Surface reconstruction of sulfur-terminated GaAs(001) observed during annealing process by scanning tunneling microscopy

The surface reconstruction of in-situ prepared sulfur-terminated (S-terminated) and sulfur-protected (S-protected) GaAs(001) is studied by scanning tunneling microscopy (STM) at high temperatures of up to 260°C. We demonstrate a new reordering process from the (4×6) Ga-stabilized surface to the (2×6) S-stabilized surface and a novel method of air protection using a S passivation layer. Moreover, the in-situ observation of the annealing process of this S-protection layer is performed by high-temperature STM, avoiding the adsorption from environments and verifying that the (2×6) structure still becomes dominant on the S-terminated GaAs(001) surface without the effects of As atoms.     

RHEED studies of MOMBE growth using TMGa or TEGa with As2

MOMBE and CBE growth has until recently been based on largely empirical studies of the epitaxial process. We have used reflection high energy electron diffraction (RHEED), previously applied to the study of MBE, to study the growth GaAs using TMGa and As₂. In this work we have extended our previous studies to include a detailed study of the effect of As₂ flux on growth rate and to compare data on singular and vicinal plane surfaces cut off orientation in two orthogonal {110} directions. Clear evidence for site blocking mechanisms is observed together with an indication that the concentration of elemental Ga present on the surface during growth is negligible even under conditions where the arrival rate of TMGa exceeds that As₂. We have compared this behaviour with that observed using TEGa and As₂ under identical conditions. Using TEGa a conversion from a (2×4) to (4×2) reconstructed surface is observed under As deficient conditions indicating the presence of elemental Ga on the surface. This is accompanied by an abrupt change in growth rate similar to that secn in MBE.     

The characterization of the growth of sub-monolayer coverages (1/200th to 1 monolayer) of Si and Be on GaAs(001): A reflectance anisotropy spectroscopy and reflection high-energy electron diffraction study

The techniques of reflectance anisotropy spectroscopy (RAS) and reflection high-energy electron diffraction (RHEED) have been employed, for the first time in concert, to characterize the growth of sub-monolayer coverages of both Si and Be deposited onto the GaAs(001)-c(4×4) surface. The RHEED observations enabled the RAS spectra collected for a series of Si and Be coverages, in the range 0.005 to 1.000 monolayer (ML), to be interpreted in terms of changes in the sample surface structure. For the case of Si/GaAs(001) the following series of surface reconstructions were observed with increasing Si coverage: c(4×4), c(4×4)/(1×2), (1×2), (1×2)/(3×1) and, (3×1). During the deposition of Be/GaAs(001), c(4×4), c(4×4)/(1×2), c(4×4)/(1×3), (1×2)/(1×3), (1×3), and (1×2) reconstructions were noted to evolve. The fact that unique, but highly reproducible, RAS signatures were obtained for each of these surface phases demonstrates the applicability of a combined RHEED/RAS system for monitoring sub-monolayer heteroepitaxial growth with a surface sensitivity of the order of 1/200th of a monolayer.     

Negative magnetoresistance in Si atomic-layer-doped GaAs

Magnetoresistance of a Si atomic-layer-doped (δ-doped) GaAs is measured to study the transport properties of the δ-doped structure. The magnetoresistance decreases as the temperature is lowered and the depth of the δ-doped layer, i.e., the distance between the surface and the δ-doped layer, becomes less than 300 nm. Negative magnetoresistance is observed below 80 K in a sample having a doping density of 1.67×10¹² cm⁻² and a δ-doped layer depth of 40 nm. The conduction channel in the δ-doped structure consists of two parts, the quantized states in the conduction band and the impurity band. The origin of the negative magnetoresistance is suggested to be the conduction in the inhomogeneous potential due to localized impurity potential.     

Growth and spectral properties of Nd:LaVO4 crystal

This paper reports the growth and spectral properties of 3.5 at% Nd³⁺:LaVO₄ crystal with diameter of 20×15 mm² which has been grown by the Czochralski method. The spectral parameters were calculated based on Judd–Ofelt theory. The intensity parameters Ω_λ are: Ω₂=2.102×10⁻²⁰ cm², Ω₄=3.871×10⁻²⁰ cm², Ω₆=3.235×10⁻²⁰ cm². The radiative lifetime τ_r is 209 μs and calculated fluorescence branch ratios are: β₁(0.88μm)=45.2, β₂(1.06μm)=46.7, β₃(1.34μm)=8.1. The measured fluorescence lifetime τ_f is 137 μm and the quantum efficiency η is 65.6%. The absorption band at 808 nm wavelength has an FWHM of 20 nm. The absorption and emission cross sections are 3×10⁻²⁰ and 6.13×10⁻²⁰ cm², respectively.     

