For potential infrared detector applications, single-crystalline InAsBi and InAsSbBi have been grown by atmospheric pressure organometallic vapor-phase epitaxy. The precursors used were trimethylindium, trimethylantimony, trimethylbismuth, and arsine at growth temperatures of 375 and 400 dc. Good quality epilayers with smooth surface morphologies were obtained by properly controlling the key growth parameter, the VillI ratio. The variation of lattice constant with solid composition for the InAs, _ xBix system, a = 6.058 + 0.966x, provides evidence that Bi atoms indeed incorporate substitutionally into the As sites of the sublattice in the InAs zinc-blende structure. An extrapolated lattice parameter for the hypothetical zincblende InBi is 7.024 A. Thermodynamic calculations of the InAs-InBi and InSb-InBi pseudobinary phase diagrams were carried out using the delta-lattice-parameter model using the lattice constant for zinc-blende InBi of 7.024 A. The results agree well with experimental data. The calculations predict that the solid solubility limit of Bi in InAs is less than 0.025 at. %. The calculated maximum solubility limit is 2. I at. % for Bi in InSb at the eutectic temperature of 132 DC. Thus, tremendously large miscibility gaps exist in both alloy systems. The critical temperature was predicted to be 2569 °C for the InAs-InBi system and 496 "C for the InSb-InBi system. The miscibility gap is the major factor limiting Bi incorporation into the InAsSb alloys. Nevertheless, metastable InAsBi and InAsSbBi alloys were grown with concentrations far exceeding the solubility limit. For example 3.1 at. % Bi was incorporated into InAs. Infrared photoluminescence measurements show a decrease of peak energy with increasing Bi concentration in the alloys, with dEgldx = -55 meV lat. %Bi.
InAs1−xBix with x≤0.026 and InAs1−x−ySbyBix with x≤0.017 and y≤0.096 have been successfully grown on InAs (100) oriented substrates by atmospheric pressure organometallic vapor phase epitaxy using the precursors trimethylindium, trimethylbismuth, trimethylantimony, and arsine. Good surface morphologies for both InAsBi and InAsSbBi epitaxial layers were obtained at a growth temperature of 400 °C. A key growth parameter is the V/III ratio. Only a very narrow range near 4 (considering the incomplete pyrolysis of AsH3) yields smooth InAsBi epilayers. Typical growth rates were 0.02 μm/min. X-ray diffractometer scans show clearly resolved Kα1 and Kα2 peaks for the layer of InAs0.889Sb0.096Bi0.015 grown on an InAs substrate with a graded transition layer to accommodate the lattice parameter difference. The half widths of the peaks are comparable to those of the substrate. For the first time, photoluminescence (PL) at 10 K from these Bi-containing alloys has been measured. The PL peak energy is seen to decrease with increasing Bi concentration at a rate of 55 meV/at. % Bi. InAsSbBi is a potential material for infrared detectors operating in the wavelength range from 8 to 12 μm.
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