Optical properties of zinc peroxide and zinc oxide multilayer nanohybrid films

Zinc peroxide and zinc oxide nanoparticles were prepared and self-assembled hybrid nanolayers were built up using layer-by-layer (LbL) technique on the surface of glass substrate using the layer silicate hectorite and an anionic polyelectrolyte, sodium polystyrene sulfonate (PSS). Light absorption, interference and morphological properties of the hybrid films were studied to determine their thickness and refractive index. The influence of layer silicates and polymers on the self-organizing properties of ZnO₂ and ZnO nanoparticles was examined. X-ray diffraction revealed that ZnO₂ powders decomposed to ZnO (zincite phase) at relatively low temperatures (less than 200 °C). The optical thickness of the films ranged from 190 to 750 nm and increased linearly with the number of layers. Band gap energies of the ZnO₂/hectorite films were independent from the layer thickness and were larger than that of pure ZnO₂ nanodispersion. Decomposition of ZnO₂ to ZnO and O₂ at 400 °C resulted in the decrease of the band gap energy from 3.75 to 3.3 eV. Concomitantly, the refractive index increased in correlation with the formation of the zincite ZnO phase. In contrast, the band gap energies of the ZnO₂/PSS hybrid films decreased with the thickness of the nanohybrid layers. We ascribe this phenomenon to the steric stabilization of primary ZnO₂ particles present in the confined space between adjacent layers of hectorite sheets.     

Optical, structural and adsorption properties of zinc peroxide/hydrogel nanohybrid films

Hybrid nanofilms from zinc-peroxide/poly(acrylamide) (ZnO₂/PAAm) and zinc-peroxide/poly(N-isopropyl-acrylamide) (ZnO₂/PNIPAAm) were prepared using the photopolymerization procedure. The thin layers were prepared by the combination of the Layer-by-Layer (LbL) self-assembly method and photopolymerization using UV light in every step of the procedure. The hybrid multilayer films consisting of layers of zinc peroxide nanoparticles and hydrogel alternating in a sandwich-like fashion with thicknesses of 65-246 nm. The chemical structures of the hybrid films were investigated by FTIR spectroscopy, their morphology was studied by atomic force microscopy (AFM). The build up of the films was studied by measuring the optical reflection spectrum, and we have calculated the refractive index and layer thickness of the hybrid layers using simulating software. The adsorption properties of the ZnO₂/hydrogel nanohybrid composite networks were investigated by measuring water and ethanol vapour adsorption by a quartz crystal microbalance (QCM). It was established that on partially hydrophobic ZnO₂/PNIPAAm hybrids the adsorbed amounts were lower, against the hydrophilic ZnO₂/PAAm film the vapour amount was higher. These results correspond to those of the bulk gel swelling results.     

Optical characterization of ZnO nanoparticles capped with various surfactants

The presence of surfactants (Hexamine, tetraethylammonium bromide (TEAB), cetyltrimethylammonium bromide (CTAB), tetraoctylammonium bromide (TOAB) and PVP) on the surface of zinc oxide (ZnO) nanoparticles resulted variation in their optical properties. The optical properties of each surfactant-capped zinc oxide nanoparticles were investigated using UV-visible absorption and fluorescence techniques. The particle size of these nanoparticles were calculated from their absorption edge, and found to be in the quantum confinement range. The absorption spectra and fluorescent emission spectra showed a significant blue shift compared to that of the bulk zinc oxide. Large reduction in the intensity of visible emission of zinc oxide/surfactant was observed and these emissions were vanished more quickly, with the decrease in excitation energy, for the smaller nanoparticles. Out of the four surfactants (other than PVP), CTAB-capped zinc oxide has smallest particle size of 2.4 nm, as calculated from the absorption spectrum. Thus the presence of surfactant on the surface of zinc oxide plays a significant role in reducing defect emissions. Furthermore, ZnO/PVP nanoparticles showed no separate UV emission peak; however, the excitonic UV emission and the visible emission at 420 nm overlap to form a single broad band around 420 nm.     

