Alloyed transition metal dichalcogenides provide an opportunity for coupling band engineering with valleytronic phenomena in an atomically-thin platform. However, valley properties in alloys remain largely unexplored. We investigate the valley degree of freedom in monolayer alloys of the phase change candidate material WSe$_{2(1-x)}$Te$_{2x}$. Low temperature Raman measurements track the alloy-induced transition from the semiconducting 1H phase of WSe$_2$ to the semimetallic 1T$_d$ phase of WTe$_2$. We correlate these observations with density functional theory calculations and identify new Raman modes from W-Te vibrations in the 1H alloy phase. Photoluminescence measurements show ultra-low energy emission features that highlight alloy disorder arising from the large W-Te bond lengths. Interestingly, valley polarization and coherence in alloys survive at high Te compositions and are more robust against temperature than in WSe$_2$. These findings illustrate the persistence of valley properties in alloys with highly dissimilar parent compounds and suggest band engineering can be utilized for valleytronic devices.
The Hall effect can be extended by inducing a temperature gradient in lieu of electric field that is known as the Nernst (-Ettingshausen) effect. The recently discovered spin Nernst effect in heavy metals continues to enrich the picture of Nernst effect-related phenomena. However, the collection would not be complete without mentioning the valley degree of freedom benchmarked by the observation of the valley Hall effect. Here we show the experimental evidence of its missing counterpart, the valley Nernst effect. Using millimeter-sized WSe$_{2}$ mono-multi-layers and the ferromagnetic resonance…
In this work, we investigate spin and valley transport properties of a WSe$_2$ monolayer placed on top of a ferromagnetic insulator. We are interested in controlling the transport properties by applying external potentials to the system. To obtain spin an valley polarizations, we have considered a single and a double barrier structure with gate potentials. We have analyzed how the efficiency of these polarized transport properties depend on the gate-potential intensities and geometrical configurations. Additionally, we investigate how the spin and valley transport properties are modified when …
We report on nanosecond long, gate-dependent valley lifetimes of free charge carriers in monolayer WSe$_2$, unambiguously identified by the combination of time-resolved Kerr rotation and electrical transport measurements. While the valley polarization increases when tuning the Fermi level into the conduction or valence band, there is a strong decrease of the respective valley lifetime consistent with both electron-phonon and spin-orbit scattering. The longest lifetimes are seen for spin-polarized bound excitons in the band gap region. We explain our findings via two distinct, Fermi level-depen…
Transconductance as a Probe of Valley Thermodynamics in Multilayer WSe$_2$
Research Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS)（物质·材料纳米结构研究センター（MANA），国立物質研究所（NIMS））；Department of Nanotechnology for Sustainable Energy, Kwansei Gakuin University（关西学院大学持続可能エネルギーナノテクノロジー学科）
One of the main tasks in the investigation of 2-dimensional transition metal dichalcogenides is the determination of valley lifetimes. In this work, we combine time-resolved Kerr rotation with electrical transport measurements to explore the gate-dependent valley lifetimes of free conduction band electrons of monolayer WSe$_2$. When tuning the Fermi energy into the conduction band we observe a strong decrease of the respective valley lifetimes which is consistent with both spin-orbit and electron-phonon scattering. We explain the formation of a valley polarization by the scattering of opticall…
A new degree of freedom, the valley pseudospin, emerges in atomically thin two-dimensional transition metal dichalcogenides (MX2) and has attracted great scientific interest. The capability to manipulate the valley pseudospin, in analogy to the control of spin in spintronics, can open up exciting opportunities in valleytronics. Here we demonstrate that an ultrafast and ultrahigh valley pseudomagnetic field can be generated using circularly polarized femtosecond pulses to selectively control the valley degree of freedom in monolayer MX2. Employing ultrafast pump-probe spectroscopy, we observed …
In monolayer transition-metal dichalcogenide semiconductors, many-body correlations can manifest in optical spectra when photoexcited electron-hole pairs (excitons) are introduced into a 2D Fermi sea of mobile carriers. At low carrier densities, the formation of positively and negatively charged excitons ($X^\pm$) is well documented. However, in WSe$_2$ monolayers, an additional absorption resonance, often called $X^{-\prime}$, emerges at high electron density. Its origin is not understood. Here we investigate the $X^{-\prime}$ state via polarized absorption spectroscopy of electrostatically-g…
