Stretchable Mesh-Patterned Organic Semiconducting Thin Films on Creased Elastomeric Substrates

Recently, many researchers have tried to develop stretchable semiconducting thin films that can maintain their electrical performance under stretching. However, the fabrication processes have not been sufficiently practical and feasible to be used for soft electronics. Here, a stretchable high-performance organic semiconducting thin film is fabricated by exploiting simultaneous patterning and pinning of a polymer semiconductor solution on an elastomeric substrate in which creasing-instability has occurred. As a result, a mesh-like polymer semiconducting thin film having vacant regions in the crease centers and surrounding crystalline regions near them can be fabricated. Due to the mesh-like morphology and the percolated crystalline regions, the polymer semiconducting thin film shows superior stretchability and charge-transport performance compared to the reference flat polymer thin film. When incorporated into organic thin-film transistors, the DPP-DTT polymer semiconducting thin film maintains its high field-effect carrier mobility (0.53 ± 0.03 cm² (V s)⁻¹) under a strain ε of 80% and is highly stable under repeated stretching cycles at an ε of 50%.     

Tailoring Morphology and Structure of Inkjet‐Printed Liquid‐Crystalline Semiconductor/Insulating Polymer Blends for High‐Stability Organic Transistors

Inkjet printing of semiconducting polymers is desirable for realizing low‐cost, large‐area printed electronics. However, sequential inkjet printing methods often suffer from nozzle clogging because the solubility of semiconducting polymers in organic solvents is limited. Here, it is demonstrated that the addition of an insulating polymer to a semiconducting polymer ink greatly enhances the solubility and stability of the ink, leading to the stable ejection of ink droplets. This bicomponent blend comprising a liquid‐crystalline semiconducting copolymer, poly(didodecylquaterthiophene‐alt‐didodecylbithiazole) (PQTBTz‐C12), and an insulating commodity polymer, polystyrene, is extremely useful as a semiconducting layer in organic field‐effect transistors (OFETs), providing fine control over the phase‐separated morphology and structure of the inkjet‐printed film. Tailoring the solubility‐induced phase separation of the two components leads to a bilayer structure consisting of a polystyrene layer on the top and a highly crystalline PQTBTz‐C12 layer on the bottom. The blend film is used as the semiconducting layer in OFETs, reducing the semiconductor content to several tens of pictograms in a single device without degrading the device performance. Furthermore, OFETs based on the PQTBTz‐C12/polystyrene film exhibit much greater environmental and electrical stabilities compared to the films prepared from homo PQTBTz‐C12, mainly due to the self‐encapsulated structure of the blend film.     

Spatial and Orientational Templating of Semiconducting Polymers in a Cholesteric Liquid Crystal

A one‐dimensional pattern‐forming state of a cholesteric liquid crystal (CLC) is used as a template for the self‐organization of ordered, spatially orientated, acetylene‐based semiconducting polymers. The polymers are formed by metathesis reaction with all chemical components contained in an ordinary electro‐optic cell. The polymer morphology consists of parallel ～ 1 μm thick bundles, uniformly spaced at ～ 10 μm over the full macroscopic active area of the cell substrates. The polymer templating can be explained by a model that predicts a corrugation in polymer density determined by the spatially periodic profile of the orientational energy density associated with the pattern‐forming CLC state.     

Kinetically Controlled Crystallization in Conjugated Polymer Films for High‐Performance Organic Field‐Effect Transistors

Ordering of semiconducting polymers in thin films from the nano to microscale is strongly correlated with charge transport properties as well as organic field‐effect transistor performance. This paper reports a method to control nano to microscale ordering of poly{[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)} (P(NDI2OD‐T2)) thin films by precisely regulating the solidification rate from the metastable state just before crystallization. The proposed simple but effective approach, kinetically controlled crystallization, achieves optimized P(NDI2OD‐T2) films with large polymer domains, long range ordered fibrillar structures, and molecular orientation preferable for electron transport leading to dramatic morphological changes in both polymer domain sizes at the micrometer scale and molecular packing structures at nanoscales. Structural changes significantly increase electron mobilities up to 3.43 ± 0.39 cm² V^?1 s^?1 with high reliability, almost two orders of enhancement compared with devices from naturally dried films. Small contact resistance is also obtained for electron injection (0.13 MΩ cm), low activation energy (62.51 meV), and narrow density of states distribution for electron transport in optimized thin films. It is believed that this study offers important insight into the crystallization of conjugated polymers that can be broadly applied to optimize the morphology of semiconducting polymer films for solution processed organic electronic devices.     

