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.     

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.     

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.     

Heterointerface study of perturbed LPE growth of AlGaAs/InGaP single heterostructure

This paper presents the perturbed growth of Al_0.7Ga_0.3As/In_0.5Ga_0.5P single heterostructure on a GaAs substrate by liquid-phase epitaxy. The AlGaAs-InGaP heterointerface was characterized by scanning electron microscopy, photoluminescence, Auger electron spectroscopy, and transmission electron microscopy. Evidence is provided showing that a small amount of droplets, after the slider operation of the In_0.5Ga_0.5P epitaxial growth, mixed with the Ga-rich AlGaAs melt, is sufficient to attack the In_0.5Ga_0.5P underlying layer. Even with complete melt removal, there is still a partial dissolution at the “flat” Al_0.7Ga_0.3As-In_0.5Ga_0.5P heterojunction. The Auger depth profiles reveal the composition-depth transition width at this interface to be 560Å from the 90%-10% of Al (or Ga, As, and In) Auger profile; however, the P atoms penetrate deeply into the Al_0.7Ga_0.3As layer due to the partial dissolution of In_0.5Ga_0.5P layer. By high-resolution electron-micrograph analysis, some dislocations are observed at the heterojunction leading to nonradiative recombination and to poor optical device performance, even though the heterointerface observed by scanning electron microscopy is very flat.     

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.     

Photoluminescence characterization of GaxIn1−xAs (0 ≤ x ≤ 0.32) strained quantum wells grown on InP by chemical beam epitaxy

We have investigated some characteristics of Ga_xIn_1−xAs/InP (x = 0, 0.2, 0.32) strained materials by growing multi-quantum wells with various well widths from 3 to 60 Å by chemical beam epitaxy. Growth conditions such as valve sequences and growth interruptions were optimised to have single-peaked photoluminescence spectra for all strained samples. Measured room temperature emission wavelengths were compared with theoretically estimated values. Photoluminescence linewidths were around 16 meV for most samples at 77 K, but broadened for well widths of less than 20 Å. Photoluminescence intensity also peaked at well width of 20 Å for all compositions. Performances of optical devices may be closely related to this “critical thickness” determined probably by the growth system limitation.     

Long and short period growth rate variations in potash alum crystals

Recent studies of the growth rate of the different faces of potash alum crystals have revealed that these grow with variable growth rates. This phenomena can be considered on two time scales. In the long term “constant” growth remains for period of hours followed by growth arrests and so on. Superimposed on this are short term (minutes) fluctuations. The potential causes for these variations were discussed.     

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.     

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).     

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.     

Formation mechanism of InxGa1−xAs bridge layers on patterned GaAs substrates

The formation mechanism of In_xGa_1−xAs (x=0.06) bridge layers on patterned GaAs (1 1 1)B substrates using liquid-phase epitaxy has been investigated. For this (i) the effect of density gradient in the solution on the formation of bridge layer and (ii) growth of bridge layer on 1 1 0 line-seed-substrates were studied. The convection induced by destabilizing density gradient in the solution led to an increase of lateral growth rate of the InGaAs bridge layers on a substrate mounted on the upper portion of the solution. However, it did not have any significant effect on the formation of the bridge layers. The formation of bridge layer on 1 1 0 line-seed-substrate took place only for the {1 1 1}B growth fronts, which indicated that “Berg effect” is responsible for the formation of bridge layers.     

Cellular-automata-based simulation of anisotropic crystal growth

Extending the simulation of anisotropic etching, a cellular-automata-based simulator is applied to anisotropic crystal growth. This simulator takes advantage of the equivalence between dissolution and growth of crystals. Metalorganic vapour-phase epitaxial growth experiments were performed on patterned (1 0 0)-oriented InP substrates with very deep V-shaped grooves with {1 1 1}A sidewalls to determine the relevant growth rates of InGaAs and InP. The capability of the simulation method is demonstrated by quantitative comparison of simulated and experimental results. In addition, the versatility of the model is shown with area-selective growth.     