The twist degree of freedom provides a powerful new tool for engineering the electrical and optical properties of van der Waals heterostructures. Here, we show that the twist angle can be used to control the spin-valley properties of transition metal dichalcogenide bilayers by changing the momentum alignment of the valleys in the two layers. Specifically, we observe that the interlayer excitons in twisted WSe$_2$/WSe$_2$ bilayers exhibit a high (>60%) degree of circular polarization (DOCP) and long valley lifetimes (>40 ns) at zero electric and magnetic fields. The valley lifetime can be tuned…
Using time-resolved optical Kerr rotation, we measure the low temperature valley dynamics of resident electrons and holes in exfoliated WSe$_2$ monolayers as a systematic function of carrier density. In an effort to reconcile the many disparate timescales of carrier valley dynamics in monolayer semiconductors reported to date, we directly compare the doping-dependent valley relaxation in two electrostatically-gated WSe$_2$ monolayers having different dielectric environments. In a fully-encapsulated structure (hBN/WSe$_2$/hBN, where hBN is hexagonal boron nitride), valley relaxation is found to…
The electronic states at the direct band gap of monolayer WSe2 at the $K^+$ and $K^-$ valleys are related by time reversal and may be viewed as pseudo-spins. The corresponding optical interband transitions are governed by robust excitons. In double resonant Raman spectroscopy, we uncover that the 2s exciton state energy differs from the 1s state energy by exactly the energy of the combination of several prominent phonons. Superimposed on the exciton photoluminescence (PL) we observe the double resonant Raman signal. This spectrally narrow peak shifts with the excitation laser energy as incomin…
Manipulation of spin and valley degrees of freedom is a key step towards realizing novel quantum technologies, for which atomically thin transition metal dichalcogenides (TMDCs) have been established as promising candidates. In monolayer TMDCs, the lack of inversion symmetry gives rise to a spin-valley correlation of the band structure allowing for valley-selective electronic excitation with circularly polarized light. Here we show that, even in centrosymmetric samples of 2H-WSe2, circularly polarized light can generate spin-, valley- and layer-polarized excited states in the conduction band. …
Semiconducting transition metal dichalcogenide monolayers have emerged as promising candidates for future valleytronics-based quantum information technologies. Two distinct momentum-states of tightly-bound electron-hole pairs in these materials can be deterministically initialized via irradiation with circularly polarized light. Here, we investigate the ultrafast dynamics of such a valley polarization in monolayer tungsten diselenide by means of time-resolved Kerr reflectometry. The observed Kerr signal in our sample stems exclusively from charge-neutral excitons. Our findings support the pict…
The newly developed two-dimensional layered materials provide perfect platform for valley-spintronics exploration. To determine the prospect of utilizing the valley degree of freedom, it is of great importance to directly detect and understand the valley dynamics in these materials. Here, the exciton valley dynamics in monolayer WSe$_2$ is investigated by the two-color pump-probe magneto-optical Kerr technique. By tuning the probe photon energy in resonance with the free excitons and trions, the valley relaxation time of different excitonic states in monolayer WSe$_2$ is determined. Valley rel…
The integration of magnetic material with semiconductors has been fertile ground for fundamental science as well as of great practical interest toward the seamless integration of information processing and storage. Here we create van der Waals heterostructures formed by an ultrathin ferromagnetic semiconductor CrI3 and a monolayer of WSe2. We observe unprecedented control of the spin and valley pseudospin in WSe2, where we detect a large magnetic exchange field of nearly 13 T and rapid switching of the WSe2 valley splitting and polarization via flipping of the CrI3 magnetization. The WSe2 phot…
Calculations combining first-principles electron-phonon ($e$-ph) interactions with the Boltzmann equation enable studies of ultrafast carrier and phonon dynamics. However, in materials with weak Coulomb screening, electrons and holes form bound excitons and their scattering processes become correlated, posing additional challenges for modeling nonequilibrium physics. Here we show calculations of ultrafast exciton dynamics and related time-domain spectroscopies using $ab~initio$ exciton-phonon (ex-ph) interactions together with an excitonic Boltzmann equation. Starting from the nonequilibrium e…
