Exposure of high index facets in KDP crystals

A series of KDP crystals doped with WO₄^2‐ additive was grown by using rapid growth method. WO₄^2‐ additive inhibited the growth of (100) faces and made (100) faces tapering. With high additive concentration, two adjacent (100) faces twisted towards their intersecting crystal edge and (100) faces became twisting. Moreover, high index facets of (512) were exposed when the additive concentration was 500 ppm. The element analysis suggested that WO₄^2‐ was prone to being incorporated with (100) face. The growth kinetics of (100) face testified that WO₄^2‐ played an inhibited role. The AFM investigation on (100) face indicated WO₄^2‐ could impede step bunching. High concentration of WO₄^2‐ could kink the terrace of the macro‐steps and create another series of macro‐steps. The motion direction of the new creative steps was vertical to that of the original steps. When the motions of the vertical steps were both inhibited by WO₄^2‐, the steps would become tapering and (100) face would twist, which ultimately led to the exposure of (512) facets. (© 2011 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)     

Growth defects in a PZNT93/7 crystal prepared by directional solidification

Novel relaxor ferroelectric crystal 0.93Pb(Zn_1/3Nb_2/3)O₃‐0.07PbTiO₃ (PZNT93/7) with dimensions about Ø40× 70 mm³ was obtained by directional solidification technique. The growth defects of the crystal were investigated. Rocking curve analysis revealed the crystalline quality of PZNT93/7 crystal was not perfect and the FWHM value was measured to be about 0.7°. Some pits and oxide particles in micro‐size were formed in the crystal due to the growth conditions. A series of growth steps parallel to (001) face were observed which were attributed to the growth behavior. Moreover, it was found the average chemical composition of the crystal was deviated slightly to the stoichiometric value of PZNT93/7. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Investigation on growth defects in Pb(Zn1/3Nb2/3)O3‐PbTiO3 crystals

Relaxor ferroelectric crystal (1‐x)Pb(Zn_1/3Nb_2/3)O₃‐xPbTiO₃ (PZNT) with x=0.07 (PZNT93/7) has been grown by the vertical Bridgman method from the high temperature solution of PZNT‐PbO system. The growth defects, such as nucleation core, inclusions, boundaries and particles, were investigated by optical microscope and scanning electron microscope. Sub‐structures were found in the flux inclusions and the lack of ZnO component in PZNT crystals was attributed to the existence of ZnO particles in the inclusions. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Experimental Study of Interface Inversion of Tb3ScxAl5‐xO12 Single Crystals Grown by the Czochralski Method

Thermal conditions and rotation rate were examined experimentally for obtaining a flat interface growth of high melting‐point oxide (Tb₃Sc_xAl_5‐xO₁₂ ‐ TSAG) by the Czochralski method. The critical crystal rotation rate can be significantly reduced, of about twice at low and very low temperature gradients comparing to medium temperature gradients in the melt and surroundings of the crystal. The interface shape of TSAG crystals is not very sensitive on crystal rotation rate at small rotations and becomes very sensitive at higher rotations, when the interface transition takes place. The range of crystal rotation rates during the interface transition from convex to concave decreases with a decrease of temperature gradients. At low temperature gradients interface inversion crystals takes place in very narrow range of rotation rates, which does not allow one to growth such crystals with the flat interface. Even changing crystal rotation rate during the growth process in a suitable manner did not prevent the interface inversion from convex to concave and thus did not allow to obtain and maintain the flat interface.     

Solution growth and morphology of CH3NH3PbBr3 single crystals in different solvents

In this work, large‐sized CH₃NH₃PbBr₃ single crystals were successful grown using solution evaporation method with hydrohalic acid and N, N‐Dimethylformamide (DMF) as solvent respectively. The lattice parameters of cubic CH₃NH₃PbBr₃ were estimated using XRD method. The solubility of CH₃NH₃PbBr₃ in hydrobromic acid was determined at the temperature range between 20 °C–90 °C. A special micro‐solution crystallizer was designed to in‐situ study the morphology of CH₃NH₃PbBr₃ crystal. The largest crystal face was indexed by the XRD patterns and it would be {110} for CH₃NH₃PbBr₃ grown from HBr solution and {100} from DMF solution. The results show that solvent would affect the morphology and crystal habit greatly during crystal growth from solution.     

