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Resolving the complex interplay between surface and bulk response is a long-standing issue in the topological insulators (TIs). Some studies have reported surface-dominated metallic responses, yet ...

Nanocrystals of group 5 tetradymites M2X3 (where M = Bi and Sb, X = Se and Te) are of high technological relevance in modern topological nanoelectronics. However, there is a current lack of a systematic understanding to predict the preferred nanocrystal morphology in experiments where commonly-used equilibrium thermodynamic models appear to fail. In this work, using first-principles DFT calculations with a rationally-extended ab initio atomistic thermodynamics approach coupled to implicit solvation models and Gibbs-Wulff shape constructions, we demonstrate that this absence of predictive power stems from the limitation of equilibrium thermodynamics. By re-tracing and carefully addressing with a more realistic chemical potential definition, we illustrate this shortcoming can be overcome and afford a more rational route to size-engineer and shape-design highly-functional group 5 tetradymite nanoparticles for targeted applications.

The ternary chalcogenide, ZnIn2S4, is known to exhibit various polymorphic expressions: from the cubic spinel phase to various polytypic layered hexagonal structures, commonly known as α, β, IIa, a...

Conductive and stretchable electrodes that can be printed directly on a stretchable substrate have drawn extensive attention for wearable electronics and electronic skins. Printable inks that contain liquid metal are strong candidates for these applications, but the insulating oxide skin that forms around the liquid metal particles limits their conductivity. This study reveals that hydrogen doping introduced by ultrasonication in the presence of aliphatic polymers makes the oxide skin highly conductive and deformable. X-ray photoelectron spectroscopy and atom probe tomography confirmed the hydrogen doping, and first-principles calculations were used to rationalize the obtained conductivity. The printed circuit lines show a metallic conductivity (25,000 S cm–1), excellent electromechanical decoupling at a 500% uniaxial stretching, mechanical resistance to scratches and long-term stability in wide ranges of temperature and humidity. The self-passivation of the printed lines allows the direct printing of three-dimensional circuit lines and double-layer planar coils that are used as stretchable inductive strain sensors. Hydrogen doping and polymer adsorption at the oxide surface of liquid metal microparticles increase the conductivity and viscoplastic behaviour of the oxide, leading to liquid-metal-based printed circuits with stable resistance up to 500% strain.

Flexible semiconducting thin films have a broad coverage of future competitive electronic and optoelectronic devices. Although the stress present in thin films has been long known to affect optical...

Experimental verification of optical modulation with external stress has not been easily available in flexible systems. Here, we intentionally induced extra stress in wide band gap ZnO thin films by a unique prestress-driven deposition processing that utilizes a stretching mode. The stretching mode provides homogeneous but biaxial stresses in the hexagonal wurtzite structure, leading to the extension of the c-axis and the contraction of the a-axis. As a result, the reduction of the optical band gap by ∼150 meV was observed for the strain of ∼4.87%. The band gap narrowing was found to occur from the respective downward and upward shifts of the conduction band minimum and valence band maximum under the applied stress. The experimental evidence of optical modulations was supported by the theoretical calculations using density functional theory. The reduced strong interactions between Zn d and O p orbitals were assumed to be responsible for the band gap narrowing.

The controlled synthesis of large-area, atomically thin molybdenum and tungsten ditelluride (MoTe2 and WTe2) crystals is crucial for their emerging applications based on the attractive electronic properties. However, the solution phase synthesis of high-quality and large-area MoTe2 or WTe2 ultrathin films have not been achieved yet. In this study, we synthesized for the first time, large-area atomically thin MoTe2 and WTe2 films in solution phase, through rapid crystal formation directly on a conducting substrate. For the synthesis, we developed a new Te precursor. The crystal growth involves an in situ chemical transformation from Te nanoparticles into MoTe2 or WTe2 thin films. The synthesis enables precise control of the number of atomic layers over a large area, from a monolayer to multilayers. Micropatterned MoTe2 thin films are also readily synthesized in situ using the same process. The photodetector made of 3-layer semiconducting MoTe2 thin films exhibits high photoresponsivity (Rλ) over a broad sp...

