MgO films grown on yttria-stabilized zirconia by molecular beam epitaxy

MgO films were grown on (0 0 1) yttria-stabilized zirconia (YSZ) substrates by molecular beam epitaxy (MBE). The crystalline structures of these films were investigated using X-ray diffraction and transmission electron microscopy. Growth temperature was varied from 350 to 550 °C, with crystalline quality being improved at higher temperatures. The MgO films had a domain structure: (1 1 1)[1 1 2¯]_MgO(0 0 1)[1 0 0]_YSZ with four twin variants related by a 90° in-plane rotation about the [1 1 1]_MgO axis. The observed epitaxial orientation was compared to previous reports of films grown by pulsed laser deposition and sputtering and explained as resulting in the lowest interface energy.     

Epitaxial growth of ZnO thin films on Si substrates by PLD technique

Epitaxial ZnO thin films have been grown on Si(1 1 1) substrates at temperatures between 550 and 700 °C with an oxygen pressure of 60 Pa by pulsed laser deposition (PLD). A ZnO thin film deposited at 500 °C in no-oxygen ambient was used as a buffer layer for the ZnO growth. In situ reflection high-energy electron diffraction (RHEED) observations show that ZnO thin films directly deposited on Si are of a polycrystalline structure, and the crystallinity is deteriorated with an increase of substrate temperature as reflected by the evolution of RHEED patterns from the mixture of spots and rings to single rings. In contrast, the ZnO films grown on a homo-buffer layer exhibit aligned spotty patterns indicating an epitaxial growth. Among the ZnO thin films with a buffer layer, the film grown at 650 °C shows the best structural quality and the strongest ultraviolet (UV) emission with a full-width at half-maximum (FWHM) of 86 meV. It is found that the ZnO film with a buffer layer has better crystallinity than the film without the buffer layer at the same substrate temperature, while the film without the buffer layer shows a more intense UV emission. Possible reasons and preventive methods are suggested to obtain highly optical quality films.     

Growth of EuTe islands on SnTe by molecular beam epitaxy

Semiconductor magnetic quantum dots are very promising structures, with novel properties that find multiple applications in spintronic devices. EuTe is a wide gap semiconductor with NaCl structure, and strong magnetic moments S=7/2 at the half filled 4f⁷ electronic levels. On the other hand, SnTe is a narrow gap semiconductor with the same crystal structure and 4% lattice mismatch with EuTe. In this work, we investigate the molecular beam epitaxial growth of EuTe on SnTe after the critical thickness for island formation is surpassed, as a previous step to the growth of organized magnetic quantum dots. The topology and strain state of EuTe islands were studied as a function of growth temperature and EuTe nominal layer thickness. Reflection high energy electron diffraction (RHEED) was used in-situ to monitor surface morphology and strain state. RHEED results were complemented and enriched with atomic force microscopy and grazing incidence X-ray diffraction measurements made at the XRD2 beamline of the Brazilian Synchrotron. EuTe islands of increasing height and diameter are obtained when the EuTe nominal thickness increases, with higher aspect ratio for the islands grown at lower temperatures. As the islands grow, a relaxation toward the EuTe bulk lattice parameter was observed. The relaxation process was partially reverted by the growth of the SnTe cap layer, vital to protect the EuTe islands from oxidation. A simple model is outlined to describe the distortions caused by the EuTe islands on the SnTe buffer and cap layers. The SnTe cap layers formed interesting plateau structures with easily controlled wall height, that could find applications as a template for future nanostructures growth.     

A structural study of phase transitions within GaN layers grown by low-temperature molecular beam epitaxy

The epitaxial growth of GaN layers on sapphire substrates by molecular beam epitaxy at low temperatures (500°C) has been investigated. Samples exhibited a transition from hexagonal to mixed hexagonal/cubic phase under conditions of increasing Ga flux as determined using a TEM-RHEED technique with complementary SEM and PL observations. Embedded cubic grains adopted two domain variants with additional evidence for twinning.     