Surface Directed Phase Separation of Semiconductor Ferroelectric Polymer Blends and their Use in Non‐Volatile Memories

The polymer phase separation of P(VDF‐TrFE):F8BT blends is studied in detail. Its morphology is key to the operation and performance of memory diodes. In this study, it is demonstrated that it is possible to direct the semiconducting domains of a phase‐separating mixture of P(VDF‐TrFE) and F8BT in a thin film into a highly ordered 2D lattice by means of surface directed phase separation. Numerical simulation of the surface‐controlled de‐mixing process provides insight in the ability of the substrate pattern to direct the phase separation, and hence the regularity of the domain pattern in the final dry blend layer. By optimizing the ratio of the blend components, the number of electrically active semiconductor domains is maximized. Pattern replication on a cm‐scale is achieved, and improved functional device performance is demonstrated in the form of a 10‐fold increase of the ON‐current and a sixfold increase in current modulation. This approach therefore provides a simple and scalable means to higher density integration, the ultimate target being a single semiconducting domain per memory cell.     

Unifying Energetic Disorder from Charge Transport and Band Bending in Organic Semiconductors

Characterizing the density of states (DOS) width accurately is critical in understanding the charge‐transport properties of organic semiconducting materials as broader DOS distributions lead to an inferior transport. From a morphological standpoint, the relative densities of ordered and disordered regions are known to affect charge‐transport properties in films; however, a comparison between molecular structures showing quantifiable ordered and disordered regions at an atomic level and its impact on DOS widths and charge‐transport properties has yet to be made. In this work, for the first time, the DOS distribution widths of two model conjugated polymer systems are characterized using three different techniques. A quantitative correlation between energetic disorder from band‐bending measurements and charge transport is established, providing direct experimental evidence that charge‐carrier mobility in disordered materials is compromised due to the relaxation of carriers into the tail states of the DOS. Distinction and quantification of ordered and disordered regions of thin films at an atomic level is achieved using solid‐state NMR spectroscopy. An ability to compare solid‐state film morphologies of organic semiconducting polymers to energetic disorder, and in turn charge transport, can provide useful guidelines for applications of organic conjugated polymers in pertinent devices.     

Self‐Assembled,Millimeter‐Sized TIPS‐Pentacene Spherulites Grown on Partially Crosslinked Polymer Gate Dielectric

Here, a highly crystalline and self‐assembled 6,13‐bis(triisopropylsilylethynyl) pentacene (TIPS‐Pentacene) thin films formed by simple spin‐coating for the fabrication of high‐performance solution‐processed organic field‐effect transistors (OFETs) are reported. Rather than using semiconducting organic small‐molecule–insulating polymer blends for an active layer of an organic transistor, TIPS‐Pentacene organic semiconductor is separately self‐assembled on partially crosslinked poly‐4‐vinylphenol:poly(melamine‐co‐formaldehyde) (PVP:PMF) gate dielectric, which results in a vertically segregated semiconductor‐dielectric film with millimeter‐sized spherulite‐crystalline morphology of TIPS‐Pentacene. The structural and electrical properties of TIPS‐Pentacene/PVP:PMF films have been studied using a combination of polarized optical microscopy, atomic force microscopy, 2D‐grazing incidence wide‐angle X‐ray scattering, and secondary ion mass spectrometry. It is finally demonstrated a high‐performance OFETs with a maximum hole mobility of 3.40 cm² V^?1 s^?1 which is, to the best of our knowledge, one of the highest mobility values for TIPS‐Pentacene OFETs fabricated using a conventional solution process. It is expected that this new deposition method would be applicable to other small molecular semiconductor–curable polymer gate dielectric systems for high‐performance organic electronic applications.     

Tacky Elastomers to Enable Tear‐Resistant and Autonomous Self‐Healing Semiconductor Composites

Mechanical failure of π‐conjugated polymer thin films is unavoidable under cyclic loading conditions, due to intrinsic defects and poor resistance to crack propagation. Here, the first tear‐resistant and room‐temperature self‐healable semiconducting composite is presented, consisting of conjugated polymers and butyl rubber elastomers. This new composite displays both a record‐low elastic modulus (<1 MPa) and ultrahigh deformability with fracture strain above 800%. More importantly, failure behavior is not sensitive to precut notches under deformation. Autonomous self‐healing at room temperature, both mechanical and electronic, is demonstrated through the physical contact of two separate films. The composite film also shows device stability in the ambient environment over 5 months due to much‐improved barrier property to both oxygen and water. Butyl rubber is broadly applicable to various p‐type and n‐type semiconducting polymers for fabricating self‐healable electronics to provide new resilient electronics that mimic the tear resistance and healable property of human skin.     

