Growth of highly-oriented CaCu3Ti4O12 thin films on SrTiO3 (1 0 0) substrates by a chemical solution route

Highly-oriented CaCu₃Ti₄O₁₂ (CCTO) thin films deposited directly on SrTiO₃ (1 0 0) substrates have been developed successfully using a chemical solution coating method. X-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM) were employed to characterize the structure and the morphology. It was observed that the CCTO thin films had the 1 μm × 1 μm domain-like microstructure that consists of compact grains of about 0.1 μm in size. The cross sectional SEM image shows that the CCTO grains grow regularly close to the clear interface between the CCTO film and the SrTiO₃ substrate. The result was discussed in terms of lattice mismatch between CCTO and SrTiO₃.     

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.     

Evidence for internal resistive barriers in a crystal of the giant dielectric constant material: CaCu3Ti4O12

Complex impedance spectra were obtained on a crystal of CaCu₃Ti₄O₁₂ (CCTO) from 289 to 456 K. As in the case of ceramic CCTO, these spectra can be interpreted as arising from a conducting material containing insulating barriers. This is then further evidence for the existence of planar defects within crystals of CCTO that act as insulating barriers and produce the large dielectric constant through a space charge mechanism.     

Reduced dielectric loss and leakage current in CaCu3Ti4O12/SiO2/CaCu3Ti4O12 multilayered films

The CaCu₃Ti₄O₁₂/SiO₂/CaCu₃Ti₄O₁₂ (CCTO/SiO₂/CCTO) multilayered films were prepared on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition method. It has been demonstrated that the dielectric loss and the leakage current density were significantly reduced with the increase of the SiO₂ layer thickness, accompanied with a decrease of the dielectric constant. The CCTO film with a 20 nm SiO₂ layer showed a dielectric loss of 0.065 at 100 kHz and the leakage current density of 6×10⁻⁷ A/cm² at 100 kV/cm, which were much lower than those of the single layer CCTO films. The improvement of the electric properties is ascribed to two reasons: one is the improved crystallinity; the other is the reduced free carriers in the multilayered films.     

Synthesis of anatase TiO2 nanowires by modifying TiO2 nanoparticles using the microwave heating method

Anatase TiO₂ nanowires with a diameter of 5-10 nm and length of 500 nm to 2 μm have been successfully synthesized by modifying TiO₂ nanoparticles (P25) using the microwave heating method. The microwave power, reaction pressure, and reaction time for the synthesis of TiO₂ nanowires were 500 W, 0.5-3.0 MPa (corresponding to a temperature range of 175-260), and 40-70 min, respectively. X-ray diffraction (XRD), field-emission scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and the BET techniques were used to investigate the phase structures, morphologies, and specific surface areas of the TiO₂ nanowires. The effects of reaction time, pressure, and different post-treatment processes on the microstructures of TiO₂ nanowires were discussed. It has been shown that the microwave heating method is efficient in transforming TiO₂ nanoparticles to anatase TiO₂ nanowires.     

Influence of Lu2O3 on electrical and microstructural properties of CaCu3Ti4O12 ceramics

In this work, the influence of Lu₂O₃ doped on the dielectric and electrical properties of CaCu₃Ti₄O₁₂ was reported. Lu₂O₃-doped CCTO was prepared by a conventional solid state technique using CuO, TiO₂, and CaCO₃ as starting materials. The samples were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM); dielectric measurements were measured in the 10² Hz–10⁷ Hz frequency range at room temperature; and the nonlinear behavior of all samples was measured. The doping of Lu₂O₃ resulted in an increase in the dielectric constant of CCTO, but decreased the stability of the frequency dependence. Increasing concentrations of Lu₂O₃ resulted in decreasing nonlinear coefficients.     

