Alkoxide precursors for controlled oxygen incorporation during metalorganic vapor phase epitaxy GaAs and AlxGa1−xAs growth

Controlled oxygen incorporation in GaAs using Al-0 bonding based precursors, dimethyl aluminum methoxide (DMALO) and diethyl aluminum ethoxide (DEALO), is presented in this investigation. A comparison study of oxygen incorporation kinetics between nominally undoped Al_xGa_1−xAs using trimethyl aluminum and DMALO-doped GaAs suggests that DMALO is one of the most important oxygen-bearing agents responsible for unintentional oxygen incorporation in Al_xGa_1−xAs. Controlled oxygen doping using DEALO is reported for the first time. Oxygen incorporation behavior, especially on the effect of the V/III ratio, was found to be quite different from the case of DMALO, mainly due to the differences between methyl- and ethyl-based growth chemistries. Physical, electrical, and optical properties of these oxygen-doped GaAs are also reported.     

Self-organization phenomenon of strained InGaAs on InP (311) substrates grown by metalorganic vapor phase epitaxy

We have demonstrated that a self-organization phenomenon occurs in strained InGaAs system on InP (311) substrates grown by metalorganic vapor phase epitaxy. This suggests that a similar formation process of nanocrystals exists not only on the GaAs (311)B substrate but also on the InP (311)B substrate. However, the ordering and the size homogeneity of the self-organized nanocrystals are slightly worse than those of the InGaAs/AlGaAs system on the GaAs (311)B substrate. The tensilely strained condition of a InGaAs/InP system with growth interruption in a PH₃ atmosphere reveals a surface morphology with nanocrystals even on the InP (100) substrate. It was found that strain energy and high growth temperature are important factors for self-organization on III-V compound semiconductors. Preliminary results indicate that the self-organized nanostructures in strained InGaAs/InP systems on InP substrates exhibit room temperature photoluminescent emissions at a wavelength of around 1.3 p.m.     

Deep level transient spectroscopy assessment of silicon contamination in AlGaAs layers grown by metalorganic vapor phase epitaxy

A systematic silicon contamination has been detected by deep level transient spectroscopy in undoped and n-type doped (Te, Se, Sn) AlGaAs layers, grown in two different metalorganic vapor phase epitaxy reactors. DX center generation by substitutional donors, with very specific capture and emission thermal barriers (fingerprints), is the key to unambiguously identifying their presence, with detection limits well below the standard secondary ion mass spectroscopy capability. We comment on the potential sources of Si contamination (most common in this epitaxial technique), and on the relevance of such contamination to interpreting correctly experimental data related to the microscopic structure of DX centers.     

Growth of high-quality GaSb by metalorganic vapor phase epitaxy

The growth of nominally undoped GaSb layers by atmospheric pressure metalorganic vapor phase epitaxy on GaSb and GaAs substrates is studied. Trimethylgallium and trimethylantimony are used as precursors for the growth at 600°C in a horizontal reactor. The effect of carrier gas flow, V/III-ratio, and trimethylgallium partial pressure on surface morphology, electrical properties and photoluminescence is investigated. The optimum values for the growth parameters are established. The carrier gas flow is shown to have a significant effect on the surface morphology. The optimum growth rate is found to be 3–8 μm/ h, which is higher than previously reported. The 2.5 μm thick GaSb layers on GaAs are p-type, having at optimized growth conditions room-temperature hole mobility and hole concentration of 800 cm² V⁻¹ s⁻¹ and 3·10¹⁶ cm^-3, respectively. The homoepitaxial GaSb layer grown with the same parameters has mirror-like surface and the photoluminescence spectrum is dominated by strong excitonic lines.     

ZnMgSSe/ZnSSe/ZnSe-heterostructures grown by metalorganic vapor phase epitaxy

ZnMgSSe heterostructures have been grown in a low-pressure metalorganic vapor phase epitaxy system with the precursors dimethylzinc triethylamine, ditertiarybutylselenide, tertiarybutylthiol, and biscyclopentadienylmagnesium at 330°C and a total pressure of 400 hPa. The optimization of the single layers was carried out by means of low temperature photoluminescence. Only the near band edge emission was observable with negligible deep levels. The heterostructures consisting of a triple ZnSe quantum well showed intense luminescence which hints at an effective carrier confinement. Scanning transmission electron microscopy investigations of the heterostructures still showed structural detects since the layers were not lattice matched to the GaAs substrate yet.     