High Energy Density All‐Solid‐State Batteries: A Challenging Concept Towards 3D Integration

Rechargeable all‐solid‐state batteries will play a key role in many autonomous devices. Planar solid‐state thin film batteries are rapidly emerging but reveal several drawbacks, such as a relatively low energy density and the use of highly reactive metallic lithium. In order to overcome these limitations a new 3D‐integrated all‐solid‐state battery concept with significantly increased surface area is presented. By depositing the active battery materials into high‐aspect ratio structures etched in, for example silicon, 3D‐integrated all‐solid‐state batteries are calculated to reach a much higher energy density. Additionally, by adopting novel high‐energy dense Li‐intercalation materials the use of metallic Lithium can be avoided. Sputtered Ta, TaN and TiN films have been investigated as potential Li‐diffusion barrier materials. TiN combines a very low response towards ionic Lithium and a high electronic conductivity. Additionally, thin film poly‐Si anodes have been electrochemically characterized with respect to their thermodynamic and kinetic Li‐intercalation properties and cycle life. The Butler‐Vollmer relationship was successfully applied, indicating favorable electrochemical charge transfer kinetics and solid‐state diffusion. Advantageously, these new Li‐intercalation anode materials were found to combine an extremely high energy density with fast rate capability, enabling future 3D‐integrated all‐solid‐state batteries.     

Spatially Controlled Transience of Graphene‐Polymer Electronics with Silicon Singulation

Transient electronics are an emerging technology for civilian and government applications that require controlled disintegration of an electronic chip into smaller components, by physical or chemical means. Here, a pillar‐on‐polymer architecture is presented for a transient system where the electronic components are partitioned on an array of silicon pillars. The pillars are mechanically tethered by a vaporizable polymer film and electrically routed with atomically thin graphene interconnects. Polymer vaporization is achieved with Joule heating of thin‐film metal heaters associated with each silicon pillar, which singulates the pillar. The pillar singulation breaks the graphene interconnects locally, without collateral damage to other on‐chip components. This process demonstrates a methodology for temporally and spatially controlled transience as any single pillar can be singulated at any time. A novel polymer‐silicon layer transfer fabrication process is used to microfabricate a 3 × 3 array of 200 µm diameter silicon pillars spaced 200 µm apart, with gold heaters and graphene interconnects, and the controlled singulation of individual pillars is demonstrated. As a demonstration of a sensor in this technology, a piezoresistive accelerometer is integrated with this platform, which uses a silicon pillar array suspended from the polymer film as a proof mass.     

Mechanism of Crystallization and Implications for Charge Transport in Poly(3‐ethylhexylthiophene) Thin Films

In this work, crystallization kinetics and aggregate growth of poly(3‐ethylhexylthiophene) (P3EHT) thin films are studied as a function of film thickness. X‐ray diffraction and optical absorption show that individual aggregates and crystallites grow anisotropically and mostly along only two packing directions: the alkyl stacking and the polymer chain backbone direction. Further, it is also determined that crystallization kinetics is limited by the reorganization of polymer chains and depends strongly on the film thickness and average molecular weight. Time‐dependent, field‐effect hole mobilities in thin films reveal a percolation threshold for both low and high molecular weight P3EHT. Structural analysis reveals that charge percolation requires bridged aggregates separated by a distance of ≈2–3 nm, which is on the order of the polymer persistence length. These results thus highlight the importance of tie molecules and inter‐aggregate distance in supporting charge percolation in semiconducting polymer thin films. The study as a whole also demonstrates that P3EHT is an ideal model system for polythiophenes and should prove to be useful for future investigations into crystallization kinetics.     

In Situ Tracking of Composition and Morphology of a Diblock Copolymer Film with GISAXS during Exchange of Solvent Vapors at Elevated Temperatures

Solvothermal vapor annealing at elevated temperature is applied to a thin film from a cylinder‐forming polystyrene‐block‐poly(dimethyl siloxane) (PS‐b‐PDMS) diblock copolymer. At this, the film is swollen in the vapor of n‐heptane (highly selective for PDMS). This vapor is stepwise replaced by the vapor of toluene (weakly selective for PS). The morphologies are investigated using in situ, real‐time grazing‐incidence small‐angle X‐ray scattering (GISAXS). The initial cylindrical morphology is transformed into, among others, the lamellar one. This novel type of experiments allows probing a trajectory in the state diagram of the PS‐b‐PDMS/n‐heptane/toluene mixture. To corroborate the morphologies, they are generated by molecular simulations, and the 2D GISAXS maps are calculated using the distorted‐wave Born approximation. To relate the morphologies to the solvent distribution in the two types of nanodomains, the latter is estimated from the intensities of the Bragg reflections in the 2D GISAXS maps along with the swelling ratio of the film. Comparison with the results from a similar experiment carried out at room temperature results in the same sequence of morphologies; however, at elevated temperature, more well‐ordered structures are obtained. This new approach proves to be efficient to achieve a block copolymer thin film having a desired morphology and orientation.     

