Recent Progress in n‐Channel Organic Thin‐Film Transistors

Particular attention has been focused on n‐channel organic thin‐film transistors (OTFTs) during the last few years, and the potentially cost‐effective circuitry‐based applications in flexible electronics, such as flexible radiofrequency identity tags, smart labels, and simple displays, will benefit from this fast development. This article reviews recent progress in performance and molecular design of n‐channel semiconductors in the past five years, and limitations and practicable solutions for n‐channel OTFTs are dealt with from the viewpoint of OTFT constitution and geometry, molecular design, and thin‐film growth conditions. Strategy methodology is especially highlighted with an aim to investigate basic issues in this field.     

25th Anniversary Article: Organic Field‐Effect Transistors: The Path Beyond Amorphous Silicon

Over the past 25 years, organic field‐effect transistors (OFETs) have witnessed impressive improvements in materials performance by 3–4 orders of magnitude, and many of the key materials discoveries have been published in Advanced Materials. This includes some of the most recent demonstrations of organic field‐effect transistors with performance that clearly exceeds that of benchmark amorphous silicon‐based devices. In this article, state‐of‐the‐art in OFETs are reviewed in light of requirements for demanding future applications, in particular active‐matrix addressing for flexible organic light‐emitting diode (OLED) displays. An overview is provided over both small molecule and conjugated polymer materials for which field‐effect mobilities exceeding > 1 cm² V^–1 s^–1 have been reported. Current understanding is also reviewed of their charge transport physics that allows reaching such unexpectedly high mobilities in these weakly van der Waals bonded and structurally comparatively disordered materials with a view towards understanding the potential for further improvement in performance in the future.     

Exploiting Ionic Coupling in Electronic Devices: Electrolyte‐Gated Organic Field‐Effect Transistors

Currently there is great interest in using organic semiconductors to develop novel flexible electronic applications. An emerging strategy in organic semiconductor materials research involves development of composite or layered materials in which electronic and ionic conductivity is combined to create enhanced functionality in devices. For example, we and other groups have employed ionic motion to modulate electronic transport in organic field‐effect transistors using solid electrolytes. Not only do these transistors operate at low voltages as a result of greatly enhanced capacitive coupling, but they also display intriguing transport phenomena such as negative differential transconductance. Here, we discuss differences in operation between traditional (e.g., SiO₂) and electrolyte‐based dielectrics, suggest further improvements to currently used electrolyte materials, and propose several possibilities for exploiting electrolytes in future applications with both organic and inorganic semiconductors.     

Halogenated Tetraazapentacenes with Electron Mobility as High as 27.8 cm2 V−1 s−1 in Solution‐Processed n‐Channel Organic Thin‐Film Transistors

Molecular engineering of tetraazapentacene with different numbers of fluorine and chlorine substituents fine‐tunes the frontier molecular orbitals, molecular vibrations, and π–π stacking for n‐type organic semiconductors. Among the six halogenated tetraazapentacenes studied herein, the tetrachloro derivative (4Cl‐TAP) in solution‐processed thin‐film transistors exhibits electron mobility of 14.9 ± 4.9 cm² V^?1 s^?1 with a maximum value of 27.8 cm² V^?1 s^?1, which sets a new record for n‐channel organic field‐effect transistors. Computational studies on the basis of crystal structures shed light on the structure–property relationships for organic semiconductors. First, chlorine substituents slightly decrease the reorganization energy of the tetraazapentacene whereas fluorine substituents increase the reorganization energy as a result of fine‐tuning molecular vibrations. Second, the electron transfer integral is very sensitive to subtle changes in the 2D π‐stacking with brickwork arrangement. The unprecedentedly high electron mobility of 4Cl‐TAP is attributed to the reduced reorganization energy and enhanced electron transfer integral as a result of modification of tetraazapentacene with four chlorine substituents.     

