Exploiting dimensionality and defect mitigation to create tunable microwave dielectrics.

The miniaturization and integration of frequency-agile microwave circuits--relevant to electronically tunable filters, antennas, resonators and phase shifters--with microelectronics offers tantalizing device possibilities, yet requires thin films whose dielectric constant at gigahertz frequencies can be tuned by applying a quasi-static electric field. Appropriate systems such as BaxSr1-xTiO3 have a paraelectric-ferroelectric transition just below ambient temperature, providing high tunability. Unfortunately, such films suffer significant losses arising from defects. Recognizing that progress is stymied by dielectric loss, we start with a system with exceptionally low loss--Srn+1TinO3n+1 phases--in which (SrO)2 crystallographic shear planes provide an alternative to the formation of point defects for accommodating non-stoichiometry. Here we report the experimental realization of a highly tunable ground state arising from the emergence of a local ferroelectric instability in biaxially strained Srn+1TinO3n+1 phases with n ≥ 3 at frequencies up to 125 GHz. In contrast to traditional methods of modifying ferroelectrics-doping or strain-in this unique system an increase in the separation between the (SrO)2 planes, which can be achieved by changing n, bolsters the local ferroelectric instability. This new control parameter, n, can be exploited to achieve a figure of merit at room temperature that rivals all known tunable microwave dielectrics.

Pb2MnTeO6 Double Perovskite: An Antipolar Anti-ferromagnet.

Pb2MnTeO6, a new double perovskite, was synthesized. Its crystal structure was determined by synchrotron X-ray and powder neutron diffraction. Pb2MnTeO6 is monoclinic (I2/m) at room temperature with a regular arrangement of all the cations in their polyhedra. However, when the temperature is lowered to ∼120 K it undergoes a phase transition from I2/m to C2/c structure. This transition is accompanied by a displacement of the Pb atoms from the center of their polyhedra due to the 6s(2) lone-pair electrons, together with a surprising off-centering of Mn(2+) (d(5)) magnetic cations. This strong first-order phase transition is also evidenced by specific heat, dielectric, Raman, and infrared spectroscopy measurements. The magnetic characterizations indicate an anti-ferromagnetic (AFM) order below TN ≈ 20 K; analysis of powder neutron diffraction data confirms the magnetic structure with propagation vector k = (0 1 0) and collinear AFM spins. The observed jump in dielectric permittivity near ∼150 K implies possible anti-ferroelectric behavior; however, the absence of switching suggests that Pb2MnTeO6 can only be antipolar. First-principle calculations confirmed that the crystal and magnetic structures determined are locally stable and that anti-ferroelectric switching is unlikely to be observed in Pb2MnTeO6.

Near constant loss regime in fast ionic conductors analyzed by impedance and NMR spectroscopies.

Universal dielectric response (UDR) and nearly constant loss (NCL) dispersive regimes have been investigated in fast ion conductors with perovskite and NASICON structure by using NMR and impedance spectroscopy (IS). In this study, the electrical behavior of La(0.5)Li(0.5)TiO3 (LLTO-05) perovskite and Li(1.2)Ti(1.8)Al(0.2)(PO4)3 (LTAP0-02) NASICON compounds was investigated. In both systems a three-dimensional network of conduction paths is present. In the Li-rich LLTO-05 sample, lithium and La are randomly distributed on A-sites of perovskites, but in LTAP0-02 Li and cation vacancies are preferentially disposed at M1 and M2 sites. In perovskite compounds, local motions produced inside unit cells are responsible for the large "near constant loss" regime detected at low temperatures, however, in the case of NASICON compounds, local motions not participating in long-range charge transport were not detected. In both analyzed systems long-range correlated motions are responsible for dc-conductivity values of ceramic grains near 10(-3) S cm(-1) at room temperature, indicating that low-temperature local motions, producing large NCL contribution, are not required to achieve the highest ionic conductivities.

Unusual features of lattice dynamics in lawsonite near its phase transitions.

Lattice dynamics of a single crystal of lawsonite were studied over a broad range of frequencies (1 Hz to 20 THz) using impedance, THz time-domain and infrared spectroscopies. Based on polarized spectra of complex permittivity [Formula: see text] measured as a function of temperature between 10 K and 500 K, we analyzed the properties of the two known phase transitions-an antiferrodistortive one near [Formula: see text] and a ferroelectric one, occurring at [Formula: see text]. The former one is accompanied by a flat maximum in the THz-range permittivity [Formula: see text] near [Formula: see text], which is due to an overdamped polar excitation in the [Formula: see text] spectra reflecting the dynamics of water and hydroxyl groups. The strength of this mode decreases on cooling below [Formula: see text], and the mode vanishes below [Formula: see text] due to hydrogen ordering. At the pseudoproper ferroelectric phase transition, two independent anomalies in permittivity were observed. First, [Formula: see text] exhibits a peak at [Formula: see text] due to critical slowing down of a relaxation in the GHz range. Second, infrared and THz spectra revealed an optical phonon softening towards [Formula: see text] which causes a smaller but pronounced maximum in [Formula: see text]. Such anomaly, consisting in a soft mode polarized perpendicularly to the ferroelectric axis, is unusual in ferroelectrics.

Structural evolution and properties of solid solutions of hexagonal InMnO3 and InGaO3.

