搜索结果：Crystal growth & design

We developed a consistent mathematical model for isotropic crystal growth on a substrate covered by the mask material with a periodic series of parallel long trenches where the substrate is exposed to the vapor phase. Surface diffusion and the flux of particles from vapor are assumed to be the main mechanisms of growth. A geometrical approach to the motion of crystal surface in two dimensions is adopted and nonlinear evolution equations are solved by a finite-difference method. The model allows the direct computation of the crystal surface shape, as well as the study of the effects due to mask regions of effectively nonzero thickness. As in experiments, lateral overgrowth of crystal onto the mask and enhanced growth in the region near the contact of the crystal and the mask is found, as well as the comparable crystal shapes. The growth rates in vertical and lateral directions are investigated.

A description is given of the traveling solvent technique, which has been used for the crystal growth of both congruently and incongruently melting materials of many classes of intermetallic, chalcogenide, semiconductor and oxide materials. The use of a solvent, growth at lower temperatures and the zoning process, that are inherent ingredients of the method, can help to grow large, high structural quality, high purity crystals. In order to optimize this process, careful control of the various growth variables is imperative; however, this can be difficult to achieve due to the large number of independent experimental parameters that can be grouped under the broad headings growth conditions, characteristics of the material being grown, and experimental configuration, setup and design.This review attempts to describe the principles behind the traveling solvent technique and the various experimental variables. Guidelines are detailed to provide the information necessary to allow closer control of the crystal growth process through a systematic approach. Comparison is made between the traveling solvent technique and other crystal growth methods, in particular the more conventional stati

Effects of the growth velocity on the crystal growth behavior of Bi_2Sr_2Ca_1Cu_2O_x (Bi-2212) have been studied by floating zone technique. The results show that a necessary condition for obtaining large single crystals along the c-axis is that the solid-liquid interface of a growing rod maintains a stable planar growth front. The planar liquid-solid growth interface tends to break down into a cellular interface, while the growth velocity is higher than 0.25 mm/h. Single crystals of up to 50x7.2x7 mm3 along the a-, b- and caxes have been cut in a 7.2 mm diameter rod with optimum growth conditions. Tconset is 91 K measured by magnetic properties measurement system (MPMS) for as-grown crystals. Optical polarization microscope and neutron diffraction show that the quality of the single crystals is good.

The high-pressure optical floating-zone method enables single crystal growth of the Pmnb high-temperature phase of Li2FeSiO4. The influence of growth conditions on crystal quality, phase homogeneity, and impurity formation in Li2FeSiO4 is studied. The use of different starting materials, i.e., either the P121/n1 or the Pmn21 polymorph, as well as optimization of various growth conditions is investigated. Several mm3-sized high-quality single crystals are obtained by the choice of the Pmn21 polymorph as the starting material. A general challenge of Li2FeSiO4 crystal growth is polymorph control during crystallization. While the temperature gradient at the solid-liquid interface seems to have significant impact on stabilizing the Pmnb high-temperature phase, growth velocity has no evident effect.

Large, high-purity single-crystals of hexagonal BN (h-BN) are essential for exploiting its many desirable and interesting properties. Here, we demonstrate via X-ray tomography, X-ray diffraction and scanning electron microscopy that h-BN crystals can be grown by traveling-solvent floating-zone (TSFZ). The diameters of grown boules range from 3 - 5 mm with lengths from 2 - 10 mm. Tomography indicates variable grain sizes within the boules, with the largest having areas of $\approx$ 1 mm $\times$ 2 mm and thickness $\approx$ 0.5 mm. Although the boules contain macroscale flux inclusions, the h-BN lattice itself is of high quality for samples grown under optimized conditions. The currently optimized growth procedure employs an Fe flux, moderate N$_2$ pressure ($P_{N2} \approx$ 6 bar), and a growth rate of 0.1 mm/h. Raman spectroscopy for an optimized sample gives an average linewidth of 7.7(2) cm$^{-1}$ for the E$_{\mathrm{2g}}$ intralayer mode at 1365.46(4) cm$^{-1}$ and 1.0(1) cm$^{-1}$ for the E$_{\mathrm{2g}}$ interlayer shear mode at 51.78(9) cm$^{-1}$. The corresponding photoluminescence spectrum shows sharp phonon-assisted free exciton peaks and minimal signal in the energy ran

We report on a modified chemical vapor transport (CVT) methodology for the growth of pure and intercalated Zr, Ti, and Hf dichalcogenide single crystals, e.g. ZrTe2, Gd0.05ZrTe2, HfTe2, and Cu0.05TiTe2. While the most common method for CVT growth is carried out in quartz tubes subjected to a temperature gradient between the charge and the growth location, the growth using this isothermal-CVT (ICVT) method takes place isothermally in sealed quartz tubes placed horizontally in box furnaces, using iodine (I2) as the transport agent. The structure and composition of crystals were determined by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), and induced coupling plasma (ICP). The crystals grown with this method can be large, and show excellent crystallinity and homogeneity. Their morphology is plate-like, and the larger dimensions can be as long as 15 mm.

