S. Francoeur

Photooxidation and quantum confinement effects in exfoliated black phosphorus

Thin layers of black phosphorus have recently raised interest owing to their two-dimensional (2D) semiconducting properties, such as tunable direct bandgap and high carrier mobilities. This lamellar crystal of phosphorus atoms can be exfoliated down to monolayer 2D-phosphane (also called phosphorene) using procedures similar to those used for graphene. Probing the properties has, however, been challenged by a fast degradation of the thinnest layers on exposure to ambient conditions. Herein, we investigate this chemistry using in situ Raman and transmission electron spectroscopies. The results highlight a thickness-dependent photoassisted oxidation reaction with oxygen dissolved in adsorbed water. The oxidation kinetics is consistent with a phenomenological model involving electron transfer and quantum confinement as key parameters. A procedure carried out in a glove box is used to prepare mono-, bi- and multilayer 2D-phosphane in their pristine states for further studies on the effect of layer thickness on the Raman modes. Controlled experiments in ambient conditions are shown to lower the A(g)(1)/A(g)(2) intensity ratio for ultrathin layers, a signature of oxidation.

Molecular beam epitaxy growth of GaAs1−xBix

GaAs1−xBix epilayers with bismuth concentrations up to x=3.1% were grown on GaAs by molecular beam epitaxy. The Bi content in the films was measured by Rutherford backscattering spectroscopy. X-ray diffraction shows that GaAsBi is pseudomorphically strained to GaAs but that some structural disorder is present in the thick films. The extrapolation of the lattice constant of GaAsBi to the hypothetical zincblende GaBi alloy gives 6.33±0.06 A. Room-temperature photoluminescence of the GaAsBi epilayers is obtained and a significant redshift in the emission of GaAsBi of ∼84 meV per percent Bi is observed.

Band gap of GaAs1−xBix, 0<x<3.6%

The band gap of GaAsBi epitaxial layers as a function of bismuth concentration up to 3.6% is determined. The optical transitions were measured by modulated electroreflectance. The energy of the band gap decreases at a linearized rate of 88 meV/% Bi, or 83 meV/% Bi for the heavy hole to conduction band transition for GaAsBi strained to GaAs. The valence-band splitting increases faster than that of GaAs under similar compressive strain whereas the temperature dependence of the observed GaAsBi transitions is similar to that of GaAs.

Band gaps of the dilute quaternary alloys GaNxAs1−x−yBiy and Ga1−yInyNxAs1−x

We report strong band gap photoluminescence at room temperature in dilute quaternary GaNxAs1−x−yBiy alloys (x<1.6%,y<2.6%) grown by molecular beam epitaxy. The band gap of the alloy can be approximated by the band gap of GaAs minus the reduction in gap associated with the effects of N and Bi alloying individually. A one-parameter method for fitting the composition dependence of the band gaps of dilute quaternary semiconductor alloys is proposed which is in excellent agreement with data for Ga1−yInyNxAs1−x.

Initiation and evolution of phase separation in heteroepitaxial InAlAs films

We have investigated the initiation and evolution of phase separation in heteroepitaxial InAlAs films. In misfit-free InAlAs layers, cross-sectional scanning tunneling microscopy (XSTM) reveals the presence of isotropic nanometer-sized clusters. For lattice-mismatched InAlAs layers with 1.2% misfit, quasiperiodic contrast modulations perpendicular to the growth direction are apparent. Interestingly, these lateral modulations are apparently initiated within the first few bilayers of film growth, and both the amplitude and wavelength of the modulations increase with film thickness. The saturation value of the modulation wavelength determined from XSTM coincides with the lateral superlattice period determined from (002) x-ray reciprocal space maps, suggesting that the lateral modulation wavelength represents a periodic composition variation. Together, these results suggest that phase separation in the heteroepitaxial InAlAs thin-film system is a misfit-driven kinetic process initiated by random compositional nonuniformities, which later develop into coupled compositional and surface morphological variations.

Band gap of sphalerite and chalcopyrite phases of epitaxial ZnSnP2

Using contactless electroreflectance, we determined the band gap of the two known phases of epitaxial ZnSnP2. Induced by small changes in Sn/Zn flux ratio during epitaxy, the order-disordered transition between the chalcopyrite and sphalerite phases reduces the band gap by 300 meV. The chalcopyrite ordered phase, unambiguously identified from x-ray diffraction, exhibits a band gap of 1.683 eV at 293 K. The band gap of the disordered sphalerite phase is 1.383 eV. Using the volume-averaged order parameter measured on the chalcopyrite sample, we find that its morphology is best described by the presence of perfectly ordered domains inside a disordered matrix.