In situ time-resolved X-ray diffraction study of octacalcium phosphate transformations under physiological conditions

The present study is focused on the in vitro investigation of octacalcium phosphate (OCP) transformations when mixed with physiological solution (aqueous isotonic 0.9% NaCl) by the energy dispersive X-ray diffraction technique. This technique allowed in situ monitoring of the processes taking place in this system in real time. It was demonstrated that when OCP is mixed with physiological solution, it undergoes two simultaneous processes: (1) amorphous-into-crystalline OCP transformation (37%), and OCP average grain size growth from 22 up to 35 nm; (2) partial phase transformation of OCP (33%) into hydroxyapatite (HA), and HA average grain growth up to 5 nm. Both processes take place simultaneously with the same characteristic time (2.90±0.25) h.     

Induction time in crystallization of gas hydrates

The kinetics of the initial stage of crystallization of one-component gas hydrates in aqueous solutions are analyzed. The temporal evolution of the volume of hydrate crystallized and the moles of gas consumed are determined. Expressions are derived for the supersaturation dependence of the hydrate crystallite growth rate and the induction time in hydrate crystallization. These expressions are used for revealing how additives in the solution that act as kinetic inhibitors of hydrate crystallization can affect the induction time of the process. The results obtained are applied to crystallization of methane, ethane and cyclopropane hydrates.     

High-resolution X-ray diffraction analysis of the Bragg peak integrated intensity in highly mismatched III-N epilayers

A new method of measuring the thickness of GaN epilayers on sapphire (0 0 0 1) substrates by using double crystal X-ray diffraction was proposed. The ratio of the integrated intensity between the GaN epilayer and the sapphire substrate showed a linear relationship with the GaN epilayer thickness up to 2.12 μm. It is practical and convenient to measure the GaN epilayer thickness using this ratio, and can mostly eliminate the effect of the reabsorption, the extinction and other scattering factors of the GaN epilayers.     

Simulation of metastable zone width and induction time for a seeded aqueous solution of potassium sulfate

The metastable zone width (MSZW, ΔT_m) and induction time (t_ind) were determined with computer simulation for seeded batch crystallization of potassium sulfate from aqueous solution. The MSZW and induction time determined with simulation showed the same behavior as experimental values reported in the literature; log (ΔT_m) increased linearly with an increase in log R (R: cooling rate) and t_ind decreases in proportion to (ΔT)⁻ⁿ (ΔT: supercooling, n: nucleation order in the secondary rate expression of B=k_n(ΔT)ⁿ). The secondary nucleation parameters (k_n and n) were deduced both from the simulated MSZW and induction times by using the previously proposed model [J. Cryst. Growth, 2010, 312, 548–554]. The secondary nucleation rate calculated with the deduced parameters was in agreement with that calculated with the parameters input for simulation.     

Nucleation and ripening of seeded InAs/GaAs quantum dots

We have investigated the nucleation and ripening of pairs of InAs/GaAs quantum dot layers separated by thin (2–20 nm) GaAs spacer layers. Reflection high energy electron diffraction (RHEED) measurements show that the 2D–3D transition in the second layer can occur for less than 1 monolayer deposition of InAs. Immediately after the islanding transition in the second layer chevrons were observed with included angles as low as 20° and this angle was seen to increase continuously to 45±2° as more material was deposited. Atomic force microscopy showed the dot density in both layers to be the same. It is proposed that surface morphology can radically alter processes that determine the nucleation and ripening of the 3D islands.     

Growth of Eu-doped GaN by gas source molecular beam epitaxy and its optical properties

Eu-doped GaN with various Eu concentrations were grown by gas source molecular beam epitaxy, and their structural and optical properties were investigated. With increasing Eu concentration from 0.1 to 2.2 at%, deterioration of the structural quality was observed by reflection high-energy electron diffraction, atomic force microscopy and X-ray diffraction. Such a deterioration may be caused by an enhancement of island growth and formation of dislocations. On the other hand, room temperature photoluminescence spectra showed red emission at 622 nm due to an intra-atomic f–f transition of Eu³⁺ ion and Fourier transform infrared spectra indicated an absorption peak at about 0.37 eV, which may be due to a deep defect level. The intensity of the red luminescence and the defect-related absorption peak increased with increasing Eu concentration, and a close correlation in the increasing behavior was observed between them. These results suggest that the deep defect level plays an important role in the radiative transition of Eu³⁺ ion in GaN and the optical process for the luminescence at 622 nm was discussed with relation to the defect.     

