In situ surface passivation of III–V semiconductors in MOVPE by amorphous As and P layers

A new process for chemical passivation of III–V semiconductor surfaces in metalorganic vapour phase epitaxy (MOVPE) is developed. A passivation layer is deposited directly after growth in the reactor. It consists of amorphous arsenic or a double-layer package of amorphous phosphorus and arsenic, which are grown by photo-decomposition of the group-V hydrides. These layers (caps) serve to protect the surfaces against contamination in air after removing the samples from the MOVPE growth reactor. Such passivation is applicable e.g. for a two-step epitaxy or for further surface characterizations.     

Properties of (Ga0.47In0.53)As epitaxial layers grown by metalorganic vapor phase epitaxy (MOVPE) using alternative arsenic precursors

In this study, the use of novel, liquid, organic arsenic precursors as substitutes for the highly toxic hydride gas arsine (AsH₃) in low pressure metalorganic vapor phase epitaxy (LP-MOVPE) of (GaIn)As lattice matched on InP has been investigated. The model precursors out of the classes of (alkyl)3-nAsH_n (n = 0,1,2) are tertiarybutyl arsine (TBAs), ditertiarybutyl arsine (DitBAsH) and diethyltertiarybutyl arsine (DEtBAs). The MOVPE growth has been investigated in the temperature range of 570–650°C using V/III ratios from 2 to 20. The obtained epitaxial layer quality as examined by means of optical and scanning electron microscopy (SEM), high resolution double crystal X-ray diffraction, temperature-dependent van der Pauw-Hall, as well as photoluminescence (PL) measurements, will be compared for the different source molecules. Under optimized conditions almost uncompensated n-type (GaIn)As layers with carrier concentrations below 1 × 10¹⁵ cm⁻³ and corresponding mobilities above 80 000 cm²/V · s have been realized. For TBAs and DitBAsH in combination with the corresponding P sources TBP and DitBuPH, respectively, we have worked out a process parameter area for the growth of layers with device quality, as proven by the realization of a pin-detector structure.     

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.     

Influence of growth temperature on the selective area MOVPE of InAs nanowires on GaAs (1 1 1) B using N2 carrier gas

The influence of temperature on selective area (SA) InAs nanowire growth was investigated for metal-organic vapor phase epitaxy (MOVPE) using N₂ as the carrier gas and (1 1 1) B GaAs substrates. In contrast to the growth temperature range – below 600 °C – reported for hydrogen ambient, the optimal growth temperature between 650 and 700 °C was 100 K higher than the optimal ones for H₂ carrier gas. At these temperatures, nanowires with aspect ratios of about 80 and a symmetric hexagonal shape were obtained. The results found are attributed to the physical and chemical properties of the carrier gas.     

Influence of substrate temperature on the shape of GaAs nanowires grown by Au-assisted MOVPE

GaAs nanowires (NWs) are grown on the GaAs(1 1 1)B substrates by the Au-assisted metal–organic vapor phase epitaxy (MOVPE). The NW shape is found to be strongly dependent on the substrate temperature during the growth. With increase in the growth temperature, the NW shape modifies from prismatic to conical. The observed temperature behavior is studied within the frame of a theoretical model. It is shown that the key process responsible for the lateral growth is the decomposition of MOVPE precursors at the NW sidewalls and the substrate. Theoretical results are in a good agreement with experimental findings and can be used for the numerical estimates of some important growth parameters as well as for the controlled fabrication of NWs with the desired shape.     

Kinetics and mechanisms of surface reactions in epitaxial growth of Si from SiH4 and Si2H6

Surface science and kinetic modelling studies of the surface chemical mechanisms active during low pressure chemical vapor deposition (CVD) and chemical beam epitaxy (CBE) growth of Si from mono- and disilane are summarized. Time-of-flight direct recoiling (DR) is discussed as an in situ method to analyze the composition of the growth interface. Steady state measurements of surface hydrogen coverage (θ_H) are made by DR in situ during CBE Si growth from Si₂H₆ and SiH₄, and are illustrated here. Key results using other experimental methods are briefly discussed.     

