‐ray diffraction (XRD). Measurements of the surface free energy of the modified dielectric enabled the calculation of the adhesion energy of perylene upon these novel DSMs by the equation‐of‐state approach. These calculations demonstrate the successful tailoring of the adhesion energy. With these novel DSMs, perylene thin‐films with a superior film quality were produced, which enabled high‐performance perylene‐based OTFTs with high charge‐carrier mobility.     

Microscopic and Nanoscopic Three‐Phase‐Boundaries of Platinum Thin‐Film Electrodes on YSZ Electrolyte

Agglomerated Pt thin films have been proposed as electrodes for electrochemical devices like micro‐solid oxide fuel cells (μ‐SOFCs) operating at low temperatures. However, comprehensive studies elucidating the interplay between agglomeration state and electrochemical properties are lacking. In this contribution the electrochemical performance of agglomerated and “dense” Pt thin film electrodes on yttria‐stabilized‐zirconia (YSZ) is correlated with their microstructural characteristics. Besides the microscopically measurable triple‐phase‐boundary (tpb) where Pt, YSZ and air are in contact, a considerable contribution of “nanoscopic” tpbs to the electrode conductivity resulting from oxygen permeable grain boundaries is identified. It is demonstrated that “dense” Pt thin films are excellent electrodes provided their grain size and thickness are in the nanometer range. The results disprove the prevailing idea that the performance of Pt thin film electrodes results from microscopic and geometrically measurable tpbs only.     

Low‐Temperature,Nontoxic Water‐Induced Metal‐Oxide Thin Films and Their Application in Thin‐Film Transistors

Here, a simple, nontoxic, and inexpensive “water‐inducement” technique for the fabrication of oxide thin films at low annealing temperatures is reported. For water‐induced (WI) precursor solution, the solvent is composed of water without additional organic additives and catalysts. The thermogravimetric analysis indicates that the annealing temperature can be lowered by prolonging the annealing time. A systematic study is carried out to reveal the annealing condition dependence on the performance of the thin‐film transistors (TFTs). The WI indium‐zinc oxide (IZO) TFT integrated on SiO₂ dielectric, annealed at 300 °C for 2 h, exhibits a saturation mobility of 3.35 cm² V^?1 s^?1 and an on‐to‐off current ratio of ≈10⁸. Interestingly, through prolonging the annealing time to 4 h, the electrical parameters of IZO TFTs annealed at 230 °C are comparable with the TFTs annealed at 300 °C. Finally, fully WI IZO TFT based on YO_x dielectric is integrated and investigated. This TFT device can be regarded as “green electronics” in a true sense, because no organic‐related additives are used during the whole device fabrication process. The as‐fabricated IZO/YO_x TFT exhibits excellent electron transport characteristics with low operating voltage (≈1.5 V), small subthreshold swing voltage of 65 mV dec^?1 and the mobility in excess of 25 cm² V^?1 s^?1.     

Self‐Adhesive Macroporous Carbon Electrodes for Efficient and Stable Perovskite Solar Cells

Carbon electrode are a low‐cost and great potential strategy for stable perovskite solar cells (PSCs). However, the efficiency of carbon‐based PSCs lags far behind compared with that of state‐of‐the‐art PSCs. The poor interface contact between the carbon electrode and the underlying layer dominates the performance loss of the reported carbon‐based PSCs. In this respect, a sort of self‐adhesive macroporous carbon film is developed as counter electrode by a room‐temperature solvent‐exchange method. Via a simple press transfer technique, the carbon film can form excellent interface contact with the underlying hole transporting layer, remarkably beneficial to interface charge transfer. A power conversion efficiency of up to 19.2% is obtained for mesoporous‐structure PSCs, which is the best achieved for carbon‐based PSCs. Moreover, the device exhibits greatly improved long‐term stability. It retains over 95% of the initial efficiency after 1000 h storage under ambient atmosphere. Furthermore, after aging for 80 h under illumination and maximum power point in nitrogen atmosphere, the carbon‐based PSC retains over 94% of its initial performance.     

