Search

We develop lattice-mismatched GaInAsP as an alternative alloy to pure As-based alloys currently used in III–V multijunction solar cells. Increasing the alloy phosphorous and indium content while maintaining an optimal bandgap may allow high efficiency multijunction devices with increased radiation hardness. Here, 1.0-eV GaInAsP is developed and implemented into single and multijunction solar cell devices. The lattice-mismatched GaInAsP must be grown strain free, and the subcell thickness must be maintained below the thickness where surface-driven phase separation occurs. As observed in transmission electron microscopy and cathodoluminescence imaging, phase separation strengthens in the GaInAsP layer and leads to interfacial defect formation when the cell thickness is too great. We show single junction 1.0-eV Ga0.5In0.5As0.7P0.3 with excellent carrier collection and a bandgap-voltage offset of 0.40 V. This material quality approaches that of 1.0-eV Ga0.7In0.3As used in inverted metamorphic multijunction devices, but has increased phosphorus content and consequently is expected to have a higher radiation resistance. We incorporate the 1.0-eV GaInAsP subcell into a 3-junction inverted metamorphic solar cell to test the performance of the subcell in a multijunction. No additional loss is observed upon integration into a multijunction cell: both the carrier collection and voltage of the GaInAsP subcell are unchanged from single junction devices. While further materials development and radiation testing is still required, these preliminary results indicate that lattice-mismatched GaInAsP can be effectively used in multijunction solar cells to replace radiation-soft materials.

Dislocations provide fast diffusion pathways for atoms in semiconductors which can alter compositional profiles of finely tuned heterostructures. We show in model lattice-mismatched IV-VI semiconductor heterostructures of SnSe/PbSe on GaAs substrates that threading dislocations are highly enriched with group IV species of the neighboring layer, with artifacts that reflect the dynamic nature of dislocations when growing dissimilar materials as well as altered bonding properties at the dislocation core. Using atom probe tomography, we characterize one-dimensional nanometer-wide Sn-enriched filaments, which extend downward from SnSe through threading dislocations in the PbSe layer and infiltrate the remote PbSe/GaAs interface through the misfit dislocation network in the short time of growth. Local Sn compositions of only 6%--8% around the dislocations are significantly lower than the 30% Sn expected in bulk PbSe. We estimate the diffusivity of Sn atoms along threading dislocations to be ${10}^{--14}\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{2}\phantom{\rule{0.16em}{0ex}}{\mathrm{s}}^{--1}$ at 300 \ifmmode^\circ\else\textdegree\fi{}C, approximately three orders of magnitude larger than the lattice diffusivity. In contrast, Pb atoms from PbSe either do not diffuse upward into the orthorhombic SnSe layer or do so only a short distance as one-dimensional filaments before abruptly stopping, likely due to the nature of SnSe on PbSe epitaxy involving lattice mismatch. Beyond compositional anomalies, we detect elevated multiple-atom evaporation events that are spatially correlated to the dislocation, over and above an already high baseline in the matrix. In mixed-bonded IV-VI materials, where previous work has linked such events to the nature of bonding, we find that dislocations show up as distinct from the matrix.

We study the early stages of growth of the IV-VI semiconductor PbSe on (001)-oriented III-V substrates with different surface chemistry and lattice parameter, with the aim of achieving high quality cube-on-cube rocksalt on zincblende epitaxy. We find that PbSe nucleation on bare GaSb, InAs, and GaAs substrates is varied, yet consistently results in mixed orientation growth due to chemistry-dependent interfacial-energy penalties, irrespective of lattice mismatch. To overcome this, we locate a growth window for cube-on-cube single-orientation nucleation of PbSe on III-arsenide surfaces utilizing a high-temperature surface treatment with PbSe flux that we find creates a better template for subsequent low-temperature growth and leads to sharp interfaces. We probe this interface between PbSe and InAs, finding a Chain[Pb,As] atomic arrangement, tantamount to a discontinuous anion sublattice between III-V and IV-VI materials. We also observe a vertical displacement of the first few monolayers of the Se sublattice that we believe has origins in the heterovalency of this interface. Our results point towards surface chemistry as the primary factor governing film orientation, and lattice mismatch governing island coalescence behavior in these heterovalent interfaces with dissimilar crystal structures.

