Low-temperature synthesis of starting materials for β-barium metaborate (β-BBO) crystal growth

Synthesis of starting materials for β-barium metaborate (β-BBO) crysal growth by a low-temperature “carbonate” method has been investigated. Materials systhesized below the σ-β phase transformation temperature of BBO have been subjected to thermogravimetry, X-ray difraction and chemical analysis. The results show that an almost carbonless stoichiometric β-phase can be obtained without the need for the widely employed high-temperature “carbonate” synthesis. Some advantages of using the β-BBO material synthesized by the low-temperature “carbonate” method are emphasized.     

GaSb/InAs heterojunctions grown by MOVPE: Effect of gas switching sequences on interface quality

The GaSb/InAs interface can be grown in two quite different ways either with In and Sb atoms forming the interface “InSb-like” or Ga and As atoms forming the interface “GaAs-like”. This is a result of both the Group III and Group V atoms changing at the interface. Different interfaces have been achieved in GaSb/InAs heterojunctions grown by atmospheric MOVPE using different gas switching sequences and the consequent changes in the electrical behaviour have been assessed using low field magnetotransport measurements. The results range from very poor (“GaAs-like”) to excellent (a particular “InSb-like”) interface. A further comparison is made to a previously used growth sequence for these structures. The effect of pauses during the interface sequence has also been investigated.     

Morphological instability due to double diffusive convection in directional solidification: the pit formation

Deep interface depression or “pit formation”, as a result of solute accumulation, due to double-diffusive convection in the directional solidification of succinonitrile (SCN) containing ethanol in an ampoule is investigated by a fully nonlinear numerical simulation. The calculated results are consistent with previous observations (Schaefer and Coriell, Metal. Trans. 15A (1984) 2109), and the instability margin falls between the convective and morphological boundaries at a low growth rate. For a high growth rate, the global interface depression becomes deep due to significant release of the heat of fusion; in this case, the critical concentration can be lower than the convective value. Near the instability margin, the pit forms at the center of the interface and is soon followed by constitutional supercooling. Also, the pit shape is affected significantly by the convective solute transport and thus the flow structures. Such pit formation, results from the nonlinear coupling of double-diffusive convection and the interface deformation, and although differs from the traditional mechanisms, it could be an important route to interface breakdown.     

Organic inclusion complex strategy for designing nonlinear optical crystals for ultraviolet applications

Based on Molecular Engineering and Crystal Engineering concepts, a new method for designing nonlinear optical (NLO) crystal materials, the Organic Inclusion Complex (OIC) method has been demonstrated. In defining an appropriate optical transparent range with respect to the Molecular Engineering method, small organic molecules containing n-π conjugation were selected as “second order harmonic generation (SHG)-active units”(guests). Together with the Crystal Engineering method, chiral molecules were used as “molecular scaffolding” (hosts) to combine with the “SHG-active units” by hydrogen bonds. The former can provide a nonlinear optical effect. The latter leads to the OIC with a noncentrosymmetric structure and are expected to enhance the macroscopic nonlinearity in a synergistic mode of guest and host by inducing the guest molecular dipole alignment as well as other properties, such as thermal stability, mechanical strength and ease of growth. Here, we report two new inclusion complex crystals, urea-(d)tartaric acid (UDT) and urea-(dl)tartaric acid (UDLT) (here, d means dextral and dl means racemic). UDT and UDLT crystals belong to P2,2,2, and P2, space group, respectively. Bulk size crystals with high optical quality were successfully obtained from aqueous solution by using a temperature-lowering method. The experimental results show that these two crystals demonstrate higher NLO effects and shorter wavelength cutoff.     

Anomalous paramagnetism in pressure quenched CdS

Very large “paramagnetic” on positive magnetization has been observed in “pressure quenched” samples of CdS. Pressure quenching is a formative process involving pressure release rates ≈10⁶ bar s⁻¹.

The pressure quenched samples were prepared by pressure quenching at room temperature from above 30 kbar, i.e. from above the insulation-to-metal like transition. magnetization as a function of magnetic field was measured at 293 and 77 K using a vibrating specimen magnetometer. A linear M versus H behavior is observed in fields above a few hundred gauss, with values of χ = (M/H) ≈ 10^-4 cgs units. In some specimens saturation occurs, while in others the magnetization passes through a maximum. The maximum value of the magnetic moment M observed is of the order of tens of gauss.     

