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)     

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)     

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)     

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)     

Grain boundary defects induced room temperature ferromagnetism in V doped ZnO thin films

Vanadium (V) doped ZnO thin films (Zn_1‐xV_x O, where x = 0, 0.05, 0.10) have been grown on sapphire substrates by RF magnetron sputtering to realize room temperature ferromagnetism (RTFM). The grown films have been subjected to X‐ray diffraction (XRD), resonant Raman scattering, photoluminescence (PL) and vibrating sample magnetometer (VSM) measurements to investigate their structural, optical and magnetic properties, respectively. The full width at half maximum of XRD and Raman scattering peaks increases with V ion concentration indicates that the V ions have been substituted on Zn²⁺ ions in the ZnO matrix. The increase in oxygen vacancies with V concentration is evidenced by PL measurements. Rutherford backscattering spectrometry analysis confirms the presence of the V ions in the films. The room temperature VSM measurements reveal the signature of ferromagnetism in V doped ZnO thin films. It has been observed that the grain boundary defects, i.e., oxygen vacancies play a crucial role in inducing RTFM in V doped ZnO films. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Paramagnetic behavior of Zn1−xMnxO at room temperature

Mn‐doped ZnO were synthesized by solid state reaction and sol‐gel method respectively. It was found that samples synthesized by solid state reaction containing Mn₂O₃ and MnO₂ are a mixture of ferromagnetic and paramagnetic phases. Contrary, samples without second phases were found to be paramagnetic at room temperature. According to previous report, interface effects between Zn‐rich Mn₂O₃ and MnO₂ interfaces may be the origin of the ferromagnetic behavior observed in our samples prepared by solid reaction, so the alloy of Zn_1−xMn_xO may be paramagnetic at room temperature. Prepared by sol‐gel technique, the samples without second phases in the XRD patterns are also room‐temperature paramagnetic. Therefore we believe that the magnetism of Zn_1−xMn_xO is paramagnetic at room temperature. (© 2008 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)     

Effect of rapid thermal annealing on Zn1‐xCdxO layers grown by radio‐frequency magnetron co‐sputtering

Zn_1‐xCd_xO layers were deposited on the sapphire substrate using the radio‐frequency magnetron co‐sputtering system. The grown Zn_1‐xCd_xO layers were carried out in the post‐annealing treatment for 1 min at the 800 °C oxygen‐ambient by the rapid thermal annealing (RTA) method. X‐ray diffraction (XRD) experiment shows that the Zn_1‐xCd_xO layers are changed from the single phase of the hexagonal structure at 0≤x ≤0.08 to the double phase of hexagonal‐and‐cubic structure at x =0.13. Thus, the maximum Cd‐composition ratio with the hexagonal structure was found out to be x =0.08. Also, the crystallinity of Zn_1‐xCd_xO layers at x =0.13 was remarkably improved by the RTA annealing treatment. This crystal quality improvement was thought to be associated with the relaxation of the compressive strain remaining in the Zn_1‐xCd_xO layers. Therefore, the results of XRD and transmittance lead that the crystal quality of the Zn_1‐xCd_xO layers forming the hexagonal ZnO phase is better than that forming the cubic CdO phase. Consequently, the reliable formation and the crystallinity of the Zn_1‐xCd_xO layers were achieved by using the RTA method of short‐time thermal‐annealing at the high temperature. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Some structural considerations on the perovskite‐type A1‐ySryCo1‐xFexO3‐δ solid solution series

Solid solution series of La_1‐ySr_yCo_1‐xFe_xO_3‐δ were extensively studied in the past as cathode materials for solid oxide fuel cells. However, the crystal structure behavior of La_1‐ySr_yCo_1‐xFe_xO_3‐δ solid solution series when La‐ions are replaced with another rare‐earth ion or metallic alkaline earth metal is at present not fully understood. Here we report X‐ray powder diffraction measurements performed on samples of the Sm_0.8Sr_0.2Co_1‐xFe_xO_3‐δ solid solution series. This study demonstrates that the average A‐cation radius, as well as the Fe content (x), affects the structural modification of the A_1‐ySr_yCo_1‐xFe_xO_3+δ solid solution series significantly. (© 2010 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.     

