Weak ferromagnetism in BiFeO3 doped with titanium

The Bi_1−xA_xFe_1−xTi_xO₃ (A—Ca, Sr, Pb, Ba) and BiFe_1−xTi_xO_3+δ systems have been studied using X-ray, neutron powder diffraction and magnetization measurements in a magnetic field up to 14 T. It was found that all Bi_1−xA_xFe_1−xTi_xO₃ solid solutions are rhombohedral up to x=0.3. In the case of BiFe_1−xTi_xO_3+δ the rhombohedral distortion preserved up to x=0.11. A homogeneous weakly ferromagnetic state was found for Bi_1−xCa_xFe_1−xTi_xO₃ (0.15≤x≤0.25) and BiFe_1−xTi_xO_3+δ (0.06≤x≤0.11), probably due to magnetoelectric interactions, whereas Bi_1−xA_xFe_1−xTi_xO₃ (A—Sr, Pb, Ba) compounds above doping level x>0.1 seem to be collinear antiferromagnets.     

Synthesis, phase and microstructure characteristics of Pb(Zr0.52Ti0.48)O3–(Bi3.25La0.75)Ti3O12 ceramics

Ceramics with formula (1 − x)Pb(Zr_0.52Ti_0.48)O₃–x(Bi_3.25La_0.75)Ti₃O₁₂ (when x = 0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1.0) were prepared by a solid-state mixed-oxide method and sintered at temperatures between 950 °C and 1250 °C. It was found that the optimum sintering temperature was 1150 °C at which all the samples had densities at least 95% of theoretical values. Phase analysis using X-ray diffraction indicated the existence of BLT- as well as PZT-based solid solutions with corresponding lattice distortion. Scanning electron micrographs of ceramic surfaces showed a plate-like structure in BLT-rich phase while the typical grain structure was observed for PZT-rich phase. The grain sizes of both pure BLT and PZT ceramics were found to decrease as the relative amount of the other phase increased. This study suggested that tailoring of properties of this PZT–BLT system was possible especially on the BLT-rich side due to its large solubility limit.     

Formation of the nanodots and change of the characteristics of thin magnetic films under laser irradiation

Results of experimental investigations of laser radiation interaction with the Ti, Co, NiFe, TbFe and LaSrMnO₃ films are presented. It is shown, that it is possible to improve magnetic characteristics and to obtain magnetic films with regular distribution of nanodots by the laser radiation. It is observed an increasing of magnetic permeability and the reduction of the coercive force after irradiation of the NiFe films by the nanosecond laser pulses that are induced by the substantial growth of the size of the nanodots in the process of recrystallization. Magnetic nanodots of 100–200 nm size are produced by the method of the laser cutting of the continuous magnetic films, or are formed in a nonmagnetic matrix by the diffusion in the multilayered films and oxidization of TbFe and LaSrMnO_3−x films at the irradiation of the nanosecond laser pulses.     

In situ hot-stage transmission electron microscopy of Pb(Zr0.52Ti0.48)O3

The domain structure of Pb(Zr_0.52Ti_0.48)O₃ before and after hot-stage experiment has been studied. The influence of maximum temperature, heating and cooling rate on the domain configuration of Pb(Zr_{1? x} , Ti _x )O₃ with x = 0.40, 0.45, 0.48 and 0.55 was analysed. A reliable basis for further hot-stage experiments of Pb(Zr_1?x, Ti_x)O₃ has been established. The investigations revealed a temperature dependent appearance and disappearance of nano- and microdomains. The appearance of microdomains in the nano scale range during cooling, denoted as domain miniaturisation, and the time dependent recovering of the former domain structure, revealed that under specific experimental conditions the domain configuration is reversible.     

Preparation and electrical properties of a pyrochlore-related Ce2Zr2O8−x phase

A pyrochlore-related Ce₂Zr₂O_8−x phase has been prepared in a reduction reoxidation process from Ce_0.5Zr_0.5O₂ powders. Ce₂Zr₂O_8−x, based on a cubic symmetry with a=1.053 nm, decomposes in nitrogen at 800 °C, but remains stable up to 900 °C in air. It shows mixed oxygen ionic and electronic conductivity. The bulk conductivity at 700 °C is 4×10⁻⁴ S cm⁻¹ in air and 1×10⁻² S cm⁻¹ in nitrogen, and the activation energy is 1.27 eV in air. In nitrogen, the Arrhenius law is not obeyed, and a curved plot was obtained from 400 to 700 °C; then, the conductivity decreased rapidly due to the thermal decomposition of Ce₂Zr₂O_8−x.     

