Growth study of AlGaAs using dimethylethylamine alane as the aluminum precursor

We present a comprehensive study on the growth of AlGaAs by using an alternative Al precursor, dimethylethylamine alane (DMEAA), and a Ga coprecursor, either triethylgallium (TEG) or trimethylgallium (TMG). The growth rate of AlAs determined by using in situ reflectometry was studied as a function of the growth temperature, V/III ratio, growth pressure, and rotation speed of the substrate. The presence of gas phase reactions of DMEAA with arsine and TEG was indicated, and their reduction was achieved at a lower growth pressure, lower V/III ratio, or a lower growth temperature. Negligible pre-reaction of DMEAA with TMG was observed. Excellent material uniformity of AlGaAs was achieved on a 2″ diameter wafer. Secondary ion mass spectroscopy measurements revealed extremely low C and O contents in the AlAs layer grown by DMEAA. Photoluminescence measurements suggested the presence of some non-radiative defects in the as-grown DMEAA AlGaAs layers.     

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.     

A study of chemical beam epitaxy of GaAs using tris-dimethylaminoarsenic

The growth of GaAs by chemical beam epitaxy using triethylgallium and trisdimethylaminoarsenic has been studied. Reflection high-energy electron diffraction (RHEED) measurements were used to investigate the growth behavior of GaAs over a wide temperature range of 300–550°C. Both group III- and group Vinduced RHEED intensity oscillations were observed, and actual V/III incorporation ratios on the substrate surface were established. Thick GaAs epitaxial layers (2–3 μm) were grown at different substrate temperatures and V/III ratios, and were characterized by the standard van der Pauw-Hall effect measurement and secondary ion mass spectroscopy analysis. The samples grown at substrate temperatures above 490°C showed n-type conduction, while those grown at substrate temperatures below 480°C showed p-type conduction. At a substrate temperature between 490 and 510°C and a V/III ratio of about 1.6, the unintentional doping concentration is n ∼2 × 10¹⁵ cm⁻³ with an electron mobility of 5700 cm²/V·s at 300K and 40000 cm²/V·s at 77K.     

Metal-organic vapor phase epitaxy growth and characterization of AlN/GaN heterostructures

Low-pressure, metal-organic vapor-phase epitaxy (MOVPE) was used to grow AlN/GaN metal-insulator-semiconductor (MIS) heterostructures with AlN thickness between 3 nm and 30 nm. The Hall mobility was found to decrease with increasing AlN thickness, with optimal mobility measured at 5-nm AlN. By decreasing the ammonia flow during AlN growth (lower V/III ratio), surface and interface quality were greatly improved with a corresponding improvement in electrical properties. For the optimal V/III ratio, room-temperature (RT) mobility and sheet charge were 891 cm²/Vs and 2.15×10¹³ cm⁻², respectively. The best RT mobility, for both optimal V/III and thickness, was 1015 cm²/Vs with a sheet charge of 1.1×10¹³ cm⁻².     

Characterization of InP grown by OMVPE using trimethylindium and tertiarybutylphosphine (TBP) at low V/III ratios and reduced TBP partial pressures

We report an OMVPE growth process for InP using trimethylindium (TMI) and tertiarybutylphosphine (TBP), a V/III ratio of 15, and a TBP partial pressure of 0.5 Torr. Growth is initiated with a 0.1 μm buffer layer employing a ramped TBP flow. Results are presented for InP grown with two different samples of both TMI and TBP and compared to previous experimental results and theoretical predictions. Good surface morphology is obtained from 540 to 600° C. The net carrier concentrations, N_d-N_a, decrease with increasing growth temperature—but never fall below 1.3 × 10¹⁶ cm^-3. Mobilities of 3990 and 11200 cm²/V.sec are observed at 300 and 77 K, respectively. At 77 K, we infer a compensation ratio of ∼0.4, independent of N_d-N_a. Photoluminescence measurements at 6 K show intense near bandgap emission with a full width half maximum proportional to N_d-N_a. Weak emission is also observed from carbon acceptors, independent of growth temperature. Secondary ion mass spectroscopy measurements are performed on an InP wafer grown with four different temperatures. The observed sulfur concentration drops from 1 × 10¹⁸ to 6 × 10¹⁶ cm^-3 with increasing growth temperature. This confirms that sulfur is an important residual impurity in TBP. The observed carbon concentration is 4–6 × 10¹⁶ cm^-3, regardless of growth temperature.     

