National Institute Of Materials Physics - Romania

Magnesium doped (Zr0.8Sn0.2)TiO4 material has been prepared by solid state reaction and characterized. The samples were sintered in the temperature range of 1270 divided by 1315 degrees C for 2 hours. The effect of sintering temperature on structural and dielectric properties was investigated. The 0.2 wt.% MgO addition improves the sintering process and well sintered samples with a high value of bulk density were achieved. The material exhibits a dielectric constant epsilon(r) similar to 36.6 and high values of the Qxf product, greater than 61000 at microwave frequencies. The dielectric properties make the magnesium doped (Zr0.8Sn0.2)TiO4 material very attractive for such microwave applications as dielectric resonators, filters, dielectric antennas, substrates for hybrid microwave integrated circuits, etc.

The problem of the thickness dependence of the dielectric constant, as well as the extrinsic contributions to its value, is analyzed for the case of epitaxial Pb(Zr,Ti)O-3 (PZT) thin films. It is shown that the frequency dependence of the measured capacitance is best simulated by an equivalent circuit incorporating the trap-containing capacitance of a Schottky contact. The thickness dependence of the dielectric constant, calculated using the formula of a plane capacitor, appears to be an extrinsic effect due to the interface phenomena in the metal-ferroelectric-metal structure. The intrinsic dielectric constant of the PZT material seems to be thickness independent and of low value of about 30-40. This is closer to the values estimated from Raman measurements or from quantum theories of ferroelectricity. The thickness independence is also proven by piezoresponse force microscopy measurements. The presence of traps is evidenced by the presence of a photovoltaic effect at subgap wavelengths.

High permittivity dielectric materials (epsilon(r) > 20) are used in mobile communications due to low dielectric loss in microwaves and millimeter waves, specific temperature dependence of the dielectric properties and high dielectric permittivity, which allows device miniaturization. Preparation of Ba(Zn1/3Ta2/3)O-3 ceramic materials (BZT) with optimal properties for applications requires special thermal treatments due to the difficult control of the cationic ordering. The samples were prepared by using solid-state reaction, doped with Eu2O3, ZrO2, Nb2O5, or Al2O3-Y2O3 and sintered at the following temperatures: 1400, 1500, 1550 degrees C for 2 or 3 hours. In order to improve the microwave properties, annealing treatments at 1410 degrees C for 10h or 30h were performed on ceramic samples. XRD was used for compositional and structural characterization. The XRD data allowed the study of the transition from the pseudo-cubic cell to the hexagonal cell. The dielectric properties were measured in the microwave range and were correlated with additives and structural properties. Sintering temperatures greater than 1500 degrees C are required for doped BZT compositions, in order to obtain high dielectric constant (epsilon(r) similar to 28) and high quality factor (Q = 10000 at 10 GHz).

New PZT type ceramic materials, doped with Ni, were prepared by the usual solid state reaction. The best composition proved to be the one containing 6% atomic Ni and having the following chemical formula: Pb0.95Bi0.03Nb0.02Zr0.51 Ti0.43Ni0.06O3. Rectangular samples of this powder were pressed and sintered at 1200 OC for 4 hours and then it was cut in thin slices used to construct an efficient bimorph type ventilator to be used in miniaturized devices for cooling. Miniature ventilators made of PZT ceramics are preferred due to their smallness, high electromechanical efficiency and lack of rotating parts and last but not least of contiguous electrical contacts. We made such a device by using two thin ceramic PZT plates of the material with the best piezoelectric properties, assembled in a flexural oscillator through a proper bimorph association. The emerging doublet behaves itself very much like a bimetal system and possesses a good developed flexural mode. Attaching a metallic elastic plate to the bimorph produces a highly efficient miniature ventilator. A theoretical quantitative study of this flexural bimorph system with elastic plate attached was proposed.

The Ba1-xPbxNd2Ti5O14 (BNT: Pb) ceramics are appropriate for microwave devices due to their high dielectric constant and low loss in the microwave domain. Samples with x Pb content in the range 0 + 0.5 were prepared by solid-state reaction and sintered at temperatures T-s = 1230 + 1260 degrees C. XRD and SEM analysis indicate very good crystalline structure and polyhedral well formed grains. Controlled temperature coefficient of resonant frequency alpha is essential for dielectric resonators. The temperature coefficient of the resonant frequency alpha takes values from - 15 ppm/degrees C to + 70 ppm/degrees C. Highdensity values and adequate microwave parameters were obtained for x = 0.5 Pb content. The BNT: Pb ceramics sintered at 1250 degrees C and 1260 degrees C for 2 hours are suitable for dielectric resonators for frequencies up to 5 GHz. epsilon r = 76 + 87 and Q x f similar to 5000 GHz).

