(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.     

The growth of AlInSb by metalorganic chemical vapor deposition

We have grown Al_xIn_1−xSb epitaxial layers by metalorganic chemical vapor deposition using tritertiarybutylaluminum (TTBAl), trimethylindium (TMIn), and triethylantimony (TESb) as sources in a high speed rotating disk reactor. Growth temperatures of 435 to 505°C at 200 Torr were investigated. The V/III ratio was varied from 1.6 to 7.2 and TTBAl/(TTBAl+TMIn) ratios of 0.26 to 0.82 were investigated. Al_xIn_1−xSb compositions from x=0.002 to 0.52 were grown with TTBAl/(TTBAl+TMIn) ratios of 0.62 to 0.82. Under these conditions, no Al was incorporated for TTBAl/(TTBAl+TMIn) ratios less than 0.62. Hall measurements of Al_xIn_1−xSb showed hole concentrations between 5×10¹⁶ cm⁻³ to 2 × 10¹⁷ cm⁻³ and mobilities of 24 to 91 cm²/Vs for not intentionally doped Al_xIn_1−xSb.     

Study of optical and electrical properties of AlxGa1−xSb grown by metalorganic chemical vapor deposition

Al_xGa_1−xSb films in the regime 0×0.25 have been grown by metalorganic chemical vapor deposition on GaAs and GaSb substrates using TMAl, TMGa, and TMSb precursors. We report growth conditions and film properties, including the effect of V/III ratio and growth temperature on electrical and optical properties. Growth temperatures in the range of 520°C and 680°C and V/III ratios from 1 to 5 have been investigated. All epilayers grown exhibit p-type behavior. The mobility decreases and the carrier concentration increases sharply when a small amount of Al is incorporated into GaSb. The sharp cutoff and Fabry-Perot oscillations of the transmission spectra of the AlGaSb layers confirm the high quality of the films. The principle photoluminescence features observed are attributed to bound exciton and donor-acceptor transitions with FWHM comparable to the best values reported elsewhere.     

Novel In0.52Al0.48As/In0.53Ga0.47As metamorphic high electron mobility transistors on GaAs substrate with InxGa1−xP graded buffer layers

Compositionally graded In_xGa_1−xP (x=0.48→x=1) metamorphic layers have been grown on GaAs substrate by solid source molecular beam epitaxy using a valved phosphorus cracker cell. Three series of samples were grown to optimize the growth temperature, V/III ratio and grading rate of the buffer layer. X-ray diffraction (XRD) and photoluminescence (PL) were used to characterize the samples. The following results have been obtained: (1) XRD measurement shows that all the samples are nearly fully strain relaxed and the strain relaxation ratio is about 96%; (2) the full-width at half-maximum (FWHM) of the XRD peak shows that the sample grown at 480°C offers better material quality; (3) the grading rate does not influence the FWHM of XRD and PL results; (4) adjustment of the V/III ratio from 10 to 20 improves the FWHM of XRD peak, and the linewidth of PL peak is close to the data obtained for the lattice-matched sample on InP substrate. The optimization of growth conditions will benefit the metamorphic HEMTs grown on GaAs using graded InGaP as buffer layers.     

Use of tertiarybutylphosphine for OMVPE growth of (AlxGa1-x)o.51 In0.49P

This paper reports the results of atmospheric pressure organometallic vapor phase epitaxial growth of (Al _x Ga_1-x )_{0.51 0.49}P thin films using tertiarybutylphosphine (TBP) as the phosphorus source. The trimethylalkyls were used as group III sources. The growth temperature was 680° C. It was observed that V/III ratio dramatically affected the surface morphology and photoluminescence (PL). The epilayers grown at a V/III ratio lower than 60 had rough surfaces and weak PL emission. An input V/III ratio larger than 70 was required to obtain good surfaces and strong PL emission. Good quality (Al_xGa_1-x )_{0.51 0.49}P epilayers forx ≤ 0.62 were obtained at a V/III ratio of 85. The surface morphologies were smooth except for the occurrence of dense oval-shaped hillocks forx > 0.42. The Al distribution coefficient using TBP is the same as for phosphine (PH₃), which was used as the phosphorus source in previous AlGalnP growth. No parasitic reactions between TBP and trimethylalkyls were observed. 10 and 300 K PL emission was observed for all epilayers withx ≤ 0.62. However, the PL peak energy did not follow the band gap, as obtained for (Al_xGa_1-x )_{0.51 0.49}P epilayers grown using PH₃. The PL peak energy at both 10 and 300 K increased with increasingx forx ≤ 0.35, and then became nearly constant with further increases inx. In this region the PL is believed to be from a process involving a deep energy level, induced by an impurity from the TBP, bound to theX conduction band minimum. It was concluded that TBP has the potential to replace PH₃ for OMVPE growth of Al-containing compounds, although the purity needs to be improved.     

