Terahertz dielectric spectra of (Ba,Sr)TiO<Subscript>3</Subscript> thin films

Reflection and transmission spectra of Ba_0.7Sr_0.3TiO₃ films with thicknesses of 36 and 800 μm on the MgO substrate are measured in the frequency range from 8 to 1000 cm^?1 at room temperature. The dielectric parameters of the film material are derived using the simulation method. The dependence of the permittivity on the film thickness is determined. It is found that the absorption spectrum of the substrate strongly affects the calculated dielectric spectra of the film material. It is demonstrated that the simulation should be performed with the inclusion of the dielectric losses in the substrate in the subphonon frequency range.     

Crystallinity and electrical properties of (Pb,Sr)TiO<Subscript>3</Subscript> films enhanced by laser-assisted low-thermal-budget annealing

The physical and electrical properties of (Pb,Sr)TiO₃ (PSrT) films annealed by various techniques are systematically investigated in this study. The crystallinity and ferroelectricity of PSrT films can be enhanced by excimer laser annealing (ELA), but the effect only works on the upper region of films. On the other hand, PSrT films treated by rapid thermal annealing (RTA) can also improve crystallinity and ferroelectricity. However, the leakage current of films is seriously increased due to defects and interfacial diffusion induced by post-RTA at high temperature. As a result, the laser-assisted two-step annealing (post-ELA+RTA) is proposed in this work. It is found that PSrT films treated by post-ELA+RTA show improved crystallinity, better ferroelectric properties, higher dielectric constant, and lower leakage currents, which bring out the longer lifetime and higher breakdown field. PACS 77.84.-s; 81.40.Ef; 42.62.-b     

Leakage current and pyroelectric properties of compositionally graded (Pb,Ca)TiO<Subscript>3</Subscript> films

Highly (100)-oriented, compositionally graded (Pb,Ca)TiO₃ (PCT) thin films with a Ca content from 0 to 24 mol% on Pt/Ti/SiO₂/Si substrates were prepared by a sol-gel process. The graded structure of the Au/PCT/Pt film capacitor showed a well-saturated hysteresis loop at an applied field of 500 kV/cm with remanent polarization (P_r), and coercive electric field (E_c) values of 9.35 C/cm² and 130 kV/cm, respectively. At 100 kHz, the dielectric constant and dielectric loss of the film were 129 and 0.024, respectively. The leakage current density of the graded PCT film was less than 1.0×10^-7 A/cm² over a voltage range from 0 to 4 V. The conduction current depended on the voltage polarity. At low electric field (110 and 180 kV/cm, respectively, for Pt and Au electrodes biased negatively), the Au/PCT and PCT/Pt interfaces form a Schottky barrier. At high electric field (>110 kV/cm), the Au electrode biased negatively shows space-charge-limited current (SCLC) behavior. The temperature dependencies of the pyroelectric coefficients of the graded PCT film were measured by a dynamic technique. From 20 to 82 °C, the pyroelectric coefficients of graded PCT film remain steady in the range 106 to 118 C/m²K. The detectivity figure of merit (F_D) of the graded PCT film was 6.7×10^-6 Pa^-0.5. PACS 77.80.-s; 77.70.+a; 77.22.-d; 51.50.+v; 68.37.-d     

<Emphasis Type="Bold">(Ba,Sr)TiO</Emphasis><Subscript>3</Subscript> thin films grown by pulsed laser deposition with low dielectric loss at microwave frequencies

We report a method for producing BST films with consistently high figures of merit for tunable microwave applications. (Ba_1-x,Sr_x)TiO₃ (x=0.4, target doped with 1% W) thin films have been deposited using pulsed laser deposition onto (100)MgO substrates. Films were deposited at low partial pressures of oxygen (50 mTorr) at a substrate temperature of 730 °C. An analysis of the X-ray diffraction data indicates that the film has a nearly cubic structure, with the overall lattice parameter enlarged relative to the bulk material due to the presence of oxygen vacancies. A post-deposition anneal of the film in flowing oxygen (1000 °C for 6 h) resulted in a decrease in the lattice parameter while remaining nearly cubic. An analysis of the microwave dielectric properties (1–20 GHz) showed that the annealed film exhibited about 10% tunability for an applied bias field of 67 kV/cm with a dielectric Q(1/tan)>600. Investigation of the films by time-resolved confocal scanning optical microscopy (CSOM) has revealed that there is an out-of-plane polarization at zero applied field (E_DC=0). The results show that the paraelectric response is relatively insensitive to applied field, while the ferroelectric response is correlated with the growth of in-plane nanodomains. We find these results to be consistent with a large number of studies that show that strain-relief is of paramount importance if ferroelectric films are to be developed as microwave circuit components. PACS 81.15.Fg; 85.50.-n     