We investigate the chirality of phonon modes in twisted bilayer WSe2 and demonstrate distinct chiral behavior of the $K/K^\prime$ valley phonons for twist angles close to $0^{\circ}$ and close to $60^{\circ}$. In particular, multiple chiral non-degenerate $K/K^\prime$ valley phonons are found for twist angles near $60^{\circ}$ whereas no non-degenerate chiral modes are found for twist angles close to $0^\circ$. Moreover, we discover two sets of emergent chiral valley modes that originate from an inversion symmetry breaking at the moiré scale and find similar modes in moiré patterns of strain-e…
Control and manipulation of single charges and their internal degrees of freedom, such as spins, is a fundamental goal of nanoscience with promising technological applications. Recently, atomically thin semiconductors such as WSe$_2$ have emerged as a platform for valleytronics, offering rich possibilities for optical, magnetic and electrical control of the valley index. While progress has been made in controlling valley index of ensemble of charge carriers, valley control of individual charges, crucial for valleytronics, remains unexplored. Here, we provide unambiguous evidence for localized …
We investigate the twist-angle and gate dependence of the proximity-induced exchange coupling in the monolayer transition-metal dichalcogenides (TMDCs) MoSe$_2$ and WSe$_2$ due to the vdW coupling to the ferromagnetic semiconductor CrI$_3$, from first-principles calculations. A model Hamiltonian, that captures the relevant band edges at the $K/K^{\prime}$ valleys of the proximitized TMDCs, is employed to quantify the proximity-induced exchange. Upon twisting from 0° to 30°, we find a transition of the TMDC valence band (VB) edge exchange splitting from about $-2$ to $2$ meV, while the conducti…
Optical interband transitions in monolayer transition metal dichalcogenides such as WSe2 and MoS2 are governed by chiral selection rules. This allows efficient optical initialization of an electron in a specific K-valley in momentum space. Here we probe the valley dynamics in monolayer WSe2 by monitoring the emission and polarization dynamics of the well separated neutral excitons (bound electron hole pairs) and charged excitons (trions) in photoluminescence. The neutral exciton photoluminescence intensity decay time is about 4ps, whereas the trion emission occurs over several tens of ps. The …
The optical properties of monolayer and bilayer transition metal dichalcogenide semiconductors are governed by excitons in different spin and valley configurations, providing versatile aspects for van der Waals heterostructures and devices. We present experimental and theoretical studies of exciton energy splittings in external magnetic field in neutral and charged WSe$_2$ monolayer and bilayer crystals embedded in a field effect device for active doping control. We develop theoretical methods to calculate the exciton $g$-factors from first principles and tight-binding for all possible spin-va…
Monolayer transition metal dichalcogenides (TMDs) hold great promise for future information processing applications utilizing a combination of electron spin and valley pseudospin. This unique spin system has led to observation of the valley Zeeman effect in neutral and charged excitonic resonances under applied magnetic fields. However, reported values of the trion valley Zeeman splitting remain highly inconsistent across studies. Here, we utilize high quality hBN encapsulated monolayer WSe$_2$ to enable simultaneous measurement of both intervalley and intravalley trion photoluminescence. We f…
We study Shubnikov-de Haas oscillations in a p-type WSe$_2$ monolayer under very high magnetic field. The oscillation pattern is complex due to a large spin and valley splitting, in the non-fully-resolved Landau level regime. Our experimental data can be reproduced with a model in which the main parameter is the ratio between the Zeeman energy and the cyclotron energy. The model takes into account the Landau levels from both valleys with the same Gaussian broadening, which allows to predict the relative amplitude of the resistance oscillation originating from each valley. The Zeeman energy is …
Valley degree of freedom in the 2D semiconductor is a promising platform for the next generation optoelectronics. Electrons in different valleys can have opposite Berry curvature, leading to the valley Hall effect (VHE). However, VHE without the plasmonic structure's assistance has only been reported in cryogenic temperature, limiting its practical application. Here, we report the observation of VHE at room temperature in the MoS2/WSe2 heterostructures. We also uncover that both the magnitude and the polarity of the VHE in the 2D heterostructure is gate tunable. We attribute this to the opposi…