Selective etching of ZnTe in HF:H2O2:H2O solution: Interpretation of extended defect‐related etch figures

HF:H₂O₂:H₂O solution (40%wt.HF: 30wt.%H₂O₂: H₂O, 3:2:1 by volume) was used to reveal extended defects (line, face and volume defects) in bulk ZnTe crystals grown from Te solution. The etch patterns were analyzed based on their size, shape and distribution. The etch figures, both in the shape of pits and hillocks with high resolution, show forms controlled by the symmetries of the respective faces were produced. Two different sizes of pits were observed, the larger‐size pits correspond to dislocations penetrating the surface, however, the smaller‐size texture pits are produced on the defect‐free region, which serve as standard pits on respect faces. The face defects, such as grain boundaries, sub‐grain boundaries, dislocation walls, twins and stacking faults, can be all displayed clearly. Another essential feature of the etchant is that, it can effectively dissolve Te‐rich phase (Te inclusion/precipitates), which makes it promising to reveal the shape of this volume defect.     

Rapid growth of α-LiIO3 crystal

A fundamental possibility of significantly increasing the growth rate of α-LiIO₃ crystals without the formation of visible defects in them is demonstrated. The corresponding equipment is designed and a technique for obtaining intermediate-size samples is developed. The crystals grown with an average rate of up to 4 mm/days along the Z axis are of high enough quality to be used as materials of optical elements for laser frequency doubling. α-LiIO₃ crystals have been grown both in an open volume via natural faceting and in a rectangular habit, where growth occurs basically through the pyramid (101) face. It is shown that that amount of limiting impurities in the raw material used can be reduced and that the applicability of this material for rapid growth can be verified.     

Characterization of a Flux-grown NdxY1-xAl3(BO3)4 Crystal by X-ray Projection Topography

Nd_xY_1-xAl₃(BO₃)₄ (NYAB) single crystal was grown by the flux method using K₂CO₃ MoO₃ as a solvent. By x-ray projection topography, the defects on a (0001) slice of the NYAB crystal are investigated. It is found that the main grown-in defects in NYAB crystal are growth bands, growth sector boundaries and inclusions. The formation of defects is discussed and methods to reduce the defects are proposed.     

The microstructure and magnetic property of TiO2‐terminated SrTiO3 substrate selected growth cubic phase CaRuO3 film

CaRuO₃ thin films with various thicknesses were synthesized by pulsed laser deposition respectively on SrTiO₃ substrates with SrO‐ and TiO₂‐termination. The microstructure of these films was studied by transmission electron microscopy. The results demonstrate that the CaRuO₃ thin films grown on TiO₂‐terminated substrates show quite uniform morphology, whilst they do the facet morphology when the substrates are SrO‐terminated. In addition, there is a 5∼7 unit‐cell‐thickness cubic CaRuO₃ layer in the films grown on TiO₂‐terminated substrates. The measured ferromagnetic hysteresis loop is attributed to the cubic CaRuO₃ layer, which is supported by a first‐principles calculations. On the contrary, there is free of cubic CaRuO₃ layer in samples grown on SrO‐terminated substrates. The crystallographic domains, the orientation relationship between domains and substrates and crystal defects in these films were studied as well. The different growth mechanism of CaRuO₃ on SrO‐ and TiO₂‐terminated SrTiO₃ substrates may be correlated with the selective nucleation and growth.     