Chemical trend observed in anisotropic surface reflectance spectra of MOVPE by surface photoabsorption

This paper investigates the origin of the surface reflectance spectrum for the group-V-stabilized III–V surface during MOVPE by using surface photoabsorption. A chemical shift is observed for the stoichiometry sensitive peak in the anisotropic spectra of arsenides and phosphides. The peaks observed in the phosphides are located at higher energies than the arsenides, besides the peak in each compound shows a red-shift as the lattice constant increases. To investigate the possibility of the critical point of the bulk energy state appearing in the reflectance spectrum induced by surface modification, the anisotropic spectrum during InAs-on-GaAs heteroepitaxy are measured. One monolayer InAs growth on GaAs results in a drastic change that a peak sign is reversed, accompanied by a red-shift. This can be interpreted by the optical transition change corresponding to the surface conversion from a two-As-layer c(4 × 4)-like surface in GaAs to a one-As-dimer layer having a bond axis perpendicular to the c(4 × 4) As dimer. The contribution of the GaAs bulk electronic state in the reflectance spectrum is not observed. These results support the model that the anisotropic peak originates from an optical transition of the group-V dimer. The anisotropic spectrum measurement also makes it possible to monitor the P/As surface exchange and the As-atom segregation during the InP-on-InAs heteroepitaxy.     

Surface reconstruction phase diagrams for InAs, AlSb, and GaSb

We present experimental flux-temperature phase diagrams for surface reconstruction transitions on the 6.1 Å compound semiconductors. The phase transitions occur within or near typical substrate temperature ranges for growth of these materials by molecular beam epitaxy and therefore provide a convenient temperature standard for optimizing growth conditions. Phase boundaries for InAs (0 0 1) [(2×4)→(4×2)], AlSb (0 0 1) [c(4×4)→(1×3)], and GaSb (0 0 1) [(2×5)→(1×3)] are presented as a function of substrate temperature and Group V-limited growth rate (proportional to flux), for both cracked and uncracked Group V species. We discuss differences between materials in the slopes and offsets of the phase boundaries for both types of Group V species.     

Metastable PbO crystal grown through alcohol-thermal process

An alcohol-thermal route has been developed to the growth of single crystals of yellow metastable PbO in largest dimensions of 11×1×0.1 mm³, using freshly synthesized β-PbO crystallites as seeds. The transformation of metastable β-PbO to stable form (-PbO) can be slowed down by choosing appropriate solvent as the growth medium. The obtained β-PbO crystals have a strong orientational growth parallel to the (0 0 1) plane and exhibit a lath shape. Studies found that cooling rate and NaOH concentration also have great influence on the crystallographic forms of the final products during the alcohol-thermal process.     

Spectrally resolved electroluminescence microscopy and μ-electroluminescence investigation of GaN-based LEDs

We have studied the luminescence properties of GaN LEDs by electroluminescence microscopy (ELM) and micro-electroluminescence (μ-EL) spectroscopy. Spatial inhomogeneity in the deep level region of the spectra is observed in spectrally resolved ELM images. Room temperature μ-EL spectra measured from 5×5 μm² regions show anti-correlation of the defect-related recombination (E=1.95–2.45 eV) with the band-edge emission (E=3.18 eV).     

A new technique for the growth of superconducting YBa2Cu3O6 + δ crystals completely separated from flux

Growth of completely flux-separated YBa₂Cu₃O_{6 + δ} (referred to as 123 phase) crystals using a novel technique is described. The technique employs a modification of the seed pulling method commonly used in crystal growth. The crystals are grown in the temperature range of 960–1000°C using a BaCuO₂ flux. A 123 flux ratio of 1:5 is maintained. Photographs of the crystals and photomicrograph of the surfaces are presented to show complete flux-separation of the crystals measuring 6 mm × 3 mm × 1 mm. The Raman spectra recorded on the as-grown crystals show that they are in the tetragonal phase. Magnetic susceptibility measurements on crystals annealed in an oxygen atmosphere show a superconducting transition starting at 71 K. The present technique offers a possibility of growing large, completely flux-separated crystals of 123 for superconductivity research.     

High-quality InP grown by chemical beam epitaxy

InP films were grown by chemical beam epitaxy using trimethylindium (TMI) and pure phosphine (PH₃) in a flow control mode with hydrogen as the carrier gas, with the TMI flow rate fixed at 3 SCCM. Substrate temperatures were varied between 505 and 580°C and V/III ratios from 3 to 9. InP layers with high optical quality (intense and narrow excitonic transition lines) and high crystalline quality (narrow and symmetric X-ray diffraction peaks) could be grown only within a narrow parameter window around a substrate temperature of 545°C (δT_s ≤ 25°C) and a V/III ratio of 5.5 (δ(V/III) ≤ 2). Carrier densities of 8 × 10¹⁴ cm^-3 with mobilities of 70000 cm²/V.s measured at 77 K were obtained for growth conditions close to the edge of this parameter window towards low V/III ratios. The growth rate of inP was also clearly at its maximum in the given parameter window. Leaving the window, by changing either the growth temperature or the V/III ratio, significantly decreased the growth rate. This reduced growth rate was accompanied by a degradation in the crystalline quality. We also demonstrate that for higher TMI flow the parameter window shifts to higher growth temperatures. The InP could be doped effectively with Si in the range from 9 × 10¹⁵ to 3 × 10¹⁸ cm^-3.     

