Influence of Li-stoichiometry on electrical and acoustic properties and temperature stability of Li(Nb,Ta)O3_{3} solid solutions up to 900 {\deg}C

The current work is focused on the impact of the lithium stoichiometry on electrical conductivity, acoustic properties and high-temperature stability of single crystalline Li(Nb,Ta)O$_{3}$ at high temperatures. The crystals grown from Li-deficient melts were treated by the vapor transport equilibration (VTE) method, achieving near stoichiometric Li-content. It is shown, that the VTE-treated specimens generally exhibit lower conductivity at temperatures below 800 {\deg}C, which is attributed to the reduced number of Li-vacancies in near stoichiometric Li(Nb,Ta)O$_{3}$, provided that the Li-ion migration dominates the conductivity in this temperature range. Further, it is shown, that above 600-650 {\deg}C different mechanism increasingly contributes to the conductivity, which is consequently attributed to the electronic conduction. Further, it is shown that losses in LNT strongly increase above about 500 {\deg}C, which is interpreted to originate from conductivity-related relaxation mechanism. Finally, the thermal stability of Li(Nb,Ta)O$_{3}$ is evaluated by the measurement of the conductivity and resonance frequency as a function of time. It is found that during annealing at 700 {\deg}C for 350 hours, the resonance frequency of LiNbO$_{3}$ remains in a {\textpm} 100 ppm range of the initial value of 3.5 MHz.Comment: Submitted to Physica Status Solidi A: Applications and Materials Science on 21st December 202

Investigations of LiNb1−xTaxO3 nanopowders obtained with mechanochemical method

Nanocrystalline compounds LiNb1−xTaxO3 of various compositions (x = 0, 0.25, 0.5, 0.75, 1) were synthesized by high-energy ball milling of the initial materials (Li2CO3, Nb2O5, Ta2O5) and subsequent high-temperature annealing of the resulting powders. Data on the phase composition of the nanopowders were obtained by X-ray diffraction methods, and the dependence of the structural parameters of LiNb1−xTaxO3 compounds on the value of x was established. As a result of the experiments, the optimal parameters of the milling and annealing runs were determined, which made it possible to obtain single-phase compounds. The Raman scattering spectra of LiNb1−xTaxO3 compounds (x = 0, 0.25, 0.5, 0.75, 1) have been investigated. Preliminary experiments have been carried out to study the temperature dependences of their electrical conductivit

Mechanosynthesis, Structure and Photoluminescent Properties of the Pr³⁺ Doped LiNbO₃, LiNbO₃:Mg, LiTaO₃ Nanopowders

In the current work, nanocrystalline powders with different compositions, namely Li0.98Pr0.02NbO3, Li0.93Pr0.02Mg0.05NbO3 and Li0.98Pr0.02TaO3 were synthesized for the first time using the method of high-energy ball milling of the starting materials (Li2CO3, Nb2O5, Ta2O5, MgO, Pr6O11), followed by high-temperature annealing. XRD data analysis confirmed the absence of parasitic phases in the obtained nanocrystalline compounds. The estimated particle sizes ranged from 20 to 80 nm. From the obtained nanopowders, ceramic samples were prepared using specially developed equipment, which allowed for pressing at elevated temperatures with a simultaneous application of a constant electric field. The obtained photoluminescence spectra exhibit characteristic features of Pr3+ ions in the crystal structure of LiNbO3 and LiTaO3 and are most efficiently excited by UV light. Samples pressed with an electric field application show higher intensity of photoluminescence. Investigations of the temperature dependence of electrical conductivity of the Li0.98Pr0.02NbO3 sample, pressed with the application of an electric field, indicate that the conductivity mechanism is similar to that of LiNbO3 single crystals and, at high temperatures, is attributed to the lithium conduction mechanism

Ferroelectric to paraelectric structural transition in LiTaO3_3 and LiNbO3_3

The ferroelectric to paraelectric phase transition in LiTaO$_3$ and in pure as well as Mg doped LiNbO$_3$ is investigated theoretically by atomistic calculations in the framework of the density functional theory, as well as experimentally by calorimetry and electrical conductivity measurements. First principles models within the stochastic self-consistent harmonic approximation (SSCHA) allow to consider anharmonic effects and thus to obtain a realistic estimate of the Curie temperature $T_C$ of both ferroelectrics. \textit{Ab initio} molecular dynamics (AIMD) calculations performed on large supercells confirm the Curie temperatures estimated with the SSCHA approach. Moreover, they also suggest that the structural phase transition is a continuous process beginning at temperatures well below $T_C$. According to AIMD, significant ionic displacements occurr already at temperatures of about 100\,K and 300\,K below $T_C$ in LiTaO$_3$ and LiNbO$_3$, respectively. To asses whether and how far the ionic displacements affect the materials properties, the AIMD results are compared with measurements of the electrical conductivity and of the heat capacity across the phase transition. Our first principles calculations moreover show that Mg ions, a frequently employed dopant, raise the Curie temperature in LiNbO$_3$