Structural and magnetic studies of Mn‐doped ZnO

The bulk samples of Mn‐doped ZnO were synthesized with the nominal compositions Zn_1‐xMn_xO (x = 0.02, 0.05, 0.10, 0.15) by the solid‐state reaction and sol‐gel methods. In both the methods the samples were finally sintered at ∼700 °C in air. The X‐ray diffraction (XRD) studies of the samples synthesized by the solid‐state reaction method exhibit the presence of wurtzite (hexagonal) crystal structure similar to the parent compound (ZnO) in all the samples, suggesting that doped Mn ions sit at the regular Zn sites. However, same studies spread over the samples with Mn content ≥5% and synthesized by the sol‐gel method reveal the occurrence of some secondary phase in addition to the majority wurtzite phase. The magnetic measurements by vibrating sample magnetometer (VSM) clearly indicate ferromagnetic interaction at room temperature in all the samples. The Curie temperatures (T_c) and magnetization vary with concentration of Mn ions in the samples. However, the samples synthesized by sol‐gel method were found to have lower Tc values and also lower magnetization as compared to the corresponding samples synthesized by solid‐state reaction method. It could possibly be due to the presence of antiferromagnetic islands and smaller crystallite sizes in the samples prepared by sol‐gel method. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Co nanoclusters as origin of ferromagnetism in sol‐gel synthesized Zn1‐xCoxO (x = 0.05, 0.10 and 0.15) samples

We report on the structural and magnetic properties of the polycrystalline samples of Zn_1‐xCo_xO (x = 0.05, 0.10 and 0.15) synthesized via sol‐gel route. The air sintered samples of all compositions exhibit paramagnetic behaviour at room temperature, on the other hand the same samples on annealing in Ar/H₂ atmosphere show room temperature ferromagnetism (RTFM) with enhanced magnetization. The value of magnetization increases with the Co concentration (x) in both the air sintered and Ar/H₂ annealed samples. The observed ferromagnetism in the Ar/H₂ annealed Zn_1‐xCo_xO (x = 0.05, 0.10 and 0.15) samples is attributed to the presence of Co nanoclusters as detected by XRD and FESEM‐EDAX. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical and magnetic properties of Nd‐doped ZnO nanoparticles

Nd‐doped ZnO nanoparticles with different concentration were synthesized by sol‐gel method. The structures, magnetic and optical properties of as‐synthesized nanorods were investigated. X‐ray diffraction (XRD) and x‐ray photoelectron spectroscopy (XPS) results demonstrated that Nd ions were incorporated into ZnO lattice; but Zn_1‐xNd_xO nanoparticles with Nd concentration of x = 0.05 showed Nd₂O₃ phase, so the saturation concentration of Nd in Zn_1‐xNd_xO is less than 5 at%. Vibrating sample magnetometer (VSM) measurements indicated that Nd doped ZnO possessed dilute ferromagnetis behaviour at room temperature. Photoluminescence spectroscopy (PL) showed that Nd ions doping induced a red slight shift and decrease in UV emission with increase of Nd concentration.     

Structure and electrical properties of Mg‐doped ZnO nanoparticles

Mg_xZn_1‐xO (x=0.01‐0.3) nanoparticles were synthesized by the sol‐gel technique using solutions of Mg and Zn based organometalic compounds. The electrical properties of Mg doped zinc oxide (ZnO) were studied within wide temperature range from 300 to 500 K under the N₂ gas flow (flow rate: 20 sccm) and in the frequency range from 40 Hz to 1 MHz for ac electrical measurements. The dc conductivities and the activation energies were found to be in the range of 10^‐9‐10^‐6 S/cm at the room temperature and 0.26‐0.86 eV respectively depending on doping rate of these samples. The ac conductivity was well represented by the power law Aω^s. The conduction mechanism for all doped ZnO could be related to correlated barrier hopping (CBH) model. The complex impedance plots (Nyquist plot) showed the data points lying on a single semicircle, implying the response originated from a single capacitive element corresponding to the nanoparticle grains. The crystal structures of the Mg_xZn_1‐xO nanoparticles were characterized using X‐ray diffraction. The calculated average particle sizes values of Zn_1‐xMg_xO samples are found between 29.72 and 22.43 nm using the Sherrer equation. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and characterization of nano ZnS doped with Mn

