Growth reactions and mechanisms in chemical beam epitaxy (CBE)

The rapidly increasing interest in chemical beam epitaxy (CBE) and related ultra-high vacuum (UHV)-based epitaxial growth techniques has arisen primarily as a result of their expected technological advantages compared to either the conventional molecular beam epitaxy (MBE) or metalorganic vapour phase epitaxy (MOVPE) processes. The CBE-related techniques do, however, provide the additional important advantage, compared to MOVPE, that the UHV environmental allows in-vacuo analytical techniques to be used to provide in-situ characterization regarding the composition and crystallography of the growing layers, and also vital information regarding the growth mechanisms involved. The present paper reviews the current understanding relating to III–V CBE reaction mechanisms, and highlights specific topics which require further investigation.     

Generation mechanism of CuAu-I type ordered structures in InGaAs crystals grown on (110) InP substrates by molecular beam epitaxy

The generation mechanism for CuAu-I type ordered structures in InGaAs grown on (110) InP substrates by molecular beam epitaxy is discussed. On the basis of previous work together with considerations of the atomic arrangement of the ordered structure and surface reconstruction on the (110) plane, we propose four possible models for the ordering. Through precise evaluation of these models, two models are selected as the most probable ones: these involve formation of the ordered structures on surfaces dominated by two monolayer steps. This model have been experimentally proven by the analyses of electron diffraction patterns from different crystals grown on different growth surfaces.     

Effects of pressure and temperature on RD detected growth oscillations

We report on the vacuum chemical epitaxy (VCE) growth of GaAs from triethylgallium and arsine at varying partial pressures of arsine and hydrogen. In situ, monolayer growth oscillations were, for the first time, detected in a hydrogen environment using reflectance difference (RD). These results offer the possibility to link surface mechanisms occuring during chemical beam epitaxy (CBE) with those taking place in metalorganic vapour phase epitaxy (MOVPE) and may lead to the observation of growth oscillations also during MOVPE. Finally, the behaviour of the RD signal as a function of substrate temperature is studied over a wider temperature interval than has previously been reported, giving further information about surface processes.     

InP同质外延的不稳定生长:小丘的形成

用原子力显微镜研究了在不同的条件下采用固态磷源分子束外延技术生长的InP同质外延薄膜的表面形貌。在样品的表面观察到不稳定三维岛状生长。其主要原因有两种,第一种是生长温度较低时,由于吸附原子受到附加的ES台阶边垒的阻碍作用,使扩散运动不能向台阶下面运动,而在台阶上面形成小丘,第二种是生长温度较高或V/III较低时,因生长中缺磷造成In的堆积而产生。在合适的生长条件下,可获得了光滑的2D层状生长。     

Molecular beam epitaxial growth and thermodynamic analysis of InGaAs and InAlAs lattice matched to InP

Reflection high-energy electron diffraction (RHEED) intensity oscillations have been used to detect the onset of metal droplet formation on the surface of InAs, InGaAs and InAlAs during molecular beam epitaxy. The growth conditions which produce such droplets are shown to be in good agreement with predictions based on thermodynamic arguments.     

Growing of bulk crystals and structuring waveguides of fluoride materials for laser applications

We report on recent progress in the synthesis, the crystal growth and the epitaxial growth of fluoride and other laser materials. Results on the fabrication of single crystalline waveguides for dielectric down - and upconversion lasers pumped by semiconductor diode lasers are summarized. Epitaxial growth (molecular beam epitaxy (MBE), liquid phase epitaxy (LPE), pulsed laser deposition (PLD)) and surface modifying techniques (high energy ion implantation, ion diffusion) have been applied in several laboratories. Progress in techniques fabricating optical waveguides from glassy media is addressed as well. Particular emphasis is given on the structuring (wet etching, chemical polishing, ion beam etching) of fluoride crystals for the purpose of obtaining 2-D and 1-D optical waveguides. Results on the structuring of LiYF₄ by wet and ion beam etching are reported. With respect to laser action, the generation of short wavelength light by upconversion (UC) processes, stimulated Raman scattering (SRS) and second harmonic generation (SHG) is discussed. Reports on the first crystalline waveguide lasers of fluoride crystals LiYF₄ and LaF₃, both doped with neodymium, are presented.     

