Growth and characterization of near stoichiometric LiNbO3 single crystal

A near stoichiometric LiNbO₃ single crystal has been grown by the Czochralski method from a 58.5% Li melt hold in a large platinum crucible. High resolution X‐ray rocking curves of 30 0 and 0006 reflections indicated that the near stoichiometric LiNbO₃ crystal possesses the high structural quality. Compared with the congruent LiNbO₃, the near stoichiometric LiNbO₃ possesses shorter ultraviolet absorption edge, thus higher Li concentration. The OH^– infrared absorption band analyses showed that the Li concentration in the near stoichiometric LiNbO₃ crystal is higher than that in the congruent LiNbO₃ crystal. This result is in good agreement with that of the ultraviolet absorption edge. The electro‐optic (EO) coefficient γ₂₂ of the near stoichiometric LiNbO₃ crystal was measured to be 6.75 pm/V higher than that of congruent LiNbO₃ crystal. It also proves the near stoichiometric LiNbO₃ electro‐optic Q‐switched requires a low driving voltage and it is advantageous for the device performance. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Bulk crystal growth of congruent MgO-doped LiNbO3 crystal with stoichiometric structure and its second-harmonic-generation properties

A new LiNbO₃ bulk crystal has been grown by doping with MgO (cs-MgO:LN; Li₂O:Nb₂O₅:MgO=45.30:50.00:4.70, (Li_0.906Mg_0.047V^Li_0.047)NbO₃), which successfully has the congruent point coinciding with the stoichiometric point. Its second-harmonic-generation (SHG) properties were evaluated. It was found that cs-MgO:LN has a much more homogeneous composition leading to uniform in-plane distribution of the non-critical phase-matching wavelength than the conventional LiNbO₃ crystals such as congruent LiNbO₃ (c-LN), stoichiometric LiNbO₃ (s-LN), and MgO-doped congruent LiNbO₃ (5MgO:LN). This homogeneity arose from the observation that none of the solute components including ionic species were segregated at the interface during growth. The SHG conversion efficiency of cs-MgO:LN is comparable to those of s-LN and 5MgO:LN.     

Czochralski grown Ga2O3 crystals

We report on the successful growth of β-Ga₂O₃ single crystals using the Czochralski method. Model calculations show that the gas phase consists of Ga₂O, GaO or Ga independent of the ratio of oxygen and Ar or N₂. We find that for growing single crystals the evaporation has to be suppressed by a finite amount of oxygen. A CO₂/Ar gas atmosphere was found to meet this requirement.     

Crystal growth and spectroscopic properties of Yb:CaYAlO4 single crystal

A Yb³⁺-doped CaYAlO₄ laser crystal has been grown by the Czochralski technique. The segregation coefficient was measured by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). The cell parameters were analyzed with X-ray diffraction experiments. Color defects in Yb:CaYAlO₄ have been evidenced to be similar to those in undoped CaYAlO₄. The polarized absorption spectra and the fluorescence spectrum of the Yb:CaYAlO₄ crystal were measured at room temperature. The fluorescence decay time of the Yb³⁺ ion was investigated. The results show that Yb:CaYAlO₄ has potential as a laser gain medium for an ultrashort laser system.     

The growth and spectroscopic characteristics of Ca3Y2(BO3)4:Er laser crystal

The Ca₃Y₂(BO₃)₄:Er³⁺ crystal with a size up to 20 mm×30 mm was grown by the Czochralski method. The absorption spectrum was measured and its absorption peaks were assigned to the corresponding transitions between the Er³⁺ energy levels. A broad emission spectrum from 1429.4 to 1662.8 nm was exhibited from 530 nm wavelength pumping. This crystal is promising as a tunable infrared laser crystal.     

