Diluted magnetic semiconductor properties in Zn<Subscript>1−x</Subscript>Cu<Subscript>x</Subscript>O nanoparticles synthesized by sol gel route

Nanoparticles of ZnO:Cu Diluted Magnetic Semiconductor (DMS) are prepared using sol gel method. The structural, optical and EPR properties of them are investigated. The XRD patterns of them show the formation of polycrystalline and hexagonal wurtzite structure without any secondary phase formation. The average size of particles ranges from 14 to 19 nm. In the optical absorption study of the samples, a red shit of optical band edge and a narrowing of the optical band gap are observed when Cu concentration is increased. The PL measurements illustrate 392 nm UV radiation of the near band-edge emissions of ZnO, blue emission at 450 nm and orange emission at 628 nm. The cause of decrease in intensity of these emission lines is the sincerely enhanced non-radiative transitions when Cu is doped in ZnO. EPR measurements provide substantial evidence for the presence of defect states and enhancement of exchange interaction.     

Structural and optical characterization of Zn doped TiO<Subscript>2</Subscript> nanoparticles prepared by sol–gel method

Undoped and zinc-doped TiO₂ nanoparticles (Ti_1−xZn_xO₂ where x = 0.00–0.10) were synthesized by a sol–gel method. The synthesized products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) and UV–VIS spectrometer. XRD pattern confirmed the tetragonal structure of synthesized samples. Average grain size was determined from X-ray line broadening using the Debye–Scherrer relation. The crystallite size was varied from 10 to 40 nm as the calcination temperature was increased from 350 to 800 °C. The incorporation of 3–5 mol% Zn²⁺ in place of the Ti⁴⁺ provoked a slight decrease in the size of nanocrystals as compared to undoped TiO₂. The SEM and TEM micrographs revealed the agglomerated spherical-like morphology with a diameter of about 10–30 nm and length of several nanometers, which is in agreement with XRD results. Optical absorption measurements indicated a blue shift in the absorption band edge upon 3–5 mol% zinc doping. Direct allowed band gap of undoped and Zn-doped TiO₂ nanoparticles measured by UV–VIS spectrometer were 2.95 and 3.00 eV at 550 °C, respectively.     

Preparation of Cd-doped SnO<Subscript>2</Subscript> nanoparticles by sol–gel route and their optical properties

Nanocrystalline cadmium doped tin oxide (SnO₂) powders of about 2.5–4.5 nm in size have been synthesized by using different solvents via sol–gel method. The obtained samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), Energy dispersive X-ray analysis (EDX), Transmission electron spectroscopy (TEM), UV-Vis absorption and Photoluminescence (PL) spectroscopy. The PL emission spectra revealed that the band centered at 452 nm might be related with oxygen vacancies. A spherical, small rod and slice like morphologies of the prepared Cd-SnO₂ nanoparticles were observed in the SEM and TEM studies. The presence of Cd modifies the structural, morphological and optical properties of the tin oxide nanoparticles.     

Synthesis of Y<Subscript>3−x</Subscript>Lu<Subscript>x</Subscript>Al<Subscript>3</Subscript>MgSiO<Subscript>12</Subscript> garnet powders by sol–gel method

Y_3−xLu_xAl₃MgSiO₁₂ (x = 0–3) garnet powders were synthesized by an aqueous sol–gel method based on metal chelates with 1,2-ethanediol in aqueous media. Target samples were characterized by powder X-ray diffraction (XRD), scanning electron microscopy and reflection spectra. XRD analysis revealed that sintering of polycrystalline Y_3−xLu_xAl₃MgSiO₁₂ powders at 1,600 °C results in single-phase garnet materials.     