Growth kinetics of GaSb by metalorganic vapor phase epitaxy

The growth rates of GaSb by metalorganic vapor phase epitaxy were studied as functions of growth temperatures and partial pressures of precursors. A Langmuir-Hinshelwood model was used to explain the GaSb growth rate in the chemical reaction controlled regime. The relationship between growth kinetics and epilayer qualities was discussed and properties of GaSb were obtained.     

Optical properties and recombination mechanisms in GaN and GaN:Mg grown by metalorganic vapor phase epitaxy

Photoluminescence (PL) and reflection spectra of undoped and Mg-doped GaN single layers grown on sapphire substrates by metalorganic vapor phase epitaxy (MOVPE) were investigated in a wide range of temperatures, excitation intensities, and doping levels. The undoped layers show n-type conductivity (μ=400 cm²/Vs, n=3×10¹⁷ cm⁻³). After annealing at T=600–700°C, the Mg-doped layers showed p-type conductivity determined by the potential-profiling technique. A small value of the full width at half maximum (FWHM=2.8 meV) of the excitonic emission and a high ratio between excitonic and deep level emission (≈5300) are evidences of the high layer quality. Two donor centers with activation energies of 35 and 22 meV were observed in undoped layers. A fine structure of the PL band with two narrow lines in the spectral range of the donor-acceptor pair (DAP) recombination was found in undoped layers. An anomaly was established in the temperature behavior of two groups of PL lines in the acceptor-bound exciton and in donor-acceptor pair regions in Mg doped layers. The lower energy line quenched with increasing temperature appreciably faster than the high energy ones. Our data does not agree with the DAP recombination model. It suggests that new approaches are required to explain the recombination mechanisms in undoped and Mg-doped GaN epitaxial layers.     

Structural properties of ZnSy Se1−yZnSe/GaAs (001) heterostructures grown by photoassisted metalorganic vapor phase epitaxy

ZnS_ySe_1−yZnSe/GaAs (001) heterostructures have been grown by photoassisted metalorganic vapor phase epitaxy, using the sources dimethylzinc, dimethylselenium, diethylsulfur, and irradiation by a Hg arc lamp. The solid phase composition vs gas phase composition characteristics have been determined for ZnSy_ySe_1−y grown with different mole fractions of dimethylselenium and different temperatures. Although the growth is not mass-transport controlled with respect to the column VI precursors, the solid phase composition vs gas phase composition characteristics are sufficiently gradual so that good compositional control and lattice matching to GaAs substrates can be readily achieved by photoassisted growth in the temperature range 360°C ≤ T ≤ 400°C. ZnSe/GaAs (001) single heterostructures were grown by a two-step process with ZnSe thicknesses in the range from 54 nm to 776 nm. Based on 004 x-ray rocking curve full width at half maximums (FWHMs), we have determined that the critical layer thickness is h_c ≤200 nm. Using the classical method involving strain, lattice relaxation is undetectable in layers thinner than 270 nm for the growth conditions used here. Therefore, the rocking curve FWHM is a more sensitive indicator of lattice relaxation than the residual strain. For ZnS_ySe_1−y layers grown on ZnSe buffers at 400°C, the measured dislocation density-thickness product Dh increases monotonically with the room temperature mismatch. Lower values of the Dh product are obtained for epitaxy on 135 nm buffers compared to the case of 270 nm buffers. This difference is due to the fact that the 135 nm ZnSe buffers are pseudomorphic as deposited. For ZnS_ySe_1−y layers grown on 135 nm ZnSe buffers at 360°C, the minimum dislocation density corresponds approximately to room-temperature lattice matching (y ∼ 5.9%), rather than growth temperature lattice matching (y ∼ 7.6%). Epitaxial layers with lower dislocation densities demonstrated superior optical quality, as judged by the near-band edge/deep level emission peak intensity ratio and the near band edge absolute peak intensity from 300K photoluminescence measurements.     

