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We proposed and investigated a refinement of technology for obtaining Mg-doped LiNbO3 (LN) crystals by co-doping it with B. LN:Mg (5.0 mol%) is now the most widely used material based on bulk lithium niobate. It is suitable for light modulation and transformation. We found that non-metal boron decreases threshold concentrations of the target dopant in many ways. In addition, we earlier determined that the method of boron introduction into the LN charge strongly affects the LN:B crystal structure. So we investigated the point structural defects of two series of LN:Mg:B crystals obtained by different doping methods, in which the stage of dopant introduction was different. We investigated the features of boron cation localization in LN:Mg:B single crystals. We conducted the study using XRD (X-ray diffraction) analysis. We have confirmed that the homogeneous doping method introduces an additional defect (MgV) into the structure of LN:Mg:B single crystals. Vacancies in niobium positions (VNb) are formed as a compensator for the excess positive charge of point structural defects. According to model calculations, boron is localized in most cases in the tetrahedron face common with the vacant niobium octahedron from the first layer (VNbIO6). The energy of the Coulomb interaction is minimal in the LN:Mg:B crystal (2.57 mol% MgO and 0.42 × 10−4 wt% B in the crystal); it was obtained using the solid-phase doping technology. The solid-phase doping technology is better suited for obtaining boron-containing crystals with properties characteristic of double-doped crystals (LN:Mg:B). [ABSTRACT FROM AUTHOR]

LiNbO3:Mg crystals ([Mg] = 6.0 and 5.54 mol%) grown by the Czochralski have been studied. The dopant concentration in both samples exceeds the threshold. The methods for crystals doping were different: directly and homogeneously. The main interest is defect structure of LiNbO3:Mg crystals. IR absorption spectroscopy, nuclear magnetic resonance (NMR, 93Nb and 7Li) were used for the study. Structure of LiNbO3:Mg is almost free of NbLi antisite defects, but defect complexes (2MgLi – 2VLi) arise. The work has shown both the effective applicability and good agreement of the results concerning the defect structure of doped LiNbO3 crystals using IR absorption spectroscopy, NMR (93Nb and 7Li). [ABSTRACT FROM AUTHOR]

The correlation between photoluminescence in the near‐IR region and point defect centers in the LiNbO3 crystals co‐doped with Zn and Mg both by homogeneous and direct methods has been studied. X‐ray diffraction (XRD) analysis shows that the LiNbO3:Zn:Mg (4.68:0.9 mol%) crystal obtained by homogeneous doping has the least number of intrinsic defects compared to the others. It has been established that ZnLi defects stimulate photoluminescence (PL) in the near‐IR region of the luminescence spectrum in the LiNbO3:Zn:Mg crystals obtained by homogeneous doping. The LiNbO3:Zn:Mg (4.68:0.90 mol%) crystal has the maximum PL intensity and the LiNbO3:Zn:Mg (3.83:0.97 mol%) crystal has the minimum. Both crystals are doped homogeneously. Such defects as niobium vacancies (VNb) and niobium in the empty octahedron (Nboct) are suggested as luminescence quenchers in the co‐doped crystals. [ABSTRACT FROM AUTHOR]

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 (NbLi, NbV), we have used only those that Rietveld found for these exact LN:B crystals, and the vacancy in the niobium octahedron (VNb) 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. [ABSTRACT FROM AUTHOR]

A nonlinear optical double-doped single-crystal LiNbO3:Gd:Mg (Gd concentration is 0.003, Mg—0.65 wt % in the crystal) has been researched by several optical methods: laser conoscopy, photoinduced light scattering (PILS), optical spectroscopy, and Raman scattering. The crystal has been shown to have no photorefraction effect and a high optical uniformity. Fine features of the crystal structure have been studied via Raman spectra. Spectra have been registered in the first and second orders, they have been excited by visible (532 nm) and near-IR (785 nm) lasers. Registered Raman spectra have the fundamental vibrations of the crystal lattice of the A1(TO,LO)- and E(TO,LO)-type symmetry located in the range of 150–900 cm−1. A number of low-intensity Raman bands in the 900–2000 cm−1 region have been determined to correspond to the second-order Raman spectrum. These bands are polarized and appear only in certain polarization-scattering geometries. They appear in the spectrum excited by visible radiation, but their number and intensity are much lower than those excited by near-IR lasers. Oxygen-octahedral MeO6 clusters in our case can contain Li, Nb, Gd, or Mg in the Me site. The clusters in the LiNbO3:Gd:Mg crystal structure are slightly distorted compared with similar clusters in the nominally pure LiNbO3 crystal. It has been established that the value R = [Li]/[Nb] in the studied crystal is ≈ 1. Such a ratio usually characterizes a nominally pure stoichiometric crystal. [ABSTRACT FROM AUTHOR]

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 (KD) 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%). [ABSTRACT FROM AUTHOR]

