Growth and optical characterization of cerium and lead‐doped Bi12TiO20 sillenite single crystals

Bi₁₂TiO₂₀ (BTO) single crystals doped with PbO and CeO₂ were grown by the Top Seeded Solution Growth (TSSG) technique from the liquid phase with nominal compositions of 10Bi₂O₃ : (1–x)TiO₂ : x PbO and 10Bi₂O₃ : (1–x)TiO₂ : xCeO₂ with x = 0.25 and 0.10. No growth‐related difficulties were encountered other than those typical of sillenite crystals. Samples with good optical quality were obtained and were characterized by optical absorption, dark current, spectral photocurrent dependence, optical activity and electro‐optic coefficient measurements. A comparison is made of the results of the optical measurements of doped and undoped BTO crystals. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effective electro‐optic coefficient of (1–x)Pb(Zn1/3Nb2/3)O3–xPbTiO3 single crystals

Refractive indices and effective electro‐optic coefficient γ_c of (1–x)Pb(Zn_1/3Nb_2/3)O₃–xPbTiO₃ (PZN‐xPT, x = 0.05, 0.09 and 0.12) single crystals were measured at 532 nm wavelength. Orientation and temperature dependences of the electro‐optic coefficient were investigated. Large electro‐optic coefficient (γ_c = 470 pm/V) was observed in [001]‐poled PZN‐0.09PT crystal. More importantly, γ_c of tetragonal PZN‐0.12PT is almost unchanged in a temperature range −20 ∼ 80 °C. The γ_c of PZN‐xPT single crystals are much higher than that of widely used electro‐optic crystal LiNbO₃ (γ_c = 20 pm/V). These results show that PZN‐xPT single crystals are very promising materials for electro‐optic modulators in optical communications.     

Crystal growth and spectral properties of Nd:Ca5(BO3)3F

A neodymium doped Ca₅(BO₃)₃F single crystal with size up to 51×48×8 mm³ has been grown by the top seeded solution growth (TSSG) technique with a Li₂O‐B₂O₃‐LiF flux. The spectra of absorption and fluorescence were measured at room temperature. According to Judd‐Ofelt (J‐O) theory, the spectroscopic parameters were calculated and the J‐O parameters Ω₂, Ω₄, Ω₆ were obtained as follows: Ω₂ = 1.41×10⁻²⁰cm², Ω₄ = 3.18×10⁻²⁰cm², Ω₆ = 2.11×10⁻²⁰cm². The room temperature fluorescence lifetime of NCBF was measured to be 51.8 μs. According to the J‐O paramenters, the emission probabilities of transitions, branching ratios, the radiative lifetime and the quantum efficiency from the Nd^{3+ 4}F_3/2 metastable state to lower lying J manifolds were also obtained. In comparasion with other Nd‐doped borate crystals, the calculated and experimental parameters show that NCBF is a promising SFD crystal.     

Laser‐induced crystal growth of nonlinear optical Ba3Ti3O6(BO3)2 on glass surface

Nonlinear optical Ba₃Ti₃O₆(BO₃)₂ crystals were patterned on the surface of CuO (1 mol%)‐doped 40BaO‐40TiO₂‐20B₂O₃ glass by irradiations of continuous‐wave Nd:YAG (wavelength: λ=1064 nm) and Yb:YVO₄ (λ=1080 nm) lasers. Laser energies absorbed by Cu²⁺ ions were transferred to the lattice system through a nonradiative relaxation process, consequently heating the glass and inducing local crystallizations. For the lines patterned by Yb:YVO₄ laser irradiations with a power of 1 W and a scanning speed of 20 μm/s, a c‐axis orientation of Ba₃Ti₃O₆(BO₃)₂ crystals along the laser scanning direction is proposed from measurements of X‐ray diffraction analyses, polarized optical photographs, polarized micro‐Raman scattering spectra, and azimuthal dependence of second harmonic generations. The laser‐induced crystallization technique is found to be applied successfully for the spatially selective patterning of nonlinear optical Ba₃Ti₃O₆(BO₃)₂ crystals in glass. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Microscopic studies on imperfections in selected YAB single crystals

The as‐grown surface and inner structures of undoped and Nd³⁺‐, Cr³⁺‐, V³⁺‐, Ce³⁺‐, Er³⁺ and Yb³⁺ – and (Er³⁺ + Yb³⁺) – doped yttrium aluminum borate (YAB) single crystals grown from (K₂Mo₃O₁₀ + B₂O₃) flux by spontaneous crystallization or top seeded solution growth (TSSG) technique, were investigated using optical and scanning electron microscopic and analytic chemical methods. Fine and rough growth hillocks of dislocational origin, growth layers, traces of inner planar defects and foreign phase crystalline debris were found and analyzed on the as‐grown faces of crystals. Irregular grains and regular block structures and foreign phase inclusions were observed and studied in the interior of the crystals. The chemical compositions measured by energy dispersive X‐ray spectrometry on perfect and imperfect micro regions are compared with those obtained by flame atomic absorption spectrometry on bulk crystals. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optimisation of chromium doping in LiNbO3 single crystals

