Structural, optical and magnetic properties of (ZnO)1−x(MnO2)x thin films deposited at room temperature

The structural, magnetic and optical properties of (ZnO)_1−x(MnO₂)_x (with x = 0.03 and 0.05) thin films deposited by pulsed laser deposition (PLD) were studied. The pellets used as target, sintered at different temperatures ranging from 500 °C to 900 °C, were prepared by conventional solid state method using ZnO and MnO₂ powders. The observation of non-monotonic shift in peak position of most preferred (1 0 1) ZnO diffraction plane in XRD spectra of pellets confirmed the substitution of Mn ions in ZnO lattice of the sintered targets. The as-deposited thin film samples are found to be polycrystalline with the preferred orientation mostly along (1 1 0) diffraction plane. The UV-vis spectroscopy of the thin films revealed that the energy band gap exhibit blue shift with increasing Mn content which could be attributed to Burstein-Moss shift caused by Mn doping of the ZnO. The deposited thin films exhibit room temperature ferromagnetism having effective magnetic moment per Mn atom in the range of 0.9-1.4μ_B for both compositions.     

Synthesis and ion conductivity of (Bi2O3)0.75(Dy2O3)0.25 ceramics with grain sizes from the nano to the micro scale

Using (Bi₂O₃)_0.75(Dy₂O₃)_0.25 nano-powder synthesized by reverse titration co-precipitation method as raw material, dense ceramics were sintered by both Spark Plasma Sintering (SPS) and pressureless sintering. According to the predominance area diagram of Bi-O binary system, the sintering conditions under SPS were optimized. (Bi₂O₃)_0.75(Dy₂O₃)_0.25 ceramics with relative density higher than 95% and an average grain size of 20 nm were sintered in only 10 min up to 500 °C. During the pressureless sintering process, the grain growth behavior of (Bi₂O₃)_0.75(Dy₂O₃)_0.25 followed a parabolic trend, expressed as D² − D₀² = Kt, and the apparent activation energy of grain growth was found to be 284 kJ mol^− 1. Dense (Bi₂O₃)_0.75(Dy₂O₃)_0.25 ceramics with different grain sizes were obtained, and the effect of grain size on ion conductivity was investigated by impedance spectroscopy. It was shown that the total ion conductivity was not affected by the grain size down to 100 nm, however lower conductivity was measured for the sample with the smallest grain size (20 nm). But, although only the δ phase was evidenced by X-ray diffraction for this sample, a closer inspection by Raman spectroscopy revealed traces of α-Bi₂O₃.     

Effects of nonstoichiometry on the properties of electron-doped manganite Pr0.1Ca0.9MnO3

Mn⁴⁺-rich perovskite manganites (nominal composition: Pr_0.1Ca_0.9MnO₃) were synthesized by using a citric acid method and sintered at different temperatures (800, 900, 1000, and 1300 °C) to adjust the concentration of charge carrier. All the samples are found to be in the cluster glass state at low temperature, as indicated by dc and ac magnetization. With the increase of sintering temperature, the ferromagnetic component in samples increases at first, and attains a maximum at 1000 °C, then decreases again at 1300 °C, which could be well interpreted by the change of charge carrier concentration induced by nonstoichiometry, consistent with the trend on the phase diagram. However, nonstoichiometry breaks long-range Mn-O-Mn interaction, resulting in the variance from the phase diagram.     

Post-sintering annealing effect on the diffuse phase transition in (Pb1−xBax)(Yb0.5Ta0.5)O3 ceramics

The effect of post sintering annealing on the dielectric response of (Pb_1−xBa_x)(Yb_0.5Ta_0.5)O₃ ceramics in the diffuse phase transition range (x=0.2) has been investigated. The samples are prepared by conventional solid-state reaction method. The samples are sintered at 1300 °C for 2 h and annealed at different temperatures (800, 900 and 1000 °C) for 8 h and at 800 °C for different time durations (8, 12 and 24 h). A significant change in the dielectric response has been observed in all the samples. The dielectric constant increases remarkably and the dielectric loss tangent decreases. The dielectric peaks of the annealed samples are observed to be more diffused with noticeable frequency dispersion compared to the as sintered sample.     

