Influence of cerium dopant on magnetic and dielectric properties of ZnO nanoparticles

Ce-doped ZnO nanoparticles (NPs) with different Ce doping concentrations (0, 0.96, 1.96, 2.52 and 3.12 at.% of Ce) were prepared by the chemical co-precipitation method. Energy-dispersive analysis of X-rays confirms the presence of Ce in Ce-doped ZnO nanoparticles. Raman spectra revealed the hexagonal wurtzite structure of pure and Ce-doped ZnO nanoparticles and presence of various defects. The photoluminescence spectra exhibited enhanced violet and blue emission peak intensities for 0.96 at.% of Ce, while broad band green emissions decreased with Ce content. Electron paramagnetic resonance (EPR) studies revealed the presence of oxygen vacancies (V _O), zinc vacancies (V _Zn) and Ce³⁺ ions in the prepared ZnO nanoparticles. VSM studies showed room temperature ferromagnetism (RTFM) in the Ce-doped ZnO NPs. The substituted Ce³⁺ions found to induce RTFM along with V _O, V _Zn in correlation with the results obtained from the EPR, PL and Raman studies. The variation of dielectric constants (ε _r), dielectric loss (ε″) and ac conductivity (σ _ac) as a function of frequency and Ce concentration is studied using ‘Maxwell–Wagner Model.’     

Optical and magnetic properties of copper doped ZnO nanorods prepared by hydrothermal method

Surfactant free ZnO and Cu doped ZnO nanorods were synthesized by hydrothermal method. The formation of ZnO:Cu nanorods were confirmed by scanning electron microscopy, X-ray diffraction and Raman analysis. Diffuse reflectance spectroscopy results shows that band gap of ZnO nanorods shifts to red with increase of Cu content. The orange-red photoluminescent emission from ZnO nanorods originates from the oxygen vacancy or ZnO interstitial related defects. ZnO:Cu nanorods showed strong ferromagnetic behavior, however at higher doping percentage of Cu the ferromagnetic behavior was suppressed and paramagnetic nature was enhanced. The presence of non-polar E ₂ ^high and E ₂ ^low Raman modes in nanorods indicates that Cu doping didn’t change the wurtzite structure of ZnO.     

Effect of annealing temperature on growth of Ce-ZnO nanocomposite thin films: X-ray photoelectron spectroscopy study

Ce-doped ZnO nanocomposite thin films with Ce/Zn ratio fixed at optimum value (10 at.%) have been prepared via sol-gel method at different annealing temperatures varied from 180 to 500 °C. The synthesized samples were characterized employing atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) techniques. According to AFM analysis, the average grain size increased from about 70 nm to 150 nm by increasing the annealing temperature from 300 to 500 °C. Moreover, based on the XPS data analysis, it was found that three major metal ions namely Ce³⁺, Ce⁴⁺, and Zn²⁺ coexist on the surface of the nanocomposite films. XPS data analysis also revealed that Ce³⁺ ion is oxidized to Ce⁴⁺ ion with increasing annealing temperature. Due to oxidation, the ratio of [Ce^3±]/[Ce total] changed from 68.8 to 38.1% by increasing the annealing temperature from 180 to 500 °C. In addition, the Ce/Zn ratio increased from 0.21 to 0.42 when increasing the annealing temperature from 180 to 500 °C indicating migration of Ce ions toward the surface at higher temperatures. Finally, the XRD measurements determined that the ZnO thin films have a hexagonal wurtzite structure and CeO₂ crystallites are formed at 500 °C in the Ce-doped ZnO nanocomposite thin films.     

Synthesis of 1-D ZnO nanorods and polypyrrole/1-D ZnO nanocomposites for photocatalysis and gas sensor applications