Growth of undoped and Cr doped (0.1, 0.25 and 0.5 mol % Cr₂O₃) congruently‐ melting‐composition LiNbO₃ single crystals by Czochralski technique is reported. Chromium doping was optimised to get crystals with potential for an integrated, broadband, tunable laser in the 700‐1100 nm spectral range. Typical sizes of the grown crystals are 25‐30 mm in diameter and 30‐40 mm in length. Symmetrical and sharp conoscopy pictures confirm the optical homogeneity of the crystals. Optical transmission was recorded for both undoped and doped crystals. 70% transmittance was observed. The grown crystals have reasonably good laser damage threshold. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth,structure, and superconducting properties of Bi2Sr2Ca2Cu3O10 and (Bi,Pb)2Sr2Ca2Cu3O10‐y crystals

Large and high‐quality single crystals of both Pb‐free and Pb‐doped high temperature superconducting compounds (Bi_1‐xPb_x)₂Sr₂Ca₂Cu₃O_10‐y (x = 0 and 0.3) were grown by means of a newly developed “Vapour‐Assisted Travelling Floating Zone” technique (VA‐TSFZ). This modified zone‐melting technique was realised in an image furnace and allowed for the first time to grow Pb‐doped crystals by compensating for the Pb losses occurring at high temperature. Crystals up to 3×2×0.1 mm³ were successfully grown. Post‐annealing under high pressure of O₂ (up to 10 MPa at T = 500°C) was undertaken to enhance T_c and improve the homogeneity of the crystals. Structural characterisation was performed by single‐crystal X‐ray diffraction (XRD) and the structure of the 3‐layer Bi‐based superconducting compound was refined for the first time. Structure refinement showed an incommensurate superlattice in the Pb‐free crystals. The space group is orthorhombic, A2aa, with cell parameters a = 27.105(4) Å, b = 5.4133(6) Å and c = 37.009(7) Å. Superconducting studies were carried out by A.C. and D.C. magnetic measurements. Very sharp superconducting transitions were obtained in both kinds of crystals (ΔT_c ≤ 1 K). In optimally doped Pb‐free crystals, critical temperatures up to 111 K were measured. Magnetic critical current densities of 2�10⁵ A/cm² were measured at T = 30 K and μ₀H = 0 T. A weak second peak in the magnetisation loops was observed in the temperature range 40‐50 K above which the vortex lattice becomes entangled. We have measured a portion of the irreversibility line (0.1‐5 Tesla) and fitted the expression for the melting of a vortex glass in a 2D fluctuation regime to the experimental data. Measurements of the lower critical field allowed to obtain the dependence of the penetration depth on temperature: the linear dependence of λ(T) for T < 30 K is consistent with d‐wave superconductivity in Bi‐2223. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and characterization of pure and Co2+‐doped Li2B4O7 single crystals

Pure and Co‐doped Li₂B₄O₇ (LBO) single crystals were grown by the Czochralski method. Starting concentrations of Co₂O₃ in the melt were: 0.5, 0.85 and 1 mol% relative to Li₂CO₃. Technological factors affecting the quality of both crystals were discussed. Optical absorption and EPR spectra were analyzed to define the oxidation states and lattice sites of cobalt ions. It was shown that Co²⁺ ions enter LBO crystal at octahedral Li⁺ site positions. Low‐temperature EPR measurements revealed that two types of Co²⁺ complexes can be distinguished in the Li₂B₄O₇:Co crystals. Additional absorption calculated for γ‐irradiated crystals showed V_k type defects suggesting the creation of cation vacancies during growth. The concentration of the defects decreases with an increase of intentional Co concentration. Introduction of cobalt ions to LBO crystal is limited probably by the formation of cobalt ion pairs or by the entrance of cobalt as Co⁺. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Luminescence characteristics of undoped and Eu‐doped GdCa4O(BO3)3 single crystals and nanopowders