Temperature fluctuations in a LiNbO3 melt during crystal growth

The synthesis of calcium carbonate (CaCO₃) crystals from aqueous solutions containing sodium dodecyl sulfate (SDS), poly(N-vinyl-1-pyrrolidone) (PVP), or SDS/PVP complexes has been performed through a slow titration method. It was found that aragonite and calcite co-existed in the prepared crystals. The formation of aragonite in the precipitation systems without magnesium ions indicates that at ambient temperature ca. 26.0°C, initially formed amorphous CaCO₃ could also transfer into aragonite in the sedimentary phase, which indicates the controlling factor of organic additives in the nucleation and growth process of CaCO₃ crystals. The appearance of hexagonal crystals in the suspensible phase confirmed the hexagonal crystallization cell of vaterite, and revealed the colloidal-dispersion function of the SDS/PVP complex in the crystallization process of CaCO₃.     

Laser heated pedestal growth of orthorhombic SrHfO3 single crystal fiber

SrHfO₃ single crystal fibers were grown by the laser heated pedestal growth technique. These fibers have orthorhombic symmetry with lattice parameters of a=5.773(1) Å, b=5.764(3) Å, c=8.157(2) Å at 300 K.     

Growth, dielectric, ferroelectric and optical properties of Ca0.28Ba0.72Nb2O6 single crystals

Calcium barium niobate Ca_0.28Ba_0.72Nb₂O₆ (CBN-28) crystals were grown by the Czochralski method. The effective segregation coefficients of Ca, Ba, Na elements in CBN-28 crystal growth were measured, and the rocking curve from 0 0 2 reflection of CBN-28 wafer was also measured by the high-resolution X-ray diffractometer D5005, and the full-width at half-maximum value was measured to be 70.6″. The measured dependence of dielectric constants on temperature showed the Curie temperature of the CBN-28 crystals is between 246.8 and 260 °C. Typical polarization–electric field (P–E) hysteresis loops were measured at room temperature. Ferroelectric 180° domains were observed by scanning electron microscopy (SEM) on the etched (0 0 1) surface of the CBN-28 crystals. The transmittance of [0 0 1]-oriented CBN-28 crystals was measured and the result shows that optical properties of CBN-28 crystal are almost the same as those of SBN for wavelengths between 2500 and 7500 nm.     

Growth, refined structural and spectroscopic characteristics of Tm-doped NaGd(WO4)2 single crystals

The details of Tm³⁺-doped NaGd(WO₄)₂ single-crystal growth are discussed, the results of precise investigations of its structural and spectroscopic characteristics, as well as the analysis of cross-relaxation process of Tm³⁺ ions (³H₄→³F₄, ³H₆→³F₄) in this crystal are presented. Based on the Judd–Ofelt theory, three intensity parameters, spontaneous emission probabilities, fluorescence branching ratios and fluorescence quantum efficiency from ³H₄ and ³F₄ levels were refined.     

Numerical simulation of MHD rotator action on hydrodynamics and heat transfer in single crystal growth processes

The article presents the results of the mathematical and physical simulations of the influence of a rotating magnetic field (RMF) on the hydrodynamics and heat transfer in processes of large semiconductor single crystal growth in ampoules. Different versions of the RMF are considered, in particular, for symmetric and asymmetric positions of a RMF inductor with regard to the melt in the ampoule, for two counter-rotating magnetic fields, for different geometrical ratios in the “RMF inductor - liquid melt” system, and for different electrical conductivities of the hard walls at their contact with the melt. The interconnection between the distribution of the electromagnetic forces in the liquid volume and the formed velocity patterns, temperature distribution and shape of the solidification front is studied. An original method for the definition of the electromagnetic forces, which considers finite dimensions of the RMF inductor and melt, was used to calculate real conditions of the RMF influence on growth processes. The numerical results obtained are compared to the data of model experiments. Their satisfactory agreement permits us to propose this calculation method for the definition of the optimal parameters of a growth process under specific conditions and to select the most rational type of RMF influence.     

Growth of pyroxene-type MnGeO3 and (Mn,Mg)GeO3 crystals by the floating-zone method

Pyroxene-type solid–solution crystals of (Mn_1−xMg_x)GeO₃ with x=0.06, 0.10 and 0.20 have been grown by the floating-zone method. The end member crystal of MnGeO₃ is broken into small pieces by the orthorhombic-to-monoclonic phase transition during cooling after growth. On the other hand, the solid–solution crystals keep the orthorhombic structure between the melting points and room temperature and no crack is formed. The unit cell volumes are significantly decreased with an increase in Mg content.     