Solid solutions InMn(1-x)Ga(x)O(3) (0 ≤ x ≤ 1) have been investigated using magnetic, dielectric, specific heat, differential scanning calorimetry (DSC), and high-temperature powder synchrotron X-ray diffraction (HT-SXRD) measurements. It was found that samples with 0.5 ≤ x ≤ 1 crystallize in space group P6(3)/mmc with a ~ 3.32 Å and c ~ 11.9 Å, and samples with 0.0 ≤ x ≤ 0.4 crystallize in space group P6(3)cm with a ~ 5.8 Å and c ~ 11.6 Å at room temperature. HT-SXRD data revealed the existence of a P6(3)cm-to-P6(3)/mmc phase transition at about 480 K in InMn(0.6)Ga(0.4)O(3) and at 950 K in InMn(0.7)Ga(0.3)O(3). However, no dielectric, phonon, second-harmonic-generation, or DSC anomalies were found to be associated with these phase transitions. The phase transition should be improper ferroelectric from the symmetry point of view, but the above-mentioned experimental facts, together with the absence of ferroelectric hysteresis loops, revealed no evidence for ferroelectricity in the low-temperature P6(3)cm structure. We suggest that InMn(1-x)Ga(x)O(3) corresponds to a nonferroelectric phase of hexagonal RMnO(3) with P6(3)cm symmetry. The antiferromagnetic phase-transition temperature decreases from 118 K for x = 0 to 105 K for x = 0.1 and 73 K for x = 0.2, and no long-range magnetic ordering could be found for x ≥ 0.3. Specific heat anomalies associated with short-range magnetic ordering were observed for 0.0 ≤ x ≤ 0.5. InMn(1-x)Ga(x)O(3) with small Mn contents (0.8 ≤ x ≤ 0.98) has a bright-blue color.

Polar Phonon Behaviour in Polycrystalline Bi-Doped Strontium Titanate Thin Films.

Strontium titanate-based materials with ferroelectric or relaxor-like properties have drawn vast attention as polar dielectrics for electronics and telecommunications. Here, we study the lattice dynamics in sol-gel-derived Sr1-1.5xBixTiO3 thin films with x = 0.0053 and 0.167, deposited on Al2O3 substrates, using a variable-temperature far-infrared spectroscopy in a transmittance mode. Bi doping, known to induce a low-frequency dielectric relaxation in SrTiO3 (ST) ceramics and films, due to off-centre dopant ion displacements generating electric dipoles, is shown to affect the polar phonon behaviour of thin films. We show that in weakly Bi-doped films, the low-frequency polar TO1 mode softens on cooling but less than in undoped ST. In heavily Bi-doped ST films, this mode displays no significant frequency variation with temperature from 300 to 10 K. The polar phonon behaviour of polycrystalline Bi-doped ST thin films is comparable with that of Bi-doped ST ceramics, which exhibit dielectric relaxations and harden soft-mode behaviour instead of the ferroelectric phase transition.

Proton dynamics in superprotonic Rb3H(SeO4)2 crystal by broadband dielectric spectroscopy.

Broadband dielectric and AC conductivity spectra (1 Hz to 1 THz) of the superprotonic single crystal Rb3H(SeO4)2 (RHSe) along the c axis were studied in a wide temperature range 10 K < T < 475 K that covers the ferroelastic (T < 453 K) and superprotonic (T > 453 K) phases. A contribution of the interfacial electrode polarization layers was separated from the bulk electrical properties and the bulk DC conductivity was evaluated above room temperature. The phase transition to the superprotonic phase was shown to be connected with the steep but almost continuous increase in bulk DC conductivity, and with giant permittivity effects due to the enhanced bulk proton hopping and interfacial electrode polarization layers. The AC conductivity scaling analysis confirms validity of the first universality above room temperature. At low temperatures, although the conductivity was low, the frequency dependence of dielectric loss indicates no clear evidence of the nearly constant loss effect, so-called second universality. The bulk (intrinsic) dielectric properties, AC and DC conductivity of the RHSe crystal at frequencies up to 1 GHz are shown to be caused by the thermally activated proton hopping. The increase of the AC conductivity above 100 GHz could be assigned to the low-frequency wing of proton vibrational modes.

Broadband dielectric spectroscopy of La0.65Sr0.35MnO3@TiO2 core-shell nanocomposites.

Core-shell composites of ferromagnetic conducting nanoparticles La0.65Sr0.35MnO3 (LSMO) embedded in an insulating matrix of TiO2 (LSMO@TiO2) have been processed, structurally and magnetically characterized, and their DC magnetoresistivity and complex dielectric response measured and fitted from Hz up to the infrared (IR) range (1014 Hz). XRD indicates that the TiO2 shells are amorphous. Modelling of the IR spectra using standard models based on the effective medium approximation has it confirmed and has characterized the effective phonon modes of the LSMO nanoceramics and LSMO@TiO2 composite. Modelling of the lower-frequency spectra has shown that TiO2 shell thicknesses are rather non-uniform down to thin nm values, which leads to giant low-frequency permittivity values and non-negligible free-carrier tunnelling among the LSMO cores. Two main dielectric dispersion regions were observed and shown to be due to the inhomogeneous conductivity-the one occuring in the 1011-1012 Hz range relates to nonmagnetic less-conducting dead layers on the surface of LSMO nanocrystallites and the broad second one below the 1010 Hz range is due to the non-uniform thicknesses of the dielectric TiO2 shells. In the IR range, effective phonon modes of the LSMO nanoceramics and LSMO@TiO2 composite were characterized from the reflectivity spectra.