Faculty Publications
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Item Third-order nonlinear optical properties of Mn doped ZnO thin films under cw laser illumination(Elsevier B.V., 2013) Nagaraja, K.K.; Pramodini, S.; Santhosh Kumar, A.; Nagaraja, H.S.; Poornesh, P.; Kekuda, D.We report the measurements of third-order nonlinear optical properties of undoped zinc oxide and manganese doped zinc oxide thin films with different doping concentrations investigated using z-scan technique. Thin films were prepared by radio frequency magnetron sputtering using a compound target on glass substrate at room temperature. The structural properties of the deposited films were analysed by X-ray diffraction studies. The atomic force microscope analysis of the deposited films reveals that the grain size and roughness of the films depend on the Mn concentration. The direct energy band gap of the deposited film increases with the increase in Mn concentration in the films. The nonlinear optical measurements were carried out using a cw He-Ne laser at 633 nm wavelength. The z-scan results reveal that the films exhibit self-defocusing nonlinearity. The third-order nonlinear optical susceptibility ?(3) is found to be of the order of 10-3 esu. The films investigated here exhibit good optical power limiting at the experimental wavelength. © 2012 Elsevier B.V. All rights reserved.Item Effect of annealing on the structural and nonlinear optical properties of ZnO thin films under cw regime(2013) Nagaraja, K.K.; Pramodini, S.; Poornesh, P.; Nagaraja, H.S.We report on the studies of the effects of annealing on the structural and third-order nonlinear optical properties of ZnO thin films deposited on quartz substrates by the RF magnetron sputtering technique. The films were annealed in the temperature range 400-1000 °C. The third-order nonlinear optical studies were carried out using the z-scan technique under continuous wave (cw) He-Ne laser irradiation at 633 nm wavelength. The effects of annealing on the structural properties were examined using x-ray diffraction and atomic force microscopy (AFM). The (0 0 2) preferred orientation increased with increase in annealing temperature up to 800 °C. The crystalline phases of SiO2 were observed at higher annealing temperatures. The appearance of an extraneous phase was confirmed by AFM images and optical transmittance spectra. The samples exhibited nonlinear absorption and nonlinear refraction under the experimental conditions. The negative sign of the nonlinear refractive index n2 indicated that the films exhibit self-defocusing property due to thermal nonlinearity. The nonlinear refractive index n2, the nonlinear absorption coefficient ?eff and the third-order optical susceptibility ?(3) were found to be of the highest orders. The estimated value of third-order optical susceptibility ?(3) was of the order of 10-3 esu. Multiple diffraction rings were observed when the samples were exposed to the laser beam. The appearance of rings was due to the refractive index change and thermal lensing. With increase in laser intensity, the variations of the self-diffraction ring patterns were studied experimentally. The films also exhibited strong optical limiting properties under cw laser excitation, and reverse saturable absorption was the dominant process leading to the observed nonlinear behaviour. © 2013 IOP Publishing Ltd.Item Effect of Sn doping on structural, optical, electrical and wettability properties of oriented ZnO nanorod arrays(2013) Santhosh Kumar, A.; Nagaraja, K.K.; Nagaraja, H.S.Herein we present a modified sol gel route for the one step fabrication of oriented ZnO nanorod arrays. The method is seed layer free, and nanorods directly attach to a substrate. We also present the effect of tin (Sn) content on the crystallinity, microstructural, optical and electrical properties of the ZnO nanorod arrays. Thermo gravimetric (TG) curves of gel precursors showed that most of the organic groups and other volatiles were removed at about 450 C. X-ray diffraction patterns confirmed that the films were polycrystalline in nature with (002) preferred orientation. The texture coefficient, grain size, dislocation density and lattice parameters of the ZnO arrays were determined. The SEM micrographs revealed that the undoped and 1 at.%Sn doped films were composed of nanorods and the concentration of 2 at.%Sn doping hindered the rod like structure growth and modulated into granular nature. UV-visible transmission spectroscopy indicated that the transparency of the films increased with Sn content. On Sn doping, the films also exhibited a red shift and slight shrinkage of band gap. The electrical studies revealed that 1 at.% of Sn doping enhanced electrical conduction in ZnO films and beyond that the distortion caused in the lattice reduced the conductivity. The contact angle of the ZnO nanostructures varied between 91 and 115 depending upon the Sn content. Therefore, 1 at.