Growth of zinc- blende GaN on GaAs (100) substrates at high temperature using low-pressure MOVPE with a Low V/lll molar ratio

Zinc-blende GaN films were grown on GaAs (100) substrates by low-pressure metalorganic vapor phase epitaxy using trimethylgallium or triethylgallium and NH₃. Films grown at lower temperatures contained considerable amounts of carbon, but the carbon concentration was reduced in high temperature growth. When the film was grown at 950°C using triethylgallium and NH₃, its carbon concentration was on the order of 10¹⁷ cm⁻³. The crystalline and optical quality of zinc-blende GaN crystal also improved with high-temperature growth at a low V/III ratio using a thin buffer layer. The films exhibited only one sharp photoluminescence peak at 3.20 eV with a full width at half maximum as low as 70 meV at room temperature.     

Electrical activity,mode of incorporation and distribution coefficient of group V elements in Hg1−xCdxTe grown from tellurium rich liquid phase epitxial growth solutions

Hg_1−xCd_xTe films were grown liquid phase epitaxially from tellurium rich solutions containing up to 10 at. % of the group V elements P, As, Sb, and Bi. Chemical analysis of the Te growth solutions and the films was carried out in conjunction with extensive Hall effect measurements on the films subsequent to various annealing treatments under Hg rich and Te rich conditions. Despite the presence of a large concentration of the group V elements in the Te source solution, the maximum concentration of these elements incorporated into the liquid phase epitaxially grown Hg_1-xCd_xTe appears to vary from <10¹⁵cm⁻³ for Bi up to 10¹⁷cm⁻³ for phosphorus and As implying a distribution coefficient varying from <10⁻⁵ for Bi up to 10⁻³ for P at growth temperature of ∼500° C. This low value of the distribution coefficient for group V elements for growths from Te rich solutions contrasts with the moderately high values reported in the literature to date for growth from Hg rich solutions as well as pseudobinary solutions (Bridgman growth). The widely differing distribution coefficients and hence the solubility of the group V elements for Hg rich and Te rich liquid phase epitaxial solutions is explained on the basis that the activity coefficient of the group V elements in Te rich solutions is probably orders of magnitude lower than it is in Hg rich solutions. Finally, the results of the anneals at 200° C under Hg saturated conditions with and without a 500° C Hg saturated preanneal have indicatedn top conversion in many of the films attesting to the amphoteric behavior of the group V elements in LPE grown Hg_1−xCd_xTe(s) similar to the previously reported behavior of P in bulk grown Hg_0.8Cd_0.2Te.     

High-Temperature Growth of GaN and Al<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ga<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>N via Ammonia-Based Metalorganic Molecular-Beam Epitaxy

The effect of high-temperature growth on the crystalline quality and surface morphology of GaN and Al _x Ga_1?x N grown by ammonia-based metalorganic molecular-beam epitaxy (NH₃-MOMBE) has been investigated as a means of producing atomically smooth films suitable for device structures. The effects of V/III ratio on the growth rate and surface morphology are described herein. The crystalline quality of both GaN and AlGaN was found to mimic that of the GaN templates, with (002) x-ray diffraction (XRD) full-widths at half- maximum (FWHMs) of ~350 arcsec. Nitrogen-rich growth conditions have been found to provide optimal surface morphologies with a root-mean-square (RMS) roughness of ~0.8 nm, yet excessive N-rich environments have been found to reduce the growth rate and result in the formation of faceted surface pitting. AlGaN exhibits a decreased growth rate, as compared with GaN, due to increased N recombination as a result of the increased pyrolysis of NH₃ in the presence of Al. AlGaN films grown directly on GaN templates exhibited Pendellösung x-ray fringes, indicating an abrupt interface and a planar AlGaN film. AlGaN films grown for this study resulted in an optimal RMS roughness of ~0.85 nm with visible atomic steps.     

