Perovskite chalcogenides are gaining substantial interest as an emerging class of semiconductors for optoelectronic applications. High-quality samples are of vital importance to examine their inherent physical properties. We report the successful crystal growth of the model system, BaZrS3 and its Ruddlesden–Popper phase Ba3Zr2S7 by a flux method. X-ray diffraction analyses showed the space group of Pnma with lattice constants of a = 7.056(3) Å, b = 9.962(4) Å, and c = 6.996(3) Å for BaZrS3 and P42/mnm with a = 7.071(2) Å, b = 7.071(2) Å, and c = 25.418(5) Å for Ba3Zr2S7. Rocking curves with full width at half maximum of 0.011° for BaZrS3 and 0.027° for Ba3Zr2S7 were observed. Pole figure analysis, scanning transmission electron microscopy images, and electron diffraction patterns also establish the high quality of the grown crystals. The octahedral tilting in the corner-sharing octahedral network is analyzed by extracting the torsion angles.

A low-temperature thin-film processing method for BaTiO3 is studied to understand microstructure development in the presence of a liquid-forming phase. The addition of a eutectic barium borate flux is found to prevent nucleation of BaTiO3 during pulsed-laser deposition on sapphire substrates at 400 °C. Subsequent thermal annealing above the flux's eutectic temperature dramatically enhances the film's microstructural development and crystallinity. A secondary reaction phase of barium aluminate is identified at the substrate interface in both unfluxed and fluxed films, although it is more pronounced in the fluxed films. This barium aluminate phase in conjunction with the liquid flux serves to nucleate {111} twins in the barium titanate, which subsequently lead to enhanced grain growth. The resulting large-grained and dense thin films result in markedly improved dielectric properties.

CZTS monograin powder samples were synthesized in CdI2 as flux material. The obtained materials were analysed by EDX, SEM, and Raman methods. It was found that Cd from flux was incorporated into the formed compound leading to the formation of solid solution Cu2Zn1-xCdxSnS4. The content of Cd in the compound was studied in the dependence of synthesis temperature and time. It was found that Cd content in the formed Cu2Zn1-xCdxSnS4 did not depend on synthesis duration at constant temperature and increased with temperature. The activation energy of the Cd incorporation process was estimated as 17.5 ± 2 kJ/mol.

Fine-sized powders of BaSi3Al3O4N5:Eu2+ phosphors with high stability and improved photoluminescence properties were successfully synthesized by the traditional solid-state reaction method under a reductive atmosphere using BaF2-fluxing additives in the raw powder mixture. The produced phosphors had strong blue emission under excitation in ultraviolet (UV) and vacuum ultraviolet (VUV) light, due to the 4f 5d–4f7 transition of Eu2+ ions. X-ray diffraction, scanning electron microscopy, XANES, and the photoluminescence (PL) spectra under UV and VUV were used to characterize the as-received samples. The experimental results showed that the addition of BaF2 flux improved the crystalline regime and the PL properties of the produced phosphors. Most significantly, it allowed control of the particle size and particle size distribution in the final powders but did not jeopardize the high thermal and chemical stability of the phosphors produced. With the modification of the BaF2 flux, the blue-emitting BaSi3Al3O4N5:Eu2+ phosphors will show excellent packing and coating properties and could be a good candidate for the light-emitting diodes and plasma display panels.

The powder pattern of Rb3Ta5O14 is reported here for the first time. Single crystals of Rb3Ta5O14 of 0.1–0.2 mm in size were grown using a RbCl flux at 1100 °C. The Rb3Ta5O14 powders were synthesized at 1200 °C by firing the Rb2CO3 and Ta2O5 raw materials with starting Rb/Ta ratios ranging from 0.450 to 0.800. The products with Rb/Ta ratios between 0.550 and 0.633 contained almost pure Rb3Ta5O14 with Rb/Ta ratio of 0.600, while those with Rb/Ta ratio larger than 0.677 also contained the α form of Rb4Ta6O17 with the Rb/Ta ratio of 0.677. Past studies of the synthesis and characterization of Rb4Ta6O17 should be carefully examined in the light of possible coexistence with Rb3Ta5O14, because the former structure has not been completely solved, and thus the powder pattern is inaccurate, while the presence of the latter had not been known until the present study.

