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.     

Surface diffusion lenght during MOMBE and CBE growth measured by μ-RHEED

The growth rates of layers grown on a mesa-etched (001) GaAs surface were measured by in-situ scanning microprobe reflection high-energy electron diffraction (μ-RHEED) from the period of the RHEED intensity oscillation in real time. The diffusion lenght of the surface adatoms of column III elements was determined from the gradient of the variation of the growth rates in the cases of MBE, MOMBE using trimethylgallium (TMGa) and CBE using TMGa or triethylgallium (TEGa) and arsine (AsH₃). The obtained values of the diffusion lengths were of the order of a micrometer in every case of the source-material combination. In the case of metalorganic materials as Ga source, it was found that the diffusion length was larger than that of Ga atom from metal Ga source. Since the substrate temperature of the present experiment is high enough to decompose TMGa and TEGa on the surface, Ga adatoms are considered to be responsible to the surface diffusion. Therefore, it is considered that the derivatives of the metalorganic molecules such as methyl radicals affect the diffusion of Ga adatoms.     

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.     

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.     

A mass spectrometric study of the decomposition of trymethylarsine (TMAs) with triethylgallium (TEGa)

The decomposition mechanisms of trimethylarsine (TMAs) with triethylgallium (TEGa) were studied using a sampling gas method with a mass spectrometer. When TEGa is present, the TMAs concentration starts to decrease at temperatures about 100°C lower than for TMAs alone. The TMAs concentration in the gas phase decreases simultaneously with TEGa decomposition. The rate constant of the TMAs concentration decrease is strongly affected by the TMAs/TEGa mole ratio. However, the TEGa decomposition rate is not affected by the TMAs/TEGa mole ratio. The TMAs concentration decrease is mostly due to the decomposition of the adduct between TMAs and TEGa. TMAs in the gas phase starts to decompose and generate methane at 400°C. However, some TMAs molecules probably adsorb on the reactor surface and/or are incorporated into the GaAs crystal as carbon. Between 340 and 450°C, the concentration of carbon in the TMAs adsorbed on the surface as TMAs and/or incorporated into GaAs as carbon atom is stable and keeps a constant concentration: the TMAs generates no methane.     

Stability of GaAs oxide under metalorganic molecular beam epitaxy process

Well-defined oxide of GaAs can be used as a mask material for selective-area metalorganic molecular beam epitaxy (MOMBE) of GaAs. In this study, the reaction between triethylgallium (TEG) and the GaAs oxide layer was studied using a quadrupole mass spectrometer (QMS) and an atomic force microscope (AFM). Results of the QMS observation showed that TEG was reflected on the GaAs oxide surface until the start of desorption of the GaAs oxide, and the GaAs oxide layer was desorbed from the wafer after a large time delay from the start of TEG supply. AFM images showed that many holes appeared on the GaAs oxide surface during the desorption of the GaAs oxide. The effect of incident TEG upon the stability of the GaAs oxide mask is discussed.     

Stabilization of the melt composition in Ga?Al?Sb?As

In this work we present a new effect of stabilization of the Ga Al Sb As melt composition when it is in contact with the GaAs substrate. It was found that the As content in the Ga Al Sb As melt did not depend on the initial Sb concentration when the liquid phase was formed by saturating the Ga Al Sb melt from the GaAs substrate. This effect is supposed to be due to the change in phase equilibria conditions caused by large lattice mismatch between the substrate and the solid in equilibrium with the liquid.     

Characteristics of GaSb growth using various gallium and antimony precursors

We report the epitaxial growth of GaSb using trimethylgallium (TMGa) or triethylgallium (TEGa) with trimethylantimony (TMSb), triethylantimony (TESb), or trisdimethylaminoantimony (TDMASb) in a low-pressure vertical rotating-disk reactor. Growth is kinetically limited for TMGa in the temperature range 560 to 640°C, and is mass-transport limited for TEGa in the range 525 to 640°C. A minimum V/III ratio is necessary to obtain stoichiometric GaSb, and is dependent on the pyrolysis temperature of Ga and Sb precursors. Featureless morphology is achieved for layers grown with TMGa or TEGa and TMSb, while surface defects are observed for layers grown with TEGa and TESb or TDMASb. These observations are consistent with Fourier transform infrared measurements, which indicate interactions between TEGa and TESb or TDMASb. All nominally undoped layers are p-type, with overall superior properties being obtained for layers grown with TEGa and TMSb. However, growth conditions that yield layers with the best electrical properties do not necessarily correspond to the same conditions for highest optical quality.     

