Edible Electronics: Biocompatible and Biodegradable Materials for Organic Field‐Effect Transistors (Adv. Funct. Mater. 23/2010)

Biocompatible‐ingestible electronic circuits and capsules for medical diagnosis and monitoring are currently based on traditional silicon technology. Organic electronics has huge potential for developing biodegradable, biocompatible, bioresorbable, or even metabolizable products. An ideal pathway for such electronic devices involves fabrication with materials from nature, or materials found in common commodity products. Transistors with an operational voltage as low as 4–5 V, a source drain current of up to 0.5 μA and an on‐off ratio of 3–5 orders of magnitude have been fabricated with such materials. This work comprises steps towards environmentally safe devices in low‐cost, large volume, disposable or throwaway electronic applications, such as in food packaging, plastic bags, and disposable dishware. In addition, there is significant potential to use such electronic items in biomedical implants.     

Super‐ and Ultrathin Organic Field‐Effect Transistors: from Flexibility to Super‐ and Ultraflexibility

Physically flexible electronics offer a wide range of benefits, including the development of next‐generation consumer electronics and healthcare products. The advancement of physical flexibility, typically achieved by the reduction of the total device thickness, including substrates and encapsulation layers, shows great promise for skin‐laminated electronics. Organic electronics—devices relying on carbon‐based materials—offer many advantages over their inorganic counterparts, including the following: significantly lower fabrication temperatures resulting in alternative fabrication techniques, including inkjet and roll‐to‐roll printing, enabling low‐cost and large‐area fabrication; biocompatibility; and spectacular physical flexibility. This article presents a review, spanning the last two decades, of organic field‐effect transistors with the total thickness of just a few microns as well as devices demonstrated in this decade with a total thickness of few hundred of nanometers. A handful of demonstrations of other organic electronic thin film devices are also presented.     

Effects of the Ionic Currents in Electrolyte‐gated Organic Field‐Effect Transistors

Polyelectrolytes are promising materials as gate dielectrics in organic field‐effect transistors (OFETs). Upon gate bias, their polarization induces an ionic charging current, which generates a large double layer capacitor (10–500 µF cm^?2) at the semiconductor/electrolyte interface. The resulting transistor operates at low voltages (<1 V) and its conducting channel is formed in ～50 µs. The effect of ionic currents on the performance of the OFETs is investigated by varying the relative humidity of the device ambience. Within defined humidity levels and potential values, the water electrolysis is negligible and the OFETs performances are optimum.     

Vertical Organic Field‐Effect Transistors

Field‐effect transistors are the fundamental building blocks for electronic circuits and processors. Compared with inorganic transistors, organic field‐effect transistors (OFETs), featuring low cost, low weight, and easy fabrication, are attractive for large‐area flexible electronic devices. At present, OFETs with planar structures are widely investigated device structures in organic electronics and optoelectronics; however, they face enormous challenges in realizing large current density, fast operation speed, and outstanding mechanical flexibility for advancing their potential commercialized applications. In this context, vertical organic field‐effect transistors (VOFETs), composed of vertically stacked source/drain electrodes, could provide an effective approach for solving these questions due to their inherent small channel length and unique working principles. Since the first report of VOFETs in 2004, impressive progress has been witnessed in this field with the improvement of device performance. The aim of this review is to give a systematical summary of VOFETs with a special focus on device structure optimization for improved performance and potential applications demonstrated by VOFETs. An overview of the development of VOFETs along with current challenges and perspectives is also discussed. It is hoped that this review is timely and valuable for the next step in the rapid development of VOFETs and their related research fields.     

The Effects of Moisture in Low‐Voltage Organic Field‐Effect Transistors Gated with a Hydrous Solid Electrolyte

The concept of using ion conducting membranes (50–150 μm thick) for gating low‐voltage (1 V) organic field‐effect transistors (OFETs) is attractive due to its low‐cost and large‐area manufacturing capabilities. Furthermore, the membranes can be tailor‐made to be ion conducting in any desired way or pattern. For the electrolyte gated OFETs in general, the key to low‐voltage operation is the electrolyte “insulator” (the membrane) that provides a high effective capacitance due to ionic polarization within the insulator. Hydrous ion conducting membranes are easy to process and readily available. However, the role of the water in combination with the polymeric semiconductor has not yet been fully clarified. In this work electrical and optical techniques are utilized to carefully monitor the electrolyte/semiconductor interface in an ion conducting membrane based OFET. The main findings are that 1) moisture plays a major part in the transistor operation and careful control of both the ambient atmosphere and the potential differences between the electrodes are required for stable and consistent device behavior, 2) the obtained maximum effective capacitance (5 μF cm^?2) of the membrane suggests that the electric double layer is distributed over a broad region within the polyelectrolyte, and 3) electromodulation spectroscopy combined with current–voltage characteristics provide a method to determine the threshold gate voltage from an electrostatic field‐effect doping to a region of (irreversible) electrochemical perturbation of the polymeric semiconductor.     