Laser-induced changes on optical band gap of amorphous and crystallized thin films of Se75S25−xAGx

Optical band gap of amorphous, crystallized, laser induced amorphous and laser induced crystallized films of Se₇₅S_25−xAg_x (x=4, 6 and 8) glassy alloys was studied from absorption spectra. The amorphous and crystallized films were induced by pulse laser for 10 min. After laser irradiation on amorphous and crystalline films, optical band gap was measured. It has been found that the mechanism of the optical absorption follows the rule of indirect transition. The amorphous thin films show an increase in the optical band gap, while the crystallized (thermally annealed) thin films show a decrease in the optical band gap by inducing laser irradiation. Crystallization and amorphization of chalcogenide films were accompanied with the change in the optical band gap. The change in optical energy gap could be determined by identification of the transformed phase. These results are interpreted in terms of concentration of localized states due to shift in Fermi level.     

Frequency–temperature response of Pb(Zr0.65−xCexTi0.35)O3 ferroelectric ceramics: Structural and dielectric studies

A high-temperature solid-state reaction technique was used to prepare polycrystalline samples of Pb(Zr_0.65−xCe_xTi_0.35)O₃ (x=0, 0.05, 0.10, 0.15) (PZCT). X-ray diffraction (XRD) technique and scanning electron microscopy (SEM) were used to study the structural and microstructural properties of the compounds, respectively. The XRD study confirmed the formation of compounds at room temperature. Microstructural analysis of the surface of the compounds exhibits that there is a change in grain size, shape and density on introduction of cerium (Ce) in PZCT. Detailed studies of the dielectric properties reveal that PZCT show: (i) increase in T_c on increasing Ce concentration and (ii) improvement in dielectric constant and ac conductivity.     

Structural and optical properties of Ba(Ti1−x,Nix)O3 thin films prepared by sol–gel process

Ba(Ti_1−x,Ni_x)O₃ thin films were prepared on fused quartz substrates by a sol–gel process. X-ray diffraction and Raman scattering measurements showed that the films are of pseudo-cubic perovskite structure with random orientation and the change of lattice constant caused by Ni-doping with different concentrations is very small. Optical transmittance spectra indicated that Ni-doping has an obvious effect on the energy band structure. The energy gap of Ba(Ti_1−x,Ni_x)O₃ decreased linearly with the increase of Ni concentration. It indicates that the adjusting of band gap can be achieved by controlling the Ni-doping content accurately in Ba(Ti_1−x,Ni_x)O₃ thin films. This has potential application in devices based on ferroelectric thin films.     

A TEM study of crystal and domain structures of Nb-Doped 95/5 PZT ceramics

95/5 PZT ceramics with compositions of Pb(Zr_1–x Ti _x )₃+1 wt% Nb₂O₅ (x=0.025 and 0.04) are studied with TEM. The coexistence of both ferroelectric (F) and antiferroelectric (AF) phases in one ceramic grain at room temperature is confirmed for these two compositions. The AF phase is mainly tetragonal, while a pseudo-cubic arrangement of AF polarization is also possibly present. When the Ti⁴⁺ concentration is increased, the F phase becomes predominant. Direct interfaces between F and AF domains can be observed, the former expands at the expense of the latter when bombarded by 200 keV electrons.     

Crystallization of lead zirconate titanate films by laser annealing

The structure of lead zirconate titanate Pb(Zr _x Ti_{1 ? x} )O₃ thin films grown by chemical solution deposition on Si-SiO₂-Ti-Pt substrates has been studied using transmission electron microscopy and energy-dispersive analysis. Films crystallization has been performed using laser annealing. It has been found that, in contrast to isothermal annealing where nucleation on the platinum layer dominates, crystallization and growth of spherical perovskite crystals occur in the film bulk. The perovskite phase crystal size increases from 10 to 120 nm with increasing laser beam energy.     

Control of the properties of Pb(TixZr1-x )O3 solid solutions by external disturbances

The influence of x-ray irradiation to absorbed radiation doses D = (0.5?12) × 10⁸ rad on the properties of ferroelectric ceramic Pb(Ti_xZr_1?x )O₃ solid solutions with compositions close to the morphotropic phase boundary was studied. The effects of x-ray radiation on the electrical conductivity of ferroelectric ceramics are shown to differ with x ranging from 0.42 to 0.60. Using empirical equations and numerical techniques, quantitative relations are established between the composition, absorbed radiation dose, and electrical conductivity for Pb(Ti_xZr_1?x )O₃.     

