Optical signature of symmetry variations and spin-valley coupling in atomically thin tungsten dichalcogenides

Motivated by the triumph and limitation of graphene for electronic applications, atomically thin layers of group VI transition metal dichalcogenides are attracting extensive interest as a class of graphene-like semiconductors with a desired band-gap in the visible frequency range. The monolayers feature a valence band spin splitting with opposite sign in the two valleys located at corners of 1st Brillouin zone. This spin-valley coupling, particularly pronounced in tungsten dichalcogenides, can benefit potential spintronics and valleytronics with the important consequences of spin-valley interplay and the suppression of spin and valley relaxations. Here we report the first optical studies of WS2 and WSe2 monolayers and multilayers. The efficiency of second harmonic generation shows a dramatic even-odd oscillation with the number of layers, consistent with the presence (absence) of inversion symmetry in even-layer (odd-layer). Photoluminescence (PL) measurements show the crossover from an indirect band gap semiconductor at mutilayers to a direct-gap one at monolayers. The PL spectra and first-principle calculations consistently reveal a spin-valley coupling of 0.4 eV which suppresses interlayer hopping and manifests as a thickness independent splitting pattern at valence band edge near K points. This giant spin-valley coupling, together with the valley dependent physical properties, may lead to rich possibilities for manipulating spin and valley degrees of freedom in these atomically thin 2D materials

Valence band structure of polytypic zinc-blende/wurtzite GaAs nanowires probed by polarization-dependent photoluminescence

We conducted temperature-dependent measurements of the photoluminescence (PL) polarization on GaAs nanowires (NWs) with polytypic zinc-blende/wurtzite structure in order to probe the symmetry and energy structure of the valence band in the wurtzite segments of the NWs. The low-temperature measurements revealed that in most of the investigated cases, the ground level of the interface excitons responsible for the PL is formed by the heavy hole. To describe the observed temperature dependence of the degree of PL polarization, we developed a theoretical model that allows an estimation of the splitting between the heavy hole and light hole exciton subbands in these NWs. This splitting is smaller than expected in pure wurtzite on the basis of recent first-principles calculations, which may be attributed to the multiple twinned nature of the wurtzite sections, which effectively behave as a polytype of lower hexagonality

Temperature induced crossing in the optical bandgap of mono and bilayer MoS2 on SiO2

Photoluminescence measurements in mono- and bilayer-MoS2 on SiO2 were undertaken to determine the thermal effect of the MoS2/SiO2 interface on the optical bandgap. The energy and intensity of the photoluminescence from monolayer MoS2 were lower and weaker than those from bilayer MoS2 at low temperatures, whilst the opposite was true at high temperatures above 200 K. Density functional theory calculations suggest that the observed optical bandgap crossover is caused by a weaker substrate coupling to the bilayer than to the monolayer

Phonon-driven spin-Floquet magneto-valleytronics in MoS2

Two-dimensional materials equipped with strong spin-orbit coupling can display novel electronic, spintronic, and topological properties originating from the breaking of time or inversion symmetry. A lot of interest has focused on the valley degrees of freedom that can be used to encode binary information. By performing ab initio time-dependent density functional simulation on MoS2, here we show that the spin is not only locked to the valley momenta but strongly coupled to the optical E '' phonon that lifts the lattice mirror symmetry. Once the phonon is pumped so as to break time-reversal symmetry, the resulting Floquet spectra of the phonon-dressed spins carry a net out-of-plane magnetization (approximate to 0.024 mu(B) for single-phonon quantum) even though the original system is non-magnetic. This dichroic magnetic response of the valley states is general for all 2H semiconducting transition-metal dichalcogenides and can be probed and controlled by infrared coherent laser excitation

Bright excitons in monolayer transition metal dichalcogenides: from Dirac cones to Dirac saddle points

In monolayer transition metal dichalcogenides, tightly bound excitons have been discovered with a valley pseudospin that can be optically addressed through polarization selection rules. Here, we show that this valley pseudospin is strongly coupled to the exciton center-of-mass motion through electron-hole exchange. This coupling realizes a massless Dirac cone with chirality index I=2 for excitons inside the light cone, i.e. bright excitons. Under moderate strain, the I=2 Dirac cone splits into two degenerate I=1 Dirac cones, and saddle points with a linear Dirac spectrum emerge in the bright exciton dispersion. Interestingly, after binding an extra electron, the charged exciton becomes a massive Dirac particle associated with a large valley Hall effect protected from intervalley scattering. Our results point to unique opportunities to study Dirac physics, with exciton's optical addressability at specifiable momentum, energy and pseudospin. The strain-tunable valley-orbit coupling also implies new structures of exciton condensates, new functionalities of excitonic circuits, and possibilities for mechanical control of valley pseudospin