Moiré heterobilayer transition metal dichalcogenides (TMDs) emerge as an ideal system for simulating the single-band Hubbard model and interesting correlated phases have been observed in these systems. Nevertheless, the moiré bands in heterobilayer TMDs were believed to be topologically trivial. Recently, it was reported that both a quantum valley Hall insulating state at filling $ν=2$ (two holes per moiré unit cell) and a valley-polarized quantum anomalous Hall state at filling $ν=1$ were observed in AB stacked moiré MoTe$_2$/WSe$_2$ heterobilayers. However, how the topologically nontrivial s…
Monolayer transition metal dichalcogenides, known for exhibiting strong excitonic resonances, constitute a very interesting and versatile platform for investigation of light-matter interactions. In this work we report on a strong coupling regime between excitons in monolayer WSe2 and photons confined in an open, voltage-tunable dielectric microcavity. The tunability of our system allows us to extend the exciton-polariton state over a wide energy range and, in particular, to bring the excitonic component of the lower polariton mode into resonance with other excitonic transitions in monolayer WS…
Local energy extrema of the bands in momentum space, or valleys, can endow electrons in solids with pseudo-spin in addition to real spin. In transition metal dichalcogenides this valley pseudo-spin, like real spin, is associated with a magnetic moment which underlies the valley-dependent circular dichroism that allows optical generation of valley polarization, intervalley quantum coherence, and the valley Hall effect. However, magnetic manipulation of valley pseudospin via this magnetic moment, analogous to what is possible with real spin, has not been shown before. Here we report observation …
In crystals, energy band extrema in momentum space can be identified by their valley index. The internal quantum degree of freedom associated with valley pseudospin indices can act as a useful information carrier analogous to electronic charge or spin. Interest in valleytronics has been revived in recent years following the discovery of atomically thin materials such as graphene and transition metal dichalcogenides. However, the valley coherence time, a key quantity for manipulating the valley pseudospin, has never been measured in any material. In this work, we use a sequence of laser pulses …
We investigate the steady-state out-of-plane spin diffusion in p-type bilayer WSe2 in the presence of the Rashba spin-orbit coupling and Hartree-Fock effective magnetic field. The out-of-plane components of the Rashba spin-orbit coupling serve as the opposite Zeeman-like fields in the two valleys. Together with the identical Hartree-Fock effective magnetic fields, different total effective magnetic field strengths in the two valleys are obtained. It is further revealed that due to the valley-dependent total effective magnetic field strength, similar (different) spin-diffusion lengths in the tw…
Excitons and trions (or exciton-polarons) in transition metal dichalcogenides (TMDs) are known to decay predominantly through intravalley transitions. Electron-hole recombination across different valleys can also play a significant role in the excitonic dynamics, but intervalley transitions are rarely observed in monolayer TMDs, because they violate the conservation of momentum. Here we reveal the intervalley recombination of dark excitons and trions through more than one path in monolayer WSe$_2$. We observe the intervalley dark excitons, which can recombine by the assistance of defect scatte…
Monolayer valley semiconductors, such as tungsten diselenide (WSe$_2$), possess valley pseudospin degrees of freedom that are optically addressable but degenerate in energy. Lifting the energy degeneracy by breaking time-reversal symmetry is vital for valley manipulation. This has been realized by directly applying magnetic fields or via pseudo-magnetic fields generated by intense circularly polarized optical pulses. However, sweeping large magnetic fields is impractical for devices, and the pseudo-magnetic fields are only effective in the presence of ultrafast laser pulses. The recent rise of…
Proximity orbital and spin-orbit effects of bilayer graphene on monolayer WSe$_2$ are investigated from first-principles. We find that the built-in electric field induces an orbital band gap of about 10 meV in bilayer graphene. Remarkably, the proximity spin-orbit splitting for holes is two orders of magnitude---the spin-orbit splitting of the valence band at K is about 2 meV---more than for electrons. Effectively, holes experience spin-valley locking due to the strong proximity of the lower graphene layer to WSe$_2$. However, applying an external transverse electric field of some 1 V/nm, coun…
Valley-Landscape Engineering in Bilayer WSe$_2$ Gate-All-Around Transistors
Research Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS)（物质·材料纳米构筑研究中心，日本国立材料研究所）；Kwansei Gakuin University（关西学院大学）
