Influences of Al doping concentration on structural,electrical and optical properties of Zn0.95Ni0.05O powders

Nanocrystalline Zn_0.95−xNi_0.05Al_xO (x = 0.01, 0.02, 0.05 and 0.10) diluted magnetic semiconductors have been synthesized by an auto-combustion method. X-ray diffraction measurements indicate that all Al-doped Zn_0.95Ni_0.05O samples have the pure wurtzite structure. Transmission electron microscope analyses show that the as-synthesized powders are of the size 40–45 nm. High-resolution transmission electron microscope, energy dispersive spectrometer and X-ray photoemission spectroscope analyses indicate that Ni²⁺ and Al³⁺ uniformly substitute Zn²⁺ in the wurtzite structure without forming any secondary phases. The Al doping concentration dependences of cell parameters (a and c), resistance and the ratio of green emission to UV emission have the similar trends.     

Effect of Fe doping on the structural and gas sensing properties of ZnO porous microspheres

Fe-doped ZnO porous microspheres composed of nanosheets were prepared by a simple hydrothermal method combined with post-annealing, and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), Brunauer–Emmett–Teller N₂ adsorption–desorption measurements and photoluminescence (PL) spectra. In this paper we report Fe doping induced modifications in the structural, photoluminescence and gas sensing behavior of ZnO porous microspheres. Our results show that the crystallite size decreases and specific surface area increases with the increase of Fe doping concentration. The PL spectra indicate that the 4 mol% Fe-doped ZnO has higher ratio of donor (V_O and Zn_i) to acceptor (V_Zn) than undoped ZnO. The 4 mol% Fe-doped ZnO sample shows the highest response value to ppb-level n-butanol at 300 °C, and the detected limit of n-butanol is below 10 ppb. In addition, the 4 mol% Fe -doped ZnO sample exhibits good selectivity to n-butanol. The superior sensing properties of the Fe-doped porous ZnO microspheres are contributed to higher donor defects contents combined with larger specific surface area.     

Effect of Ce and Cu co-doping on the structural,morphological, and optical properties of ZnO nanocrystals and first principle investigation of their stability and magnetic properties

Ce, Cu co-doped ZnO (Zn_1−2xCe_xCu_xO: x=0.00, 0.01, 0.02, 0.03, 0.04 and 0.05) nanocrystals were synthesized by a microwave combustion method. These nanocrystals were investigated by using X-ray diffraction (XRD), UV–visible diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), and vibrating sample magnetometer (VSM). The stability and magnetic properties of Ce and Cu co-doped ZnO were probed by first principle calculations. XRD results revealed that all the compositions are single crystalline. hexagonal wurtzite structure. The optical band gap of pure ZnO was found to be 3.22 eV, and it decreased from 3.15 to 3.10 eV with an increase in the concentration of Cu and Ce content. The morphologies of Ce and Cu co-doped ZnO samples confirmed the formation of nanocrystals with an average grain size ranging from 70 to 150 nm. The magnetization measurement results affirmed the antiferro and ferromagnetic state for Ce and Cu co-doped ZnO samples and this is in agreement with the first principles theoretical calculations.     

Luminescence properties of green emission of SiO2/Zn2SiO4:Mn nanocomposite prepared by sol–gel method

Green light emitting Mn²⁺ doped Zn₂SiO₄ particles embedded in SiO₂ host matrix were synthesized by a sol–gel method. After the incorporation of ZnO:Mn nanoparticles in a silica monolith using sol–gel method with supercritical drying of ethyl alcohol in two steps, it was heat treated in air at 1200 °C for 2 h in order to obtain the SiO₂/α-Zn₂SiO₄:Mn nanocomposites. The microstructure of phosphor crystals was characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). XRD results indicate that the pure phase α-Zn₂SiO₄ with rhombohedral structure was obtained after thermal treatment at 1200 °C. The SiO₂/α-Zn₂SiO₄:Mn nanocomposites with a Mn doping concentration of 1.5 at% exhibit two broadband emissions in the visible range: a strong green emission at around 525 nm and a second one in the range between 560 and 608 nm. This nanocomposite with a Mn doping concentration of 0.05 shows the highest relative emission intensity. Upon 255 nm excitation, the luminescence decay time of the green emission of Zn₂SiO₄:Mn around 525 nm is 11 ms. The luminescence spectra at 525 nm (⁴T₁–⁶A₁) and lifetime of the excited state of Mn²⁺ ions-doped Zn₂SiO₄ nanocrystals are investigated.     

