Long-lived photoluminescence polarization of localized excitons in liquid exfoliated monolayer enriched WS2.

Monolayer transition metal dichalcogenides (TMDs) constitute a family of materials, in which coupled spin-valley physics can be explored and which could find applications in novel optoelectronic devices. However, before applications can be designed, a scalable method of monolayer extraction is required. Liquid phase exfoliation is a technique providing large quantities of the monolayer material, but the spin-valley properties of thus obtained TMDs are unknown. In this work, we employ steady-state and time-resolved photoluminescence (PL) to investigate the relaxation dynamics of localized excitons (LXs) in liquid exfoliated WS2. The results reveal that the circular polarization lifetime of the PL exceeds by at least an order of magnitude the PL lifetime. A rate equations model allows us to reproduce quantitatively the experimental data and to conclude that the observed large and long-lived PL polarization originates from efficient trapping of free excitons at localization sites hindering the intervalley relaxation. Furthermore, our results show that the depolarization process is inefficient for LXs. We discuss various mechanisms leading to this effect such as suppression of intervalley scattering of the LXs or inefficient spin relaxation of the holes.

Probing the Interlayer Exciton Physics in a MoS2/MoSe2/MoS2 van der Waals Heterostructure.

Stacking atomic monolayers of semiconducting transition metal dichalcogenides (TMDs) has emerged as an effective way to engineer their properties. In principle, the staggered band alignment of TMD heterostructures should result in the formation of interlayer excitons with long lifetimes and robust valley polarization. However, these features have been observed simultaneously only in MoSe2/WSe2 heterostructures. Here we report on the observation of long-lived interlayer exciton emission in a MoS2/MoSe2/MoS2 trilayer van der Waals heterostructure. The interlayer nature of the observed transition is confirmed by photoluminescence spectroscopy, as well as by analyzing the temporal, excitation power, and temperature dependence of the interlayer emission peak. The observed complex photoluminescence dynamics suggests the presence of quasi-degenerate momentum-direct and momentum-indirect bandgaps. We show that circularly polarized optical pumping results in long-lived valley polarization of interlayer exciton. Intriguingly, the interlayer exciton photoluminescence has helicity opposite to the excitation. Our results show that through a careful choice of the TMDs forming the van der Waals heterostructure it is possible to control the circular polarization of the interlayer exciton emission.

Revealing Large-Scale Homogeneity and Trace Impurity Sensitivity of GaAs Nanoscale Membranes.

III-V nanostructures have the potential to revolutionize optoelectronics and energy harvesting. For this to become a reality, critical issues such as reproducibility and sensitivity to defects should be resolved. By discussing the optical properties of molecular beam epitaxy (MBE) grown GaAs nanomembranes we highlight several features that bring them closer to large scale applications. Uncapped membranes exhibit a very high optical quality, expressed by extremely narrow neutral exciton emission, allowing the resolution of the more complex excitonic structure for the first time. Capping of the membranes with an AlGaAs shell results in a strong increase of emission intensity but also in a shift and broadening of the exciton peak. This is attributed to the existence of impurities in the shell, beyond MBE-grade quality, showing the high sensitivity of these structures to the presence of impurities. Finally, emission properties are identical at the submicron and submillimeter scale, demonstrating the potential of these structures for large scale applications.

Disorder-Induced Stabilization of the Quantum Hall Ferromagnet.

We report on an absolute measurement of the electronic spin polarization of the ν=1 integer quantum Hall state. The spin polarization is extracted in the vicinity of ν=1 (including at exactly ν=1) via resistive NMR experiments performed at different magnetic fields (electron densities) and Zeeman energy configurations. At the lowest magnetic fields, the polarization is found to be complete in a narrow region around ν=1. Increasing the magnetic field (electron density) induces a significant depolarization of the system, which we attribute to a transition between the quantum Hall ferromagnet and the Skyrmion glass phase theoretically expected as the ratio between Coulomb interactions and disorder is increased. These observations account for the fragility of the polarization previously observed in high mobility 2D electron gas and experimentally demonstrate the existence of an optimal amount of disorder to stabilize the ferromagnetic state.

Revealing the nature of excitons in liquid exfoliated monolayer tungsten disulphide.