Effect of sintering atmosphere on the electrical and optical properties of (ZnO)1−x(MnO2)x NTCR ceramics

Nominal composition of (ZnO)_1−x(MnO₂)_x (0.005≤x≤0.2) ceramics have been prepared by the standard solid-state reaction method in three different sintering atmospheres: Ar, air, and reductive atmosphere. The effect of sintering atmosphere on the electron spin resonance (ESR), negative temperature coefficient of resistivity (NTCR), and photoluminescence (PL) properties of (ZnO)_1−x(MnO₂)_x ceramics has been investigated in detail. The results demonstrate that the sintering atmosphere has significant effects on the ESR signals of (ZnO)_1−x(MnO₂)_x; the NTCR of the samples sintered in air is larger than those sintering in Ar and reductive atmosphere; the deep-level PL related to oxygen vacancy increases when sintered in the reductive atmosphere.     

The influence of the sintering temperature on the structural and the magnetic properties of doped manganites: La0.95Ag0.05MnO3 and La0.75Ag0.25MnO3

La_1−xAg_xMnO₃ samples were synthesized by standard sol-gel method with Ag concentrations of x=0.05 and 0.25. The samples from each concentration were pressed and sintered at 1000, 1200 and 1400 °C for 24 h in air for a systematic study. They were examined structurally by Atomic Force Microscopy (AFM), Scanning Electron Microscopy (SEM) with Energy Dispersive Spectroscopy (EDS) and X-ray Diffraction (XRD) and magnetically by Magnetic Properties Measurements System (MPMS). AFM and SEM analyses show that surface morphology changes with Ag concentration and sintering temperature (T_S). It was observed that high temperature sintering leads Ag to leave material as determined from EDS analyses. XRD spectra exhibited that the crystal structure changes with Ag concentration while showing pronounced change with the sintering temperature. From the magnetic measurements, the Curie temperatures (T_C) and the isothermal magnetic entropy changes (−ΔSM) were calculated. It was observed that T_C increases with Ag concentration and decreases with T_S. The maximum −ΔSM was calculated to be 7.2 J/kg K under the field change of 5 T for the sample sintered at 1000 °C with x=0.25.     

Discussion again of the magnetic and transport property of Ag-doped LaMnO3

Samples La_1−aAg_aMnO₃ (0.05?a?0.50) were sol–gel fabricated. A part of Ag was found to dissociate and run off the samples in sintering process when sintering temperature exceeds 700 °C, resulting in a composite of La_1−xAg_xMnO₃ and MnO₂/Mn₂O₃. The magnetic and transport properties of the composite have been studied. The sample with the nominal composition La_0.7Ag_0.3MnO₃ was found to show the greatest magnetoresistance in the sample group. Detailed analysis on average Mn valence reveals a composite of (La_0.985Ag_0.015MnO₃)_0.776[(MnO₂)_0.590(Mn₂O₃)_0.410]_0.224. Its MR ratio at room temperature exceeds 24% under a field of 1.8 T. A conductivity leap has been observed around a=0.30. It suggests a kind of field-induced fluctuation in percolation in the samples investigated.     

Synthesis process and the luminescence properties of rare earth doped NaLa(WO4)2 nanoparticles

Rare earth doped NaLa(WO₄)₂ nanoparticles have been prepared by a simply hydrothermal synthesis procedure. The X-ray diffraction (XRD) pattern shows that the Eu³⁺-doped NaLa(WO₄)₂ nanoparticles with an average size of 10-30 nm can be obtained via hydrothermal treatment for different time at 180 °C. The luminescence intensity of Eu³⁺-doped NaLa(WO₄)₂ nanoparticles depended on the size of the nanoparticles. The bright upconversion luminescence of the 2 mol% Er³⁺ and 20 mol% Yb³⁺ codoped NaLa(WO₄)₂ nanoparticles under 980 nm excitation could also be observed. The Yb³⁺-Er³⁺ codoped NaLa(WO₄)₂ nanoparticles prepared by the hydrothermal treatment at 180 °C and then heated at 600 °C shows a 20 times stronger upconversion luminescence than those prepared by hydrothermal treatment at 180 °C or by hydrothermal treatment at 180 °C and then heated at 400 °C.     