A Review of Low‐Temperature Solution‐Processed Metal Oxide Thin‐Film Transistors for Flexible Electronics

Solution processing, including printing technology, is a promising technique for oxide thin‐film transistor (TFTs) fabrication because it tends to be a cost‐effective process with high composition controllability and high throughput. However, solution‐processed oxide TFTs are limited by low‐performance and stability issues, which require high‐temperature annealing. This high thermal budget in the fabrication process inhibits oxide TFTs from being applied to flexible electronics. There have been numerous attempts to promote the desired electrical characteristics of solution‐processed oxide TFTs at lower fabrication temperatures. Recent techniques for achieving low‐temperature (<350 °C) solution‐processed and printed oxide TFTs, in terms of the materials, processes, and structural engineering methods currently in use are reviewed. Moreover, the core techniques for both n‐type and p‐type oxide‐based channel layers, gate dielectric layers, and electrode layers in oxide TFTs are addressed. Finally, various multifunctional and emerging applications based on low‐temperature solution‐processed oxide TFTs are introduced and future outlooks for this highly promising research are suggested.     

Diketopyrrolopyrrole Organic Thin‐Film Transistors: Impact of Alkyl Substituents and Tolerance of Ethylhexyl Stereoisomers

Bis(thiophen‐2‐yl)‐diketopyrrolopyrrole (DPP) dyes bearing various alkyl substituents at the amide positions (n‐butyl, n‐pentyl, n‐hexyl, n‐heptyl, n‐octyl, 2‐ethylhexyl) and chlorine (Cl), bromine (Br), or cyano (CN) substituents at the thiophene positions have been synthesized and investigated with regard to their molecular and semiconducting properties. Intense absorption, strong fluorescence, and reversible oxidation and reduction processes are common to all of these dyes. Their characterization as organic semiconductors in vacuum‐processed thin‐film transistors reveals p‐channel operation with field‐effect mobilities ranging from 0.01 to 0.7 cm² V^?1 s^?1. The highest mobility is found for the DPP dyes bearing the 2‐ethylhexyl substituents, which is surprising, considering that as a result of the chiral substituents, this material is a mixture of (R,R), (S,S), and (R,S) stereoisomers. The high carrier mobility in the films of the DPPs bearing stereoisomerically inhomogeneous ethylhexyl groups is rationalized here by single‐crystal X‐ray diffraction (XRD) analysis in combination with XRD and atomic force microscopy studies on thin films, which reveal the presence of slightly different 2D layer arrangements for the n‐alkyl and the 2‐ethylhexyl derivatives. For the cyano‐substituted DPPs possessing the lowest LUMO levels, ambipolar transport characteristics are observed.     

Paper‐Like,Thin, Foldable,and Self‐Healable Electronics Based on PVA/CNC Nanocomposite Film

The facile fabrication of thin and foldable self‐healing electronics on a poly(vinyl alcohol)/cellulose nanocrystal (PVA/CNC) composite film is reported. The self‐healing property of the PVA/CNC nanocomposite film can be activated by spraying water on the film surface, via dynamic formation of hydrogen bonding. The self‐healing efficiency of PVA/CNC is influenced by the content of CNC in the film, pH of the spraying solution, and the temperature. Via vacuum filtration and pattern transfer techniques, both a supercapacitor and a temperature sensor are fabricated on the same PVA/CNC film using gold nanosheet (AuNS) and polyaniline/multiwalled nanotube (PANI/MWCNT) electrodes. The fabricated supercapacitor with a gel‐type electrolyte exhibits a high electrochemical performance, and the thermoresistive temperature sensor shows a linear sensitivity with a fast response. Both devices exhibit superior mechanical stability and self‐healing property over 100 repetitive folding and five repetitive healing cycles, respectively, retaining the device performance owing to the percolated network of the conductive materials. This work demonstrates that our paper‐like thin PVA/CNC film‐based self‐healable devices can serve as highly durable and deformable electronics with longevity.     