A comparative study of GaAs- and InP-based HBT growth by means of LP-MOVPE using conventional and non gaseous sources

Low-pressure metalorganic vapor phase epitaxy (LP-MOVPE) growth of carbon doped (InGa)P/GaAs and InP/(InGa)As heterojunction bipolar transistors (HBT) is presented using a non-gaseous source (ngs-) process. Liquid precursors TBAs/TBP for the group-V and DitBuSi/CBr₄ for the group-IV dopant sources are compared to the conventional hydrides AsH₃/PH₃ and dopant sources Si₂H₆/CCl₄ while using TMIn/TEGa in both cases. The thermal decomposition of the non gaseous sources fits much better to the need of low temperature growth for the application of carbon doped HBT. The doping behavior using DitBuSi/CBr₄ is studied by van der Pauw Hall measurements and will be compared to the results using Si₂H₆/CCl₄. Detailed high resolution X-ray diffraction (HRXRD) analysis based on 004 and 002 reflection measurements supported by simulations using BEDE RADS simulator enable a non-destructive layer stack characterization. InGaP/GaAs HBT structures designed for rf-applications are grown at a constant growth temperature of T_gr=600°C and at a constant V/III-ratio of 10 for all GaAs layers. P-type carbon concentrations up to P = 5·10¹⁹cm⁻³ and n-type doping concentrations up to N = 7·10¹⁸cm⁻³ are achieved. The non self-aligned devices (A_E = 3·10 μm²)_show excellent performance, like a dc-current gain of B_max = 80, a turn on voltage of V_offset = 110 mV (Breakdown Voltage V_CEBr,0 > 10 V), and radio frequency properties of f_T/f_max = 65 GHz/59 GHz.

In the non-gaseous source configuration the strong reduction in the differences of V/III-ratios and temperatures during HBT structure growth enable easier LP-MOVPE process control. This is also found for the growth InP/InGaAs HBT where a high dc-current gain and high transit frequency of f_T= 120 GHz are achieved.     

Heavily carbon-doped GaAs grown on various oriented GaAs substrates by MOMBE

Heavily carbon-doped GaAs epitaxial layers have been grown simultaneously on (100), (111)A, (111)B, (411)A, (411)B and (711)A semi-insulating (SI) GaAs substrates by metalorganic molecular beam epitaxy (MOMBE) using trimethylgallium (TMG) and elemental As (As₄). The hole concentration and surface flatness strongly depend on the substrate orientation. The highest carbon incorporation was observed for the layers grown on a (411)A substrate with a hole concentration of 1.0 × 10²¹ cm^{− 3} and a lattice mismatch of Δd/d = −0.48%. Atomic force microscope (AFM) images reveal that the epilayers grown on (411)A substrates exhibit extremely flat surfaces, although these layers contain the highest carbon concentration.     

MOMBE GaAs and AlGaAs for microelectronic devices

This paper reviews the state of the art of GaAs and AlGaAs materials and microelectronic devices grown by MOMBE (metalorganic molecular beam epitaxy) and related techniques. FET, HEMT and HBT devices have been grown using MOMBE and in the case of FETs and HBTs excellent device and MMIC power performance has been obtained. For example, MOMBE HBTs show current gains in excess of 100 and MMIC power HBT circuits are delivering 2 W of power at 8.5 GHz. We will examine device behavior and relate this to properties of the GaAs and AlGaAs materials.     

Hydrogen and nitrogen ambient effects on epitaxial growth of GaN by hydride vapour phase epitaxy

This study presents the influence of the composition of the carrier gas on the growth of GaN by HVPE. Since no hydrogen is introduced in the vapour phase, the deposition is expected to be controlled by Cl desorption in the form of GaCl₃, as has been proposed for GaAs. However, our published model predicts much lower growth rates than those observed. We can account for both the observed parasitic deposition and GaN growth rate if we assume that GaCl₃ is not at its equilibrium pressure in the deposition zone and where nucleation takes place on the walls as well as on the substrate. This yields a high rate of parasitic nucleation even though the nominal supersaturation is vanishing small. Very little growth takes place on the substrate where the equilibrium pressure of GaCl₃ is reached. We describe similar experiments performed with a H₂/N₂ mixture as the carrier gas. In this case, we expect GaN deposition to be controlled by desorption of Cl as HCl, which is known as the H₂ mechanism. It is speculated that the results show the existence of a new growth mechanism.     

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.     

Reaction kinetics for the CBE growth of GaAs from triethylgallium; computer modelling studies incorporating recent surface spectroscopic data

A new model for the decomposition of triethylgallium on GaAs(100), with kinetic parameters derived from the results of surface science experiments, is presented. Deficiencies of early models are corrected by including surface coverage and site blocking effects, and lateral interactions between absorbed DEG species are included. The model successfully predicts variations in the rate of CBE growth of GaAs with substrate temperature, and addresses effects induced by variations in arsenic overpressure. This dependence of growth rate on the arsenic flux is modelled by computing the steady state concentrations of absorbed arsenic as a function of temperature and As₂ and TEG flux. Excess arsenic is shown to inhibit GaAs growth by blocking sites for TEG absorption.     

