Incorporation of group III,IV and V elements in 3C–SiC(1 1 1) layers grown by the vapour–liquid–solid mechanism

We report on a comparative investigation of the incorporation of group III, IV and V impurities in 3C–SiC heteroepitaxial layers grown by the vapour–liquid–solid (VLS) mechanism on on-axis α-SiC substrates. To this end, various Si-based melts have been used with addition of Al, Ga, Ge and Sn species. Homoepitaxial α-SiC layers grown using Al-based melts were used for comparison purposed for Al incorporation. Nitrogen incorporation depth profile systematically displays an overshoot at the substrate/epilayer interface for all the layers. Ga and Al incorporations follow the same distribution shape as N whereas this is not the case for the isoelectronic impurities Ge and Sn. This suggests some interaction between Ga/Al and N coming from the high bonding energy between the group III and V elements, which does not exist with Ge and Sn. This is why both incorporate as a cluster. A model of incorporation is proposed taking into account metal-N and metal-C bonding energies together with the solid solubility of the corresponding nitrides.     

The effects of annealing on non-polar (1 1 2¯ 0) a-plane GaN films

Non-polar a-plane (1 1 2¯ 0) GaN films were grown on r-plane sapphire by metal–organic vapor phase epitaxy and were subsequently annealed for 90 min at 1070 °C. Most dislocations were partial dislocations, which terminated basal plane stacking faults. Prior to annealing, these dislocations were randomly distributed. After annealing, these dislocations moved into arrays oriented along the [0 0 0 1] direction and aligned perpendicular to the film–substrate interface throughout their length, although the total dislocation density remained unchanged. These changes were accompanied by broadening of the symmetric X-ray diffraction 1 1 2¯ 0 ω-scan widths. The mechanism of movement was identified as dislocation glide, occurring due to highly anisotropic stresses (confirmed by X-ray diffraction lattice parameter measurements) and evidenced by macroscopic slip bands observed on the sample surface. There was also an increase in the density of unintentionally n-type doped electrically conductive inclined features present at the film–substrate interface (as observed in cross-section using scanning capacitance microscopy), suggesting out-diffusion of impurities from the substrate along with prismatic stacking faults. These data suggest that annealing processes performed close to film growth temperatures can affect both the microstructure and the electrical properties of non-polar GaN films.     

Polar dependence of impurity incorporation and yellow luminescence in GaN films grown by metal-organic chemical vapor deposition

We have investigated the unintentional impurities, oxygen and carbon, in GaN films grown on c-plane, r-plane as well as m-plane sapphire by metal-organic chemical vapor deposition. The GaN layer was analyzed by secondary ion mass spectroscopy. The different trend of the incorporation of oxygen and carbon has been explained in the polar (0 0 0 1), nonpolar (1 1 2¯ 0) and semipolar (1 1 2¯ 2) GaN by a combination of the atom bonding structure and the origin direction of the impurities. Furthermore, it has been found that there is a stronger yellow luminescence (YL) in GaN with higher concentration of carbon, suggesting that C-involved defects are originally responsible for the YL.     

Vacancy defects in bulk ammonothermal GaN crystals

We have applied positron annihilation spectroscopy to study in-grown vacancy defects in bulk GaN crystals grown by the ammonothermal method. We observe a high concentration of Ga vacancy related defects in n-type samples in spite of the low growth temperature, suggesting that oxygen impurities promote the formation of vacancies also through other mechanisms than a mere reduction of thermodynamical formation enthalpy. On the other hand, no positron trapping at vacancy defects is observed in Mg-doped p-type samples, as expected when the Fermi level is close to the valence band and intrinsic defects are dominantly positively charged. Annealing of the samples at temperatures well above the growth temperature is found to change significantly the defect structure of the material.     

The crystal growth and perfection of 2,4,6-trinitrotoluene

Large crystals of TNT were grown from ethyl acetate solution by both temperature lowering and solvent evaporation. The perfection of crystals grown from seeds under carefully controlled conditions was generally higher than those prepared by uncontrolled solvent evaporation. Examination by X-ray topography revealed the crystals to have a characteristic growth induced defect structure comprising growth sectors and boundaries, growth banding, solvent inclusions and dislocations. Twins and stacking faults (SF) were also observed. Many of the defects noted in the topographs can be attributed to impurities. The influence of the highly anisotropic crystal structure on the nature of growth defects is discussed. A structural model proposed to explain twinning and SF formation is partially supported by topographic evidence.     