Photo‐Stable Organic Thin‐Film Transistor Utilizing a New Indolocarbazole Derivative for Image Pixel and Logic Applications

Small molecule pentacene layer has been a representative among many organic thin‐film transistor (OTFT) channels with decent p‐type mobilities, but it is certainly light‐sensitive due to its relatively small highest occupied molecular orbital‐lowest unoccupied molecular orbital (HOMO‐LUMO) gap (1.85 eV). Although a few other small molecule‐based layers have been reported later, their photo‐stabilities or related device applications have hardly been addressed. Here, a new photostable organic layer is reported, heptazole (C₂₆H₁₆N₂), which has almost the same HOMO level as that of pentacene but with a higher HOMO‐LUMO gap (≈2.95 eV). This heptazole OTFT displays a decent mobility comparable to that of conventional amorphous Si TFTs, showing good photostability unlike pentacene OTFTs. An image pixel driving the photostable heptazole OTFT connected to a pentacene/Al Schottky photodiode is demonstrated. This heptazole OTFT also conveniently forms a logic inverter coupled with a pentacene OTFT, sharing Au for source/drain.     

Wafer‐Level Self‐Organized Copolymer Templates for Nanolithography with Sub‐50 nm Feature and Spatial Resolutions

Robust lithographic templates, with sub‐50 nm feature and spatial resolutions, that exhibit high patterning integrity across a full‐wafer are demonstrated using self‐organized copolymer reverse micelles on 100 mm Si wafers. A variation of less than 5% in the feature size and periodicity of polymeric templates across the entire wafer is achieved simply by controlling the spin‐coating process. Lithographic pattern transfer using these templates yields Si nanopillar arrays spanning the entire wafer surface and exhibiting high uniformity inherited from the original templates. The variation in geometric characteristics of the pillar arrays across the full‐wafer surface is validated to be less than 5% using reflectance spectroscopy. The physical basis of the change in reflectance with respect to sub‐10 nm variations in geometric parameters of pillar arrays is shown by theoretical modelling and simulations. Successful fabrication of highly durable TiO₂ masks for nanolithography with sub‐50 nm feature width and spatial resolutions is achieved through highly controlled vapour phase processing of reverse micelle templates. This allows lithographic pattern‐transfer of organic templates with a feature thickness and separation of less than 10 nm, which is otherwise not possible through other approaches reported in literature.     

Exploiting In Situ Redox and Diffusion of Molybdenum to Enable Thin‐Film Circuitry for Low‐Cost Wireless Energy Harvesting

Direct additive fabrication of thin‐film electronics using a high‐mobility, wide‐bandgap amorphous oxide semiconductor (AOS) can pave the way for integration of efficient power circuits with digital electronics. For power rectifiers, vertical thin‐film diodes (V‐TFDs) offer superior efficiency and higher frequency operation compared to lateral thin‐film transistors (TFTs). However, the AOS V‐TFDs reported so far require additional fabrication steps and generally suffer from low voltage handling capability. Here, these challenges are overcome by exploiting in situ reactions of molybdenum (Mo) during the solution‐process deposition of amorphous zinc tin oxide film. The oxidation of Mo forms the rectifying contact of the V‐TFD, while the simultaneous diffusion of Mo increases the diode's voltage range of operation. The resulting V‐TFDs are demonstrated in a full‐wave rectifier for wireless energy harvesting from a commercial radio‐frequency identification reader. Finally, by using the same Mo film for V‐TFD rectifying contacts and TFT gate electrodes, this process allows simultaneous fabrication of both devices without any additional steps. The integration of TFTs alongside V‐TFDs opens a new fabrication route for future low‐cost and large‐area thin‐film circuitry with embedded power management.     

Thin‐Film Electrodes: Microscopic and Nanoscopic Three‐Phase‐Boundaries of Platinum Thin Film Electrodes on YSZ Electrolyte (Adv. Funct. Mater. 3/2011)

Agglomerated Pt thin films have been proposed as electrodes for electrochemical devices like micro‐solid oxide fuel cells (μ‐SOFCs) operating at low temperatures. However, comprehensive studies elucidating the interplay between agglomeration state and electrochemical properties are lacking. In this contribution the electrochemical performance of agglomerated and “dense” Pt thin film electrodes on yttria‐stabilized‐zirconia (YSZ) is correlated with their microstructural characteristics. Besides the microscopically measurable triple‐phase‐boundary (tpb) where Pt, YSZ and air are in contact, a considerable contribution of “nanoscopic” tpbs to the electrode conductivity resulting from oxygen permeable grain boundaries is identified. It is demonstrated that “dense” Pt thin films are excellent electrodes provided their grain size and thickness are in the nanometer range. The results disprove the prevailing idea that the performance of Pt thin film electrodes results from microscopic and geometrically measurable tpbs only.     