A study on the Raman spectra of Al-doped and Ga-doped ZnO ceramics

Al_xZn_1−xO and Ga_yZn_1−yO ceramics were synthesized through a solid-state reaction technique. The crystal phase of the samples was identified by an X-ray diffraction experiment. For each sample, the electrical resistivity was determined. The Al 2-mol%-doped and Ga 0.5-mol%-doped ZnO ceramics had the lowest resistivity. Raman measurement was performed to study the doping effects in the ZnO ceramics including ZnO single crystal as a reference. The line-shape parameters, q₁ and Γ₁, at the same certain doping rate and the solubility limit of Al (2 mol%) and Ga (0.5 mol%) in ZnO ceramics, are strongly related to the each other, and that the solubility limit plays an important role. The second-order Raman peak at 1162 cm⁻¹ of the ZnO ceramics was fitted by Fano formalism. The Fano’s fitting parameters, such as the lifetime of phonon and the degree of asymmetry degree of the second-order Raman peak changed as the amounts of dopants were varied.     

Structural and optical properties of Mn-doped ZnO nanocrystalline thin films with the different dopant concentrations

The transparent nanocrystalline thin films of undoped zinc oxide and Mn-doped (Zn_1−xMn_xO) have been deposited on glass substrates via the sol–gel technique using zinc acetate dehydrate and manganese chloride as precursor. The as-deposited films with the different manganese compositions in the range of 2.5–20 at% were pre-heated at 100 °C for 1 h and 200 °C for 2 h, respectively, and then crystallized in air at 560 °C for 2 h. The structural properties and morphologies of the undoped and doped ZnO thin films have been investigated. X-ray diffraction (XRD) spectra, scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS) were used to examine the morphology and microstructure of the thin films. Optical properties of the thin films were determined by photoluminescence (PL) and UV/Vis spectroscopy. The analyzed results indicates that the obtained films are of good crystal quality and have smooth surfaces, which have a pure hexagonal wurtzite ZnO structure without any Mn related phases. Room temperature photoluminescence is observed for the ZnO and Mn-doped ZnO thin films.     

Low-temperature synthesis of Zn2SiO4:Mn green photoluminescence phosphor

Zn₂SiO₄:Mn green phosphor having comparable photoluminescence (PL) efficiency with commercial phosphor has been synthesized at 1000 °C using solid state reactions involving ZnO, silicic acid and manganese acetate. The water of crystallization attached to SiO₂ in silicic acid whose dissociation at 1000 °C seem to promote the sintering efficiency of Zn₂SiO₄:Mn. Incremental ZnO addition and re-firing at 1000 °C promote the diffusion rate of ZnO and SiO₂. The formation of a single crystalline phase of willemite structure in the samples was confirmed by powder XRD measurements. The phosphor exhibit an intense excitation band centered around 275 nm and a relatively weak excitation centered around 380 nm while the broad band green emission peaks at 524 nm. Other parameters studied include PL spectra, grain morphology, ZnO/SiO₂ molar ratio, Mn concentration, co-dopant/flux and the effect of chemical forms of Mn dopant as well as silica on the PL efficiency.     

Effects of Cd concentration on structure and optical properties of the ternary Zn1−xCdxO nanopowder prepared by sol–gel method

Zn_1−xCd_xO nanocrystalline powder with different Cd contents (0≤x≤1) has been prepared by new facile sol–gel route. The crystal structure and optical properties were investigated by X-ray diffraction patterns, Transmission electron microscope, X-ray photoelectron spectroscopy, Photoluminescence. As x varied from x=0 to 0.25, the Zn_1−xCd_xO nanopowder exhibits a hexagonal wurtzite structure of pure ZnO without any significant formation of a separated CdO phase. For the samples with 0.5≤x≤0.85, the Zn_1−xCd_xO nanopowder exhibits the coexistence of hexagonal ZnO and cubic CdO phase, meanwhile, the content of ZnO phase decreases while that of CdO increases with increasing the Cd content x. The ultra-violet near-band-edge emission of the Zn_1−xCd_xO nanopowder was monotonously red-shifted from 389 nm (x=0) to 406 nm (x=0.25) due to the direct modulation of band gap caused by Cd substitution.     