Study of batch maltitol (4-O-α-d-glucopyranosyl-d-glucitol) crystallization by cooling and water evaporation

It is obvious that maltitol, like other disaccharides, owes some of its functional properties to structural features such as the flexibility of the glycosidic bond and hydrogen bonding and to its aqueous solution physicochemical properties, especially solubility and metastable zone width. This is particularly the case for molecular arrangements, which take place before and during crystallization process. We have previously used FTIR spectra to study structural properties of the maltitol molecule in concentrated solution like molecular associations or changes in conformation [1]. To complement these molecular properties, the different maltitol solution physicochemical properties having a relationship with maltitol–water or maltitol–maltitol interactions like solubility, metastable zone width, viscosity, and density were determined [2]. In this work we used these physicochemical results to optimize maltitol crystallization both by reducing the process duration and by improving the obtained crystal quality. Two strategies have been tested: the optimization of the time/temperature profile during the classical cooling crystallization and the application to maltitol of evaporative crystallization, a process usually used for sucrose preparation. The obtained results mainly showed remarkable difference in crystal mean size and crystal size distribution when the cooling profile was modified. On the other hand, evaporative crystallization was shown to make it possible to lower considerably the crystallization time compared to the cooling process but crystal morphological properties seem to be considerably modified by evaporation.     

Investigation of nonpolar (1 1 2¯ 0) a-plane ZnO films grown under various Zn/O ratios by plasma-assisted molecular beam epitaxy

Structural and optical properties of nonpolar a-plane ZnO films grown with different II/VI ratios on r-plane sapphire substrates by plasma-assisted molecular beam epitaxy were investigated. Even by increasing the II/VI ratio across the stoichiometric flux condition a consistent surface morphology of striated stripes along the ZnO 〈0 0 0 1〉 direction without any pit formation was observed, which is contrary to polar c-plane ZnO films. Root mean square surface roughness, full width at half maximum values of X-ray rocking curves, defect densities, and photoluminescence were changed with the II/VI ratio. The sample grown with stoichiometric flux condition showed the lowest value of rms roughness, the smallest threading dislocation and stacking fault densities of ∼4.7×10⁸ cm⁻² and ∼9.5×10⁴ cm⁻¹, respectively, and the highest intensity of D^oX peak. These results imply that the stoichiometric flux growth condition is suitable to obtain superior structural and optical properties compared to other flux conditions.     

Surface growth mechanisms and structural faulting in the growth of large single and spherulitic titanosilicate ETS-4 crystals

Morphological, surface and crystallographic analyses of titanosilicate ETS-4 products, with diverse habits ranging from spherulitic particles composed of submicron crystallites to large single crystals, are presented. Pole figures revealed that crystal surfaces with a-, b- and c- axes corresponded to 110, 010 and 001 directions, respectively. Thus, technologically important 8-membered ring pores and titania chains in ETS-4 run along the b-axis of single crystals and terminate at the smallest crystal face. Height of the spiral growth steps observed on 1 0 0 and 0 0 1 surfaces corresponded to the interplanar spacings associated with their crystallographic orientation, and is equivalent to the thickness of building units that form the ETS-4 framework. Data suggest that the more viscous synthesis mixtures, with a large driving force for growth, increased the two- and three-dimensional nucleation, while limiting the transport of nutrients to the growth surface. These conditions increase the tendency for stacking fault formation on 1 0 0 surfaces and small angle branching, which eventually results in spherulitic growth. The growth of high quality ETS-4 single crystals (from less viscous synthesis mixtures) occurred at lower surface nucleation rates. Data suggest that these high quality, large crystals grew due to one-dimensional nucleation at spiral hillocks, and indicate that under these conditions un-faulted growth is preferred.     

Impurity segregation in directional solidified multi-crystalline silicon

In this paper numerical results on the impurity segregation in directional solidified multi-crystalline silicon are presented and compared with experimental results. A solute transport model has been established to predict the final segregation pattern of impurities in the ingot. The segregation is analyzed experimentally on the basis of Fourier transform infrared (FTIR) spectroscopy and glow-discharge mass spectrometry (GDMS). Precipitates were located by IR-transmission microscopy (IRM). Qualitative agreement between simulation and experiment is found. It is demonstrated how the flow pattern can influence the final solute distribution. The simulation also shows that the solubility limit of carbon and nitrogen is reached locally in the ingot and SiC and Si₃N₄ precipitates are likely to form.     

