Raman spectra of lithium niobate single crystals strongly doped by zinc and magnesium, it has been established, contain low-intense bands with frequencies 209, 230, 298, 694, and 880 cm⁻¹. Ab ignition calculations fail to attribute these bands to fundamental vibrations of A₂ symmetry type unambiguously. Such vibrations are prohibited by the selection rules in the space group C_3V⁶ (R3c). Ab initio calculations also proved that low-intense “extra” bands with frequencies 104 and 119 cm⁻¹ definitely do not correspond to vibrations of A₂ symmetry type. We have paid special attention to these extra bands that appear in LiNbO₃ single crystals Raman spectra despite the fact that they are prohibited by the selection rules. In order to do so, we have studied a number of lithium niobate single crystals, both nominally pure and doped, by Raman spectroscopy. We have assumed that some “extra” bands correspond to two-particle states of acoustic phonons with a total wave vector equal to zero. We have also detected a Zn concentration area (0.05–0.94 mol.% ZnO in a crystal) where doped crystal structure is more ordered: The order of alternation of the main, doping cations, and vacancies along the polar axis is increased, and oxygen octahedra are less distorted.

Two series of LiNbO₃:Mg:B crystals have been grown and studied. Two doping methods—have been used. The crystals—have been co-doped with Mg and a non-metallic dopant, B. The physicochemical features of the growth—have been considered for LiNbO₃:Mg:B crystals obtained from a boron-doped melt. The charge—has been prepared using different technologies: homogeneous (HG) and solid-phase (SP) doping. The same two methods have been used to grow single-doped LiNbO₃:Mg crystals. A control near-stoichiometric (NSLN) crystal—has been grown via the HTTSSG (high-temperature top-seeded solution growth) method from a congruent melt (Li/Nb ≈ 0.946) with 5.5 wt% K₂O. The characteristics of the LiNbO₃:Mg:B crystals—have been compared with those of the LiNbO₃:Mg and NSLN crystals. Physicochemical and structural reasons have been established for the differences in the distribution coefficients of magnesium (K_D) during the growth of the HG- and SP-doped LiNbO₃:B:Mg and LiNbO₃:Mg crystals. The optical characteristics of the LiNbO₃:B:Mg crystals—have been studied via optical spectroscopy, laser conoscopy and photoinduced light scattering (PILS). The influence of boron on the microstructure, compositional and optical uniformities and optical damage resistance of the LiNbO₃:Mg:B crystals—has been estimated. Optimal technological approaches to growing optically uniform LiNbO₃:B:Mg crystals have been determined. LiNbO₃:Mg:B crystals have been shown to have a significant advantage over the commercially used LiNbO₃:Mg crystals since large LiNbO₃:Mg:B crystals can be grown without stripes. Such stripes usually appear perpendicular to the growth axis. In addition, the photorefractive effect is suppressed in LiNbO₃:Mg:B crystals at lower magnesium concentrations ([Mg] ≈ 2.5 mol%) than in LiNbO₃:Mg ([Mg] ≈ 5.5 mol%).

Physical and chemical properties have been studied in lithium niobate (LiNbO₃, LN) crystals grown by Czochralski from a boron doped melt. Optical uniformity and optical damage resistance of LiNbO₃:B crystals have been compared with control crystals of nominally pure congruent (CLN) and near-stoichiometric (NSLN K₂O) composition. LiNbO₃:B crystals structure has been studied. Studied LiNbO₃:B crystals have been grown from differently synthesized charges. The charges have been synthesized from a mixture Nb₂O₅:B-Li₂CO₃ using homogeneously doped Nb₂O₅:B precursor (sample 1, (B) = 0.0034 wt% in the charge) and by a direct solid phase synthesis from Nb₂O₅-Li₂CO₃-H₃BO₃ mixture (sample 2, (B) = 0.0079 wt% in the charge). Only traces of boron (10⁻⁵–10⁻⁴ wt%) have been detected in the samples. We have established that concentration of anti-site defects Nb_Li is lower in both LiNbO₃:B than in CLN crystals. XRD analysis has confirmed that B³⁺ cations localize in faces of tetrahedral voids O₄ of LN structure. The voids act as buffers at the anion sublattice distortion. Sample 1 has been shown to have a structure closer to NSLN K₂O crystal than sample 2. We have also shown that the chemical purity of LN crystal increases compared to the melt purity because boron creates strong compounds with impurities in the melt system Li₂O-Nb₂O₅-B₂O₃. Metals impurities thus stay in the melt and do not transfer to the crystal.

We have established that relatively simple calculations of the Coulomb interaction in the lattice of doped lithium niobate (LN, LiNbO₃) can confirm the physical properties of real crystals. We have developed a method for the double adjustment of real XRD data for calculations of Coulomb interaction in a LN cluster. The study considers two crystals doped with boron (LN:B); LN:B(1) has been grown from a charge with 0.02 mol% B₂O₃, boron has been introduced by homogeneous doping, LN:B(2) has been grown from a charge with 0.547 mol% B₂O₃, and boron has been introduced by direct solid-state doping. XRD and Rietveld method data have been obtained for these crystals. The obtained data have been used to build a model of the LN cluster; the cluster in the calculations consists of six oxygen octahedra of the LN structure. The cluster configuration has been chosen in such a way that the structure contains two tetrahedral voids. We have studied 10 variants of filling a cluster with intrinsic cations (Li, Nb), defects, and vacancies. There are 10 of them because, in addition to the basic cations in their positions, defects are present in the structure. In terms of the defects used (Nb_Li, Nb_V), we have used only those that Rietveld found for these exact LN:B crystals, and the vacancy in the niobium octahedron (V_Nb) compensates for these defects, according to the models known for LN. The energy of the Coulomb interaction between the cluster structure of a real crystal and the boron cation localized in it in different positions has been calculated for each of the configurations. Calculations have demonstrated that B is more likely to be embedded near a defect than in a regular structure. This means that boron positively influences the local substructure of doped LN crystals, not only structures the melt during crystal growth. Calculations have shown that the type and location of structural defects affect the position of boron in the structure of a LN crystal. Calculations have also shown that LN:B(1) has a more stable structure, including optical damage resistance. The photoinduced light scattering (PILS) patterns and conoscopic patterns confirm this conclusion for the studied LN:B crystals. The information obtained in this study may be useful for interpreting the defective structure of LN crystals co-doped with boron and metals (Mg, Zn, etc.). This will supplement the knowledge available in the literature regarding models that describe the structure of complexly doped LN crystals.