Solution Processed Metal Oxide High‐κ Dielectrics for Emerging Transistors and Circuits

The electronic functionalities of metal oxides comprise conductors, semiconductors, and insulators. Metal oxides have attracted great interest for construction of large‐area electronics, particularly thin‐film transistors (TFTs), for their high optical transparency, excellent chemical and thermal stability, and mechanical tolerance. High‐permittivity (κ) oxide dielectrics are a key component for achieving low‐voltage and high‐performance TFTs. With the expanding integration of complementary metal oxide semiconductor transistors, the replacement of SiO₂ with high‐κ oxide dielectrics has become urgently required, because their provided thicker layers suppress quantum mechanical tunneling. Toward low‐cost devices, tremendous efforts have been devoted to vacuum‐free, solution processable fabrication, such as spin coating, spray pyrolysis, and printing techniques. This review focuses on recent progress in solution processed high‐κ oxide dielectrics and their applications to emerging TFTs. First, the history, basics, theories, and leakage current mechanisms of high‐κ oxide dielectrics are presented, and the underlying mechanism for mobility enhancement over conventional SiO₂ is outlined. Recent achievements of solution‐processed high‐κ oxide materials and their applications in TFTs are summarized and traditional coating methods and emerging printing techniques are introduced. Finally, low temperature approaches, e.g., ecofriendly water‐induced, self‐combustion reaction, and energy‐assisted post treatments, for the realization of flexible electronics and circuits are discussed.     

Thin‐Film Transistors

Thin‐film transistors (TFTs) matured later than silicon integrated circuits, but in the past 15 years the technology has grown into a huge industry based on display applications, with amorphous and polycrystalline silicon as the incumbent technology. Recently, an intense search has developed for new materials and new fabrication techniques that can improve the performance, lower manufacturing cost, and enable new functionality. There are now many new options – organic semiconductor (OSCs), metal oxides, nanowires, printing technology as well as thin‐film silicon materials with new properties. All of the new materials have something to offer but none is entirely without technical problems.     

Corrugated Heterojunction Metal‐Oxide Thin‐Film Transistors with High Electron Mobility via Vertical Interface Manipulation

A new strategy is reported to achieve high‐mobility, low‐off‐current, and operationally stable solution‐processable metal‐oxide thin‐film transistors (TFTs) using a corrugated heterojunction channel structure. The corrugated heterojunction channel, having alternating thin‐indium‐tin‐zinc‐oxide (ITZO)/indium‐gallium‐zinc‐oxide (IGZO) and thick‐ITZO/IGZO film regions, enables the accumulated electron concentration to be tuned in the TFT off‐ and on‐states via charge modulation at the vertical regions of the heterojunction. The ITZO/IGZO TFTs with optimized corrugated structure exhibit a maximum field‐effect mobility >50 cm² V^?1 s^?1 with an on/off current ratio of >10⁸ and good operational stability (threshold voltage shift <1 V for a positive‐gate‐bias stress of 10 ks, without passivation). To exploit the underlying conduction mechanism of the corrugated heterojunction TFTs, a physical model is implemented by using a variety of chemical, structural, and electrical characterization tools and Technology Computer‐Aided Design simulations. The physical model reveals that efficient charge manipulation is possible via the corrugated structure, by inducing an extremely high carrier concentration at the nanoscale vertical channel regions, enabling low off‐currents and high on‐currents depending on the applied gate bias.     

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.     

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.