Electro‐optic,Piezoelectric and Dielectric Properties of Langasite (La3Ga5SiO14), Langanite (La3Ga5.5Nb0.5O14) and Langataite (La3Ga5.5Ta0.5O14)

Refractive indices were determined of single crystals of La₃Ga₅SiO₁₄ (langasite, LGS), La₃Ga_5.5Nb_0.5O₁₄ (langanite, LGN) and La₃Ga_5.5Ta_0.5O₁₄ (langataite, LGT) in the wavelength region between 0.36 μm and 2.33 μm. While phase‐matched optical second harmonic generation is not possible in LGS it occurs in the isotypic compounds LGN and LGT. Temperature‐dependent examination of the dielectric properties of LGS up to 600 °C showed anomalous behaviour. For all three substances the electro‐optic [r^σ_ijk] (“unclamped”) and the piezoelectric [d_ijk ] tensors were determined at room temperature. In addition, the temperature‐dependence of these properties was studied for LGS between –200 °C and +200 °C by a Jamin interferometer in combination with a modified Sénarmont compensator.     

Czochralski growth and characterization of Dy: La3Ga5.5Nb0.5O14 single crystals

Dysprosium (Dy) doped La₃Ga_5.5Nb_0.5O₁₄ single crystals were grown by the traditional Czochralski method along z‐axis. The structure of the crystal has been studied by X‐ray powder diffraction method, and the unit‐cell parameters are calculated to be a=8.22070 Å, c=5.12533 Å and V=299.965 ų. The segregation coefficient of Dy³⁺ in La₃Ga_5.5Nb_0.5O₁₄ crystal was measured by X‐ray fluorescence analysis. For 1 mol% doping level in the melt, the distribution coefficient of Dy³⁺ was determined to be 0.341 wt%. Specific heat, thermal expansion and transmission spectrum of Dy: La₃Ga_5.5Nb_0.5O₁₄ single crystals have been measured. The fluorescence spectra of Dy³⁺: La₃Ga_5.5Nb_0.5O₁₄ crystals were measured at room temperature, and there were four emission transitions occurring at 479, 576, 662 and 754 nm, respectively. The fluorescent lifetimes measurement results show 1.0% Dy: La₃Ga_5.5Nb_0.5O₁₄ possesses shorter fluorescence decay time (303.4 μs) than does 1.0%Dy:LGS (436.12 μs). (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Studies on the growth and defects of La3Ga5SiO14 (LGS) crystals

New and high quality piezoelectric crystals La₃Ga₅SiO₁₄ (LGS) grown by the Czochralski method in a Platinum or Iridium crucible are reported in this paper. The growth defects in the LGS crystals were investigated by Transmission electron microscopy (TEM). It was found that cracks, inclusions, grain boundary and thermal stress in the LGS crystals. Their formation mechanisms and the method of eliminating these defects are discussed. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Neutron diffraction and X-ray diffraction investigations of langasite crystals

Crystals of langasite La₃Ga₄(GaSi)O₁₄ grown by the Czochralski method are studied using neutron diffraction for the first time. It is established that the compositions of the upper and lower parts of an orange crystal grown from the La₃Ga_5.14Si_0.86O₁₄ seed in an (Ar + O₂) atmosphere (the 〈 0001 〉 growth direction) can be written as(La_2.85(2)□_0.15)(Ga_0.95(2)□_0.05) Ga₃(Ga_1.15 Si_0.85(5))(O_13.72□_0.28(7)) and(La_2.89(1)□_0.11)·(Ga_0.98(1)□_0.02) Ga₃(Ga_1.06Si_0.94(4))(O_13.81□_0.19(9)), respectively. The La content in the upper and lower parts of this crystal is lower and higher than the Ga content, respectively, and the Ga content exceeds the Si content in the (GaSi) position. By contrast, in a colorless crystal of the composition(La _2.97(4)□_0.03) Ga(1)(Ga_2.94(9)□_0.06)(Ga_0.7(1) Si_1.3)(O_13.9□_0.1(1)), which is grown from the La₃ Ga₅SiO₁₄ seed in an argon atmosphere (the 〈 01\(\bar 1\)1 ?growth direction), the Ga content in the (GaSi) position is lower than the Si content. A relation between the Ga: Si ratio and the (Ga,Si)-3O interatomic distances is found.     

