Full set of piezo-optic and elasto-optic coefficients of Ca3TaGa3Si2O14 crystals at room temperature.

The photoelasticity of the Ca3TaGa3Si2O14 (CTGS) crystal was studied by an interferometric method based on a single-pass Mach-Zehnder interferometer. The maximum number of sample orientations for the piezo-optic experiments was applied to prove accuracy in the determination of the piezo-optic coefficients. Based on the matrices of the piezo-optic coefficients and the elastic stiffness coefficients, all the coefficients pik of the elastic-optic matrix are calculated. For the highest pik coefficient, the acousto-optic efficiency is evaluated. The results obtained for CTGS are compared with the corresponding results for La3Ga5SiO14 (langasite) crystals. The highest acousto-optic figure of merit of CTGS M2=1.66⋅10-15s3/kg is two and three times higher, compared with langasite and strontium borate, respectively, which are often used for acousto-optic modulation of light in the ultraviolet spectral range.

Determination of the Dielectric Properties of Storage Materials for Exhaust Gas Aftertreatment Using the Microwave Cavity Perturbation Method.

Recently, a laboratory setup for microwave-based characterization of powder samples at elevated temperatures and different gas atmospheres was presented. The setup is particularly interesting for operando investigations on typical materials for exhaust gas aftertreatment. By using the microwave cavity perturbation method, where the powder is placed inside a cavity resonator, the change of the resonant properties provides information about changes in the dielectric properties of the sample. However, determining the exact complex permittivity of the powder samples is not simple. Up to now, a simplified microwave cavity perturbation theory had been applied to estimate the bulk properties of the powders. In this study, an extended approach is presented which allows to determine the dielectric properties of the powder materials more correctly. It accounts for the electric field distribution in the resonator, the depolarization of the sample and the effect of the powder filling. The individual method combines findings from simulations and recognized analytical approaches and can be used for investigations on a wide range of materials and sample geometries. This work provides a more accurate evaluation of the dielectric powder properties and has the potential to enhance the understanding of the microwave behavior of storage materials for exhaust gas aftertreatment, especially with regard to the application of microwave-based catalyst state diagnosis.

Compressional-Wave Effects in the Operation of a Quartz Crystal Microbalance in Liquids:Dependence on Overtone Order.

The operation of the quartz crystal microbalance (QCM) in liquids is plagued by small flexural admixtures to the thickness-shear deformation. The resonator surface moves not only in the transverse direction, but also along the surface normal, thereby emitting compressional waves into the liquid. Using a simple analytical model and laser Doppler vibrometry, we show that the flexural admixtures are stronger on the fundamental mode than on the overtones. The normal amplitude of motion amounts to about 1% of the transverse motion on the fundamental mode. This ratio drops by a factor of two on the overtones. A similar dependence on overtone order is observed in experiments, where the resonator is immersed in a liquid and faces an opposite planar wall, the distance of which varies. Standing compressional waves occur at certain distances. The amplitudes of these are smaller on the overtones than on the fundamental mode. The findings can be rationalized with the tensor form of the small-load approximation.

Small electron polarons bound to interstitial tantalum defects in lithium tantalate.

The absorption features of optically generated, short-lived small bound electron polarons are inspected in congruent lithium tantalate, LiTaO3(LT), in order to address the question whether it is possible to localize electrons at interstitial TaV:VLidefect pairs by strong, short-range electron-phonon coupling. Solid-state photoabsorption spectroscopy under light exposure and density functional theory are used for an experimental and theoretical access to the spectral features of small bound polaron states and to calculate the binding energies of the small bound TaLi4+(antisite) and TaV4+:VLi(interstitial site) electron polarons. As a result, two energetically well separated (ΔE≈0.5 eV) absorption features with a distinct dependence on the probe light polarization and peaking at 1.6 eV and 2.1 eV are discovered. We contrast our results to the interpretation of a single small bound TaLi4+electron state with strong anisotropy of the lattice distortion and discuss the optical generation of interstitial TaV4+:VLismall polarons in the framework of optical gating of TaV4+:TaTa4+bipolarons. We can conclude that the appearance of carrier localization at TaV:VLimust be considered as additional intermediate state for the 3D hopping transport mechanisms at room temperature in addition to TaLi, as well, and, thus, impacts a variety of optical, photoelectrical and electrical applications of LT in nonlinear photonics. Furthermore, it is envisaged that LT represents a promising model system for the further examination of the small-polaron based photogalvanic effect in polar oxides with the unique feature of two, energetically well separated small polaron states.