Phase evolution and microwave dielectric properties of Bi3SbO7 ceramic

The Bi₃SbO₇ ceramic was prepared by the solid state reaction method and its phase evolution at different temperatures was studied. Low temperature phase α-Bi₃SbO₇ was formed at about 890 °C and it started to transform to high temperature phase β-Bi₃SbO₇ at about 960 °C. Microwave dielectric constants of α-Bi₃SbO₇ ceramic and β-Bi₃SbO₇ ceramic were 43.2 and 37.6, Qf value were 2080 and 5080 GHz, respectively. TCF of α-Bi₃SbO₇ ceramic was near zero and TCF of β-Bi₃SbO₇ ceramic was about −120 ppm/°C. The Bi₃SbO₇ ceramic is a promising candidate for low temperature co-fired ceramic (LTCC) technology due to its large dielectric constant, low dielectric loss at microwave region, low sintering temperature and simple composition.     

Synthesis of (Mg0.476Mn0.448Zn0.007)(Fe1.997Ti0.002)O4 powder and sintered ferrites by high energy ball-milling process

(Mg_0.476Mn_0.448Zn_0.007)(Fe_1.997Ti_0.002)O₄ nanocrystalline powder prepared by high energy ball-milling process were consolidated by microwave and conventional sintering processes. Phases, microstructure and magnetic properties of the ferrites prepared by different processes were investigated. The (Mg_0.476Mn_0.448Zn_0.007)(Fe_1.997Ti_0.002)O₄ nanocrystalline powder could be prepared by high energy ball-milling process of raw Fe₃O₄, MnO₂, ZnO, TiO₂ and MgO powders. Prefired and microwave sintered ferrites could achieve the maximum density (4.86 g/cm⁻³), the average grain size (15 μm) was larger than that (10 μm) prepared by prefired and conventionally sintered ferrites with pure ferrite phase, and the saturation magnetization (66.77 emu/g) was lower than that of prefired and conventionally sintered ferrites (88.25 emu/g), the remanent magnetization (0.7367 emu/g) was higher than that of prefired and conventionally sintered ferrites (0.0731 emu/g). Although the microwave sintering process could increase the density of ferrites, the saturation magnetization of ferrites was decreased and the remanent magnetization of ferrites was also increased.     

Influence of sintering conditions and doping on the dielectric relaxation originating from the surface layer effects in CaCu3Ti4O12 ceramics

Detailed investigations into the dielectric dispersion phenomenon in the giant dielectric constant material CaCu₃Ti₄O₁₂ (CCTO) around room temperature revealed the existence of two successive dielectric relaxations. In the temperature domain, a new dielectric relaxation was clearly observed around 250 K, in addition to the well-investigated dielectric relaxation close to 100 K. The effect of sintering and doping (La³⁺) on the strength of these dielectric relaxations were studied in detail. The sintering temperature as well as its duration was found to have tremendous influence on the dielectric relaxation that was encountered around 250 K. This Maxwell-Wagner (M-W) type of relaxation was found to be originating from the surface layer containing the Cu-rich phase, which was ascribed to the difference in the oxygen content between the surface and the interior of the sample. Interestingly, this particular additional relaxation was not observed in La_2/3Cu₃Ti₄O₁₂, a low dielectric constant member of the CCTO family, in which the segregation of Cu-rich phase on the surface was absent. Indeed the correlation between the new relaxation and the presence of Cu-rich phase in CCTO ceramics was further corroborated by the absence of the same after removing the top and bottom layers.     

Dielectric properties and magnetoelectric effect of (x)NiFe2O4+(1−x)Ba0.8Sr0.2TiO3 composites

Magnetoelectric composites of NiFe₂O₄ and Ba_0.8Sr_0.2TiO₃ were prepared using conventional double-sintering ceramic method. The phase formation of magnetoelectric composites was confirmed by XRD technique. Variation of dielectric constant and loss tangent at room temperature with frequency in the range 100 Hz-1 MHz has been studied. Also the variation of dielectric constant and loss tangent with temperature and composition at fixed frequencies of 1 kHz, 10 kHz, 100 kHz and 1 MHz is reported. The static value of the magnetoelectric conversion factor was measured as a function of intensity of the magnetic field. The ME voltage coefficient of about 430 μV/cm Oe was observed for 15% NiFe₂O₄+85% Ba_0.8Sr_0.2TiO₃ composite. All the samples show linear variation of magnetoelectric conversion in the presence of static magnetic field.     

