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Investigation of structural perfection of lithium niobate single crystals of different composition and genesis by IR spectroscopy in the area of valent vibrations of hydrogen bonds
Russian version
DOI: 10.21883/EOS.2022.01.53001.12-21
Bobreva L. A. 1, Sidorov N. V. 1, Teplyakova N. A. 1, Palatnikov M. N. 1, Klimin S.A.2, Novikova N.N.2
1Tananaev Institute of Chemistry – Subdivision of the Federal Research Centre «Kola Science Centre of the Russian Academy of Sciences», Apatity, Russia
2Institute of Spectroscopy, Russian Academy of Sciences, Troitsk, Moscow, Russia
Email: l.bobreva@ksc.ru, n.sidorov@ksc.ru, n.tepliakova@ksc.ru, m.palatnikov@ksc.ru
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We have analyzed complex defects due to the presence of hydrogen bonds in the crystal structure in nominally pure lithium niobate crystals with different Li/Nb ratio, in crystals alloyed with magnesium and zinc in a wide concentration range (LiNbO3 : Mg (0.19-5.91 mol.% MgO) and LiNbO3 : Zn (0.04-6.5 mol.% ZnO)) and in the double-alloyed crystals (LiNbO3 : Y(0.24) : Mg(0.63 wt.%) and LiNbO3 : Gd( 0.25) : Mg(0.75 wt.%)), obtained by technology of direct melt alloying, and also in the double-alloyed crystal (LiNbO3 : Mg(5.05 mol.% MgO) : Fe(0.009 mol.% Fe2O3)) grown from a charge synthesized using the technology of homogeneous alloying with magnesium and iron Nb2O5. We revealed the influence of doping impurities on the concentration of OH-groups, the type and localization of complex defects in the crystal structure. The change in the number of hydrogen atom positions in the structure of the LiNbO3 crystal allow us to judge with sufficient accuracy whether the crystal composition is stoichiometric or congruent. For doped crystals of different compositions data were obtained testifying to changes in the character of complexation of OH-groups with point defects of the cationic sublattice with formation of defects: MeLi-OH-, MeLi-MeNb-OH. A change in the mechanism of entry of the dopant cation into the structure dramatically affects the change in the properties of the crystal.The difference in the frequencies (and, correspondingly, in the values of the quasi-elastic constants of the O-H bonds) in the spectrum of a congruent crystal and doped crystals can also be contributed by differences in the electronegativity and ionic radii of the principal and doping cations. Keywords: lithium niobate crystal, doping, complex and point structural defects, IR absorption spectroscopy, valence vibrations of OH-groups
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