Growth and spectral properties of Nd-doped Sr3Y(BO3)3 crystal

A new crystal of Nd³⁺:Sr₃Y(BO₃)₃ with dimension up to 25×35 mm² was grown by Czochralski method. Absorption and emission spectra of Nd³⁺: Sr₃Y(BO₃)₃ were investigated . The absorption band at 807 nm has a FWHM of 18 nm. The absorption and emission cross sections are 2.17×10⁻²⁰ cm² at 807 nm and 1.88×10⁻¹⁹ cm² at 1060 nm, respectively. The luminescence lifetime τ_f is 73 μs at room temperature     

The electrical, optical and crystalline properties of GaAs: C grown by GSMBE using TMG and AsH3 for application to HBTs

We report the results of a comprehensive study on the electrical, optical and crystalline properties of heavily carbon doped p-type (100) GaAs epilayers (p = 6.3 × 10¹⁸−1.3 × 10²⁰ cm^-3; THICKNESS = 250−420 nm) grown by gas source molecular beam epitaxy using trimethylgallium and arsine. X-ray analysis showed epilayer lattice contraction with a mismatch of δa/a = -1.8 × 10^-3 at p = 1.3 × 10²⁰ cm^-3. Room temperature photoluminescence peak energy shifted from 1.40 eV (p = 6.3 × 10¹⁸ cm^-3) to 1.37 eV (p = 1.3 × 10²⁰ cm^-3). Stokes Raman spectra showed two modes assigned as the unscreened LO phonon (292 cm^-1) and the low frequency branch of the coupled hole-plasmon-LO-phonon (266 cm^-1). Conservation of Raman scattering rules under all incident light configurations showed that the (100) GaAs:C epilayers were of high crystalline quality without the presence of faceting or other such crystalline defects. Annealing at 900°C for between 30 s to 45 min, resulted in a significant reduction in the hole concentration, lattice contraction and photoluminescence intensity for all epilayers. The implications of these results for the development of GaAs/AlGaAs HBTs are discussed.     

Surface reconstructions and growth mode transitions of AlAs(100)

The surface reconstructions of AlAs(100) layers grown by molecular beam epitaxy (MBE) on GaAs(100) were mapped as a function of substrate temperature and arsenic flux. Three main reconstructions were observed - a c(4×4) at lower temperatures and higher arsenic fluxes, a (2×4) at middle temperatures, and a (3×2) at higher temperatures and lower arsenic fluxes. Growth of AlAs on AlAs(100) is layer-by-layer for the high temperature and low temperature reconstructions. In the mid-temperature region, AlAs grows rough on (2×4) reconstructed AlAs(100) as indicated by rapidly damped reflection high-energy electron diffraction (RHEED) intensity oscillations and the appearance of three-dimensional (3D) features. The addition of fractional layers of Ga enhances the smooth growth of AlAs. A metastable (5×2) reconstruction was observed when a fraction of a layer of Ga was present on the surface. The results indicate that Ga segregates during the growth of AlAs on GaAs(100) at temperatures at least as low as 500°C, and that annealing at temperatures above 700°C removes most of the Ga from the surface.     

Density and surface tension of molten calcium fluoride

The density and the surface tension of molten calcium fluoride have been measured in the temperature range from 1690 to 1790 K by an improved Archimedian method and a ring depressing technique (J. Crystal Growth 187 (1998) 391), respectively. The ring depressing technique was demonstrated as an effective technique to measure the surface tension in comparison with the conventional ring pulling technique. The density varied with the temperature change corresponding to a linear relationship: ρ=3.767−6.94×10⁻⁴T (K). The density of the CaF₂ melt at the melting point is 2.594 g/cm³, which is equal to the result obtained by Shiraishi and Watanabe (Bull. Res. Inst. Miner. Dressing Metal, Tohoku Univ. 34 (1978) 1), but the temperature coefficient of the density is different from the results obtained by other investigators. The thermal expansion coefficient of calcium fluoride melt linearly increases with temperature heating. The surface tension of molten calcium fluoride indicates a negative linear relationship as a function of the melt temperature: γ(T)=442.4−0.0816×T(K) (mN/m). The surface tension measured using the ring depressing technique is larger than those results obtained by other techniques.     