Phonon Engineering in Isotopically Disordered Silicon Nanowires

The introduction of stable isotopes in the fabrication of semiconductor nanowires provides an additional degree of freedom to manipulate their basic properties, design an entirely new class of devices, and highlight subtle but important nanoscale and quantum phenomena. With this perspective, we report on phonon engineering in metal-catalyzed silicon nanowires with tailor-made isotopic compositions grown using isotopically enriched silane precursors (28)SiH4, (29)SiH4, and (30)SiH4 with purity better than 99.9%. More specifically, isotopically mixed nanowires (28)Si(x)(30)Si(1-x) with a composition close to the highest mass disorder (x ∼ 0.5) were investigated. The effect of mass disorder on the phonon behavior was elucidated and compared to that in isotopically pure (29)Si nanowires having a similar reduced mass. We found that the disorder-induced enhancement in phonon scattering in isotopically mixed nanowires is unexpectedly much more significant than in bulk crystals of close isotopic compositions. This effect is explained by a nonuniform distribution of (28)Si and (30)Si isotopes in the grown isotopically mixed nanowires with local compositions ranging from x = ∼0.25 to 0.70. Moreover, we also observed that upon heating, phonons in (28)Si(x)(30)Si(1-x) nanowires behave remarkably differently from those in (29)Si nanowires suggesting a reduced thermal conductivity induced by mass disorder. Using Raman nanothermometry, we found that the thermal conductivity of isotopically mixed (28)Si(x)(30)Si(1-x) nanowires is ∼30% lower than that of isotopically pure (29)Si nanowires in agreement with theoretical predictions.

Observation of large optical anisotropy and valence band splitting in AlInAs self-assembled lateral quantum wells

Self-assembled lateral quantum wells in alloys of AlInAs, epitaxially deposited by metal–organic chemical vapor deposition on InP, are studied by transmission electron microscopy, modulation spectroscopy, and photoluminescence. Under particular growth conditions, the growth of a homogeneous layer results in the spontaneous self-assembly of a sequence of quantum wells with quantization axes oriented along the [110] direction. With respect to a homogeneous alloy of similar average composition, the band gap reduction observed is as large as 360 meV. A polarization anisotropy exceeding 90% is observed for the lowest energy transition and a large valence band splitting of 139 meV separates the heavy- and light-hole-like valence bands.

Complete quantum control of exciton qubits bound to isoelectronic centres

In recent years, impressive demonstrations related to quantum information processing have been realized. The scalability of quantum interactions between arbitrary qubits within an array remains however a significant hurdle to the practical realization of a quantum computer. Among the proposed ideas to achieve fully scalable quantum processing, the use of photons is appealing because they can mediate long-range quantum interactions and could serve as buses to build quantum networks. Quantum dots or nitrogen-vacancy centres in diamond can be coupled to light, but the former system lacks optical homogeneity while the latter suffers from a low dipole moment, rendering their large-scale interconnection challenging. Here, through the complete quantum control of exciton qubits, we demonstrate that nitrogen isoelectronic centres in GaAs combine both the uniformity and predictability of atomic defects and the dipole moment of semiconductor quantum dots. This establishes isoelectronic centres as a promising platform for quantum information processing.

Optical properties of spontaneous lateral composition modulation in AlAs/InAs short-period superlattices

The effect of lateral composition modulation, spontaneously generated during the epitaxial growth of a AlAs/InAs short-period superlattice, on the electronic band structure is investigated using photo-transmission and photoluminescence spectroscopy. Compared with uniform layers of similar average composition, the presence of the composition modulation considerably reduces the band gap energy and produces strongly polarized emission and absorption spectra. The authors demonstrate that the dominant polarization can selectively be aligned along the [{bar 1}10] or [010] crystallographic directions. In compressively strained samples, the use of (001) InP substrates slightly miscut toward [111]A or [101] resulted in modulation directions along [110] or [100], respectively, and dominant polarizations along a direction orthogonal to the respective composition modulation. Band gap reduction as high as 350 meV and 310 meV are obtained for samples with composition modulation along [110] and [100], respectively. Polarization ratios up to 26 are observed in transmission spectra.