Single crystals of Ruddlesden-Popper nickelates La$_4$Ni$_3$O$_{10}$ were grown by means of the floating-zone technique at oxygen pressure of 20~bar. Our results reveal the effects of the annealing process under pressure on the crystal structure. We present the requirements for crystal growth and show how a reported ferromagnetic impurity phase can be avoided. The different growth and post-annealing processes result in two distinct phases $P2_1/a$ and {\it Bmab} in which the metal-to-metal transitions occur at 152~K and 136~K, respectively.

When calcium titanate crystals are grown from stoichiometric melts, they crystallize in the cubic perovskite structure. Upon cooling to room temperature they undergo subsequent phase transitions to tetragonal and orthorhombic modifications. These phase transitions are disruptive and result in severely damaged crystals. This paper presents differential thermal analysis data for several prospective solvents, with the aim to identify a system offering the possibility to perform crystal growth of undistorted CaTiO$_3$ crystals by crystallizing them significantly below the melting point directly in the low temperature modification. From mixtures CaF$_2$:TiO$_2$:CaTiO$_3$ = 3:1:1 (molar ratio) the growth of undistorted, at least millimeter-sized CaTiO$_3$ crystals is possible.

Single crystal growth of α-Na$_x$MnO$_2$ (x = 0.90) is reported via the floating zone technique. The conditions required for stable growth and intergrowth-free crystals are described along with the results of trials under alternate growth atmospheres. Chemical and structural characterizations of the resulting α-Na$_{0.90}$MnO$_2$ crystals are performed using ICP-AES, NMR, XANES, XPS, and neutron diffraction measurements. As a layered transition metal oxide with large ionic mobility and strong correlation effects, α-Na$_x$MnO$_2$ is of interest to many communities, and the implications of large volume, high purity, single crystal growth are discussed.

An eutectic AlCl$_3$/KCl molten salt method in a horizontal configuration was employed to grow millimeter-sized and composition homogeneous CuFeSe$_2$ single crystals due to the continuous growth process in a temperature gradient induced solution convection. The typical as-grown CuFeSe$_2$ single crystals in cubic forms are nearly 1.6$\times$1.2$\times$1.0 mm3 in size. The chemical composition and homogeneity of the crystals was examined by both inductively coupled plasma atomic emission spectroscopy and energy dispersive spectrometer with Cu:Fe:Se = 0.96:1.00:1.99 consistent with the stoichiometric composition of CuFeSe$_2$. The magnetic measurements suggest a ferrimagnetic or weak ferromagnetic transition below T$_C$ = 146 K and the resistivity reveals a semiconducting behavior and an abrupt increase below T$_C$.

We report a systematic study on the crystal growth of the rare-earth titanates $R_2$Ti$_2$O$_7$ ($R$ = Gd, Tb, Dy, Ho, Y, Er, Yb and Lu) and Y-doped Tb$_{2-x}$Y$_x$Ti$_2$O$_7$ ($x$ = 0.2 and 1) using an optical floating-zone method. High-quality single crystals were successfully obtained and the growth conditions were carefully optimized. The oxygen pressure was found to be the most important parameter and the appropriate ones are 0.1--0.4 MPa, depending on the radius of rare-earth ions. The growth rate is another parameter and was found to be 2.5--4 mm/h for different rare-earth ions. X-ray diffraction data demonstrated the good crystallinity of these crystals. The basic physical properties of these crystals were characterized by the magnetic susceptibility and specific heat measurements.

Single crystals of iridates are usually grown by a flux method well above the boiling point of the SrCl2 solvent. This leads to non-equilibrium growth conditions and dramatically shortens the lifetime of expensive Pt crucibles. Here, we report the growth of Sr2IrO4, Sr3Ir2O7 and SrIrO3 single crystals in a reproducible way by using anhydrous SrCl2 flux well below its boiling point. We show that the yield of the different phases strongly depends on the nutrient/solvent ratio for fixed soak temperature and cooling rate. Using this low-temperature growth approach generally leads to a lower temperature-independent contribution to the magnetic susceptibility than previously reported. Crystals of SrIrO3 exhibit a paramagnetic behavior that can be remarkably well fitted with a Curie-Weiss law yielding physically reasonable parameters, in contrast to previous reports. Hence, reducing the soak temperature below the solvent boiling point not only provides more stable and controllable growth conditions in contrast to previously reported growth protocols, but also extends considerably the lifetime of expensive platinum crucibles and reduces the corrosion of heating and thermoelements of standa

Polycrystalline Ba4NbIr3O12 has recently been shown to be a promising spin liquid candidate. We report an easy and reliable method to grow millimeter-sized single crystals of this trimer based spin liquid candidate material with the actual stoichiometry of Ba4Nb0.8Ir3.2O12. The growth of large crystals is achieved using BaCl2 as flux. The crystals show hexagonal plate-like habit with edges up to 3 mm in length. The structure is confirmed by single crystal X-ray diffraction and is found to be the same as of previously reported phase Ba12Nb2.4Ir9.6O36 [Ba4Nb0.8Ir3.2O12], indeed with a mixed occupancy of Nb/Ir at 3a site. The magnetic and calorimetric study on the individual single crystals confirms the possibility of a spin liquid state consistent with a recent report on a polycrystalline sample