Low-temperature sintering and microwave dielectric properties of Ca2Zn4Ti15O36 ceramics

The sintering behavior, microstructures, and microwave dielectric properties of Ca₂Zn₄Ti₁₅O₃₆ ceramics with B₂O₃ addition were investigated. The crystalline phases and microstructures of Ca₂Zn₄Ti₁₅O₃₆ ceramics with 0-10 wt% B₂O₃ addition were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS). The sintering temperature of Ca₂Zn₄Ti₁₅O₃₆ ceramic was lowered from 1170 to 930 °C by 10 wt% B₂O₃ addition. Ca₂Zn₄Ti₁₅O₃₆ ceramics with 8 wt% B₂O₃ addition sintered at 990 °C for 2 h exhibited good microwave dielectric properties, i.e., a quality factor (Qf) 11,400 GHz, a relative dielectric constant (ε_r) 41.5, and a temperature coefficient of resonant frequency (τ_f) 94.4 ppm/°C.     

Structural transformations of Fe81B13Si4C2 amorphous alloy induced by heating

Thermal stability and crystallization of the Fe₈₁B₁₂Si₄C₂ alloy were investigated in the temperature range 25-700 °C by the XRD and Mössbauer analysis. It was shown that on heating the as-prepared amorphous Fe₈₁B₁₂Si₄C₂ alloy undergoes thermal stabilization through a series of structural transformations involving the process of stress-relieving (temperature range 200-400 °C), followed by a loss of ferromagnetic properties (Curie temperature at 420 °C) and finally crystallization (temperature range 450-530 °C). The process of crystallization begins by formation of two crystal phases: Fe₃B and subsequently Fe₂B, as well as a solid solution α-Fe(Si). With increase in annealing temperature, the completely crystallized alloy involved only two phases, Fe₂B and solid solution α-Fe(Si).XRD patterns established a difference in phase composition and size of the formed crystallites during crystallization depending on the side (fishy or shiny) of the ribbon. The first nuclei of the phase α-Fe₃Si were found on the shiny side by XRD after heat treatment even at 200 °C but the same phase on the fishy side of ribbon was noticed after heat treatment at 450 °C. The largest difference between the contact and free surface was found for the Fe₂B phase crystallized by heating at 700 °C, showing the largest size of crystallites of about 130 nm at 700 °C on the free (shiny) surface.     

Electrical conduction and magnetoelectric effect of (x) BaTiO3 + (1−x) Ni0.92Co0.03Cu0.05Fe2O4 composites in ferroelectric rich region

Particulate composites with composition (x)BaTiO₃+(1−x)Ni_0.92Co_0.03Cu_0.05Fe₂O₄ in which x varies as 1, 0.85, 0.70, 0.55 and 0 (in mol%) were prepared by the conventional double sintering ceramic technique. The presence of two phases viz. ferromagnetic (Ni_0.92Co_0.03Cu_0.05Fe₂O₄) and ferroelectric (BaTiO₃) was confirmed by X-ray diffraction analysis. The dc resistivity and thermo-emf measurements were carried out with variation of temperature. The ac conductivity (σ_ac) measurements investigated in the frequency range 100 Hz to 1 MHz conclude that the conduction in these composites is due to small polarons. The variation of dielectric constant and loss tangent with frequency (20 Hz to 1 MHz) was studied. The static magnetoelectric conversion factor, i.e. dc (dE/dH)_H was measured as a function of intensity of applied magnetic field. The changes were observed in electrical properties as well as in magnetoelectric voltage coefficient as the molar ratio of the constituent phases was varied. A maximum value of magnetoelectric conversion factor of 536.06 μV/cm Oe was observed for the composite with 70% BaTiO₃+30% Ni_0.92Co_0.03Cu_0.05Fe₂O₄ at a dc magnetic field of 2.3 K Oe. The maximum magnetoelectric conversion output has been explained in terms of ferrite-ferroelectric content, applied static magnetic field and resistivity.     