Hydrothermal synthesis, characterization and Raman studies of Eu activated Gd2O3 nanorods

Eu³⁺ (8 mol%) activated gadolinium oxide nanorods have been prepared by hydrothermal method without and with surfactant, cityl trimethyl ammonium bromide (CTAB). Powder X-ray diffraction (PXRD) studies reveal that the as-formed product is in hexagonal Gd(OH)₃:Eu phase and subsequent heat treatment at 350 and 600 °C transforms the sample to monoclinic GdOOH:Eu and cubic Gd₂O₃:Eu phases, respectively. The structural data and refinement parameters for cubic Gd₂O₃:Eu nanorods were calculated by the Rietveld refinement. SEM and TEM micrographs show that as-obtained Gd(OH)₃:Eu consists of uniform nanorods in high yield with uniform diameters of about 15 nm and lengths of about 50-150 nm. The temperature dependent morphological evolution of Gd₂O₃:Eu without and with CTAB surfactant was studied. FTIR studies reveal that CTAB surfactant plays an important role in converting cubic Gd₂O₃:Eu to hexagonal Gd(OH)₃:Eu. The strong and intense Raman peak at 489 cm⁻¹ has been assigned to A_g mode, which is attributed to the hexagonal phase of Gd₂O₃. The peak at ∼360 cm⁻¹ has been assigned to the combination of F_g and E_g modes, which is mainly attributed to the cubic Gd₂O₃ phase. The shift in frequency and broadening of the Raman modes have been attributed to the decrease in crystallite dimension to the nanometer scale as a result of phonon confinement.     

Structural and optical properties of WO3-ZnO-PbO-B2O3 glasses

Glass samples of compositions 20PbO-80B₂O₃ and xWO₃—(20−x) ZnO-20PbO-60B₂O₃ with x varying from 0% to 10% mole fraction are prepared by the melt quench technique. Decrease in the band gap from 2.86 to 2.16 eV for ZnO-PbO-B₂O₃ glasses with an increase in the WO₃ content has been observed and discussed. The FTIR spectral studies have pointed out the conversion of structural units of BO₃ to BO₄ and WO₄ to WO₆ with the presence of W-O-W vibration of tungsten and incorporation of ZnO₄ structural units of zinc in these glasses. The increase in density from 2.75 to 4.03 gcm⁻³ for ZnO-PbO-B₂O₃ glasses is observed with an increase in WO₃ content. Due to the formation of WO₆, WO₄ and BO₄ units, changes in the atomic structure with WO₃ composition are observed and discussed.     

Two-step synthesis and characterization of ZnO nanoparticles

A novel two-step procedure has been employed for the synthesis of ZnO nanoparticles: (1) mechanochemical synthesis of ZnC₂O₄2H₂O nanoparticles by grinding a mixture of zinc acetate and oxalic acid in an agate mortar at 27 °C and (2) thermal decomposition of ZnC₂O₄2H₂O nanoparticles at 400 °C to form ZnO nanoparticles. XRD and FESEM characterize the final product as highly crystalline ZnO with wurtzite structure and crystallite sizes in the range 5–20 nm. FTIR and EPR are used to identify molecular species during thermal decomposition and impurity/defect status of the ZnO powder respectively.     

Synthesis of ZnO2 nanoparticles by laser ablation in liquid and their annealing transformation into ZnO nanoparticles

A pulsed laser emitting UV radiations generated by the third harmonic of Nd:YAG was applied for the synthesis of nano-structured ZnO₂ and ZnO. For the synthesis of nanoparticles of ZnO₂, a high-purity metallic plate of Zn target was fixed at the bottom of a glass cell, in the presence of deionized water mixed with oxidizing agent H₂O₂, under repeated laser irradiation. The optical properties, size and the morphology of the synthesized ZnO₂ and ZnO by laser ablation was influenced strongly by post-annealing conditions which is not previously reported. By annealing ZnO₂ at 200 °C for 8 h, the product (ZnO₂) synthesized primarily was converted completely to ZnO. By variation of the annealing temperatures from 200 to 600 °C, the grain size of ZnO changes from 5 to 19 nm with a change in lattice parameters, the band gap and some other optical properties of nano-ZnO.     

Surfactant effect on the conductivity behavior of CsH2PO4: Characterization by electrochemical impedance spectroscopy

Cesium dihydrogen phosphate (CDP) nanoparticles were synthesized using the surfactants cetyltrimethyl ammonium bromide (CTAB), polyoxyethylene-polyoxypropylene (F-68) and (F-68:CTAB) with molar ratio 0.06. The samples conductivity such as CDP_CTAB, CDP_F-68 and CDP_{(F-68:CTAB)0.06} was studied by impedance spectroscopy in the frequency range 0.01 Hz to 1 MHz. The Nyquist plots were drawn at different temperatures of 210, 230 and 260 °C, which are defined below transition, phase transition and above transition, respectively. The measured conductivities obey the Arrhenius relation. The influence of surfactants on conductivity are more significant at higher temperature due to grain boundary. The conductivity of CDP_CTAB increased slightly with increasing temperature to 260 °C, whereas the conductivity of other samples decreased with increasing temperature over 230 °C. The results indicated that the conductivities increase in the order of CDP_CTAB>CDP_{(F-68:CTAB)0.06}>CDP_F-68. These are in accordance to the ion exchange capacities of the samples that the surfactant shows a direct influence on the samples proton mobility. It is found that the conductivity of CsH₂PO₄ is influenced by surfactant type.     