1-D ZnO nanorods and PPy/1-D ZnO nanocomposites were prepared by the surfactant-assisted precipitation and in situ polymerization method, respectively. The synthesized nanorods and nanocomposites were characterized by UV–Vis spectrophotometer, Fourier transform-infrared spectroscopy (FTIR), X-ray diffraction (XRD) and field emission scanning electron microscope (FE-SEM), which gave the evidence of 1-D ZnO nanorods, polymerization of pyrrole monomer and strong interaction between PPy and 1-D ZnO nanorods, respectively. Photocatalytic activity of 1-D ZnO nanorods was conducted by 3³ level full-factorial design to evaluate the effect of three independent process variables viz., dye concentration (crystal violet), catalyst concentration (1-D ZnO nanorods) and the reaction time on the preferred response: photodegradation efficiency (%). The PPy/1-D ZnO nanocomposites were used for the sensing of NH₃, LPG, CO₂ and H₂S gases, respectively, at room temperature. It was observed that PPy/1-D ZnO nanocomposites with different 1-D ZnO nanorod weight ratios (15 and 25%) had better selectivity and sensitivity towards NH₃ at room temperature.     

ZnO nanorod arrays grown on glass substrates below glass transition temperature by metalorganic chemical vapor deposition

High density, well-aligned ZnO nanorods with uniform distributions in their diameters and lengths are successfully prepared on amorphous substrates by metalorganic chemical vapor deposition. The X-ray diffraction measurements indicate that the ZnO nanorods are of wurtzite crystal structure, and are grown preferentially on glass substrates along the [0001]_ZnO direction. The degree of the preferred orientation of the ZnO nanorods is enhanced by increasing the growth temperature, as confirmed by the X-ray diffraction and selected area electron diffraction patterns. Photoluminescence investigations revealed the enhancement of the band edge emission with increasing growth temperature, suggesting the improvement in the optical quality of the ZnO nanorods with increasing temperature.     

Sonochemical synthesis of nitrogen doped ZnO nanorods: effect of anions on growth and optical properties

Sonochemical synthesis of nitrogen doped zinc oxide (ZnO:N) nanorods using acetate and nitrate of the starting materials is reported. X-ray diffraction studies reveal the formation of hexagonal wurtzite phase of ZnO in both the cases whereas the crystallite size is found to be greater in acetate route. Precursor dependent growth process is observed as the time period for precipitation is found to be different with different starting materials. Electron microscopic studies show the formation of rod like structures of ZnO and ZnO:N in both acetate and nitrate routes. But, high aspect ratio and uniformity in the morphology of ZnO:N nanorods is observed in acetate route. High resolution images and selected area diffraction patterns of ZnO:N illustrate the nanorods to be c-axis oriented in both the cases. But in nitrate medium, the growth along [0001] direction is affected due to the adsorption of NO₃ ^? ions onto polar Zn²⁺ surface leading to smaller length of the nanorods. FTIR studies also support these results showing the existence of sharp N–O symmetric stretching in ZnO:N in nitrate route. Photoluminescence (PL) measurements show red shift of excitonic emission band for ZnO in acetate route.     

The effect of Ce4 + incorporation on structural,morphological and photocatalytic characters of ZnO nanoparticles

We report a simple chemical precipitation method for the preparation of undoped and cerium doped ZnO nanocrystals. The concentration of cerium in the products can be controlled in the range of 0.025–0.125 mol. The structure and chemical compositions of the products were characterized by X-ray diffraction, X-ray photoelectron spectroscopy; energy dispersive spectrum and Fourier transform infrared spectroscopy. The results demonstrate that Ce^4 + ions were successfully incorporated into the lattice position of Zn^2 + ions in ZnO. The morphology of the products was analyzed by field emission scanning electron microscopy and confirmed by high resolution transmission electron microscope analysis. The optical properties of the products were studied by ultraviolet–visible and room temperature photoluminescence measurements. The photoluminescence emission spectra of Ce-doped ZnO showed enhanced visible emissions as a result of 5d → 4f transition of cerium. In particular, a novel photocatalytic activity of the products was assessed using methylene blue. The obtained result reveals that Ce-doped products show higher reduction efficiency for methylene blue than the undoped ZnO.     