Recently, a subclass of binary perovskite-structured metal trioxides, such as WO3 and MoO3, have been propounded for many key optoelectronic applications due to their proper band edge positions and appropriate band gap sizes. Unlike their superclass perovskites, the structure–property relationship for these binary metal trioxides is less apparent, given that they suffer from much larger structural deformities within the octahedra. In this work, by using first-principles density-functional theory calculations and atomistic scale models, we examine the internal and external distortions of WO3 and MoO3 polymorphs. We then compare our results with conventional polyhedral distortion descriptors and finally use a refined data set of different perovskite-structured oxides to establish and demonstrate how these binary metal trioxides operate with a different structure–property relationship from the conventional oxide perovskites.

Despite the ubiquitous nature of the Peltier effect in low-dimensional thermoelectric devices, the influence of finite temperature on the electronic structure and transport in the Dirac heterointerfaces of the few-layer graphene and layered tetradymite, Sb2Te3 (which coincidently have excellent thermoelectric properties) are not well understood. In this work, using the first-principles density-functional theory calculations, we investigate the detailed atomic and electronic structure of these Dirac heterointerfaces of graphene and Sb2Te3 and further re-examine the effect of finite temperature on the electronic band structures using a phenomenological temperature-broadening model based on Fermi–Dirac statistics. We then proceed to understand the underlying charge redistribution process in this Dirac heterointerfaces and through solving the Boltzmann transport equation, we present the theoretical evidence of electron–hole asymmetry in its electrical conductivity as a consequence of this charge redistributio...

Strain engineering has been extensively explored for tailoring the material properties and, in turn, improving the device performance of semiconducting thin films. In particular, the effects of strain on the optical properties of these films have attracted considerable research interest, but experimental demonstrations in flexible systems have rarely been reported. Here, we exploited the variable optical properties of flexible ZnS thin films by imposing a controllable external compressive stress during a stretching-driven deposition process. This stress induced crystal anisotropy with an increase in tetragonality, which differs from that of the unstrained cubic ZnS thin films. The refractive index of the films was estimated by means of an envelope method using interference fringes. As a result, the reductions in the refractive index and optical band gap were observed by applying the stretching-driven strains with the resultant compressive stress. The modulated refractive index and its dispersion behavior were further investigated by employing a single-oscillator model to drive subsequent correlative parameters such as dispersion energy, oscillating strength, and high-frequency permittivity. As a proof of concept, an optical lens of ZnS was designed to confirm the effect of in situ stress-mediated optical modulation by detecting the variable focal length with stress.

In an attempt to promote energy saving through the clever control of varying amounts of visible light and solar energy in modern buildings, there has been a surge of interest in the novel design of multifunctional glass windows otherwise known as “smart windows”. The use of chromogenic materials (e.g., tungsten oxides and their alloys) is widespread in this cooling energy technology, and for the case of hexagonal tungsten oxide (h-WO3)-based systems, the overall efficiency is often hindered by the lack of a systematic and fundamental understanding of the interplay of intrinsic charge transfer between the alkali-metal ions and the host h-WO3. In this work, we present a first-principles hybrid density-functional theory investigation of bulk hexagonal tungsten bronzes (i.e., alkali-metal-intercalated h-WO3) and examine the influence of the intercalation chemistry on their thermodynamic stability as well as optoelectronic properties. We find that the introduction of the alkali-metal ion induces a persistent n...

Wetting of the liquid metal on the solid electrolyte of a liquid metal battery controls the operating temperature and performance of the battery. Liquid sodium electrodes are particularly attractive because of their low cost, natural abundance, and geological distribution. However, they wet poorly on a solid electrolyte near its melting temperature, limiting their widespread suitability for low-temperature batteries to be used for large-scale energy storage systems. Herein, we develop an isolated metal-island strategy that can improve sodium wetting in sodium-beta alumina batteries that allows operation at lower temperatures. Our results suggest that in situ heat treatment of a solid electrolyte followed by bismuth deposition effectively eliminates oxygen and moisture from the surface of the solid electrolyte, preventing the formation of an oxide layer on the liquid sodium, leading to enhanced wetting. We also show that employing isolated bismuth islands significantly improves cell performance, with cells retaining 94% of their charge after the initial cycle, an improvement over cells without bismuth islands. These results suggest that coating isolated metal islands is a promising and straightforward strategy for the development of low-temperature sodium-β alumina batteries.