Shape and size transformation of gold nanorods (GNRs) via oxidation process: A reverse growth mechanism

The anisotropic shape transformation of gold nanorods (GNRs) with H₂O₂ was observed in the presence of “cethyl trimethylammonium bromide” (CTAB). The adequate oxidative dissolution of GNR is provided by the following autocatalytic scheme with H₂O₂: Au⁰ → Au⁺, Au⁰ + Auⁿ⁺ → 2Au³⁺, n = 1 and 3. The shape transformation of the GNRs was investigated by UV-vis spectroscopy and transmission electron microscopy (TEM). As-synthesised GNRs exhibit transverse plasmon band (TPB) at 523 nm and longitudinal plasmon band (LPB) at 731 nm. Upon H₂O₂ oxidation, the LPB showed a systematic hypsochromic (blue) shift, while TPB stays at ca. 523 nm. In addition, a new emerging peak observed at ca. 390 nm due to Au(III)-CTAB complex formation during the oxidation. TEM analysis of as-synthesised GNRs with H₂O₂ confirmed the shape transformation to spherical particles with 10 nm size in 2 h, whereas centrifuged nanorod solution showed no changes in the aspect ratio under the same condition. Au³⁺ ions produced from oxidation, complex with excess free CTAB and approach the nanorods preferentially at the end, leading to spatially directed oxidation. This work provides some information to the crystal stability and the growth mechanism of GNRs, as both growth and shortening reactions occur preferentially at the edge of single-crystalline GNRs, all directed by Br⁻ ions.     

Sonochemical synthesis,structural, magnetic and grain size dependent electrical properties of NdVO4 nanoparticles

NdVO₄ nanoparticles are successfully synthesized by efficient sonochemical method using two different structural directing agents like CTAB and P123. The phase formation and functional group analysis are carried out using X-ray diffraction (XRD) and fourier transform infra red (FT-IR) spectra, respectively. Using Scherrer equation the calculated grain sizes are 27 nm, 24 nm and 20 nm corresponding to NdVO₄ synthesized by without surfactant, with CTAB and P123, respectively. The TEM images revealed that the shape of NdVO₄ particles is rice-like and rod shaped particles while using CTAB and P123 as surfactants. The growth mechanism of NdVO₄ nanoparticles is elucidated with the aid of TEM analysis. From electrical analysis, the conductivity of NdVO₄ nanoparticles synthesized without surfactant showed a higher conductivity of 5.5703 × 10⁻⁶ S cm⁻¹. The conductivity of the material depends on grain size and increased with increase in grain size due to the grain size effect. The magnetic measurements indicated the paramagnetic behavior of NdVO₄ nanoparticles.     

Controlling oxygen vacancies and properties of ZnO

Intrinsic defects in semiconductors play crucial roles on their electrical and optical properties. In this article, we report on a facile method to control concentration of oxygen vacancies inside ZnO nanostructures and related physical properties based on adjustment of thermal transformation conditions from ZnO₂ to ZnO, including annealing atmosphere and temperature. ZnO₂ spheres assembled with nanoparticles were formed through the reaction between zinc nitrate and hydrogen peroxide. Significantly, it was found that the adopted temperature and atmosphere have remarkable impact on the concentration of oxygen vacancies, which was revealed by the variations of featured Raman scattering peaks at 584 cm⁻¹. Furthermore, with the increase of oxygen vacancies inside ZnO, the optical band-gap was found to red-shift 350 meV and the room-temperature ferromagnetism became stronger up to 1.6 emu/mg. The defect formation and evolution were discussed according to the chemical equilibrium of decomposition reaction under special local heating environment. This work demonstrated that ZnO₂ decomposition is an effective process to control the defect states inside ZnO and related properties.     

