Recent results on metalorganic vapor phase epitaxially grown HgCdTe heterostructure devices

The ability to grow complex multilayer structures in Hg_1-xCd_xTe by epitaxial techniques has made it possible to produce a range of new devices such as infrared LEDs, lasers, and two-color infrared detector arrays. The devices described here, however, are designed to operate at temperatures above 145K and include both infrared sources and detectors. Three layer ppn structures, where the underlined symbols mean wider gap, have close to Auger limited R_oAs at temperatures above 145K. Under reverse bias, the devices exhibit Auger suppression leading to useful detectivities at room temperature. The diodes exhibit forward biased electroluminescence at room temperature although the efficiency of this emission is found to fall rapidly as the peak wavelength is increased toward 9 μm due to increased Auger recombination rates. By reverse biasing them, however, the devices show negative luminescence as a result of reducing the electron and hole densities below their thermal equilibrium value. The diode emitters have a higher quantum efficiency when used in this mode due to Auger suppression of the dark current.     

On the role of interface properties in the degradation of metalorganic vapor phase epitaxially grown Fe profiles in InP

Fe doping profiles in InP layers grown by low-pressure metalorganic vapor phase epitaxy (LP-MOVPE) were investigated by secondary ion mass spectroscopy. Different pre-treatments of the InP substrates proved to have substantially different effects on the Fe profiles which strongly indicate the relevance of underlying interfaces to dopant diffusion in subsequent layers, at least in the case of dopants occupying the group-III sublattice. We attribute the degradation of Fe profiles observed for some kinds of treatment to the emission of In interstitials from surfaces covered by oxides or other residues which are incompletely removed during the MOVPE preheat cycle. A favorable substrate preparation method for avoiding Fe profile degradation relies on etching by 5:1:1 H₂SO₄:H₂O₂:H₂O at room temperature followed by 30 min deionized water rinsing.     

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.     

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.     

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

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

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.     

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.     

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.     

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.     

Direct growth of high-quality thick CdTe epilayers on Si (211) substrates by metalorganic vapor phase epitaxy for nuclear radiation detection and imaging

Direct growth of high-quality, thick CdTe (211) epilayers, with thickness up to 100 μm, on Si (211) substrates in a vertical metalorganic vapor phase epitaxy system is reported. In order to obtain homo-orientation growth on Si substrates, pretreatment of the substrates was carried out in a separate chamber by annealing them together with pieces of GaAs at 800–900°C in a hydrogen environment. Grown epilayers had very good substrate adhesion. The full-width at half-maximum (FWHM) value of the x-ray double-crystal rocking curve from the CdTe (422) reflection decreased rapidly with increasing layer thickness and remained between 140–200 arcsec for layers >18 μm. Photoluminescence measurement at 4.2 K showed high-intensity, bound excitonic emission and very small defect-related deep emissions, indicating the high crystalline quality of the grown layers. Furthermore, a CdTe/n⁺-Si heterojunction diode was fabricated that exhibited clear rectifying behavior.     

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.     

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.     

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.     

Metalorganic vapor phase epitaxyin-situ growth of p-on-n and n-on-p Hg1-xCdxTe junction photodiodes using tertiarybutylarsine as the acceptor source

We report arsenic doping of Hg_1-xCd_xTe (0.2 < x < 0.3) grown using metalorganic vapor phase epitaxy (MOVPE) by the direct alloy growth (DAG) technique. Tertiarybutylarsine (TBAs) was used as a precursor for As doping. Several epilayers were grown at different Hg partial pressures and TBAs bubbler temperatures in order to study the doping characteristics. The amount of As incorporated in the layer as well as the acceptor concentration were found to be a strong function of the Hg pressure. Secondary ion mass spectrometric studies on heterostructures showed that the compositional interdiffusion is less than the diffusion of As during growth. P-N junctions were grown using TBAs for the first time and several of these layers were processed to fabricate photodiodes. A p-on-n grown junction photodiode with a cutoff wavelength of 8.2 μm had an R_oA value of 241 ohm-cm² at 80K and is the highest reported value for p-on-n DAG-MOVPE devices. Methods to improve the device R_oA of the grown junctions are also proposed.     

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.     

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.     

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.     

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.     

The origin of hillocks in (Hg, Cd)Te grown by MOVPE

Dimethylcadmium, a precursor for the metalorganic vapor phase epitaxy of mercury cadmium telluride, has been shown to react with gallium arsenide to form trimethylarsine and dimethylarsine. An analogous reaction occurs between di-iso-propyltelluride and gallium arsenide to form iso-propylarsine and di-iso-propylarsine. It is proposed that if these reactions remove sufficient arsenic from a gallium arsenide substrate, metallic droplets will form on the wafer surface thereby creating the nucleation sites for hillocks. Analogous reactions have been observed between the precursors and a range of other substrates which can in turn be used to explain the origin of hillocks in epitaxial layers grown onto these materials.