Gulin Vardar

Growth, disorder, and physical properties of ZnSnN2

We examine ZnSnN2, a member of the class of materials contemporarily termed “earth-abundant element semiconductors,” with an emphasis on evaluating its suitability for photovoltaic applications. It is predicted to crystallize in an orthorhombic lattice with an energy gap of 2 eV. Instead, using molecular beam epitaxy to deposit high-purity, single crystal as well as highly textured polycrystalline thin films, only a monoclinic structure is observed experimentally. Far from being detrimental, we demonstrate that the cation sublattice disorder which inhibits the orthorhombic lattice has a profound effect on the energy gap, obviating the need for alloying to match the solar spectrum.

Mechanisms of droplet formation and Bi incorporation during molecular beam epitaxy of GaAsBi

We have examined the mechanisms of droplet formation and Bi incorporation during molecular beam epitaxy of GaAsBi. We consider the role of the transition from group-V-rich to group-III-rich conditions, i.e., the stoichiometry threshold, in the presence of Bi. For As-rich GaAsBi growth, Bi acts as a surfactant, leading to the formation of droplet-free GaAsBi films. For films within 10% of the stoichiometric GaAsBi growth regime, surface Ga droplets are observed. However, for Ga-rich GaAsBi growth, Bi acts as an anti-surfactant, inducing Ga-Bi droplet formation. We propose a growth mechanism based upon the growth-rate-dependence of the stoichiometry threshold for GaAsBi.

Electrochemistry of Magnesium Electrolytes in Ionic Liquids for Secondary Batteries

The electrochemistry of Mg salts in room-temperature ionic liquids (ILs) was studied using plating/stripping voltammetry to assess the viability of IL solvents for applications in secondary Mg batteries. Borohydride (BH4(-)), trifluoromethanesulfonate (TfO(-)), and bis(trifluoromethanesulfonyl)imide (Tf2N(-)) salts of Mg were investigated. Three ILs were considered: l-n-butyl-3-methylimidazolium (BMIM)-Tf2N, N-methyl-N-propylpiperidinium (PP13)-Tf2N, and N,N-diethyl-N-methyl(2-methoxyethyl)ammonium (DEME(+)) tetrafluoroborate (BF4(-)). Salts and ILs were combined to produce binary solutions in which the anions were structurally similar or identical, if possible. Contrary to some prior reports, no salt/IL combination appeared to facilitate reversible Mg plating. In solutions containing BMIM(+), oxidative activity near 0.8 V vs Mg/Mg(2+) is likely associated with the BMIM cation, rather than Mg stripping. The absence of voltammetric signatures of Mg plating from ILs with Tf2N(-) and BF4(-) suggests that strong Mg/anion Coulombic attraction inhibits electrodeposition. Cosolvent additions to Mg(Tf2N)2/PP13-Tf2N were explored but did not result in enhanced plating/stripping activity. The results highlight the need for IL solvents or cosolvent systems that promote Mg(2+) dissociation.

A robust and active hybrid catalyst for facile oxygen reduction in solid oxide fuel cells

The sluggish oxygen reduction reaction (ORR) greatly reduces the energy efficiency of solid oxide fuel cells (SOFCs). Here we report our findings in dramatically enhancing the ORR kinetics and durability of the state-of-the-art La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) cathode using a hybrid catalyst coating composed of a conformal PrNi0.5Mn0.5O3 (PNM) thin film with exsoluted PrOx nanoparticles. At 750 °C, the hybrid catalyst-coated LSCF cathode shows a polarization resistance of ∼0.022 Ω cm2, about 1/6 of that for a bare LSCF cathode (∼0.134 Ω cm2). Further, anode-supported cells with the hybrid catalyst-coated LSCF cathode demonstrate remarkable peak power densities (∼1.21 W cm−2) while maintaining excellent durability (0.7 V for ∼500 h). Near Ambient X-ray Photoelectron Spectroscopy (XPS) and Near Edge X-Ray Absorption Fine Structure (NEXAFS) analyses, together with density functional theory (DFT) calculations, indicate that the oxygen-vacancy-rich surfaces of the PrOx nanoparticles greatly accelerate the rate of electron transfer in the ORR whereas the thin PNM film facilitates rapid oxide-ion transport while drastically enhancing the surface stability of the LSCF electrode.

Spin lifetime measurements in GaAsBi thin films

Photoluminescence spectroscopy and Hanle effect measurements are used to investigate carrier spin dephasing and recombination times in the semiconductor alloy GaAsBi as a function of temperature and excitation energy. Hanle effect measurements reveal the product of g-factor and effective spin dephasing time (gTs) ranges from 0.8 ns at 40 K to 0.1 ns at 120 K. The temperature dependence of gTs provides evidence for a thermally activated effect, which is attributed to hole localization at single Bi or Bi cluster sites below 40 K.

Identifying the dominant interstitial complex in dilute GaAsN alloys

Significant composition-dependent incorporation of N into non-substitutional sites is often reported for dilute GaAsN alloys. To distinguish (N-N)As, (N-As)As, and (AsGa-NAs) complexes, we compare Rutherford backscattering spectrometry and nuclear reaction analysis (NRA) spectra with Monte Carlo-Molecular Dynamics simulations along the [100], [110], and [111] directions. For the Monte Carlo simulation, we assume that (N-N)As is aligned along the [111] direction, while (N-As)As is aligned along the [010] direction. The measured channeling NRA spectra exhibit the highest (lowest) yield in the [111] ([100]) directions. Similar trends are observed for simulations of (N-As)As, suggesting that (N-As)As is the dominant interstitial complex in dilute GaAsN.