Nanocrystalline samples of Zn_1‐xMn_xS (x = 0.0, 0.02, 0.04) were synthesized by chemical precipitation method and characterized for magnetism. EPR studies showed an evidence of ferromagnetism around room temperature. Hysterisis from vibrating sample magnetometer supports the observation. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

XRD,IR, and Raman investigations of structural properties of Dy2‐xHox O3 prepared by sol gel procedure

The Rare earth mixed oxides Dy_2‐xHo_x O₃ (0.0 ≤ x ≤ 2.0) solid solution was synthesized by a sol–gel process. X‐ray diffraction (XRD) data were collected and crystal structure and microstructure analyses were performed applying Rietveld refinement method. Infrared and Raman spectroscopy were used to define the microstructure and to locally probe the structure of the samples. The cationic distribution over the two non‐equivalent sites 8b and 24d of the space group Ia3 is found to be randomly. The crystallite size and microstrain as well as Raman modes positions are influenced by Ho³⁺ concentration. The apparent size is isotropic but significant anisotropy is found for the microstrain with its largest value along the crystallographic direction [h00]. Inspite the single phase solid solution confirmed by Rietveld analysis for all samples, Raman spectra detected the coexistence of two phases; cubic and distorted monoclinic of too small amount or highly disordered, i.e. amorphous like, to be detected by XRD. The result indicates the ability of Raman spectroscopy to detect minor phases in solid solutions. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ferromagnetic insulating and reentrant spin glass behavior in Mg doped La0.75Sr0.25MnO3 manganites

In this study, the effect of Mg substitution on structural, magnetic and electrical properties of La_0.75Sr_0.25Mn_1?xMg_xO₃ and La_0.75Sr_0.25?xMg_xMnO₃ (nominal compositions) samples are investigated by XRD, Ac susceptibility and electrical resistivity measurements. It is found that Mg does not replace La in the perovskite lattice. Also the results show that by increasing Mg doping levels, the paramagnetic–ferromagnetic and metal–insulator transition temperatures decrease. The reason for decreasing transition temperatures with increasing Mg concentration is, that the long-range FM order has been destroyed by the Mg, which is randomly occupying Mn site. This leads to the suppression of double-exchange interaction in the Mn³⁺–O–Mn⁴⁺ networks. Also the reentrant spin glass (RSG) state accompanied by FM transition, exists in high doped samples. The RSG state could be understood on the basis of double exchange ferromagnetic interaction in Mn³⁺–O–Mn⁴⁺ and super-exchange antiferromagnetic interaction in the Mn⁴⁺–O–Mn⁴⁺ networks.     

Spin disorder in Fe-doped manganites

Ln_0.7M_0.3MnO₃ compounds are well-known ferromagnets mediated by a double exchange mechanism. As Mn atoms are substituted by Fe in the ratio Mn_1−xFe_x the magnetic structure dramatically changes, because the ferromagnetic double exchange chain is broken. At low Fe concentrations all compounds are magnetically ordered. For intermediate values ferro (FM), antiferro (AF) and paramagnetic (PM) phases co-exist in a large temperature range, and at x ≈ 0.2 spin or cluster-glass behavior is found. Magnetization, Mössbauer, polarized and low angle neutron scattering as well as muon spin relaxation experiments have been performed on 0 ⩽ x ⩽ 0.30 compounds showing the transit from long range ferromagnetism to spin glass. Co-existence of FM and AF clusters of different size has been found for all doped compounds.     