Electrical properties of SrBi2(Nb0.5Ta0.5)2O9 ceramics

Aurivillius SrBi₂(Nb_0.5Ta_0.5)₂O₉ (SBNT 50/50) ceramics were prepared using the conventional solid-state reaction method. Scanning electron microscopy was applied to investigate the grain structure. The XRD studies revealed an orthorhombic structure in the SBNT 50/50 with lattice parameters a=5.522 Å, b=5.511 Å and c=25.114 Å. The dielectric properties were determined by impedance spectroscopy measurements. A strong low frequency dielectric dispersion was found to exist in this material. Its occurrence was ascribed to the presence of ionized space charge carriers such as oxygen vacancies. The dielectric relaxation was defined on the basis of an equivalent circuit. The temperature dependence of various electrical properties was determined and discussed. The thermal activation energy for the grain electric conductivity was lower in the high temperature region (T>303.6 °C, E_a−ht=0.47 eV) and higher in the low temperature region (T<303.6 °C, E_a−lt=1.18 eV).     

Simple recipe to synthesize single-domain BaFe12O19 with high saturation magnetization

We report a new synthesis route for preparation of single-domain barium hexaferrite (BaFe₁₂O₁₉) particles with high saturation magnetization. Nitric acid, known as a good oxidizer, is used as a mixing medium during the synthesis. It is shown that formation of BaFe₁₂O₁₉ phase starts at 800 °C, which is considerably lower than the typical ceramic process and develops with increasing temperature. Both magnetization measurements and scanning electron microscope micrographs reveal that the particles are single domain up to 1000 °C at which the highest coercive field of 3.6 kOe was obtained. The best saturation magnetization of ≈60 emu/g at 1.5 T was achieved by sintering for 2 h at 1200 °C. Annealing at temperatures higher than 1000 °C increased the saturation magnetization, on the other hand, decreased the coercive field which was due to the formation of multi-domain particles with larger grain sizes. It is shown that the best sintering to obtain fine particles of BaFe₁₂O₁₉ occurs at temperatures 900-1000 °C. Finally, magnetic interactions between the hard BaFe₁₂O₁₉ phase and impurity phases were investigated using the Stoner-Wohlfarth model.     

Electrical conductivity and amorphization of Sc2(WO4)3 at high pressures and temperatures

Impedance spectroscopy measurements and synchrotron X-ray diffraction studies of Sc₂(WO₄)₃ at 400°C have been carried out as a function of pressure up to 4.4 GPa. Ionic conductivity shows normal decrease with increase in pressure up to 2.9 GPa, but then increases at higher pressures. The XRD results show that Sc₂(WO₄)₃ undergoes pressure-induced amorphization at pressures coincident with the reversal in conductivity behavior. The loss of crystal structure at high pressure is consistent with growing evidence of pressure-induced amorphization in negative thermal expansion materials, such as Sc₂(WO₄)₃. The increase in conductivity in the amorphized state is interpreted as the result of an increase in structural entropy and a concomitant reduction of energy barriers for ionic transport.     

Bismuth zinc niobate (Bi1.5ZnNb1.5O7) ceramics derived from metallo-organic decomposition precursor solution