Study on phase diagram of Bi2O3---SiO2 system for Bridgman growth of Bi4Si3O12 single crystal

Phase relation of Bi₂O₃---SiO₂ system was evaluated experimentally from DTA and XRD measurements and its stable and metastable phase diagrams were proposed. Although BSO melts near-congruently at 1025°C in the stable phase equilibrium, its melt crystallizes to form metastable phase Bi₂SiO₅ in accordance with the metastable phase diagram while cooling. Therefore, BSO couldn't nucleate and crystallize spontaneously without crystal seed and only Bi₂SiO₅ crystallized at about 850°C with significant supercooling during Bridgman growth. BSO single crystal with 20×20×100mm³ was grown in a vertical Bridgman furnace with a BSO seed according to its phase diagram. The measuring results of scintillation properties of BSO specimen show that its decay constant is 91 ns (about 1/3 of BGO) and light output is 23% of BGO.     

Growth, thermal and spectral properties of Nd-doped NaGd(MoO4)2 crystal

Nd³⁺-doped NaGd(MoO₄)₂ crystal with dimensions were grown by Czochralski method. Nd³⁺:NaGd(MoO₄)₂ crystal melts at 1182 °C. The hardness of Nd³⁺:NaGd(MoO₄)₂ crystal is 334 VDH. The specific heat is 72.6 cal/mol K. The thermal expansion coefficients are for c-axis and for a-axis, respectively. The absorption cross-sections of Nd³⁺:NaGd(MoO₄)₂ crystal are with a FWHM of 9 nm at the 804 nm for π-polarization and with a FWHM of 17 nm at 807 nm for σ-polarization, respectively. The emission cross-section σ_em are at 1063 nm for π-polarization and 1.94×10^-20 at 1070 nm cm² for σ-polarization, respectively. The fluorescence lifetime τ_f is 93.9 μs at room temperature.     

Crystal growth and spectroscopic properties of erbium doped Lu2SiO5

A high optical quality erbium doped Lu₂SiO₅ single crystal has been grown by the Czochralski method. The distribution coefficient of Er³⁺ was measured to be ∼0.926. The absorption and emission spectra as well as the fluorescence decay curve of the excited state ⁴I_13/2 were measured at room temperature. The spectroscopic parameters were calculated using the Judd–Ofelt theory, and the J–O parameters Ω₂, Ω₄ and Ω₆ were found to be 4.451×10^-20, 1.614×10^-20 and 1.158×10^-20 cm², respectively. The room-temperature fluorescence lifetime of the Er³⁺⁴I_13/2→⁴I_15/2 transition was measured to be 7.74 ms. The absorption and emission cross-section as well as the gain cross-section in the eye-safe regime of 1400–1700 nm were also determined and discussed.     

Growth and characterization of ferromagnetic shape memory alloy Co50Ni20FeGa29 single crystals

Single crystals of Co₅₀Ni₂₀FeGa₂₉ with B2 phase have been obtained in a deep supercooling condition. The interface-facets and the segregation effect lead to the formation of ordered defects that store a directional internal stress. These defects give to a large energy barrier that leads to a very sharp martensitic transformation within a temperature window of only 2 K. The single crystals show good shape memory effect and superelasticity, which are anisotropic between the growth direction [0 0 1] and its equivalent direction [0 1 0]. The anisotropic behaviors are attributed to the directional internal stress caused by the ordered defects.     

Crystal growth and luminescent properties of Pr-doped K(Y,Lu)3F10 single crystal for scintillator application

Pr1%:K(Y_1−xLu_x)₃F₁₀ (x=0, 0.2, 0.4) single crystals were grown by the μ-PD method. All the grown crystals were greenish and perfectly transparent without any inclusions or cracks. Radioluminescence spectra and decay kinetics of the Pr1%:K(Y,Lu)₃F₁₀ crystals were measured. Emission from the Pr³⁺ 5d–4f transition, peaking around 260 nm and of the decay time of around 22 ns were observed. The 5d–4f emission intensities of the Pr1%:K(Y,Lu)₃F₁₀ crystals were higher than that of the standard BGO scintillator.     