Transition metal dichalcogenides (TMD) hold promise for applications in novel optoelectronic devices. There is therefore a need for materials that can be obtained in large quantities and with well understood optical properties. In this report, we present thorough photoluminescence (PL) investigations of monolayer tungsten disulphide obtained via liquid phase exfoliation. As shown by microscopy studies, the exfoliated nanosheets have dimensions of tens of nanometers and thickness of 2.5 monolayers on average. The monolayer content is about 20%. Our studies show that at low temperature the PL is dominated by excitons localized on nanosheet edges. As a consequence, the PL is strongly sensitive to the environment and exhibits an enhanced splitting in magnetic field. As the temperature is increased, the excitons are thermally excited out of the defect states and the dominant transition is that of the negatively charged exciton. Furthermore, upon excitation with a circularly polarized light, the PL retains a degree of polarization reaching 50% and inherited from the valley polarized photoexcited excitons. The studies of PL dynamics reveal that the PL lifetime is on the order of 10 ps, which is probably limited by non-radiative processes. Our results underline the potential of liquid exfoliated TMD monolayers in large scale optoelectronic devices.

Optical Investigation of Monolayer and Bulk Tungsten Diselenide (WSe2) in High Magnetic Fields.

Optical spectroscopy in high magnetic fields B ≤ 65 T is used to reveal the very different nature of carriers in monolayer and bulk transition metal dichalcogenides. In monolayer WSe2, the exciton emission shifts linearly with the magnetic field and exhibits a splitting that originates from the magnetic field induced valley splitting. The monolayer data can be described using a single particle picture with a Dirac-like Hamiltonian for massive Dirac Fermions, with an additional term to phenomenologically include the valley splitting. In contrast, in bulk WSe2 where the inversion symmetry is restored, transmission measurements show a distinctly excitonic behavior with absorption to the 1s and 2s states. Magnetic field induces a spin splitting together with a small diamagnetic shift and cyclotron like behavior at high fields, which is best described within the hydrogen model.

Unintentional high-density p-type modulation doping of a GaAs/AlAs core-multishell nanowire.

Achieving significant doping in GaAs/AlAs core/shell nanowires (NWs) is of considerable technological importance but remains a challenge due to the amphoteric behavior of the dopant atoms. Here we show that placing a narrow GaAs quantum well in the AlAs shell effectively getters residual carbon acceptors leading to an unintentional p-type doping. Magneto-optical studies of such a GaAs/AlAs core-multishell NW reveal quantum confined emission. Theoretical calculations of NW electronic structure confirm quantum confinement of carriers at the core/shell interface due to the presence of ionized carbon acceptors in the 1 nm GaAs layer in the shell. Microphotoluminescence in high magnetic field shows a clear signature of avoided crossings of the n = 0 Landau level emission line with the n = 2 Landau level TO phonon replica. The coupling is caused by the resonant hole-phonon interaction, which points to a large two-dimensional hole density in the structure.

High magnetic field reveals the nature of excitons in a single GaAs/AlAs core/shell nanowire.

Magneto-photoluminescence measurements of individual zinc-blende GaAs/AlAs core/shell nanowires are reported. At low temperature, a strong emission line at 1.507 eV is observed under low power (nW) excitation. Measurements performed in high magnetic field allowed us to detect in this emission several lines associated with excitons bound to defect pairs. Such lines were observed before in epitaxial GaAs of very high quality, as reported by Kunzel and Ploog. This demonstrates that the optical quality of our GaAs/AlAs core/shell nanowires is comparable to the best GaAs layers grown by molecular beam epitaxy. Moreover, strong free exciton emission is observed even at room temperature. The bright optical emission of our nanowires in room temperature should open the way for numerous optoelectronic device applications.

Phase space for the breakdown of the quantum Hall effect in epitaxial graphene.

We report the phase space defined by the quantum Hall effect breakdown in polymer gated epitaxial graphene on SiC (SiC/G) as a function of temperature, current, carrier density, and magnetic fields up to 30 T. At 2 K, breakdown currents (I(c)) almost 2 orders of magnitude greater than in GaAs devices are observed. The phase boundary of the dissipationless state (ρ(xx)=0) shows a [1-(T/T(c))2] dependence and persists up to T(c)>45 K at 29 T. With magnetic field I(c) was found to increase ∝B(3/2) and T(c)∝B2. As the Fermi energy pproaches the Dirac point, the ν=2 quantized Hall plateau appears continuously from fields as low as 1 T up to at least 19 T due to a strong magnetic field dependence of the carrier density.