The preparation, microstructure development and dielectric properties of Bi_1.5ZnNb_1.5O₇ pyrochlore ceramics by metallo-organic decomposition (MOD) route are reported. Homogeneous precalcined ceramic powders of 13-36 nm crystallite size were obtained at temperatures ranging from 500 to 700 °C. The thermal decomposition/oxidation of the gelled precursor solution was chemically analyzed, TG/DTA, XRD, and SEM, led to the formation of a pure cubic pyrochlore phase with a stoichiometry close to Bi_1.5ZnNb_1.5O₇ which begins to form at 500 °C. The metallo-organic precursor synthesis method, where Bi, Zn and Nb ions are chelated to form metal complexes, allows the control of Bi/Zn/Nb stoichiometric ratio on a molecular scale leading to the rapid formation of bismuth zinc niobate (Bi_1.5ZnNb_1.5O₇) ceramic fine powders with pure pyrochlore structure. The powders were pressed into pellets and can be sintered at temperatures as low as 800-1000 °C. Fine crystalline ceramics with the grain size in the range of 200-500 nm have been obtained at the sintering temperature of 800 °C. The dielectric properties in high frequency to microwave range were measured and discussed.     

Dielectric and AC ionic conductivity investigations in K3H(SeO4)2 single crystal

Optical observation under the polarizing microscope and DSC measurements on K₃H(SeO₄)₂ single crystal have been carried out in the temperature range 25-200 °C. It reveals a high-temperature structural phase transition at around 110 °C. The crystal system transformed from monoclinic to trigonal. Electrical impedance measurements of K₃H(SeO₄)₂ were performed as a function of both temperature and frequency. The electrical conduction and dielectric relaxation have been studied. The temperature dependence of electrical conductivity indicates that the sample crystal became a fast ionic conductor in the high-temperature phase. The frequency dependence of conductivity follows the Jonscher's universal dynamic law with the relation σ(ω)=σ(0)+Aωⁿ, where ω is the frequency of the AC field, and n is the exponent. The obtained n values decrease from 1.2 to 0.1 from the room temperature phase to fast ionic phase. The high ionic conductivity in the high-temperature phase is explained by the dynamical disordering of protons between the neighboring SeO₄ groups, which provide more vacant sites in the crystal.     

Magnetic and bioactivity evaluation of ferrimagnetic ZnFe2O4 containing glass ceramics for the hyperthermia treatment of cancer

Glass ceramics of the composition xZnO·25Fe₂O₃·(40−x)SiO₂·25CaO·7P₂O₅·3Na₂O were prepared by the melt-quench method using oxy-acetylene flame. Glass-powder compacts were sintered at 1100 °C for 3 h and then rapidly cooled at −10 °C. X-ray diffraction (XRD) revealed 3 prominent crystalline phases: ZnFe₂O₄, CaSiO₃ and Ca₁₀(PO₄)₆(OH)₂. Vibrating sample magnetometer (VSM) data at 10 KOe and 500 Oe showed that saturation magnetization, coercivity and hence hysteresis area increased with the increase in ZnO content. Nano-sized ZnFe₂O₄ crystallites were of pseudo-single domain structure and thus coercivity increased with the increase in crystallite size. ZnFe₂O₄ exhibited ferrimagnetism due to the random distribution of Zn²⁺ and Fe³⁺ cations at tetrahedral A sites and octahedral B sites. This inversion/random distribution of cations was probably due to the surface effects of nano-ZnFe₂O₄ and rapid cooling of the material from 1100 °C (thus preserving the high temperature state of the random distribution of cations). Calorimetric measurements were carried out using magnetic induction furnace at 500 Oe magnetic field and 400 KHz frequency. The data showed that maximum specific power loss and temperature increase after 2 min were 26 W/g and 37 °C, respectively for the sample containing 10% ZnO. The samples were immersed in simulated body fluid (SBF) for 3 weeks. Scanning electron microscope (SEM), energy dispersive spectroscopy (EDX) and XRD results confirmed the growth of precipitated hydroxyapatite phase after immersion in SBF, suggesting that the ferrimagnetic glass ceramics were bioactive and could bond to the living tissues in physiological environment.     

Structural and luminescence characterization of synthetic Cr-doped Ni3(PO4)2

Ni_3–xCr_2x/3(PO₄)₂ (x=0 and 0.02) microcrystalline powders were obtained as single phases via a modified sol–gel Pechini-type in situ polymerizable complex method. The samples were characterized using scanning electron microscopy, X-ray diffraction, cathodoluminescence (CL), and thermoluminescence (TL) techniques. We found that Cr³⁺ doping modified the average particle and distribution. The mean particle size was 0.441 μm for Ni₃(PO₄)₂ and 0.267 μm for Ni_2.98Cr_0.013(PO₄)₂. The results also reveal that Cr³⁺ doping notably enhanced the CL and TL UV-blue emission.     