Spectroscopic properties of La3Ga5SiO14:Er3+ (1%) crystals

Single crystals of Erbium (Er) doped La₃Ga₅SiO₁₄ (LGS) have been grown along c‐axis by using the Czochralski method. The absorption and fluorescence spectra of LGS: Er³⁺ single crystals have been measured and analyzed according to the Judd‐Ofelt theory. When applied, the following spectral parameters have been obtained: intensity parameters Ω_t, Ω₂= 2.741674×10^‐20cm², Ω₄= 0.66934×10^‐20 cm² and Ω₆= 0.592591×10^‐20 cm², radiative transition probabilities A_J,J”, P_J,J”. The radiative lifetime of levels ⁴I_13/2, ⁴H_9/2, ⁴S_3/2 are 11.333ms, 0.447ms and 0.704ms, respectively. The fluorescence branching ratios and the integrated emission cross sections are also calculated. The results suggest that LGS: Er crystals have potential applications as a laser material. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of Starting Melt Composition on Crystal Growth of La3Nb0.5Ga5.5O14

Single crystals of La₃Nb_0.5Ga_5.5O₁₄ were grown from different starting melt compositions by the Czochralski technique. The effect of the melt composition on crystal quality was examined by measuring the variation of chemical composition and lattice parameters along the growth axis. The existence of a solid solution range of La₃Nb_0.5Ga_5.5O₁₄ is discussed using X-ray crystal structure analysis.     

Neutron Diffraction Investigation of Langanite Crystals

The upper and lower parts of a single crystal with a nominal composition La₃Ga_5.5Nb_0.5O₁₄grown by the Czochralski method (Ir crucible, 99%Ar + 1%O₂, growth direction) have been studied by neutron diffraction for the first time. The compositions of the upper and lower parts are found to differ ((La_2.935(2)□_0.065)(Ga_0.450Nb_0.550(3))Ga₃(Ga_1.965(4) □_0.035)(O_13.90(1) □_0.10) and (La_2.940(1) □_0.060)(Ga_0.590Nb_0.410(2))Ga₅(O_13.82(1) □_0.18), respectively), and microtwin formation was observed in the upper part, with two unit cells related by the translation 1/2Z. Based on a comparison of the refined crystal composition and optical transmission spectra, the absorption bands at 30 000, 24 500, and 20 500 cm_-1 were assigned to divacancies (2 V _La^', 3 V _O^..), oxygen vacancies, and color centers, respectively. A relationship between the crystal color and oxygen content is established.     

Point defects in langatate crystals

Langatate crystals of the general composition La₃(Ga_0.5Ta_0.5)Ga₅O₁₄, grown by the Czochralski method, have been investigated by neutron diffraction (single crystals) and X-ray diffraction (ground single crystals). The crystals were grown in an atmosphere of 99% Ar + 1% O₂ in the Y54° direction (rotation by 54° with respect to the y axis), without subsequent annealing (orange crystal) or with vacuum annealing (colorless crystal). It is established that colorless crystals have a higher gallium content and, therefore, a larger number of oxygen vacancies in comparison with colored crystals; this is a possible reason for their lower microhardness.     

Angular stability of electric field‐induced effects in crystalline materials

We analyze angular bandwidths of extrema of the indicative surfaces describing spatial anisotropy of piezoelectric (PE) and electrooptic (EO) properties of doped lithium niobate (LiNbO₃:MgO) and langasite (La₃Ga₅SiO₁₄) crystals. A number of highly efficient experimental geometries are suggested, which are promising for PE and EO devices. Our data obtained with both analytical and numerical techniques characterize angular stability of those devices and, in particular, their angular aperture. We show that, besides of a maximal size of the electric field‐induced effects, ‘nondirect crystal cuts’ offer considerably higher angular stability of their characteristics, when compared with that typical for ‘direct crystal cuts’ usually employed in PE and EO devices.     

Optical properties of Ga3PO7 single crystals

Ga₃PO₇ crystal with size 18×15×12 mm³ and good optical quality has been grown by the top-seeded solution growth (TSSG) slow-cooling method from a Li₂O–3MoO₃ flux system. The Vickers microhardness and optical properties of the as-grown Ga₃PO₇ crystal have been carefully studied. The results show that the Ga₃PO₇ crystal belongs to the harder materials, and Meyer's index numbers for (1 1 0) and (0 0 1) planes were about 1.45 and 1.60, respectively. The Ga₃PO₇ crystal has a wide transmission range from 215 to 4300 nm. The smaller difference between the refractive indices values of n_o and n_e indicated that the Ga₃PO₇ crystal is an optically uniaxial negative crystal.     