Defect chemistry, redox kinetics, and chemical diffusion of lithium deficient lithium niobate.

High-temperature optical in situ spectroscopy was used to investigate the defect absorption, redox kinetics, and chemical diffusion of a lithium deficient (48.4 mol% Li(2)O) congruent melting lithium niobate single crystal (c-LN). Under reducing atmospheres of various oxygen activities, a(O(2)), UV-Vis-NIR spectra measured at 1000 °C are dominated by an absorption band due to free small polarons centered at about 0.93 eV. The polaron band intensity was found to follow a power law of the form a(O(2))(m) with m = -1/4. A chemical reduction model involving electrons localized on niobium ions on regular lattice sites can explain the observed defect absorption and its dependence on oxygen activity. The kinetics of reduction and oxidation processes upon oxygen activity jumps and the associated chemical diffusion coefficients are found in close agreement over a range from -0.70 to -14.70 in log a(O(2)), indicating a reversible redox process. Assuming coupled fluxes of lithium vacancies and free small polarons for the attainment of stoichiometry, the diffusion coefficients of lithium vacancies as well as of lithium ions in the lithium deficient c-LN have been determined at 1000 °C.

Linking the Electrical Conductivity and Non-Stoichiometry of Thin Film Ce1-xZrxO2-δ by a Resonant Nanobalance Approach.

Bulk ceria-zirconia solid solutions (Ce1-xZrxO2-δ, CZO) are highly suited for application as oxygen storage materials in automotive three-way catalytic converters (TWC) due to the high levels of achievable oxygen non-stoichiometry δ. In thin film CZO, the oxygen storage properties are expected to be further enhanced. The present study addresses this aspect. CZO thin films with 0 ≤ x ≤ 1 were investigated. A unique nano-thermogravimetric method for thin films that is based on the resonant nanobalance approach for high-temperature characterization of oxygen non-stoichiometry in CZO was implemented. The high-temperature electrical conductivity and the non-stoichiometry δ of CZO were measured under oxygen partial pressures pO2 in the range of 10-24-0.2 bar. Markedly enhanced reducibility and electronic conductivity of CeO2-ZrO2 as compared to CeO2-δ and ZrO2 were observed. A comparison of temperature- and pO2-dependences of the non-stoichiometry of thin films with literature data for bulk Ce1-xZrxO2-δ shows enhanced reducibility in the former. The maximum conductivity was found for Ce0.8Zr0.2O2-δ, whereas Ce0.5Zr0.5O2-δ showed the highest non-stoichiometry, yielding δ = 0.16 at 900 °C and pO2 of 10-14 bar. The defect interactions in Ce1-xZrxO2-δ are analyzed in the framework of defect models for ceria and zirconia.

Microwave Acoustic Attenuation in CTGS Single Crystals.

This article presents a study of special material properties of the single crystalline material Ca3TaGa3Si2O14 (CTGS = Catangasite). The comparatively highly ordered crystal structure and acceptable piezoelectric strength make it a candidate for microacoustic applications under extreme conditions. Obviously, low-loss dynamic behavior is typical for this crystal which consequently enables high-temperature use. As a particular challenge, the behavior at gigahertz frequencies is investigated here. For that, High overtone Bulk Acoustic wave Resonator (HBAR) type measurements in the range of 1-6 GHz are performed. The selection of five distinctive propagation directions for exclusively pure or quasi-longitudinal modes enables to derive the dynamic viscosities from the quality factors of HBAR results. The observed frequency dependences exhibit Akhiezer behavior as the predominant loss mechanism in the cases examined.

Single crystals of ferroelectric lithium niobate-tantalate LiNb1-xTaxO3 solid solutions for high-temperature sensor and actuator applications.