XPS characterization of YAlO3:Co single crystals

YAlO₃:Co (YAP:Co) single crystals have been obtained by the Czochralski method. The XPS spectra of YAP:Co annealed in reducing atmospheres: H₂, vacuum and vacuum plus H₂ are presented and discussed. As confirmed by magnetic measurements and the electron spectroscopy XPS the dopant concentration of Co is lower than a nominal one. The annealing processes removed colour centers due to relocation and some reduction of oxygen ions in the structure. The increased unit volume during the long annealing process may be caused by the change in some Co³⁺ ions into Co²⁺ ions. This explains the occurrence of the violet colour of the longtime annealed samples. The chemical shift analysis shows more ionic bond of Y–O than Al–O. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of Ba ions substitution on multiferroic properties of BiFeO3 perovskite

Dielectric, magnetic and ferroelectric properties of Bi_1‐xBa_xFeO₃(x = 0.1, 0.2 and 0.3) synthesized by solid state reaction method are reported. X‐ray diffraction pattern showed that Bi_1‐xBa_xFeO₃was single phase. Ba substitution has led to a decrease in grain size and hence an increase in the electrical resistivity. The variation of dielectric constant and loss has been studied over a frequency range of 1 kHz – 2 MHz at room temperature. Ba doping leads to effective suppression of the spiral spin structure of BiFeO₃, resulting in the appearance of net magnetization. Improved multiferroic properties of Bi_0.8Ba_0.2FeO₃ ceramic with remnant magnetization and polarization 0.093 emu/g and 0.808 µC/cm², respectively, were obtained. The evidence of ferromagnetism and ferroelectric hysteresis loops in Bi_1‐xBa_xFeO₃system at room temperature makes it a good candidate for potential applications. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural properties of Zn1–xMgxO nanomaterials prepared by sol‐gel method

The mixed oxides Zn_1‐xMg_xO (ZMO) were prepared as nano‐polycrystalline powders and thin films by a simple sol–gel process and dip coating method. Thermogravimetric (TG) and differential thermal analysis (DTA) were used to study the thermal chemistry properties of dried gel. Structural and microstructural analysis was carried out applying x‐ray diffraction (XRD) and Rietveld method. Analysis showed that for x < 0.25, Mg replaces Zn substitutionally yielding ZMO single phase, while for x ≥ 0.25 two phases are identified ZMO and MgO. Replacing Zn²⁺ by Mg²⁺ distorts the cation tetrahedrons and decreases the lattice constants ratio c/a of the wurtzite ZMO which deviate the lattice gradually from the hexagonal structure as Mg⁺² increases. These distortions are attributed to the difference in electronic configuration of the two cations which suppress the paraelectric‐ferroelectric phase transition in the ZMO wurtzite. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Multimode phonon structure of Be‐containing II ‐ VI mixed crystals determined by IR spectroscopic ellipsometry

Spectroscopic ellipsometry in the infrared spectral range 250‐5000 cm^‐1 is used for analysis of the dielectric response of Zn_1‐x‐yBe_xMg_ySe and Zn_1‐x‐yBe_xMn_ySe crystals grown by a high‐pressure Bridgman method. Ellipsometric spectra display features in the spectral range 390‐500 cm^‐1 associated with BeSe‐type phonon modes. In the optical spectra of Zn_1‐x‐yBe_xMg_ySe crystals both BeSe‐type and MgSe‐type lattice absorption bands are detected. The MgSe‐like modes are located at approximately 300 cm^‐1. The complex dielectric functions can be reproduced using a model with two or three and one or two classical damped oscillators corresponding to the BeSe‐like and the MgSe‐like transverse‐optical phonon modes, respectively. The frequencies of longitudinal‐optical phonons have been derived from the dielectric loss functions. A red‐shift of the BeSe‐like phonons frequencies with a mean rate 0.42 cm^‐1 (0.50 cm^‐1) per mole percent of Mg (Mn) incorporated to the alloy has been found for examined concentration range x, y ≤ 0.25. A noticeable damping the intensities of BeSe‐type modes with increasing fraction of Mg and Mn dopant is observed in comparison to the strengths of BeSe‐type modes in Zn_1‐xBe_xSe crystals. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Magneto‐transport properties of polycrystalline YBa2(Cu1‐xMx)3O7‐δ (M = B and Mn)