Controllable thermal expansion properties of In2 − xCrxMo3O12

Solid solutions In_{2 − x}Cr_xMo₃O₁₂ have been prepared via the solid state reaction method. The structural and thermal expansion properties have been characterized using X‐ray diffraction. All compounds exhibit monoclinic structure with space group P2₁/a at room temperature, and transform to orthorhombic structure at higher temperature. Compounds In_{2 − x}Cr_xMo₃O₁₂ (x = 0.7, 1.0 and 1.3) possess strong positive thermal expansion in the monoclinic structure, while their thermal expansion coefficients of orthorhombic structure vary from negative to positive with increasing Cr content. It is worthwhile to note that In_1.3Cr_0.7Mo₃O₁₂ and InCrMo₃O₁₂ have near zero thermal expansion properties.     

Experimental and first‐principle investigation of Cu‐doped ZnO ferromagnetic powders

Zn_1‐xCu_x O powders were synthesized by using sol‐gel method. Electronic band structure and ferromagnetic properties of Zn_1‐xCu_x O powders were studied experimentally and theoretically. The simulations are based upon the Perdew‐Burke‐Ernzerhof form of generalized gradient approximation within the density functional theory. Zn_1‐xCu_x O shows dilute ferromagnetism, as a saturated magnetization of 0.9×10^‐3emu/g was observed for Zn_0.95Cu_0.05O powders. The strong p ‐d hybridization between Cu and its four neighbouring O atoms is responsible for the ferromagnetism. Comparing with ZnO whose Fermi level locates at the valence band maximum, the Fermi level of the Zn_1‐xCu_x O shifts upward into the valence band and hence the Zn_1‐xCu_x O system exhibits theoretically a p ‐type metallic semiconducting property. The Zn_1‐xCu_x O system may be a potential candidate in spintronics. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electrical and magnetotransport properties of La0.7Sr0.3MnO3/TiO2 composites

The composite samples with nominal compositions of (1‐x) La_0.7Sr_0.3MnO₃ + x TiO₂ (x = 0, 0.05, 0.10, 0.15 and 0.20) were synthesized via solid state reaction process. The X‐ray diffraction and scanning electronic microscopy observations reveal no reaction between La_0.7Sr_0.3MnO₃ (LSMO) and TiO₂ phases. Temperature dependence resistivity measurements show that TiO₂ phase shifts the metal‐insulator transition temperature (T_p) towards lower temperature and increases the resistivity. Moreover, the magnetization of the composite samples decreases with TiO₂ content. An enhancement in magnetoresistance is observed in the composite samples with x = 0.05 and x = 0.10 at low magnetic fields, which is encouraging for potential application of magnetoresistive materials at low field. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure,microstructure and magnetic properties of mixed rare earth oxide (Dy1‐xErx)2O3

The mixed rare earth oxide (Dy_1‐xEr_x)₂O₃ (0.0 ≤ x ≤ 1.0) were synthesized by a sol–gel process. X‐ray and neutron diffraction data were collected and crystal structure and microstructure analyses were performed using Rietveld refinement method. All samples were found to have the same crystal structure and formed solid solutions over the whole range of x. Preferential cationic distribution is found for all samples but with different extent with Dy³⁺ preferring the 8b among the two non‐equivalent sites 8b and 24d of the space group Ia3. The lattice parameter is found to vary linearly with the composition x and a systematic variation is found in the r.m.s microstrain . Magnetization measurements were done in the temperature range 5‐300 K and a behavior in accordance with Curie‐Weiss law was found. Anomalous concentration dependence is found in magnetic susceptibility which is ascribed to the concentration dependence of effective crystal field combined with the contribution of ⁴I_15/2 and ⁶H_15/2 manifold at elevated temperature. The effective magnetic moments μ_eff is found to decrease linearly with composition parameter x, except for sample x=0.5 where the magnetization is enhanced. The Curie‐Weiss paramagnetic temperatures indicated antiferromagnetic interaction. These magnetic results are discussed in view of the cationic distribution. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and photoluminescence properties of CdS solid solution semiconductor