Effect of growth interruptions on ultra-thin InAs/InP quantum wells grown by chemical beam epitaxy

We have studied the effect of growth interruptions on 2 monolayer thick InAs/InP strained quantum wells (QWs) grown by chemical beam epitaxy. The main feature is the formation of up to 8 monolayer thick InAs islands during As₂ annealing of the QW. Their formation is characterized by a two- to three-dimensional transition of the reflection high energy electron diffraction (RHEED) pattern and by multiple-line photoluminescence spectra. This interpretation of the data is confirmed by transmission electron microscopy (TEM).     

Growth of ZnO bulk crystals: A review

A critical review is proposed of the different techniques of bulk growth of ZnO crystals for their use as a substrate in the homoepitaxial growth of this attractive compound. The crystals are assessed from their structural and electrical properties and from the structural properties and purity of homoepitaxial films grown on them by various techniques such as plasma-assisted molecular beam epitaxy, pulsed laser deposition, magnetron sputtering, chemical vapor deposition, metalorganic chemical vapor epitaxy, liquid phase epitaxy.     

In situ processing of III–V semiconductors: Mile stones and future prospects

In situ processing combined with metalorganic vapor phase epitaxy (MOVPE), molecular beam epitaxy, or chemical beam epitaxy appears to be an attractive method for fabricating sophisticated optoelectronic devices such as buried heterostructure lasers, vertical cavity surface emitting lasers, and photonic integrated circuits. Successful reduction of residual contaminants at the regrowth interface and improvement in the optical and electrical quality of the regrown layer has been achieved by using in situ processing techniques. Device fabrication is alrady taking advantage of this kind of technology. Nevertheless, interface quality between an in situ etched layer and a regrown layer has not yet reached the status of continuously grown interfaces. In this paper, progress of in situ processing is reviewed mainly focusing on our recent studies on in situ HCl gas etching in MOVPE. The approach of two-step HCI gas etching has proven superior to obtain clean regrowth interfaces, leading to the conclusion that the in situ processing can be widely used for advanced optoelectronic device fabrication.     

Formation and characterization of GaAs/As superlattice grown by molecular beam epitaxy at low substrate temperature

High-resolution X-ray diffractometer and transmission electron microscope (TEM) are used to characterize the redistribution of As precipitates in Si δ-doped GaAs grown by molecular beam epitaxy at low substrate temperature (230°C). The superlattice satellite peaks are observed for samples annealed at 700-800°C for 10 min, which is attributed to the formation of a GaAs/As superlattice during the annealing period. The degree of As precipitates confined on the δ-doped planes is revealed on the intensity of satellite peaks in the X-ray rocking curves, as confirmed by the TEM observations. The lattice expansion and contraction of the annealed low-temperature epitaxial layers can be easily observed from the asymmetry of the satellite peaks.     

Growth of InGaAs/GaAs heterostructures with abrupt interfaces on the monolayer scale

Segregation processes entail severe deviations from the nominal composition profiles of heterostructures grown by molecular beam epitaxy for most semiconductor systems. It is, however, possible to compensate exactly these effects, as shown here for InGaAs/GaAs. The deposition of a one-monolayer-thick indium-rich prelayer of InGaAs (or of a sub-monolayer amount of InAs) prior to growth of In_xGa_1−xAs allows forming a perfectly abrupt In_xGa_1−xAs-on-GaAs interface. Thermal annealing can furthermore be performed at the GaAs-on-InGaAs inter face, so as to desorb surface indium atoms and suppress In incorporation in the GaAs overlayer. This powerful approach has been validated from a detailed study of the surface composition at various stages of the growth of InGaAs/GaAs quantum wells, as well as from high-resolution transmission electron microscopy and photoluminescence investigations.     