Stress measurements in sol-gel films

Thin solid films of a wide variety of materials have received increased attention during the past decade. These films have been instrumental in the growth of numerous technologies. Until recently, “thin films” have primarily described layers of metallic or dielectric materials deposited onto substrates by evaporation, electron beam or ion beam techniques.

Advances in sol-gel technology have extended film research to include “glassy” materials of either crystalline, or amorphous nature. Sol-gel films can be tailor-made to accommodate a diverse range of applications due primarily to flexibility in chemical make up which determines the respective film's structure. One important characteristic of such films is their inherent residual stress. This inherent stress, and the stress the film introduces to the substrate as it is deposited, can result in a complex stress profile. While “thin” in the case of sol-gel films generally means <1 μm in thickness, large (10–100s of nm of retardance) inherent stress per unit thickness can severely limit a film's performance and subsequent application.

We describe our efforts to quantify the residual stress in silica-based sol-gel films as a function of several processing parameters.     

Effect of steady ampoule rotation on radial dopant segregation in vertical Bridgman growth of GaSe

For vertical Bridgman growth of the nonlinear optical material GaSe in an ampoule sufficiently long that flow and dopant transport are not significantly influenced by the upper free surface, we show computationally that steady rotation about the ampoule axis strongly affects the flow and radial solid-phase dopant segregation. Radial segregation depends strongly on both growth rate U and rotation rate Ω over the ranges 0.25 μms⁻¹U3.0 μms⁻¹ and 0Ω270 rpm. For each growth rate considered, the overall radial segregation passes through two local maxima as Ω increases, before ultimately decreasing at large Ω. Rotation has only modest effects on interface deflection. Radial segregation computed using a model with isotropic conductivity (one-third the trace of the conductivity tensor) predicts much less radial segregation than the “correct” model using the anisotropic conductivity, with the segregation decreasing monotonically with Ω. Consideration of a model in which centrifugal acceleration is deliberately omitted shows that, as Ω increases, diminution and ultimately disappearance of the “secondary” vortex lying immediately above the interface is due to centrifugal buoyancy, while axial distension of the larger “primary” vortex above is due to Coriolis effects. These results, which are qualitatively different from those accounting for centrifugal buoyancy, suggest that several earlier computational and analytical predictions of rotating vertical Bridgman growth are either limited to rotation rates sufficiently low that centrifugal buoyancy is unimportant, or are artifacts associated with its neglect. The overall radial segregation depends approximately linearly on the product of and the growth rate U for the conditions considered, where is the segregation coefficient.     

Low lying electronic tail spectrum of the attractive δ-potential random system by the path integral method and coherent state representation variational method

By using the path integral method to study the “partition function” and therefore the density of states of the attractive Frisch-Lloyd random system, it is found that the “partition function” is divergent. Therefore, we modify the Frisch-Lloyd model to a system with regular lattice sites on which the atoms are randomly distributed. Path integral and coherent state representation variational methods are applied to this random system; by using the effective Hamiltonian theory of a periodic potential with slowly varying envelope, the low lying tail spectrum which is consistent with the Lifshitz conjecture for a random system is obtained.     

Porous crystal structures obtained from directionally solidified eutectic precursors

Interconnecting cage-like porous structures of several halide compounds were prepared by the selective leaching of one eutectic phase method. The binary eutectic precursors were prepared by directional solidification using the Bridgman crystal growth technique. Porous NaMgF₃ (40% pore volume), CaF₂ (57% pore volume) and BaF₂ (43% pore volume) crystals were obtained after water leaching the NaF component of the directionally solidified NaF/NaMgF₃, NaF/CaF₂ and NaF/BaF₂ eutectics with the appropriate entangled microstructure. The growth conditions for eutectic-coupled growth and the morphology of the eutectics have been determined. In the coupled growth regime, the size of the eutectic phases “λ” is fairly uniform and varies with the eutectic growth rate “v” as λ²v=constant, which allows us to control the pore size within the 0.5–10 μm range. The simplicity and versatility of the eutectic growth also allows us to fabricate highly aligned porous structures at relatively high production rates.     