Organic Junction Field‐Effect Transistor

The realization and performance of a novel organic field‐effect transistor—the organic junction field‐effect transistor (JFET)—is discussed. The transistors are based on the modulation of the thickness of a depletion layer in an organic pin junction with varying gate potential. Based on numerical modeling, suitable layer thicknesses and doping concentrations are identified. Experimentally, organic JFETs are realized and it is shown that the devices clearly exhibit amplification. Changes in the electrical characteristics due to a variation of the intrinsic and the p‐doped layer thickness are rationalized by the numerical model, giving further proof to the proposed operational mechanism.     

Control of Polymorphism and Morphology in Solution Sheared Organic Field‐Effect Transistors

During the last decades, small molecule organic semiconductors have been successfully used as active layer in organic field‐effect transistors (OFETs). Despite the high mobility achieved so far with organic molecules, in order to progress in the field it is crucial to find techniques to process them from solution. The device reproducibility is one of the principal weak points of organic electronics for further commercialization. To achieve a high device‐to‐device reproducibility it is essential to control the morphology and polymorphism of the active layer for OFET application. In this work, the preparation of thin films is reported based on blends of the organic semiconductor dibenzo‐tetrathiafulvalene (DB‐TTF) and polystyrene by a solution shearing technique compatible with upscaling. Here, it is demonstrated that varying the deposition parameters (i.e., speed and temperature) or the solution formulation (i.e., semiconductor/binder polymer ratio) is possible to control the film morphology and semiconductor polymorphism and, hence, the different intermolecular interactions. It is demonstrated that the control of the thermodynamics and kinetics of the crystallization process is key for the device performance optimization. Further, this is the first time that DB‐TTF thin films of the α‐polymorph are reported.     

Non‐Volatile Organic Memory Elements Based on Carbon‐Nanotube‐Enabled Vertical Field‐Effect Transistors

High‐performance non‐volatile memory elements based on carbon‐nanotube‐enabled vertical field‐effect transistors (CN‐VFETs) are demonstrated. A thin crosslinking polymer layer, benzocyclobutene (BCB), on top of the gate dielectric acts as the charge storage layer. This results in a large, fully gate sweep programmable, hysteresis in the cyclic transfer curves exhibiting on/off ratios >4 orders of magnitude. The carbon nanotube random network source electrode facilitates charge injection into the charge storage layer, realizing the strong memory effect without sacrificing mobility in the vertical channel. Given their intrinsically simple fabrication and compact size CN‐VFETs could provide a path to cost‐effective, high‐density organic memory devices.     

Epindolidiones—Versatile and Stable Hydrogen‐Bonded Pigments for Organic Field‐Effect Transistors and Light‐Emitting Diodes

Hydrogen‐bonded pigments are remarkably stable high‐crystal lattice energy organic solids. Here a lesser‐known family of compounds, the epindolidiones, which demonstrates electronic transport with extraordinary stability, even in highly demanding aqueous environments, is reported. Hole mobilities in the range 0.05–1 cm² V^–1 s^–1 can be achieved, with lower electron mobilities of up to 0.1 cm² V^–1 s^–1. To help understand charge transport in epindolidiones, X‐ray diffraction is used to solve the crystal structure of 2,8‐difluoroepindolidione and 2,8‐dichloroepindolidione. Both derivatives crystallize with a linear‐chain H‐bonding lattice featuring two‐dimensional π–π stacking. Powder diffraction indicates that the unsubstituted epindolidione has very similar crystallinity. All types of epindolidiones measured here display strong low‐energy optical emission originating from excimeric states, which coexists with higher‐energy fluorescence. This can be exploited in light‐emitting diodes, which show the same hybrid singlet and low‐energy excimer electroluminescence. Low‐voltage FETs are fabricated with epindolidione, which operate reliably under repeated cyclic tests in different ionic solutions within the pH range 3–10 without degradation. Finally, in order to overcome the insolubility of epindolidiones in organic solvents, a chemical procedure is devised to allow solution‐processing via the introduction of suitable thermolabile solubilizing groups. This work shows the versatile potential of epindolidione pigments for electronics applications.     