Electromagnetic and microwave absorption properties of carbonyl iron/La0.6Sr0.4MnO3 composites

In this work carbonyl iron/La_0.6Sr_0.4MnO₃ composites were prepared to develop super-thin microwave absorbing materials. The complex permittivity, permeability and microwave absorption properties are investigated in the frequency range of 8-12 GHz. An optimal reflection loss of −12.4 dB is reached at 10.5 GHz with a matching thickness of 0.8 mm. The thickness of carbonyl iron/La_0.6Sr_0.4MnO₃ absorber is thinner, compared with conventional carbonyl iron powders with the same absorption properties. The bandwidth with a reflection loss exceeding −7.4 dB is obtained in the whole measured frequency range with the thickness of 0.8 mm. The excellent microwave absorption properties are attributed to a better electromagnetic matching established by the combination of the enhanced dielectric loss and nearly invariable magnetic loss with the addition of La_0.6Sr_0.4MnO₃ nanoparticles in the composites. Our work indicates that carbonyl iron/La_0.6Sr_0.4MnO₃ composites may have an important application in wide-band and super-thin electromagnetic absorbers in the frequency range of 8−12 GHz.     

Nanoparticles of the giant dielectric material, CaCu3Ti4O12 from a precursor route

A method of preparing the nanoparticles of CaCu₃Ti₄O₁₂ (CCTO) with the crystallite size varying from 30 to 200 nm is optimized at a temperature as low as 680 °C from the exothermic thermal decomposition of an oxalate precursor, CaCu₃(TiO)₄(C₂O₄)₈·9H₂O. The phase singularity of the complex oxalate precursor is confirmed by the wet chemical analyses, X-ray diffraction, FT-IR and TGA/DTA analyses. The UV-vis reflectance and ESR spectra of CCTO powders indicate that the Cu(II) coordination changes from distorted octahedra to nearly flattened tetrahedra (squashed) to square-planar geometry with increasing annealing temperature. The HRTEM images have revealed that the evolution of the microstructure in nanoscale is related to the change in Cu(II) coordination around the surface regions for the chemically prepared powder specimens. The nearly flattened tetrahedral geometry prevails for CuO₄ in the near surface regions of the particles, whereas square-planar CuO₄ groups are dominant in the interior regions of the nanoparticles. The powders derived from the oxalate precursor have excellent sinterability, resulting in high-density ceramics which exhibited giant dielectric constants upto 40,000 (1 kHz) at 25 °C, accompanied by low dielectric loss <0.07.     

Synthesis and characterization of NiCoMnCuFe1.96O4 for circulator application

Modern accelerator design practice includes the use of high-quality ferrites for circulator applications with ever-increasing requirements on power handling ability. Modeling studies of new designs are of increasing economic importance, but are frequently hindered by lack of measured values of the ceramic loss factors. We have developed a nanocrystalline ferrite material with composition Ni_0.94Co_0.03Mn_0.04Cu_0.03Fe_1.96O₄. Nanocrystalline NiCoMnCu ferrite powders were synthesized using a microwave-hydrothermal method at 160 °C for 40 min. The ferrite formation conditions, such as pH, temperature and time, were optimized. The phase of the samples was identified by X-ray diffraction and was characterized by Fourier transformation infrared spectroscopy. The size of the nanocrystalline ferrite of as-synthesized powders was 10 nm. The powder was densified at different temperatures using a microwave sintering method. The complex permittivity and permeability of the sintered samples were measured over a frequency range from 10 kHz to 1.8 GHz at room temperature. The applicability of the samples for circulators was tested via the measurement of the ferromagnetic resonance linewidth and the results are presented.     