Glass formation, physico-chemical properties, and structure of glasses based on Ga2S3-GeS2-Sb2S3 system

We prepared sulfide glasses based on a Ga₂S₃-GeS₂-Sb₂S₃ system and investigated the compositional dependences of their physico-chemical properties and structure. Additivities were observed for density and refractive index; i.e., these properties were presented by the summation of the contribution from each component. With the increase of Sb₂S₃ content, the density, refractive index, and thermal expansion coefficient increased while the glass transition and softening temperatures decreased, and the short-wavelength absorption edge shifted to the longer wavelength side. These variations are expected from the incorporation of a heavy element (Sb) into the glasses. On the other hand, the replacement of GeS₂ by Ga₂S₃ increased the density and refractive index, and shifted the short-wavelength absorption edge to the longer wavelength side. These variations were explained by the increase of the number densities of the cations with the replacement and the formation of metal-metal bonds. The latter was confirmed from the Raman spectra. We also investigated the effects of Ag₂S incorporation on the optical properties. The incorporation of Ag₂S increased the density and refractive index whereas the position of the short-wavelength absorption edge varied little. These results show the possibility of fabricating an optical waveguide by Ag incorporation into the glasses.     

Correlation between interfacial structure and c-axis-orientation of LiNbO3 films grown on Si and SiO2 by electron cyclotron resonance plasma sputtering

Thin films of crystalline lithium niobate (LN) grown on Si(1 0 0) and SiO₂ substrates by electron cyclotron resonance plasma sputtering exhibit distinct interfacial structures that strongly affect the orientation of respective films. Growth at 460–600 °C on the Si(1 0 0) surface produced columnar domains of LiNbO₃ with well-oriented c-axes, i.e., normal to the surface. When the SiO₂ substrate was similarly exposed to plasma at temperatures above 500 °C, however, increased diffusion of Li and Nb atoms into the SiO₂ film was seen and this led to an LN–SiO₂ alloy interface in which crystal-axis orientations were randomized. This problem was solved by solid-phase crystallization of the deposited film of amorphous LN; the degree of c-axis orientation was then immune to the choice of substrate material.     

Glass formation in the MoO3–Nd2O3–La2O3–B2O3 system

In MoO₃–Nd₂O₃–B₂O₃ and MoO₃–Nd₂O₃–La₂O₃–B₂O₃ systems, glasses were obtained in the region between 20 and 30 mol% Ln₂O₃. A liquid-phase separation region was observed near the MoO₃–B₂O₃ side up to 20 mol% Ln₂O₃ (La, Nd). The amorphous phases were characterized by X-ray diffraction (XRD), differential thermal analysis (DTA), UV–VIS and infrared spectroscopy (IR). According to DTA data B₂O₃-rich glasses are stable up to 630 °C while glasses rich in MoO₃ are stable up to 430 °C. The glasses are transparent in the visible region. Structural models for the glasses network were suggested on the basis of IR spectral investigations. It was established that BO₃ (1380 cm⁻¹), BO₄ (1100–950 cm⁻¹) and MoO₄ (860 cm⁻¹) groups build up the glass network. MoO₆ units (band at 880 cm⁻¹) together with BO₃ units participate in the formation of the glass network with a high MoO₃ content (80–90 mol%).     

Growth and self-frequency doubling laser output of Nd : Ca4Gd0.275Y0.725O(BO3)3 crystal

In this letter, Nd : Ca₄Gd_0.275Y_0.725O(BO₃)₃ (Nd : GdYCOB) single crystal with good optical quality and large size has been grown by the Czochralski method. The absorption and fluorescence spectra have been measured. The self-frequency doubling (SFD) laser output of Nd : GdYCOB at 0.53 μm has been demonstrated when a Nd : GdYCOB crystal sample with dimensions of 3 mm×3 mm×7 mm (the phase-matched angle is θ=78.8°, Φ=90°) is pumped by a cw Ti : sapphire laser.