Impurity induced periodic mesostructures in Sb-doped SnO2 nanowires

Impurity doping on semiconductor nanowires formed via vapor–liquid–solid (VLS) mechanism has been investigated with the intention being to control the transport properties. Here we demonstrate that an addition of excess impurity dopants induces a mesostructure of long range periodic arched-shape in Sb-doped SnO₂ nanowires. The microstructural and composition analysis demonstrated the importance of the presence of impurities at the growth interface during VLS growth rather than the dopant incorporation into nanowires, indicating kinetically induced mechanisms.     

Impact of the gas flow ratio on the physical properties of GaN grown by vertical flow metalorganic chemical vapour deposition

We studied the effect of gas flow ratio of the H₂ carrier gas to the NH₃ precursor on the physical and crystal properties of GaN. GaN was grown by vertical reactor metalorganic chemical vapour deposition (MOCVD) on a low-temperature-deposited GaN buffer layer. A (0 0 0 1) sapphire substrate was used. The impact of the gas flow ratio as it was varied from 0.25 to 1 was investigated and discussed. With increase in flow ratio, the concentrations of magnesium and carbon impurities in GaN increased. The flow ratio of 0.5 is the optimum value to minimise the background electron concentration and to maintain crystal quality. The decrease in the background electron concentration is due to the compensation mechanism of acceptor-like magnesium and carbon impurities.     

On the effect of impurities on the metastable zone width of phosphoric acid

The experimental data published in the literature on the metastable zone width, as determined by the maximum supercooling ΔT_max using the conventional polythermal method, of phosphoric acid aqueous solutions containing impurities were analyzed to understand an increase in ΔT_max/T₀ with an increase in saturation temperature T₀ of solute–solvent system and the effect of impurities on the metastable zone width. For the analysis the following relations were used: ln(ΔT_max/T₀)=Φ+βln R (K. Sangwal, Cryst. Res. Technol. 44, 2009, 231−247) and (T₀/ΔT_max)²=F(1−Zln R) (K. Sangwal, Cryst. Growth Des. 9, 2009, 942−950; J. Cryst. Growth 311, 2009, 4050−4061), where Φ, β, F and Z are constants. Analysis of the experimental data revealed that: (1) the parameters Φ and F strongly depend on saturation temperature T₀ and concentration c_i of impurities, but the constants β and Z are independent of T₀ and depend on c_i, (2) the dependence of the parameters Φ and F on T₀ follows an Arrhenius-type equation with activation energy E_sat, (3) the activation energy E_sat for diffusion of ions/molecules of phosphoric acid containing impurity ions is equal to the differential heat of adsorption Q_diff for these impurities, (4) the effectiveness of an impurity is directly connected with the values of their differential heat of adsorption Q_diff; the lower the values of Q_diff for an impurity, the lower is its effectiveness in promoting nucleation, (5) the activation energy E_sat is not related with its heat of dissolution ΔH_s and (6) the increase in ΔT_max/T₀ with an increase in T₀ for phosphoric acid is associated with the activation energy E_sat for diffusion of solute molecules in the solution such that E_sat<0.     

Stacking faults in deformed zinc and magnesium single crystals

Using the transmission electron microscopy dissociated dislocations containing stacking faults were observed in Mg single crystals, deformed in (0001) <1120> slip system, and in Zn single crystals deformed in {1122} <1123> slip system. The overlapping flat stacking faults lying in {1102} planes and dissociated triple nodes in (0001) planes are observed in Mg. In Zn flat stacking faults are found in {112 2} planes. The value of stacking fault energy γ has been determined in Mg crystals (γ ⋍ 10 erg/cm²). Such a low value of γ is attributed to the segregation of impurities on dislocations.     

Cs2LiGdCl6 (Ce): New scintillation material

We investigated the scintillation properties of Cs₂LiGdCl₆:Ce³⁺ as a function of the Ce concentration. X-ray excited luminescence spectra of the scintillation material showed broad emission bands between 360 and 460 nm, with two overlapping peaks, due to the d→f transitions on Ce³⁺ ions. The samples provide good scintillation results. The energy resolution was found to be 5.0% (FWHM) at 662 keV for 10% Ce sample. Under γ-ray excitation, Cs₂LiGdCl₆:Ce³⁺ showed three exponential decay time components of about 130–200 ns decay time constant. The light output of the investigated samples was 20,000 photons/MeV for a 10% Ce concentration. The light output deviation from the linear response is within 7% between the energy range of 31 and 1333 keV. Overall, the scintillation properties confirm that Cs₂LiGdCl₆:Ce³⁺ single crystal is a promising candidate for medical imaging and radiation detection.     