GaAs1−xSbx growth by OMVPE

The system GaAs_1−xSb_x has a solid phase miscibility gap ranging from x = 0.2 to x = 0.8 at the typical growth temperature of 600 C; however, metastable alloys covering this entire composition range have been grown by organometallic vapor phase epitaxy (OMVPE) using trimethylgallium, antimony and -arsenic as the source materials. The solid composition is studied for various values of growth temperature, the ratio of Sb to total group V elements in the vapor phase and the ratio of group III to group V elements in the vapor phase. The fraction of trimethylarsenic (TMAs) pyrolyzed in the vapor phase is found to be < 1 and to vary with temperature. Taking into account the incomplete pyrolysis of TMAs, solid composition is found to be controlled by thermodynamics. The effects of temperature and vapor composition are all accurately predicted using a simple thermodynamic model assuming equilibrium to be established at the solid-vapor interface. The properties of these metastable GaAs_1−x Sb_x alloys were explored using interference contrast microscopy, room temperature and 4 K photoluminescence, Hall effect and conductivity measurements. The alloy GaAs_0.5Sb_0.5 grown lattice matched to the InP substrate has excellent surface morphology, is p-type, and the photoluminescence spectrum consists of a single, intense, fairly broad (23.5 meV half width) peak at a wavelength of 1.54 Μm.     

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.     

Basic studies of gallium nitride growth on sapphire by metalorganic chemical vapor deposition and optical properties of deposited layers

We have studied the growth of gallium nitride on c-plane sapphire substrates. The layers were grown in a horizontal metalorganic chemical vapor deposition reactor at atmospheric pressure using trimethylgallium (TMG) and ammonia (NH₃). Variation of the V/III ratio (150–2500) shows a distinct effect on the growth rate. With decreasing V/III ratio, we find an increasing growth rate. Variation of the growth temperature (700–1000°C) shows a weak increase in growth rate with temperature. Furthermore, we performed secondary ion mass spectroscopy measurements and find an increasing carbon incorporation in the GaN films with decreasing ammonia partial pressure and a growing accumulation of carbon at the substrate interface. Photoluminescence measurements show that samples with high carbon content show a strong yellow luminescence peaking at 2.2 eV and a near band gap emission at 3.31 eV. With increasing carbon content, the intensity of the 3.31 eV line increases suggesting that a carbon related center is involved.     

InSb,GaSb, and GaInSb grown using trisdimethylaminoantimony

GalnSb alloys as well as the constituent binaries InSb and GaSb have been grown by organometallic vapor phase epitaxy using the new antimony precursor trisdimethylaminoantimony (TDMASb) combined with conventional group III precursors trimethylindium (TMIn) and trimethylgallium (TMGa). InSb layers were grown at temperatures between 275 and 425°C. The low values of V/III ratio required to obtain good morphologies at the lowest temperatures indicate that the pyrolysis temperature is low for TDMASb. In fact, at the lowest temperatures, the InSb growth efficiency is higher than for other antimony precursors, indicating the TDMASb pyrolysis products assist with TMIn pyrolysis. A similar, but less pronounced trend is observed for GaSb growth at temperatures of less than 500°C. No excess carbon contamination is observed for either the InSb or GaSb layers. Ga_1-xIn_xSb layers with excellent morphologies with values of x between 0 and 0.5 were grown on GaSb substrates without the use of graded layers. The growth temperature was 525°C and the values of V/III ratio, optimized for each value of x, ranged between 1.25 and 1.38. Strong photoluminescence (PL) was observed for values of x of less than 0.3, with values of halfwidth ranging from 13 to 16 meV, somewhat smaller than previous reports for layers grown using conventional precursors without the use of graded layers at the interface. The PL intensity was observed to decrease significantly for higher values of x. The PL peak energies were found to track the band gap energy; thus, the luminescence is due to band edge processes. The layers were all p-type with carrier concentrations of approximately 10¹⁷ cm³. Transmission electron diffraction studies indicate that the Ga_0.5In_0.5 Sb layers are ordered. Two variants of the Cu-Pt structure are observed with nearly the same diffracted intensities. This is the first report of ordering in GalnSb alloys.     