On the role of interface properties in the degradation of metalorganic vapor phase epitaxially grown Fe profiles in InP

Fe doping profiles in InP layers grown by low-pressure metalorganic vapor phase epitaxy (LP-MOVPE) were investigated by secondary ion mass spectroscopy. Different pre-treatments of the InP substrates proved to have substantially different effects on the Fe profiles which strongly indicate the relevance of underlying interfaces to dopant diffusion in subsequent layers, at least in the case of dopants occupying the group-III sublattice. We attribute the degradation of Fe profiles observed for some kinds of treatment to the emission of In interstitials from surfaces covered by oxides or other residues which are incompletely removed during the MOVPE preheat cycle. A favorable substrate preparation method for avoiding Fe profile degradation relies on etching by 5:1:1 H₂SO₄:H₂O₂:H₂O at room temperature followed by 30 min deionized water rinsing.     

Electrical and optical properties of lodine doped CdZnTe layers grown by metalorganic vapor phase epitaxy

Electrical and photoluminescence properties of iodine doped CdZnTe (CZT) layers grown by metalorganic vapor phase epitaxy have been studied. Doped layers showed an n-type conductivity from the Zn composition x=0 (CdTe) to 0.07. Above x=0.07, resistivities of doped layers increased steeply up to 10⁶ Ω-cm. Resistivities of doped CZT layers were higher than those of undoped layers above x=0.6. Photoluminescence intensity of doped layers increased compared to undoped layers. Doped CdTe and ZnTe layers showed neutral donor bound exciton emission lines at the exciton related region. Also, these layers showed an increase in emission intensity at the donor acceptor pair recombination bands. Sharp emission lines were observed in doped CZT layers at around 1.49 eV. These emission lines were considered to be originated from GaAs substrates which were optically excited by the intense emission from doped CZT layers.     

Interface structure in arsenide/phosphide heterostructun grown by gas-source MBE and low-pressure MOVPE

We have used cross-sectional scanning tunneling microscopy (STM) to study interface structure in arsenide/phosphide heterostructures grown by gas-source molecular beam epitaxy (GSMBE) and by low-pressure metalorganic vapor phase epitaxy (LP-MOVPE). High-resolution images of GSMBE samples consisting of GaAs interrupted at 200Å intervals with a 40 s P₂ flux reveal substantial, growth-temperature-dependent incorporation of phosphorus with nanometer-scale lateral variations in interface structure. STM images of InGaAs/InP multiple quantum well structures grown by LP-MOVPE show evidence of interface asymmetry and extensive atomic cross-incorporation at the interfaces. Data obtained by STM have been corroborated by high-resolution x-ray diffraction and reflection high-energy electron diffraction. Together, these studies provide direct information about nanometer-scale grading and lateral nonuniformity of arsenide/phosphide interfaces that can occur under these growth conditions.     

(AlGa)As grown by low pressure metalorganic vapor phase epitaxy using a N2 carrier

We have studied the growth of Al_xGa_1−xAs (0.24<x<0.34) using a N₂ carrier in low pressure metalorganic vapor phase epitaxy. Growth temperature, gas velocity, and V/III ratio were varied to achieve optimum growth conditions. Layers with excellent morphology and electrical and optical properties comparable to samples grown using standard conditions (with a H₂ carrier) can be deposited in a nitrogen ambient. Al_0.24Ga_0.76As bulk material grown on an AlAs buffer layer with a background doping of 1.3×10¹⁶ cm⁻³ showed Hall mobilities of 4500 and 2300 cm²/Vs at 77 and 300K. Photoluminescence studies at 2K revealed strong bound exciton transitions with a full width at half maximum of 5.2 meV for Al_0.29Ga_0.71AS.     

Interdiffusion and relaxation in metalorganic vapor phase epitaxy grown InGaAs/GaAs strained layer quantum wells

Low pressure metalorganic vapor phase epitaxy grown strained InGaAs/GaAs quantum well structures have been characterized by photoluminescence and x-ray diffraction. It is shown that beyond the pseudomorphic limit, these structures show considerable gallium/indium interdiffusion at the interfaces and partial strain relaxation in the quantum well layers.     