Shift of the Branching Point of the Side‐Chain in Naphthalenediimide (NDI)‐Based Polymer for Enhanced Electron Mobility and All‐Polymer Solar Cell Performance

The branching point of the side‐chain of naphthalenediimide (NDI)‐based conjugated polymers is systematically controlled by incorporating four different side‐chains, i.e., 2‐hexyloctyl (P(NDI1‐T)), 3‐hexylnonyl (P(NDI2‐T)), 4‐hexyldecyl (P(NDI3‐T)), and 5‐hexylundecyl (P(NDI4‐T)). When the branching point is located farther away from the conjugated backbones, steric hindrance around the backbone is relaxed and the intermolecular interactions between the polymer chains become stronger, which promotes the formation of crystalline structures in thin film state. In particular, thermally annealed films of P(NDI3‐T) and P(NDI4‐T), which have branching points far away from the backbone, possess more‐developed bimodal structure along both the face‐on and edge‐on orientations. Consequently, the field‐effect electron mobilities of P(NDIm‐T) polymers are monotonically increased from 0.03 cm² V⁻¹ s⁻¹ in P(NDI1‐T) to 0.22 cm² V⁻¹ s⁻¹ in P(NDI4‐T), accompanied by reduced activation energy and contact resistance of the thin films. In addition, when the series of P(NDIm‐T) polymers is applied in all‐polymer solar cells (all‐PSCs) as electron acceptor, remarkably high‐power conversion efficiency of 7.1% is achieved along with enhanced current density in P(NDI3‐T)‐based all‐PSCs, which is mainly attributed to red‐shifted light absorption and enhanced electron‐transporting ability.     

Tuning the Morphology of Isoindigo Donor–Acceptor Polymer Film for High Sensitivity Ammonia Sensor

Monitoring the ammonia gas is of great interest to both environmental benefits and human health. The recent advance in polymer thin film transistors (TFTs) can realize high sensitivity and low‐cost gas sensors. Ammonia gas interacts with charge carrier channels and polymer/dielectrics interface through Coulomb force. This is the first report of high sensitivity and reusable ammonia sensor fabricated from thiophene‐isoindigo donor–acceptor conducting polymer. This kind of polymer has advantages of simple synthesis and excellent air stability. The systematic study is carried out to investigate relationship among chemical structure variation and morphology control of polymer to the performance of ammonia sensor. High crystallinity, favored crystal orientation, and direct percolation routes for analytes are found to be essential to increase the susceptibility of polymers to ammonia gas. By strengthening edge‐on morphology, the sensitivity can be enhanced fivefold for the same polymer. The idea can put forward the development of sensor array in a time‐efficient manner by employing the morphology effect.     

Self‐Assembled Dense Colloidal Cu2Te Nanodisk Networks in P3HT Thin Films with Enhanced Photocurrent

The integration of colloidal nanocrystals with polymers adds optoelectronic functionalities to flexible and mechanically robust organic films. In particular, self‐assembled structures of nanocrystals in polymers can act as functional components enhancing, for instance, transport or optical properties of the hybrid material. This study presents Cu₂Te hexagonal nanodisks that assemble into ribbons with a face‐to‐face configuration in poly(3‐hexylthiophene‐2,5‐diyl) through a controlled solvent evaporation process. The ribbons form weaving patterns that create 3D networks fully embedded in the thin polymer film at high nanodisk concentration. The photoresponse of these composite films measured in a layered vertical geometry demonstrates increased photocurrent with increasing nanocrystal loading. This study attributes this behavior to the presence of networks of Cu₂Te nanodisks that form a bulk heterojunction with the semiconducting polymer, which improves exciton dissociation and the overall photoelectric response.     

