Chemical,morphological, structural,optical, and magnetic properties of Zn<Subscript>1−x</Subscript>Nd<Subscript>x</Subscript>O nanoparticles

In the present investigation, we made an endeavor to fabricate the ZnO nanoparticles and achieved the tunable properties with Nd doping. The Nd-doped ZnO nanoparticles were characterized via X-ray diffraction (XRD), Raman, and X-ray photoelectron spectroscopy (XPS) studies that confirmed the successful doping of Nd ions in the ZnO crystal lattice without amending its hexagonal phase. The particle morphology revealed nearly spherical particles with uniform size distribution. The band gap of these samples was determined using diffuse-reflectance spectra (DRS) and was found to vary from 3.17 to 3.21 eV with increasing Nd concentration. A broad and intense emission band at 1083 nm for Nd doped ZnO nanoparticles is observed and is assigned to corresponding emission transition ⁴F_3/2?→?⁴I_11/2 of Nd³⁺ ions. Furthermore, the magnetic studies indicate that the Nd doping altered the magnetic behavior of nanocrystalline ZnO particles from diamagnetic to ferromagnetic at 300 K and that the magnetization of these samples decreased with increasing Nd concentration. The tunable optical band gap as well as room-temperature ferromagnetism of these samples may find applications in both optoelectronics and spintronics.     

Wet chemical route to transparent BiFeO3 films on SiO2 substrates

BiFeO₃ nanoparticles were prepared by a wet chemical synthesis method. Transparent films were deposited on glass and quartz substrates by dip and spin coating processes from the synthesized sol. We obtained thicker films (~ 2 µm) by dip coating process and thinner films (~ 200 nm) by spin coating process. Transmission electron microscopy images confirmed that the particles are nanocrystalline in size. From the optical transmittance spectra the band gap of the BiFeO₃ nanoparticles was determined in the range of ~ 3.03-2.88 eV (~ 410-430 nm). Electrical resistivity, polarization, zero-field-cooled and field-cooled magnetizations versus temperature characteristics were also studied for these films.     

Novel synthesis of nanocrystalline CeO2 by mechanochemical and water-in-oil microemulsion methods

Nanocrystalline cerium dioxide (CeO₂) had been synthesized by two different methods which were mechanochemical and water-in-oil microemulsion. Effects of synthesis conditions on properties of nanocrystalline cerium dioxide were investigated. X-ray diffraction (XRD) was used to characterize the phase and crystallite size of synthesized cerium dioxide nanoparticles. XRD results showed that face centered cubic CeO₂ nanoparticles with crystallite size in nanometer scale were formed. The crystallinity increased with increasing annealing temperature. The average specific surface area of the particles was probed using gas adsorption-desorption measurements. The average particles size was calculated from the specific surface area and was determined to be 5.2 nm for microemulsion samples and 6.9 nm for mechanochemical samples. These results showed that properties of synthesized cerium dioxide could be tailored by adjusting the synthesis conditions.     

Nanocrystalline TiO<Subscript>2</Subscript> by three different synthetic approaches: A comparison

A comparison of the efficiency of three different synthetic routes viz. sol-gel method involving templating, mechanochemical synthesis and combustion synthesis for the production of nanostructured TiO₂, is reported. In the sol-gel method, nanocrystalline TiO₂ is produced when titanium tetraisopropoxide is templated onto dodecylamine which forms the liquid crystalline hexagonal structure and the template is then extracted using 1:1 solution of ethanol-hydrochloric acid mixture. Mechanochemical synthesis of nanocrystalline TiO₂ involved mechanical milling of stoichiometric amounts of titanium and cupric oxide in a planetary ball mill using stainless steel vial with wear resistant stainless steel balls. Nanocrystalline TiO₂ is produced by the combustion reaction involving titanyl nitrate and fuels like glycine and citric acid. Nanostructured TiO₂ with an average particle size of ∼ 14 nm is produced by the sol-gel method whereas the mechanochemical reaction between titanium and cupric oxide resulted in the formation of nanocrystalline TiO₂ with an average particle size of ∼20 nm after 12 h of milling. On the other hand, combustion synthesis resulted in the formation of nanocrystalline TiO₂ with an average particle size of less than ∼50 nm. The microstructures of nanocrystalline TiO₂ produced by the above three methods are analysed.     