Stoichiometry-dependent deep levels in undoped p-type Al0.38Ga0.62As grown by liquid phase epitaxy

Photocapacitance (PHCAP) and photoluminescence (PL) measurements were applied to unintentionally doped p-type Al_0.38Ga_0.62As grown by liquid phase epitaxy using the temperature difference method under controlled vapor pressure. PHCAP spectra revealed three dominant deep levels at E_v+0.9, E_v + 1.45, and E_v+1.96 eV, and a deep level at E_v+0.9−1.5 eV which was not neutralized by forward bias injection. These level densities increase with increasing arsenic vapor pressure and net shallow acceptor density. Furthermore, PL spectra reveal a deep level at 1.6–1.7 eV. The PL intensity of this deep level increases with increasing arsenic vapor pressure. These deep levels are thought to be associated with excess As.     

Properties of GaN epitaxial layers grown at high growth rates by metalorganic chemical vapor deposition

GaN epitaxial layers were grown at high growth rates by increasing the input trimethylgallium (TMG) flow rate while keeping the NH₃ flow rate constant in metalorganic chemical vapor deposition. The electrical and optical properties of the grown layers have been investigated. With the increasing TMG flow rate, the electron concentration tends to decrease gradually and the Hall mobility decreases significantly. Considering the temperature dependence of the Hall mobility and the correlation between the Hall mobility and the electron concentration, it has been indicated that the more acceptors are incorporated and consequently the compensation ratio becomes higher with increasing the TMG flow rate. Photoluminescence measurements have revealed that the intensity ratio of the bound exciton emission to the 2.2 eV band emission, which is assumed to correlate to carbon or Ga vacancies, was decreased with increasing the TMG flow rate. It might be reasonable to take a lot of acceptor incorporation to explain the degradation of the electrical and optical properties in the samples grown at high growth rates by increasing the TMG flow rate.     

Optimization studies of CVD growth of GaAs0.6P0.4

CVD growth conditions, particularly growth temperature and partial pressures of the reactant gases, strongly affect the growth characteristics and properties of GaAs_0.6P_0.4 epitaxial layers grown on GaAs substrates. For LED’s the most important properties of the material are B/J (brightness per unit current density) and surface morphology. This paper presents the results of a systematic study of the effect of temperature and reactant gas partial pressure (at a fixed III/V ratio) on B/J, surface morphology, growth rate, impurity doping and layer composition. Growth conditions which yield the optimum properties for LED’s are determined. The results are interpreted on the basis of kinetic and thermodynamic mechanisms controlling the growth process under various growth conditions. At constant temperature and constant III/V ratio, increasing the partial pressures causes the growth process to change from mass transport limited, where the growth rate increases with increasing partial pressures, to kinetically limited, where the growth rate is independent of partial pressures. Good morphology layers are obtained over a range of partial pressures around the transition from mass transport limited to kinetically limited growth. The B/J peaks at a value of partial pressure in the kinetically limited regime at which good morphology layers are obtained. Although B/J increases with increasing growth rate in the mass transport regime, the maximum B/J occurs in the region where growth rate is independent of partial pressures so that growth rate alone is not sufficient to determine B/J. In contrast to the “parabolic≓ dependence of growth rate on growth temperature, caused by the transition from the mass transport regime to the kinetic regime, the relative incorporation of As, P, and Te varies with temperature in the manner predicted from thermodynamics in both regimes. This behavior is consistent with the growth rate in the kinetic regime being limited by the desorption of chlorine atoms from the growth surface, with the reaction of As, P, and Te with the Ga proceeding thermodynamically at all temperatures.     

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.     

