Pendeo-epitaxial growth of gallium nitride on silicon substrates

Pendeo-epitaxy (PE)¹ from raised, [0001] oriented GaN stripes covered with silicon nitride masks has been employed for the growth of coalesced films of GaN(0001) with markedly reduced densities of line and planar defects on Si(111)-based substrates. Each substrate contained previously deposited 3C-SiC(111) and AlN(0001) transition layers and a GaN seed layer from which the stripes were etched. The 3C-SiC transition layer eliminated chemical reactions between the Si and the NH₃ and the Ga metal from the decomposition of triethylgallium. The 3C-SiC and the GaN seed layers, each 0.5 μm thick, were also used to minimize the cracking and warping of the GaN/SiC/silicon assembly caused primarily by the stresses generated on cooling due to the mismatches in the coefficients of thermal expansion. Tilting in the coalesced GaN epilayers of 0.2° was confined to areas of lateral overgrowth over the masks; no tilting was observed in the material suspended above the trenches. The strong, low-temperature PL band-edge peak at 3.456 eV with a FWHM of 17 meV was comparable to that observed in PE GaN films grown on AlN/6H-SiC(0001) substrates.     

Scanning electron microscopy and cathodoluminescence study of the epitaxial lateral overgrowth (ELO) process for gallium nitride

Traditional epitaxial growth of GaN by metalorganic vapor phase epitaxy (MOVPE) on mismatched substrates such as sapphire or SiC produces a columnar material consisting of many hexagonal grains ∼0.2–1.0 μm in diameter. The epitaxial-lateral-overgrowth (ELO) process for GaN creates a new material: single-crystal GaN. We have studied the ELO process for GaN grown by MOVPE in a vertical flow rotating substrate reactor. Characterization consisted of plan-view SEM and vertical-cross-section TEM studies, which revealed a large reduction in dislocation density in the overgrown regions of the GaN. Panchromatic and monochromatic cathodoluminescence images and spectra were used to study the spatial variation of the optical properties within the GaN ELO samples. The effects of growth temperature and stripe material on the overgrown layers were examined. Through the use of a higher substrate temperature during growth and the use of a SiN_x stripe material, the overgrown crystal shape has a smooth 2D top surface with vertical sidewalls. Applying a second ELO step, rotated by 60°, over a fully coalesced ELO layer yields a further reduction of defects in GaN overgrown surfaces.     

Structural study of GaN grown on (001) GaAs by organometallic vapor phase epitaxy

Detailed transmission electron microscope (TEM) and transmission electron diffraction (TED) examination has been performed on organometallic vapor phase epitaxial GaN layers grown on (001) GaAs substrate to investigate microstructures and phase stability. TED and TEM results exhibit the occurrence of a mixed phase of GaN. The wurtzite (α) phase grains are embedded in the zinc-blende (β) phase matrix. It is shown that there are two types of the wurtzite GaN phase, namely, the epitaxial wurtzite and the tilted wurtzite. The tilted wurtzite grains are rotated some degrees ranging from ∼5° to ∼35° regarding the GaAs substrate. A simple model is presented to describe the occurrence of the mixed phases and the two types of the wurtzite phase.     

Lateral epitaxial overgrowth of GaN films on SiO2 areas via metalorganic vapor phase epitaxy

Lateral epitaxial growth and coalescence of GaN regions over SiO₂ masks previously deposited on GaN/AlN/6H-SiC(0001) substrates and containing 3 μm wide rectangular windows spaced 7 μm apart have been achieved. The extent and microstructural characteristics of these regions of lateral overgrowth were a complex function of stripe orientation, growth temperature, and triethylgallium (TEG) flow rate. The most successful growths were obtained from stripes oriented along 〈1 00〉 at 1100°C and a TEG flow rate of 26 μmol/min. A density of ∼10⁹ cm⁻² threading dislocations, originating from the underlying GaN/AlN interface, were contained in the GaN grown in the window regions. The overgrowth regions, by contrast, contained a very low density of dislocations. The surfaces of the coalesced layers had a terrace structure and an average root mean square roughness of 0.26 nm.     

Metalorganic vapor phase epitaxial growth and structural characterization of GaAs/InP heterostructures

Highly mismatched GaAs epitaxial layers with thickness ranging from 15 nm to 7 μm have been grown on InP substrates by atomospheric pressure metalorganic vapor phase epitaxy. Layers thinner than 30 nm exhibited 3-D growth mechanism; in the thicker layers, the islands coalesced and then the growth followed the layer by layer mechanism. The elastic strain and the extended defects have been studied by high resolution x-ray diffraction and transmission electron microscopy, respectively. The common observation of planar defects, misfit, and threading dislocations in the layers has been confirmed. The results on the elastic strain release have been discussed on the basis of the equilibrium theory.     

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.     