Current-voltage characteristics of polycrystalline (La<Subscript>0.5</Subscript>Eu<Subscript>0.5</Subscript>)<Subscript>0.7</Subscript>Pb<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> at low temperatures

The current-voltage characteristics of the polycrystalline substituted lanthanum manganite (La_0.5Eu_0.5)_0.7Pb_0.3MnO₃ have been measured at temperatures close to the metal-insulator transition temperature and at low temperatures. In both cases, the current-voltage characteristics exhibit nonlinear properties that are strongly dependent on the strength of an applied magnetic field. The mechanisms responsible for the nonlinear properties at these temperatures are found to be different: near the metal-insulator transition, the current-voltage characteristics are determined by the phase layering inside granules, while at low temperatures, they are determined by tunneling of carriers through insulating interlayers of the granules.     

Anisotropic in-plane strain in W-doped (Ba,Sr)TiO<Subscript>3</Subscript> thin films deposited by pulsed-laser deposition on (001)MgO

The structural and the microwave dielectric properties of Ba_xSr_(1-x)TiO₃ films (BST) with x=0.5, 0.6 and 0.7, containing 1 mol % W have been investigated. The films were grown by pulsed-laser deposition on MgO (001) substrates at a temperature of 720 °C in an oxygen pressure from 3 to 500 mTorr. The film structures were determined by X-ray diffraction. The lattice parameters were fitted to a tetragonal distortion of a cubic lattice. The out-of-plane lattice parameter (c) was calculated from the position of the (004) reflection. Using c, the in-plane lattice parameter, a, was calculated from the position of the (024) and (224) reflections. A deviation in the calculated values for a, beyond the systematic error, was found in the in-plane lattice parameter, suggesting an in-plane orthorhombic distortion (a, a’). Films with x=0.7 showed a minimum in-plane distortion due to a better lattice match with the substrate. The ratio of the in-plane and out-of-plane lattice parameters was calculated as a measure of the lattice distortion (a/c and a’/c). The dielectric properties of the films deposited were measured at room temperature at 2 GHz using gap capacitors fabricated on top of the dielectric film. For all Ba/Sr ratios investigated in the W-doped material, the dielectric Q (1/cosδ) was observed to be insensitive to the oxygen deposition pressure. A peak in the change in the dielectric constant, as a function of an applied electric field (0–80 kV/cm), was observed for films deposited in 50 mTorr of oxygen. The largest K-factor, K=(ε(0)-ε(V )/ε(0)×Q(0)), for films deposited from a BST x=0.6 (1 mol % W-doped) target was observed in the film that had a minimum in-plane strain, where a∼a’ and c was greater than a and a’. Received: 4 July 2002 / Accepted: 5 July 2002 / Published online: 17 December 2002 RID="*" ID="*"Permanent address: Nuclear Research Center–Negev, P.O. Box 9001 Beer-Sheva, Israel RID="**" ID="**"Corresponding author. Fax: +1-202/767-5301, E-mail: horwitz@ccsalpha3.nrl.navy.mil     

X-ray study of [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>]<Subscript>2</Subscript>ZnCl<Subscript>4</Subscript> at low temperatures

The unit cell parameters a, b, and c of [N(CH₃)₄]₂ZnCl₄ have been measured by x-ray diffraction in the temperature range 80–293 K. Temperature dependences of the thermal expansion coefficients α_a, α_b, and α_c along the principal crystallographic axes and of the unit cell thermal expansion coefficient α_V were determined. It is shown that the a=f(T), b=f(T), and c=f(T) curves exhibit anomalies in the form of jumps at phase transition temperatures T₁=161 K and T₂=181 K and that the phase transition occurring at T₃=276 K manifests itself in the a=f(T) and b=f(T) curves as a break. A slight anisotropy in the coefficient of thermal expansion of the crystal was revealed. The phase transitions occurring at T₁=161 K and T₂=181 K in [N(CH₃)₄]₂ZnCl₄ were established to be first-order.     

Physical properties of Ba<Subscript>0.8</Subscript>Sr<Subscript>0.2</Subscript>TiO<Subscript>3</Subscript> thin films

The behavior of material constants in ferroelectric Ba_0.8Sr_0.2TiO₃ thin films is studied depending on the misfit strain at room temperature in the context of nonlinear thermodynamic potential of the phenomenological theory. Some constants are found to undergo drastic changes with the alternating strain at the interfaces. The gathered results allow one to evaluate the material constants for a specific film and to outline the direction in searching the ways to synthesize films with the needed properties.     

