Epitaxial heterostructures of narrow-gap IV-VI and III-V semiconductors offer a platform for new electronics and mid-infrared photonics. Stark dissimilarities in the bonding and the crystal structure between the rocksalt IV–VIs and the zincblende III–Vs, however, mandate the development of nucleation and growth protocols to reliably prepare high-quality heterostructures. In this work, we demonstrate a route to single crystal (111)-oriented PbSe epitaxial films on nearly lattice-matched InAs (111)A templates. Without this technique, the high-energy heterovalent interface readily produces two populations of PbSe grains that are rotated 180° in-plane with respect to each other, separated by rotational twin boundaries. We find that a high-temperature surface treatment with the PbSe flux extinguishes one of these interfacial stackings, resulting in single-crystalline films with interfaces that are mediated by a monolayer of distorted PbSe. While very thin PbSe-on-InAs films do not emit light, hinting toward a type-III band alignment, we see strong room temperature photoluminescence from a 1.5 μm thick film with a minority carrier lifetime of 20 ns at low-excitation conditions and bimolecular recombination at high excitation conditions, respectively, even with threading dislocation densities exceeding 108 cm−2. We also note near-complete strain relaxation in these films despite large thermal expansion mismatch to the substrate, with dislocations gliding to relieve strain even at cryogenic temperatures. These results bring to light the exceptional properties of IV-VI semiconductors and the new IV-VI/III-V interfaces for a range of applications in optoelectronics.
Here we study and correlate structural, electrical, and optical properties of three GaN samples: GaN grown by metalorganic chemical vapor deposition on sapphire (GaN/Al2O3), freestanding GaN crystals grown by the high nitrogen pressure solution method (HNPS GaN), and GaN grown by hydride vapor phase epitaxy on silicon (GaN/Si). Defect and impurity densities and carrier concentrations are quantified by x-ray diffraction, secondary mass ion spectroscopy, and Hall effect studies, respectively. Power-dependent photoluminescence measurements reveal GaN near-band-edge emissions from all samples having mixtures of free exciton and band-to-band transitions. Only the defect luminescence in the GaN/Si sample remains unsaturated, in contrast to those from the HNPS GaN and GaN/Al2O3 samples. Carrier lifetimes, extracted from time-resolved photoluminescence measurements, and internal quantum efficiencies, extracted from temperature-dependent photoluminescence measurements, are used to extract radiative and nonradiative lifetimes. Shockley–Read–Hall (A) and radiative recombination coefficients (B) are then calculated accordingly. Overall, the A coefficient is observed to be highly sensitive to the point defect density rather than dislocation density, as evidenced by three orders of magnitude reduction in threading dislocation density reducing the A coefficient by one order of magnitude only. The B coefficient, while comparable in the higher quality and lowly doped GaN/Al2O3 and HNPS GaN samples, was severely degraded in the GaN/Si sample due to high threading dislocation density and doping concentration.
We report on photoluminescence in the 3–7 µm mid-wave infrared (MWIR) range from sub-100 nm strained thin films of rocksalt PbSe(001) grown on GaAs(001) substrates by molecular beam epitaxy. These bare films, grown epitaxially at temperatures below 400 °C, luminesce brightly at room temperature and have minority carrier lifetimes as long as 172 ns. The relatively long lifetimes in PbSe thin films are achievable despite threading dislocation densities exceeding 109 cm−2 arising from island growth on the nearly 8% lattice- and crystal-structure-mismatched GaAs substrate. Using quasi-continuous-wave and time-resolved photoluminescence, we show that the Shockley–Read–Hall recombination is slow in our high dislocation density PbSe films at room temperature, a hallmark of defect tolerance. Power-dependent photoluminescence and high injection excess carrier lifetimes at room temperature suggest that degenerate Auger recombination limits the efficiency of our films, although the Auger recombination rates are significantly lower than equivalent III–V bulk materials and even a bit slower than expectations for bulk PbSe. Consequently, the combined effects of defect tolerance and low Auger recombination rates yield an estimated peak internal quantum efficiency of roughly 30% at room temperature, unparalleled in the MWIR for a severely lattice-mismatched thin film. We anticipate substantial opportunities for improving performance by optimizing crystal growth as well as understanding Auger processes in thin films. These results highlight the unique opportunity to harness the unusual chemical bonding in PbSe and related IV–VI semiconductors for heterogeneously integrated mid-infrared light sources constrained by tight thermal budgets in new device designs.
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