p-Type GaAs doped by diiodomethane (CI2H2) in molecular beam epitaxy, metalorganic molecular beam epitaxy, and chemical beam epitaxy

Highly p-type carbon-doped GaAs epitaxial layers were obtained using diiodomethane (CI₂H₂) as a carbon source. In the low 10¹⁹ cm⁻³ range, almost all carbon atoms are electrically activated and at 9×10¹⁹ cm⁻³, 91% are activated. The carbon incorporation efficiency in GaAs layers grown by metalorganic molecular beam epitaxy (MBE) and chemical beam epitaxy (CBE) is lower than that by MBE due to the site-blocking effect of the triethylgallium molecules. In addition, in CBE of GaAs using tris-dimethylaminoarsenic (TDMAAs), the carbon incorporation is further reduced, but it can be increased by cracking TDMAAs. Annealing studies indicate no hydrogenation effect.     

The transition from As-doped GaN, showing blue emission, to GaNAs alloys in films grown by molecular beam epitaxy

We have studied the transition from As-doped GaN showing strong blue emission (2.6 eV) at room temperature to the formation of GaN_1−xAs_x alloys for films grown by plasma-assisted molecular beam epitaxy. We have demonstrated that with increasing N-to-Ga ratio there is first an increase in the intensity of blue emission at about 2.6 eV and then a transition to the growth of GaN_1−xAs_x alloy films. We present a model based on thermodynamic considerations, which can explain how this might occur.     

How to Avoid Plastic Deformation in GaAs Wafers during Molecular Beam Epitaxial Growth

Plastic deformation in two‐inch diameter GaAs wafers resulted from standard thermal treatments which accompanied epitaxial growth in molecular beam epitaxy (MBE) machines of three different makes. Synchrotron based X‐ray transmission topography was used to distinguish between thermal treatment induced dislocation bundles and misfit dislocations. Eradication of the wafer slip related dislocation bundles has been achieved by modifications to the sample holder of a user built MBE machine. These modifications are discussed, the extent of the problem is briefly outlined, and an extrapolation of the susceptibility of GaAs wafers of higher diameters to this type of plastic deformation is given.     

MOMBE growth characteristics of antimonide compounds

This paper describes the MOMBE (metalorganic molecular beam epitaxy) growth characteristics of antimonide compounds using TMIn (trimethylindium), TEGa (triethylgallium) and TIBAl (triisobutylaluminium) as group III sources, and As₄, Sb₄, TEAs (triethylarsine) and TESb (triethylstibine) as group V sources. Large differences in the growth characteristics of GaAs and GaSb MOMBE are observed. These are explained, using a theoretical consideration of the growth mechanism, by the difference in the effective surface coverage of excess As and Sb atoms during the growth. The use of TEAs and TESb instead of As₄ and Sb₄ alters the growth rate variation of both GaAs and GaSb with substrate temperature (T_sub), which results from the interaction of alkyl Ga species with the alkyl radicals coming from the thermally cracked TEAs and TESb. The alkyl exchange reaction process is observed in the growth of AlGaSb using TIBAl and TEGa, where the incorporation rate of Al is suppressed by the coexistence of TEGa on the growth surface, in the low T_sub region. This is caused by the formation of an ethyl-Al bond which is stronger than the isobutyl-Al bond. The composition and the growth rate variations of InGaSb with T_sub are similar to those of InGaAs, which are closely related to the MOMBE growth process and are quite different from those of MBE (molecular beam epitaxy) and MOVPE (metalorganic vapor phase epitaxy) growth. In the MOMBE growth of InAsSb and GaAsSb using TEAs and TESb, the composition variation with T_sub is weaker than that of MBE. This is a superior point of MOMBE growth for the composition control. The electrical and optical properties of MOMBE grown films as well as the quantum well structures are also described.     