Comparison of MOVPE grown GaAs solar cells using different substrates and group-V precursors

We have investigated the influence of substrate type (GaAs vs. germanium) and of group-V precursor (AsH₃ vs. TBAs) on the epitaxial quality of (In)(Al)GaAs layers. We evaluated these layers in terms of morphology, background contamination and doping characteristics. For final benchmarking of the individually optimised processes, we produced p-on-n single junction GaAs solar cells and compared their relative performance. This type of device is an excellent performance monitor for epitaxial layers as the fundamental operating mechanism is drift of minority carriers. The solar cell grown with TBAs on a germanium-substrate has a conversion efficiency under the AM1.5 solar spectrum, which compares favourably with the highest reported value for a p-on-n GaAs solar cell on Ge (Prog. Photovolt. Res. Appl. 8 (2000) 377).     

Laser-assisted chemical beam epitaxy for selective growth

A recent exciting development in the growth of compound semiconductors is the use of light to modify the film growth rate in the irradiation area. We report Ar⁺-laser-assisted CBE of GaAs, InP, GaP and InGaAs to generate various patterned films without lithography. A linked-circle pattern is formed by laser beam scanning and a 0.85 μm pitch corrugation pattern formed by a holographic interference technique. Relationships between the growth rate and substrate temperature for the materials are compared. The mechanism of the growth rate enhancement is revealed to be photolytic decomposition of metalorganic molecules. In the case of InGaAs, laser irradiation above 500°C results in new phenomena of growth rate suppression and composition variation.     

A theoretical treatment of GaAs growth by vapour phase transport for {001} orientation

The normal growth rate of a {001} face has been theoretically studied; by considering either direct fixation of gallium arsenide molecules, or formation of intermediate surface compounds. From the theory of rate processes, it appears that experimental results can be interpreted by considering the reactions of desorption of the chlorine atoms adsorbed on surface as limiting the growth. A theoretical expression of the normal growth rate based on desorption by hydrogen has been performed. The descending portions of the curves with decreasing substrate temperature or increasing partial pressure of gallium monochloride, appear as due to an increasing coverage of surface with gallium monochloride molecules. Absolute theoretical values agree with experimental published measures, except for the weakest substrate temperatures. This disagreement may be due to the possibility of desorption of two chlorine atoms by gallium monochloride and formation of gallium trichloride molecules.     

Arsenic-free GaAs substrate preparation and direct growth of GaAs/AlGaAs multiple quantum well without buffer layer

High-temperature treatment of GaAs substrate without As flux in a preparation chamber was investigated as a substrate surface cleaning method for molecular beam epitaxial (MBE) growth. Oxide gases such as CO and CO₂ were almost completely desorbed at a temperature above which Ga and As started to evaporate from the substrate. During the cleaning at a temperature as high as 575°C for 30 min, about 100 nm thick GaAs was evaporated from the substrate, but its surface maintained mirror-like smoothness and showed streak pattern with surface reconstruction pattern in the reflection high energy electron diffraction (RHEED) observation. Direct growth of GaAs/Al GaAs quantum well (QW) structures was tried on such surfaces without introducing any buffer layers. The QW structure showed photoluminescence with both intensity and full width at half maximum comparable with those for the QW grown on the substrate cleaned by the conventional method with introducing a GaAs buffer layer.     

HigHighly strained InGaAs/GaAs quantum wells emitting beyond 1.2 µm

Highly strained In_xGa_1–xAs quantum wells (QWs) with GaAs barriers emitting around 1.2 µm are grown on GaAs substrates by metal organic vapour phase epitaxy (MOVPE) at low growth temperatures using conventional precursors. The effects of growth temperature, V/III ratio and growth rate on QW composition and luminescence properties are studied. The variation of indium incorporation with V/III ratio at a growth temperature of 510 °C is found to be opposite to the results reported for 700 °C. By an appropriate choice of the growth parameters, we could extend the room temperature photoluminescence (PL) wavelength of InGaAs/GaAs QWs up to about 1.24 µm which corresponds to an average indium content of 41% in the QW. The results of the growth study were applied to broad area laser diodes emitting at 1193 nm with low threshold current densities. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Incorporation behaviors of group V elements in GaAsSbN grown by gas-source molecular-beam epitaxy

We report the incorporation behaviors of As, Sb, and N atoms in GaAsSbN grown by gas-source molecular-beam epitaxy. We found that N atom is more reactive and competitive than Sb atom at the growth temperature ranging from 420 to 450 °C. The increment in Sb beam flux hardly changes the N composition. However, the increment in N flux retards the incorporation of Sb. In addition, the increment in As₂ flux makes the Sb and N compositions decrease at the same rate. Based on these results, we have successfully grown GaAsSbN epilayers lattice-matched to GaAs substrates. The energy gap at room temperature is as low as 0.803 eV. Negative deviation from Vegard's law in lattice constant is observed in these layers.