Porous Organic Field‐Effect Transistors for Enhanced Chemical Sensing Performances

The thin‐film structures of chemical sensors based on conventional organic field‐effect transistors (OFETs) can limit the sensitivity of the devices toward chemical vapors, because charge carriers in OFETs are usually concentrated within a few molecular layers at the bottom of the organic semiconductor (OSC) film near the dielectric/semiconductor interface. Chemical vapor molecules have to diffuse through the OSC films before they can interact with charge carriers in the OFET conduction channel. It has been demonstrated that OFET ammonia sensors with porous OSC films can be fabricated by a simple vacuum freeze‐drying template method. The resulted devices can have ammonia sensitivity not only much higher than the pristine OFETs with thin‐film structure but also better than any previously reported OFET sensors, to the best of our knowledge. The porous OFETs show a relative sensitivity as high as 340% ppm^?1 upon exposure to 10 parts per billion (ppb) NH₃. In addition, the devices also exhibit decent selectivity and stability. This general and simple strategy can be applied to a wide range of OFET chemical sensors to improve the device sensitivity.     

Biodegradable Materials for Transient Organic Transistors

Electronic devices that can physically disappear in a controlled manner without harmful by-products unveil a wide range of opportunities in medical devices, environmental monitoring, and next-generation consumer electronics. Their property of transience is indispensable for mitigating the global problem of electronic waste accumulation. Additionally, transient technologies that are biocompatible and can be biologically resorbed are of great potential for applications in temporary medical implants, since it eliminates the need for expensive device recovery surgery. Transistors are the key building blocks of modern electronics, and their fabrication using organic materials is beneficial due to their low cost, unprecedented flexibility and facile processing. This contribution reviews the technological application of biodegradable materials in four major classes of organic transistors, namely organic field-effect transistors (OFETs), organic synaptic transistors, electrolyte-gated OFETs, and organic electrochemical transistors. The fundamental biodegradation mechanism is discussed in detail, followed by a perspective of various biodegradable materials utilized as active semiconductors, dielectrics, electrolytes and substrates in the various types of organic transistor devices. This contribution comprehensively discusses the role and application of biodegradable materials in all of the key modern-day organic transistors, highlighting their unique properties that allow the fabrication of biodegradable, eco-friendly, and sustainable devices.     

Contact Resistance in Organic Field‐Effect Transistors: Conquering the Barrier

Organic semiconductors have sparked interest as flexible, solution processable, and chemically tunable electronic materials. Improvements in charge carrier mobility put organic semiconductors in a competitive position for incorporation in a variety of (opto‐)electronic applications. One example is the organic field‐effect transistor (OFET), which is the fundamental building block of many applications based on organic semiconductors. While the semiconductor performance improvements opened up the possibilities for applying organic materials as active components in fast switching electrical devices, the ability to make good electrical contact hinders further development of deployable electronics. Additionally, inefficient contacts represent serious bottlenecks in identifying new electronic materials by inhibiting access to their intrinsic properties or providing misleading information. Recent work focused on the relationships of contact resistance with device architecture, applied voltage, metal and dielectric interfaces, has led to a steady reduction in contact resistance in OFETs. While impressive progress was made, contact resistance is still above the limits necessary to drive devices at the speed required for many active electronic components. Here, the origins of contact resistance and recent improvement in organic transistors are presented, with emphasis on the electric field and geometric considerations of charge injection in OFETs.     