Study of indium droplets formation on the InxGa1−xN films by single crystal x-ray diffraction

Indium droplet formation during the epitaxial growth of In_xGa_1−xN films is a serious problem for achieving high quality films with high indium mole fraction. In this paper, we studied the formation of indium droplets on the In_xGa_1−xN films grown by metalorganic chemical vapor deposition (MOCVD) using single crystal x-ray diffraction. It is found that the indium (101) peak in the x-ray diffraction spectra can be utilized as a quantitative measure to determine the amounts of indium droplets on the film. It is shown by monitoring the indium diffraction peak that the density of indium droplets increases at lower growth temperature. To suppress these indium droplets, a modulation growth technique is used. Indium droplet formation in the modulation growth is investigated and it is revealed in our study that the indium droplets problem has been partially relieved by the modulation growth technique.     

A study of polycrystalline Cd(Zn,Mn)Te/Cds films and interfaces

Polycrystalline films of Cd_1-x Zn _x Te (x = 0–0.4) and Cd_1-x Mn _x Te (x = 0–0.25) were grown by MBE and MOCVD, respectively, on CdS/SnO₂/glass substrates to investigate their feasibility for solar cell applications. The compositional uniformity and interface quality of the films were analyzed by x-ray diffraction, surface photovoltage, and Auger depth profile measurements to establish a correlation between growth conditions and lattice constant, atomic concentration, and bandgap of the ternary films. MBE-grown polycrystalline Cd_1-x Zn _x Te films showed a linear dependence between Zn/(Cd + Zn) beam flux ratio, Zn concentration in the film, and the bandgap. Polycrystalline Cd_1-x Zn _x Te films grown at 300° C showed good compositional uniformity in contrast to compositionally non-uniform Cd_1-x Mn _x Te films grown by MOCVD in the temperature range of 420–450° C. The MBE-grown Cd_1-x Zn _x Te interface also showed significantly less interdiffusion compared to the MOCVD-grown Cd_1-x Mn _x Te/CdS interface, where preferential exchange between Cd from the CdS layer and Mn from the Cd_1-x Mn _x Te film was observed. The compositional uniformity of MOCVD-grown polycrystalline Cd_1-x Mn _x Te films grown on CdS/SnO₂/glass substrates was found to be a strong function of the growth conditions as well as the Mn source.     

Characteristics of GaN stripes grown by selective-area metalorganic chemical vapor deposition

We report on the selective-area metalorganic chemical vapor deposition of GaN stripes in the size range of 50 to 125 urn and the characterization of the morphology, topography, and optical properties of these stripes. GaN films (∼1–3 μm) grown on (0001) sapphire are used as the substrates. Excellent surface morphology is achieved under optimized growth conditions which include a higher V/III ratio than broad area growth. It is found that, under certain growth conditions, (0001) terraces of ~5 μm in width develop at the edges of all stripes, independent of stripe size and orientation. The selectively grown GaN yields stronger band-edge emission than the “substrate” GaN which indicates an improvement in optical quality. However, the donor-acceptor pair recombination (or conduction band to acceptor transition) and yellow emission are also enhanced in certain areas of the stripes. The spatial correlation of these emission bands is established by cathodoluminescence wavelength imaging, and the origin of these emissions is speculated.     

InGaN/GaN quantum well growth on pyramids of epitaxial lateral overgrown GaN

InGaN/GaN quantum wells (QW) were grown by metalorganic chemical vapor deposition (MOCVD) on pyramids of epitaxial lateral overgrown (ELO) GaN samples. The ELO GaN samples were grown by MOCVD on sapphire (0001) substrates that were patterned with a SiN_x mask. Scanning electron microscopy and cathodoluminescence (CL) imaging experiments were performed to examine lateral variations in structure and QW luminescence energy. CL wavelength imaging (CLWI) measurements show that the QW peaks on the top of the grooves are red-shifted in comparison with the QW emission from the side walls. The results show that In atoms have migrated to the top of the pyramids during the QW growth. The effects of V/III ratio, growth temperature as well as ELO GaN stripe orientation on the QW properties are also studied.     