Effects of growth temperature and V/III ratio on surface structure and ordering in Ga0.5In0.5P

Surface photoabsorption (SPA) measurements were used to clarify the CuPt ordering mechanism in Ga_0.5In_0.5P layers grown by organometallic vapor phase epitaxy. The CuPt ordering is known to be strongly affected by the growth temperature and the input partial pressure of the phosphorus precursor, i.e. the V/III ratio. The SPA peak at 400 nm was found to be a measure of the concentration of [ 10]-oriented phosphorus dimers on the surface, which are characteristic of the (2 × 4) reconstruction. Both ordering, measured using the low temperature photoluminescence peak energy, and the SPA signal difference due to P dimers were studied versus the growth temperature and V/III ratio. The degree of order decreases markedly with increasing growth temperature above 620°C at a constant V/III ratio of 40. This corresponds directly to a decrease of the [ 10]-oriented P dimer concentration on the surface determined using SPA. Below 620°C, the degree of order decreases as the growth temperature decreases, even though the concentration of P dimers increases. The presence of an isotropic “excess P” phase observed in the SPA spectrum at 480 nm might be responsible for the decrease of CuPt ordering, although it has previously been attributed to the slow rearrangement of adatoms. The degree of order is found to decrease monotonically with decreasing V/III ratio in the range from 160 to 8 at 670°C and from 40 to 8 at 620°C. This also corresponds directly to the decrease of the P dimer concentration on the surface measured using SPA. At 620°C and a V/III ratio of 160, the degree of order decreased despite an increase of the P dimer concentration. This may also be due to the formation of the isotropic “excess P” phase on the surface. The direct correlation of the [ 10]-oriented P dimer concentration and the degree of order with changes in temperature ( ≥ 620°C) and V/III ratio (≤ 160 at 670°C and ≤ 40 at 620°C) suggests that, in this range of growth parameters, the (2 × 4) surface reconstruction is necessary to form the CuPt structure, in agreement with published theoretical studies.     

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.     

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.     

Thermodynamic analysis of GaAs growth by molecular beam epitaxy at the surface structure transition from 3 × 1 to 4 × 2

The molecular beam epitaxy (MBE) growth of GaAs layers on a single crystal is studied in relation with the stability domain of the GaAs compound in the Ga-As binary system. The growth parameters, i.e. The Ga and As impinging atomic flows, are compared to the necessary flows as calculated by thermodynamics. In order to take into account in the real growth situation, which is not strictly at equilibrium, the flow balance at the surface of the crystal between the impinging flows and the growth and evaporated flows is written for quasi-equilibrium growth conditions, including condensation and evaporation coefficients that split the “so-called” sticking coefficient in parts related to the condensation or the evaporation phenomenon for each gaseous species. A comparison between the quasi-equilibrium simulation of the growth and the experiment is made with the assumption that the surface structure transition from gallium-stabilized to arsenic-stabilized surface corresponds to the growth of a GaAs crystal at its solidus boundary rich in gallium. The surface structure transitions are observed by reflection high energy electron diffraction (RHEED) and the impinging atomic flows are carefully calibrated and also controlled by RHEED oscillations as observed after gallium or arsenic excess as deposited on the surface. The results show that the growth is effectively performed close to equilibrium conditions as evidenced by the values of the condensations and evaporation coefficients. The evaporation coefficient of gallium is 0.4, showing that this component is the supersaturated one at the surface, and this value agrees with theoretical predictions for an evaporation process (during growth) controlled by the surface diffusion process of monoatomic species between steps.     

Decoration of growth and dissolution steps on the surfaces of L-arginine phosphate monohydrate crystals

Observations of decoration of growth and dissolution steps on the {100} surfaces of non-linear optical L-arginine phosphate monohydrate (LAP) crystals during their withdrawal through an n-hexane layer placed above its supersaturated and undersaturated solutions are described. This is the first report of decoration of growth or dissolution steps on the surfaces of crystals at or near room temperature in a liquid medium by the crystallizing or dissolving material.     

The theoretical growth form of potassium nitrate from an aqueous solution

The theoretical growth form the potassium nitrate, obtained from a PBC analysis, is compared to the growth forms obtained from aqueous solutions. The discrepancies are explained satisfactorily in a semi-quantitative way by taking the solvent interaction into account. It was assumed that the desolvation of the crystal surface determines the growth rate. The solvent interaction was obtained from molecular mechanics calculations on water molecules at the solvent accessible surfaces of the crystal faces. It was observed that the water molecules orient preferentially with their dipole moments parallel to the surface to form a “skin”, kept together by hydrogen bonds.     

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.     

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.