Photoluminescence (PL) emitted from Cd_1‐xZn_xS and CdS_1‐ySe_y solid solution semiconductor was significantly stronger than PL from the pure CdS and CdSe semiconductor. The samples were prepared using an improved Se‐S‐Na₂S flux route. Photoluminescence in Cd_1‐xZn_xS crystal was brightly yellow at the room temperature under VU radiation. The phase and composition of the solid solution was measured by the XRD and was confirmed by UV‐NIS spectrum as x of 0.3 and y of 0.2. The enhanced photoluminescence was presumably due to the introduction of extra defect (vacancies) by solid solution action and consequently the increasing of luminescence center concentration. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Studies on electrical conduction behavior of La1‐3xCaxBaxSrxMnO3 synthesized by chemical route

In the manganite La_1‐xM_xMnO₃ (M = Ca, Ba, Sr) the doping concentration introduces a mixed valency (Mn³⁺, Mn⁴⁺) which governs the magnetic and electrical properties of the compound. The perovskite oxides La_1‐3xCa_xBa_xSr_xMnO₃ (x = 0.00, 0.05, 0.10) were prepared by chemical method. Single‐phase formation is confirmed by XRD studies. The electrical behavior of compositions with x = 0.00, 0.05 and 0.10 in the system La_1‐3xCa_xBa_xSr_xMnO₃ was studied in the temperature range 300‐420 K. It is observed that conductivity decreases with increasing temperature as well as dopants concentration. Metallic behavior of these compositions decreases with increasing dopants concentration (x). The microstructures of these samples have been characterized using scanning electron microscopy (SEM). (© 2007 WILEY ‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

X‐ray diffraction analysis of powder and thin film of (Gd1‐x Yx)2O3 prepared by sol‐gel process

The mixed oxide (Gd_1‐xY_x)₂O₃ (0.0 ≤ x ≤ 1.0) were synthesized, as powder and thin film, by a sol‐gel process. X‐ray diffraction data were collected and crystal structure and microstructure analysis were performed using Rietveld refinement method. All samples were found to have the same crystal system and formed solid solutions over the whole range of x. The cationic distribution, Gd³⁺ and Y³⁺, over the two non‐equivalent sites 8b and 24d of the space group Ia3 is found to be random for all values of (x). The lattice parameter is found to vary linearly with the composition (x). Replacing Gd³⁺ and Y³⁺ by each other introduces a systemic decrease in the x‐coordinate of cation position (24d) and slight changes in the oxygen coordinates. Crystallite size and microstrain analysis is performed along different crystallographic directions and anisotropic changes are found with the composition parameter (x). The average crystallite size ranges from 75 to 149 nm and the r.m.s strain from 0.027 to 0.068 x10^‐2. Textured Gd_1.841Y_0.159O₃ (400) buffer layers, with a high degree of alignment in both out‐plane and in‐plan, are successfully grown on cube textured Ni (001) tape substrates by sol–gel dip coating process. The resulting buffer layers are crack‐free, pinhole‐free, dense and smooth. YbBa₂Cu₃O_7‐x (YbBCO) thin film could be (00l) epitaxially grown on the obtained buffer layer using sol–gel dipping technique. (© 2007 WILEY ‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and characterization of compounds LixMn1+xFe2–2xO4 with spinel structure in the quasiternary system “LiO0,5 – MnOx – FeOx“

The thermal decomposition of freeze‐dried Li‐Mn(II)‐Fe(III)‐formate precursors was investigated by means of DTA, TG and mass spectroscopy. By the thermal treatment of the prefired precursors between 400 and 1000°C, single phase solid solutions Li_xMn_1+xFe_2–2xO₄ (0 ≤ x ≤ 1) with cubic spinel structure were obtained. To get single phase spinels, special conditions concerning the temperature T and the oxygen partial pressure p(O₂) during the synthesis are required. Because of the high reactivity of the freeze‐dried precursors, in comparison with the conventional solid state reaction, the reaction temperature can be lowered by 200°C. The cation distribution and the properties of the Li‐Mn‐ferrites were studied by chemical analysis, X‐ray powder diffraction and magnetization measurements. It was found that for high substitution rates, almost all lithium occupies the tetrahedral coordinated A‐sites of the spinel lattice AB₂O₄, while at small x‐values, lithium ions are distributed over the tetrahedral and octahedral sites. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and characterization of hexagonal ferrites BaFe12‐2xZnxTixO19 (0 ≤ x ≤ 2) by thermal decomposition of freeze‐dried precursors