The effect of solution temperature on crystallite size and magnetic properties of Zn substituted Co ferrite nanoparticles

In this work zinc substituted cobalt ferrite nanoparticles (Co_0.5Zn_0.5Fe₂O₄) have been synthesized by the coprecipitation method, using stable ferric, zinc and cobalt salts with sodium hydroxide, at different solution temperatures, from room temperature to 363 K. The cobalt-zinc ferrite crystalline phase, the particle size and the morphology of the resulting nanoparticles were studied by X-ray diffraction and transmission electron microscopy. The average crystallite size of each sample was calculated from the broadening of the most intense peak (3 1 1), using Scherrer's formula and the results show crystallite sizes increased from 6 to 8 nm by increasing the solution temperature from room temperature to 363 K respectively. Room temperature VSM measurements show that the prepared nanoparticles have superparamagnetic behavior and did not saturate at maximum field of 800 kA/m. The variation of AC-susceptibility of the samples with respect to temperature was measured and it was found that the blocking temperature increased from 198 to 270 K by increasing the solution temperature from room temperature to 363 K respectively. FTIR spectra of the samples have been analyzed in the frequency range 400-4000 cm⁻¹, which also confirms the results of XRD.     

Electrochemical synthesis of Ag nanoparticles supported on glassy carbon electrode by means of p-isopropyl calix[6]arene matrix and its application for electrocatalytic reduction of H2O2

The silver nanoparticles were prepared on the glassy carbon (GC) electrode, modified with p-iso propyl calix[6]arene, by preconcentration of silver ions in open circuit potential and followed by electrochemical reduction of silver ions. The stepwise fabrication process of Ag nanoparticles was characterized by scanning electron microscopy and electrochemical impedance spectroscopy. The prepared Ag nanoparticles were deposited with an average size of 70 nm and a homogeneous distribution on the surface of electrode. The observed results indicated that the presence of calixarene layer on the electrode surface can control the particle size and prevent the agglomeratione and electrochemical deposition is a promising technique for preparation of nanoparticles due to its easy-to-use procedure and low cost of implementation. Cyclic voltammetry experiments showed that Ag nanoparticles had a good catalytic ability for the reduction of hydrogen peroxide (H₂O₂). The effects of p-isopropyl calix[6]arene concentration, applied potential for reduction of Ag⁺, number of calixarene layers and pH value on the electrocatalytic ability of Ag nanoparticles were investigated. The present modified electrode exhibited a linear range from 5.0 × 10⁻⁵ to 6.5 × 10⁻³ M and a detection limit 2.7 × 10⁻⁵ M of H₂O₂ (S/N = 3) using amperometric method.     

Hydrogen peroxide treatment on ZnO substrates to investigate the characteristics of Pt and Pt oxide Schottky contacts

We utilize hydrogen peroxide (H₂O₂) treatment on (0 0 0 1) ZnO substrates to investigate the characteristics of Pt and Pt oxide Schottky contacts (SCs). X-ray rocking curves show the mosaicity structure becomes larger after H₂O₂ treatment. Photoluminescence (PL) spectra show the yellow-orange emission peaking at ∼576-580 nm with respect to deep level of oxygen interstitials introduced by H₂O₂ treatment. The threshold formation of ZnO₂ resistive layer on H₂O₂-treated ZnO for 45 min is observed from grazing-incidence X-ray diffraction. The better electrical characteristic is performed by Pt oxide SC with the larger barrier height (1.09 eV) and the lower leakage current (9.52 × 10⁻¹¹ A/cm² at −2 V) than Pt SC on the H₂O₂-treated ZnO for 60 min. X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometer (SIMS) examinations indicate the promoted interface oxide bonding and Zn outdiffusion for Pt oxide contact, different from Pt contact. Based on current-voltage, capacitance-voltage, X-ray diffraction, PL spectra, XPS, and SIMS results, the possible mechanism for effective rectifying characteristic and enhanced Schottky behavior is given.     

Nanoscale assembly of amine-functionalized colloidal iron oxide

We demonstrate a single-step facile approach for highly water-stable assembly of amine-functionalized Fe₃O₄ nanoparticles using thermal decomposition of Fe-chloride precursors in ethylene glycol medium in the presence of ethylenediamine. The average size of nanoassemblies is 40±1 nm, wherein the individual nanoparticles are about 6 nm. Amine-functionalized properties are evident from Fourier transform infrared spectrometer (FTIR), thermal and elemental analyses. The saturation magnetization and spin-echo r₂ of the nanoassemblies were measured to be 64.3 emu/g and 314.6 mM⁻¹ s⁻¹, respectively. The higher value of relaxivity ratio (r₂/r₁=143) indicates that nanoassemblies are a promising high-efficiency T2 contrast agent platform.     