A Skin‐Inspired Integrated Sensor for Synchronous Monitoring of Multiparameter Signals

Electronic skins, as the integration of multiple distinct sensors, have aroused broad interests owing to their great potential in sensing applications. However, problems including the interference between sensing components and the difficulty in synchronous monitoring are practically encountered when they are applied to mixed signals. In this work, efforts are devoted to trouble‐free technical strategies for laminating three sensors with different sensing abilities into a skin‐like electronic device. The use of ionic liquid, combined with particular circuit topologies, ensures the reliable stability against mechanical disturbance during the real‐time sensing tests. The intrinsic layered structure and three independent sensing functions of natural skins are successfully presented by this particular device in which three sensors with the ease of preparation are spatially integrated. The changes of temperature, pressure, and infrared light can be recorded simultaneously yet without mutual signal interference. The perfect integration of multiple functional sensors into a single skin‐like device without any signal interference makes an important progress for pursuing the goal of future electronic skins that can practically be used as skin.     

Enhancement of Interconnectivity in the Channels of Pentacene Thin‐Film Transistors and Its Effect on Field‐Effect Mobility

With the aim of improving the field‐effect mobility of transistors by promoting the interconnectivity of the grains in pentacene thin films, deposition conditions of the pentacene molecules using one‐step (total thickness of layer 50 nm: 0.1 Å s^–1) and two‐step (first layer 10 nm: 0.1 Å s^–1, second layer 40 nm: 4.0 Å s^–1) depositions are controlled. Significantly, it is found that the continuities of the pentacene thin films vary with the deposition conditions of the pentacene molecules. Specifically, a smaller number of voids is observed at the interface for the two‐step deposition, which results in field‐effect mobilities as high as 1.2 cm² V^–1 s^–1; these are higher by more than a factor of two than those of the pentacene films deposited in one step. This remarkable increase in field‐effect mobility is due in particular to the interconnectivity of the pentacene grains near the insulator substrate.     

All‐Solution‐Processed Indium‐Free Transparent Composite Electrodes based on Ag Nanowire and Metal Oxide for Thin‐Film Solar Cells

Fully solution‐processed Al‐doped ZnO/silver nanowire (AgNW)/Al‐doped ZnO/ZnO multi‐stacked composite electrodes are introduced as a transparent, conductive window layer for thin‐film solar cells. Unlike conventional sol–gel synthetic pathways, a newly developed combustion reaction‐based sol–gel chemical approach allows dense and uniform composite electrodes at temperatures as low as 200 °C. The resulting composite layer exhibits high transmittance (93.4% at 550 nm) and low sheet resistance (11.3 Ω sq^‐1), which are far superior to those of other solution‐processed transparent electrodes and are comparable to their sputtered counterparts. Conductive atomic force microscopy reveals that the multi‐stacked metal‐oxide layers embedded with the AgNWs enhance the photocarrier collection efficiency by broadening the lateral conduction range. This as‐developed composite electrode is successfully applied in Cu(In_1‐x,Ga_x)S₂ (CIGS) thin‐film solar cells and exhibits a power conversion efficiency of 11.03%. The fully solution‐processed indium‐free composite films demonstrate not only good performance as transparent electrodes but also the potential for applications in various optoelectronic and photovoltaic devices as a cost‐effective and sustainable alternative electrode.     

Highly Robust Bendable Oxide Thin‐Film Transistors on Polyimide Substrates via Mesh and Strip Patterning of Device Layers

Advancement in thin‐film transistor (TFT) technologies has extended to applications that can withstand extreme bending or folding. The changes of the performances of amorphous‐indium‐gallium‐zinc‐oxide (a‐IGZO) TFTs on polyimide substrate after application of extreme mechanical bending strain are studied. The TFT designs include mesh and strip patterned source/drain metal lines as well as strip patterned a‐IGZO semiconductor layer. The robustness of the a‐IGZO TFTs with the strain of 2.17% corresponding to the radius of 0.32 mm is tested and no crack generation even after 60 000 bending cycles is found. The split of source/drain electrodes and semiconductor layer can improve the mechanical bending stability of the TFTs. This can be possible by using conventional TFT manufacturing process so that this technology can be easily applied to build robust TFT array for foldable displays.     

