Liquid Phase Isolation of SnS Monolayers with Enhanced Optoelectronic Properties.

Recent advances in atomically thin two dimensional (2D) anisotropic group IVA -VI metal monochalcogenides (MMCs) and their fascinating intrinsic properties and potential applications are hampered due to an ongoing challenge of monolayer isolation. Among the most promising MMCs, tin (II) sulfide (SnS) is an earth-abundant layered material with tunable bandgap and anisotropic physical properties, which render it extraordinary for electronics and optoelectronics. To date, however, the successful isolation of atomically thin SnS single layers at large quantities has been challenging due to the presence of strong interlayer interactions, attributed to the lone-pair electrons of sulfur. Here, a novel liquid phase exfoliation approach is reported, which enables the overcome of such strong interlayer binding energy. Specifically, it demonstrates that the synergistic action of external thermal energy with the ultrasound energy-induced hydrodynamic force in solution gives rise to the systematic isolation of highly crystalline SnS monolayers (1L-SnS). It is shown that the exfoliated 1L-SnS crystals exhibit high carrier mobility and deep-UV spectral photodetection, featuring a fast carrier response time of 400 ms. At the same time, monolayer-based SnS transistor devices fabricated from solution present a high on/off ratio, complemented with a responsivity of 6.7 × 10-3 A W-1 and remarkable stability upon prolonged operation in ambient conditions. This study opens a new avenue for large-scale isolation of highly crystalline SnS and other MMC manolayers for a wide range of applications, including extended area nanoelectronic devices, printed from solution.

Optical polarization of excitons and trions under continuous and pulsed excitation in single layers of WSe2.

The potential for valleytronic operation has stimulated much interest in studying polarized emission from transition metal dichalcogenides. In most studies, however, little regard is given to the character of laser excitation. We measure the circularly polarized photoluminescence of WSe2 monolayers as a function of excitation energy for both continuous-wave (cw) and pulsed laser excitation sources. Using cw excitation, the temperature dependence of the depolarization of the trion follows the same trend as that of the neutral exciton and involves collisional broadening. However, the polarization of the trion is nearly twice the polarization of the neutral exciton at low temperatures. When a pulsed laser with the same average fluence is used as the excitation source, the degrees of polarization become very similar, in stark contrast to the cw results. The difference in polarization behaviors is linked to the different amounts of energy deposited in the system during these measurements for similar average fluences. At a moderate fluence, pulsed excitation also has the potential to fundamentally alter the emission characteristics of WSe2.

Spatial non-uniformity in exfoliated WS2 single layers.

Monolayers of transition metal dichalcogenides (TMDs) are atomically thin two-dimensional crystals with attractive optoelectronic properties, which are promising for emerging applications in nanophotonics. Here, we report on the extraordinary spatial non-uniformity of the photoluminescence (PL) and strain properties of exfoliated WS2 monolayers. Specifically, it is shown that the edges of such monolayers exhibit remarkably enhanced PL intensity compared to their respective central area. A comprehensive analysis of the recombination channels involved in the PL process demonstrates a spatial non-uniformity across the monolayer's surface and reflects on the non-uniformity of the intrinsic electron density across the monolayer. Auger electron imaging and spectroscopy studies complemented with PL measurements in different environments indicate that oxygen chemisorption and physisorption are the two fundamental mechanisms responsible for the observed non-uniformity. At the same time Raman spectroscopy analysis shows remarkable strain variations among the different locations of an individual monolayer, however such variations cannot be strictly correlated with the non-uniform PL emission. Our results shed light on the role of the chemical bonding in the competition between exciton complexes in monolayer WS2, providing a method of engineering new nanophotonic functions using WS2 monolayers. It is therefore envisaged that our findings could find diverse applications towards the development of TMD-based optoelectronic devices.

Optical polarization and intervalley scattering in single layers of MoS2 and MoSe2.

Single layers of MoS2 and MoSe2 were optically pumped with circularly polarized light and an appreciable polarization was initialized as the pump energy was varied. The circular polarization of the emitted photoluminescence was monitored as a function of the difference between the excitation energy and the A-exciton emission at the K-point of the Brillouin zone. Our results show a threshold of twice the LA phonon energy, specific to the material, above which phonon-assisted intervalley scattering causes depolarization. In both materials this leads to almost complete depolarization within ~100 meV above the threshold energy. We identify the extra kinetic energy of the exciton (independent of whether it is neutral or charged) as the key parameter for presenting a unifying picture of the depolarization process.

Anomalous temperature-dependent spin-valley polarization in monolayer WS2.