Structural, vibrational and dielectric properties of new potassium hydrogen sulfate arsenate: K4(SO4)(HSO4)2(H3AsO4)

A new compound, K₄(SO₄)(HSO₄)₂(H₃AsO₄) was synthesized from water solution of KHSO₄/K₃H(SO₄)₂/H₃AsO₄. This compound crystallizes in the triclinic system with space group P1¯ and cell parameters: a=8.9076(2) Å, b=10.1258(2) Å, c=10.6785(3) Å; α=72.5250(14)°, β=66.3990(13)°, γ=65.5159(13)°, V=792.74(3) Å³, Z=2 and ρ_cal=2.466 g cm⁻³. The refinement of 3760 observed reflections (I>2σ(I)) leads to R₁=0.0394 and wR₂=0.0755. The structure is characterized by SO₄²⁻, HSO₄⁻ and H₃AsO₄ tetrahedra connected by hydrogen bridge to form two types of dimer (H(16)S(3)O₄⁻?S(1)O₄²⁻ and H(12)S(2)O₄⁻?H₃AsO₄). These dimers are interconnected along the [1¯ 1 0] direction by the hydrogen bonds O(3)-H(3)?O(6). They are also linked by the hydrogen bridge assured by the hydrogen atoms H(2), H(3) and H(4) of the H₃AsO₄ group to build the chain S(1)O₄?H₃AsO₄ which are parallel to the “a” direction. The potassium cations are coordinated by eight oxygen atoms with K-O distance ranging from 2.678(2) to 3.354(2) Å.Crystals of K₄(SO₄)(HSO₄)₂(H₃AsO₄) undergo one endothermic peak at 436 K. This transition detected by differential scanning calorimetry (DSC) is also analyzed by dielectric and conductivity measurements using the impedance spectroscopy techniques. The obtained results show that this transition is protonic by nature.     

Photoluminescence and thermoluminescence characterization of Eu- and Dy -activated Ca3(PO4)2 phosphor

Rare-earth-doped polycrystalline Ca₃(PO₄)₂:Eu, Ca₃(PO₄)₂:Dy and Ca₃(PO₄)₂:Eu,Dy phosphors prepared by a modified solid-state synthesis has been studied for its X-ray diffraction, thermoluminescence (TL) and photoluminescence (PL) characteristics. The PL emission spectra of the phosphor suggest the presence of Eu³⁺ ion in Ca₃(PO₄)₂:Eu and Dy³⁺ ion in Ca₃(PO₄)₂:Dy lattice sites. The TL glow curve of the Ca₃(PO₄)₂:Eu compounds has a simple structure with a prominent peak at 228 °C, while Ca₃(PO₄)₂:Dy peaking at 146 and 230 °C. TL sensitivity of phosphors are compared with CaSO₄: Dy and found 1.52 and 1.20 times less in Ca₃(PO₄)₂:Eu and Ca₃(PO₄)₂:Dy phosphors, respectively. The Ca₃(PO₄)₂:Eu,Dy phosphors shows switching behavior under two different excitation wavelengths and enhancement in PL intensity of Dy³⁺ ions were reported. The paper discusses the photoluminescence and thermoluminescence behavior of Eu³⁺ and Dy³⁺ ion in Ca₃(PO₄)₂ hosts, it may be applicable to solid-state lighting as well as thermoluminescence dosimetry applications.     