Level set methods have been used for Solid phase epitaxial regrowth, etching and deposition.This study is to model the growth of nickel silicide accurately using the level set method. NiSi growth has been observed to follow a linear-parabolic law which takes into account both diffusion and interfacial reaction. This linear-parabolic system is very similar to the Deal and Grove model of SiO2 growth. This model uses similar diffusion transport and reaction rate equations. This simulation models the growth of silicide coupling diffusion solutions to level-set techniques. Dual level sets have been used for top and bottom interface propagation of silicide; velocities were estimated based on nickel concentrations at both interfaces as well as diffusivity and reaction rate of nickel. This is important to predict precise shape of silicide that will allow current crowding and field focusing effects to be modeled in transport out of the intrinsic device into the contacting layers. These simulation models can be used for latest technology nodes at 45, 32, 22nm and special devices such as FinFET’s etc. The level set method is successfully implemented and verified in Florida Object Oriented Process Simulator and growth shapes matches well with the literature Transmission Electron Microscopy data.

ZnO bulk crystals can be grown by several methods. 1) From the gas phase, usually by chemical vapor transport. Such CVT crystals may have high chemical purity, as the growth is performed without contact to foreign material. The crystallographic quality is often very high (free growth). 2) From melt fluxes such as alkaline hydroxides or other oxides (MoO3, V2O5, P2O5, PbO) and salts (PbCl2, PbF2). Melt fluxes offer the possibility to grow bulk ZnO under mild conditions (<1000°C, atmospheric pressure), but the crystals always contain traces of solvent. The limited purity is a severe drawback, especially for electronic applications. 3) From hydrothermal fluxes, usually alkaline (KOH, LiOH) aqueous solutions beyond the critical point. Due to the amphoteric character of ZnO, the supercritical bases can dissolve it up to several per cent of mass. The technical requirements for this growth technology are generally hard, but this did not hinder its development as the basic technique for the growth of α-quartz, and meanwhile also of zinc oxide, during the last decades. 4) From pure melts, which is the preferred technology for numerous substances applied whenever possible, e.g. for the growth of silicon, gallium arsenide, sapphire, YAG. The benefits of melt growth are (i) the high growth rate and (ii) the absence of solvent related impurities. In the case of ZnO, however, it is difficult to find container materials that are compatible from the thermal (fusion point Tf = 1975°C) and chemical (required oxygen partial pressure) point of view. Either cold crucible (skull melting) or Bridgman (with reactive atmosphere) techniques were shown to overcome the problems that are inherent to melt growth. Reactive atmospheres allow to grow not only bulk ZnO single crystals, but also other TCOs such as β-Ga2O3 and In2O3.

The crystallographic properties of bulk icosahedral boron arsenide (B12As2) crystals grown by precipitation from molten nickel solutions were characterized. Large crystals (5-8 mm) were produced by dissolving the boron in nickel at 1150°C for 48-72 hours, reacting with arsenic vapor, and slowly cooling to room temperature. The crystals varied in color from black and opaque to clear and transparent. Raman spectroscopy, x-ray topography (XRT), and defect selective etching revealed that the B12As2 single crystals were high quality with low dislocation densities. Furthermore, XRT results suggest that the major face of the plate-like crystals was (111) type, while (100), (010) and (001) type facets were also observed optically. The predominant defect in these crystals was edge character growth dislocations with a <001> Burgers vector, and <-110> line direction. In short, XRT characterization shows that solution growth is a viable method for producing good quality B12As2 crystals.

We have synthesized single crystalline Ba8AlxSix-46 clathrates by using the flux Czochralski (CZ) method with Al-rich melt. The specific electric resistivity, the Seebeck coefficient and the power factor of single crystalline Ba8Al14Si32 were 0.73 mΩcm,70.0μV/K and 6.8×10-4 V2/K2Ωm, respectively. These values are higher than that of single crystalline Ba8Al12Si34 clathrate because of the reduced carrier concentration. It is indicated that Al contents and the carrier concentration of single crystalline Ba8AlxSi46-x can be controlled by using the flux Czochralski method.

