Reaction kinetics control in preparation of CdTe and HgCdTe by hot wall metalorganic vapor phase epitaxy

The growth rates of CdTe and HgCdTe by hot wall metalorganic vapor phase epitaxy were studied as functions of growth temperatures and partial pressures of precursors. It is suggested that the growth of CdTe and HgCdTe was controlled by reaction kinetics. The relationship between growth processes and epilayer properties was discussed and high quality epilayers were obtained.     

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.     

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.     

Controlled oxygen incorporation in indium gallium arsenide and indium phosphide grown by metalorganic vapor phase epitaxy

The defect engineering in metalorganic vapor phase epitaxy In_xGa_1-xAs and InP by controlled oxygen doping using diethyl aluminum ethoxide (DEALO) was developed in this study. DEALO doping has led to the incorporation of Al and O, and the compensation of shallow Si donors in In_xGa_1−xAs: Si with 0 ≤ x ≤ 0.25. With the same DEALO mole fraction during growth, the incorporation of Al and O was found to be independent of x, but the compensation of Si donors decreases with increasing In content. Deep level transient spectroscopy analysis on a series of In_xGa_1-xAs: Si. samples with 0 ≤ x ≤ 0.18 revealed that oxygen incorporation led to a set of deep levels, similar to those found in DEALO doped GaAs. As the In composition was increased, one or more of these deep levels became resonant with the conduction band and led to a high electron concentration in oxygen doped In_0.53Ga_0.47As. Low temperature photoluminescence emission measurements at 12K on the same set of samples revealed the quenching of the near-band edge peak, and the appearance of new oxygen-induced emission features. DEALO doping in InP has also led to the incorporation of Al and O, and the compensation of Si donors due to oxygen-induced multiple deep levels.     

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.     

High quality compressively strained InP-based GaInAs(P)/GaInAsP multi-quantum well laser structures grown by metalorganic vapor phase epitaxy

The growth and characterization of strained GaInAs and GaInAsP multiquantum well (MQW) laser structures has been investigated. The use of triple axis x-ray diffraction (XRD), in addition to the conventional high resolution double crystal XRD, yields further information about the structural integrity of these complex structures. Buried heterostructure lasers with eight GaInAsP wells (+1.0% strain, 80Å thick) exhibit a record low threshold current of 3.1 mA. By using a constant As/P ratio in the wells and barriers of an MQW laser structure, we have shown that the structure can be annealed at 700°C for 1 h with only a minimal shift (-4 nm) in the photoluminescence emission wavelength. Conventional lattice-matched GaInAs/GaInAsP MQW structures exhibit a shift of-46 nm under the same conditions.     

Growth characteristics of CdZnTe layers grown by metalorganic vapor phase epitaxy using dimethylzinc, dimethylcadmium, diethyltelluride, and dimethyltelluride as precursors

Growth characteristics of (100)-oriented CdZnTe layers grown by atmospheric-pressure metalorganic vapor phase epitaxy have been studied using dimethylzinc (DMZn), dimethylcadmium (DMCd), diethyltelluride (DETe), and dimethyltelluride (DMTe) as precursors. Variations of Zn composition and layer growth rate were examined by changing the DMZn supply ratio, defined as DMZn/(DMCd+DMZn), where the precursors are expressed in appropriate units of flow rate, from 0 (no DMZn) to 1.0 (no DMCd), while keeping the total group II supply rate constant. The growth rate of CdZnTe layers was found to decrease monotonically with increase of the DMZn supply ratio. On the other hand, the Zn composition x of grown layers increased gradually up to x=0.04 with increase of the DMZn supply ratio from 0 to 0.8, beyond which the Zn composition increased abruptly to ZnTe. The abrupt transition of Zn composition was suppressed by increasing the VI/II ratio. The growth mechanism of CdZnTe layers was studied based on the observed growth characteristics of CdTe and ZnTe. A higher desorption rate from the growth surface for Zn species than for Cd species, and a higher rate of CdTe formation than ZnTe formation are believed to cause the observed growth characteristics. CdZnTe layers with high crystal quality were grown in a wide range of Zn compositions. The full-width at half-maximum values for x-ray double-crystal rocking-curve measurements were lower than 320 arc-sec for x<0.3 and x>0.75.     