M/Li+(M = Mg2+, Zn2+, and Mn2+) ion-exchange on lithium ion-conducting perovskite-type oxides and their properties

Lithium ions of perovskite-type lithium ion conductor La_0.55Li_0.35TiO₃ were replaced by divalent Mg²⁺, Zn²⁺, and Mn²⁺ ions in an ion-exchange reaction using molten chlorides. The polycrystalline Mg-exchanged and Zn-exchanged samples are solid electrolytes for divalent Mg²⁺ and Zn²⁺ ions, whose dc ionic conductivities (σ = 2.0 × 10^− 6 S cm^− 1 at 558 K for the Mg-exchanged sample, La_0.56(2)Li_0.02(1)Mg_0.16(1)TiO_3.01(2) and σ = 1.7 × 10^− 6 S cm^− 1 at 708 K for the Zn-exchanged samples, La_0.55(1)Li_0.0037(2)Zn_0.15(1)TiO_2.98(2)) were compared to those of the known highest Mg²⁺ and Zn²⁺ inorganic solid electrolytes. The Mn-exchanged sample, then, showed paramagnetic behavior in the temperature range of 2 to 300 K. The Mn ions in the exchanged sample are divalent and the spin configuration is in high spin state (S = 5/2).     

Improved critical current density in Zn doped YBCO single crystals

Magnetic measurements were made using pure YBCO and Zn doped YBa₂(Cu_1?xZn_x)₃O_7?σ. Single crystals with Zn concentration of 0.5%, 1.5%, 3.0% and 4.3%. The magnetic hysteresis loops for these samples were measured in the temperature range 0.1 ? T/T_c ? 0.96 under magnetic fields of 5 T using SQUID. It was found that the critical current density J_c increased for low Zn content samples up to 3% Zn concentration compared to pure YBCO sample and decreased for the higher Zn content samples. These values varied consistently when compared at magnetic fields of 1 T and 3 T. Moreover Zn doped samples showed significant values of J_c in the temperature range of 0.7–0.9T_c, close to critical temperature compared to pure YBCO sample. The irreversibility field H_irr was also enhanced in this temperature range showing consistent decrease with increase of Zn concentration. The peak field H_p above H_c1 and irreversibility field H_irr, both show power law dependence of the form H = m₁(1 ? T/T_c)^m2 in the temperature range of 0.75–0.96T_c. The values of parameter m₂ increased from 1.44 to 1.95 for the samples up to 3% Zn content and decreased to 1.37 for higher Zn contents. The ratio H_irr/H_p was found to be 3–4 for the lower Zn content samples and was 7–8 for the sample with high Zn content indicating more disorder for higher Zn content samples. The region between peak field H_p and irreversibility field H_irr was broadened with the increase of Zn concentration. The strong effect of Zn substitution in modifying behavior of these samples even at elevated temperatures is possibly due to the changes in the anisotropy of our samples with the increase of Zn concentration and also due to the locally induced changes in magnetic moments by Zn substitution.     

Microstructure and varistor properties of ZnO–V2O5–MnO2 ceramics with Ta2O5 addition

The effect of Ta₂O₅ addition on microstructure, electrical properties, and dielectric characteristics of the quaternary ZnO–V₂O₅–MnO₂ vaistor ceramics was investigated. Analysis of the microstructure indicated that the quaternary ZnO–V₂O₅–MnO₂–Ta₂O₅ ceramics consisted of mainly ZnO grain and minor secondary phases such as Zn₃(VO₄)₂, ZnV₂O₄, TaVO₅, and Ta₂O₅. As the amount of Ta₂O₅ increased, the sintered density increased from 94.8 to 97.2% of the theoretical density (5.78 g/cm³ for ZnO), whereas the average grain size decreased from 7.7 to 6.0 μm. The ceramics added with 0.05 mol% Ta₂O₅ exhibited the highest breakdown field (2715 V/cm) and the highest nonlinear coefficient (20). However, further increase caused α to abruptly decrease. The Ta₂O₅ acted as a donor due to the increase of electron concentration in accordance with the amount of Ta₂O₅. The donor concentration increased from 1.97×10¹⁸ to 3.04×10¹⁸cm^?3 with increasing the amount of Ta₂O₅ and the barrier height exhibited the maximum value (0.95 eV) at 0.05 mol% Ta₂O₅.     

Optical properties of oxide magnetic ZnO, Zn0.95Mn0.05O and Cu2O nanopowders

ZnO, Zn_0.95Mn_0.05O and Cu₂O nanocrystals are synthesized. Excitonic lines in absorption spectra of these materials are detected. In photoluminescence and photoluminescence excitation spectra of Zn_0.95Mn_0.05O the dangling bond hybrid (DBH) state is found. It has splitted out from the top of the valence band due to the hybridization between d-states of the Mn impurity and the p-states of oxygen.     

