K. Dileep

Probing optical band gaps at the nanoscale in NiFe2O4 and CoFe2O4 epitaxial films by high resolution electron energy loss spectroscopy

Nanoscale optical band gap variations in epitaxial thin films of two different spinel ferrites, i.e., NiFe2O4 (NFO) and CoFe2O4 (CFO), have been investigated by spatially resolved high resolution electron energy loss spectroscopy. Experimentally, both NFO and CFO show indirect/direct band gaps around 1.52 eV/2.74 and 2.3 eV, and 1.3 eV/2.31 eV, respectively, for the ideal inverse spinel configuration with considerable standard deviation in the band gap values for CFO due to various levels of deviation from the ideal inverse spinel structure. Direct probing of the regions in both the systems with tetrahedral A site cation vacancy, which is distinct from the ideal inverse spinel configuration, shows significantly smaller band gap values. The experimental results are supported by the density functional theory based modified Becke-Johnson exchange correlation potential calculated band gap values for the different cation configurations.

Electron energy loss spectroscopy of ZnO nanocrystals with different oxygen vacancy concentrations

ZnO nanocrystals with different oxygen vacancy concentrations were characterized by high-resolution electron energy loss spectroscopy (HREELS). ZnO nanocrystals show a decrease in green emission with increasing annealing temperature in an oxygen environment and which significantly quenches in a sample annealed at 400 °C. O K and Zn L3 pre-edge absorption structures of ZnO nanocrystals were studied by HREELS as a function of annealing temperature. Absorption edge peak broadening and variation in pre-edge absorption edge structure of Zn L3 were observed in experimental electron energy loss spectroscopy spectra with different oxygen defect concentrations. All electron density functional theory (DFT) based (WIEN2k) calculation of electronic density of states and electron energy loss near edge structure were carried out with different oxygen vacancy concentrations and compared with experimental observations. Appearance of additional peaks in pre-edge electron energy loss structure with increasing oxygen vacanc...

Pd-Pt alloys nanowires as support-less electrocatalyst with high synergistic enhancement in efficiency for methanol oxidation in acidic medium.

In a facile approach, Pd73Pt27 alloy nanowires (NWs) with large aspect ratios were synthesized in high yield by using sacrificial templates. Unlike majority of processes, our synthesis was carried out in aqueous solution with no intermittent separating stages for the products, while maintaining the NW morphology up to ∼30% of Pt. Upon evaporation of their dispersion, the NWs transform into a stable porous membrane due to self-entanglement and can be directly lifted and employed for electrocatalytic applications without external catalyst supports. We show that the NW membranes exhibit efficient electrocatalytic performance for methanol oxidation reaction (MOR) with 10 times higher mass activity and 4.4 times higher specific activity in acidic media as compared to commercial Pt catalysts. The membrane electrocatalysts is robust and exhibited very good stability with retention of ∼70% mass-activity after 4000 potential cycles. Since Pd was found to be inert towards MOR in acidic medium, our investigation provides a direct estimate of synergistic enhancement of efficiency. Over 10 times increment of mass activity appears to be significantly higher than previous investigations in various other reaction media.

Layer specific optical band gap measurement at nanoscale in MoS2 and ReS2 van der Waals compounds by high resolution electron energy loss spectroscopy

Layer specific direct measurement of optical band gaps of two important van der Waals compounds, MoS2 and ReS2, is performed at nanoscale by high resolution electron energy loss spectroscopy. For monolayer MoS2, the twin excitons (1.8 and 1.95 eV) originating at the K point of the Brillouin zone are observed. An indirect band gap of 1.27 eV is obtained from the multilayer regions. Indirect to direct band gap crossover is observed which is consistent with the previously reported strong photoluminescence from the monolayer MoS2. For ReS2, the band gap is direct, and a value of 1.52 and 1.42 eV is obtained for the monolayer and multilayer, respectively. The energy loss function is dominated by features due to high density of states at both the valence and conduction band edges, and the difference in analyzing band gap with respect to ZnO is highlighted. Crystalline 1T ReS2 forms two dimensional chains like superstructure due to the clustering between four Re atoms. The results demonstrate the power of HREELS...

Native defects affecting the Li atom distribution tune the optical emission of ZnO:Li epitaxial thin film

It is found that the oxygen vacancy (VO) defect concentration affecting the separation between individual species in LiZn-Lii complex influences the optical emission property of Li0.06Zn0.94O epitaxial thin film grown by pulsed laser deposition. The film grown under low oxygen partial pressure (n-type conductivity)/higher partial pressure (resistive-type) has broad emission at ∼2.99 eV/∼2.1 eV and a narrower emission at 3.63 eV/3.56 eV, respectively. First principle based mBJLDA electronic structure calculation suggests that the emission at 2.99 eV is due to the LiZn-Lii pair complex and the emission at 2.1 eV is when the component species are away from each other.

Robust room temperature ferromagnetism in epitaxial CoO thin film

Co vacancy (VCo) induced robust room temperature ferromagnetism (Ms ∼ 60 emu/cm3 and coercivity ∼ 603 Oe) is experimentally realized in rock-salt CoO epitaxial thin film (∼110 nm) grown by pulsed laser deposition. Co charge state is found to be higher ∼+3.2 (from Co L3/L2 white line ratio) and this is due to the VCo induced charge transfer from the neighboring Co-3d to O-2p states in order to compensate for the hole formation. O-K and cathodoluminescence spectra corroborate the existence of VCo and higher charge state. Temperature dependent magnetization and exchange bias experiments confirm the coexistence of ferromagnetic and antiferromagnetic phases.