Influences of ZnO buffer layers on the quality of ZnO films synthesized by the metal-organic chemical vapor deposition process

High-quality ZnO thin films were prepared by metal-organic chemical vapor deposition (MOCVD) on a sapphire (a-Al₂O₃) substrate. The synthesis of ZnO films was performed over a substrate temperature of 400–700°C and at chamber pressures of 0.1–10 torr. The structural and optical properties of ZnO films were investigated in terms of deposition conditions, such as substrate temperature, working pressure, and the ratio of Zn precursor (Diethylzinc (DEZn)) to oxygen. The ZnO films, preferentially oriented to 34.42° diffraction because of the (002) plane, were obtained under processing conditions of 700°C and 3 torr. This film shows a full-width at half-maximum (FWHM) of 0.4–0.6°. The results of photoluminescence (PL) spectroscopy also show a strong near band-edge emission at 3.36 eV at 10 K as well as a very weak emission at deep levels around 2.5 eV at room temperature. In addition, we are interested in the introduction of ZnO buffer-layer growth by the sputtering process to reduce lattice mismatch stress. This paper addresses how to advance the crystalline and optical properties of film. The ZnO film grown with the aid of a buffer layer shows a FWHM of 0.06–0.1° in the x-ray diffraction (XRD) pattern. This result indicates that crystalline properties were highly improved by the ZnO buffer layers. The PL spectroscopy data of ZnO film also shows a strong near band-edge emission and very weak deep-level emission similar to films synthesized without a buffer layer. Accordingly, synthesized ZnO films with buffer layers indicate fairly good optical properties and low defect density as well as excellent crystallinity.     

Schottky barrier height dependence on the metal work function for p-type 4H-silicon carbide

We investigated Schottky barrier diodes of several metals (Ti, Ni, and Au) having different metal work functions to p-type 4H−SiC (0001) using I–V and C–V characteristics. Contacts showed excellent Schottky behavior with stable ideality factors of 1.07, 1.23, and 1.06 for Ti, Ni, and Au, respectively, in the range of 24°C to 300°C. The measured Schottky barrier height (SBH) was 1.96, 1.41, and 1.42 eV for Ti, Ni, and Au, respectively, in the same temperature range from I–V characteristics. Based on our measurements for p-type 4H−SiC, the SBH (φ_Bp) and metal work functions (φ_m) show a linear relationship of φ_Bp = 4.58 − 0.61φ_m and φ_Bp = 4.42 − 0.54φ_m for I–V and C–V characteristics at room temperature, respectively. We observed that the SBH strongly depends on the metal work function with a slope (S ≡ φ_Bp/φ_m) of 0.58 even though the Fermi level is partially pinned. We found the sum of the SBH (φ_Bp + φ_Bn = E_g) at room temperature for n-and p-type 4H−SiC to be 3.07 eV, 3.12 eV, and 3.21 eV for Ti, Ni, and Au, respectively, using I–V and C–V measurements, which are in reasonable accord with the Schottky-Mott limit.     

Characterization of InGaAs/GaAs(001) films grown by metalorganic vapor phase epitaxy using alternative sources

Thin films of In_xGa_1−xAs (0<x<0.012) on GaAs (001) were grown by metalorganic vapor phase epitaxy using triisopropylindium, triisobutylgallium, and tertiarybutylarsine. The effect of the process conditions, temperature, and V/III ratio on the film quality was studied using high resolution x-ray diffraction, scanning tunneling microscopy, and Hall measurements. High quality films were grown at temperatures as low as 475 °C and at a V/III ratio of 100. However, under these conditions, a change in growth mode from step flow to two-dimensional nucleation was observed.     