Morphology and defect structures of GaSb islands on GaAs grown by metalorganic vapor phase epitaxy

The initial nucleation of GaSb on (001) GaAs substrates by metalorganic vapor phase epitaxy has been investigated using transmission electron microscopy (TEM) and high resolution electron microscopy (HREM). TEM results showed that the GaSb islands experience a morphological transition as the growth temperature increases. For growth at 520°C, the islands are longer along the [110] direction; at 540°C, they are nearly square, and at 560°C, they are longer along the direction. Possible mechanisms are proposed to describe such a transition. TEM and HREM examination showed that lattice misfit relaxation mechanisms depend on the growth temperature. For the sample grown at 520°C, the lattice mismatch strain was accommodated mainly by 90° dislocations; for the sample grown at 540°C, the misfit strain was relieved mostly by 90° dislocations with some of 60° dislocations, and for the sample grown at 560°C, the strain was accommodated mainly by 60° dislocations which caused a local tilt of the GaSb islands with respect to the GaAs substrate. The density of threading dislocations was also found to be dependent on the growth temperature. Mechanisms are proposed to explain these phenomena.     

HgCdTe growth on (552) oriented CdZnTe by metalorganic vapor phase epitaxy

We report the growth of HgCdTe on (552)B CdZnTe by metalorganic vapor phase epitaxy (MOVPE). The (552) plane is obtained by 180 rotation of the (211) plane about the [111] twist axis. Both are 19.47 degrees from (111), but in opposite directions. HgCdTe grown on the (552)B-oriented CdZnTe has a growth rate similar to the (211)B, but the surface morphology is very different. The (552)B films exhibit no void defects, but do exhibit ∼40 μm size hillocks at densities of 10–50 cm⁻². The hillocks, however, are significantly flatter and shorter than those observed on (100) metalorganic vapor phase epitaxy (MOVPE) HgCdTe films. For a 12–14 μm thick film the height of the highest point on the hillock is less than 0.75 μm. No twinning was observed by back-reflection Laue x-ray diffraction for (552)B HgCdTe films and the x-ray double crystal rocking curve widths are comparable to those obtained on (211)B films grown side-by-side and with similar alloy composition. Etch pit density (EPD) measurements show EPD values in the range of (0.6–5)×10⁵ cm⁻², again very similar to those currently observed in (211)B MOVPE HgCdTe. The transport properties and ease of dopant incorporation and activation are all comparable to those obtained in (211)B HgCdTe. Mid-wave infrared (MWIR) photodiode detector arrays were fabricated on (552)B HgCdTe films grown in the P-n-N device configuration (upper case denotes layers with wider bandgaps). Radiometric characterization at T=120–160 K show that the detectors have classical spectral response with a cutoff wavelength of 5.22 μm at 120 K, quantum efficiency ∼78%, and diffusion current is the dominant dark current mechanism near zero bias voltage. Overall, the results suggest that (552)B may be the preferred orientation for MOVPE growth of HgCdTe on CdZnTe to achieve improved operability in focal plane arrays.     

Integrated in situ monitoring of a metalorganic vapor phase epitaxy reactor for II–VI epitaxy

The focus of this paper is the integrated use of system and wafer monitors to obtain a complete picture of the growth process and to identify the major causes of variance. In situ monitoring of a growing layer of Hg_1-xCd_xTe using laser reflectometry has been compared with the outputs of various system monitors such as pyrometer, organometallic concentration, and flow. Differences between the expected and measured concentrations were corrected by initially adjusting the organometallic flows, and the remaining variance in CdTe interdiffused multilayer process layer thickness was then corrected by increasing the CdTe cycle time. The remainder of the layer gave a homogenized alloy composition of 0.256 for a target value of 0.258. This example shows how different in situ monitors have been integrated to give a comprehensive picture of the growth process, which were then related to known kinetic behavior. As a result of this monitoring, it was possible to identify critical parameters for control.     

