Woosun Jang

Understanding the advantage of hexagonal WO3 as an efficient photoanode for solar water splitting: a first-principles perspective

Polycrystalline WO3 has been suggested as an alternative photoanode material for the water splitting reaction. However, the band gap and band edge positions of the most commonly used γ-monoclinic WO3 phase are found to be not optimal for effective water oxidation. In this work, by using first-principles density-functional theory calculations with an ab initio thermodynamic model, we demonstrate the potential advantage of using h-WO3 (and its surfaces) over the larger band gap γ-WO3 phase for the anode in water splitting. Notably, after addressing the relative thermodynamic stability of the various h-WO3 surfaces, we carefully quantify and compare the electronic band structure of these two bulk phases of WO3 (using their valence and conduction band edges as descriptors). We then provide a simple perspective as to illustrate how the surface band edges of h-WO3 match up with the redox potential of water and other possible cathode materials.

One-Step Solution Phase Growth of Transition Metal Dichalcogenide Thin Films Directly on Solid Substrates

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 precursors 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.

Remarkably low-energy one-dimensional fault line defects in single-layered phosphorene.

Systematic engineering of atomic-scale low-dimensional defects in two-dimensional nanomaterials is a promising method 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 their physio-chemical properties is pivotal for 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 have investigated the temperature-dependent energetics and electronic structure of 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.

Control over Electron–Phonon Interaction by Dirac Plasmon Engineering in the Bi2Se3 Topological Insulator

Understanding the mutual interaction between electronic excitations and lattice vibrations is key for understanding electronic transport and optoelectronic phenomena. Dynamic manipulation of such interaction is elusive because it requires varying the material composition on the atomic level. In turn, recent studies on topological insulators (TIs) have revealed the coexistence of a strong phonon resonance and topologically protected Dirac plasmon, both in the terahertz (THz) frequency range. Here, using these intrinsic characteristics of TIs, we demonstrate a new methodology for controlling electron-phonon interaction by lithographically engineered Dirac surface plasmons in the Bi2Se3 TI. Through a series of time-domain and time-resolved ultrafast THz measurements, we show that, when the Dirac plasmon energy is less than the TI phonon energy, the electron-phonon coupling is trivial, exhibiting phonon broadening associated with Landau damping. In contrast, when the Dirac plasmon energy exceeds that of the phonon resonance, we observe suppressed electron-phonon interaction leading to unexpected phonon stiffening. Time-dependent analysis of the Dirac plasmon behavior, phonon broadening, and phonon stiffening reveals a transition between the distinct dynamics corresponding to the two regimes as the Dirac plasmon resonance moves across the TI phonon resonance, which demonstrates the capability of Dirac plasmon control. Our results suggest that the engineering of Dirac plasmons provides a new alternative for controlling the dynamic interaction between Dirac carriers and phonons.

Origin of Prestress-Driven Optical Modulations of Flexible ZnO Thin Films Processed in Stretching Mode

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.

Erratum: A rational computational study of surface defect-mediated stabilization of low-dimensional Pt nanostructures on TiN(100) (Physical Chemistry Chemical Physics (2015) 17 (9680-9686))

Fig. 2 Average binding energy of Pt for 71 different Pt nanostructures on the TiN(100) surface with different concentrations of surface N or Ti vacancies (xv), which refers to the number of vacancies per possible vacancy sites. (a) The average binding energy per Pt atom, as calculated according to eqn (1), versus Pt surface coverage (Y) for up to 3 adlayers (36 Pt atoms) of Pt on the clean TiN(100) surface. Light, medium, and dark blue colors indicate one, two, and three atomic-layer thickness of the Pt nanostructures, respectively. (b) The surface vacancy formation energies of surface N and Ti vacancies on TiN(100), as calculated using eqn (2). (c) The average binding energy per Pt atom versus surface vacancy concentration at TiN(100) for the Pt/TiN nanostructures (as shown in Fig. 1a). The gray filled circle represents the binding energy of a nano-layer of Pt on the defect-free TiN(100) surface. Orange and blue symbols distinguish the considered N-lean and N-rich conditions, respectively. Open circles denote a Pt nano-layer on TiN(100) with surface N vacancies, and open squares for those with surface Ti vacancies. Filled red triangles show the single Pt atom results from ref. 16 for comparison: the upright red triangle represents that of a single Pt atom adsorbed as a substitutional atom at an surface N vacancy ( 1.11 eV), and the inverse red triangle for that at a surface Ti vacancy site (2.33 eV) under N-lean conditions. All possible surface vacancy configurations within our p(3 3) surface supercell are considered in this figure.