RHEED studies of the growth of Si(001) by gas source MBE from disilane

The growth of Si(001) from a gas source molecular beam epitaxy system (Si-GSMBE) using disilane (Si₂H₆) was investigated using reflection high-energy electron diffraction (RHEED). The surface reconstructions occurring between 100 and 775°C were studied as a function of both substrate temperature and surface coverage. We report the first observation of (2x2) and c(4x4) reconstructions during growth at substrate temperatures near 645°C using Si₂H₆. All growth was found to be initiated by the formation of three-dimensional (3D) islands which coalesced at substrate temperatures above 600°C. The surface reconstruction was found to change from a disordered to an ordered (2x1)+(1x2) structure at 775°C via intermediate (2x2) and c(4x4) phases. Thereafter, growth was found to proceed in a 2D layer-by-layer fashion, as evidenced by the observation of RHEED intensity oscillations. This technique has been used, for the first time, to calibrate growth rates during Si-GSMBE. The intensity oscillations were measured as a function of both substrate temperature and incident beam flux. Strong and damped oscillations were observed between 610 and 680°C, in the two-dimensional growth regime. At higher temperatures, growth by step propagation dominated while at lower temperatures, growth became increasingly three-dimensional and consequently oscillations were weak or absent. Similarly, there was a minimum flux limit ( <0.16 SCCM), below which no oscillations were recorded.     

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.     

Growth process studies by reflectance anisotropy spectroscopy on MOVPE ZnSe

The growth of ZnSe on GaAs by metal organic vapour phase epitaxy (MOVPE) has been studied using reflectance anisotropy spectroscopy (RAS). The RA spectra of ZnSe are significantly different for growth on initially Se- or Zn-exposed GaAs surfaces. The Se-terminated GaAs (001) RA spectrum has Se-dimer-related features at 3.3 and 5.1 eV, and the large, high energy peak dominates during ZnSe growth on this surface. Transmission electron microscopy (TEM) analysis has been used to show that these large RA signals arise from anisotropic surface corrugation of the growing ZnSe epilayer. Under initially Zn-stabilised growth conditions, the ZnSe epilayer RA spectrum is largely featureless, showing only a weak peak at 4.7 eV and a dip at 5.1 eV. The corresponding surface anisotropy is greatly reduced in comparison with growth from the initially Se-terminated surface. These observations reveal RAS to the an important technique for ensuring the desired initial GaAs surface since the grown ZnSe surface morphology is critically dependent on the pre-growth substrate surface treatment. However, as the characteristic ZnSe RA spectra are relatively insensitive to changes in substrate temperature and VI–II ratio, RAS is of more limited use as an in-growth surface probe for MOVPE-grown ZnSe.     

Growth of InAs on GaAs(1 0 0) by low-pressure metalorganic chemical vapor deposition employing in situ generated arsine radicals

InAs was grown by low-pressure metalorganic chemical vapor deposition on vicinal GaAs(1 0 0) substrates misoriented by 2° toward [0 0 1]. We observed InAs crystal growth, at substrate temperatures down to 300°C, employing in situ plasma-generated arsine radicals as the arsenic source. The in situ generated arsine was produced by placing solid arsenic downstream of a microwave driven hydrogen plasma. Trimethylindium (TMIn) feedstock carried by hydrogen gas was used as the indium source. The Arrhenius plot of InAs growth rate vs. reciprocal substrate temperature displayed an activation energy of 46.1 kcal/mol in the temperature range of 300–350°C. This measured activation energy value is very close to the energy necessary to remove the first methyl radical from the TMIn molecule, which has never been reported in prior InAs growth to the best of authors’ knowledge. The film growth mechanism is discussed. The crystallinity, infrared spectrum, electrical properties and impurity levels of grown InAs are also presented.     

