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.     

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.     

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.     

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.     

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.     

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.     

GaN grown by hydride vapor phase epitaxy on p-type 6H-SiC layers

6H-SiC/GaN pn-heterostructures were grown by subsequent epitaxial growth of p-SiC by low temperature liquid phase epitaxy (LTLPE) and n-GaN by hydride vapor phase epitaxy (HVPE). For the first time, p-type epitaxial layers grown on 6H-SiC wafers were used as substrates for GaN HVPE growth. The GaN layers exhibit high crystal quality which was determined by x-ray diffraction. The full width at a half maximum (FWHM) for the ω-scan rocking curve for (0002) GaN reflection was ∼120 arcsec. The photoluminescence spectra for these films were dominated by band-edge emission. The FWHM of the edge PL peak at 361 nm was about 5 nm (80K).     

Probing the mechanisms of growth of gallium arsenide by metalorganic vapor phase epitaxy using experimental and theoretical studies of designed precursors

Decomposition of o-CH₃C₆H₄AsD₂ in the gas phase at 600–1000°C produces toluenes with 0-3 D atoms in the methyl group. It is shown that this cannot be accounted for by conventional mechanisms involving initial As-C bond cleavage or reductive elimination, but rather that the first step is As-D bond cleavage and this is followed by reductive elimination of o-CH₃C₆H₄D or H atom transfer to give o-HDAsC₆H₄CH₂· which abstracts D from an intact o-tolylarsine to give o-CH₂DC₆H₄AsHD. Repetition of these steps can lead to multiple D incorporation. The free energies of activation for reductive elimination or multiple D incorporation are found to be very similar. Theoretical studies on the decomposition of^tBuAsH₂ show that the first step for decomposition can be As-H bond cleavage to give^tBuAsH· or loss of H₂ to^tBuAs.^tBuAsH· decomposes to^tBu· which abstracts H· from^tBuAsH₂ to give 2-methylpropane or by β-H abstraction to give 2-methylpropene.^tBuAs, on the other hand only gives 2-methylpropene,via a β-H abstraction mechanism. Measured effects of total reactor pressure on product distribution are modeled qualitatively. Hex-5-enylarsine also decomposesvia initial As-H bond cleavage followed by reductive elimination of 1-hexene. However, it reacts in the liquid or solution phase with Me₃Ga to give the adduct. [Me₃Ga.AsH₂hex]. On heating, this loses methane to give first [Me₂Ga.AsHhex]₃ then [MeGa.Ashex]_n. Finally, GaAs is produced with the formation of methane and methylenecyclopentane. The last product indicates a free radical mechanism involving cleavage of the As-hex bond for the last step. In the gas phase at 600°C, GaAs is again formed but the major C₆ product is 1-hexene. This is interpreted as meaning that the adduct, [Me₃Ga.AsH₂hex] is not formed in the gas phase under growth conditions.     

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.     

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.     

(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.     

Effect of dislocations on 1/f noise of long wavelength infrared photodiodes fabricated with HgCdTe layers grown on GaAs by metalorganic vapor phase epitaxy

We studied the effect of dislocations on the 1/f noise current of long wavelength infrared photodiodes fabricated with HgCdTe layers grown on GaAs by metalorganic vapor phase epitaxy. N-on-p junctions were formed by boron ion implantation into Hg-vacancy doped epilayers. The 1/f noise dominated from 0.5 to 100 Hz, and shot noise caused by photocurrent (√2eI_p) dominated at higher frequencies. We observed two types of 1/f noise. One is caused by the leakage current generated at dislocations, and the other is induced by the photocurrent. The 1/f noise current increased with the photon flux in the low-etch pit density (EPD) range independently of EPD. It increased with EPD in the high-EPD range. The 1/f noise current measured at zero field of view increased with EPD. This suggests that the 1/f noise generated by the photocurrent dominated in the low-EPD range, and that the 1/f noise current caused by dislocations dominated in the high-EPD range. In order to obtain a thermal image of a room-temperature object, the 1/f noise current induced by background photon flux is as high as that caused by dislocations of more than 10⁷ cm⁻². Therefore, the 1/f noise current induced by the photocurrent is dominant in photodiodes fabricated with HgCdTe layers on GaAs, since the EPD is less than 2 x 10⁶ cm⁻². We expect the detectivity to be as high as with LPE-layers. We fabricated 64 x 64 photodiode arrays, and obtained a thermal image.     

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.     

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.     

Properties of Bi-doped PbTe layers grown by liquid phase epitaxy under controlled Te vapor pressure

Effects of Bi doping in PbTe liquid-phase epitaxial layers grown by the temperature difference method under controlled vapor pressure (TDM-CVP) are investigated. For Bi concentrations in the solution, x_Bi, lower than 0.2 at.%, an excess deep-donor level (activation energy E_d≈0.03–0.04 eV) appears, and Hall mobility is low. In contrast, for x_Bi>0.2 at.%, Hall mobility becomes very high, while carrier concentration is in the range of 10¹⁷ cm⁻³. Inductive coupled plasma (ICP) emission analysis shows that, for x_Bi=1 at.%, Bi concentration in the epitaxial layer is as high as N_Bi=2.3–2.7 × 10¹⁹ cm⁻³. These results indicate that Bi behaves not only as a donor but also as an acceptor, and the nearest neighbor or very near donor-acceptor (D-A) pairs are formed, so that strong self-compensation of Bi takes place. Carrier concentration for highly Bi-doped layers shows a minimum at a Te vapor pressure of 2.2 × 10⁻⁵ torr for growth temperature 470°C, which is coincident with that of the undoped PbTe.     

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.     

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.     

Low temperature growth of (100) HgCdTe layers with DtBTe in metalorganic vapor phase epitaxy

Growth characteristics of (100) HgCdTe (MCT) layers by MOVPE at low temperature of 275°C were studied using ditertiarybutyltelluride as a tellurium precursor. Growths were conducted in a vertical narrow-spacing growth cell at atmospheric pressure. Cd composition of MCT layers were controlled from 0 to 0.98 using dimethylcadmium (DMCd) flow. The growth rate was constant for increase of DMCd flow. During the growth, Cd was incorporated preferentially into the MCT layers. Enhancement of Cd incorporation in the presence of Hg was also observed. Crystal quality and electrical properties were also evaluated, which showed that high quality MCT layers can be grown at 275°C. Strain in CdTe layers grown at 425 and 275°C was also evaluated. Lattice parameter of layers grown at 425°C approached bulk value at thickness of 5 μm, while layers grown at 275°C relaxed at 1 μm. The rapid strain relaxation of layers grown at 275°C was considered due to the layer growth on the strain relaxed buffer layer. The effect of the thermal stress on the relaxation of CdTe lattice strain was also discussed.     

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.