Insulator Polarization Mechanisms in Polyelectrolyte‐Gated Organic Field‐Effect Transistors

Electrolyte‐gated organic field‐effect transistors (OFETs) hold promise for robust printed electronics operating at low voltages. The polarization mechanism of thin solid electrolyte films, the gate insulator in such OFETs, is still unclear and appears to limit the transient current characteristics of the transistors. Here, the polarization response of a thin proton membrane, a poly(styrenesulfonic acid) film, is controlled by varying the relative humidity. The formation of the conducting transistor channel follows the polarization of the polyelectrolyte, such that the drain transient current characteristics versus the time are rationalized by three different polarization mechanisms: the dipolar relaxation at high frequencies, the ionic relaxation (migration) at intermediate frequencies, and the electric double‐layer formation at the polyelectrolyte interfaces at low frequencies. The electric double layers of polyelectrolyte capacitors are formed in ～1 µs at humid conditions and an effective capacitance per area of 10 µF cm^?2 is obtained at 1 MHz, thus suggesting that this class of OFETs might operate at up to 1 MHz at 1 V.     

Toward High‐Output Organic Vertical Field Effect Transistors: Key Design Parameters

The performance of C₆₀‐based organic vertical field‐effect transistors (VFETs) is investigated as a function of key geometrical parameters to attain a better understanding of their operation mechanism and eventually to enhance their output current for maximal driving capability. To this end, a 2D device simulation is performed and compared with experimental results. The results reveal that the output current scales mostly with the width of its drain electrode, which is in essence equivalent to the channel width in conventional lateral‐channel transistors, but that of the source electrode and the thickness of C₆₀ layers underneath the source electrode also play subtle but important roles mainly due to the source contact‐limited behavior of the organic VFETs under study. With design strategies acquired from this study, a VFET with an on/off ratio of 5.5 × 10⁵ and on‐current corresponding to a channel length of near 1 μm in a conventional lateral‐channel organic field‐effect transistor (FET) is demonstrated, while the drain width of the VFET and the channel width of the lateral‐channel organic FET are the same.     

Fabrication of Organic Thin‐Film Transistors on Three‐Dimensional Substrates Using Free‐Standing Polymeric Masks Based on Soft Lithography

Here, a novel fabrication technique for integrated organic devices on substrates with complex structure is presented. For this work, free‐standing polymeric masks with stencil‐patterns are fabricated using an ultra‐violet (UV) curable polyurethaneacrylate (PUA) mixture, and used as shadow masks for thermal evaporation. High flexibility and adhesive properties of the free‐standing PUA masks ensure conformal contact with various materials such as glass, silicon (Si), and polymer, and thus can also be utilized as patterning masks for solution‐based deposition methods, such as spin‐coating and drop‐casting. Based on this technique, a number of integrated organic transistors are fabricated simultaneously on a cylindrical glass bottle with high curvature, as well as on a flat silicon wafer. It is anticipated that these results will be applied to the development of various integrated organic devices on complex‐structured substrates, which can lead to further applications.     

Solution‐Processed Monolayer Organic Crystals for High‐Performance Field‐Effect Transistors and Ultrasensitive Gas Sensors

This work innovatively develops a dual solution‐shearing method utilizing the semiconductor concentration region close to the solubility limit, which successfully generates large‐area and high‐performance semiconductor monolayer crystals on the millimeter scale. The monolayer crystals with poly(methyl methacrylate) encapsulation show the highest mobility of 10.4 cm² V^?1 s^?1 among the mobility values in the reported solution‐processed semiconductor monolayers. With similar mobility to multilayer crystals, light is shed on the charge accumulation mechanism in organic field‐effect transistors (OFETs), where the first layer on interface bears the most carrier transport task, and the other above layers work as carrier suppliers and encapsulations to the first layer. The monolayer crystals show a very low dependency on channel directions with a small anisotropic ratio of 1.3. The positive mobility–temperature correlation reveals a thermally activated carrier transport mode in the monolayer crystals, which is different from the band‐like transport mode in multilayer crystals. Furthermore, because of the direct exposure of highly conductive channels, the monolayer crystal based OFETs can sense ammonia concentrations as low as 10 ppb. The decent sensitivity indicates the monolayer crystals are potential candidates for sensor applications.     