Precise structure control of GaAs/InGaP hetero-interfaces using metal organic vapor phase epitaxy and its abruptness analyzed by STEM

Fabrication of abrupt InGaP on GaAs (InGaP/GaAs) and GaAs on InGaP (GaAs/InGaP) hetero-interfaces has been difficult using metal organic vapor phase epitaxy (MOVPE) due to the exchange of P and As during the fabrication steps. Indium (In) surface segregation during InGaP growth also degrades the abruptness. Here, the MOVPE gas-switching sequence to fabricate atomically abrupt hetero-interfaces was optimized and the effects of this optimization on the hetero-interface abruptness were quantitatively evaluated using the Z-contrast method with scanning transmission electron microscopy (STEM). Results revealed that (a) in the fabrication of InGaP/GaAs hetero-interface, the GaAs top layer should be stabilized using As-source gas supply, and the excess As layer on GaAs should be terminated using an additional supply of Ga species, and (b) in the fabrication of GaAs/InGaP interface, the InGaP layer should be grown using the flow modulation method to suppress In surface segregation. In conclusion, the abruptness of hetero-interfaces of InGaP/GaAs and GaAs/InGaP was improved by using these optimized gas-switching sequences.     

MOVPE of GaN using a specially designed two-flow horizontal reactor

GaN epilayers have been grown on (0001) sapphire substrates with a specially designed two-flow horizontal metalorganic vapor phase epitaxy (MOVPE) reactor. Epilayers with flat and smooth surfaces were obtained at the growth temperature of 950°C with relatively low source supply rates. This indicates a relatively high growth efficiency of the reactor. Characterization by photoluminescence, X-ray diffraction and Hall measurements reveal that the epilayers are of reasonably high quality.     

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.     

Visible (683 to 713 nm) room-temperature AlGaAs vertical cavity surface emitting lasers (VCSELs)

We compare the materials parameters for visible emitting, vertical cavity surface emitting lasers (VCSELs) and conclude that AlGaAs-based materials are a good choice. All-AlGaAs devices were produced by metalorganic vapour phase epitaxy (MOVPE) growth using ultra-high purity source reagents. Lasing was obtained at wavelengths in the range of 683 to 713 nm using four 45 Å wide Al_0.18Ga_0.82 As quantum wells in the active region. A threshold current density of 3.8 kA cm⁻² was measured for a cavity wavelength of 692 nm at room temperature. Growth of the epitaxial mirrors at 5.2 μm/h results in a total device growth time of only two and a half hours.     

Low temperature growth of AlGaAs by MOMBE (CBE) using trimethylamine alane

In order to gain further insight into the surface chemistry of AlGaAs growth by metalorganic molecular beam epitaxy, we have investigated the deposition behavior and material quality of AlGaAs grown at temperatures from 350 to 500°C using trimethylamine alane (TMAA), triethylgallium (TEG) and arsine (AsH₃). Though the Al incorporation rate decreases with decreasing temperature, Ga-alkyl pyrolysis, and hence Ga incorporation rate, declines more rapidly. Thus the Al content increases from X_AlAs = 0.25 at 500°C to X_AlAs = 0.57 at 350°C. Below 450°C, the Ga incorporation rate appears to be determined by the desorption of diethylgallium species, rather than interaction with adsorbed AlH₃. Similarly, carbon incorporation is enhanced by 2 orders of magnitude over this temperature range due to the increasingly inefficient pyrolysis of the Ga-C bond in TEG. Additionally, active hydrogen from the TMAA1, which normally is thought to getter the surface alkyls, is possibly less kinetically active at lower growth temperatures. Contrary to what has been observed in other growth methods, low growth temperatures produced a slight decrease in oxygen concentration. This effect is likely due to reduced interaction between Ga alkoxides (inherent in the TEG) and the atomic hydrogen blocked Al species on the growth surface. This reduction in oxygen content and increase in carbon concentration causes the room temperature PL intensity to actually increase as the temperature is reduced from 500 to 450°C. Surprisingly, the crystalline perfection as measured by ion channeling analysis is quite good, χ_min≤5%, even at growth temperatures as low as 400°C. At 350°C, the AlGaAs layers exhibit severe disorder. This disorder is indicative of insufficient Group III surface mobility, resulting in lattice site defects. The disorder also supports our conclusions of kinetically limited surface mobility of all active surface components.     

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.     

