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Growth, structure peculiarities, and dielectric properties of ferroelectric KDP/TiO2 single crystals

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Abstract

Potassium dihydrogen phosphate KH2PO4 (KDP) single crystals, both pure and with incorporated titanium dioxide TiO2 nanoparticles, are ferroelectric materials with dipole structure used in nonlinear optics, optoelectronics, and acoustooptics. To date, a comprehensive analysis of structural features and defect states in the KDP and KDP/TiO2 matrix is absent in literature data. Pure KH2PO4 (KDP) single crystals and KDP/TiO2 crystals with different TiO2 nanoparticles with anatase structure, synthesized by the sulfate and chloride methods, and with η-TiO2 structure, prepared by the sulfate method, grown by the temperature lowering method and cut from the pyramidal and prismatic growth sectors, have been investigated by the X-ray diffraction methods and by EDX spectroscopy. According to the energy-dispersive X-ray microanalysis, the sulfur content is higher in the sample with η-TiO2 and in the KDP/η-TiO2 crystal if compared with the samples with anatase and KDP/TiO2 (anatase). It was revealed that the sulfur content is higher in the prismatic growth sector if compared with the pyramidal one. Based on results of the X-ray single-crystal diffraction analysis, it is possible to assume the substitution of \( \text{PO}_{4}^{3 - } \) tetrahedra by \( \text{SO}_{4}^{2 - } \) ones in the KDP/TiO2 structures, which is greater in KDP/η-TiO2. The general composition of the KDP/η-TiO2 crystal from the prismatic growth sector with the highest titanium content can be written as \( (\text{K}_{0.950(1)} \square_{0.050} )\text{Ti}_{0.052\left( 2 \right)i} \left( {\text{H}_{2 - x}^{1 + } \square_{x} } \right)\left[ {\left( {\text{PO}_{4} } \right)_{y}^{3 - } \left( {\text{SO}_{4}^{2 - } } \right)_{1 - y} } \right] (\square \text{ - vacancies}). \) It was first found that the Ti4+ ions occupy the interstitial site (−0.048, 0.045, 0.550) in the KDP crystal matrix. Analysis of frequency-dependant dielectric characteristics revealed that the incorporation of TiO2 nanoparticles reduces the dielectric permittivity values of KDP/TiO2 samples compared with the pure KDP ones. It was found that the KDP/η-TiO2 sample has the smallest value of the dielectric permittivity.

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Acknowledgements

This work was carried out as a part of a state task of the Ministry of Education and Science of Russian Federation (No. 4.745.2014/K; 2014-2016). X-ray studies were fulfilled using a STOE Stadi Vari PILATUS 100 K single-crystal diffractometer purchased by MSU Development Program.

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Authors and Affiliations

  1. Department of Materials Science and Technology of Functional Materials and Structures, Lomonosov State University of Fine Chemical Technologies, Moscow, Russia, 119571

    Galina M. Kuz’micheva, Olesya I. Timaeva & Irina A. Kaurova

  2. Department of Chemistry, Lomonosov State University, Moscow, Russia, 119992

    Victor B. Rybakov

  3. State Scientific Institution “Institute for Single Crystals” of National Academy of Sciences, Kharkiv, 61178, Ukraine

    Anna V. Kosinova

  4. Shubnikov Institute of Crystallography of Russian Academy of Sciences, Moscow, Russia, 117333

    Vadim V. Grebenev

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  1. Galina M. Kuz’micheva
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  2. Olesya I. Timaeva
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Correspondence to Irina A. Kaurova.

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Kuz’micheva, G.M., Timaeva, O.I., Rybakov, V.B. et al. Growth, structure peculiarities, and dielectric properties of ferroelectric KDP/TiO2 single crystals. J Mater Sci 51, 3045–3055 (2016). https://doi.org/10.1007/s10853-015-9615-7

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