Multimodal Characterization of Crystal Structure and Formation in Rubrene Thin Films Reveals Erasure of Orientational Discontinuities

Multimodal multiscale characterization provide opportunities to study organic semiconducting thin films with multiple length scales, across multiple platforms, to elucidate crystallization mechanisms of the various microstructures that impact functionality. With polarized scanning transmission X-ray and 4D-scanning transmission electron microscopy, hybrid crystalline structures in rubrene thin films in which large crystalline domains surround a common nucleus and transition to a spherulite morphology at larger radii is observed. These high-resolution techniques reveal how azimuthal orientational discontinuities at smaller radii are erased as spherulite morphology takes hold. In situ crystallization in the films with optical microscopy is also captured, discovering the importance of considering the initial temperature increase of a film during thermal annealing over the crystallization timescale. This kinetic information of the radial crystallization rate and of corresponding film heating kinetics is used to estimate the temperature at which the larger crystalline regions transition into a spherulite. By combining the results obtained from the different characterization modes, it is learned that thermal conditions can sensitively affect the crystallization of rubrene and other organic thin films. The observations suggest opportunities for more complex temperature-dependent processing to maximize hybrid structures’ functionality in organic thin films and demonstrate that multimodal studies deepen the understanding of structure-function dynamics.     

Vertically Segregated Structure and Properties of Small Molecule–Polymer Blend Semiconductors for Organic Thin‐Film Transistors

A comprehensive structure and performance study of thin blend films of the small‐molecule semiconductor, 2,8‐difluoro‐5,11‐bis(triethylsilylethynyl)anthradithiophene (diF‐TESADT), with various insulating binder polymers in organic thin‐film transistors is reported. The vertically segregated composition profile and nanostructure in the blend films are characterized by a combination of complementary experimental methods including grazing incidence X‐ray diffraction, neutron reflectivity, variable angle spectroscopic ellipsometry, and near edge X‐ray absorption fine structure spectroscopy. Three polymer binders are considered: atactic poly(α‐methylstyrene), atactic poly(methylmethacrylate), and syndiotactic polystyrene. The choice of polymer can strongly affect the vertical composition profile and the extent of crystalline order in blend films due to the competing effects of confinement entropy, interaction energy with substrate surfaces, and solidification kinetics. The variations in the vertically segregated composition profile and crystalline order in thin blend films explain the significant impacts of binder polymer choice on the charge carrier mobility of these films in the solution‐processed bottom‐gate/bottom‐contact thin‐film transistors.     

Highly Oriented Nanofibrils of Regioregular Poly(3‐hexylthiophene) Formed via Block Copolymer Self‐Assembly in Liquid Crystals

A novel method making use of block copolymer self‐assembly in nematic liquid crystals (LCs) is described for preparing macroscopically oriented nanofibrils of π‐conjugated semiconducting polymers. Upon cooling, a diblock copolymer composed of regioregular poly(3‐hexylthiophene) (P3HT) and a liquid crystalline polymer (LCP) in a block‐selective LC solvent can self‐assemble into oriented nanofibrils exhibiting highly anisotropic absorption and polarized photoluminescence emission. An unusual feature of the nanofibrils is that P3HT chains are oriented along the fibrils' long axis. This general method makes it possible to use LCs as an anisotropic medium to grow oriented nanofibrils of many semiconducting polymers insoluble in LCs.     

Impact of Substrate and Processing on Confinement of Nafion Thin Films

Thin films of ion‐conducting polymers are an important area of study due to their function in many electrochemical devices and as analogues for interfacial phenomena that occur in bulk films. In this paper, the properties of Nafion, a prototypical ionomer, are investigated as thin films (4 to 300 nm) on carbon, gold, and platinum substrates that are fabricated using different casting methods and thermal histories. Specifically, water uptake, swelling, and morphology are investigated by quartz‐crystal microbalance, ellipsometry, and grazing‐incidence X‐ray scattering to develop structure/property/processing relationships. For all substrates, as the films' thickness decreased, there is an initial decrease in swelling followed by a subsequent increase for film thicknesses below ≈20 nm due to a disordering of the film hydrophilic/hydrophobic structure. Decreased swelling and less structural order is observed on gold for spin‐cast films compared to self‐assembled films; the opposite effect is observed for films on carbon. The presented systematic data set and analyses represent a thorough study of the behavior of Nafion thin films on model substrates of interest in metal catalyst/carbon electrodes, and these insights help to elucidate the underlying polymer physics and confinement effects in these and related systems.     

19%‐efficient and 43 µm‐thick crystalline Si solar cell from layer transfer using porous silicon

We present a both‐sides‐contacted thin‐film crystalline silicon (c‐Si) solar cell with a confirmed AM1.5 efficiency of 19.1% using the porous silicon layer transfer process. The aperture area of the cell is 3.98 cm². This is the highest efficiency ever reported for transferred Si cells. The efficiency improvement over the prior state of the art (16.9%) is achieved by implementing recent developments for Si wafer cells such as surface passivation with aluminum oxide and laser ablation for contacting. The cell has a short‐circuit current density of 37.8 mA cm⁻², an open‐circuit voltage of 650 mV, and a fill factor of 77.6%. Copyright © 2011 John Wiley & Sons, Ltd.