An analytical study of the dependence of shear and von-Mises stress distributions, which develop during PVT (Physical Vapor Transport) growth of 4H-SiC, has been executed. The key parameters investigated include thermal conditions of the crystal growth and parameters of the growing boule geometry. The evaluation was conducted via a 24 full factorial DOE (Design of Experiments). Parameters of the growing boule geometry, i.e. seed diameter, growth front height, inclination angle and height of the side surface were set as the DOE factors, while responses were calculated using numerical simulations. It is found that unique SiC boule growth conditions, which simultaneously minimize both the shear stress and von Mises stress magnitudes, cannot be achieved. Optimization of the shear stress distribution favors longer SiC boules with small seed diameters, small expansion angles and flat growth fronts. Alternatively, optimization of von-Mises stress favors short crystals with small seed diameters and small expansion angles but with curved growth fronts. Consequently, optimization of stress components in SiC crystals involves careful investigation of the interaction and compromise of the reaction cell geometry and growth conditions.

Boron carbide crystals ranging in size from 50 microns to several millimeters have been grown from a copper-boron carbide flux at temperatures from 1500°C to 1750°C. The crystal size increased with growth temperature although copper evaporation limited growth at the higher temperatures. Synchrotron X-ray Laue patterns were indexed according to (001) orientation boron carbide structure, indicating the bulk crystals were single crystalline with {001} growth facets. Raman spectrum of boron carbide indicates an improved crystal quality compared to the source powder, but peaks of crystals grown from 11B -enriched source shifted to the lower energy by 1-4 cm−1 from literature values, possibly due to the boron isotope dependency. Five fold symmetry defects and twin planes were common as observed by optical microscope and scanning electron microscope. Raindrop shape etch pits were formed after defect selective etching in molten potassium hydroxide at 600°C for 6 minutes. Typically, the etch pit density was on the order of 106/cm2.

The growth of new phases out of high temperature hydroxide solutions as a means of discovering new materials is discussed. We have succeeded in solubilizing rare earth cations and platinum group metal cations in molten hydroxides and have grown single crystals with a large number of new compositions and new structure types. The use of sealed silver tubes has enabled us to control the water content and, hence, the acidity of the hydroxide melts, and thereby to grow crystals via slow cooling. The synthetic conditions and structures of several new oxides including Ln1-xNa1+xIrO4 (Ln = Gd-Er, Y; x = 0.04-0.26), Ln3RuO7 (Ln = La, Sm, Eu), LnNaPd6O8 (Ln = Tb-Lu, Y) and La9RbIr4O24 are presented.

Agglomerates of aligned crystals of CaxCo2O4 with a layer of CoO2 were grown using a chloride flux technique, and their thermoelectric properties in air were determined. The agglomerates take the form of a very thin flakelike cluster of crystals with a typical size of almost 3 × 2 × 0.07 mm. The values of thermoelectric power along the ab-plane are larger than 200 μV K−1 at temperatures above 873 K and reach almost 300 μV K−1 at 973 K. The temperature dependence of the electrical resistivity along the ab-plane shows bends around 450 and 825 K, and the ln ρab−T−1 curve followed an Arrhenius-type behavior below 450 K. Temperature dependence of thermal conductivity indicated that stacking faults along the c axis induce phonon scattering like that in a misfit-layered structure. The effect of the CoO2 layer on thermoelectric performance is discussed in comparison with related compounds.

We explored a new fluid flux stabilized even in the vacuum condition at high temperature by combinatorial pulsed laser deposition (PLD) approach. A small amount of CuO doped in BiOx was found to effectively stabilize BiOx even in 6 Torr O2 at 800°C. The application of this novel Bi-Cu-O flux to the vacuum process lead to the successful fabrication of a single crystal Bi4Ti3O12 film and the establishment of a more reliable process for preparation of an atomically flat LaAlO3(001) substrate.

Single crystals of Y4PtGa12 have been synthesized and characterized by X-ray diffraction. The compound crystallizes in the cubic Im3m space group with lattice parameters a = 8.530(5) Å. Magnetic property measurements show that Y4PtGa12 does not order magnetically. Structure-property relationships with the isostructural antiferromagnet Tb4PtGa12 are discussed.