Piezoelectric coefficients of multilayer Pb(Zr,Ti)O<Subscript>3</Subscript> thin films

Sol–gel techniques were used to prepare thin films of Pb(Zr _x ,Ti_1−x )O₃ (PZT) with three different Zr/Ti ratios and a graded PZT film with three different compositional layers. A Michelson interferometer was used to measure the thickness strains due to an applied ac electric field. Effective d ₃₃ piezoelectric strain coefficients were computed from the experimental data. Interfacial pinning caused these coefficients to differ from the true ones. They were corrected for the pinning using both an analytical model and finite-element analysis. The corrected coefficients of the PZT (52/48) sample were in excellent agreement with values of bulk materials. The coefficients of the multilayer sample were very low, probably due to insufficient poling or domain switching.     

Phase transition behavior of highly (100) textured sol-gel-derived Ba<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> thin films

We have investigated the relations between microstructure and dielectric properties in order to fabricate sol-gel-derived highly (100) oriented Ba_0.5Sr_0.5TiO₃ (BST 50/50) thin films with properties comparable to those of the bulk material. For the first time, we were able to fabricate BST thin films which exhibited the orthorhombic-to-tetragonal transition in addition to the commonly observed tetragonal-to-cubic transition. We were successful in explaining the commonly observed degradation of the dielectric behavior of BST thin films, when compared to that of the bulk material, in terms of grain size, compositional inhomogeneity (measured in terms of Sr/Ba ratio) between the grain bulk and grain boundary, and mechanical stresses. PACS 77.55.+f; 77.22Gm; 77.80.Bh; 77.80.Dj     

Nonlinear dielectric response of epitaxial Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript> TiO<Subscript> 3</Subscript> thin films

Based on Landau-Devonshire (LD)-type phenomenological thermodynamic theory, the electric field dependence of the dielectric properties of tetragonal single-domain barium strontium titanate(Ba_1-xSr_xTiO₃) films on cubic substrates is theoretically investigated by taking into account the high order terms of the polarization. At room temperature, the nonlinear dielectric responses of epitaxial Ba_0.6Sr_0.4TiO₃ films are provided by adjusting the film thickness and growth temperature. The strong nonlinearity of relative dielectric constant and pyroelectric coefficient are attained around critical film thickness on MgO (69 nm) and LaAlO₃ (132 nm) substrates or critical growth temperature on MgO (337 °C) substrate with respect to epitaxy-induced lattice misfit and thermal stresses during deposition. This can be explained that small compressive stresses are effective to support high nonlinearity of dielectric constant and pyroelectric coefficient for Ba_0.6Sr_0.4TiO₃ films irrespective of whether they are on compressive substrate or tensile substrate. It is also predicted that a large tunability may be achieved by altering processing conditions, such as the film thickness and growth temperature for different substrates. Our theoretical results are in good agreement with the experimental data reported in literature.     

Hysteresis of magnetoresistance in granular La<Subscript>0.7</Subscript>Ca<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> at low temperatures

The magnetoresistance of granular La_0.7Ca_0.3MnO₃ is studied experimentally over wide ranges of temperatures and magnetic fields. The emphasis is on anomalously large hysteresis of magnetoresistance at low temperatures (T = 4.2 K). The observed ρ(H) dependence can be qualitatively explained by spin-dependent tunneling of electrons through the dielectric boundaries of conducting granules characterized by a wide spread in the magnetic-moment magnitudes.     

Observation of the magnetic domain structure in Cu<Subscript>0.47</Subscript>Ni<Subscript>0.53</Subscript> thin films at low temperatures

We report on the first experimental visualization of domain structure in films of weakly ferromagnetic Cu_0.47Ni_0.53 alloy with different thickness at liquid helium temperatures. Improved high-resolution Bitter decoration technique was used to map the magnetic contrast on the surface of the films well below the Curie temperature T_Curie (∼60 K). In contrast to magnetic force microscopy, this technique allowed visualization of the domain structure without its disturbance while the larger areas of the sample were probed. Maze-like domain patterns, typical for perpendicular magnetic anisotropy, were observed. The average domain width was found to be about 100 nm. The article is published in the original.     

Crystal-structure and magnetic phase transformations in solid solutions of BiFeO<Subscript>3</Subscript>-AFe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> (A = Ca,Sr, Ba,Pb)

Solid solutions of Bi_{1 ? x} A _x (Fe_{1 ? x/2}Nb _x/2)O₃, where A = Ca, Ba, and Pb, are obtained and their crystal structure and magnetic properties are investigated. It is shown that for A = Ca and x ≈ 0.15, the symmetry of the unit cell changes from rhombohedral (space group R3c) to orthorhombic (Pbnm). The transformation leads to the emergence of spontaneous magnetization due to the Dzyaloshinskii-Moriya interaction. Solid solutions with A = Pb remain rhombohedral up to a concentration of x = 0.3. Spontaneous magnetization sharply increases in the compound with x ≈ 1 at low temperatures and is due to the formation of the spin-glass component.     