Polarization switching in (CH3NH3)5Bi2Cl11 ferroelectric crystals

The polarization switching in methylammonium chlorobismuthate, (CH₃NH₃)₅Bi₂Cl₁₁, single crystal was investigated by optical observations of the domain structure and switching current registration. It is shown that defects introduced during crystal growth influence the polarization switching kinetics. For the analysis of switching current data the statistical Avrami model of phase transformation kinetics was employed. Direct observation of the domain structure enabled us to verify the assumptions of the Avrami model in the case of non‐uniform (CH₃NH₃)₅Bi₂Cl₁₁ crystals. It is found that application of this model to non‐uniform crystals can yield physically unclear values of some fitting parameters; e.g. the effective domain growth dimension is not constant with respect to the electric field. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of SiO32‐ impurity on growth habit of potassium dihydrogen phosphate crystal

By altering the concentration of silicate (SiO₃^2‐) impurity in the solution, a series of potassium dihydrogen phosphate (KDP) crystals was obtained by the conventional temperature cooling and the rapid growth methods, respectively. It was observed that the presence of SiO₃^2‐ made KDP crystals tapering in conventional cooling method, while more SiO₃^2‐ induced inclusions at prismatic sectors in the rapid growth method. Laser‐polarization‐interference results showed that SiO₃^2‐ extended the dead zone and reduced the growth rate of (100) face of KDP crystals. The negative influence of SiO₃^2‐on the growth was considered absolutely similar to the effect of cations. It was also suggested that the stability of solution doped with SiO₃^2‐ was improved without seed crystals, while it was destructed with seed crystals. The inhibition mechanism was analyzed in terms of SiO₃^2‐ absorption on (100) face. (© 2010 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)     

SQUID magnetometry,EPR and XPS characterization of Y3Al5O12: Co,Si single crystals

Single crystals of garnet Y₃Al₅O₁₂ (YAG): Co and Co, Si were grown by Czochralski method as materials for optoelectronic applications. Silicon doping is responsible for the change of the Co³⁺ ions into Co²⁺ in order to keep charge neutrality of the material and for a coloration of materials. Magnetization and Electron Paramagnetic Resonance measurements show that the most cobalt ions in the silicon co‐doped crystals were Co²⁺ in octahedral positions. Estimated concentration of the Co²⁺ ions were close to Si⁴⁺ nominal concentration. A little excess of Co²⁺ may be ascribed to defects present in the crystals. For the crystal doped only with Co, the concentration of Co²⁺ was about 13% of the nominal Co amount and might be caused by crystal defects. X‐ray Photoelectron Spectroscopy measurements exhibit aluminium deficiency. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Lattice disorder and optical absorption of PbTiO3 crystals

The electric conductivity and the optical absorption of PbTiO₃ crystals are explained by the existence of Pb³⁺ ions and free holes as electronic defects and of O^– vacancies and interstitials as ionic anti-Frenkel defects. The absorption band at 475 nm is caused by Pb³⁺ ions and produces the yellowish or brownish colour of the crystals. Using fluoridic fluxes instead of oxidic fluxes for the crystals growth a small part of O^– ions is replaced by F⁻ foreign ions. This substitution diminishes the Pb³⁺ ion content and causes an increased optical transmission of the PbTiO₃ crystals.     

The influence of Yb3+ concentration on Yb:YAl3(BO3)4

The Yb:YAl₃(BO₃) ₄ crystals with different Yb³⁺ doping concentration have been grown by the flux method. The lattice parameters and decomposition of the Yb:YAl₃(BO₃)₄ crystal with different Yb³⁺ doping concentration were measured by X‐ray and DTA method. The transmission and fluorescence spectra of Yb³⁺:YAl₃(BO₃)₄ crystal have been measured. The growth defects of Yb_xY_1‐xAl₃(BO₃)₄ crystals were also detected by using the chemical etching method. The results show that the ytterbium concentration influences these properties of Yb:YAl₃(BO₃)₄. As the Yb³⁺ concentration increased, the crystal lattice parameter was decreased. At high doping level, the absorption peak concerned at about 980 nm shift to short wavelength. It is also found that the perfection of Yb:YAl₃(BO₃) ₄ crystal with low Yb³⁺ doping concentration is better than that with high Yb³⁺ concentration. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

An effective growth method to improve the homogeneity of relaxor ferroelectric single crystal Pb(In1/2Nb1/2)O3‐ Pb(Mg1/3Nb2/3)O3‐PbTiO3