The magnetic and transport properties of polycrystalline YBa₂ (Cu_1‐xM_x)₃ O_7‐δ (M = B and Mn) superconductor was investigated. Samples of YBa₂(Cu_1‐xB_x)₃O_7‐δ doped with several concentrations of boron B(x = 0.05 and 0.1) were investigated using magnetization measurements. A YBa₂(Cu_1‐xMn_x)₃O_7‐δ sample doped with Mn with concentration of x = 0.02 was investigated using current‐voltage (I‐V) measurements. Our results on the YBa₂(Cu_1‐xB_x)₃O_7‐δ samples reveal a considerable increase in the hysterisis width of the magnetization, M versus the applied magnetic field H with increasing boron concentration. The lower critical field was also found to be enhanced by boron doping. The critical current density, J_c was found to be significantly enhanced in the Mn‐doped sample. The enhancement of J_c was found to be more significant at the lower temperatures for all applied magnetic fields used (0 Oe, 300 Oe, and 500 Oe). Thus, chemical doping is suggested to enhance the vortex pinning forces in the YBCO samples. From the resistivity (R‐T) measurements, chemical doping of the samples was found to have no significant effect on the critical temperature, T_c. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

Some physical and magnetic properties of Mg‐Zn ferrite

Some physical properties (such as lattice parameter, density and porosity) and magnetic properties of the system Mg_1‐xZn_xFe₂O₄; where x=0,0.1,0.2,0.3,0.4,0.5and 0.6 have been studied. It was found that the lattice parameter increases with increasing the zinc concentration. The composition dependence of the physical properties is divided into two regions. The first one is for x ≤ 0.3 and the second one is for x > 0.3. From the magnetization measurements, the basic composition (MgFe₂O₄) shows the lowest magnetization, while the composition of x=0.4 shows the highest one. The behaviour of magnetization M versus composition shows also two regions for x <>0.3. The behaviour of M versus x was discussed in the bases of cation distribution. From the B‐H loops, the remanence induction B_r, saturation induction B_s and the coercive force H_c were determined and studied with x. The Curie temperature T_C was determined from the measurements of the initial permeability μ_i versus temperature. It was found T_C decreases with increasing Zn‐content. Also paramagnetic temperature T_P was determined from the behaviour of M_S vs. T. In general it was found T_P > T_C by about 7‐10 K.     

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)     

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)     

Heat‐treatment influence on the microstructure and magnetic properties of rare‐earth substituted SrFe12O19

Rare‐earth substituted strontium ferrite nanopowders SrFe_12‐xR_xO₁₉ (R = La, Gd and Er; x = 0.2, 0.5 and 1) were prepared by sol‐gel‐autocombustion method and subsequent heat treatments. Structural and magnetic properties of SrFe_12‐xR_xO₁₉ powders heat treated at 800, 900 and 1000⁰C, for various times, were characterized with an X‐ray diffractometer, a vibrating sample magnetometer and a scanning electron microscope. The results of X‐ray diffraction measurements showed the M‐type hexagonal structure formation by heat treatments. Magnetic properties, such as specific saturation magnetization σ_s, specific remanent magnetization σ_r and coercivity H_c, as well as microstructure depend on the heat treatment conditions (temperature and time). The coercivity H_c exhibits a great increase after a critical heat treatment time. When the heat treatment time increases, one obtains an increase in H_c after a shorter heat treatment time. This jump of H_c was explained by a transition from the superparamagnetic state to normal state of the single domain nanoparticles. The occurrence of an agglomerated structure composed of magnetically interacting ultrafine crystallites also contributes to the increase of H_c.The heat treatment determines a reduced grain growth due to the internal stress generated by R ions. With increasing R content the σ_s and σ_r decrease due to the dissolution of R ions into the hexaferrite lattice. We believe that by selecting the time and temperature of the heat treatment, microstructure and magnetic properties suitable for magnetic recording media application can be obtained. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)