Bridgman growth and properties of potassium lithium niobate single crystals

Transparent KLN crystals 10mm in diameter and 25 to 45mm in length have been grown by the modified vertical Bridgman technique from different melts in the range of 3035mol% K₂O, 1723mol% Li₂O and 4350mol% Nb₂O₅. The growth conditions are a growth rate of less than 0.25 mm/hr, temperature gradient in solid-liquid interface of 23 °C/mm and growth direction of <110>. As-grown KLN crystals have tetragonal tungsten bronze structure. Most of the as-grown crystals do not crack when cooling through the paraelectric/ferroelectric phase transition. 180° domain structures are observed after the KLN crystal was etched in boiling 2HNO₃:Hf. Dielectric properties and transmission spectrum of the as-grown KLN crystals are measured.     

Mössbauer studies on some glasses and crystals in the Na2O---Fe2O3---SiO2 system

Mössbauer absorption measurements have been made at room temperature on ⁵⁷Fe in iron sodium silicate glasses containing 3–15 mol% Fe₂O₃ and various iron alkali silicate crystals in order to study the state of iron in these glasses. The spectra of all the glasses gave one doublet with a quadrupole splitting varying from 0.73–0.78 mm s⁻¹, while those of Na₂O · Fe₂O₃ · 4 SiO₂ and 5 Na₂O · Fe₂O₃ · 8 SiO₂ crystals showed much smaller quadrupole splitting, 0.28 mm s⁻¹ and 0.10 mm s⁻¹, respectively, and an asymmetrical doublet of much narrower linewidth. When sodium was replaced by other alkali metals of larger size, such as K and Cs, in MFeSi₂O₆ and MFeSi₃O₈ crystals, the quadrupole splitting became wider and approached to 0.73 mm s⁻¹. Such a variation was not observed for glasses. These results suggest that a larger number of non-identical sites exist in iron sodium silicate glasses than in the corresponding crystals.     

Crystallization of In2O3 by vapor reaction

Crystallization of In₂O₃ occured in closed porcelain crucibles in air at 960–1200°C by vapor phase reaction of In₂O or In vapor with the oxygen diffusing into the system. The In₂O or In vapors were thermally generated from mixtures such as graphite/In₂O₃, graphite/In, In₂O₃/In and graphite/In₂O₃/In. The graphite/In₂O₃ system at a mole ratio of 30/1 and 1000°C produced yellow, transparent needle crystals with a maximum size of 0.5 X 0.5 X 8 mm and electrical resistivity of 5.5 X 10^-2 ω cm at 25°C.     

Experimental observation of the surface roughening transition in vapor phase growth

The surface roughening transition has been observed in growth from the vapor phase in both C₂Cl₆ and NH₄Cl. Both these materials are plastic crystals which have cubic structures and sublime at atmospheric pressure rather than melting. The surface roughening transition was detected by observing changes in the growth morphology in these two materials. In C₂Cl₆ the roughening transition is approximately at 100°C where the equilibrium vapor pressure is 40 mm, and in NH₄Cl it is at approximately 365°C and 3 atm pressure.     

A new technique for the growth of superconducting YBa2Cu3O6 + δ crystals completely separated from flux

Growth of completely flux-separated YBa₂Cu₃O_{6 + δ} (referred to as 123 phase) crystals using a novel technique is described. The technique employs a modification of the seed pulling method commonly used in crystal growth. The crystals are grown in the temperature range of 960–1000°C using a BaCuO₂ flux. A 123 flux ratio of 1:5 is maintained. Photographs of the crystals and photomicrograph of the surfaces are presented to show complete flux-separation of the crystals measuring 6 mm × 3 mm × 1 mm. The Raman spectra recorded on the as-grown crystals show that they are in the tetragonal phase. Magnetic susceptibility measurements on crystals annealed in an oxygen atmosphere show a superconducting transition starting at 71 K. The present technique offers a possibility of growing large, completely flux-separated crystals of 123 for superconductivity research.     