Electrical Tuning of Valley Magnetic Moment via Symmetry Control

Crystal symmetry governs the nature of electronic Bloch states. For example, in the presence of time reversal symmetry, the orbital magnetic moment and Berry curvature of the Bloch states must vanish unless inversion symmetry is broken. In certain 2D electron systems such as bilayer graphene, the intrinsic inversion symmetry can be broken simply by applying a perpendicular electric field. In principle, this offers the remarkable possibility of switching on/off and continuously tuning the magnetic moment and Berry curvature near the Dirac valleys by reversible electrical control. Here we demonstrate this principle for the first time using bilayer MoS2, which has the same symmetry as bilayer graphene but has a bandgap in the visible that allows direct optical probing of these Berry-phase related properties. We show that the optical circular dichroism, which reflects the orbital magnetic moment in the valleys, can be continuously tuned from -15% to 15% as a function of gate voltage in bilayer MoS2 field-effect transistors. In contrast, the dichroism is gate-independent in monolayer MoS2, which is structurally non-centrosymmetric. Our work demonstrates the ability to continuously vary orbital magnetic moments between positive and negative values via symmetry control. This represents a new approach to manipulating Berry-phase effects for applications in quantum electronics associated with 2D electronic materials.Comment: 13 pages main text + 4 pages supplementary material

Vacancy and Doping States in Monolayer and bulk Black Phosphorus.

The atomic geometries and transition levels of point defects and substitutional dopants in few-layer and bulk black phosphorus are calculated. The vacancy is found to reconstruct in monolayer P to leave a single dangling bond, giving a negative U defect with a +/- transition level at 0.24 eV above the valence band edge. The V(-) state forms an unusual 4-fold coordinated site. In few-layer and bulk black P, the defect becomes a positive U site. The divacancy is much more stable than the monovacancy, and it reconstructs to give no deep gap states. Substitutional dopants such as C, Si, O or S do not give rise to shallow donor or acceptor states but instead reconstruct to form non-doping sites analogous to DX or AX centers in GaAs. Impurities on black P adopt the 8-N rule of bonding, as in amorphous semiconductors, rather than simple substitutional geometries seen in tetrahedral semiconductors

Intervalley scattering by acoustic phonons in two-dimensional MoS2 revealed by double-resonance Raman spectroscopy

Double-resonance Raman scattering is a sensitive probe to study the electron-phonon scattering pathways in crystals. For semiconducting two-dimensional transition-metal dichalcogenides, the double-resonance Raman process involves different valleys and phonons in the Brillouin zone, and it has not yet been fully understood. Here we present a multiple energy excitation Raman study in conjunction with density functional theory calculations that unveil the double-resonance Raman scattering process in monolayer and bulk MoS2. Results show that the frequency of some Raman features shifts when changing the excitation energy, and first-principle simulations confirm that such bands arise from distinct acoustic phonons, connecting different valley states. The double-resonance Raman process is affected by the indirect-to-direct bandgap transition, and a comparison of results in monolayer and bulk allows the assignment of each Raman feature near the M or K points of the Brillouin zone. Our work highlights the underlying physics of intervalley scattering of electrons by acoustic phonons, which is essential for valley depolarization in MoS2

Directed emission of CdSe nanoplatelets originating from strongly anisotropic 2D electronic structure

ntrinsically directional light emitters are potentially important for applications in photonics including lasing and energy-efficient display technology. Here, we propose a new route to overcome intrinsic efficiency limitations in light-emitting devices by studying a CdSe nanoplatelets monolayer that exhibits strongly anisotropic, directed photoluminescence. Analysis of the two-dimensional k-space distribution reveals the underlying internal transition dipole distribution. The observed directed emission is related to the anisotropy of the electronic Bloch states governing the exciton transition dipole moment and forming a bright plane. The strongly directed emission perpendicular to the platelet is further enhanced by the optical local density of states and local fields. In contrast to the emission directionality, the off-resonant absorption into the energetically higher 2D-continuum of states is isotropic. These contrasting optical properties make the oriented CdSe nanoplatelets, or superstructures of parallel-oriented platelets, an interesting and potentially useful class of semiconductor-based emitters