%Sn doping into ZnO nanorods improves the crystallinity, electrical conductivity and water contact angle. © 2013 Springer Science+Business Media New York.Item Influence of Sn doping on photoluminescence and photoelectrochemical properties of ZnO nanorod arrays(Kluwer Academic Publishers, 2014) Santhosh Kumar, A.S.; Huang, N.M.; Nagaraja, H.S.Herein, the nanostructured Sn containing ZnO is directly synthesized on the surface of substrate by modified sol gel approach under low-temperature condition. The samples are characterized by scanning electron microscopy (SEM), x-ray diffraction (XRD), Raman-scattering, photoluminescence (PL) and photoelectrochemical analyses. The SEM micrographs show that the undoped and 1 at. % Sn doped films are composed of nanorods and the concentration of 2 at. % Sn doping hinders the rod-like structure's growth and modulates into granular nature. The investigations of XRD reveal that the synthesized undoped and Sn doped ZnO nanorods possess a perfect hexagonal growth habit of wurtzite zinc oxide, along the (002) direction of preference. The Raman spectra demonstrate that the vibrational mode of E1(LO), which is very weak in undoped and 1at. % Sn doped ZnO, is strongly enhanced with 2 at. % Sn doping into ZnO lattice. PL spectra show that strong UV emission in pure and 1 at. % Sn doped ZnO, while there is dominant green emission in 2 at. % Sn doped ZnO. Moreover, all the samples are photo electrochemically active and exhibit the highest photocurrent of 28 ?A for the 1 at. % Sn doped ZnO nanorod arrays in 0.2M Na2SO4 electrolyte, on light irradiation. Time dependent photoresponse tests are carried out by measuring the photocurrent under chopped light irradiation. © 2014 The Korean Institute of Metals and Materials and Springer Science+Business Media Dordrecht.Item Solar exfoliated graphene and its application in supercapacitors and electrochemical H2O2 sensing(Elsevier Ltd, 2015) Moolayadukkam, M.; Huang, N.M.; Nagaraja, H.S.In the present study, graphene nanosheets are synthesized using sunlight irradiation focussed onto graphite oxide. The morphological characteristics of graphene are examined using Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). Raman spectroscopy and X-ray diffraction (XRD) are used for the structural characterization of the sample. The electrochemical performance is evaluated using cyclic voltammetry (CV), charge-discharge characteristics and impedance spectroscopy. A high specific capacitance value of 223 F g-1 is obtained using cyclic voltammetry. The electrochemical detection of H2O2, a common biological species using solar graphene is demonstrated. The impedance spectroscopy and CV are used to study the electrocatalytic activity of the material. High sensitivity of 64.79 ?A mM-1 cm-2 is reported. © 2015 Elsevier Ltd. All rights reserved.Item Effect of shape and magnetocrystalline anisotropies in ordered Co nanorod arrays with smaller diameter(Elsevier, 2016) Boominathasellarajan, B.; Nagaraja, H.S.; Barshilia, H.C.; Chowdhury, P.Template assisted growth of Co nanorod arrays through electrochemical route was investigated. During this investigation, the template with nano-pore diameter was kept at a fixed value of 45 nm, whereas the length of the as grown nanorod array was varied from 25 to 400 nm keeping in mind that the aspect ratio (L/D) covers both below and above the unity. X-ray diffraction patterns indicate that the nanorod arrays initiate its textured growth with fcc (111) phase, however, the change in growth texture to hcp (100) was observed as it grows above 200 nm in length. The anisotropy fields extracted from the measured magnetization data reveal that a cross-over from in-plane to out-of-plane anisotropy takes place for L/D ?2.0. Based on the analytical approach, it seems that the shape anisotropy originated from the demagnetization factor with the change in geometry and magnetostatic interaction among the nanorods cause this crossover. However the micromagnetic simulation yields that both magnetocrystalline anisotropy and the magnetostatic interaction along with shape anisotropy are very much important to explain the experimental observations. © 2015 Elsevier B.V. All rights reserved.Item Porous nickel telluride nanostructures as bifunctional electrocatalyst towards hydrogen and oxygen evolution reaction(Elsevier Ltd, 2017) Bhat, K.S.; Barshilia, H.C.; Nagaraja, H.S.Electrochemical water splitting technology has attracted researchers for the development of next generation fuels. Herein, we report the synthesis of nanostructured porous hollow nickel telluride nanosheets and their use as bifunctional electrocatalyst towards hydrogen and oxygen evolution reaction, anticipating an enhanced performance owing to their 2D sheet like morphology, conductivity, porous nature providing larger catalytic surface for water splitting reaction. In this regard, nickel telluride nanostructures were synthesized via an anion-exchange-reaction between