Recent results on metalorganic vapor phase epitaxially grown HgCdTe heterostructure devices

The ability to grow complex multilayer structures in Hg_1-xCd_xTe by epitaxial techniques has made it possible to produce a range of new devices such as infrared LEDs, lasers, and two-color infrared detector arrays. The devices described here, however, are designed to operate at temperatures above 145K and include both infrared sources and detectors. Three layer ppn structures, where the underlined symbols mean wider gap, have close to Auger limited R_oAs at temperatures above 145K. Under reverse bias, the devices exhibit Auger suppression leading to useful detectivities at room temperature. The diodes exhibit forward biased electroluminescence at room temperature although the efficiency of this emission is found to fall rapidly as the peak wavelength is increased toward 9 μm due to increased Auger recombination rates. By reverse biasing them, however, the devices show negative luminescence as a result of reducing the electron and hole densities below their thermal equilibrium value. The diode emitters have a higher quantum efficiency when used in this mode due to Auger suppression of the dark current.     

Metalorganic vapor phase epitaxy of InP using the novel P-source ditertiarybutyl phosphine (DitBuPH)

In this study, the use of a novel phosphorous precursor for low pressure metalorganic vapor phase epitaxy (LP-MOVPE) application has been investigated. Ditertiarybutyl phosphine ((C₄H₉)₂-P-H, DitBuPH) as substitute for the standardly used hydrid gas phosphine (PH₃) promises apart from strongly reduced toxicity due to the reduction of P-H bonds, an enhancement in cracking efficiency as well as a reduction in growth temperature. Layer quality has been examined by means of optical and scanning electron microscopy (SEM), temperature-dependent van der Pauw Hall as well as photoluminescence (PL) measurements. Uncompensated n-type InP-layers (1.0 x 1.5 cm^-3; 59600 cm²Vs)^-1 at 77K) are realized using DitBuPH in combination with commercial TMIn. All results are compared with those obtained by using PH₃ and commercial tertiarybutyl phosphine (TBP) as P-source, respectively.     

Residual impurities in GaN/Al2O3 grown by metalorganic vapor phase epitaxy

Residual impurities in GaN films on sapphire (A1₂O₃) substrates grown by two-step metalorganic vapor phase epitaxy (MOVPE) have been investigated. We have mainly investigated the incorporation of carbon into the GaN films with GaN buffer layers on A1₂O₃ during MOVPE growth, comparing trimethygallium (TMGa) and triethygallium (TEGa) as the typical gallium precursors. The films were characterized by secondary ion mass spectroscopy analysis, photolu-minescence, and Hall measurements. The carbon, hydrogen, and oxygen concentrations increase with decreasing growth temperature in using TMGa. Especially the carbon concentration increases with decreasing a V/III ratio, for both TMGa and TEGa. There is about two times more carbon in the GaN films grown using TEGa than those using TMGa. The carbon from TMGa mainly enhances the D-A pair emission (∼378 nm), which shows the carbon makes an acceptor level at nitrogen sites in GaN. On the other hand, the carbon from TEGa enhances a deep emission (∼550 nm), which shows the carbon makes not only an acceptor level but deep levels at interstitial sites in GaN. The carbon impurities originate from methyl radicals for TMGa, or ethyl radicals for TEGa. It is supposed that, in the case of TEGa, the carbon impurities are not always located at nitrogen sites, but are also located at interstitial sites because of the C-C bonding in ethyl radicals.     

Thermal annealing effects on p-type conductivity of nitrogendoped ZnSe grown by metalorganic vapor phase epitaxy

Post-growth thermal annealing (e.g., 500°C, 30 min), is proposed as one of the promising techniques to realize and to improve the quality of p-type ZnSe layers grown by metalorganic vapor phase epitaxy (MOVPE). The layers were grown at low temperature (350°C) by photo-assisted MOVPE with doping nitrogen from tertiarybutylamine (t-BuNH₂). The flow rate of t-BuNH₂ was limited to be relatively low, in order to avoid heavy doping, with which as-grown layers exhibited electrically high-resistivity; but the thermal annealing converted the layers to p-type. As the as-grown layers exhibited the stronger donor-to-acceptor pair recombination lines or the weaker donor-bound excitonic emission (I_x) lines in photoluminescence, the annealed layers resulted in higher net acceptor concentration, which was 1 x 10¹⁷ cm⁻⁴ at the optimum conditions at present.