Pyroelectric properties in three phases coexistence Pb[(Mn0.33Nb0.67)0.5(Mn0.33Sb0.67)0.5]0.08(ZrxTi1−x)0.92O3 lead ceramics

The bulk dense Pb[(Mn_0.33Nb_0.67)_0.5(Mn_0.33Sb_0.67)_0.5]_0.08(Zr_xTi_1−x)_0.92O₃ pyroelectric ceramics have been successfully prepared by the conventional solid method. The effect of three phases coexistence in the ceramics is studied. When x = 0.95 and 0.85 in the ceramics, the maximum pyroelectric coefficient peaks appear at 23 °C and 45 °C, and the maximum values are 26.5 × 10⁻⁴ C/m² °C and 25.5 × 10⁻⁴ C/m² °C, respectively. The maximum pyroelectric coefficient appears large while the peaks widths are small. When the two kinds of ceramic powders mixed with the mol ratio of 2:1, the pyroelectric coefficient of the ceramics is above 10.0 × 10⁻⁴ C/m² °C in a broad temperature range from 20 °C to 55 °C. The possible physical mechanism of the temperature broadened phenomenon is briefly discussed.     

Effect of Ti on the Structure and Mechanical Properties of TixZr2.5-xTa Alloys

To determine the effects of Ti and mixing entropy (ΔS_mix) on the structure and mechanical proper-ties of Zr-Ta alloys and then find a new potential energetic structural material with good me-chanical properties and more reactive elements, Ti_xZr_2.5−xTa (x = 0, 0.5, 1.0, 1.5, 2.0) alloys were investigated. The XRD experimental results showed that the phase transformation of Ti_xZr_2.5−xTa nonequal-ratio ternary alloys depended not on the value of ΔS_mix, but on the amount of Ti atoms. With the addition of Ti, the content of the HCP phase decreased gradually. SEM analyses revealed that dendrite morphology and component segregation increasingly developed and then weakened gradually. When x increases to 2.0, Ti_xZr_2.5−xTa with the best mechanical properties can be ob-tained. The yield strength, compressive strength and fracture strain of Ti_2.0Zr_0.5Ta reached 883 MPa, 1568 MPa and 34.58%, respectively. The dependence of the phase transformation and me-chanical properties confirms that improving the properties of Zr-Ta alloys by doping Ti is feasible.     

Concentration dependences of the properties of multicomponent PZT-based piezoelectric ceramics in the morphotropic transition range

The following three ternary PZT-based systems are studied in detail: 0.98Pb(Ti_xZr_1−x )O₃-0.02Pb(Nb_1/2Bi_1/2)O₃, 0.98(Pb_0.9727Sr_0.0273)(Ti_xZr_1−x )O₃-0.02Pb(Nb_1/2Bi_1/2)O₃ + 1 wt% PbO, and 0.98(Pb_0.9727Sr_0.0273)(Ti_xZr_1−x )O₃-0.02Pb(Nb_1/2Bi_1/2)O₃ + 2 wt % PbGeO₃, where 0.45 ≤ x ≤ 0.49 and the concentration step is Δx = 0.025. A number of concepts are formulated regarding the phase diagrams of PZT-type systems near the morphotropic transition. A scheme for real tetragonal-rhombohedral transformation is given. The maxima of the electrophysical characteristics of the solid solutions from the morphotropic range are shown to be caused mainly by an appearing intermediate phase. Analysis of the insulating, piezoelectric, and mechanical properties of the samples demonstrates that there is a group of solid solutions that are promising materials for high-temperature piezoelectric devices operating in the medium-frequency band.     

Polaronic effects on laser dressed donor impurities in a quantum well

The effect of laser field on the binding energy in a GaAs/Ga1_1−xAl_xAs quantum well within the single band effective mass-approximation is investigated. Exciton binding energy is calculated as a function of well width with the renormalization of the semiconductor gap and conduction valence effective masses. The calculation includes the laser dressing effects on both the impurity Coulomb potential and the confinement potential. The valence-band anisotropy is included in our theoretical model. The 2D Hartree–Fock spatial dielectric function and the polaronic effects have been employed in our calculations. We investigate that reduction of binding energy in a doped quantum well due to screening effect and the intense laser field leads to semiconductor–metal transition.     

High permeability and low power loss of Ti and Zn substitution lithium ferrite in high frequency range

The effect of Zn and Ti on the magnetic, power loss and structural properties of Li_0.5Zn_xTi_xMn_0.05Fe_2.45−2xO₄ ferrites (x=0.0 to 0.30 in step of 0.05)+0.5 wt% Bi₂O_3, prepared by standard ceramic technique, has been investigated. Complex permeability (μ*=μ′−jμ″) has been analyzed at room temperature in frequency range from 1 to 10³ MHz. It was found an enhancement in permeability with Ti and Zn concentration in Li_0.5Zn_xTi_xMn_0.05Fe_2.45−2xO₄ and exhibits the maximum value 106 for x=0.20 sample. Complex permeability of these ferrites exhibits stable frequency response up to 7 MHz beyond which the real part decreases sharply and imaginary part increases to have a peak at the relaxation frequency. Power loss measurements have been carried out in induction condition (B=10 mT) in frequency range of 50 kHz to 3 MHz. Power loss has been found to be quite low with the substitution of Ti and Zn in lithium ferrite.     