pre-synthesized nickel hydroxide hexagonal nanosheets and tellurium ions under hydrothermal conditions. The as-synthesized nanostructures were characterized for structural, morphological and compositional properties using X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, high resolution transmission electron microscopy and energy dispersive X-ray spectroscopy. Nickel telluride modified electrodes were tested as bifunctional electrocatalyst under acidic and alkaline conditions, through linear sweep voltammetry and constant current chronopotentiometry methods. The modified electrodes revealed an onset potential of ?422 mV and 87.4 mV dec?1 Tafel slope towards HER and overpotential of 679 mV and 151 mV dec?1 Tafel slope towards OER. The lower onset potentials are complimented with excellent electrocatalytic stability. © 2017 Hydrogen Energy Publications LLCItem Porous cobalt chalcogenide nanostructures as high performance pseudo-capacitor electrodes(Elsevier Ltd, 2017) Bhat, K.S.; Shenoy, S.; Nagaraja, H.S.; Sridharan, K.Electrochemical supercapacitor is an essential technology that is pivotal for the development of reliable energy storage devices. Herein, we report the fabrication of supercapacitor electrodes using nanostructured porous cobalt chalcogenide (CoTe2 and CoSe2) electrodes, anticipating an enhanced performance owing to their higher contact area with electrolyte and large pore volume enabling shorter diffusion paths for ion exchange. In this regard, we synthesized CoTe2 and CoSe2 nanostructures via an anion-exchange-reaction between pre-synthesized Co(OH)2 hexagonal nanosheets and chalcogen (tellurium and selenium) ions under hydrothermal conditions. Structural, morphological and compositional properties of the as-synthesized materials are examined using X-ray diffraction, Raman spectroscopy, scanning electron microscopy, high resolution transmission electron microscopy and energy dispersive X-ray spectroscopy. Pseudo-capacitive properties of CoTe2 and CoSe2 nanostructures as working electrodes are studied through cyclic voltammetry and galvanostatic charge-discharge methods using an electrochemical workstation. CoSe2 electrode delivered a specific capacitance of 951 F g?1 at a scan rate of 5 mV s?1, which surprisingly is almost three times higher in comparison to CoTe2 electrode (360 F g?1). Both CoTe2 and CoSe2 electrodes exhibited good capacitance retention capability for 2500 CV cycles. The superior electrochemical performance of the nanoporous CoSe2 electrode indicate their applicability for high-performance energy storage device applications. © 2017 Elsevier LtdItem Adsorption and photocatalytic properties of NiO nanoparticles synthesized via a thermal decomposition process(Cambridge University Press, 2018) Ramesh, M.; Rao, M.P.C.; Anandan, S.; Nagaraja, H.S.NiO nanoparticles (NPs) were synthesized at different annealing temperatures via a thermal decomposition process and characterized using X-ray diffraction, scanning electron microscopy, and UV-vis spectroscopy. The NiO NPs prepared at higher annealing temperature (400 °C) were shown excellent adsorption and photocatalytic activity toward textile dyes reactive black 5 (RB-5) and methylene blue (MB). About 87.2% of RB-5 in 60 min and 70.2% of MB in 5 h was removed using NiO NPs synthesized at 400 °C. The photocatalytic degradation of MB was found to increase with an increase in the annealing temperature of the catalyst. Moreover, the kinetic study revealed that the adsorption and photocatalytic activity of NiO NPs followed the second and first-order kinetics, respectively. The enhanced performance of NiO NPs toward dye removal might be related to its optical and structural properties. © Materials Research Society 2018.Item Chemically prepared Polypyrrole/ZnWO 4 nanocomposite electrodes for electrocatalytic water splitting(Elsevier Ltd, 2019) Brijesh, K.; Bindu, K.; Shanbhag, D.; Nagaraja, H.S.ZnWO 4 , PPy, and PPy/ZnWO 4 nanoparticles were prepared using chemical synthesis. The structural, compositional and morphological properties of the prepared samples have been investigated using XRD, FTIR, SEM, and HRTEM respectively. The powder XRD reveals the monoclinic wolframite structure for both ZnWO 4 and PPy/ZnWO 4 nanocomposite. SEM confirms the wrapping of ZnWO 4 with PPy. The electrodes of ZnWO 4 , PPy, and PPy/ZnWO 4 have been tested as bifunctional electrocatalyst towards HER and OER using constant current chronopotentiometry (CP) and Linear Sweep Voltammetry (LSV). The electrochemical surface area and the electrocatalytic activity PPy/ZnWO 4 nanocomposite towards HER and OER are greater than that of pure ZnWO 4 and PPy. The Tafel slope of PPy/ZnWO 4 nanocomposite is 76 and 84 mV dec ?1 in 0.5 M H 2 SO 4 and 1 M KOH at room temperature for HER and OER respectively. The results suggest that PPy/ZnWO 4 nanocomposite is a good candidate for the bifunctional electrocatalyst for water splitting. © 2018 Hydrogen Energy Publications LLC