Many different forms of mechanical and structural deformations have been employed to alter the electronic structure of various modern two-dimensional (2D) nanomaterials. Given the recent interest in the new class of 2D nanomaterials - phosphorene, here we investigate how the rotational strain-dependent electronic properties of low-dimensional phosphorene may be exploited for technological gain. Here, using first-principles density-functional theory, we investigate the mechanical stability of twisted one-dimensional phosphorene nanoribbons (TPNR) by measuring their critical twist angle (θc) and shear modulus as a function of the applied mechanical torque. We find a strong anisotropic, chirality-dependent mechano-electronic response in the hydrogen-passivated TPNRs upon vortical deformation, resulting in a striking difference in the change in the carrier effective mass as a function of torque angle (and thus, the corresponding change in carrier mobility) between the zigzag and armchair directions in these TPNRs. The accompanied tunable band-gap energies for the hydrogen-passivated zigzag TPNRs may then be exploited for various key opto-electronic nanodevices.

We present the photoinduced terahertz responses of topological insulators Bi2Se3. The photoconductance sign is determined by the competition between the topological surface state and the bulk response in n-type, p-type and bulk-insulating Bi 2 Se 3 .

Systematic engineering of atomic-scale low-dimensional defects in two-dimensional nanomaterials is a promising way to modulate the electronic properties of these nanomaterials. Defects at interfaces such as grain boundaries and line defects can often be detrimental to technologically important nanodevice operations and thus a fundamental understanding of how such one-dimensional defects may have an influence on its physio-chemical properties is pivotal to optimizing their device performance. Of late, two-dimensional phosphorene has attracted much attention due to its high carrier mobility and good mechanical flexibility. In this study, using density-functional theory, we investigate the temperature-dependent energetics and electronic structure of a single-layered phosphorene with various fault line defects. We have generated different line defect models based on a fault method, rather than the conventional rotation method. This has allowed us to study and identify new low-energy line defects, and we show how these low-energy line defects could well modulate the electronic band gap energies of single-layered two-dimensional phosphorene -- offering a range of metallic to semiconducting properties in these newly proposed low-energy line defects in phosphorene., 16 pages, 7 figures (including TOC), Accepted in Nanoscale (RSC)

Platinum is known as a catalyst with exceptional reactivity for many important reactions, e.g. the oxygen reduction reaction. To reduce the high cost of pure platinum catalysts, platinum on a carbon support is widely used in industrial fuel cell applications. However, these Pt/C systems suffer from poor stability. As a cost-efficient and more durable alternative, Pt single-atom catalysts on a TiN support have recently been suggested, and it has been shown that the single-atom catalysts are stable when anchored at a nitrogen vacancy site on the TiN surface in a nitrogen-lean environment. To further explore the perspective of Pt/TiN catalytic systems, we provide insights into the stability and morphology of Pt nanostructures at the TiN(100) surface, using a density-functional theory approach in combination with ab initio atomistic thermodynamics. Our results show that the formation of two-dimensional Pt nano-layers is preferred over the formation of three-dimensional Pt nano-clusters on the TiN substrate. Similar to the single-atom catalysts, nano-layers of Pt can be stabilized on the TiN(100) surface by surface nitrogen vacancies under nitrogen-lean conditions. By analyzing the electronic metal–support interaction (EMSI) between the Pt nano-layer and the TiN surface with surface defects, we demonstrate that a strong EMSI between the surrounding Ti and Pt atoms is important for stabilizing the catalyst nano-layer at the TiN surface, and that N vacancies lead to stronger Pt–Ti interaction. This work provides a rational computational platform for the design of new generation high-performance Pt-based fuel cells.

Ultrathin transition metal dichalcogenides (TMDs) have exotic electronic properties. With success in easy synthesis of high quality TMD thin films, the potential applications will become more viable in electronics, optics, energy storage, and catalysis. Synthesis of TMD thin films has been mostly performed in vacuum or by thermolysis. So far, there is no solution phase synthesis to produce large-area thin films directly on target substrates. Here, this paper reports a one-step quick synthesis (within 45–90 s) of TMD thin films (MoS2, WS2, MoSe2, WSe2, etc.) on solid substrates by using microwave irradiation on a precursor-containing electrolyte solution. The numbers of the quintuple layers of the TMD thin films are precisely controllable by varying the precursor's concentration in the electrolyte solution. A photodetector made of MoS2 thin film comprising of small size grains shows near-IR absorption, supported by the first principle calculation, exhibits a high photoresponsivity (>300 mA W−1) and a fast response (124 µs). This study paves a robust way for the synthesis of various TMD thin films in solution phases.

Correction for ‘A rational computational study of surface defect-mediated stabilization of low-dimensional Pt nanostructures on TiN(100)’ by Young Joo Tak et al., Phys. Chem. Chem. Phys., 2015, 17, 9680–9686.