Phase transitions and molecular motions in [Zn(NH3)4](BF4)2 studied by nuclear magnetic resonance, infrared and Raman spectroscopy

Middle infrared absorption, Raman scattering and proton magnetic resonance relaxation measurements were performed for [Zn(NH₃)₄](BF₄) in order to establish relationship between the observed phase transitions and reorientational motions of the NH₃ ligands and BF₄⁻ anions. The temperature dependence of spin-lattice relaxation time (T₁(¹H)) and of the full width at half maximum (FWHM) of the bands connected with ρ_r(NH₃), ν₂(BF₄) and ν₄(BF₄) modes in the infrared and in the Raman spectra have shown that in the high temperature phase of [Zn(NH₃)₄](BF₄)₂ all molecular groups perform the following stochastic reorientational motions: fast (τ_R≈10⁻¹² s) 120° flips of NH₃ ligands about three-fold axis, fast isotropic reorientation of BF₄⁻ anions and slow (τ_R≈10⁻⁴ s) isotropic reorientation (“tumbling”) of the whole [Zn(NH₃)₄]²⁺ cation. Mean values of the activation energies for uniaxial reorientation of NH₃ and isotropic reorientation of BF₄⁻ at phases I and II are ca. 3 kJ mol⁻¹ and ca. 5 kJ mol⁻¹, respectively. At phases III and IV the activation energies values for uniaxial reorientation of both NH₃ and of BF₄⁻ equal to ca. 7 kJ mol⁻¹. Nearly the same values of the activation energies, as well as of the reorientational correlation times, at phases III and IV well explain existence of the coupling between reorientational motions of NH₃ and BF₄⁻. Splitting some of the infrared bands at T_C2=117 K suggests reducing of crystal symmetry at this phase transition. Sudden narrowing of the bands connected with ν₂(BF₄), ν₄(BF₄) and ρ_r(NH₃) modes at T_C3=101 K implies slowing down (τ_R?10⁻¹⁰ s) of the fast uniaxial reorientational motions of the BF₄⁻ anions and NH₃ ligands at this phase transition.     

Ionic to electronic dominant conductivity in Al2(WO4)3 at high pressure and high temperature

Electrical conduction and crystal structure of Al₂(WO₄)₃ at 400 °C have been studied as a function of pressure up to 5.5 GPa using impedance methods and synchrotron radiation X-ray diffraction, respectively. AC impedance spectroscopy and DC polarization measurements reveal an ionic to electronic dominant transition in electrical conductivity at a pressure as low as 0.9 GPa. Conductivity increases with pressure and reaches a maximum at 4.0 GPa, where the conductivity value is 5 orders of magnitude greater than the 1 atm value. Upon decompression, the conductivity retains the maximum value until the sample is cooled at 0.5 GPa. The high pressure-temperature X-ray diffraction results show that the lattice parameters decrease as pressure increases and the crystal structure undergoes an orthorhombic to tetragonal-like transformation at a pressure ∼3.0 GPa. The change of conduction mechanism from ionic to electronic may be explained by means of pressure-induced valence change of W⁶⁺→W⁵⁺, which results in electron transfer between W⁵⁺-W⁶⁺ sites at high pressure.     

Low-field transport properties of (1−x)La0.7Ca0.2 Sr0.1MnO3+x(ZnO) composites

Composite samples (1−x)La_0.7Ca_0.2Sr_0.1MnO₃(LCSMO)+x(ZnO) with different ZnO doping levels x have been investigated systematically. The structure and morphology of the composites have been studied by the X-ray diffraction (XRD) and scanning electronic microscopy (SEM). The XRD and SEM results indicate that no reaction occurs between LCSMO and ZnO grains, and that ZnO segregates mostly at the grain boundaries of LCSMO. The magnetic properties reveal that the ferromagnetic order of LCSMO is weakened by addition of ZnO. The results also show that ZnO has a direct effect on the resistance of LCSMO/ZnO composites, especially on the low-temperature resistance. With increase of the ZnO doping level, T_P shifts to a lower temperature and the resistance increases. It is interesting to note that an enhanced magnetoresisitance (MR) effect for the composites is found over a wide temperature range from low temperature to room temperature in an applied magnetic field of 3 kOe. The maximum MR appears at x=0.1. The low field magnetoresistance (LFMR) results from spin-polarized tunneling. However, around room temperature, the enhanced MR of the composites is caused by magnetic disorder.