Single crystals of GdCa₄O(BO₃)₃ (GdCOB) pure and doped with Eu concentration of 1 and 4 at% were grown by the Czochralski and micropulling‐down methods. The distribution of Eu ions in GdCOB crystals was uniform. The substitutions of Eu³⁺ in Gd, Ca(1) and Ca(2) cation sites and eventually formation Eu²⁺ have been investigated. The spectroscopic properties of crystals are compared with the properties of nanopowders obtained by sol‐gel method. Radioluminescence spectra of undoped GdCOB crystal show the characteristic emission of Gd³⁺ at about 312 nm, whereas this emission dramatically decreases in Eu‐doped crystals upon X‐ray excitation, as well as in Eu‐doped nanopowders excited in vacuum ultraviolet (VUV) region. The VUV excitation in the range 125‐333 nm for Eu‐doped samples leads to strong emission in red coming from the ⁵D₀ multiplet of Eu³⁺, only. In the photoluminescence decay kinetics of 312 nm emissions substantial shortening and departure for single exponential decay in Eu‐doped samples is clearly observed. Higher Eu doping results in further acceleration of the decay. In undoped GdCOB crystal, the lifetime of the Gd^{3+ 6}P_7/2 multiplet is 2.79 ms. The Eu^{3+ 5}D₀ decay kinetics monitored at 613 nm are rather constant. Numerical fitting of fully exponential curves, reveals lifetimes 2.7 ms for nanopowder and 2.5 ms for single crystal. The results suggest that this material may be used as a red phosphor in plasma display panels in nanopowder form because of strong excitation band of Eu³⁺ luminescence in the 160‐200 nm regions. Contrary to nanopowder sample, such an excitation band, attributed to the Gd³⁺–O^2– charge transfer was not observed in crystal obtained by the micropulling‐down method. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of doping on OH absorption in LiNbO3 crystals

Undoped, Cr doped and Mg, Cr codoped LiNbO₃ crystals were grown by conventional Czochralski technique. Comparative study was carried out using Fourier transform infrared (FTIR) and UV‐Visible spectroscopy. Infrared optical absorption for OH^– ion has been used to study the effect of dopants on the crystals. The peak position of OH^– shift to 3535 cm^‐1 for Mg, Cr codoped crystals compared to 3484 cm^‐1 for undoped and Cr doped crystals. Prominent absorption bands are found in the visible region centered at 480 nm (20833 cm^‐1) and 653 nm (15313 cm^‐1) in Cr doped crystals. Whereas in Mg, Cr codoped crystals these broad absorption bands are red shifted to 517 nm (19342 cm^‐1) and 678 nm (14749 cm^‐1). UV cutoff in Cr doped crystals shift towards higher wavelength compared to undoped LiNbO₃ crystals. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Micro‐Pulling Down Growth of Co‐doped Lithium Niobate Single Crystal Fibers According Er and Mg Contents and Photolumenescence Properties

The Er³⁺doped Mg:LiNbO₃single crystal fibers employed in our experiment were grown in air by a micro‐pulling down (μ‐PD) method from host materials of a congruent Li/Nb (0.945) ratio which were melt‐doped with a nominal molar concentration of 1, 3, 5% MgO and 0.6% Er₂O₃. The X‐ray diffraction analysis results indicated that the co‐doped crystals main tained the same structural characteristics as the undoped LiNbO₃, however the lattice parameters with Mg differed; c (Å) value decreased, and a (Å) increased than of pure LiNbO₃. The influence of dopants on the photoluminescence (PL) properties of the Er:Mg:LiNbO₃ single crystal fibers excited by laser lines of 514 nm was reported. Also, the PL properties according to temperature and the excitation power of Er:Mg:LiNbO₃ crystal fibers were analyzed.     

Structural and optical investigations on Mn doped Li2B4O7 crystals

Lithium tetraborate crystals have great demand due to its non‐critical phase matching at 90°. Transparent and good optical quality single crystals of undoped and Mn doped Li₂B₄O₇ were grown by Czochralski technique in air atmosphere. The crystalline phase was determined by X‐ray diffraction. Doping of Mn in the grown crystals was confirmed by energy dispersive analysis of X‐rays (EDAX) technique. Transmission spectra show that the crystal is transparent in the visible region. Birefringence interferograms were recorded to qualitatively analyse the optical homogeneity of the grown crystals and to quantify the birefringence of the samples in desired crystal direction. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The influence of Pb‐ion irradiation on melt‐textured YBa2Cu3Ox crystals

Melt‐textured YBa₂Cu₃O_x crystals have been irradiated along the c‐axis with ²⁰⁸Pb⁵⁶⁺ ions corresponding to dose matching fields, B_Φ = 0.5 T and B_Φ = 2.0 T. Magnetization measurements were conducted along the ab plane of the samples. The strength of pinning sites was investigated by measuring magnetization hysterisis and the saturation remanent magnetization M_R at several temperatures. We have found that the pinning strength was considerably enhanced after irradiation at both doses. Interestingly, the pinning strength at a Pb‐ion irradiation which corresponds to the dose matching field B_Φ = 0.5 T, was found to be significantly larger than that at the dose matching field B_Φ = 2.0 T at all temperatures. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Flux growth and characterization of Ti‐ and Ni‐doped forsterite single crystals

