High-temperature electrical conductivity and electromechanical properties of stoichiometric lithium niobate

High temperature properties such as electrical conductivity (σ) and resonance behaviour of stoichiometric lithium niobate (LiNbO3) are determined in the temperature range from 20 to 950 °C. The activation energy of the conductivity is found to be 0.9 and 1.7 eV in the temperature range from 500 to 750 °C and from 800 to 950 °C, respectively. During thermal treatments in ambient air up to 950 °C and back, the conductivity remains unchanged at a given temperature, i.e., the crystal is stable under these conditions. The oxygen partial pressure (pO2) dependence of the conductivity shows two distinct ranges. At 750 °C, the property remains unchanged down to 10−15 bar. Below 10−15 bar, the conductivity increases according to σ ~ (pO2)−1/5. Z-cut LiNbO3 plates can be excited to thickness mode vibrations up to at least 900 °C. At this temperature, the quality factor Q is found to be between 30 and 100. As for changes of the conductivity, a decrease of the resonance frequency is observed below 10−15 bar indicating a correlation of both properties. In order to evaluate the lithium evaporation, the crystals are tempered at 900 °C in ambient air for 24 h. A depth profile of the constituents does not indicate lithium loss within the accuracy of the secondary ion mass spectroscopy. The preliminary results underline the potential of stoichiometric LiNbO3 for high-temperature applications and justify its closer investigation

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. Copyright © Materials Research Society 2019

Correlation of electrical properties and acoustic loss in single crystalline lithium niobate-tantalate solid solutions at elevated temperatures

Electrical conductivity and acoustic loss Q−1 of single crystalline Li(Nb,Ta)O3 solid solutions (LNT) are studied as a function of temperature by means of impedance spectroscopy and resonant piezoelectric spectroscopy, respectively. For this purpose, bulk acoustic wave resonators with two different Nb/Ta ratios are investigated. The obtained results are compared to those previously reported for congruent LiNbO3. The temperature dependent electrical conductivity of LNT and LiNbO3 show similar behavior in air at high temperatures from 400 to 700 °C. Therefore, it is concluded that the dominant transport mechanism in LNT is the same as in LN, which is the Li transport via Li vacancies. Further, it is shown that losses in LNT strongly increase above about 500 °C, which is interpreted to originate from conductivity-related relaxation mechanism. Finally, it is shown that LNT bulk acoustic resonators exhibit significantly lower loss, comparing to that of LiNbO3

Comparison of the electrical conductivity of bulk and film Ce1–xZrxO2–d in oxygen-depleted atmospheres at high temperatures

Featuring high levels of achievable oxygen non-stoichiometry d, Ce1-xZrxO2-d solid solutions (CZO) are crucial for application as oxygen storage materials in, for example, automotive three-way catalytic converters (TWC). The use of CZO in form of films combined with simple manufacturing methods is beneficial in view of device miniaturization and reducing of TWC manufacturing costs. In this study, a comparative microstructural and electrochemical characterization of film and conventional bulk CZO is performed using X-ray diffractometry, scanning electron microscopy, and impedance spectroscopy. The films were composed of grains with dimensions of 100 nm or less, and the bulk samples had about 1 lm large grains. The electrical behavior of nanostructured films and coarse-grained bulk CZO (x [ 0) was qualitatively similar at high temperatures and under reducing atmospheres. This is explained by dominating effect of Zr addition, which masks microstructural effects on electrical conductivity, enhances the reducibility, and favors strongly electronic conductivity of CZO at temperatures even 200 K lower than those for pure ceria. The nanostructured CeO 2 films had much higher electrical conductivity with different trends in dependence on temperature and reducing atmospheres than their bulk counterparts. For the latter, the conductivity was dominantly electronic, and microstructural effects were significant at T \ 700 °C. Nanostructural peculiarities of CeO 2 films are assumed to induce their more pronounced ionic conduction at medium oxygen partial pressures and relatively low temperatures. The defect interactions in bulk and film CZO under reducing conditions are discussed in the framework of conventional defect models for ceria

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