Thermodynamic analysis of the MOVPE growth of InxGa1−xN

A chemical equilibrium model is applied to the growth of the In_xGa_1−xN alloy grown by metalorganic vapor-phase epitaxy (MOVPE). The equilibrium partial pressures and the phase diagram of deposition are calculated for the In_xGa_1−xN alloy. The vapor-solid distribution relationship is discussed in comparison with the experimental data reported in the literature. It is shown that the solid composition of the In_xGa_1−xN alloy grown by MOVPE is thermodynamically controlled and that the incorporation of group III elements into the solid phase deviates from a linear function of the input mole ratio of the group III metalorganic sources under the conditions of high mole fraction of decomposed NH₃ (high value of ), high temperature and low input V/III ratio. The origin of the deviation of the solid composition from the linear relation is also discussed.     

Growth monitoring by reflectance anisotropy spectroscopy in MOVPE reactors for device fabrication

Reflectance anisotropy spectroscopy (RAS) has proved its capability to study surface processes during metalorganic vapour phase epitaxy (MOVPE) growth of a variety of III–V compounds. However, these investigations up to now have been mostly restricted to specialized research reactors. Therefore, we studied the feasibility of in-situ monitoring by RAS during growth on two production-type MOVPE reactors: horizontal 2 inch single wafer reactor AIX 200 and Planetary Reactor™ AIX 2000 for 5 × 3 inch. The slight modifications of the reactors necessary to gain normal incidence optical access to the sample do not alter the properties of the grown materials. While in the horizontal reactor the strain-free optical window allows one to obtain well-resolved RAS spectra the signals in the multiwafer reactor are affected by the anisotropy of the ceiling plate. Even in this case RAS spectra can be extracted. First measurements on rotating samples in the horizontal reactor demonstrate the possibility to obtain RAS spectra by multitransient spectroscopy. As an application monitoring of the growth of p-type layers for the base of GaInP/GaAs hetero-bipolar-transistors (HBTs) is discussed. The linear electro-optic effect (LEO) gives information on doping type and doping level. Time-resolved transients at specific energies are used to study the impact of different switching schemes on the properties of the base-emitter interface.     

Stress control by micropits density variation in strained AlGaN/GaN/SiN/AlN/Si(111) heterostructures

AlGaN/GaN heterostructures were deposited on Si utilizing in‐situ SiN masking layer as a mean to decrease stress present in the final heterostructures. Structures were grown under different V/III ratio using metalorganic vapour phase epitaxy (MOVPE). Additional approach was applied to obtain crack‐free heterostructures which was deposition of 15 nm low temperature AlN interlayer. Each of the heterostructure contained GaN layer of 2.4 μm total thickness. In‐situ SiN masking layer were obtained via introduction of SiH4 precursor into reactor under high temperature growth conditions for 100 s. In that manner, few monolayers of SixNx masking layer were deposited, which due to the partial coverage of AlN, played role of a mask leading to initial 3D growth mode enhancing longer coalescence of GaN buffer layer. To study surface morphology AFM images were observed. Three methods were used in order to obtain basal plane stress present in multilayer structures ‐ MicroRaman spectroscopy, XRD studies and optical profilometry. It was found that varying V/III precursors ratio during GaN layer growth characteristic for structures with the SiN mask approach formation of triangular micropits can be minimized. Outcomes for three different methods turned out to be coherent. It was found that certain amount of micropits on the surface can be advantageous lowering stress introduced during cooling after process to the AlGaN/GaN/SiN/AlN/Si(111) structure.     

Review: GaN growth by ammonia based methods – density functional theory study

Recent results in Density Functional Theory (DFT) simulations of ammonia‐based growth of gallium nitride on GaN (0001) are reviewed. These simulations are important to the following GaN growth methods that use ammonia as active nitrogen source: ammonothermal, MOVPE, HVPE and also ammonia‐source MBE. In the simulations of GaN growth, the two main approaches were discussed: (1) equilibrium, based on chemical potentials of the components, and (2) dynamic, based on consideration of atomistic processes on the surface. These two approaches are unified by the kinetic procedure of determination of the chemical potential levels for nitrogen and hydrogen as a function of partial pressure of ammonia. Here the DFT modeling of GaN(0001) surface employing the technique of the simulation of subsurface electric field is described and employed. The results of DFT modeling include the ammonia and molecular hydrogen adsorption on GaN(0001) surface that allows to determine some basic features of ammonia‐based growth of GaN. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)