Magnetic and photocatalytic properties of nanocrystalline ZnMn<Subscript>2</Subscript>O<Subscript>4</Subscript>

The present study describes the synthesis of ZnMn₂O₄ nanoparticles with the spinel structure. These oxide nanoparticles are obtained from the decomposition of metal oxalate precursors synthesized by (a) the reverse micellar and (b) the coprecipitation methods. Our studies reveal that the shape, size and morphology of precursors and oxides vary significantly with the method of synthesis. The oxalate precursors prepared from the reverse micellar synthesis method were in the form of rods (micron size), whereas the coprecipitation method led to spherical nanoparticles of size, 40–50 nm. Decomposition of oxalate precursors at low temperature (∼ 450°C) yielded phase pure ZnMn₂O₄ nanoparticles. The size of the nanoparticles of ZnMn₂O₄ obtained from reverse micellar method is relatively much smaller (20–30 nm) as compared to those made by the co-precipitation (40–50 nm) method. Magnetic studies of nanocrystalline ZnMn₂O₄ confirm antiferro-magnetic ordering in the broad range of ∼ 150 K. The photocatalytic activity of ZnMn₂O₄ nanoparticles was evaluated using photo-oxidation of methyl orange dye under UV illumination and compared with nanocrystalline TiO₂. Dedicated to Prof. C N R Rao on his 75th birthday     

Synthesis,structural and optical properties of nanoparticles (Al,V) co-doped zinc oxide

The synthesis by the sol–gel method, structural and optical properties of ZnO, Zn_0.99Al_0.01O (AlZ), Zn_0.9V_0.1O (VZ) and Zn_0.89Al_0.01V_0.1O (AlVZ) nanoparticles was reported. The approach was slow release of water for hydrolysis by esterification reaction followed by a supercritical drying in ethyl alcohol. After thermal treatment at 500^°C in air, the obtained nanopowders were characterized by various techniques such as transmission electron microscopy, X-ray diffraction and photoluminescence (PL) spectroscopy. The structural properties showed that the ZnO nanoparticles with an average particle size of 25 nm exhibit hexagonal wurtzite structure. From the optical studies, it was found that the optical band gap was located between 2.97 and 3.17 eV. The obtained electrical properties showed the potential application of the samples in optoelectronic devices. The powder of AlVZ presented a strong luminescence band in the visible range. The PL band energy position presented a small blue shift with the increase of measurement temperature. Different possible attributions of this emission band will be discussed.     

Effect of pyrolysis temperature on structural,microstructural and optical properties of nanocrystalline ZnO powders synthesised by ultrasonic spray pyrolysis technique

In this article, we report on the effect of pyrolysis temperature on structural, microstructural and optical properties of nanocrystalline ZnO powder synthesised by ultrasonic spray pyrolysis (USP) technique. Powder samples P1, P2 and P3 were prepared at various pyrolysis temperatures (temperature of 2nd zone) of 973, 1073 and 1273?K, respectively. Phases were identified and crystallite sizes were calculated from X-ray diffraction (XRD) diagrams. The morphology and size of ZnO nanocrystallites associated with nanopowder were studied using transmission electron micrograph (TEM). It revealed that the powder consisted of crystallites ranging in size from 9 to 20?nm. These values were matching with the crystallite sizes calculated from XRD. Both XRD and TEM studies of ZnO nanopowders showed that the crystallite sizes increased with an increase in the pyrolysis temperature. The synthesised nanopowders exhibited direct band gap (E _g) in the range 3.37–3.40?eV.     

Grain size dependent optical band gap of CdI2 films

The thermally evaporated stoichiometric CdI₂ films show goodc-axis alignment normal to substrate plane for film thickness up to 200 nm. The optical absorption data indicate an allowed direct interband transition across a gap of 3.6 eV in confirmation with earlier band structure calculations. However, part of the absorption data near band edge can be fitted to an indirect band gap of 3 eV. The dependence of band gap on film thickness (> 200 nm) can be explained qualitatively in terms of decreasing grain boundary barrier height with grain size.     