Effects of Na-doping on the efficiency of ZnO nanorods-based dye sensitized solar cells

Na-doped ZnO nanorods (Zn_1?xNa_xO: x = 0.0, 0.02, 0.04) were grown by a chemical bath deposition method on ZnO seeded FTO substrates. The influence of Na-doping on the efficiency of ZnO nanorods-based dye-sensitized solar cells (DSSCs) was investigated. Undoped and Na-doped ZnO nanorods were used as photo-anodes for the fabricated DSSCs. X-ray diffraction measurements exhibited that all the samples had a wurtzite structure of ZnO with a preferred orientation of (002) plane. Scanning electron microscopy images of the samples revealed that all the samples displayed hexagonal shaped nanorods. It was observed from optical measurements that the band gap energy gradually decreased from 3.29 to 3.21 eV for undoped and 4 at.% Na-doped ZnO nanorods, respectively. Photoluminescence spectrum for undoped ZnO showed three peaks located at 379, 422, and 585 nm corresponding to UV emission, zinc vacancy, and deep level emission (DLE) peaks, respectively. When ZnO nanorods were doped with 2 at.% Na, the intensity of UV peak increased whereas the intensity of DLE peak decreased. The maximum conversion efficiency of DSSCs was found to be 0.22 % with a J_sc of 0.80 mA/cm², V_oc of 0.49 V, and fill factor of 0.523 as ZnO nanorods were doped with 2 at.% Na atoms.     

Galvanic deposition of ZnO using mixed electrolyte and their photoluminescence properties

The effects of Zn(OAc)₂ concentrations and chemical nature of supporting electrolytes on the galvanic deposition of ZnO have been investigated using scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy-dispersive X-ray (EDX) microanalysis. The results show that the taper-like ZnO crystals are apt to be produced at lower Zn(OAc)₂ concentrations, while the rod-like ZnO crystals tend to be grown at higher Zn(OAc)₂ concentrations. The photoluminescence of as-prepared ZnO nanorods shows that there exist a strong UV emission band, a broad blue band at 468 nm, and a very weak green band at 550 nm. The blue-shift of UV emission is attributed to the Cl doping of ZnO in chloride electrolyte.     

Influence of VI/II ratios on the growth of ZnO thin films on sapphire substrates by low temperature MOCVD

We investigated the structural, electrical, and optical properties of ZnO thin films grown at different VI/II ratios on sapphire substrates by metalorganic chemical vapor deposition. Transmission electron microscopy and X-ray diffraction revealed the epitaxial nature with a reduced dislocation density of the ZnO films grown at increased VI/II ratios. The carrier concentration of the films increased to 4.9 × 10¹⁸ cm^− 3 and their resistivity decreased to 1.4 × 10^− 1 Ω cm at a VI/II ratio of 513.4 μmol/min. The ZnO films also showed good optical transmittance (> 80%) in the visible and near-infrared wavelength regions. The room temperature PL revealed a strong band-edge emission with a weak deep level emission, suggesting the good crystalline quality of the ZnO films on the sapphire substrates. Furthermore, the intensity ratio of the band-edge emission to the deep-level emission (I_UV/I_Vis) increased with increasing VI/II ratio.     

Microstructural,chemical and textural characterization of ZnO nanorods synthesized by aerosol assisted chemical vapor deposition

ZnO nanorods were synthesized by aerosol assisted chemical vapor deposition onto TiO₂ covered borosilicate glass substrates. Deposition parameters were optimized and kept constant. Solely the effect of different nozzle velocities on the growth of ZnO nanorods was evaluated in order to develop a dense and uniform structure. The crystalline structure was characterized by conventional X-ray diffraction in grazing incidence and Bragg–Brentano configurations. In addition, two-dimensional grazing incidence synchrotron radiation diffraction was employed to determine the preferred growth direction of the nanorods. Morphology and growth characteristics analyzed by electron microscopy were correlated with diffraction outcomes. Chemical composition was established by X-ray photoelectron spectroscopy. X-ray diffraction results and X-ray photoelectron spectroscopy showed the presence of wurtzite ZnO and anatase TiO₂ phases. Morphological changes noticed when the deposition velocity was lowered to the minimum, indicated the formation of relatively vertically oriented nanorods evenly distributed onto the TiO₂ buffer film. By coupling two-dimensional X-ray diffraction and computational modeling with ANAELU it was proved that a successful texture determination was achieved and confirmed by scanning electron microscopy analysis. Texture analysis led to the conclusion of a preferred growth direction in [001] having a distribution width Ω = 20° ± 2°.     