A Skin‐Inspired Substrate with Spaghetti‐Like Multi‐Nanofiber Network of Stiff and Elastic Components for Stretchable Electronics

Mimicking the skin's non‐linear self‐limiting mechanical characteristics is of great interest. Skin is soft at low strain but becomes stiff at high strain and thereby can protect human tissues and organs from high mechanical loads. Herein, the design of a skin‐inspired substrate is reported based on a spaghetti‐like multi‐nanofiber network (SMNN) of elastic polyurethane (PU) nanofibers (NFs) sandwiched between stiff poly(vinyldenefluoride‐co‐trifluoroethylene) (P(VDF‐TrFE)) NFs layers embedded in polydimethylsiloxane elastomer. The elastic moduli of the stretchable skin‐inspired substrate can be tuned in a range that matches well with the mechanical properties of skins by adjusting the loading ratios of the two NFs. Confocal imaging under stretching indicates that PU NFs help maintain the stretchability while adding stiff P(VDF‐TrFE) NFs to control the self‐limiting characteristics. Interestingly, the Au layer on the substrate indicates a negligible change in the resistance under cyclic (up to 7000 cycles at 35% strain) and dynamic stretching (up to 35% strain), which indicates the effective absorption of stress by the SMNN. A stretchable chemoresistive gas sensor on the skin‐inspired substrate also demonstrates a reasonable stability in NO₂ sensing response under strain up to 30%. The skin‐inspired substrate with SMNN provides a step toward ultrathin stretchable electronics.     

Eliminating the Trade‐Off between the Throughput and Pattern Quality of Sub‐15 nm Directed Self‐Assembly via Warm Solvent Annealing

The directed self‐assembly (DSA) of block copolymers (BCPs) has been suggested as a promising nanofabrication solution. However, further improvements of both the pattern quality and manufacturability remain as critical challenges. Although the use of BCPs with a high Flory‐Huggins interaction parameter (χ) has been suggested as a potential solution, this practical self‐assembly route has yet to be developed due to their extremely slow self‐assembly kinetics. In this study, it is reported that warm solvent annealing (WSA) in a controlled environment can markedly improve both the self‐assembly kinetics and pattern quality. A means of avoiding the undesirable trade‐off between the quality and formation throughput of the self‐assembled patterns, which is a dilemma which arises when using the conventional solvent vapor treatment, is suggested. As a demonstration, the formation of well‐defined 13‐nm‐wide self‐assembled patterns (3σ line edge roughness of ≈2.50 nm) in treatment times of 0.5 min (for 360‐nm‐wide templates) is shown. Self‐consistent field theory (SCFT) simulation results are provided to elucidate the mechanism of the pattern quality improvement realized by WSA.     

Bilayer Organic–Inorganic Gate Dielectrics for High‐Performance,Low‐Voltage,Single‐Walled Carbon Nanotube Thin‐Film Transistors,Complementary Logic Gates,and p–n Diodes on Plastic Substrates

High‐capacitance bilayer dielectrics based on atomic‐layer‐deposited HfO₂ and spin‐cast epoxy are used with networks of single‐walled carbon nanotubes (SWNTs) to enable low‐voltage, hysteresis‐free, and high‐performance thin‐film transistors (TFTs) on silicon and flexible plastic substrates. These HfO₂–epoxy dielectrics exhibit excellent properties including mechanical flexibility, large capacitance (up to ca. 330 nF cm^–2), and low leakage current (ca. 10^–8 A cm^–2); their low‐temperature (ca. 150 °C) deposition makes them compatible with a range of plastic substrates. Analysis and measurements of these dielectrics as gate insulators in SWNT TFTs illustrate several attractive characteristics for this application. Their compatibility with polymers used for charge‐transfer doping of SWNTs is also demonstrated through the fabrication of n‐channel SWNT TFTs, low‐voltage p–n diodes, and complementary logic gates.