Structural Investigation and Zero-Field-Cooled Exchange Bias in Nanocrystalline LaFeO<Subscript>3</Subscript>

In the present work, synthesis of nanocrystalline LaFeO₃ by using a mechanochemical activation (ball milling) method with oxide precursors (La₂ O ₃ and Fe₂ O ₃) at low temperature is discussed. The thermal and X-ray diffraction studies were used to analyze the formation of intermediate phases during the growth of LaFeO₃. The single crystallographic phase of LaFeO₃ was confirmed using X-ray diffraction analysis. The detailed structural characteristics of the nanocrystalline LaFeO₃ powders were studied by the Rietveld refinement using the FullProff program. Field emission scanning electron microscopy (FESEM) and AFM study revealed the formation of spherical morphology of the nanoparticles. TEM images confirm the formation of homogeneously distributed nanoparticles with their average particle size of about 36 nm. The magnetic measurements were carried on the as-prepared powder, both as a function of temperature and magnetic field. Results of field-cooled (FC) and zero-field-cooled (ZFC) magnetic measurements point out to the existence of spin glass (SG) phases. The exchange bias phenomenon at zero fields cooled is found in hysteresis loop measurements at low temperature.     

Preparation, Growth, and Magnetic Properties of Co-doped Yb2O3 Nanoparticles and Thin Films by the Sol–Gel Process

In this study, the preparation, growth, structure and magnetic properties of Co-doped Yb₂O₃ (with the Co concentration of x=0.2) nanoparticles and thin films are studied. Precursor solutions were prepared by using the sol?Cgel synthesis process to produce nanoparticles and thin films. Co-doped Yb₂O₃ thin films with different thickness were produced on Si(100) substrate using the sol?Cgel dip coating procedure. The particle size and the crystal structure of nanoparticles were ascertained by X-ray diffraction and Scanning Electron Microscope. The surface morphologies and the microstructure of all samples were investigated by means of the Scanning Electron Microscope and the X-ray diffraction. A Quantum Design PPMS was used for magnetic measurements. Surface morphologies of Co-doped Yb₂O₃ thin films were found to be dense, without porosity, uniform, and devoid of cracks and pinholes. The grain size and thin-film thickness of Co-doped Yb₂O₃ were determined to be approximately 50?nm and 84?nm, respectively.     

Magnetic and dielectric properties of HoMnO3 nanoparticles synthesized by the polymerized complex method

In this paper, we report on the magnetic and dielectric properties of HoMnO₃ nanoparticles with different size synthesized by a polymerized complex method have been investigated. The HoMnO₃ nanoparticles crystallized in hexagonal perovskite-type structure. The zero-field-cooled magnetic susceptibility curve of HoMnO₃ nanoparticles with averaged size of 30 nm shows that complicated magnetic transitions occurred in a temperature range from 2 to 100 K, which was confirmed by magnetic hysteresis loops. With increasing the particle size, the antiferromagnetic (AFM) transition temperature increases from 56 to 77 K, due to the reduced surface-to-volume ratio. Moreover, with a decrease in particle size, the Mn-spin reorientation temperature (T_SR) is enhanced from 44 to 48 K.     

Optical properties of nanostructured ruthenium dioxide thin films via sol–gel approach

High purity ruthenium dioxide (RuO₂) nanoparticles with the average size is about 9 nm in diameter are readily synthesized through a low cost sol–gel method. RuO₂ thin films have been deposited on SiO₂ substrates by sol–gel spin coating techniques at room temperature, followed by annealing at 500 °C for 2 h. The result of X-ray diffraction indicates that the RuO₂ nanoparticles are well crystallized with a rutile tetragonal structure. Morphological of RuO₂ films were characterized using atomic force microscopy (AFM), transmission electron microscopy and high resolution transmission electron microscopy. The AFM images confirmed a spherical-shape nanoparticles with diameter of 9 nm and surface roughness of 12 nm of the films. The optical absorption studies showed the presence of direct band transition with band gap equal to 1.87 eV. Refractive index and dielectric properties of the films were estimated from optical measurements. Room temperature photoluminescence of RuO₂ film showed an emission band at 432 nm.     