Vertically aligned Fe-doped ZnO nanorod arrays by ultrasonic irradiation and their photoluminescence properties

A facile sonochemical route was demonstrated for the direct fabrication of Fe-doped ZnO nanorod arrays on a Si substrate under ambient conditions. By adding Fe³⁺ ions in reaction solution, Fe is readily in situ doped into ZnO nanorod arrays via ultrasound irradiation. The morphology and structural characteristic of the Fe-doped ZnO nanorods were investigated using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). And crystal structure was characterized by X-ray diffraction (XRD) spectroscopy. Inductively-coupled plasma atomic emission spectroscopy (ICP-AES) confirmed the Fe-doping of ZnO nanorod arrays with a concentration of 0.9 wt.%. In addition, Fe-doped ZnO nanorod showed the enhancement of photoluminescence (PL) intensity in green-yellow emission.     

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.     

Scintillation properties of Ce-doped LuLiF4 and LuScBO3

The crystals of 1 mol% Ce-doped LuLiF₄ (Ce:LLF) grown by the micro-pulling down (μ-PD) method and 1 mol% Ce-doped LuScBO₃ (Ce:LSBO) grown by the conventional Czochralski (Cz) method were examined for their scintillation properties. Ce:LLF and Ce:LSBO demonstrated ∼80% transparency at wavelengths longer than 300 and 400 nm, respectively. When excited by ²⁴¹Am α-ray to obtain radioactive luminescence spectra, Ce³⁺ 5d-4f emission peaks were detected at around 320 nm for Ce:LLF and at around 380 nm for Ce:LSBO. In Ce:LSBO, the host luminescence was also observed at 260 nm. By recording pulse height spectra under γ-ray irradiation, the absolute light yield of Ce:LLF and Ce:LSBO was measured to be 3600±400 and 4200±400 ph/MeV, respectively. Decay time kinetics was also investigated using a pulse X-ray equipped streak camera system. The main component of Ce:LLF was ∼320 ns and that of Ce:LSBO was ∼31 ns. In addition, the light yield non-proportionality and energy resolution against the γ-ray energy were evaluated.     

A facile and green approach for the fabrication of ZnO nanorods using bamboo charcoal as the template

A green synthetic approach was presented for the fabrication of ZnO nanorods via the bamboo charcoal-assisted impregnation route with ZnC₂O₄ colloid in ethanol as the inorganic precursor, followed by calcination at 800 °C for 7 h in air. These ZnO samples were characterized by means of X-ray diffraction (XRD) and transmission electron microscopy (TEM). It is shown that wurtzite hexagonal structured ZnO nanorods were fabricated, with an average diameter of about 300 nm and a length up to several micrometers. Bamboo charcoal played a key role in the formation of ZnO nanorods. The possible formation mechanism for ZnO nanorods was proposed.     

A study of structural, optical and magnetic properties of Cr, Ce co-doping in ZnO diluted magnetic semiconductors

We present the structural, optical and magnetic properties of pure ZnO, Zn_0.97Cr_0.03O and Zn_0.96Cr_0.03Ce_0.01O samples, the samples were synthesized by sol–gel method. The microstructures, optical and magnetic properties of samples were investigated by X-ray diffraction (XRD), transmission electron microscope , X-ray photoelectron spectroscopy (XPS), photoluminescence spectroscopy (PL), Raman spectroscopy and vibrating sample magnetometer. XRD and XPS data confirmed the formation of a single phase wurtzite type ZnO structure for all the samples. PL measurements revealed that all the three samples had an UV emission and a defect emission, and the Ce ions doping induced a red shift in the UV emission and an increase in the defect emission. Zn_0.97Cr_0.03O and Zn_0.96Cr_0.03Ce_0.01O samples showed the obvious hysteresis loops at room temperature and the saturation magnetization (Ms) increases with incorporating of Ce.     

Synthesis of Sn-doped ZnO nanorods and their photocatalytic properties

Sn-doped ZnO nanorods were fabricated by a hydrothermal route, and characterized by X-ray diffraction, field emission scanning electron microscope, UV-vis spectroscopy, Raman spectra, solid-state nuclear magnetic resonance (NMR) spectra, and room temperature photoluminescence spectroscopy. Solid-state NMR result confirms that Sn⁴⁺ was successfully incorporated into the crystal lattice of ZnO. Room temperature photoluminescence showed that all the as-synthesized products exhibited a weak UV emission (380 nm) and a strong visible emission (540 nm), but the intensities of the latter emission increased with increase in Sn concentration. The improvement of visible emission at 540 nm in the Sn-doped ZnO samples was suggested to be a result of the lattice defects increased by doping of Sn in zinc oxide. In addition, the photocatalytic studies indicated that Sn-doped ZnO nanorods are a kind of promising photocatalyst in remediation of water polluted by some chemically stable azo dyes.     