We report on photoluminescence in the 3-7 $\mu$m 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 {\deg}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 $10^9$ $cm^{-2}$ 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 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, though 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., Comment: 24 pages, 6 figures

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.

We use an electron beam to induce and directly observe dislocation glide in strained GaAs thin films on silicon substrates at room temperature using electron channeling contrast imaging (ECCI). Plastic behavior in this brittle material is kinetically facilitated by a lowering of the Peierls barrier for glide due to recombination of cathodogenerated electron-hole pairs at dislocations. The high residual strain in the GaAs film provides the overall driving force for motion. The dynamics of a variety of previously inaccessible dislocation interactions are studied by tracking individual threading dislocations with high spatial and temporal resolution. The ECCI technique has an inherently high resolution and was conducted in a convenient scanning electron microscope environment. The results and methods described in this Rapid Communication provide insight into dislocation-filtering processes and failure mechanisms in technologically important III-V devices on silicon, as well as other mismatched heteroepitaxial systems.

Although contacts to III-nitride visible and UV-A based emitters has been well explored, understanding the contacts to III-nitride deep-UV emitters have attracted research attention recently. Owing to the wide bandgap, both n-type and p-type contact metallization techniques result in a Schottky barrier at the metal-semiconductor interface. A way to reduce the contact resistance is to achieve a higher free carrier concentration in the epitaxial layer. As a result, growth of III-nitride epitaxial layers on native substrates are providing pathways for significant performance improvement. However, understanding the contacts to deep-UV emitters grown on native substrates are necessary to allow further performance improvement.

In this work, the authors characterized the interface of plasma enhanced chemical vapor deposition (PECVD) dielectrics, SiO2 and SiNx with AlGaN as a function of Al composition. SiO2 is found to exhibit type I straddled band alignment with positive conduction and valence band offsets for all Al compositions. However, the interface Fermi level is found to be pinned within the bandgap, indicating a significant density of interface states. Hence, SiO2 is found to be suitable for insulating layers or electrical isolation on AlGaN with breakdown fields between 4.5 and 6.5 MV cm−1, but an additional passivating interlayer between SiO2 and AlGaN is necessary for passivation on Al-rich AlGaN. In contrast, Si-rich PECVD SiNx is found to exhibit type II staggered band alignment with positive conduction band offsets and negative valence band offsets for Al compositions 40% and is, hence, found to be unsuitable for insulating layers or electrical isolation on Al-rich AlGaN in general. In contrast to passivating stoichiometric LPCVD Si3N4, no evidence for interface state reduction by depositing SiNx on AlGaN is observed.

In this work, we report on voltage dependent contact characteristics of Al-rich n-AlGaN due to the presence of a Schottky barrier at the metal–AlGaN interface. Current–voltage characteristics appear to be linear at low voltages, but a clear nonlinearity is evident at high voltages. Unlike Ga-rich n-AlGaN where V-based contact marginally outperforms the Ti-based contact, V-based contact to Al-rich n-AlGaN outperforms the Ti-based contact by ~2 orders of magnitude for all voltage ranges. The improved performance of V-based contacts is likely due to a lower Schottky barrier and partly due to ease of formation of a low barrier V–AlGaN interface.

Four orders of magnitude improvement in specific contact resistivity of Al-rich n-AlGaN grown on single crystal AlN substrates is achieved by surface treatment based on reactive ion etching (RIE). The ohmic contacts to as-grown Al-rich n-AlGaN/AlN exhibit a high contact resistance and nonlinearity due to a large Schottky barrier and low dislocation density. The RIE surface treatment reduces the barrier height at the free surface by ~0.5 eV and is also expected to introduce a defective surface required for ohmic contact formation.