We report the first single crystal growth of the correlated metal LaNiO3 using a high-pressure optical-image floating zone furnace. The crystals were studied using single crystal/powder x-ray diffraction, resistivity, specific heat, and magnetic susceptibility. The availability of bulk LaNiO3 crystals will (i) promote deep understanding in this correlated material, including the mechanism of enhanced paramagnetic susceptibility, and (ii) provide rich opportunities as a substrate for thin film growth such as important ferroelectric and/or multiferroic materials. This study demonstrates the power of high pO2 single crystal growth of nickelate perovskites and correlated electron oxides more generally.

CuFeO$_2$ single crystals up to 50 mm in length and up to 10 mm in diameter were grown by the optical floating-zone method. Stoichiometric polycrystalline rods with a diameter of 6-12 mm were used as feed materials to produce crystals of sufficient size to be used as substrates for the growth of thin films of delafossites. For stable growth along the $c$-axis, low growth rates of 0.4 mm/h are necessary. Due to the incongruent melting behavior of CuFeO$_2$, a stable melt zone requires adjustment of the lamp power during growth. The melting of CuFeO$_2$ is not simply incongruent because the thermodynamic equilibrium includes more than two solid phases and the melt; the gas phase is also involved. The crystals were characterized by X-ray diffraction and X-ray fluorescence measurements.

The heat transfer (conductive, convective, radiative) and the related problems (the unknown phase boundary fluid/crystal, the assessment of the quality of the grown crystals) encountered in the melt and vapour growth of single crystal as well as the corresponding macroscopic models are reviewed. The importance of the adequate description of the optical crystal properties (semitransparency, absorption, scattering, refraction, diffuse and specular reflecting surfaces) and their effect on the heat transfer is stressed. The problems of the code verification and validation are discussed; differences between the crystal growth simulation codes intended for the research and for the industrial applications are indicated.

In this work, we have thoroughly studied the effects of flux composition and temperature on the crystal growth of the BaCu2As2 compound. While Pb and CuAs self-flux produce the well-known α-phase ThCr2Si2-type structure (Z=2), a new polymorphic phase of BaCu2As2 (\b{eta} phase) with a much larger c lattice parameter (Z=10), which could be considered an intergrowth of the ThCr2Si2- and CaBe2Ge2-type structures, has been discovered via Sn flux growth. We have characterized this structure through single-crystal X-ray diffraction, transmission electron microscopy (TEM), and scanning transmission electron microscopy (STEM) studies. Furthermore, we compare this new polymorphic intergrowth structure with the α-phase BaCu2As2 (ThCr2Si2 type with Z=2) and the \b{eta}-phase BaCu2Sb2 (intergrowth of ThCr2Si2 and CaBe2Ge2 types with Z=6), both with the same space group I4/mmm. Electrical transport studies reveal p-type carriers and magnetoresistivity up to 22% at 5 K and under a magnetic field of 7 T. Our work suggests a new route for the discovery of new polymorphic structures through flux and temperature control during material synthesis.

We report the growth of mm-sized Pmnb-Li2FeSiO4 single crystals by means of the optical floating-zone method at high argon pressure and describe the conditions required for a stable growth process. The crystal structure is determined and refined by single-crystal X-ray diffraction. The lattice constants amount to a = 6.27837(3) A, b = 10.62901(6) A and c = 5.03099(3) A at 100 K. In addition, we present high-resolution neutron powder diffraction data that suggest that the slight Li-Fe site exchange seems to be intrinsic to this material. High quality of the crystal is confirmed by very sharp anomalies in the static magnetic susceptibility and in the specific heat associated with the onset of long-range antiferromagnetic order at TN = 17.0(5) K and pronounced magnetic anisotropy for the three crystallographic axes. Furthermore, magnetic susceptibility excludes the presence of sizable amounts of magnetic impurity phases.

Ce3+ doped oxide materials are promising for optical emission in the green spectral range. The growth of CaSc2O4:Ce3+ single crystals is reported here for the first time. Laser heated pedestal growth (LHPG) proved to be suitable for this refractive material, if performed in nitrogen of 99.999% purity. If the oxygen content of the growth atmosphere is substantially larger, Ce4+ is formed, which shows no useful optical emission. If the oxygen content is substantially lower, severe evaporation of calcium impedes stable crystal growth. Thermodynamic equilibrium calculations allowed to describe evaporation of species and cerium dopant charging under different growth conditions. The evaporation could be investigated by quadrupole mass spectrometry of emanating gases and by chemical analysis of fibers with ICP-OES. The congruent melting point was confirmed by DTA at 2110 degrees centigrade. Photoluminescence spectrometry of fibers revealed the dependence of optical emission in the green spectral range on growth conditions.