Heteroepitaxy of CdTe on tilting Si(2 1 1) substrates by molecular beam epitaxy

CdTe(2 1 1)B epilayers were grown on 3 in Si(2 1 1) substrates which misoriented 0–10° toward [1 1 1] by molecular beam epitaxy (MBE). The relationship of X-ray double-crystal rocking curve (XRDCRC) FWHM and deflection angle from CdTe(2 1 1) to Si(2 1 1) was studied. For 4.2–4.5 μm CdTe, the best value of FWHM 83 arcsec was achieved while deflection angle is 2.76°. A FWHM wafer mapping indicated a good crystalline uniformity of 7.4 μm CdTe on tilting Si(2 1 1), with FWHM range of 60–72 arcsec. The shear strains of these epilayers were analyzed, using reciprocal lattice points of symmetric and asymmetric reflections measured by high-resolution multi-crystal multi-reflection X-ray diffractometer (HRMCMRXD). It was found that the shear strain angle of epilayer is effectively reduced by using proper tilting Si(2 1 1) substrate. It was also proved that the lattice parameter of CdTe(2 1 1)B is affected by the shear strain and thermal strain.     

The tri-methyl-Sb flow and the surfactant time effect on InGaAsN/GaAs-strained MQWs grown by MOCVD

The tri-methyl-Sb flow and the surfactant time dependence of photocurrent (PC) spectra was studied on InGaAsN/GaAs-strained multiple quantum wells (MQWs) structures grown by using metalorganic chemical vapor deposition (MOCVD). The structural properties of InGaAsN/GaAs-strained MQWs were investigated by using high-resolution X-ray diffraction (HRXRD). In the case of InGaAsN/GaAs-strained MQWs, an increase in compressive strain from an analysis of the satellite peaks in HRXRD was observed on increasing the tri-methyl-Sb flow and the surfactant time. For InGaAsN/GaAs-strained MQWs, the peaks observed in the photocurrent spectra were preliminarily assigned to electron–heavy hole (e₁–hh) and electron–light hole (e₁–lh) fundamental excitonic transitions. Their peaks are red-shifted with increasing tri-methyl-Sb flow and surfactant time. But the photocurrent peak is blue-shifted at the surfactant time of . It seems to be due to the improvement of structure properties at interface owing to a surfactant-suppressing surface diffusion phenomenon during growth. We compared this with the result of the experimental energies for InGaAsN/GaAs-strained MQWs.     

Droplet epitaxy of zinc-blende GaN quantum dots

Zinc-blende GaN quantum dots were grown on 3C-AlN(0 0 1) by a vapor–liquid–solid process in a molecular beam epitaxy system. We were able to control the density of the quantum dots in a range of 5×10⁸–5×10¹² cm⁻². Photoluminescence spectroscopy confirmed the optical activity of the GaN quantum dots in a range of 10¹¹–5×10¹² cm⁻². The data obtained give an insight to the condensation mechanism of the vapor–liquid–solid process in general, because the GaN quantum dots condense in metastable zinc-blende crystal structure supplied by the substrate, and not in the wurtzite crystal structure expected from free condensation in the droplet.     

Simultaneous reflection high-energy electron diffraction oscillations and mass spectroscopy investigations during molecular beam epitaxy growth of (001) GaAs - smooth surfaces or stoichiometric films?