Charge Injection in Solution‐Processed Organic Field‐Effect Transistors: Physics,Models and Characterization Methods

A high‐mobility organic semiconductor employed as the active material in a field‐effect transistor does not guarantee per se that expectations of high performance are fulfilled. This is even truer if a downscaled, short channel is adopted. Only if contacts are able to provide the device with as much charge as it needs, with a negligible voltage drop across them, then high expectations can turn into high performances. It is a fact that this is not always the case in the field of organic electronics. In this review, we aim to offer a comprehensive overview on the subject of current injection in organic thin film transistors: physical principles concerning energy level (mis)alignment at interfaces, models describing charge injection, technologies for interface tuning, and techniques for characterizing devices. Finally, a survey of the most recent accomplishments in the field is given. Principles are described in general, but the technologies and survey emphasis is on solution processed transistors, because it is our opinion that scalable, roll‐to‐roll printing processing is one, if not the brightest, possible scenario for the future of organic electronics. With the exception of electrolyte‐gated organic transistors, where impressively low width normalized resistances were reported (in the range of 10 Ω·cm), to date the lowest values reported for devices where the semiconductor is solution‐processed and where the most common architectures are adopted, are ～10 kΩ·cm for transistors with a field effect mobility in the 0.1–1 cm²/Vs range. Although these values represent the best case, they still pose a severe limitation for downscaling the channel lengths below a few micrometers, necessary for increasing the device switching speed. Moreover, techniques to lower contact resistances have been often developed on a case‐by‐case basis, depending on the materials, architecture and processing techniques. The lack of a standard strategy has hampered the progress of the field for a long time. Only recently, as the understanding of the rather complex physical processes at the metal/semiconductor interfaces has improved, more general approaches, with a validity that extends to several materials, are being proposed and successfully tested in the literature. Only a combined scientific and technological effort, on the one side to fully understand contact phenomena and on the other to completely master the tailoring of interfaces, will enable the development of advanced organic electronics applications and their widespread adoption in low‐cost, large‐area printed circuits.     

Organic Light‐Emitting Transistors: Materials,Device Configurations,and Operations

Organic light‐emitting transistors (OLETs) represent an emerging class of organic optoelectronic devices, wherein the electrical switching capability of organic field‐effect transistors (OFETs) and the light‐generation capability of organic light‐emitting diodes (OLEDs) are inherently incorporated in a single device. In contrast to conventional OFETs and OLEDs, the planar device geometry and the versatile multifunctional nature of OLETs not only endow them with numerous technological opportunities in the frontier fields of highly integrated organic electronics, but also render them ideal scientific scaffolds to address the fundamental physical events of organic semiconductors and devices. This review article summarizes the recent advancements on OLETs in light of materials, device configurations, operation conditions, etc. Diverse state‐of‐the‐art protocols, including bulk heterojunction, layered heterojunction and laterally arranged heterojunction structures, as well as asymmetric source‐drain electrodes, and innovative dielectric layers, which have been developed for the construction of qualified OLETs and for shedding new and deep light on the working principles of OLETs, are highlighted by addressing representative paradigms. This review intends to provide readers with a deeper understanding of the design of future OLETs.     

Device Physics of Solution‐Processed Organic Field‐Effect Transistors

Field‐effect transistors based on solution‐processible organic semiconductors have experienced impressive improvements in both performance and reliability in recent years, and printing‐based manufacturing processes for integrated transistor circuits are being developed to realize low‐cost, large‐area electronic products on flexible substrates. This article reviews the materials, charge‐transport, and device physics of solution‐processed organic field‐effect transistors, focusing in particular on the physics of the active semiconductor/dielectric interface. Issues such as the relationship between microstructure and charge transport, the critical role of the gate dielectric, the influence of polaronic relaxation and disorder effects on charge transport, charge‐injection mechanisms, and the current understanding of mechanisms for charge trapping are reviewed. Many interesting questions on how the molecular and electronic structures and the presence of defects at organic/organic heterointerfaces influence the device performance and stability remain to be explored.