Self-Aligned Ionic Doping of TiO2 Thin-Film Transistors for Enhanced Current Drivability via Postfabrication Superacid Treatment.

Oxide semiconductor thin-film transistors (TFTs) have shown great potential in emerging applications such as flexible displays, radio-frequency identification tags, sensors, and back-end-of-line compatible transistors for monolithic 3D integration beyond their well-established flat-plane display technology. To meet the requirements of these appealing applications, high current drivability is essential, necessitating exploration in materials science and device engineering. In this work, we report for the first time on a simple solution-based superacid (SA) treatment to enhance the current drivability of top-gate TiO2 TFTs with a gate-offset structure. The on-current of these transistors is limited by the relatively low mobility of TiO2 due to its d-orbital conduction nature. It is found that the on-current of TiO2 TFTs is nearly doubled via a quick dip in a SA solution at room temperature in ambient air. A series of experiments, including comparative I-V measurements of TFTs with different treatments and gate structures, C-V measurements, X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, and device simulation, were performed to uncover the underlying reason for the current enhancement. It is believed that the protons (H+) from SA are doped into the offset region of TiO2 TFTs, forming an electron double layer and thus boosting the on-current, with the top gate serving as a self-aligned mask for ionic doping. Furthermore, the ionic size and the proportion of the offset region to the channel play crucial roles in the effectiveness of ionic doping, while the position of the incorporated ions, whether in the channel or dielectric, may result in distinct shifts in the turn-on voltage (VON) and affect the functionality of ionic doping. This study provides a pathway for enhancing the current drivability of TiO2 TFTs via selective ionic doping enabled by SA treatment and deepens our understanding of ion incorporation in electronic devices. This approach could be applicable to other material systems and may also benefit TFTs with miniaturized dimensions, thus opening up unprecedented opportunities for TiO2 TFTs in future applications requiring high current drivability.

High pressure nanoarchitectonics and metallization of barium chloride and barium bromide.

As one of the most prototypicalAX2-type compounds, barium halide shared the cubic structure withFm-3msymmetry for BaCl2or orthorhombic structure withPnmasymmetry for BaBr2at ambient pressure. In this work, we explored the crystal structures of BaCl2and BaBr2under high pressure. We predicted a thermodynamically more favored structure with orthorhombicCmcmsymmetry for both BaCl2and BaBr2, at 74 and 47 GPa, respectively. Our simulations reveal that the metallic feature ofCmcmBaCl2andCmcmBaBr2under high pressure. The present results improve the understanding of high-pressure structures ofAX2compounds at extremely high-pressure conditions.

High-Pressure Structures and Superconductivity of Barium Iodide.

Generally, pressure is a useful tool to modify the behavior of physical properties of materials due to the change in distance between atoms or molecules in the lattice. Barium iodide (BaI2), as one of the simplest and most prototypical iodine compounds, has substantial high pressure investigation value. In this work, we explored the crystal structures of BaI2 at a wide pressure range of 0-200 GPa using a global structure search methodology. A thermodynamical structure with tetragonal I4/mmm symmetry of BaI2 was predicted to be stable at 17.1 GPa. Further electronic calculations indicated that I4/mmm BaI2 exhibits the metallic feature via an indirect band gap closure under moderate pressure. We also found that the superconductivity of BaI2 at 30 GPa is much lower than that of CsI at 180 GPa based on our electron-phonon coupling simulations. Our current simulations provide a step toward the further understanding of the high-pressure behavior of iodine compounds at extreme conditions.

Globally stable structures of LixZn (x = 1-4) compounds at high pressures.

Pressure can change the properties of atoms and bonding patterns, leading to the synthesis of novel compounds with interesting properties. The intermetallic lithium-zinc (Li-Zn) compounds have attracted increasing attention because of their fascinating mechanical properties and widespread applications in rechargeable Li-ion batteries. Using the effective CALYPSO searching method in combination with first-principles calculations, we theoretically investigated the LixZn (x = 1-4) compounds at pressures of 0 to 100 GPa. We found several stable structures with a variety of stoichiometries and the phase diagram on the Li-rich side under high pressure. The electronic structures of these compounds reveal transferred charges from lithium to zinc mainly fill Zn 4p states and compounds with negatively charged Zn atoms are dramatic. We also calculated the elastic constants to discuss their mechanical properties. Our results enrich the crystal structures of the Li-Zn system and provide a further understanding of structural features and their properties.

Hypervalent Iodine with Linear Chain at High Pressure.

Iodine is an element of fascinating chemical complexity, and numerous hypervalent iodine compounds reveal vital value of applications in organic synthesis. Investigation of the synthesis and application of new type of hypervalent iodine compound has extremely significant meaning. Here, the formation of CsIn (n > 1) compounds is predicted up to 200 GPa using an effective algorithm. The current results show that CsI3 with space group of Pm-3n is thermodynamically stable under high pressure. Hypervalence phenomenon of iodine atoms in Pm-3n CsI3 with endless linear chain type structure appears under high pressure, which is in sharp contrast to the conventional understanding. Our study further reveals that Pm-3n CsI3 is a metallic phase with several energy bands crossing Fermi-surface, and the pressure creates a peculiar reverse electron donation from iodine to cesium. The electron-phonon coupling calculations have proposed superconductive potential of the metallic Pm-3n CsI3 at 10 GPa which is much lower than that of CsI (180 GPa). Our findings represent a significant step toward the understanding of the behavior of iodine compounds at extreme conditions.

High-pressure phase transition of cesium chloride and cesium bromide.

The high-symmetry cubic cesium chloride (CsCl) structure with a space group of Pm3¯m (Z = 1) is one of the prototypical AB-type compounds, which is shared with cesium halides and many binary metallic alloys. The study of high-pressure evolution of the CsCl phase is of fundamental importance in helping to understand the structural sequence and principles of crystallography. Here, we have systematically investigated the high-pressure structural transition of cesium halides up to 200 GPa using an effective CALYPSO algorithm. Strikingly, we have predicted several thermodynamically favored high-pressure phases for cesium chloride and cesium bromide (CsBr). Further electronic calculations indicate that CsCl and CsBr become metallic via band-gap closure at strong compression. The current predictions have broad implications for other AB-type compounds that likely harbor similar novel high-pressure behavior.