Modifications in band gap and optical properties of Zn0.96−xNd0.04CuxO (x = 0, 0.05, 0.1 and 0.15) nanoparticles

Nd-doped and Nd, Cu co-doped ZnO nanoparticles (Zn_0.96?xNd_0.04Cu_xO, x = 0, 0.05, 0.1 and 0.15) were synthesized by sol–gel method. The structural and optical properties of the samples were investigated by X-ray diffraction (XRD) and UV–visible photo-spectrometer. The synthesized nanoparticles have different microstructure without changing a hexagonal wurtzite structure. CuO phase was noticed in XRD spectra at 38.73° after Cu = 5 % which was formed from remaining un-reacted Cu²⁺ ions. The average crystal size was gradually increased from Cu = 0 % (17 nm) to 15 % (17.6 nm) having lowest value (16.7 nm) at Cu = 5 %. The change in lattice parameters confirmed the substitution of Cu in Zn–Nd–O lattice. The observed constant c/a ratio revealed that there was no change in hexagonal wurtzite structure by Cu-doping. The energy dispersive X-ray spectra confirmed the presence of appropriate amount of Nd and Cu in Zn–O lattice. The optical absorption was increased gradually from Cu = 0–10 % and showed maximum at Cu = 10 % due to the presence of more nucleation centres and defect states. The defects related green band between 487 and 493 nm was due to the oxygen vacancies and intrinsic defects. The higher transmittance (≈ 90 %) noticed at Cu = 15 % leads to the industrial applications. The observed blue shift in energy gap from 3.49 eV (Cu = 0 %) to 3.65 eV (Cu = 10 %) and the red shift from Cu = 10 % (3.65 eV) to Cu = 15 % (3.61 eV) can be explained by the Burstein–Moss effect. Presence of chemical bonding was confirmed by Fourier transform infrared spectra.     

Cu-doping effect on structural, optical and photoluminescence properties of Zn0.96−xFe0.04CuxO (x = 0, 0.02, 0.04, 0.06, 0.08 and 0.1) nanopowders by sol–gel method

Zn_0.96?xFe_0.04Cu_xO (x = 0, 0.02, 0.04, 0.06, 0.08, 0.10) nanopowders have been synthesized by sol–gel method. The synthesized samples have been characterized by powder X-ray diffraction, energy dispersive X-ray spectra, X-ray photoelectron spectroscopy, UV–visible spectrophotometer and Fourier transform infrared spectroscopy. The XRD measurement reveals that the prepared nanopowders have different microstructure without changing a hexagonal wurtzite structure. The calculated average crystalline size increases from 20.9 to 22.1 nm for x = 0 to 0.02 then gradually decreases to 18.2 nm for x = 0.10 which were confirmed by SEM and TEM micrographs. The change in lattice parameters, micro-strain, and shift of X-ray diffraction peaks towards lower angles and increase of energy gap reveal the substitution of Cu²⁺ ions into Zn–Fe–O matrix. X-ray photoelectron spectroscopy study described the increase of oxygen vacancies with increase of Cu concentrations, which was found to enhance the green emission. The presence of functional groups and the chemical bonding is confirmed by FTIR spectra. Photoluminescence spectra of Zn_0.96?xFe_0.04Cu_xO system shows that the blue shift in NBE ultraviolet emission from 389 to 369 nm and the same blue shift in green band emission from 552 to 535 nm with enhancing intensity confirms the substitution of Cu into the Zn–Fe–O lattice. Cu-doped Zn_0.96?xFe_0.04Cu_xO system is appreciable for the fabrication of nano-optoelectronic devices like tunable light emitting diode in the near future.     

Particulate sol–gel synthesis and optical and electrical properties of CeO<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> nanocomposite

CeO₂/TiO₂ nanocomposite was synthesized by particulate sol–gel method. The X-ray diffractogram shows the presence of cubic CeO₂ and anatase TiO₂ in the composite. The high resolution scanning electron micrographs reveal the nanoparticulate nature of the prepared composite. The composite absorbs UV light and exhibits near-band gap emission corresponding to TiO₂ and deep level emission due to crystal defects. The Nyquist plot displays two semicircular arcs indicating the material heterogeneity. The physicochemical characteristics of the synthesized nanocomposite are in favour of its application as an ingredient of sunscreen formulations; under UV light the photocatalytic activity of CeO₂/TiO₂ composite, tested through the degradation of rhodamine B, is very much less than that by pristine anatase TiO₂. Reduced adsorption of moisture by the nanocomposite is a possible reason for the observed very low photocatalytic activity.     