Substituted barium hexaferrites, BaFe_12‐2xZn_xTi_xO₁₉ (0 ≤ x ≤ 2), have been synthesized by thermal decomposition of freeze‐dried acetate precursors. Decomposition and phase formation were investigated by means of thermal analysis, XRD and IR spectroscopy. The initially amorphous decomposed precursor reacts to the substituted hexaferrite via a spinel‐like maghemite (γ‐Fe₂O₃) and Zn/Ti containing spinel ferrites. The synthesis method allows a decrease of the reaction temperature and time, necessary for producing a single phase hexaferrite. At relative low reaction temperatures, the substitution rate x shows remarkable differences at different iron sublattices. For x ≤ 0,8 this selective substitution results in an increase of magnetization as x grows. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Magnetic properties of TiCx/C nanocomposites

The magnetic properties of nanocrystalline titanium carbide dispersed in a carbon matrix (TiC_x/C) prepared by the non-hydrolytic sol–gel process have been studied by dc magnetization measurements. The superconducting phase of titanium carbide has been observed at low temperatures with the onset of the superconducting transition temperature T_c at about 3.5 K, superimposed on a ferromagnetic component. At T > T_c the magnetic response of TiC_x/C is determined by the interplay of the ferromagnetic contribution with the paramagnetic/diamagnetic signal of the metallic system and the contribution of exchange coupled paramagnetic ions. Moreover, significant differences are observed in the magnetic response for samples of the same preparation batch, indicative of the magnetic/electronic inhomogeneity of nanocrystalline titanium carbide which is important for its practical applications.     

Structure and optical properties of Mg‐doped ZnO nanoparticles by polyacrylamide method

Mg‐doped ZnO (Mg_xZn_1‐xO) nanoparticles with precise stoichiometry are synthesized through polyacrylamide polymer method. Calcination of the polymer precursor at 650 °C gives particles of the homogeneous solid solution of the (Mg_xZn_1‐xO) system in the composition range (x < 0.15). ZnO doping with Mg causes shrinkage of lattice parameter c. The synthesized Mg_xZn_1‐xO nanoparticles are typically with the diameter of 70–85 nm. Blue shift of band gap with the Mg‐content is demonstrated, and photoluminescence (PL) from ZnO has been found to be tunable in a wide range from green to blue through Mg doping. The blue‐related PL therefore appeared to be caused by energetic shifts of the valence band and/or the conduction band of ZnO. Mg_xZn_1‐xO nanoparticles synthesized by polyacrylamide‐gel method after modified by polyethylene glycol surfactant have a remarkable improvement of stability in the ethanol solvent, indicating that these MZO nanoparticles could be considered as the candidate for the application of solution–processed technologies for optoelectronics at ambient temperature conditions.     

Structural and magnetic properties of ZnO and Zn1−xMnxO nanocrystals

Chemical precipitation of metal-ions from aqueous solution has been successfully used to produce Zn_1?xMn_xO nanocrystals, in the form of nano-powder. X-ray diffraction (XRD) measurements reveal that the as-prepared samples are single-phase materials and their lattice constant changes with the variation of Mn-concentration, which indicates the incorporation of Mn²⁺ into the hosting ZnO. These findings are corroborated by the observation of the well defined six hyperfine lines of Mn²⁺ ion in the electron paramagnetic resonance (EPR) spectra of the samples with a low Mn-concentration, and of a broad EPR line, which manifests the onset of Mn–Mn exchange interaction, in the samples with an elevated value of x.