Strain accommodation in mismatched layers by molecular beam epitaxy: Introduction of a new compliant substrate technology

Compliant substrates allow a new approach to the growth of strained epitaxial layers, in which part of the strain is accommodated in the substrate. In this article, compliant substrates are discussed and a new compliant substrate technology based on bonded thin film substrates is introduced. This technology has several advantages over previously published methods, including the ability to pattern both the top and bottom of the material. A new concept enabled by this compliant substrate technology,strain-modulated epitaxy, will be introduced. Using this technique, the properties of the semiconductor material can be controlled laterally across a substrate. Results of two experiments are presented in which low composition In_xGa_1−xAs was grown by molecular beam epitaxy on GaAs compliant substrates at thicknesses both greater than and less than the conventional critical thickness. It was found that for t > t_c, there was an inhibition of defect production in the epitaxial films grown on the compliant substrates as compared to those grown on conventional reference substrates. For t < t_c, photoluminescence and x-ray diffraction show the compliant substrates to be of excellent quality and uniformity as compared to conventional substrates.     

Growth and characterization of Ga1−xInxAs by low pressure metalorganic chemical vapor deposition

Conditions for growth at 550°C of high structural quality GaInAs by LPMOCVD are presented. The sensitivity of compositional grading to changes in the V/III molar ratio, growth rate and inclusion of InP buffer layers is discussed. Crystalline uniformity is indicated by double crystal x-ray rocking curves with FWHM (GaInAs) = 0.017°. By careful control of the V/III molar ratio, epitaxial GaInAs/InP heterostructures with δa/a ≤ 10⁻⁴ can be grown. Quantitative data for the TEIn-AsH₃ elimination reaction rate is presented. The composition of Ga_1−xIn_xAs which is expected in the presence of this reaction is calculated; evaluation of the corresponding rate constant shows that the adduct formation reaction proceeds at a modest but detectable rate. The problems associated with the purity of electronic grade triethylindium (TEIn) are addressed. Impurities in commercial TEIn have been determined by low resolution mass spectroscopy.     

Surface and Interface Properties of Metal-Organic Chemical Vapor Deposition Grown a -Plane Mg x Zn1– x O (0?≤ x ≤?0.3) Films

The a-plane Mg _x Zn_1−x O (0 ≤ x ≤ 0.3) films were grown on r-plane () sapphire substrates using metal-organic chemical vapor deposition (MOCVD). Growth was done at temperatures from 450°C to 500°C, with a typical growth rate of ∼500 nm/h. Field emission scanning electron microscopy (FESEM) images show that the films are smooth and dense. X-ray diffraction (XRD) scans confirm good crystallinity of the films. The interface of Mg _x Zn_1−x O films with r-sapphire was found to be semicoherent as characterized by high-resolution transmission electron microscopy (HRTEM). The Mg _x Zn_1−x O surfaces were characterized using scanning tunneling microscopy (STM) in ultrahigh vacuum (UHV). Low-energy electron diffraction (LEED) shows well-ordered and single-crystalline surfaces. The films have a characteristic wavelike surface morphology with needle-shaped domains running predominantly along the crystallographic c-direction. Photoluminescence (PL) measurements show a strong near-band-edge emission without observable deep level emission, indicating a low defect concentration. In-plane optical anisotropic transmission was observed by polarized transmission measurements.     

Acceptor and donor doping of AlxGa1−xN thin film alloys grown on 6H-SiC(0001) substrates via metalorganic vapor phase epitaxy

Thin films of Si-doped Al_xGa_1−xN (0.03≤x≤0.58) having smooth surfaces and strong near-band edge cathodoluminescence were deposited at 0.35–0.5 μm/h on on-axis 6H-SiC(0001) substrates at 1100°C using a 0.1 μm AlN buffer layer for electrical isolation. Alloy films having the compositions of Al_0.08Ga_0.92N and Al_0.48Ga_0.52N exhibited mobilities of 110 and 14 cm²/V·s at carrier concentrations of 9.6×10¹⁸ and 5.0×10¹⁷ cm⁻³, respectively. This marked change was due primarily to charge scattering as a result of the increasing Al concentration in these random alloys. Comparably doped GaN films grown under similar conditions had mobilities between 170 and ∼350 cm²/V·s. Acceptor doping of Al_xGa_1−xN for x≤0.13 was achieved for films deposited at 1100°C. No correlation between the O concentration and p-type electrical behavior was observed.