Hydride vapor phase epitaxy for gallium nitride substrate

Due to the remarkable growth rate compared to another growth methods for gallium nitride(GaN)growth,hydride vapor phase epitaxy(HVPE)is now the only method for mass product GaN substrates.In this review,commercial HVPE systems and the GaN crystals grown by them are demonstrated.This article also illustrates some innovative attempts to develop homebuilt HVPE systems.Finally,the prospects for the further development of HVPE for GaN crystal growth in the future are also discussed.     

Deposition of InGaAsP alloys on GaAs by low pressure metalorganic vapor phase epitaxy: Theory and experiments

A combined thermodynamic-kinetic approach to the epitaxial deposition of InGaAsP alloys on GaAs substrates is presented. Good agreement with experimental group V solid phase incorporation has been found when neglecting the 2V₂ = V₄ (V = As,P) vapor phase reactions, while the group III solid phase composition is well described by simple mass-transport limited processes. InGaAsP materials, lattice matched to GaAs, have been grown in a wide composition range toward the ternary limit [In(0.49)Ga(0.51)P]. Furthermore, high quality InGaAsP/GaAs strained quantum wells with a bandgap below that of GaAs are realized for the first time.     

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.     

Effect of AlInGaN barrier layers with various TMGa flows on optoelectronic characteristics of near UV light-emitting diodes grown by atmospheric pressure metalorganic vapor phase epitaxy

Near ultraviolet light-emitting diodes (LEDs) with quaternary AlInGaN quantum barriers (QBs) are grown by atmospheric pressure metalorganic vapor phase epitaxy. The indium mole fraction of AlInGaN QB could be enhanced as we increased the TMG flow rate. Both the wavelength shift in EL spectra and forward voltage at 20 mA current injection were reduced by using AlInGaN QB. Under 100 mA current injection, the LED output power with Al_0.089In_0.035Ga_0.876N QB can be enhanced by 15.9%, compared to LED with GaN QB. It should be attributed to a reduction of lattice mismatch induced polarization mismatch in the active layer.     

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.     

Crystallographic orientation dependence of the growth rate for GaAs low pressure organometallic vapor phase epitaxy

The complete crystallographic orientation dependence of the growth rate for GaAs low pressure organometallic vapor phase epitaxy (LPOMVPE) is determined using a previously described semi-empirical model. A set of LPOMVPE growth rate polar diagrams is presented for reactor temperatures near 550°C as well as near 700°C. Also, the variation of the growth rate polar diagrams as a function of process variables is given. The experimental data utilized in the semiempirical model was attained using a typical horizontal reactor LPOMVPE system and typical LPOMVPE process parameters.     

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.     

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 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.     

Nitrogen doping in ZnSe by photo-assisted metalorgani vapor phase epitaxy

Doping characteristics of nitrogen in ZnSe using photo-assisted vapor phase epitaxy were investigated. The source precursors and the doping source were diethylzinc, dimethylselenide, and tertiarybutylamine. Photoluminescence, electrical properties of Schottky diodes, and electroluminescence from homo and double heterojunction diodes consistently supported p-type behavior of the ZnSe:N layers. At the conditions investigated, higher doping was achieved at lower substrate temperature and irradiation intensity; e.g., 350°C and 45 mW/ cm², respectively. As a guideline, net acceptor concentration was estimated as 2 x 10¹⁷ cm^-3 for the ZnSe:N layer with nitrogen concentration of 5 x 10¹⁷ cm^-3 revealed by secondary ion mass spectroscopy.     

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.     

Optimization of selective area growth of GaAs by low pressure organometallic vapor phase epitaxy for monolithic integrated circuits

GaAs MESFET device structures have been grown on silicon nitride or silicon dioxide masked 50 and 76 mm GaAs substrates by low pressure organometallic vapor phase epitaxy. Very smooth, featureless morphology and 100 percent selectivity of GaAs islands have been achieved over a range of growth conditions. Optimization of the GaAs p-buffer of the field effect transistor structure has led to improved device performance, including increased breakdown voltage. Device characteristics of the 0.5 μm gate low noise metal semiconductor field-effect transistors fabricated on these islands show good performance and wafer to wafer reproducibility on the second device lot.     

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.