Crystal growth and structure of MnGa2Te4

Single crystals of MnGa₂Te₄ were grown from the melt using the directional freezing technique. They crystallize in the monoclinic system, a=11.999(3), b=11.999(3), c=24.922(6) Å, β=104.01(2)°, Z=16 MnGa₂Te₄ units, space group C2/c. The structure was solved by direct methods and refined to R_w=0.035 for 791 observed reflections and to R_w=0.062 for 3067 independently measured reflections. Te atoms form an arrangement which is a superlattice of anion lattice of β-Cu₂HgI₄. On the contrary, the same model does not conform cation lattice, because 1/3 of metal atoms occupy positions displaced from tetrahedral sites.     

A new method for fabricating water repellent silica films having high heat-resistance using the sol–gel method

There has been a great demand in the field of kitchen appliances to develop transparent water repellent films which have high heat-resistance around 300°C. However, those films have not been obtained by conventional sol–gel methods. In this paper, we propose a new method for fabricating transparent water repellent films with high heat-resistance using the sol–gel method, in which silicon or germanium substrates were coated with a solution including tetraethoxysilane (Si(OC₂H₅)₄) and (2-perfluorooctyl)ethyltrimethoxysilane (CF₃(CF₂)₇C₂H₄Si(OCH₃)₃), followed by ‘ammonia-treatment' and annealed at 300°C. The contact angles of water on the ammonia-treated film maintained its initial value, 110° after the heat treatment at 300°C for 250 h while those on the untreated film decreased to 70°, indicating that the ammonia-treatment improves heat-resistance on the film. The mechanism of ammonia-treatment was inferred from FT-IR results; the ammonia-treatment should accelerate hydrolysis and polymerization of FAS and TEOS molecules, resulting in high density of siloxane bonds between FAS and silica glass. These bonds suppress the evaporation of FAS molecules from the film during the heat treatment at 300°C, thus the film has high heat-resistance.     

Contributions on the thermal behaviour of sulfates XI. On the chemical vapour transport of Fe2(SO4)3 with HCl; thermochemical calculations and experimental results

Using HCl as a transport agent, well-shaped crystals of rhombohedral Fe₂(SO₄)₃ with edge length up to 1 mm were formed in the less hot zone of a silica ampoule. The dependence of the deposition rate on the mean transport temperature for a constant concentration of the transport agent (C = 4.5 × 10⁻² mmol HCl/cm³) shows a distinct maximum at = 560°C. Additionally, the influence of the concentration of the transport agent at a constant temperature gradient was investigated. On the basis of thermochemical calculations, an explanation of the observed transport behaviour is given in the present paper.     

Crystallization habit of calcium carbonate in presence of sodium dodecyl sulfate and/or polypyrrolidone

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 coexisted 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.     

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.     

Growth and morphology of ruby crystals with unusual chromium concentration

Single crystals of ruby have been obtained from fluxed melts based on the systems Li₂O–MoO₃, Li₂O–WO₃, Na₂O–WO₃, 2PbO–3V₂O₅, PbO–V₂O₅–WO₃, PbF₂–Bi₂O₃ and Na₃AlF₆ by both the TSSG method and spontaneous crystallization at the temperatures 1330–900 °C. Al₂O₃ solubility has been measured for the flux composition of 2Bi₂O₃–5PbF₂ in the temperature range 1200–1000 °C and dissolution enthalpy has been defined as 29.4 KJ/Mol. The composition of grown crystals was studied by electron microprobe analysis. The synthetic ruby contains from 0.51 to 6.38 at% of chromium admixture depending on the crystal growth conditions. Experimental results on growth conditions, composition and morphology of grown crystals are presented for each flux and temperature interval.     