Bulk photovoltaic and photorefractive effects in a piezoelectric La3Ga5SiO14: Fe crystal

The linear and the circular bulk photovoltaic and photorefractive effects in a piezoelectric La₃Ga₅SiO₁₄: Fe crystal have been studied. It is shown that the photorefractive effect is induced by generation of the photovoltaic voltage.     

The absorption and circular dichroism spectra of langasite family crystals doped with chromium ions

The absorption and circular dichroism spectra of langasite family crystals, La₃Ga₅SiO₁₄, La₃Ga₅GeO₁₄, Ca₃Ga₂Ge₄O₁₄, Sr₃Ga₂Ge₄O₁₄ (red), Sr₃Ga₂Ge₄O₁₄ (green), La₃Ta_0.5Ga_5.5O₁₄, and La₃Nb_0.5Ga_5.5O₁₄, which were doped with chromium ions, have been investigated in the range of 240–850 nm. It is shown that chromium ions are incorporated into the structure of the investigated crystals both in the octahedrally (Cr³⁺ ion in 1a octahedron) and tetrahedrally (Cr⁴⁺ ion in 2d tetrahedron) coordinated positions. The ion ratio Cr³⁺/Cr⁴⁺ changes in a wide range in the crystals studied.     

Growth of Nd:Sr3Ga2Ge4O14 crystals by a modified Bridgman method

Bridgman growth of Nd:SGG (Sr₃Ga₂Ge₄O₁₄) crystals has been investigated for the first time. Pt crucible of ∅︁25mm×250mm with a seed well of ∅︁10mm×80 mm is used, and seed is SGG crystal of ∅︁10mm×50mm grown by Bridgman method in advance. The growth parameters are optimized as the furnace temperature is set to 1450∼1500°C, temperature gradient in the crystal‐melt interface is less than 25 K/cm and growth rate is less than 0.5mm/h. The Nd:SGG crystals with 25mm in diameter and 60mm in length are grown successfully from 1.5 to 8at% Nd³⁺ doped stoichiometric Sr₃Ga₂Ge₄O₁₄ melt. The distribution coefficient and concentration of Nd³⁺ in Nd:SGG crystals are obviously higher than those of Nd:YAG crystal. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Bridgman growth of langasite‐type piezoelectric crystals

Three langasite family crystals of Sr₃Ga₂Ge₄O₁₄ (SGG), Ca₃NbGa₃Si₂O₁₄ (CNGS), and Sr₃NbGa₃Si₂O₁₄ (SNGS) were successfully grown by the modified Bridgman method. Among them, SGG crystals up to 2 inches were obtained with the multi‐crucible industrial Bridgman furnace; SNGS crystal grown in any orientation direction other than along a‐axis was realized. Commercially availability SGG boules and the advantage in SNGS crystal indicated that the modified Bridgman technique is a prospective method to realize the mass‐production of the langasite‐type crystals. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal growth and defects in Ga3PO7 crystals

Crystals with a non‐centrosymmetric structure are of great interest owing to their properties such as ferroelectricity, piezoelectricity, dielectric behavior and optical properties. In this letter, Ga₃PO₇ crystals are grown by the top‐seeded solution growth (TSSG) method from a Li₂O‐3MoO₃ flux. It crystallizes in a non‐centrosymmetric trigonal crystal system with space group R3m within point group 3m. The growth defects are investigated by means of chemical etching method. The results reveal hot concentrated phosphoric acid to be a good etchant for Ga₃PO₇. The main defects are cracks, inclusions, dislocations and twin. In the meantime, the effective measures for reducing the defects are proposed. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Single‐crystal growth and characterization of mullite‐type orthorhombic Bi2M4O9 (M = Al3+, Ga3+, Fe3+)