Fe-EDTA Thermal Decomposition,a Route to Highly Crystalline Hematite (Alpha Fe2O3) Nanoparticle Synthesis

In this study, we develop an experimental procedure to synthesize hematite nanoparticles by hydrothermal decomposition of Fe-EDTA complex in the presence of hydrogen peroxide, starting from ferric ammonium sulfate and Na ₄ EDTA as main precursors. The product was investigated by X-ray diffraction, scaning electron microscopy, dispersive X-ray spectroscopy, magnetic measurements, and UV-vis optical absorption measurements. The size of nanoparticles was determined to be 42 nm evaluated by XRD patterns using the Scherrer equation. This method allowed the formation of pure hematite nanoparticles with good and stable crystallographic characteristics. This procedure can be an effective method for synthesizing hematite nanoparticles exhibiting good crystallinity, stoichiometry, magnetic, and optical band gap properties. A possible mechanism for the formation of hematite nanocrystals was suggested.     

Facile synthesis and optical band gap calculation of Mn3O4 nanoparticles

Mn₃O₄ nanoparticles were prepared by a simple solid state decomposition method. Four manganese benzoic acid complexes were synthesized through semi-solid phase reaction method as precursors for the preparation of Mn₃O₄ nanoparticles. The calcination temperature of the precursors was determined from thermal gravimetrical analyses (TGA). The resulting nanoparticles were characterized by XRD, SEM, STM and HRTEM. The obtained particle size is in the range 39–90 nm. HRTEM indicated the formation of spherical nanoparticles. The optical absorption measurements for the obtained nanoparticles showed that the fundamental absorption edge obeys Tauc's relation for the allowed direct transition. It was found that, the optical band gap (E_g) increases with the decrease of the particle size of the Mn₃O₄ nanoparticles.     

Structural, Optical and Magnetic Properties of Multiferroic GdMnO3 Nanoparticles

The structural, optical, and magnetic properties of multiferroic GdMnO₃ nanoparticles synthesized by the modified sol–gel route have been investigated. Raman spectroscopy and X-ray diffraction along with Rietveld refinement confirm the pure phase of the GdMnO₃ nanoparticles having an orthorhombic perovskite (space group: Pnma) type structure. The morphology was examined by scanning electron microscopy. Energy dispersive spectroscopy confirms the stoichiometry of the composition. The room temperature UV-visible absorption spectrum using Tauc’s relation gives an optical band gap of ～2.9 eV. A magnetization study of the GdMnO₃ nanoparticles was performed over a temperature range of 2–300 K at an applied field of 0.05 T by using a vibrating sample magnetometer. An effective magnetic moment (μ _eff) of ～9.2μ _B was obtained. The system is paramagnetic at room temperature and shows a ferromagnetic-like nature at 2 K as the applied magnetic field aligns the Gd moments and the contribution of the net moment of Gd spins is larger than that of the anti-ferromagnetically canted state of the Mn spins.     

SrTi1−x Fe x O3 nanoparticle: a study of structural,optical, impedance and magnetic properties

We investigate the effects of Fe-dopant concentration on the structure, as well as optical, electrical transport and magnetic properties of SrTi_{1? x} Fe _x O₃ (x?=?0.00, 0.10, 0.20, 0.30, 0.40 and 0.50) nanoparticles prepared by sol–gel method. The dopant-induced changes are studied by X-ray diffraction (XRD), Raman, optical absorption, impedance and magnetic measurements. The results show an average particle size of about 15–30?nm, depending on the Fe-doped concentration. The decrease in lattice parameters and the change of phonon modes related to structural changes, decreasing gap with increasing dopant concentration in conjunction with increasing grain boundary contribution to the impedance. The Fe-doped content has affected the structure, absorption and Raman spectroscopy of the samples. These indicate that the Fe ion has replaced the site of Ti in unit cell. By this method, we have decreased the annealing temperature considerably than that in the conventional solid-state reaction.     