Improved area density and luminescence properties of InP quantum dots grown on In<Subscript>0.5</Subscript>Al<Subscript>0.5</Subscript>P by metal-organic chemical vapor deposition

We report on the growth of InP self-assembled quantum dots (QDs) on In_0.5Al_0.5P matrices by metal-organic chemical vapor deposition (MOCVD) on (001) GaAs substrates. The effects of the growth temperature and V/III-precursor flow ratio on the areal density and the cathodoluminescence (CL) properties of the grown QDs were systematically studied. We found that, when the growth temperature is ≤630°C, coherent QDs as well as large dislocated InP islands can be observed on the matrix surface. However, by using a two-step growth method, i.e., by growing the InAlP matrix layer at higher temperatures and growing InP QDs at lower temperatures, the formation of large dislocated islands can be effectively suppressed. Moreover, the areal density of the InP QDs is increased as the QD growth temperature is reduced. Furthermore, we found that the V/III ratio used in growing QDs and in growing the InAlP matrix layers has a quite different effect. In growing QDs, decreasing the V/III ratio results in an increase in the CL intensity and a decrease in CL line width; while in growing the InAlP matrix layers, increasing the V/III ratio results in an increase in the CL intensity of the InP QDs.     

Quantitative oxygen measurements in OMVPE Al x Ga1−x As grown by methyl precursors

Oxygen has always been considered to be a major contaminant in the organo-metallic vapor phase epitaxy (OMVPE) of Al _x Ga_1−x As. Oxygen incorporation has been invoked as a contributor to low luminescence efficiency, dopant compensation and degradation of surface morphology among other deleterious effects. This study presents quantitative measurements of oxygen concentration in nominally high purity Al _x Ga_1−x As. The oxygen concentration was measured as a function of alloy composition, growth temperature, andV/III ratio. Quantitative secondary ion mass spectroscopy (SIMS) measurements were used to determine the oxygen content as well as the carbon concentration in the film. The oxygen concentration increases with decreased growth temperature and V/III ratio while increasing superlinearly with Al content in the epitaxial layer.     

The role of the V/III ratio in the growth and structural properties of metalorganic vapor phase epitaxy GaAs/Ge heterostructures

GaAs epitaxial layers have been grown on (001) 6† off-oriented toward (110) Ge substrates by metalorganic vapor phase epitaxy. In order to study the influence of V/III ratio on the growth mechanisms and the structural properties of the layers, the input flow of arsine was changed over a wide range of values, while keeping constant all other experimental settings. Optical microscopy in the Nomarski contrast mode, x-ray topography and high resolution diffractometry, transmission electron microscopy and Rutherford backscattering have been used to investigate the epilayers. It has been found that the growth rate increases and the surface morphology worsens with increasing V/III ratio. The abruptness of the layer-substrate interface has also been found to strongly depend on the V/III ratio, the best results being obtained under Ga-rich conditions. The main structural defects within the layers are stacking faults and misfit dislocations. Layers grown under As-rich conditions only contain stacking faults, probably originated by a growth island coalescence mechanism, whereas layers grown under Ga-rich conditions contain both misfit dislocations and stacking faults generated by dissociation of threading segments of interfacial dislocations. In spite of the different defects, the strain relaxation has been found to follow the same trend irrespective of the V/III ratio. Finally, the relaxation has been found to start at a thickness exceeding the theoretical critical value.     

Characterization of silicon oxide films grown at room temperature by point-to-plane corona discharge

Oxide films grown on silicon in dry oxygen ambient at room temperature by negative point-to-plane corona discharge are investigated. A significant oxidation rate is observed at room temperature using this technique. Electrical properties of these room termperature grown oxides are examined. The capacitance-voltage measurements on the MOS structures fabricated from these oxides indicate a negative flat-band voltage of −1.5 V. Interface state density distribution in the range of 10¹⁰−10¹³ cm⁻²(eV)⁻¹ is observed with a value of 2×10¹⁰ cm⁻²(eV)⁻¹ at 0.17 eV above the valence band edge. Electrical conduction through the oxide is greater for negative values of applied gate bias voltages and the magnitude of conduction through the oxide decreases with decreasing current density during the corona discharge. Oxides grown at room temperature by this technique may find selective application in low temperature device processing.     

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.     