InAIGaAs selective MOVPE growth with bandgap energy shift

We studied the bandgap energy shift by varying the SiO₂ mask width in selective MOVPE growth of InAIGaAs with almost no polycrystals on the masks. We found that the photoluminescence (PL) peak shifts toward the longer wavelength with wider mask width and narrower mesa width, where the In content is enhanced, and observed a maximum PL peak wavelength shift of 170 nm.     

Doping of gallium nitride using disilane

The silicon doping of n-type GaN using disilane has been demonstrated for films grown on sapphire substrates by low pressure organometallic vapor phase epitaxy. The binding energy of an exciton bound to a neutral Si donor has been determined from low temperature (6K) photoluminescence spectra to be 8.6 meV. Nearly complete activation of the Si impurity atom in the GaN lattice has been observed.     

Maskless pendeo-epitaxial growth of GaN films

High-resolution x-ray diffraction (XRD) and atomic force microscopy (AFM) of pendeo-epitaxial (PE) GaN films confirmed transmission electron microscopy (TEM) results regarding the reduction in dislocations in the wings. Wing tilt ≤0.15° was due to tensile stresses in the stripes induced by thermal expansion mismatch between the GaN and the SiC substrate. A strong D°X peak at ≈3.466 eV (full-width half-maximum (FWHM) ≤300 μeV) was measured in the wing material. Films grown at 1020°C exhibited similar vertical [0001] and lateral [11 0] growth rates. Increasing the temperature increased the latter due to the higher thermal stability of the GaN(11 0). The (11 0) surface was atomically smooth under all growth conditions with a root mean square (RMS)=0.17 nm.     

MOVPE growth of InPSb/InAs heterostructures for mid-infrared emitters

We investigated the growth of InPSb on GaSb or InAs by low pressure (20 mbar) metalorganic vapor phase epitaxy (MOVPE). Trimethylindium, triethylantimony, and phosphine were used as starting materials. High resolution x-ray diffraction, photoluminescence at 10K, Hall measurements at 300 and 77K as well as scanning electron microscopy and scanning tunneling electron microscopy investigations were carried out to verify the layer properties. Lattice-matched InPSb layers on InAs substrate grown at 520°C show mirror-like surfaces and sharp x-ray peaks. N-type doping of InP_0.69Sb_0.31 was carried out with H₂S and p-type doping was achieved with DEZn. Maximum electron concentrations of 2×10¹⁹ cm⁻³ and hole concentrations exceeding 10¹⁸ cm⁻³ were obtained after annealing in N₂ ambient. The thermal stability of InPSb was studied during annealing experiments carried out at 500°C up to 30 min. The compositional integrity of the lattice proves to be stable and the InAs/InPSb interface can be improved. Multiple quantum well structures, pn-junction diodes and the two-dimensional electron gas at the InPSb/InAs/InPSb quantum wells were investigated to demonstrate the properties of the material.     

MOVPE production reactors for high temperature electronics

For the fabrication of epitaxial films of silicon carbide or the Group III nitrides, high growth temperatures (up to 1700°C) and fast heating and cooling of the growth environment have been found to be necessary. A range of production systems meeting these requirements has been designed with different loading capacities. In this paper, we present results from various machines showing the high quality and excellent homogeneity obtainable for 3C-SiC on Si and on 6H-SiC, as well as GaN on sapphire.     

The impact of nitridation and nucleation layer process conditions on morphology and electron transport in GaN epitaxial films

A systematic study has been performed to determine the characteristics of an optimized nucleation layer for GaN growth on sapphire. The films were grown during GaN process development in a vertical close-spaced showerhead metalorganic chemical vapor deposition reactor. The relationship between growth process parameters and the resultant properties of low temperature GaN nucleation layers and high temperature epitaxial GaN films is detailed. In particular, we discuss the combined influence of nitridation conditions, V/III ratio, temperature and pressure on optimized nucleation layer formation required to achieve reproducible high mobility GaN epitaxy in this reactor geometry. Atomic force microscopy and transmission electron microscopy have been used to study improvements in grain size and orientation of initial epitaxial film growth as a function of varied nitridation and nucleation layer process parameters. Improvements in film morphology and structure are directly related to Hall transport measurements of silicon-doped GaN films. Reproducible growth of silicon-doped GaN films having mobilities of 550 cm²/Vs with electron concentrations of 3 × 10¹⁷ cm⁻³, and defect densities less than 10⁸ cm⁻² is reported. These represent the best reported results to date for GaN growth using a standard two-step process in this reactor geometry.     

The role of surface adsorbates in the metalorganic vapor phase epitaxial growth of (Hg,Cd)Te onto (100) GaAs Substrates

It has been established that a compound present as an impurity in the propan-2-ol used in the preparation of GaAs (100) substrates for the metalorganic vapor phase epitaxy growth of (Hg,Cd)Te has a marked effect on the crystalline perfection and surface morphology of the resulting layers. In particular, the presence of this species, which contains Na, ensures that (i) the epitaxial overgrowth is of (100) orientation without the need for ZnTe nucleation layers, and (ii) the density of pyramidal hillocks on the surface can be reproducibly < 10 cm⁻².     