Modification in structural and optical properties of ZnO, CeO2 doped Al2O3-PbO-B2O3 glasses

The structural and optical analysis of glasses is carried out by XRD, FTIR, density and UV visible spectroscopic measurement techniques. XRD results have confirmed the glassy nature of the samples. The FTIR spectral analysis reveals that with the combined presence of ZnO and CeO₂ contents in Al₂O₃-PbO-B₂O₃ glasses, more BO₃ groups are transformed into BO₄. The optical analysis reveals that optical band gap energy decreases more for CeO₂-ZnO-Al₂O₃-PbO-B₂O₃ glasses (from 2.28 to 1.84 eV). The presence of CeO₂ and ZnO in the glass samples causes more compaction of the borate network due to the formation of more BO₄ groups and the presence of ZnO₄ groups, which results an increase in density, refractive index and decrease of molar volume.     

Nanostructural,magnetic and Mössbauer studies of nanosized Co1−xZnxFe2O4 synthesized by co-precipitation

This work presents a systematic investigation on the structural and magnetic properties of Co_1−xZn_xFe₂O₄ (0.5<x<0.75) nanoparticles synthesized by the chemical co-precipitation method. The X-ray diffraction analysis, the Fourier Transform Infrared (FTIR) and the Vibrating Sample Magnetometer were carried out at room temperature to study the micro-structural and magnetic properties. The X-ray measurements revealed the production of a broad single cubic phase with the crystallite size within the range of 6–10 nm. The FTIR measurements between 400 and 4000 cm⁻¹ confirmed the intrinsic cation vibrations of the spinel structure. The magnetic measurements show that the saturation magnetization and coercivity decrease by increasing the zinc content. Furthermore, the results reveal that the sample with a chemical composition of Co_0.3Zn_0.7Fe₂O₄ exhibits the super-paramagnetic behavior and the Curie point of 97 °C.     

Structural and magnetic properties of Co1−xZnxFe2O4 nanoparticles by co-precipitation method

Co_1−xZn_xFe₂O₄ nanoparticles were prepared by co-precipitation method with x varying from 0 to 1.0. The powder samples were characterized by X-ray diffraction (XRD), vibrating sample magnetometer (VSM) and Fourier transform infrared spectroscopy (FTIR). The average crystallite sizes of the particles were determined from XRD. X-ray analysis showed that the samples were cubic spinel. The average crystallite size (D_aveXR) of the particles precipitated was found to vary from 6.92 to 12.02 nm decreasing with the increase in zinc substitution. The lattice constant (a_o) increased with the increase in zinc substitution. The specific saturation magnetization (M_S) of the particles was measured at room temperature. The magnetic parameters such as M_S, H_c, and M_r were found to decrease with the increase in zinc substitution. FTIR spectra of the Co_1−xZn_xFe₂O₄ with x varying from 0 to 1.0 in the range 400–4000 cm⁻¹ were reported. The spinel structure and the crystalline water adsorption of Co_1−xZn_xFe₂O₄ nanoparticles were studied by using FTIR.     

Structural characterization and magnetic properties of superparamagnetic zinc ferrite nanoparticles synthesized by the coprecipitation method

Single phase zinc ferrite (ZnFe₂O₄) nanoparticles have been prepared by the coprecipitation method without any subsequent calcination. The effects of precipitation temperature in the range 20–80 °C on the structural and the magnetic properties of zinc ferrite nanoparticles were investigated. The crystallite size, microstructure and magnetic properties of the prepared nanoparticles were studied using X-ray diffraction (XRD), Fourier transmission infrared spectrum, transmission electron microscope (TEM), energy dispersive X-ray spectrometer and vibrating sample magnetometer. The XRD results showed that the coprecipitated nanoparticles were single phase zinc ferrite with mixture of normal and inverse spinel structures. Furthermore, ZnFe₂O₄ nanoparticles have the crystallite size in the range 5–10 nm, as confirmed by TEM. The magnetic measurements exhibited that the zinc ferrite nanoparticles synthesized at 40 °C were superparamagnetic with the maximum magnetization of 7.3 emu/g at 10 kOe.     

Effect of annealing on TiO2 nanoparticles

TiO₂ nanoparticles have been prepared by simple chemical precipitation method and annealed at different temperatures. The as-prepared TiO₂ are amorphous, and they transform into anatase phase on annealing at 450 °C, and rutile phase on annealing at 900 °C. The X-ray diffraction results showed that TiO₂ nanoparticles with grain size in the range of 21–24 nm for anatase phase and 69–74 nm for rutile phase have been obtained. FESEM images show the formation of TiO₂ nanoparticles with small size in structure. The FTIR and Raman spectra exhibited peaks corresponding to the anatase and rutile structure phases of TiO₂. Optical absorption studies reveal that the absorption edge shifts towards longer wavelength (red shift) with increase of annealing temperature.