Raman spectra have been excited by the radiation of lasers generatingon in the visible (532 nm) and near-IR (785 nm) ranges in a LiTaO3:Cr3+ (0.005 wt%) crystal. The obtained spectra were compared. Recorded Raman spectra contained bands in the range of <900 cm−1 (first order) up to 2000 cm−1 (second order). The Raman spectra of the second order, excited by near-IR laser radiation, were located against the background of a wide, luminescent halo. The frequency of a single low-intensity band exceeded the exact frequency of an overtone corresponding to the completely symmetric fundamental 4A1(z)LO mode. The attribution of other second-order bands with higher frequencies remains unclear. [ABSTRACT FROM AUTHOR]

The paper studies LiNbO3 (LN) crystals with a near-stoichiometric composition (NSLN). The study establishes the possibility of different physical methods to reveal NSLN crystals' exact composition. The main goal was to establish how precisely these methods can reveal a NSLN composition, including a defective structure. This structure determines properties that are important for the application of the crystals. Two NSLN crystals with a different Li/Nb ratio have been studied by IR and NMR spectroscopy. NSLN crystals have been grown from a congruent melt with different K2O flux contents (5.0 and 5.5 wt%). The data on NSLN have been compared with the data on congruent (CLN) crystals. CLN are the most widely used LN crystals. The study has established that analysis of the IR spectra can determine the Li/Nb ratio within [Li2O] = 48.6 – 50.0 mol% range, while the 93Nb NMR spectra has a wider range of sensibility. LN crystals' stoichiometry or the Li/Nb ratio determine the concentration of antisite defects NbLi. Niobium substitutes lithium in its octahedron. Such defects appear up to [Li2O] = 49.9 mol%. Thus, the study shows that IR and NMR spectroscopy are sensitive methods that can complement each other when determining the precise LN composition (Li/Nb ratio) and the presence of intrinsic defects in the crystals. [ABSTRACT FROM AUTHOR]

Ceramic samples of polycomponent solid solutions (SSs) Na0.90K0.05Cd0.05NbO3 (Cd-modified KNN) and [(Na0.90K0.05Cd0.05)0.95REE0.05]NbO3, where REE = La, Pr, Tb, Dy, Ho, were obtained by the uniaxial hot pressing (UHP) method. The crystal lattice structures, morphological features of the microstructure, and dielectric and thermophysical properties of these ceramics have been investigated. For the first time, their strength characteristics (Young's modulus) and the critical stress intensity factor of the mode I Kic have been estimated. Photoluminescent properties have been compared in SSs [(Na0.90K0.05Cd0.05)0.95REE0.05]NbO3 in the visible wavelength range. [ABSTRACT FROM AUTHOR]

A compositionally homogeneous nonlinear optical single crystal of double-doped LiNbO3:Gd3+(0.003):Mg2+(0.65 wt.%) was obtained. Fine features of the LiNbO3:Gd3+(0.003):Mg2+(0.65 wt.%) crystal structure were studied from the Raman spectra of the first and second orders upon excitation by laser lines in the visible (532 nm) and near-IR (785 nm) regions. When the Raman spectrum was excited by a 785 nm laser line in the frequency range of 1000–2000 cm−1 for the first time, a number of low-intensity lines in the range of 900–2000 cm−1, corresponding to the second-order Raman spectrum, were discovered. The same lines also appear in the spectrum upon excitation by a laser line with a wavelength of 532 nm, but their intensities are significantly (by an order of magnitude or more) lower. It is shown that in the structure of the double-doped LiNbO3:Gd3+(0.003):Mg2+(0.65 wt.%), the crystal oxygen-octahedral clusters MeO6 (Me–Li, Nb, Gd, Mg) are slightly distorted, and in addition, the value R = [Li]/[Nb] ≈ 1 is close to that for a nominally pure stoichiometric crystal. [ABSTRACT FROM AUTHOR]

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 NbLi 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. [ABSTRACT FROM AUTHOR]

We have established that luminescence in lithium niobate crystals both congruent and near-stoichiometric (R ≈ 1) is due to point defects in the cationic sublattice and intraconfigurational transitions in the oxygen-octahedral NbO6 clusters. We have also determined that the main contribution to the luminescence in the visible and near IR regions is made by luminescence centers with the participation of NbLi defects: the NbLi-NbNb bipolaron pair and the NbLi-O defect in a congruent crystal. The minimum intensity of bipolaron luminescence has been observed in stoichiometric crystals obtained using different technologies. Weak luminescence of the NbLi-NbNb bipolaron pair indicates a small number of NbLi defects in the crystal structure. The number of NbLi defects in the crystal structure indicates a deviation of the crystal composition from stoichiometry. [ABSTRACT FROM AUTHOR]

The Raman spectra of a lithium tantalate crystal doubly doped with chromium and neodymium LiTaO3:Cr(0.2):Nd(0.45 wt%) have been studied in this paper. Raman spectra of the first and second orders have been found to be located against the background of a luminescent halo with a maximum at ≈1250 cm−1. Several Raman bands have been detected in the frequency range of 900–2000 cm−1. Their frequencies were 940, 1034, 1113, 1171, 1250, 1343, 1428, 1491, 1582, 1735, 1838, and 1925 cm−1. These bands correspond to overtone processes. We have determined that the frequencies of 1838 and 1925 cm−1 bands are significantly higher than the exact value of the overtone frequency corresponding to the fundamental mode 4A1(z)LO (864 cm−1). [ABSTRACT FROM AUTHOR]