Structural characterization of amorphous silicon nitride by molecular dynamics simulation

Computer simulation, using the molecular dynamics (MD) technique, has been carried out on amorphous silicon nitride (a-Si₃N₄) with simple Busing-type potentials. From the MD simulation, the following points have been deduced. (1) The average Si---N bond length obtained from MD results is r_Si---N=1.74 Å, and its coordination number, N_Si---N, is 3.95. The bond angles around a Si and a N atom, N---Si---N and Si---N---Si, are found to be 109.8° ± 12.36° and 127.08° ± 16.63°, respectively. The N---Si---N value obtained is in very good agreement with the tetrahedral bond angle (= 109.47°). Hence, the short-range structural arrangement of a-Si₃N₄ comprises tetrahedral SiN₄ units. The MD results presented in this study also indicate that there exist only a small number of defects such as dangling bonds. (2) These MD results are in good agreement with the reported X-ray and neutron data. The a-Si₃N₄ structure can be reproduced by the MD simulation given in this study.     

Microanalytical study of Er-doped LiNbO3 crystals obtained by Er–Li ion exchange

Erbium-doped lithium niobate (LiNbO₃) crystals were produced by Er–Li ion exchange (IE) process. The role of the process parameters such as exchange time and temperature, crystal cut direction, composition and heating rate of the Er ions liquid source was investigated by means of secondary ion mass spectrometry, X-ray diffraction (XRD) and microluminescence techniques. We demonstrated that Er effective diffusion coefficient is two orders of magnitude greater with respect to the thermal diffusion from Er film. We observed that no Li deficient phase can be achieved and that active Er ions are homogeneously incorporated in the substrate. The method is suitable for Er doping of LiNbO₃ crystals at relative low temperature (from 570°C to 650°C).     

Characteristic crystal growth from amorphous WO3 film by vacuum heating

Selective growth of WO₂, W and WO_3−x crystals from amorphous WO₃ film by vacuum heating at 400–900°C was clarified. The grown WO_3−x crystals were incommensurate structure based on crystallographic share structure. The growth process of WO₂ crystal in the amorphous film was directly observed at high temperature in the electron microscope. The growth front of the WO₂ crystal consumes WO₃ microcrystallites with various orientations. The growth speed of the WO₂ depended on WO₃ microcrystallites orientation. The origin of the wavy growth front of WO₂ was due to an orientation dependence of the WO₃ microcrystallites.     

Growth and properties of Pb[(Zn1/3Nb2/3)0.91Ti0.09]O3 single crystals directly from melt

Pb[(Zn_1/3Nb_2/3)_0.91Ti_0.09]O₃ (PZNT91/9) single crystals were grown by a modified Bridgman method directly from melt using an allomeric Pb[(Mg_1/3Nb_2/3)_0.69Ti_0.31]O₃ (PMNT69/31) single crystal as a seed. X-ray diffraction (XRD) measurement confirmed that the as-grown PZNT91/9 single crystals are of pure perovskite structure. Electrical properties and thermal stabilization of PZNT91/9 crystals grown directly from melt exhibit different characters from those of PZNT91/9 crystals grown from flux, although segregation and the variation of chemical composition are not seriously confirmed by X-ray fluorescence analysis (XPS). The [0 0 1]-oriented PZNT91/9 crystals cut from the middle part of the as-grown crystal boules exhibit broad dielectric-response peaks at around 105 °C, accompanied by apparent frequency dispersion. The values of piezoelectric constant d₃₃, remnant polarization P_r, and induced strain are about 1800–2200 pC/N, 38.8 μC/cm², and 0.3%, respectively, indicating that the quality of PZNT crystals grown directly from melt can be comparable to those of PZNT91/9 single crystals grown from flux. However, further work deserves attention to improve the dielectric properties of PZNT crystals grown directly from melt. Such unusual characterizations of dielectric properties of PZNT crystals grown directly from melt are considered as correlating with defects, microinhomogeneities, and polar regions.     

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.     