Compositional segregation usually has negative effects on the growth of solid solution ferroelectric single crystals of Pb(In_1/2Nb_1/2)O₃‐Pb(Mg_1/3Nb_2/3)O₃‐PbTiO₃ (abbr. PIN‐PMN‐PT or PIMNT). A modified Bridgman method was adopted in this work to control the segregation and improve the compositional homogeneity significantly. The characteristic of this work is to use multiround growths and gradient composition raw materials in order to keep the PbTiO₃ concentration constant during the crystal growth. As an example, the two‐round growth of ternary PIN‐PMN‐PT single crystal is conducted in the same Pt crucible with gradient raw materials, where the first‐round boule was used as the seed crystal for the second‐round growth. Our results show that the as‐grown (Ф80 mm × 270 mm) PIN‐PMN‐PT crystals exhibit higher phase transition temperatures (T_c∼180 °C, T_r/t∼110 °C) and larger coercive field (E_c∼5–5.5 kV/cm), which are much better than the performances of Pb(Mg_1/3Nb_2/3)O₃‐PbTiO₃ crystals, and similar dielectric and piezoelectric performances (ε∼5000, tanδ∼1.25%, d₃₃∼1500 pC/N, k_t∼60%). And about 85 percent of the crystal boule grown by the two‐round growth technique could maintain its compositions around the morphotropic phase boundary.     

Effect of Mn(II) ions on the growth of ammonium oxalate monohydrate crystals from aqueous solutions: II. Growth kinetics

The experimental results of the effect of concentration of Mn(II) ions on the growth kinetics of different faces of ammonium oxalate monohydrate single crystals from aqueous solutions at a constant temperature and different predefined supersaturations are described and discussed. It was observed that: (1) at a given supersaturation σ, Mn(II) ions lead to a decrease in the growth rates of different faces of AO crystals, (2) the growth of a particular face of the crystals occurs above a critical supersaturation σ_d but there is also another supersaturation barrier σ* when the rate abruptly increases with σ, (3) the values of σ_d and σ* increase with increasing concentration of the impurity, and (4) the values of σ_d depend on the growth kinetics of a face but those of σ* are independent of face growth kinetics. The experimental R(σ) data for different Mn(II) concentrations c_i were analysed according to the model involving complex source of cooperating screw dislocations and concepts of instantaneous and time‐dependent impurity adsorption. It was found that: (1) for a given face the differential heat of adsorption Q_diff is higher during instantaneous impurity adsorption than that during time‐dependent adsorption, and (2) the values of Q_diff involved during instantaneous adsorption are related with face growth kinetics but those during time‐dependent adsorption are independent of face growth kinetics.     

Growth and characterization of ferroelectric‐ferroelastic Tb2(MoO4)3 crystals

Transparent and nearly colorless ferroelectric‐ferroelastic β′‐Tb₂(MoO₄)₃ (TMO) single crystals have been grown by the Czochralski (CZ) method. The single crystal structure was investigated by X‐ray powder diffraction and was shown to be a single phase with the structure similar as the β′‐Gd₂(MoO₄)₃ crystal. The optical transparency of the TMO crystal has been measured and the crystal is almost transparent in the visible and near infrared regions. The defects of TMO crystal were evaluated by etching technique and the ferroelectric domain structures were observed by an optical microscope. A high‐resolution X‐ray diffraction analysis demonstrates that the as‐grown TMO crystal possesses relatively high optical quality. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Experimental study of bubble generation during β‐BaB2O4 single crystal growth

The generation of bubble‐inclusions during BaB₂O₄ (BBO) crystal growth from high temperature solution has been optically observed by an in situ observation technique. It was found that bubbles are formed from the peripheries of some hexagonal defects in the (0001) plane of the growing crystal, which may be caused by the evaporation of the air‐opened interface at the high temperature. In addition, atomic force microscope (AFM) was used to investigate the distribution of bubbles. Results revealed that the bubble generation and distribution depend strongly on the microscopic structure of the interface: on a rough interface, bubbles are easily formed and grow rapidly; however, they are greatly suppressed by step trains on a vicinal interface. In the latter case, the height value of a bubble is close to that of the step, which is in the order of several tens of nanometers. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)