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.     

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.     

New mechanisms in photo-assisted MOVPE of II-VI semiconductors

The first detailed comparison has been made of the metalorganic vapor phase epitaxy growth rates of CdTe, ZnTe, and ZnSe, measured in situ with laser reflectometry. The comparison also includes the photo-assisted growth with visible radiation from an argon ion laser. Using a standard Group II precursor (DMCd or DMZn.TEN) partial pressure of 1.5 × 10⁻⁴ atm, VI/II ratio of 1 and DIPM (M = Te, Se) the maximum growth rates are in the region of 10 to 15 AU/ s. Decrease in growth rates of ZnTe at higher temperatures or higher laser powers have been attributed to the desorption from the substrate of unreacted Te precursor. The behavior of DTBSe is quite different from DIPSe for both pyrolytic and photo-assisted growth. The maximum growth rate is around 1 AU/ s with very little photo-enhancement, except at 300°C. Secondary ion mass spectroscopy analysis of hydrogen concentration in the ZnSe layers shows high concentrations, up to 5.9 × 10¹⁹ atoms cm⁻³ for DTBSe grown ZnSe under pyrolytic conditions. These results show that the growth kinetics play an important part in the incorporation of hydrogen and passivation of acceptor doped material.     

MOVPE growth of AlGaAs/GaInP diode lasers

GaAs-based diode lasers for emission wavelengths between 800 nm and 1060 nm with AlGaAs-cladding and GaInP-waveguide layers were grown by MOVPE. For wavelengths above 940 nm broad area devices with InGaAs QWs show state-of-the-art threshold current densities. Ridge-waveguide lasers fabricated by selective etching achieve 200 mW CW monomode output powers. (In)GaAsP QW-based diode lasers with an emitting wavelengths around 800 nm suffer from problems at the upper GaInP/AlGaAs interface. Asymmetric structures with a lower AlGaAs/GaInP and an upper AlGaAs/AlGaAs waveguide not only avoid this interface but also offer better carrier confinement. Such structures show very high slope efficiencies and a high T₀. Maximum output powers of 7 W CW are obtained from 4 mm long devices.     

Flow modulation epitaxy of indium gallium nitride

InGaN layers were grown on GaN films by flow modulation epitaxy (FME) using the precursors trimethylgallium, trimethylindium, and ammonia. The indium composition of the FME grown layers was generally lower than of films grown under the same conditions in the continuous growth mode, but which had been of poor optical quality. The indium incorporation efficiency increased with decreasing ammonia flush time, increasing ammonia flow during group-III injection, and increasing group-III precursor injection time. Films grown under optimized conditions showed intense band edge related luminescence at room temperature up to a wavelength of 465 nm. Atomic force microscopy investigations revealed a strong dependence of the surface morphology of the InGaN films on the growth mode.     

Effect of temperature on InGaAsP alloy composition

The influence of growth temperature on the composition of InGaAsP films grown by low pressure metalorganic vapor phase epitaxy (MOVPE) is reported for quaternary (Q) alloys having bandgap wavelengths of λ_g = 1.1, 1.3, and 1.5 μn. Films with these different Q-compositions were deposited lattice matched to InP at a growth temperature of 675°C. Subsequent growth experiments were then performed for each Q-composition in which the input gas flow rates were kept the same and only the temperature changed in 25°C decrements down to 600°C. Photoluminescence (PL) and lattice mismatch (LMM) measurements of the resulting films were used to determine the effect of growth temperature on film composition. The PL data indicate a temperature shift in the PL wavelength of −1.8 nm/ °C for the 1.5Q composition, −2.9 nm/°C for 1.3Q, and −4.3 nm/°C for 1.1Q. Negative shifts were also observed in LMM of −80 ppm/°C for 1.5Q, −150 ppm/°C for 1.3Q, and −250 ppm/°C for 1.1Q. The Ga/In and P/As ratios of the Q-filmswere measured by secondary ion mass spectroscopy and correlated with full-wafer maps of the PL wavelength and lattice mismatch to gain insight into the processes responsible for wafer nonuniformity in MOVPE.     

Low temperature growth and characterization of ZnSe films grown on GaAs

Metalorganic vapor phase epitaxy (MOVPE) growth experiments of ZnSe on GaAs (100) are described using ditertiary butylselenide as the selenium source. The growth temperature was varied between 300 and 400°C and the growth rate was determined. Below a vapor pressure ratio P_Se/P_Zn of about 5, the selenium is the growth limiting component. The quality of the samples was analyzed by Nomarski microscopy, x-ray diffraction, high resolution transmission electron microscopy, and photoluminescence. Although the selenium-precursor was not specially purified, a sharp excitonic luminescence appears in samples grown at 400°C. The MOVPE growth of ZnSe still suffers from prereactions when H₂Se is used. The optimum growth is above 450°C even with precursors as DMSe or DESe which are less harmful than the hydride. This paper reports results obtained with a novel selenium-precursor: ditertiarybutylselenide.¹