Barium strontium titanate with molar formula Ba0.75Sr0.25 TiO3 (BST) was prepared from raw materials by solid-state reaction. Samples were sintered at 1230 degrees C and 1260 degrees C for 2 h. In order to improve the sintering process, 1 wt. % MgO and 1 wt. % MnO2 were used as sintering additives. The sinterability, structural, morphological and dielectric properties of pure and doped BST samples were investigated. Perovskite structure of polycrystalline BST ceramics was determined by Xray diffraction. SEM investigations revealed a grain and pore size distribution, which is shifted to higher values by a slight increase of the sintering temperature from 1230 degrees C to 1260 degrees C. In the presence of additives, a better sintering and grain refining could be observed, whereas their lack induce a strong effect of exaggerated grain growth, by forming of large faceted grains. The presence of Mn ions in the doped BST ceramics was revealed by the EDX analysis. On the other hand, Mg ions are not evidenced. Temperature dependence of dielectric constant measured at 1 kHz shows a diffuse ferroelectric-paraelectric transition, which can be attributed to the large size dispersion of grains. The increase of sintering temperature leads to a shift of the Curie temperature to higher values.

A new method for the preparation of PbS/PZT composite materials is proposed. The PZT matrix has been obtained using the sol-gel method on Pt-coated Si substrates. The PbS (nano) crystals were subsequently obtained by dipping the porous PZT matrix in Pb(NO3)(2) and Na2S solutions at room temperature. The XRD spectra show the presence of the tetragonal phase of PZT. The microstructure of the film was analyzed using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The size of the PbS (nano)-particles at the sample's surface is about 25 nm, estimated from the AFM analysis. The roughness of the sample's surface is about 5 nm. The porosity of the composite, estimated from the SEM analysis in cross-section is smaller than for the reference PZT porous matrix. The equivalent dielectric constant of the composite increases by a factor of 4-5 in comparison with the porous PZT reference and does not depend on the thickness of the surface PbS (nano)-crystalline layer. The saturated polarization (Ps) value for the PZT-PbS composite is smaller than that corresponding to the bulk PZT but higher than for the reference porous PZT. We attribute these effects to the partial filling of the pores in the PZT matrix with PbS.

Photovoltaic properties of the metal-ferroelectric-metal structures, having SrRuO3 metal oxide electrodes and Pb(Zr,Ti)O-3 (PZT) as ferroelectric layer, are investigated by the short-circuit photocurrent (SC-PHC) in the 200-800 nm wavelength domain. The band-gap dependence on the Zr content was determined from the spectral distribution of the SC-PHC signal. It was found that the band-gap value increases linearly with the Zr content, from about 3.9 eV to about 4.4 eV. It is shown that the sign and the magnitude of the signal depend on the internal bias and on the spontaneous polarization direction and value. The photocurrent describes a hysteresis loop similar to that of the ferroelectric polarization and can be used as a nondestructive readout of the nonvolatile memories based on PZT films. The existence of a significant SC-PHC signal at wavelengths corresponding to subgap energies is attributed to the presence of charged, deep levels in the forbidden band. It is also shown that the epitaxial PZT films have the potential for solid-state UV detectors, with current responsivity as high as 1 mA/W. The results are not entirely consistent with a bulk photovoltaic effect and are discussed in the frame of a Schottky barrier model for the metal-ferroelectric interface. (c) 2007 American Institute of Physics.

Leakage current measurements were performed on epitaxial, single-crystal quality Pb(Zr,Ti)O-3 films with thicknesses in the 50-300 nm range. It was found that the voltage behavior of the leakage current has a minor dependence on thickness, which rules out the space-charge limited currents as main leakage source. Temperature-dependent measurements were performed to obtain more information on the transport mechanism through the metal-ferroelectric-metal (MFM) structure. The results are analyzed in the frame of interface-controlled Schottky emission. A surprisingly low value of only 0.12-0.13 eV was obtained for the potential barrier, which is much smaller than the reported value of 0.87 eV [I. Stolichnov , Appl. Phys. Lett. 75, 1790 (1999)]. The result is explained by the effect of the ferroelectric polarization on the potential barrier height. The low value of the effective Richardson constant, of the order of 10(-7)-10(-6) A/cm(2) K-2, suggests that the pure thermionic emission is not the adequate conduction mechanism for epitaxial MFM structures. The true mechanism might be interface-controlled injection, followed by a low mobility drift through the film volume.

The microscopic damage produced in diodes made of n-type Magnetic Czochralski (MCz) silicon by 24 GeV and 26 MeV protons, up to the fluence of 1.3 x 10(15) cm(-2) 1 MeV equivalent neutrons, has been investigated and results are compared to the damage produced in devices made of standard Floating Zone (STFZ) silicon. It is found by means of Thermally Stimulated Currents (TSC) that the production of a radiation induced charged defect is enhanced in MCz, and might be in part responsible for the differences observed in the two materials at room temperature. The influence of defects on the sign of the space charge density has been studied by current transients at constant temperature i(T, t) and by Transient Current Technique (TCT). Type inversion is not revealed up to the highest investigated fluence. Full depletion voltage V-dep measurements versus fluence exhibits a minimum close to 2 x 10(14) cm(-2) 1 MeV equivalent neutrons; at the same fluence, V-dep measured as a function of annealing time changes its initial slope from positive to negative. It is shown by numerical simulations that these features can be accounted by the formation of a double junction, even in absence of type inversion. (c) 2006 Elsevier B.V. All rights reserved.