Coalescence of InP Epitaxial Lateral Overgrowth by MOVPE with V/III Ratio Variation

The effects of V/III ratio and seed window orientation on the coalescence of epitaxial lateral overgrowth InP over SiO₂ using metal organic vapor-phase epitaxy with tertiary butyl phosphine were investigated. Parallel lines having θ = 60° and 30° off [0[`1] \bar{1} 1] were coalesced, and their lateral growth rate variation with V/III was measured. Coalescence of lines separated by narrow angles in a star-like pattern was also studied. We find the greatest extent of coalescence to occur when the window stripe is oriented just off of the ⟨010⟩ directions. V/III ratio strongly affects the extent of coalescence, showing an alternating enhancement or inhibition depending on which side of the ⟨010⟩ direction the stripes are oriented. The variation in quality of coalesced material between stripes separated by narrow angles is examined with cross-sectional transmission electron microscopy, illustrating the most problematic growth directions under two V/III ratio conditions.     

Non-hydride group V sources for OMVPE

A major limitation to the continuing development of organometallic vapor phase epitaxy (OMVPE) for the growth of III/V semiconductor materials is the hazard posed by the hydride sources, AsH₃ and PH₃, which are virtually universally used, in high pressure cylinders, as the group V source materials for the growth of the highest quality materials. The ideal group V source would be a nontoxic liquid with a moderate vapor pressure (50-500 Torr). To be suitable for OMVPE growth, the molecule must pyrolyze at ordinary growth temperatures, be stable against decomposition in the bottle at room temperature, and not participate in undesirable parasitic reactions with the group III source molecules. The new sources have additional constraints related to purity. They must be easily purified without decomposing and produce no detectable carbon contamination in the resultant epitaxial layers. This set of stringent requirements eliminates most commonly available non-hydride group V sources. Recent research on newly developed sources has shown considerable promise. The entire area of group V sources, including the elemental sources, for OMVPE growth of III/V materials will be reviewed. The sources with no hydrogen atoms attached to the group V atom, the elemental, trimethyl-V, and triethyl-V, sources all appear to give unacceptably high carbon incorporation. Diethylarsine, which has one H attached to the As, produces high quality GaAs but has an inconveniently low vapor pressure. Trimethylphosphine and triethylphosphine o not pyrolyze at low enough temperatures to be useful for conventional OMVPE growth. Tertbutylarsine (TBAs) and tertbutylphosphine (TBP) appear to be promising source materials. TBP has a very low toxicity, a vapor pressure ideal for OMVPE growth, and the pyrolysis occurs at lower temperatures than for PH₃, allowing the use of low values of V/III ratio for the growth of high quality material. No carbon contamination can be attributed to the TBP. Control of the As/P ratio in OMVPE grown GaAsP is much improved for TBP as compared with PH₃ due to the more rapid pyrolysis. At normal growth temperatures the P distribution coefficient is nearly unity. TBAs has been less studied, but appears to have similar attributes including a favorable vapor pressure and lower pyrolysis temperature than AsH₃, allowing OMVPE growth of GaAs at low values of V/III ratio. The substitution of TBAs for AsH₃ results in no observable increase in carbon in the epitaxial GaAs.     

MOCVD growth of GaBN on 6H-SiC (0001) substrates

B_xGa_1−xN films were deposited on 6H-SiC (0001) substrates at 1000°C by low pressure MOVPE using diborane, trimethylgallium, and ammonia as precursors. The presence of boron was detected by Auger scanning microprobe, the shift of the (00.2) x-ray diffraction peak, and low-temperature photoluminescence. A single-phase B_xGa_1−xN alloy with x=1.5% was produced at the gas phase B/Ga ratio of 0.005. Phase separation into wurtzite BGaN and the B-rich phase occurred for a B/Ga ratio in the 0.01–0.2 range. Only BN was formed for B/Ga >0.2. The B-rich phase was identified as h-BN with sp² bonding based on the results of Fourier transform infrared spectroscopy. As the diborane flow exceeds the threshold concentration, the growth rate of BGaN decreases sharply, because the growth of GaN is poisoned by the formation of the slow growing BN phase. The bandedge emission of B_xGa_1−xN varies from 3.451 eV for x=0% with FWHM of 39.2 meV to 3.465 eV for x=1.5% with FWHM of 35.1 meV. The narrower FWHM indicates that the quality of GaN epilayer is improved with a small amount of boron incorporation. The PL linewidths become broader as more boron is introduced into the solid solution.