Quantum transport measurements on Si δ- and slab-doped In0.53Ga0.47As grown by molecular beam epitaxy

A series of high quality δ-doped In_0.53Ga_0.47As samples have been grown lattice matched to InP with design doping densities in the range 2×10¹² to 5×10¹² cm⁻². Analysis of the individual sub-band densities deduced from the Shubnikov-De Haas effect shows that both spreading and amphoteric behaviour increase with doping density.     

Structural distribution and rigidity of the glass network determined by EPR of Cu

The linewidth-broadening of the EPR spectra of Cu²⁺ in silicate, borate and phosphate glasses was analyzed in terms of the distribution of g_| and A_| (δ_| and δA_|) and related to the distribution of the rigidity of the network structure. X- and K-band spectra were measured for the glasses doped with ⁶³Cu²⁺ (93% abundance). The linewidth of the HFS shoulders with parallel orientation to H increased linearly with increasing m or microwave frequency. δg_| and δA_| showed a marked dependence on glass composition. For example, in Na₂O---B₂O₃ glasses, on going from x (mol% of Na₂O) being small through intermediate to large, δg_| varied from small through large to negligibly small. In contrast to these glasses δg_| was extremely large for 75PbO · 25B₂O₃ glass. The large δg_| for the Na₂O---B₂O₃ glassesof intermediate x was attributed to the coexistence of various borate groups competitively coordinating to Cu²⁺. Negligibly small δg_| for 70Na₂O · 30B₂O₃ glass and extremely large δg_| for 75PbO ·25B₂O₃ glass, both with a narrower structural distribution, reflect regidity of the glass network. The Pb---O bonding is strong enough to distort the coordination of Cu²⁺-complex. The situation is the reverse in Na₂O---B₂O₃ glasses.     

Crystal growth of KTiOPO4 isomorphs from tungstate and molybdate fluxes

Large inclusion-free crystal of KTiOPO₄, RbTiOPO₄, KTiOAsO₄ and RbTiOAsO₄ have been grown from the tungstate and molybdate fluxes. In this paper, we report the typical growth parameters, the solubilities, and the heats of solution (δH_sol) for these crystals, and briefly comment on their optical quality. In addition to being nonvolatile and of low viscosity, the tungstate and the molybdate fluxes also have significantly faster dissolution kinetics than the pure phosphate or arsenate self-flux. This makes them especially versatile for the exploratory crystal growth of the KTP isomorphs and their solid solutions. Using these fluxes, single crystal boules of up to 2.5×3×5 cm³ have been grown from a 250 ml melt. We have also observed a modification in the crystal growth habit, which in the case of KTiOAsO₄, results in the formation of stable, singular {111} faces.     

A scanning tunnelling microscopy study of the deposition of Si on GaAs(001); Implications for Si δ-doping

Atomic resolution scanning tunnelling microscopy (STM) has been used to study the adsorption of Si on GaAs(001) surfaces, grown in situ by molecular beam epitaxy (MBE), with a view to understanding the incorporation of Si in δ-doped GaAs structures. Under the low-temperature deposition conditions chosen, the clean GaAs surface is characterized by a well-defined c(4×4) reflection high-energy electron diffraction (RHEED) pattern, a structure involving termination with two layers of As. Filled states STM images of this surface indicate that the basic structural unit, when complete, consists of rectangular blocks of six As atoms with the As-As bond in the surface layer aligned along the [110] direction. Deposition of <0.05 ML of Si at 400°C onto this surface shows significant disruption of the underlying structure. A series of dimer rows are formed on the surface which, with increasing coverage, form anisotropic "needle-like" islands which show no tendency to coalesce even at relatively high coverages (0.5 ML). The formation of these islands accompanies the splitting of the 1/2 order rods in the RHEED pattern along [110]. As the Si is known to occupy only Ga sites, the Si atoms displace the top layer As atoms of the c(4×4) structure, with the displaced As atoms forming dimers in a new top layer. The results are consistent with a recently proposed site exchange model and subsequent island formation for surfactant mediated epitaxial growth.     

Diffusion of Zn in stoichiometric LiTaO3

As stoichiometric LiTaO₃ (LT) draws a considerable attention for integrated optical waveguide devices, we have investigated Zn diffusion into this material by diffusing 70- nm-thick ZnO films deposited on y-cut LT substrates at 700–900 °C under various atmospheres. It was observed that the surface quality was very sensitive to pressure, but weakly affected by other diffusion conditions such as temperature and atmosphere. While the surface degraded, being covered with some residuals after heat treatment at the atmospheric pressure, it was very smooth and clear when the pressure was lowered below about 10 Torr. Another feature of Zn-diffused stoichiometric LT is that the crystal maintains its transparency even after diffusion at a pressure as low as 0.1 Torr, thus without a post-annealing step required. The diffusion coefficient varied from D=1.1×10^-2 to 5.5×10⁻¹ μm²/h in the given temperature range, with an activation energy of .