White-light emission from annealed ZnO:Si nanocomposite thin films

As grown ZnO:Si nanocomposites of different compositional ratios were fabricated by thermal evaporation techniques. These films were subjected to post-deposition annealing under high vacuum at a temperature of 250 °C for 90 min. The photoluminescence (PL) spectra of annealed samples have shown marked improvements both in terms of intensity and broadening. Structural and Raman analyses show formation of a Zn–Si–O shell around ZnO nanoclusters wherein on heating Zn₂SiO₄ compound forms resulting in huge UV, orange and red peaks at 310, 570 and 640 nm in PL. The new emissions due to Zn₂SiO₄ completes white light spectrum. The study not only suggests that 1:2 ratio is the best suited for material manipulation but also shows process at the interface of ZnO nanoclusters and silicon matrix leads to new PL emissions.     

Effect of heat treatments on the luminescence properties of Zn2SiO4:Mn2+ phosphors prepared by glycothermal methods

Manganese-doped Zn₂SiO₄ phosphors with different crystal structures and morphologies were synthesized by glycothermal reactions of zinc acetate dihydrate and manganese(II) acetate tetrahydrate with tetraethyl orthosilicate in various glycols at 315 °C. The reactions in 1,3-propanediol and 1,4-butanediol yielded α-Zn₂SiO₄:Mn²⁺, whereas the reactions in ethylene glycol and 1,5-pentanediol yielded β-Zn₂SiO₄:Mn²⁺ and ZnO, respectively. The samples obtained in 1,4-butanediol and 1,3-propanediol emitted green light (522 nm), and the sample prepared in 1,4-butanediol showed a higher emission intensity. The photoluminescence intensity of the Zn_1.96Mn_0.04SiO₄ phosphor prepared by a glycothermal reaction in 1,4-butanediol and subsequently calcined at 1100 °C was twice as high as that of the sample synthesized by a conventional solid-state reaction. The high emission efficiency was obtained because the highly homogeneous distribution of Mn²⁺ in the α-Zn₂SiO₄ host synthesized by the glycothermal reaction was maintained during calcination treatment in air.     

Sonocatalytic degradation of a textile dye over Gd-doped ZnO nanoparticles synthesized through sonochemical process

The present study was performed to sonochemically synthesize Gd_xZn_1 − xO (x = 0–0.1) nanoparticles for sonocatalysis of Acid Orange 7 (AO7) in an aqueous medium. The results of X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) analysis confirmed proper synthesis of Gd-doped sonocatalyst. 5% Gd-doped ZnO nanoparticles with band gap of 2.8 eV exhibited the highest sonocatalytic decolorization efficiency of 90% at reaction time of 90 min. The effects of initial dye concentration and sonocatalyst dosage on decolorization efficiency were evaluated. In the presence of sodium sulfate, sodium carbonate and sodium chloride the decolorization efficiency decreased from 90 to 78, 65 and 56%, respectively. Among various enhancers, the addition of potassium periodate improved the decolorization efficiency from 90 to 100%. The highest decolorization efficiency was obtained at pH value of 6.34 (90%). The decolorization efficiency decreased only 6% after 4 repeated runs. Therefore, Gd-doped ZnO nanoparticles can be used as a promising catalyst for degradation of organic pollutants with great reusability potential.     

Suppression of superconductivity in Zn-doped SmFeAsO0.8F0.2 system

A series of SmFe_1?xZn_xAsO_0.8F_0.2 samples with x = 0, 0.05, 0.1, 0.2 and 0.4 have been successfully synthesized using a solid state method. The lattice parameters are found to increase with increasing Zn doping content. The superconductivity has been definitely suppressed by Zn doping at Fe site with the transition temperature T_c being reduced from 52.5 K to 23.3 K for the sample of x = 0.05, and to 18.2 K for the sample of x = 0.1. For the samples with x > 0.1, the superconducting transition vanishes, and, at the meantime, the spin-density-wave anomaly recovers at 140 K. The metal to semiconductor transition is also observed in the SmFe_1?xZn_xAsO_0.8F_0.2 system. The behavior of SmFe_1?xZn_xAsO_0.8F_0.2 is very different from that of R_EFeAsO (R_E = rare earth metal), which reveals a very strong electron correlation in SmFe_1?xZn_xAsO_0.8F_0.2.     