Microwave sintering of high-permeability (Ni0.20Zn0.60Cu0.20)Fe1.98O4 ferrite at low sintering temperatures

The (Ni_0.20Zn_0.60Cu_0.20)Fe_1.98O₄ ferrite was sintered using microwave sintering and conventional sintering technique, respectively. It was found that microwave sintering technique can effectively promote the forward diffusion of ions and thus accelerate the sintering process, resulting in the grain growth and the densification of matrix. At the low frequency of 100 kHz, the magnetizing contribution of domain wall motion is predominant, and compact and coarse matrixes are favorable for domain wall motion, giving rise to improvement of relative initial permeability and loss of ferrites. Using microwave sintering technique, for the (Ni_0.20Zn_0.60Cu_0.20)Fe_1.98O₄ ferrite, the relative initial permeability μ_i of about 2000 and the relative loss factor tanδ/μ_i of about 8.7×10⁻⁶ at 100 kHz were achieved at only 980 °C sintering temperature. In addition, the sintering time of ferrites was reduced from 5 to 0.5 h by using microwave sintering technique.     

Effect of surface-topology on magnetic properties in (La0.6Eu0.4)0.67Ca0.33MnO3 of anisotropic shape of nanoplates

(La_0.6Eu_0.4)_0.67Ca_0.33MnO₃ has been prepared in the shape of nanoplates of single crystallites (an orthorhombic structure) through polymer templates. HRTEM images reveal 18, 25, and 30 nm thicknesses of plates after heating a precursor powder at 873, 1073, and 1273 K in air for 2 h. These values present average crystallite size determined from broadening of the X-ray diffraction peaks. A spin-glass-like surface (GS) overlayer (3-5 nm thickness) in such plates facilitates a ferromagnetic→ferrimagnetic reordering with markedly suppressed Curie point T_C, i.e., as small as 90 K in a 873 K heated sample, from the parent value 268 K. The T_C point increases to 103 K (or 120 K) when heating at higher temperature 1073 (or 1273 K), during which the core grows at the expense of the overlayer. The GS tailors as high coercivity H_c as 617 Oe in the zero field cooled (ZFC) sample that is decreased to 500 Oe in the field cooled (FC) sample in the surface spin-freezing along the field direction. The H_c-value (ZFC) that steps down successively to 252 Oe on the overlayer is thinned down by heating at 1273 K. Samples heated at 873, 1073, or 1273 K have regularly increased saturation magnetization 35.3, 63.9, or 69.6 emu/g in ZFC, while 43.7, 70.2, or 75.5 emu/g in FC measured at 10 K. The ferrimagnetic reordering are described based on the scenario of an antiferromagnetic exchange coupling between the Eu³⁺ and Mn³⁺ (or Mn⁴⁺) sublattices.     

Antiferromagnetic resonance in ferroborate NdFe3(BO3)4

The AFMR spectra of the NdFe₃(BO₃)₄ crystal are measured in a wide range of frequencies and temperatures. It is found that by the type of its magnetic anisotropy the compound is an “easy-plane” antiferromagnet with a weak anisotropy in the basal plane. The effective magnetic parameters are determined: anisotropy fields H_a1=1.14 kOe and H_a2=60 kOe and magnetic excitation gaps Δν₁=101.9 GHz and Δν₂=23.8 GHz. It is shown that commensurate-incommensurate phase transition causes a shift in resonance field and a considerable change in absorption line width.At temperatures below 4.2 K nonlinear regimes of AFMR excitation at low microwave power levels are observed.     

Adjustable microwave absorption properties of flake shaped (Ni0.5Zn0.5)Fe2O4/Co nanocomposites with stress induced orientation

Flake shaped (Ni_0.5Zn_0.5)Fe₂O₄/Co nanocomposites were successfully fabricated by co-precipitating of Ni-Zn ferrite on the surface of cobalt nanoflakes. The electromagnetic characteristics of the samples were studied at the frequency of 0.1–14 GHz. The results showed that the cobalt nanoflakes in compacted nanocomposites were well orientated, and the nanocomposites were characterized with low optimal reflection loss (RL) of −33.8 dB at 11.5 GHz and broad RL bandwidth for <−20 dB in the frequency range of 7.6–12.1 GHz. At the same time, the position of the absorptive band can be adjusted by changing the mass ratio of ferrite to cobalt in the nanocomposites. It is proposed that the excellent microwave absorption properties are related to the combination of strong shape anisotropy of cobalt nanoflakes and adjustable dielectric loss.