Structure,microstructure and physicochemical properties of BaW<Subscript>1−x</Subscript>Nb<Subscript>x</Subscript>O<Subscript>4−δ</Subscript> materials

Nb-doped BaWO₄ with the assumed formula BaW_1?xNb_xO_4?δ (x = 0, 0.005, 0.01, 0.02 and 0.05) were prepared by solid-state reaction method. Crystal structure and phase composition were determined by X-ray diffraction method. Scanning electron microscopy (SEM) coupled with energy-dispersive spectrometry (EDS) was used to describe microstructure and chemical composition of synthesised materials. It was found that solubility limit of niobium in the BaWO₄ structure is the range 0.5–1 mol%, as formation of second phase—Ba₅Nb₄O₁₅—was observed for samples with higher dopant content. For evaluation of the chemical stability of synthesized materials, the comparative CO₂/H₂O exposure test was performed. Samples were exposed to carbon dioxide- and water vapour-rich atmosphere (7% CO₂ in air, 100% RH) at 298 K for 700 h. During this exposition, the chemical reactions between the samples and the surrounding gaseous atmosphere resulting in formation of barium hydroxide and/or barium carbonate can process. Thermogravimetry (TG) method was used for chemical stability evaluation. The comparison of samples before and after the CO₂/H₂O exposure test was performed. To support the interpretation of TG results, the analysis of gaseous products evolved during thermal treatment of the samples was done using mass spectrometer. The effect of dopant on the BaWO₄ chemical stability improvement was observed. In order to determine the electrical properties of obtained materials, the DC resistance measurements in synthetic air atmosphere were taken. It was shown that niobium doping and the presence of second phase—Ba₅Nb₄O₁₅—leads to an increase in the total conductivity of synthesised materials.     

Thermal behavior of Co<Subscript>x</Subscript>Fe<Subscript>3−x</Subscript>O<Subscript>4</Subscript>/SiO<Subscript>2</Subscript> nanocomposites obtained by a modified sol–gel method

The thermal behavior of Co_xFe_3?xO₄/SiO₂ nanocomposites obtained by direct synthesis starting from nonahydrate ferric nitrate and hexahydrate cobalt nitrate in different ratios with and without the addition of 1,4-butanediol was studied. For the synthesis of Co_xFe_3?xO₄ (x = 0.5–2.5) dispersed in the silica matrix a wide Co/Fe molar ratio was used. The decomposition processes, formation of crystalline phases, gases evolvement and mass changes during gels annealing at different temperatures were assessed by thermal analysis. The absence of succinate precursor and a low mass loss were observed in the case of the gel obtained in the absence of 1,4-butanediol. In case of gels obtained using a stoichiometric ratio of Co/Fe, no clear delimitation between Co and Fe succinates was observed, while for samples with a Fe or Co excess, the formation of the two succinates was observed. The evolution of the crystalline phase after annealing (673, 973 and 1273 K) investigated by X-ray diffraction analysis and Fourier transformed infrared spectrometry revealed that in samples with Fe excess, stoichiometric Fe/Co ratio or low Co excess, the cobalt ferrite (CoFe₂O₄) was obtained as a single phase, while in samples with higher cobalt excess, olivine (Co₂SiO₄) as a main phase, cobalt oxide and CoFe₂O₄ as secondary phases were obtained after annealing at 1273 K. The SEM images confirmed the nanoparticles embedding in the silica matrix, while the TEM and X-ray diffraction data showed that the obtained nanoparticles’ size was below 10 nm in most samples.     