Graphene oxide modified ZnO nanorods hybrid with high reusable photocatalytic activity under UV-LED irradiation

In this work, graphene oxide/zinc oxide (GO/ZnO) hybrid was prepared through a facile hydrothermal process. Transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectra and N₂ adsorption and desorption isotherms were used to investigate the morphology, crystal structure, optical properties and specific surface area of GO/ZnO hybrid. It was shown that the well-dispersed ZnO nanorods were deposited on GO homogeneously. Photocatalytic properties of GO/ZnO nanorods hybrid were evaluated under 375 nm light-emitting diode light irradiation for photodegradation of methylene blue (MB). The synergic effect between GO and ZnO was found to lead to an improved photo-generated carrier separation. An optimal GO content has been determined to be 3 wt%, and corresponding the apparent pseudo-first-order rate constant kapp$k_{\text{app}}$ is 0.0248 min⁻¹, 4.3 times and 2.5 times more than that of pure ZnO nanorods and commercial P25 photocatalyst, respectively. Moreover, the cyclic photocatalytic test indicated that GO/ZnO hybrid can be reused for degradation of MB, suggesting the possible application of GO/ZnO hybrid as excellent candidate for water treatment.     

Fabrication of flower-like ZnO microstructures from ZnO nanorods and their photoluminescence properties

In the present work, we reported a novel method for the synthesis of well-dispersed flower-like ZnO microstructures derived from highly regulated, well-dispersed ZnO nanorods by using low temperature (100 °C) hydrothermal process and without using any additional surfactant, organic solvents or catalytic agent. The phase and structural analysis were carried out by X-ray diffraction (XRD) which confirms the high crystal quality of ZnO with hexagonal (wurtzite-type) crystal structure. The morphological and structural analyses were carried out by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) which indicate the formation of well-dispersed ZnO nanorods as well as flower-like ZnO. It has been shown that flower-like ZnO is made up of dozen of ZnO nanorods building block units. The high resolution transmission electron microscopy (HRTEM) and their corresponding selected area electron diffraction (SAED) pattern show that both ZnO nanorods and flower-like ZnO microstructures are single crystalline in nature and preferentially grow along [0 0 0 1] direction. Their optical property was characterized by photoluminescence spectroscopy; shows ZnO nanorods have only violet emission and no other emission while flower-like ZnO microstructures have a weak violet emission and a strong visible emission. A plausible growth mechanism of ZnO nanorods as well as flower-like ZnO microstructures has been given.     

The effects of divalent and trivalent dopants on the luminescence properties of ZnO fine particle with oxygen vacancies

The engineering, various factors, and mechanism responsible for emission and high intensity of ZnO luminescence are well developed. Only a few researchers investigate the role of oxygen vacancy on the luminescence properties of doped ZnO. The objective of this research is to synthesize the ZnO fine particle with tailored oxygen vacancy by doping with 5 at.% of divalent and trivalent dopants, i.e., magnesium (ZnO:Mg²⁺), calcium (ZnO:Ca²⁺), gadolinium (ZnO:Gd³⁺), and lanthanum (ZnO:La³⁺) using spray pyrolysis method. The samples prepared at 700 °C with 5 l/min carrier gas flow characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL) spectroscopy. The oxygen vacancy was successfully tuned by introducing various doping into ZnO fine particles. It is found that the oxygen vacancy responsible for the increase of DLE intensity (I_DLE) on the deconvoluted of PL spectra. When the ZnO fine particle doped with trivalent ions (Gd³⁺, La³⁺), the contribution of NBE intensity (I_NBE) is higher than I_DLE. Important phenomena also observed when the excitation wavelength was tuned. The contribution of I_DLE and I_NBE changes, lead to control the luminescence properties.