Single layers of transition metal dichalcogenides (TMDs) are direct gap semiconductors with nondegenerate valley indices. An intriguing possibility for these materials is the use of their valley index as an alternate state variable. Several limitations to such a utility include strong intervalley scattering, as well as multiparticle interactions leading to multiple emission channels. We prepare single-layer WS2 films such that the photoluminescence is from either the neutral or charged exciton (trion). After excitation with circularly polarized light, the neutral exciton emission has zero polarization. However, the trion emission has a large polarization (28%) at room temperature. The trion emission also has a unique, non-monotonic temperature dependence that is a consequence of the multiparticle nature of the trion. This temperature dependence enables us to determine that intervalley scattering, electron-hole radiative recombination, and Auger processes are the dominant mechanisms at work in this system. Because this dependence involves trion systems, one can use gate voltages to modulate the polarization (or intensity) emitted from TMD structures.

Magnetoluminescence and valley polarized state of a two-dimensional electron gas in WS2 monolayers.

Materials often exhibit fundamentally new phenomena in reduced dimensions that potentially lead to novel applications. This is true for single-layer, two-dimensional semiconductor crystals of transition-metal dichalcogenides, MX2 (M = Mo, W and X = S, Se). They exhibit direct bandgaps with energies in the visible region at the two non-equivalent valleys in the Brillouin zone. This makes them suitable for optoelectronic applications that range from light-emitting diodes to light harvesting and light sensors, and to valleytronics. Here, we report the results of a magnetoluminescence study of WS2 single-layer crystals in which the strong spin-orbit interaction additionally locks the valley and spin degrees of freedom. The recombination of the negatively charged exciton in the presence of a two-dimensional electron gas (2DEG) is found to be circularly polarized at zero magnetic field despite being excited with unpolarized light, which indicates that the existence of a valley polarized 2DEG is caused by valley and spin locking and strong electron-electron interactions.

Insights into theory of mind in schizophrenia: the impact of cognitive impairment.

The ability to mentalize and attribute beliefs, intentions and desires to others has been found by the vast majority of studies to be impaired in patients with schizophrenia. However, it is not yet clear if this deficit in Theory of Mind (ToM) is independent of their also well established deficits in basic cognitive functioning. In the present study, we sought to clarify the above relationship by exploring patients' ToM impairment after controlling for their putative cognitive deficits. We examined 36 patients with schizophrenia and 30 healthy matched controls on first and second order tasks of ToM and on commonly used neuropsychological tests. Patients performed poorly on ToM tasks even after controlling for their cognitive deficits, particularly on second order ToM. The present findings contribute to the understanding of the mechanism of ToM, suggesting that ToM deficits are core characteristics in schizophrenia and relatively independent of patients' cognitive impairment.

Intershell exchange and sequential electrically injected spin populations of InAs quantum-dot shell states.

We report sequential spin population of individual shell states of self-assembled InAs quantum dots controlled by a spin-polarized current from an Fe contact, and determine the s-p and p-d intershell exchange energies. We resolve excitonic features in the electroluminescence (EL) spectra associated with individual quantum levels. In contrast with simple models of shell occupation, the EL circular polarization exhibits maxima shifted with respect to the intensity peaks. Calculations show that this is due to intershell exchange. Exchange energies for the s-p and p-d shells are 7+/-2 and 13.5+/-1 meV, respectively.

Interface magnetization reversal and anisotropy in Fe/AlGaAs(001).

The reversal process of the Fe interface layer magnetization in Fe/AlGaAs heterostructures is measured directly using magnetization-induced second-harmonic generation, and is compared with the reversal of the bulk magnetization as obtained from magneto-optic Kerr effect. The switching characteristics are distinctly different due to interface-derived anisotropy--single step switching occurs at the interface layer, while two-jump switching occurs in the bulk Fe for the magnetic field orientations employed. The angle between the interface and bulk magnetization may be as large as 40-85 degrees. Such interface switching will dominate the behavior of nanoscale structures.

Reduction of spin injection efficiency by interface defect spin scattering in ZnMnSe/AlGaAs-GaAs spin-polarized light-emitting diodes.

We report the first experimental demonstration that interface microstructure limits diffusive electrical spin-injection efficiency across heteroepitaxial interfaces. An inverse correlation be-tween spin-polarized electron injection efficiency and interface defect density is demonstrated for ZnMnSe/AlGaAs-GaAs spin-polarized light-emitting diodes that exhibit quantum well spin polarizations up to 85%. A theoretical treatment shows that the suppression of spin injection due to interface defects results from the contribution of the defect potential to the spin-orbit interaction, which increases the spin-flip scattering.

Studies of impurities in magnetic semiconductors: an example of important XAFS applications.

The x-ray absorption fine structure (XAFS) technique has been employed to investigate the local structure and valency about Mn and Fe ions in the III-V diluted magnetic semiconductors In(1-x)Mn(x)As and Ga(1-x)Fe(x)As, prepared by molecular-beam-epitaxy under various growth conditions. These new systems are promising magnetic materials of considerable current interest and with important technical applications including photo-carrier induced magnetism and spin-polarized current devices. The local structure around the magnetic ions can play a pivotal role in affecting the magnetic properties of these semiconductors. Local structure information obtained from XAFS has provided the first direct evidence that the magnetic impurities can indeed substitute for the cation host atoms in samples prepared under appropriate conditions.