In this work, we employed X-ray photoelectron spectroscopy to determine the band offsets and interface Fermi level at the heterojunction formed by stoichiometric silicon nitride deposited on AlxGa1-xN (of varying Al composition “x”) via low pressure chemical vapor deposition. Silicon nitride is found to form a type II staggered band alignment with AlGaN for all Al compositions (0 ≤ x ≤ 1) and present an electron barrier into AlGaN even at higher Al compositions, where Eg(AlGaN) > Eg(Si3N4). Further, no band bending is observed in AlGaN for x ≤ 0.6 and a reduced band bending (by ∼1 eV in comparison to that at free surface) is observed for x > 0.6. The Fermi level in silicon nitride is found to be at 3 eV with respect to its valence band, which is likely due to silicon (≡Si0/−1) dangling bonds. The presence of band bending for x > 0.6 is seen as a likely consequence of Fermi level alignment at Si3N4/AlGaN hetero-interface and not due to interface states. Photoelectron spectroscopy results are corroborated by current-voltage-temperature and capacitance-voltage measurements. A shift in the interface Fermi level (before band bending at equilibrium) from the conduction band in Si3N4/n-GaN to the valence band in Si3N4/p-GaN is observed, which strongly indicates a reduction in mid-gap interface states. Hence, stoichiometric silicon nitride is found to be a feasible passivation and dielectric insulation material for AlGaN at any composition.

Ohmic contacts to AlGaN grown on sapphire substrates have been previously demonstrated for various compositions of AlGaN, but contacts to AlGaN grown on native AlN substrates are more difficult to obtain. In this paper, a model is developed that describes current flow through contacts to Si-doped AlGaN. This model treats the current through reverse-biased Schottky barriers as a consequence of two different tunneling-dependent conduction mechanisms in parallel, i.e., Fowler-Nordheim emission and defect-assisted Frenkel-Poole emission. At low bias, the defect-assisted tunneling dominates, but as the potential across the depletion region increases, tunneling begins to occur without the assistance of defects, and the Fowler-Nordheim emission becomes the dominant conduction mechanism. Transfer length method measurements and temperature-dependent current-voltage (I-V) measurements of Ti/Al-based contacts to Si-doped AlGaN grown on sapphire and AlN substrates support this model. Defect-assisted tunneling plays a much larger role in the contacts to AlGaN on sapphire, resulting in nearly linear I-V characteristics. In contrast, contacts to AlGaN on AlN show limited defect-assisted tunneling appear to be only semi-Ohmic.

Optical gain spectra for ∼250 nm stimulated emission were compared in three different AlGaN-based structures grown on single crystalline AlN substrates: a single AlGaN film, a double heterostructure (DH), and a Multiple Quantum Well (MQW) structure; respective threshold pumping power densities of 700, 250, and 150 kW/cm2 were observed. Above threshold, the emission was transverse-electric polarized and as narrow as 1.8 nm without a cavity. The DH and MQW structures showed gain values of 50–60 cm−1 when pumped at 1 MW/cm2. The results demonstrated the excellent optical quality of the AlGaN-based heterostructures grown on AlN substrates and their potential for realizing electrically pumped sub-280 nm laser diodes.

Transmission electron microscopy (TEM) techniques and potassium hydroxide (KOH) etching confirmed that inversion domains in the N-polar AlN grown on c-plane sapphire were due to the decomposition of sapphire in the presence of hydrogen. The inversion domains were found to correspond to voids at the AlN and sapphire interface, and transmission electron microscopy results showed a V-shaped, columnar inversion domain with staggered domain boundary sidewalls. Voids were also observed in the simultaneously grown Al-polar AlN, however no inversion domains were present. The polarity of AlN grown above the decomposed regions of the sapphire substrate was confirmed to be Al-polar by KOH etching and TEM.