Ferroelectric LiNb1-xTaxO3 solid solutions with various Nb/Ta ratio were grown from the melt by the Czochralski method. The exact composition of the grown crystals was determined by inductively coupled plasma atomic mass spectrometry. The dependence of the crystal composition on the composition of the initial melt was obtained and explained by a wide separation between the phase boundaries of the liquid and solid phases on the LiNbO3-LiTaO3 phase diagram. Using high-resolution X-ray diffraction, the parameters a and c of a crystal unit cell were determined (LiNb0.88Ta0.12O3: a = 5.1574 Šand c = 13.8498 Å). Further, the Curie temperature TC of the crystals was measured using the differential scanning calorimetry technique. TC was found to depend on the composition of the crystals that allowed conditions for the monodomainization of the grown crystals to be defined (LiNb0.88Ta0.12O3: TC = 1102°C; LiNb0.33Ta0.67O3: TC = 794°C). Finally, the velocity of surface acoustic waves was determined by scanning electron microscopy and X-ray diffraction techniques (YZ-cut of a LiNb0.88Ta0.12O3 crystal: V = 3440 m s-1).

Transport and Electromechanical Properties of Ca3TaGa3Si2O14 Piezoelectric Crystals at Extreme Temperatures.

Transport mechanisms in structurally ordered piezoelectric Ca3TaGa3Si2O14 (CTGS) single crystals are studied in the temperature range of 1000-1300 °C by application of the isotope 18O as a tracer and subsequent analysis of diffusion profiles of this isotope using secondary ion mass spectrometry (SIMS). Determined oxygen self-diffusion coefficients enable calculation of oxygen ion contribution to the total conductivity, which is shown to be small. Since very low contributions of the cations have to be expected, the total conductivity must be dominated by electron transport. Ion and electron conductivities are governed by different mechanisms with activation energies (1.9±0.1) eV and (1.2±0.07) eV, respectively. Further, the electromechanical losses are studied as a function of temperature by means of impedance spectroscopy on samples with electrodes and a contactless tone-burst excitation technique. At temperatures above 650 °C the conductivity-related losses are dominant. Finally, the operation of CTGS resonators is demonstrated at cryogenic temperatures and materials piezoelectric strain constants are determined from 4.2 K to room temperature.

Diffusion-related implications for langasite resonator operation.

Oxygen and gallium diffusivities in langasite were experimentally determined by analysis of diffusion profiles of 18O and 71Ga tracers by SIMS analysis as functions of temperature and doping. Strontium-enhanced diffusivities and activation energies of approximately 1.2+/-0.2 eV confirm the predominant role of oxygen vacancies in controlling the electrical conductivity of langasite at elevated temperature and oxygen partial pressure. The potential impact of high levels of porosity and the use of an oxygen primary ion beam on the accuracy of some of the data is discussed. The gallium diffusivity, with activation energy of 3.13 eV, was found to be more than two orders of magnitude lower than that of oxygen. Surface exchange measurements enabled estimation of gallium loss at elevated temperatures and oxygen partial pressure; the level is not believed to be of major concern for resonator performance.

High-temperature electroacoustic characterization of Y-cut and singly-rotated Ca3TaGa3Si2O14 resonators.

Synthetic piezoelectric crystals in the P321 crystal class have been a focus of substantial research that is largely driven by applications in high-temperature resonant BAW and SAW sensing. Fully ordered crystals in this class, such as Ca3TaGa3Si2O14 (CTGS), have been suggested as offering the potential of electroacoustic performance that is superior to more extensively studied langasite (LGS) and langatate (LGT), which are partially disordered. In this study, the resonant frequencies, acoustic damping, and electrical conductivity of CTGS bulk acoustic resonators with Y-cut and (YXl)-30° crystal orientations and fundamental frequencies near 5 MHz are investigated at temperatures between ambient and 1100°C. (YXl)-30° resonators are found to have turnover temperatures near 200°C for the third and fifth overtones, in contrast to a monotonic decrease in resonant frequencies of Y-cut crystals with increasing temperature. The maximum temperature derivative of fractional changes in fifth-overtone frequency of (YXl)-30° CTGS is 40 × 10-6K-1 (near 1100°C), and this value is not greatly different from the temperature derivative of Y-cut CTGS frequencies over a broader range of temperatures. At ambient temperatures, the acoustic loss Q-1 of CTGS with both crystal orientations is found to be greater than the lowest values previously reported for LGS and LGT. The electrical conductivity of the CTGS specimens between 500°C and 1100°C is substantially lower than that previously reported for LGS. Corresponding to this lower conductivity, the piezoelectric/conductive contribution to Q-1 at elevated temperatures is reduced. Additional anelastic relaxation peaks observed between 100°C and 700°C are similar to those previously reported for LGS and LGT.