Pure and homogeneous single crystals of orthorhombic mullite‐type Bi₂M₄O₉ (M = Al³⁺, Ga³⁺, Fe³⁺), and a mixed Bi₂Fe_1.7Ga_2.3O₉ crystal from an equimolar Ga/Fe composition were grown by the top seeded solution growth (TSSG) method. All these compounds melt incongruently in the range of about 800 and 1100 °C. In case of bismuth gallate and ferrate inclusion‐free crystals with dimensions up to several cubic centimeters can be grown. Limited solubility in Bi₂O₃ and the high steepness of the liquidus curve are the reasons for getting only small imperfect bismuth aluminate crystals. In contrast to ceramic materials preparation reported in literature, divalent calcium and strontium could not be incorporated into the mullite‐type structure during the melt growth process. Several fundamental physical properties like heat capacity, thermal expansion, heat conductivity, elastic constants, high‐pressure behavior and oxygen diffusivity were determined by different research groups using single‐crystalline samples from the as‐grown materials. Furthermore, the refractive indices of Bi₂Ga₄O₉ were measured in the range of 0.430 and 0.700 μm. Such as many other bismuth containing compounds the refractive indices of Bi₂Ga₄O₉ are larger than 2, and Bi₂Ga₄O₉ is an optic biaxial positive crystal. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Comparison of the Spectral Characteristics of Chromium-Containing Crystals of the Calcium Gallogermanate Type with Their Structural Features

The molecular refractions and characteristics of the circular dichroism spectra of unactivated and chromium_activated La₃Ga_5.5Ta_0.5O₁₄, La₃Ga_5.5Nb_0.5O₁₄, La₃Ga₅GeO₁₄, La₃Ga₅SiO₁₄, Sr₃Ga₂Ge₄O₁₄, and Ca₃Ga₂Ge₄O₁₄crystals are compared with their structural parameters. Correlations between the molecular refractions and the structural distortions responsible for the optical activity of crystals and correlations between the characteristics of circular dichroism bands of defects and chromium ions and the interatomic distances in polyhedra and their distortions are found. The calcium gallogermanate structures exhibit a unique correspondence between the electronic configuration of host ions and the local symmetry.     

Growth and characterization of a new langasite‐type single crystal Sr3NbAl1.5Ga1.5Si2O14

Single crystals of Sr₃NbAl_1.5Ga_1.5Si₂O₁₄ (SNAGS) with langasite structure have been successfully grown by Czochralski method. The X‐ray diffraction (XRD) verified that the as‐grown crystal was isostructural with A₃BC₃D₂O₁₄ structure and the lattice parameters were calculated as follows: a = 8.242 Å, c = 5.041 Å, V = 296.6 ų. The piezoelectric coefficient d₁₁ was 5.7pC/N, which was 2.47 times of α‐quartz (d₁₁=2.31pC/N). The electric resistivity was up to 3.04×10⁶ Ωcm at 700 °C for X‐cut sample. In addition, the transmission spectrum of the SNAGS crystal showed that it had a high transmittance (>80%) in the range of 350‐800 nm and exceeded 90% above 520 nm. These results suggest that the SNAGS crystals have potential applications in high‐temperature piezoelectric sensors and optical techniques. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

<Emphasis Type="Italic">Ab Initio</Emphasis> calculation of elastic and electromechanical constants of langasite family crystals

Elastic and electromechanical (piezoelectric) constants for six langasite family crystals Ca₃TaGa₃Si₂O₁₄, Sr₃TaGa₃Si₂O₁₄, Ba₃TaGa₃Si₂O₁₄, La₃Ta_0.5Ga_5.5O₁₄, La₃Nb_0.5Ga_5.5O₁₄, La₃Ga₅SiO₁₄ are calculated within the density-functional perturbation theory.     

Refinement of the crystal structures of the La3Ta0.5Ga5.5O14 and La3Nb0.5Ga5.5O14 compounds

This paper reports on the results of accurate X-ray structural investigations of single crystals La₃Ta_0.5Ga_5.5O₁₄ (a = 8.2260(1) ?, c = 5.1207(1) ?, R/R _w = 1.09%/1.10%, 3868 unique reflections) and La₃Nb_0.5Ga_5.5O₁₄ (a = 8.2237(1) ?, c = 5.1247(1) ?, R/R _w = 1.02%/1.03%, 3735 unique reflections) (space group P321, Z = 1, sinϑ/λ|_max ≈ 1.34 ?⁻¹ for both compounds). Using sets of data with a large number of high-angle reflections makes it possible to reliably compare the crystal structures by applying statistical tests. The structural differences between the La₃Ta_0.5Ga_5.5O₁₄ and La₃Nb_0.5Ga_5.5O₁₄ crystals are weakly pronounced, which correlates with the closeness of their piezoelectric characteristics. Original Russian Text ? A.P. Dudka, B.V. Mill, Yu.V. Pisarevsky, 2009, published in Kristallografiya, 2009, Vol. 54, No. 4, pp. 599–607.