Photoaccumulating film systems based on TiO<Subscript>2</Subscript>/MoO<Subscript>3</Subscript> and TiO<Subscript>2</Subscript>/MoO<Subscript>3</Subscript>:V<Subscript>2</Subscript>O<Subscript>5</Subscript> nanoheterostructures

The thin-film photocatalysts TiO₂/MoO₃ and TiO₂/MoO₃:V₂O₅ obtained by a combination of sol–gel and sintering techniques were studied using the photooxidation of probing dyes, EPR spectroscopy, X-ray diffraction analysis, and electron microscopy. It was shown that due to charge accumulation caused by UV irradiation, these photocatalysts retain their oxidative activity and ability for self-sterilization in the dark for a long time after irradiation was terminated (up to 5 h for TiO₂/MoO₃:V₂O₅).     

Highly (100) oriented Pb(Zr<Subscript>0.52</Subscript>Ti<Subscript>0.48</Subscript>)O<Subscript>3</Subscript>/LaNiO<Subscript>3</Subscript> films grown on amorphous substrates by pulsed laser deposition

Pb(Zr_0.52Ti_0.48)O₃ (PZT)/LaNiO₃ (LNO) thin films with highly (100) out of plane orientation were produced on SiO₂/Si(100) and alkaline earth aluminosilicate glass substrates by pulsed laser deposition (PLD). Orientations of both PZT and LNO films were evaluated using X-ray diffraction. The pure (100)-oriented PZT/LNO films were obtained under optimized deposition conditions. Time of flight-secondary ion mass spectrometry analysis showed that LNO could effectively block interdiffusion between the PZT films and the substrates. Fairly smooth surfaces of the PZT films with roughness of about 4 nm were observed using an atomic force microscope. Cross sectional examination revealed that the films grew in columnar grains. The PZT films grown on both SiO₂/Si and glass substrates demonstrated very good ferroelectric characteristic at room temperature with remnant polarization of up to 26 μC/cm². PACS 79.20.DS; 77.84.DY; 78.70.Ck     

Memory effect in Ba<Subscript>0.85</Subscript>Sr<Subscript>0.15</Subscript>TiO<Subscript>3</Subscript> ferroelectric films on silicon substrates

Ba_0.85Sr_0.15TiO₃ ferroelectric films on single-crystal silicon wafers were grown and studied. X-ray diffraction and electron microscopy studies showed that the films are characterized by a limited texture with a perovskite structure. It was shown that the grown films can be used as recording media for nonvolatile rerecorded data carriers in kinematic-type external memory devices. A possible mechanism of data recording and storage in the structures was considered.     

Ferromagnetic resonance in (Bi,Tm)<Subscript>3</Subscript>(Fe,Ga)<Subscript>5</Subscript>O<Subscript>12</Subscript>(210) epitaxial films

It is shown that the ferromagnetic resonance spectrum in (Bi,Tm)₃(Fe,Ga)₅O₁₂ films grown in Gd₃Ga₅O₁₂(210) substrates has a single peak. The azimuthal and polar dependences of the resonance field possess 180° symmetry. The angular dependences of the ferromagnetic resonance line width and intensity are studied.     

Acoustic emission and thermal expansion of Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> and Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>-PbTiO<Subscript>3</Subscript> crystals

The temperature dependence of the elongation per unit length for Pb(Mg_1/3Nb_2/3)O₃ crystals unannealed after growth and mechanical treatment is investigated in the course of thermocycling. It is revealed that this dependence deviates from linear behavior at temperatures below 350°C. The observed deviation is characteristic of relaxors, is very small in the first cycle, increases with increasing number n of thermocycles, and reaches saturation at n≥3. In the first cycle, a narrow maximum of the acoustic emission activity is observed in the vicinity of 350°C. In the course of thermocycling, the intensity of this maximum decreases and becomes zero at n>3. For (1?x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃ crystals, the dependence of the temperature of this acoustic emission maximum on x exhibits a minimum. It is assumed that the phenomena observed are associated with the phase strain hardening due to local phase transitions occurring in compositionally ordered and polar nanoregions.     

Domain dynamics in (210)-oriented single-crystal (Bi,Y,Lu,Pr)<Subscript>3</Subscript>(Fe,Ga)<Subscript>5</Subscript>O<Subscript>12</Subscript> films

Using high-speed photography, dynamic magnetic structures are studied in Bi-containing (210)-oriented single-crystal films of (Bi,Y,Lu,Pr)₃(Fe,Ga)₅O₁₂ grown through liquid-phase epitaxy from an overcooled solution in the melt on (Gd,Ga)₃(Mg,Zr,Ga)₅O₁₂ substrates. At various temperatures, the ranges of pulsed magnetic fields are determined in which unidirectional anisotropy of domain wall velocity and spatial distortions of moving domain walls are observed.