A simple method to synthesize single-crystalline β-wollastonite nanowires

The single-crystalline β-wollastonite (β-CaSiO₃) nanowires were prepared via a simple hydrothermal method, in the absence of any template or surfactant using cheap and simple inorganic salts as raw materials. Xonotlite [Ca₆(Si₆O₁₇)(OH)₂] nanowires were first obtained after hydrothermal treatment at a lower temperature of 200 °C for 24 h, and after being calcinated at 800 °C for 2 h, xonotlite nanowires completely transformed into β-wollastonite nanowires and the wire-like structure was preserved. The synthesized β-wollastonite nanowires had a diameter of 10–30 nm, and a length up to tens of micrometers, and the single-crystalline monoclinic parawollastonite structured β-wollastonite was identified by XRD with the space group of P2₁/a and cell constants of a=15.42 Å, b=7.325 Å, c=7.069 Å and β=95.38°. A possible growth mechanism of β-wollastonite nanowires was also proposed. The advantages of this method for the nanowire synthesis lie in the high yield, low temperature and mild reaction conditions, which will allow large-scale production at low cost.     

Effect of CaO on the surface morphology and strength of water soaked Na2O–B2O3–Al2O3–SiO2 vitrified bond

The surface morphology of Na₂O–B₂O₃–Al₂O₃–SiO₂ vitrified bond with and without calcium oxide was studied by soaking vitrified bonded microcrystalline alumina composites in water. The content of water introduced to the vitrified bond was determined by thermal gravity analysis, and the effects of water and calcium on the phase separation and nucleation of the vitrified bond were investigated using scanning electron microscope and energy-dispersive X-ray spectrometer. Soaked in water for 72 h, the Na₂O–B₂O₃–Al₂O₃–SiO₂ vitrified bond presented a porous surface, and its bending strength declined with increasing sintering temperature. However, the Na₂O–CaO–B₂O₃–Al₂O₃–SiO₂ vitrified bond was more durable against aqueous coolant even needle-shape crystals were found clustered on the surface of the vitrified bond. The crystals were enriched with aluminosilicate tested by energy-dispersive X-ray spectrums. The appearance of crystals lessened the dissolution of the vitrified bond and made the bending strength increase in the sintering temperature region between 870 °C and 930 °C.     

Growth and raman scattering of aluminium gallium orthophosphate piezoelectric crystals

A new series of non-ferroelectric crystals, the piezoelectric solid solution aluminium gallium orthophosphate Al_1-xGa_xPO₄ (AGP, 0 < x < 1) system has been successfully developed by a hydrothermal method. The AGP crystal with X = 0.10 shows a phase transition temperature T_−β = 587 ± 3 °C with a cell parameters A = b = 0.49386(3) and C = 1.09563(2) nm. Raman spectra including directional dispersion in AGP are similar to those from -AIPO4 and -quartz crystals, indicating all of them belong to an isomorphic family, the short-range interaction being dominant in AGP. Comparison with -AIPO4 crystals, there exists an apparent red shift of the mode frequency and a smaller TO/LO mode splitting of the E species in the AGP crystals.     

Effect of lattice oxygen on optical absorption, radiation hardness and thermally stimulated luminescence of BaF2 crystal

The influence of the presence of BaO impurity on the optical absorption, radiation hardness and thermally stimulated luminescence of BaF₂ has been investigated. The presence of oxygen impurity gives rise to three absorption bands in the UV region, peaking around 220, 280 and 335 nm. Further, the impurity is found to be detrimental to crystal hardness against ionizing radiations. The thermally stimulated luminescence (TSL) has been studied from gamma-irradiated crystals containing different fractions of BaO impurity. Four prominent glow peaks around 100°C (peak I), 150°C (peak II), 220°C (peak III) and 290°C (peak IV) are observed for crystals containing BaO impurity concentrations lower than 0.5% (by wt). For crystals containing higher impurity concentrations, two additional peaks around 75°C and 260°C are also observed. The kinetics of TSL emission is observed to be of first order, implying that the absorption and the emission centers responsible for TSL are the same. The normalized TSL output for peak I is found to vary linearly with the concentration of oxide impurity. This fact can be utilized to detect the presence of minute amounts of oxygen in BaF₂ lattice, which is crucial to the growth of crystals exhibiting high radiation hardness.