Synthesis of CeO<Subscript>2</Subscript> or α–Mn<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles via sol–gel process and their optical properties

Nanocrystalline cubic fluorite/bixbyite CeO₂ or α–Mn₂O₃ has been successfully synthesized by using methanol as a solvent via sol–gel method calcined at 400 °C. The obtained products were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), UV–vis absorption and Photoluminescence (PL) spectroscopy. TEM reveals that the as-synthesized ultra-fine samples consist of elliptical/spherical and sheet-like morphology of crystalline particles of 8/30 nm, which are weakly aggregated. Optical absorbance spectra reveal that the absorption of ceria in the UV region originates from the charge- transfer transition between the O²⁻ (2p) and Ce⁴⁺ (4f) orbit in CeO₂. However, α–Mn₂O₃ nanostructures with nearly pure band gap emission should be of importance for their applications as UV emitters.     

First-order phase transformation and structural studies in Se<Subscript>85</Subscript>In<Subscript>15−x</Subscript>Zn<Subscript>x</Subscript> chalcogenide glasses

Present research work describes the crystallization kinetics and structural studies in Se₈₅In_15?xZn_x chalcogenide glasses. Bulk alloys of Se₈₅In_15?xZn_x were synthesized by melt-quenching procedure. High resolution X-ray diffraction (HRXRD) was used to confirm the amorphous nature of synthesized samples. Non-isothermal differential scanning calorimetry (DSC) measurements were performed at 5, 10, 15, 20 and 25 K min^?1 heating rates to study kinetics of crystallization in Se₈₅In_15?xZn_x. Various crystallization parameters such as glass transition (T _g), onset crystalline (T _c), peak crystallization (T _p) and melting temperature (T _m) were calculated from DSC curves. The activation energies of structural relaxation (ΔE _t) and crystallization (ΔE _c) were determined by using Kissinger, Moynihan and Ozawa approaches. ΔE _t is found to be the lowest for Se₈₅In₆Zn₉ sample which shows this sample has the highest probability of escape to a state of lower configurational energy and has greater stability. Thermal stability of various compositions was studied and found to vary with Zn content. Further, HRXRD and field emission scanning electron microscope were used for the study of first phase transformation in Se₈₅In_15?xZn_x samples.     

Correlation between structural and optical properties of TiO<Subscript>2</Subscript>:ZnO thin films prepared by sol–gel method

We have studied structural and optical properties of thin films of TiO₂, doped with 5% ZnO and deposited on glass substrate (by the sol–gel method). Dip-coated thin films have been examined at different annealing temperatures (350–450 °C) and for various layer thicknesses (89–289 nm). Refractive index, porosity and energy band gap were calculated from the measured transmittance spectrum. The values of the index of refraction are in the range of 1.97–2.44, the porosity is in the range of 0.07–0.46 and the energy band gap is in the range of 3.32–3.43. The coefficient of transmission varies from 50 to 90%. In the case of the powder of TiO₂, doped with 5% ZnO, and aged for 3 months in ambient temperature, we have noticed the formation of the anatase phase (tetragonal structure with 20.23 nm grains). However, the undoped TiO₂ exhibits an amorphous phase. After heat treatments of thin films, titanium oxide starts to crystallize at the annealing temperature 350 °C. The obtained structures are anatase and brookite. The calculated grain size, depending on the annealing temperature and the layer thickness, is in the range of 8.61–29.48 nm.     

NiTiO<Subscript>3</Subscript> nanoparticles encapsulated with SiO<Subscript>2</Subscript> prepared by sol–gel method

NiTiO₃ (NTO) nanoparticles encapsulated with SiO₂ were prepared by the sol–gel method resulting on core-shell structure. Changes on isoelectric point as a function of silica were evaluated by means of zeta potential. The NTO nanoparticles heat treated at 600°C were characterized by X-ray diffraction, transmission electron microscopy (TEM) and energy dispersive X-ray analysis. TEM observations showed that the mean size of NTO is in the range of 2.5–42.5 nm while the thickness of SiO₂ shell attained 1.5–3.5 nm approximately.     