Growth of freestanding GaN using pillar-epitaxial lateral overgrowth from GaN nanocolumns

Dislocation-free and strain-free GaN nanopillars, grown on Si by molecular beam epitaxy, were used as nanoseeds for a new form of epitaxial lateral overgrowth (ELO) by metalorganic vapour phase epitaxy (MOVPE) until full coalescence. Such overgrown GaN films are almost relaxed and were used as templates for producing thick GaN layers by halide vapour phase epitaxy (HVPE). The final GaN film is easily separated from the starting Si substrate. This is henceforth a new technology to produce freestanding GaN. The GaN crystal quality was assessed by transmission electron microscopy (TEM), photo- and cathodoluminescence (PL, CL). It was seen that the pillar-ELO is produced from a limited number of nanopillars. Some dislocations and basal stacking faults are formed during the coalescence. However, those that propagate parallel to the substrate do not replicate in the top layer and it is expected that the thickened material present a reduced defect density.     

Hillock formation observed in MOMBE of InGaAs grown on a patterned GaAs substrate

We observed hillock formation during metalorganic molecular beam epitaxy (MOMBE) of InGaAs on a mesa-grooved (100) GaAs substrate. Hillocks were formed under specific growth conditions and comprised mostly InAs. The distribution of hillocks formed in InGaAs MOMBE using trimethylindium (TMIn) and metal Ga depended strongly on the widths of mesa-grooves; the density decreased with decreasing width and hillocks were hardly observed on the ridges. The hillock density also varied, depending on the off-angle of the substrate from the (100) plane. This indicates that the observed anomalous distribution of InGaAs hillocks was caused by both the formation of facets and a vicinal tilted surface near the edge of mesa-grooves, due to the growth of a GaAs buffer layer on a patterned substrate.     

AlGaAs/GaAs/AlGaAs quantum wells as a sensitive tool for the MOVPE reactor environment

We present in this work a simple quantum well (QW) structure consisting of GaAs wells with AlGaAs barriers as a probe for measuring the performance of arsine purifiers within a metalorganic vapour phase epitaxy system. Comparisons between two different commercially available purifiers are based on the analysis of low-temperature photoluminescence emission spectra from thick QWs, grown on GaAs substrates misoriented slightly from (1 0 0). Neutral excitons emitted from these structures show extremely narrow linewidths, comparable with those that can be obtained by molecular beam epitaxy in an ultra-high vacuum environment, suggesting that purifications well below the 1 ppb level are needed to achieve high quality quantum well growth.     

Blue emission from arsenic doped gallium nitride

We have observed strong blue emission at room temperature from arsenic doped GaN samples grown by molecular beam epitaxy. Similar results were obtained for samples doped with both arsenic dimers and tetramers. The origin of this blue emission is discussed and a growth model proposed to account for our observations. We propose that arsenic doped GaN may be a suitable replacement for (InGa)N as the active region for blue light emitting devices.     

Influence of semi-insulating InP substrates on InAlAs epilayers grown by molecular beam epitaxy

Tensile-strained InAlAs layers have been grown by solid-source molecular beam epitaxy on as-grown Fe-doped semi-insulating (SI) InP substrates and undoped SI InP substrates obtained by annealing undoped conductive InP wafers (wafer-annealed InP). The effect of the two substrates on InAlAs epilayers and InAlAs/InP type II heterostructures has been studied by using a variety of characterization techniques. Our calculation data proved that the out-diffusion of Fe atoms in InP substrate may not take place due to their low diffusion coefficient. Double-crystal X-ray diffraction measurements show that the lattice mismatch between the InAlAs layers and the two substrates is different, which is originated from their different Fe concentrations. Furthermore, photoluminescence results indicate that the type II heterostructure grown on the wafer-annealed InP substrate exhibits better optical and interface properties than that grown on the as-grown Fe-doped substrate. We have also given a physically coherent explanation on the basis of these investigations.