LPE growth of GaAs by yo-yo solute feeding method

The effect of gravity on both dissolution and growth of GaAs in the Ga---As system has been investigated using a horizontal “sandwich” system consisting of a substrate-solution-substrate configuration. Remarkable differences were observed in growth and dissolution between upper and lower substrates. These phenomena were attributed to the solutal convection driven by a concentration gradient. Based on these facts, a layer with a thickness of about 80 μm was successively grown by the yo-yo solute feeding method with 8 yo-yo repetition times between 700 and 650°C.     

An improved apparatus for measuring the inhomogeneity of glasses

An improved apparatus capable of quantatively measuring the inhomogeneity of glasses within several minutes was developed as a prototype for practical use. Inhomogeneities were measured for several kinds of glass articles on the market, such as plate, bottle and optical glasses etc. and a “relative homogeneity” has been proposed for the purpose of deciding a ranking of glasses measured in comparison to the powdered single crystal of CaF₂ as a standard material of uniformity.     

Glass composition for spinning fibre

The performance of polymer composites reinforced with neutral glass fibres was compared with that of “E” glass reinforced composites. The strength and fatigue characteristics of composites, and the polymerisation kinetics at the glass-polymer interface, were studied. The results show that “N” glass fibre composites possess superior wet strength and are suitable for general application.     

Highly uniform growth in a low-pressure MOVPE multiple wafer system

A novel horizontal metal organic vapor phase epitaxy (MOVPE) system, which is capable of handling six 3 inch wafers or eighteen 2 inch wafers mounted on a 10 inch diameter susceptor, has been developed for the growth of III–V compound semiconductors. The characteristic features in this system are “triple flow channel” gas injection and “face-down” wafer setting configuration. The inlet for the source gas flow is divided into three zones (upper, middle and lower flows for hydrides, organometals and hydrogen, respectively) to control the concentration boundary layer and the growth area. The wafers are placed inversely to prevent thermal convection and particles on the growing surface. The independent controlled three-part heating system is also adopted to achieve a uniform temperature distribution over an 8 inch growing surface. The thickness and the doping of GaAs, Al_0.3Ga_0.7As, In_0.48Ga_0.52P and In_0.2Ga_0.8As grown by this system are uniform within ± 2% over all 3 inch wafers.     

The electrical properties of coal slag

The inorganic constituents of coal remaining after high temperature combustion in a MHD (Magnetohydrodynamic) power plant combustor form an iron-rich, “dirty” glass whose electrical properties are important in the operation of the MHD generator. In particular, alkali “seed” (K₂CO₃) is added to enhance the conductivity of the plasma so the slag layer which coats the walls and electrodes of the generator is rich in K₂O. We present results of a systematic study of the electrical conductivity of a Rosebud coal ash with graded amounts of K₂CO₃ added. At high temperatures, the conductivity curves are smooth with many ions contributing. At lower temperatures the curves become more complex with the presence of crystalline phases in the glass.     

Thermal radiation and low-temperature-vapour growth of HgI2 crystal in production furnace

Heat exchanges in a sealed ampoule in the LTVG (low temperature vapour growth) furnace have been modelled in order to compute temperature fields and control the growth of HgI₂ crystals from vapour phase at low temperatures. We use a coupled conductive-radiative model to determine the shapes of the source and the crystal at different equilibrium states (i.e. without growth rate). The model involves conductivity anisotropy in the crystal and radiative exchanges between grey and diffuse surfaces (source and crystal interfaces, Pyrex walls), which are considered as opaque. Internal buoyancy effect is not taken into account as the pressure inside the ampoule is very small. The source temperature is fixed. For different undercoolings, i.e. for different cold finger temperatures, the “equilibrium” isotherm between the source/gas and crystal/gas interface has been numerically obtained. This “equilibrium” isotherm, which is associated with the stop of the growing process, gives a crystal shape. This shape is compared with experimental results given by the ETH-Zürich group. The model would permit a better understanding and control of the future HgI₂ crystal growth experiment. The computations are performed using a finite element package (FIDAP).     