Forsterite monocrystals doped with Ti and Ni were grown by the flux growth technique. A suitable mixture of flux (MoO₃, V₂O₅, Li₂CO₃) and nutrient was slowly cooled down to 750 °C from 1250 °C or 1350 °C. The crystals were then characterized by powder and single‐crystal X‐ray diffraction, scanning electron microscopy and differential scanning calorimetry (DSC). Variations observed in crystal size were attributed by both the varying experimental conditions in which they had been obtained, and to the amount of Ni substituted for Mg in the structure. High abundances of doped forsterite required a cooling rate of 1.8 K h^‐1. These synthetic, well‐characterized Ti and Ni doped forsterite crystals may have potential for exploitation in industrial fields. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal growth of zirconium‐doped KTiOPO4 crystals in the K2O‐P2O5‐TiO2‐ZrF4 system

Zirconium‐doped KTiOPO₄ (KTP) crystals were grown using a high temperature flux method in the K₂O‐P₂O₅‐TiO₂‐ZrF₄ system. The dopant content in the single crystals with general composition KTi_1‐xZr_xOPO₄ (where x = 0 – 0.026) strongly depends on zirconium concentration in the homogeneous melts. AES‐ICP method and X‐ray fluorescence analysis were used to determine the composition of the obtained crystals. Phase analyses of the products were performed using the powder XRD. The structures of KTiOPO₄ containing different quantities of Zr were refined on the basis of single crystal XRD data. Applying ZrF₄ precursor for zirconium injection into the flux allowed growing the zirconium‐doped KTP crystals at 930–750°C. (© 2008 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)     

Crystal structure,dielectric properties of (K0.5Na0.5)NbO3 single crystal grown by flux method using B2O3 flux

Lead free piezoelectric single crystals of sodium potassium niobate (K_0.5Na_0.5)NbO₃ (KNN) were grown by high‐temperature solution method using two different fluxes; one with a mixture of NaF and KF and other with addition of B₂O₃ along with the mixture. In the present study, the growth of KNN crystals without B₂O₃ flux and the same with B₂O₃ flux were compared. It was found that additions of small amounts of B₂O₃ lowered the melting temperature of the solid solution and enabled better dielectric properties. Phase analysis showed that all samples were crystallized in pure orthorhombic perovskite phase. AFM morphological studies showed that the addition of B₂O₃ flux increased the roughness of the grown crystal. Further, addition of B₂O₃ flux slightly decreased the orthorhombic to tetragonal phase transition temperature T_(O—T) and the Curie temperature T_C. The ferroelectric behaviour of KNN single crystal has been investigated at room temperature. The crystal grown using B₂O₃ flux exhibited a remanent polarization (P_r) ∼ 32 μC/cm² and coercive field (Ec) of ∼11.8 kV/cm whereas the crystal grown without the use of B₂O₃ flux had a remanent polarization (P_r) ∼ 36 μC/cm² and coercive field (Ec) of ∼14.6 kV/cm.     

Investigation of structural perfection and faceting in highly Er‐doped Yb3Al5O12 crystals

The undoped Yb₃Al₅O₁₂ (YbAG) single crystals and doped with 1.5, 10 and 30 at% erbium were grown by the Czochralski method. The YbAG crystals offer efficient emission of laser beam of 2.94 µm and 1.55 µm important for practical applications in communication and medicine. The crystals were investigated by various synchrotron X‐ray diffraction methods including white beam topographic methods, monochromatic beam topography and recording of the rocking curves. The experiments were performed at E2 and F1 experimental stations in HASYLAB. The investigations proved a good crystallographic perfection of the crystals, in most cases revealing only segregation fringes and growth facets. The crystallographic identification of the facets was performed together with direct evaluation of growth front radius from the transmission section topographs. Relative lattice parameter changes connected with erbium segregation were found to be less than 2 × 10^‐5 inside the segregation fringes and 8 × 10^‐5 in the facets. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Sintering behavior of ZnO:Al ceramics fabricated by sol‐gel derived nanocrystalline powders

ZnO:Al ceramics (Zn:Al, 0.95:0.05) were prepared by using sol‐gel derived nanocrystalline powders. XRD patterns of the doped ceramics revealed the existence of both zincite (JCPDS 36‐1451) and gahnite (JCPDS 5‐0669) phases. Gahnite phase (ZnAl₂O₄) was segregated along the ZnO grain boundaries. At the sintering temperature of 1200 °C, relative density of the undoped and Al doped ceramics were measured as 0.695 and 0.628, respectively. Both grain size and relative density of the ceramics decreased with Al doping. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.