Structural and optical characterization of Ag-doped TiO2 nanoparticles prepared by a sol–gel method

Undoped and silver-doped TiO₂ nanoparticles (Ti_1?x Ag _x O₂, where x?=?0.00?C0.10) were synthesized by a sol?Cgel method. The synthesized products were characterized by X-ray diffraction (XRD), particle size analyzer (PSA), scanning electron microscope (SEM), and UV?CVisible spectrophotometer. XRD pattern confirmed the tetragonal structure of synthesized samples. Average crystallite size of synthesized nanoparticles was determined from X-ray line broadening using the Debye?CScherrer formula. The crystallite size was varied from 8 to 33?nm as the calcination temperature was increased from 300 to 800?°C. The incorporation of 3 to 5% Ag⁺ in place of Ti⁴⁺ provoked a decrease in the size of nanocrystals as compared to undoped TiO₂. The SEM micrographs revealed the agglomerated spherical-like morphology of particles. SEM, PSA, and XRD measurements show that the particles size of the powder is in nanoscale. Optical absorption measurements indicated a red shift in the absorption band edge upon silver doping. Direct allowed band gap of undoped and Ag-doped TiO₂ nanoparticles measured by UV?CVis spectrometer were 3.00 and 2.80?eV, respectively, at 500?°C.     

Structural and optical characterization of sol–gel derived boron doped Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanostructured films

Pure and boron (B) doped iron oxide (Fe₂O₃) nanostructured thin films were prepared by sol–gel spin coating method. The effects of B (0.1, 0.2, 0.5 and 1 %) content on the crystallinity and morphological properties of Fe₂O₃ films were investigated by X-ray diffractometer and atomic force microscopy. X-ray diffraction patterns revealed that the Fe₂O₃ films have a rhombohedral crystalline phase of α-Fe₂O₃ phase (hematite) with nanostructure and their crystallite size (D) is changed from 27 ± 2 to 45 ± 5 nm with B dopant content. The minimum crystallite size value of 27 ± 2 nm was obtained for 0.2 % B doped Fe₂O₃ film. Carrying out UV–VIS absorption study for both doped and undoped films at room temperature, it was realized that allowed optical transitions may be direct or indirect transitions. The direct and indirect energy gap values for pure Fe₂O₃ were obtained to be 2.07 and 1.95 eV, respectively. The optical band gap value of the films was changed with 0.1 % B doping to reach 1.86 eV for direct band gap and 1.66 eV in case of indirect band gap.     

Effect of annealing atmosphere on structural,optical and electrical properties of Al-doped Zn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O thin films

1 at.% Al-doped Zn_1−x Cd _x O (x = 0–8 at.%) thin films were prepared on glass substrates by sol–gel method. The codoping films retained the hexagonal wurtzite structure of ZnO, and showed preferential c-axis orientation. The effect of annealing ambient (in vacuum and nitrogen) on the optical and electrical properties of (Cd,Al)-codoped ZnO films were investigated using transmission spectra and electrical measurements. The transmittances of the codoping films were obviously degraded by vacuum annealing to 50–60 %, but enhanced to 70–80 % after nitrogen annealing. The carrier concentration and Hall mobility both increased, and resistivity decreased with narrowing band gap of Al-doped Zn_1−x Cd _x O, below different critical concentrations x = 4 % (in vacuum) and x = 6 % (in nitrogen). It is revealed that the conductivity is also improved by Cd doping along with band gap modification. The variations in optical and electrical properties are ascribed to both the changes of the crystallinity and concentration of oxygen vacancies under different ambient. In view of transmittance and conductivity, nitrogen annealing might be a more effective post-annealing way than vacuum annealing for our (Cd,Al)-codoped ZnO films to meet the requirements of transparent conducting oxide (TCO).