Computer simulation, thermodynamic and microstructural studies of benzamide–benzoic acid eutectic system

Phase diagram of benzamide–benzoic acid system has been studied by the thaw–melt method. Linear velocities of crystallization of the components and the eutectic mixture were determined at different undercoolings. Values of the heat of fusion were obtained from DSC studies. Excess Gibbs free energy, excess enthalpy and excess entropy of mixing were calculated. In order to know the nature of interaction between the two components, FT-IR spectral analyses were done. In addition to these studies, computer simulation has been done to obtain an idea about the interaction energy and the optimized geometry of the eutectic mixture. Microstructural studies showed the formation of an irregular structure in the eutectic mixture, which changed with aging and on addition of impurities.     

Stacking pattern of multi-layer InAs quantum wires embedded in In0.53Ga0.47−xAlxAs matrix layers grown lattice-matched on InP substrate

Multi-layer InAs quantum wires were grown on, and embedded in In_0.53Ga_0.47−xAl_xAs (with x=0, 0.1, 0.3 and 0.48) barrier/spacer layers lattice matched to an InP substrate. Correlated stacking of the quantum wire arrays were observed with aluminum content of 0 and 0.1. The quantum wire stacks became anti-correlated as the aluminum content was increased to 0.3 and 0.48. The origin of such stacking pattern variation was investigated by finite element calculations of the chemical potential distribution for indium on the growth front surface of the capping spacer layer. It is shown that the stacking pattern transition is determined by the combined effect of strain and surface morphology on the growth front of the spacer layers.     

Low-energy ion-assisted control of interfacial structures in metallic multilayers

A molecular dynamics method has been used to simulate the argon ion-assisted deposition of Cu/Co/Cu multilayers and to explore ion beam assistance strategies that can be used during or after the growth of each layer to control interfacial structures. A low-argon ion energy of 5–10 eV was found to minimize a combination of interfacial roughness and interlayer mixing (alloying) during the ion-assisted deposition of multilayers. However, complete flattening with simultaneous ion assistance could not be achieved without some mixing between the layers when a constant ion energy approach was used. It was found that multilayers with lower interfacial roughness and intermixing could be grown either by modulating the ion energy during the growth of each metal layer or by utilizing ion assistance only after the completion of each layers deposition. In these latter approaches, relatively high-energy ions could be used since the interface is buried and less susceptible to intermixing. The interlayer mixing dependence upon the thickness of the over layer has been determined as a function of ion energy.     

The influence of the intensity of melt stirring on the radial impurity distribution in proustite single crystals grown by the Stockbarger method using ACRT

The influence of the intensity of melt stirring on the radial impurity distribution and optical quality of proustite single crystals grown by the Stockbarger method using ACRT is studied by the example of Cu, Sb and Mg impurities. We report results obtained in a wide range of Taylor numbers (1.9×10⁵<Ta<7.12×10⁷). The studies revealed that the ACRT can be applied validly to decrease the impurity content during the growing of high-quality single crystals.     

The effect of inserting strain-compensated GaNAs layers on the luminescence properties of GaInNAs/GaAs quantum well

Photoluminescence (PL) properties of GaInNAs/GaAs quantum wells (QWs) with strain-compensated GaNAs layers grown by molecular beam epitaxy are investigated. The temperature-dependent PL spectra of GaInNAs/GaAs QW with and without GaNAs layers are compared and carefully studied. It is shown that the introduction of GaNAs layers between well and barrier can effectively extend the emission wavelength, mainly due to the reduction of the barrier potential. The PL peak position up to 1.41 μm is observed at the room temperature. After adding the GaNAs layers into QW structures, there is no essential deterioration of luminescence efficiency. N-induced localization states are also not remarkably influenced. It implies that with optimized growth condition, high-quality GaInNAs/GaAs QWs with strain-compensated GaNAs layers can be achieved.     

Synthesis of monodispersed cubic magnetite particles through the addition of small amount of Fe into Fe(OH)2 suspension

Magnetite particles were synthesized through a process including dissolution of Fe(OH)₂ and precipitation of an oxidized phase in aqueous solution. The Fe³⁺ ion was added at the beginning of the synthesis to accelerate the formation of magnetite, control the particle size and improve the monodispersibility. It was found that the addition of Fe³⁺ ion affected the nucleation and the formation of magnetite particles significantly. Magnetite nanoparticles with small particle size and narrow size distribution were obtained. Furthermore, high magnetic properties were obtained in small particle size. The particle size and magnetic properties increased through the increase of Fe²⁺/Fe³⁺ ratio.