Structure and magnetostriction of RFex (1.6 x 2.0) and R(Fe1−yTiy)1.8 (y 0.2) alloys (R=Dy0.65Tb0.25Pr0.1)

Structure, Curie temperature and magnetostriction of RFe_x (1.6 x 2.0) and R(Fe_1−yTi_y)_1.8 (y 0.2) alloys (R=Dy_0.65Tb_0.25Pr_0.1) have been investigated using optical microscopy, X-ray diffraction, AC initial susceptibility and standard strain gauge techniques. The homogenized RFe_x alloys are found to be essentially single phase in the range of 1.8 x 1.85. The second phase is a rare-earth-rich phase when x 1.8, and (Dy, Tb, Pr)Fe₃ phase when x 1.85. X-ray diffraction indicates that the R(Fe_1−yTi_y)_1.8 alloys contain a small amount of Fe₂Ti phase when y 0.05, which increases with the increment of Ti content. The Curie temperature of R(Fe₁−_yTi_y)_1.8 alloys slightly enhances with increasing Ti concentration when y 0.05, then remains almost unchanged in the range of 0.05 y 0.20. The magnetostriction of RFe_x alloys is improved when x 1.80 and reduced by increasing Fe content when x 1.85. The magnetostriction of R(Fe_1−yTi_y)_1.8 alloys is lowered by increasing Ti content.     

Structural and vibrational properties of dilute GaNxAs1−x(P1−x)

We report a comprehensive analyzes of the Fourier transform infrared (FTIR) absorption and Raman scattering data on the structural and vibrational properties of dilute ternary GaAs_1−xN_x,[GaP_1−xN_x] (x<0.03) alloys grown on GaAs [GaP] by metal organic chemical vapor deposition (MOCVD) and solid source molecular beam epitaxy (MBE). By using realistic total energy and lattice dynamical calculations, the origin of experimentally observed N-induced vibrational features are characterized. Useful information is obtained about the structural stability, vibrational frequencies, lattice relaxations and compositional disorder in GaNAs (GaNP) alloys. At lower composition (x<0.015) most of the N atoms occupy the As [P] sublattice {N_As[N_P]}—they prefer moving out of their substitutional sites to more energetically favorable locations at higher x. Our results for the N-isotopic shifts of local mode frequencies compare favorably well with the existing FTIR data.     

Effect of electric field on electrocaloric effect in Pb(Zr1 − xTix)O3 solid solution

A thermodynamic analysis is employed to investigate the intrinsic electrocaloric effect of Pb(Zr_1 − xTi_x)O₃ solid solution system under the different electric field. Theoretical analysis indicates that Pb(Zr_1 − xTi_x)O₃ system has the giant electrocaloric coefficient and the large adiabatic temperature change near its ferroelectric Curie temperature. The applied electric field decreases not only the electrocaloric coefficient but also its temperature dependence. Furthermore, it increases the adiabatic temperature change as well as its dependence of temperature. The temperature corresponding to the maximum of electrocaloric coefficient and adiabatic temperature change increases with the enhancement of electric field because of its first-order phase transition between ferroelectric phase and paraelectric phase.     

Chemical vapor deposition of ZrxTi1−xO2 and HfxTi1−xO2 thin films using the composite anhydrous nitrate precursors

Zr-Ti and Hf-Ti composite nitrates were successfully developed as single-source precursors for the chemical vapor deposition (CVD) of Zr_xTi_1−xO₂ and Hf_xTi_1−xO₂ thin films. The Zr-Ti nitrate can be assumed as a solid solution of the individual Zr and Ti nitrates, and the Zr/Ti molar ratio in the deposited Zr_xTi_1−xO₂ films is consistent with that in the precursor. The Hf-Ti nitrate appears to be a mixture of the Hf and Ti nitrates and the composition of the deposited Hf_xTi_1−xO₂ films depends remarkably on the heating time of precursor. Both Zr_xTi_1−xO₂ and Hf_xTi_1−xO₂ films exhibit trade-off properties between band gap and dielectric constant. The obtained results suggest that Zr_xTi_1−xO₂ and Hf_xTi_1−xO₂ films are promising candidates for gate dielectric application to improve the scalability and reduce the leakage current of the future complementary metal-oxide-semiconductor (CMOS) devices.