Star‐Shaped Oligothiophenes for Solution‐Processible Organic Field‐Effect Transistors

We have designed and successfully synthesized star‐shaped oligothiophenes, which could be used as semiconducting materials for solution‐processible organic field‐effect transistors (FETs). By systematically changing the chemical structure of the star‐shaped oligothiophenes we obtained the structural requirements needed for making working FETs from them. UV‐vis fluorescence measurements showed that a molecule of the star‐shaped compounds under consideration is not a fully conjugated molecule, but it has three independently conjugated oligothienyl‐phenylene blocks. A possible scheme of molecular packing of the star‐shaped oligothiophenes in a lamellar structure was proposed and confirmed by atomic force microscopy (AFM) and X‐ray diffraction (XRD) measurements. Although the star‐shaped semiconductors show a somewhat lower mobility than their linear analogs, they possess better solubility and film‐forming properties, leading to improved spin‐coating processing. The best FETs were made by spin‐coating 1,3,5‐tris(5″‐decyl‐2,2′:5′,2″‐terthien‐5‐yl)benzene from a chloroform solution, which resulted in a mobility of 2 × 10^–4 cm² V ^–1s^–1, a 10² on/off ratio at gate voltages of 0 V and –20 V, and a threshold voltage close to 0 V.     

Sensing of Alkylating Agents Using Organic Field‐Effect Transistors

Alkylating agents are simple and reactive molecules that are commonly used in many and diverse fields, such as organic synthesis, medicine, and agriculture. Some highly reactive alkylating species are also being used as blister chemical warfare agents. The detection and identification of alkylating agent is not a trivial issue because of their high reactivity and simple structure. Here, a novel polythiophene derivative that is capable of reacting with alkylating agents is reported, along with its application in direct electrical sensing of alkylators using an organic field‐effect transistor, OFET, device. Upon reacting with alkylators, the OFET containing the new polythiophene analogue as its channel becomes conductive, and the gate effect is lost; this is in marked contrast to the response of the OFET to “innocent” vapors, such as alcohols and acetone. By following the drain–source current under gate bias, one can easily follow the processes of absorption of the analyte to the polythiophene channel and their subsequent reaction.     

Detailed Characterization of Contact Resistance,Gate‐Bias‐Dependent Field‐Effect Mobility,and Short‐Channel Effects with Microscale Elastomeric Single‐Crystal Field‐Effect Transistors

The organic field‐effect transistor (OFET) has proven itself invaluable as both the fundamental element in organic circuits and the primary tool for the characterization of novel organic electronic materials. Crucial to the success of the OFET in each of these venues is a working understanding of the device physics that manifest themselves in the form of electrical characteristics. As commercial applications shift to smaller device dimensions and structure/property relationships become more refined, the understanding of these phenomena become increasingly critical. Here, we employ high‐performance, elastomeric, photolithographically patterned single‐crystal field‐effect transistors as tools for the characterization of short‐channel effects and bias‐dependent parasitic contact resistance and field‐effect mobility. Redundant characterization of devices at multiple channel lengths under a single crystal allow the morphology‐free analysis of these effects, which is carried out in the context of a device model previously reported. The data show remarkable consistency with our model, yielding fresh insight into each of these phenomena, as well as confirming the utility of our FET design.     

Solution Processable Fluorenyl Hexa‐peri‐hexabenzocoronenes in Organic Field‐Effect Transistors and Solar Cells

The organization of organic semiconductor molecules in the active layer of organic electronic devices has important consequences to overall device performance. This is due to the fact that molecular organization directly affects charge carrier mobility of the material. Organic field‐effect transistor (OFET) performance is driven by high charge carrier mobility while bulk heterojunction (BHJ) solar cells require balanced hole and electron transport. By investigating the properties and device performance of three structural variations of the fluorenyl hexa‐peri‐hexabenzocoronene (FHBC) material, the importance of molecular organization to device performance was highlighted. It is clear from ¹H NMR and 2D wide‐angle X‐ray scattering (2D WAXS) experiments that the sterically demanding 9,9‐dioctylfluorene groups are preventing π–π intermolecular contact in the hexakis‐substituted FHBC 4 . For bis‐substituted FHBC compounds 5 and 6 , π–π intermolecular contact was observed in solution and hexagonal columnar ordering was observed in solid state. Furthermore, in atomic force microscopy (AFM) experiments, nanoscale phase separation was observed in thin films of FHBC and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PC₆₁BM) blends. The differences in molecular and bulk structural features were found to correlate with OFET and BHJ solar cell performance. Poor OFET and BHJ solar cells devices were obtained for FHBC compound 4 while compounds 5 and 6 gave excellent devices. In particular, the field‐effect mobility of FHBC 6 , deposited by spin‐casting, reached 2.8 × 10^?3 cm² V^?1 s and a power conversion efficiency of 1.5% was recorded for the BHJ solar cell containing FHBC 6 and PC₆₁BM.