Film composition and surface morphology of molecular beam epitaxy (MBE)-grown GaAs(001) surfaces were investigated in situ as a function of flux ratio J_Ga/J_As4. The flux of As₄ molecules desorbing from the sample surface was measured with a quadrupole mass spectrometer (QMS) simultaneously with the observation of reflection high energy electron diffraction (RHEED) intensity oscillations. The incorporation ratio, given by the number of incorporated Ga atoms per As atom, was calculated independent of both the QMS data and the decreasing growth rate for growth conditions with As deficiency, as obtained from the RHEED oscillation frequency. Stoichiometric growth was found up to a flux ratio J_Ga/J_As4 ≈ 0.9. At flux ratios of 1.1 to 1.2, a minimum of the damping of the RHEED oscillation amplitude indicates a very smooth growth front profile, but Ga excess appears to be incorporated mainly in As sites without disturbing the crystal lattice. This assumption was confirmed by photoluminescence (PL) spectroscopy of films grown at a flux ratio J_Ga/J_As4 of 1.2. An additional PL peak was observed, which indicates the incorporation of Ga atoms on As sites.     

Influence of cooling rate on the liquid-phase epitaxial growth of Zn3P2

We report the liquid-phase epitaxial growth of Zn₃P₂ on InP (1 0 0) substrates by conventional horizontal sliding boat system using 100% In solvent. Different cooling rates of 0.2–1.0 °C/min have been adopted and the influence of supercooling on the properties of the grown epilayers is analyzed. The crystal structure and quality of the grown epilayers have been studied by X-ray diffraction and high-resolution X-ray rocking measurements, which revealed a good lattice matching between the epilayers and the substrate. The supercooling-induced morphologies and composition of the epilayers were studied by scanning electron microscopy and energy dispersive X-ray analysis. The growth rate has been calculated and found that there exists a linear dependence between the growth rate and the cooling rate. Hall measurements showed that the grown layers are unintentionally doped p-type with a carrier mobility as high as 450 cm²/V s and a carrier concentration of 2.81×10¹⁸ cm⁻³ for the layers grown from 6 °C supercooled melt from the cooling rate of 0.4 °C/min.     

X-ray and cathodoluminescence study on the effect of intentional long time annealing of the InGaN/GaN multiple quantum wells grown by MOCVD

GaN-based InGaN/GaN multiple quantum wells (MQWs) structure having a high-quality epilayer and coherent periodicity was grown by metalorganic chemical vapor deposition. After thermal annealing of InGaN/GaN MQWs, the increase in temperature and annealing time caused the intermixing between the barrier and the wells, which in turn caused a decrease in periodicity on the high-resolution X-ray diffraction patterns. Thereby, we confirmed that the structural performance of InGaN MQWs is successively degrading with increasing thermal annealing temperature. Especially, InGaN MQWs of the sample annealed at 950 °C were profoundly damaged. The cathodoluminescence (CL) measurement indicated that MQWs emission intensity decreases with increasing thermal annealing temperature. Thus, the integrated CL intensity ratio of InGaN MQWs to GaN dramatically decreased while thermal annealing temperatures increased. This result caused the intermixing in MQWs to deteriorate the active layer performance. Furthermore, the peak position of MQWs showed a tendency of the red shift after high thermal annealing. It is suggested that the annealing-induced red shift in MQWs is attributed to the reduction of the inhomogeneity of the In content in the MQWs leading to the reduction of the quantized energies. Consequently, it indicates that the high temperature and the long-time thermal annealing would be inevitably followed by the structural destruction of InGaN MQWs.     

The incorporation behavior of arsenic and antimony in GaAsSb/GaAs grown by solid source molecular beam epitaxy

GaAsSb ternary epitaxial layers were grown on GaAs (0 0 1) substrate in various Sb₄/As₂ flux ratios by solid source molecular beam epitaxy. The alloy compositions of GaAs_1−ySb_y were inferred using high-resolution X-ray symmetric (0 0 4) and asymmetric (2 2 4) glance exit diffraction. The non-equilibrium thermodynamic model is used to explain the different incorporation behavior between the Sb₄ and As₂ under the assumption that one incident Sb₄ molecule produces one active Sb₂ molecule. It is inferred that the activation energy of Sb₄ dissociation is about 0.46 eV. The calculated results for the incorporation efficiency of group V are in good agreement with the experimental data.