Structural, electrical and optical studies of SILAR deposited cadmium oxide thin films: Annealing effect

Successive ionic layer adsorption and reaction (SILAR) method has been successfully employed for the deposition of cadmium oxide (CdO) thin films. The films were annealed at 623 K for 2 h in an air and changes in the structural, electrical and optical properties were studied. From the X-ray diffraction patterns, it was found that after annealing, H₂O vapors from as-deposited Cd(O₂)_0.88(OH)_0.24 were removed and pure cubic cadmium oxide was obtained. The as-deposited film consists of nanocrystalline grains of average diameter about 20-30 nm with uniform coverage of the substrate surface, whereas for the annealed film randomly oriented morphology with slight increase in the crystallite size has been observed. The electrical resistivity showed the semiconducting nature with room temperature electrical resistivity decreased from 10⁻² to 10⁻³ Ω cm after annealing. The decrease in the band gap energy from 3.3 to 2.7 eV was observed after the annealing.     

Mechanochemical synthesis and characterization of nanocrystalline BiSe, Bi2Se3 semiconductors

Mechanochemical synthesis of bismuth selenides (BiSe, Bi₂Se₃) was performed by high-energy milling of bismuth and selenium powders in a planetary ball mill. The particle size distribution and the specific surface area of Bi/Se and 2Bi/3Se powder mixtures were analysed at increasing milling time. The products were characterized by X-ray diffraction, differential scanning calorimetry and transmission electron microscopy. The presence of bismuth selenide phases was observed after only 1?min of milling and full conversion into hexagonal BiSe phase (nevskite) and rhombohedral Bi₂Se₃ phase (paraguanajuatite) was reached after 10?min of milling. The nanocrystalline nature of both mechanochemically synthesised bismuth selenides was confirmed and their optical band gap energies were obtained on the basis of the recorded absorption spectra in UV–Vis spectral region.     

Effect of annealing on microstructural and optoelectronic properties of nanocrystalline TiO2 thin films

In this study, semi-transparent nanostructured titanium oxide (TiO₂) thin films have been prepared by sol–gel technique. The titanium isopropoxide was used as a source of TiO₂ and methanol as a solvent and heat treated at 60°C. The as prepared powder was sintered at various temperatures in the range of 400–700°C and has been deposited onto a glass substrate using spin coating technique. The effect of annealing temperature on structural, morphological, electrical and optical properties was studied by using X-ray diffraction (XRD), high resolution transmittance electron microscopy (HRTEM), atomic force microscopy (AFM), scanning electron microscopy (SEM), dc resistivity measurement and optical absorption studies. The XRD measurements confirmed that the films grown by this technique have good crystalline nature with tetragonal-mixed anatase and rutile phases and a homogeneous surface. The HRTEM image of TiO₂ thin film (annealed at 700°C) showed grains of about 50–60?nm in size with aggregation of 10–15?nm crystallites. Electron diffraction pattern shows that the TiO₂ films exhibited a tetragonal structure. SEM images showed that the nanoparticles are fine and varies with annealing temperature. The optical band gap energy decreases with increasing annealing temperature. This means that the optical quality of TiO₂ films is improved by annealing. The dc electrical conductivity lies in the range of 10^?6 to 10^?5?Ω?cm^?1 and it decreases by the order of 10 with increase in annealing temperature from 400°C to 700°C. It is observed that the sample Ti700°C has a smooth and flat texture suitable for different optoelectronic applications.     

Mechanochemical synthesis of amorphous and crystalline magnesium diboride

We have studied the phase composition of materials obtained by mechanochemical processing and subsequent heat treatment of mixtures of magnesium and boron powders in the atomic ratio 1: 2. Differential dissolution, differential scanning calorimetry, and X-ray diffraction data indicate that, during mechanical processing, some of the magnesium reacts with boron to form amorphous magnesium diboride. During annealing of the activated powder mixture, X-ray amorphous magnesium diboride forms at 340°C and crystallizes at 480°C. As shown by high-resolution transmission electron microscopy, the unreacted crystalline magnesium is covered with an amorphous layer consisting of magnesium diboride and boron. The amorphous material obtained by milling contains nuclei of MgB₂ crystallites 3–5 nm in size. During subsequent heating of the activated mixture, magnesium and boron react further to form amorphous magnesium diboride and the amorphous phase crystallizes. Heating of mechanically activated mixtures to just below the crystallization temperature allow MgB₂ nanoparticles to be produced. The formation of nanocrystalline magnesium diboride nuclei along with the amorphous phase during mechanochemical processing facilitates mechanochemical synthesis compared to thermal synthesis.