Using the de Haas-van Alphen effect to map out the closed three-dimensional Fermi surface of natural graphite.

The Fermi surface of graphite has been mapped out using de Haas-van Alphen (dHvA) measurements at low temperature with in-situ rotation. For tilt angles θ>60° between the magnetic field and the c axis, the majority electron and hole dHvA periods no longer follow a cos(θ) behavior demonstrating that graphite has a three-dimensional closed Fermi surface. The Fermi surface of graphite is accurately described by highly elongated ellipsoids. A comparison with the calculated Fermi surface suggests that the Slonczewski-Weiss-McClure trigonal warping parameter γ(3) is significantly larger than previously thought.

NMR probing of the spin polarization of the ν=5/2 quantum Hall state.

Resistively detected nuclear magnetic resonance is used to measure the Knight shift of the 75As nuclei and determine the electron spin polarization of the fractional quantum Hall states of the second Landau level. We show that the 5/2 state is fully polarized within experimental error, thus confirming a fundamental assumption of the Moore-Read theory. We measure the electron heating under radio frequency excitation and show that we are able to detect NMR at electron temperatures down to 30 mK.

Interlayer excitons in MoSe2/2D perovskite hybrid heterostructures - the interplay between charge and energy transfer.

van der Waals crystals have opened a new and exciting chapter in heterostructure research, removing the lattice matching constraint characteristics of epitaxial semiconductors. They provide unprecedented flexibility for heterostructure design. Combining two-dimensional (2D) perovskites with other 2D materials, in particular transition metal dichalcogenides (TMDs), has recently emerged as an intriguing way to design hybrid opto-electronic devices. However, the excitation transfer mechanism between the layers (charge or energy transfer) remains to be elucidated. Here, we investigate PEA2PbI4/MoSe2 and (BA)2PbI4/MoSe2 heterostructures by combining optical spectroscopy and density functional theory (DFT) calculations. We show that band alignment facilitates charge transfer. Namely, holes are transferred from TMDs to 2D perovskites, while the electron transfer is blocked, resulting in the formation of interlayer excitons. Moreover, we show that the energy transfer mechanism can be turned on by an appropriate alignment of the excitonic states, providing a rule of thumb for the deterministic control of the excitation transfer mechanism in TMD/2D-perovskite heterostructures.

Optical probing of the spin polarization of the ν=5/2 quantum Hall state.

We apply polarization resolved photoluminescence spectroscopy to measure the spin polarization of a two dimensional electron gas in perpendicular magnetic field. We find that the splitting between the σ+ and σ- polarizations exhibits a sharp drop at ν=5/2 and is equal to the bare Zeeman energy, which resembles the behavior at even filling factors. We show that this behavior is consistent with filling factor ν=5/2 being unpolarized.

Manipulating and imaging the shape of an electronic wave function by magnetotunneling spectroscopy.

We measure the current due to electrons tunneling through the ground state of hydrogenic Si donors placed in a GaAs quantum well in the presence of a magnetic field tilted at an angle to the plane of the well. The component of B parallel to the direction of current compresses the donor wave function. By measuring the current as a function of the perpendicular component of B, we probe how the magnetocompression affects the spatial form of the wave function and observe directly the transition from Coulombic to magnetic confinement at high fields.

Observation of A Raman mode splitting in few layer black phosphorus encapsulated with hexagonal boron nitride.

We investigate the impact of encapsulation with hexagonal boron nitride (h-BN) on the Raman spectrum of few layer black phosphorus. The encapsulation results in a significant reduction of the line width of the Raman modes of black phosphorus, due to a reduced phonon scattering rate. We observe a so far elusive peak in the Raman spectra ∼4 cm-1 above the A mode in trilayer and thicker flakes, which had not been observed experimentally. The newly observed mode originates from the strong black phosphorus inter-layer interaction, which induces a hardening of the surface atom vibration with respect to the corresponding modes of the inner layers. The observation of this mode suggests a significant impact of h-BN encapsulation on the properties of black phosphorus and can serve as an indicator of the quality of its surface.