Electrical and mechanical properties of diluted magnetic semiconductor Zn1−xMnxS nanocrystalline films

Nanostructured Zn_1−xMn_xS films (0 ⩽ x ⩽ 0.25) were deposited on glass substrates by simple resistive thermal evaporation technique. All the films were deposited at 300 K in a vacuum of 2 × 10⁻⁶ m bar. All the films temperature dependence of resistivity revealed semiconducting behaviour of the samples. Hot probe test revealed that all the samples exhibited n-type conductivity. The nanohardness of the films ranges from 4.7 to 9.9 GPa, Young’s modulus value ranging 69.7–94.2 GPa.     

Effects of a Cu-contained compound on the microstructures and thermoelectric properties of Zn–Sb based alloys

Zn–Sb based alloys with Cu₂Sb addition were prepared using spark plasma sintering technique and the effects of a Cu-contained intermetallic phase on the microstructures and thermoelectric properties were examined. Rietveld refinement reveals that there are many phases in the alloys, which involve β-Zn₄Sb₃, a major phase ZnSb, a small amount of an intermetallic compound Cu₅Zn₈ and unidentified impurity phases, the quantities of ZnSb and Cu₅Zn₈ increase from 67.3 wt.% to 91.8 wt.% and 0–4.3 wt.% with Cu₂Sb additive increasing, respectively. The ZnSb plays a fundamental role in controlling the thermoelectric properties, and Cu₅Zn₈ is of great significance to optimize the transport properties. The maximum thermoelectric figure of merit ZT of 0.72 is obtained for the alloy (Cu₂Sb)_0.05–(Zn₄Sb₃)_0.95 at 654 K, which is 0.25 higher than that of undoped β-Zn₄Sb₃ at the same conditions. Therefore, we conclude that a proper addition of Cu₂Sb can contribute to the improvement of thermoelectric properties of Zn–Sb based alloys.     

Stable barium compounds in YBa2Cu3Oy superconductors

The stability of various amounts of Ba₃Cu₃In₄O₁₂ (334) or BaTbO₃ (BTO) in a sintered YBa₂Cu₃O_y (YBCO) matrix was examined. Samples with added 334 or BTO exhibited critical temperatures (T_c) above 90 K for up to 20 vol.% addition and improved critical current densities (J_c) under a magnetic field. X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX) analysis indicated that 334 and BTO did not react with the YBCO matrix under the sintering conditions used. The normalized J_c under a magnetic field of 1 T reached a maximum at 14 vol.% of 334 addition and 20 vol.% BTO addition. YBCO thin films with added BTO showed a gradual decrease in the T_c with increasing BTO content. YBCO films with added 334 showed a constant T_c of 87 K up to a 334 content of 4 vol.%.     

Structural and electrochemical properties of LiNi0.5Mn0.5 − xAlxO2 (x = 0, 0.02, 0.05, 0.08, and 0.1) cathode materials for lithium-ion batteries

Layered LiNi_0.5Mn_0.5 ? xAl_xO₂ (x = 0, 0.02, 0.05, 0.08, and 0.1) series cathode materials for lithium-ion batteries were synthesized by a combination technique of co-precipitation and solid-state reaction, and the structural, morphological, and electrochemical properties were examined by XRD, FT-IR, XPS, SEM, CV, EIS, and charge–discharge tests. It is proven that the aliovalent substitution of Al for Mn promoted the formation of LiNi_0.5Mn_0.5 ? xAl_xO₂ structures and induced an increase in the average oxidation number of Ni, thereby leading to the shrinkage of the lattice volume. Among the LiNi_0.5Mn_0.5 ? xAl_xO₂ materials, the material with x = 0.05 shows the best cyclability and rate ability, with discharge capacities of 219, 169, 155, and 129 mAh g^? 1 at 10, 100, 200, and 400 mA g^? 1 current density respectively. Cycled under 40 mA g^? 1 in 2.8–4.6 V, LiNi_{0. 5}Mn_0.45Al_0.05O₂ shows the highest discharge capacity of about 199 mAh g^? 1 for the first cycle, and 179 mAh g^? 1 after 40 cycles, with a capacity retention of 90%. EIS analyses of the electrode materials at pristine state and state after first charge to 4.6 V indicate that the observed higher current rate capability of LiNi_{0. 5}Mn_0.45Al_0.05O₂ can be understood due to the better charge transfer kinetics.