In-situ and ex-situ characterization of GaAs/AlAs quantum well structures using spectroscopic ellipsometry

Spectroscopic ellipsometer is used to monitor the MBE growth of quantum well structures. Real time monitoring of the growth enabled the measurement of growth rate and correlation with RHEED oscillations. The growth of a single GaAs/AlAs quantum well is also monitored in real time using multiple wavelengths. Interface roughness of the interrupted “inverted” AlAs/GaAs interface was also monitored with SE. Under our growth conditions, we measure approximately a 2 ML interfacial region at the inverted interface. A correlation with photoluminescence is also discussed.     

Numerical simulation of MHD rotator action on hydrodynamics and heat transfer in single crystal growth processes

The article presents the results of the mathematical and physical simulations of the influence of a rotating magnetic field (RMF) on the hydrodynamics and heat transfer in processes of large semiconductor single crystal growth in ampoules. Different versions of the RMF are considered, in particular, for symmetric and asymmetric positions of a RMF inductor with regard to the melt in the ampoule, for two counter-rotating magnetic fields, for different geometrical ratios in the “RMF inductor - liquid melt” system, and for different electrical conductivities of the hard walls at their contact with the melt. The interconnection between the distribution of the electromagnetic forces in the liquid volume and the formed velocity patterns, temperature distribution and shape of the solidification front is studied. An original method for the definition of the electromagnetic forces, which considers finite dimensions of the RMF inductor and melt, was used to calculate real conditions of the RMF influence on growth processes. The numerical results obtained are compared to the data of model experiments. Their satisfactory agreement permits us to propose this calculation method for the definition of the optimal parameters of a growth process under specific conditions and to select the most rational type of RMF influence.     

Temperature quenching mechanisms for photoluminescence of MBE-grown chlorine-doped ZnSe epilayers

We report on a detailed investigation on the temperature-dependent behavior of photoluminescence from molecular beam epitaxy (MBE)-grown chlorine-doped ZnSe epilayers. The overwhelming neutral donor bound exciton (Cl⁰X) emission at 2.797 eV near the band edge with a full-width at half-maximum (FWHM) of 13 meV reveals the high crystalline quality of the samples used. In our experiments, the quick quenching of the Cl⁰X line above 200 K is mainly due to the presence of a nonradiative center with a thermal activation energy of 90 meV. The same activation energy and similar quenching tendency of the Cl⁰X line and the I₃ line at 2.713 eV indicate that they originate from the same physical mechanism. We demonstrate for the first time that the dominant decrease of the integrated intensity of the I₃ line is due to the thermal excitation of the “I₃ center”-bound excitons to its free exciton states, leaving the “I₃ centers” as efficient nonradiative centers. The optical performance of ZnSe materials is expected to be greatly improved if the density of the “I₃ center” can be controlled. The decrease in the luminescence intensity at moderately low temperature (30–200 K) of the Cl⁰X line is due to the thermal activation of neutral-donor-bound excitons (Cl⁰X) to free excitons.     

Reflectance anisotropy as an in situ monitor for the growth of InP on (001) InP by pseudo-atmospheric pressure atomic layer epitaxy

Single wavelength reflectance anisotropy (RA) has been used to monitor the growth of InP onto (001) InP substrates in real time under atmospheric pressure atomic layer epitaxy “(ALE)-like” conditions in which the In and P precursors were introduced sequentially into the reactor. The RA data indicates that at temperatures below 325°C the initial interaction of TMI with surface P-dimers results in a change in anisotropy and that the resulting surface is unreactive towards phosphine or additional TMI possibly as a result of a residual species of the type In(CH₃)_x where x = 1–3 acting as a site blocker or preventing In dimer formation. At higher temperatures, the RA data indicates that for InP growth on (001) InP using phosphine and trimethylindium (TMI) the onset of growth occurs between 300–325°C. This observation is implied directly from the appearance of the recovery portion of the RA transient which indicates that the second half of the ALE-like cycle restores the surface to the starting P-stabilised conditions. This low temperature for the onset of growth as compared to conventional InP MOCVD is attributed to the operation of a surface catalysed reaction of both phosphine and TMI.