Spatially resolved studies of the phases and morphology of methylammonium and formamidinium lead tri-halide perovskites.

The family of organic-inorganic tri-halide perovskites including MA (MethylAmmonium)PbI3, MAPbI3-xClx, FA (FormAmidinium)PbI3 and FAPbBr3 are having a tremendous impact on the field of photovoltaic cells due to the combination of their ease of deposition and high energy conversion efficiencies. Device performance, however, is known to be still significantly affected by the presence of inhomogeneities. Here we report on a study of temperature dependent micro-photoluminescence which shows a strong spatial inhomogeneity related to the presence of microcrystalline grains, which can be both bright and dark. In all of the tri-iodide based materials there is evidence that the tetragonal to orthorhombic phase transition observed around 160 K does not occur uniformly across the sample with domain formation related to the underlying microcrystallite grains, some of which remain in the high temperature, tetragonal, phase even at very low temperatures. At low temperature the tetragonal domains can be significantly influenced by local defects in the layers or the introduction of residual levels of chlorine in mixed halide layers or dopant atoms such as aluminium. We see that improvements in room temperature energy conversion efficiency appear to be directly related to reductions in the proportions of the layer which remain in the tetragonal phase at low temperature. In FAPbBr3 a more macroscopic domain structure is observed with large numbers of grains forming phase correlated regions.

Giant quantum Hall plateaus generated by charge transfer in epitaxial graphene.

Epitaxial graphene has proven itself to be the best candidate for quantum electrical resistance standards due to its wide quantum Hall plateaus with exceptionally high breakdown currents. However one key underlying mechanism, a magnetic field dependent charge transfer process, is yet to be fully understood. Here we report measurements of the quantum Hall effect in epitaxial graphene showing the widest quantum Hall plateau observed to date extending over 50 T, attributed to an almost linear increase in carrier density with magnetic field. This behaviour is strong evidence for field dependent charge transfer from charge reservoirs with exceptionally high densities of states in close proximity to the graphene. Using a realistic framework of broadened Landau levels we model the densities of donor states and predict the field dependence of charge transfer in excellent agreement with experimental results, thus providing a guide towards engineering epitaxial graphene for applications such as quantum metrology.

W line shape in the resistively detected nuclear magnetic resonance.

The resistively detected nuclear magnetic resonance (RDNMR) performed on a two-dimensional electron gas is known to exhibit a peculiar 'dispersive' line shape at some filling factors, especially around ν = 1. Here, we study in detail the inversion of the dispersive line shape as a function of the filling factor from ν = 1 to 2/3. The RDNMR spectra show a new characteristic W line shape in the longitudinal resistance, whereas dispersive lines detected in the Hall resistance remain unchanged. This W resonance, like the dispersive line, can be fitted correctly by a model of two independent response functions, which are the signatures of polarized and unpolarized electronic sub-systems.

Consistent interpretation of the low-temperature magnetotransport in graphite using the Slonczewski-Weiss-McClure 3D band-structure calculations.

Magnetotransport of natural graphite and highly oriented pyrolytic graphite has been measured at mK temperatures. Quantum oscillations for both electron and hole carriers are observed with an orbital angular momentum quantum number up to N approximately 90. A remarkable agreement is obtained when comparing the data and the predictions of the Slonczewski-Weiss-McClure tight binding model for massive fermions. No evidence for Dirac fermions is observed in the transport data which are dominated by the crossing of the Landau bands at the Fermi level, corresponding to dE/dk_{z}=0, which occurs away from the H point where Dirac fermions are expected.

Graphite from the viewpoint of Landau level spectroscopy: an effective graphene bilayer and monolayer.

We describe an infrared transmission study of a thin layer of bulk graphite in magnetic fields up to B=34 T. Two series of absorption lines whose energy scales as sqrt[B] and B are present in the spectra and identified as contributions of massless holes at the H point and massive electrons in the vicinity of the K point, respectively. We find that the optical response of the K point electrons corresponds, over a wide range of energy and magnetic field, to a graphene bilayer with an effective interlayer coupling 2gamma_{1}, twice the value for a real graphene bilayer, which reflects the crystal ordering of bulk graphite along the c axis. The K point electrons thus behave as massive Dirac fermions with a mass enhanced twice in comparison to a true graphene bilayer.