In single-layer WSe$_2$, a paradigmatic semiconducting transition metal dichalcogenide, a circularly polarized laser field can selectively excite electronic transitions in one of the inequivalent $K^{\pm}$ valleys. Such selective valley population corresponds to a pseudospin polarization. This can be used as a degree of freedom in a valleytronic device provided that the time scale for its depolarization is sufficiently large. Yet, the mechanism behind the valley depolarization still remains heavily debated. Recent time-dependent Kerr experiments have provided an accurate way to visualize the v…
In atomically thin two-dimensional semiconductors such as transition metal dichalcogenides (TMDs), controlling the density and type of defects promises to be an effective approach for engineering light-matter interactions. We demonstrate that electron-beam irradiation is a simple tool for selectively introducing defect-bound exciton states associated with chalcogen vacancies in TMDs. Our first-principles calculations and time-resolved spectroscopy measurements of monolayer WSe2 reveal that these defect-bound excitons exhibit exceptional optical properties including a recombination lifetime app…
Layered two-dimensional materials exhibit rich transport and optical phenomena in twisted or lattice-incommensurate heterostructures with spatial variations of interlayer hybridization arising from moiré interference effects. Here, we report experimental and theoretical studies of excitons in twisted heterobilayers and heterotrilayers of transition metal dichalcogenides. Using MoSe$_2$-WSe$_2$ stacks as representative realizations of twisted van der Waals bilayer and trilayer heterostructures, we observe contrasting optical signatures and interpret them in the theoretical framework of interlay…
A monolayer of a transition metal dichalcogenide (TMD) such as WSe$_2$ is a two-dimensional (2D) direct band-gap valley-semiconductor having an effective Honeycomb lattice structure with broken inversion symmetry. The inequivalent valleys in the Brillouin zone could be selectively addressed using circularly-polarized light fields, suggesting the possibility for magneto-optical measurement and manipulation of the valley pseudospin degree of freedom. Here we report such experiments that demonstrate the valley Zeeman effect -- strongly anisotropic lifting of the degeneracy of the valley pseudospi…
Moiré materials provide fertile ground for the correlated and topological quantum phenomena. Among them, the quantum anomalous Hall (QAH) effect, in which the Hall resistance is quantized even under zero magnetic field, is a direct manifestation of the intrinsic topological properties of a material and an appealing attribute for low-power electronics applications. The QAH effect has been observed in both graphene and transition metal dichalcogenide (TMD) moiré materials. It is thought to arise from the interaction-driven valley polarization of the narrow moiré bands. Here, we show surprisingly…
Controlling the momentum of carriers in semiconductors, known as valley polarization, is a new resource for optoelectronics and information technologies. Materials exhibiting high polarization are needed for valley-based devices. Few-layer WS$_2$ shows a remarkable spin-valley polarization above 90%, even at room temperature. In stark contrast, polarization is absent for few-layer WSe$_2$ despite the expected material similarities. Here, we explain the origin of valley polarization in both materials based on the interplay between two indirect optical transitions. We show that the relative ener…
Monolayers of semiconducting transition metal dichalcogenides are two-dimensional direct-gap systems which host tightly-bound excitons with an internal degree of freedom corresponding to the valley of the constituting carriers. Strong spin-orbit interaction and the resulting ordering of the spin-split subbands in the valence and conduction bands makes the lowest-lying excitons in WX$_2$ (X~being S or Se) spin-forbidden and optically dark. With polarization-resolved photoluminescence experiments performed on a WSe$_2$ monolayer encapsulated in a hexagonal boron nitride, we show how the intrinsi…
We present a combined experimental and theoretical study of valley populations in the valence bands of trilayer WSe$_2$. Shubnikov$-$de Haas oscillations show that trilayer holes populate two distinct subbands associated with the $K$ and $Γ$ valleys, with effective masses 0.5$m_e$ and $1.2m_e$, respectively; $m_e$ is the bare electron mass. At a fixed total hole density, an applied transverse electric field transfers holes from $Γ$ orbitals to $K$ orbitals. We are able to explain this behavior in terms of the larger layer polarizability of the $K$ orbital subband.
Excitons, Coulomb bound electron-hole pairs, are composite bosons and their interactions in traditional semiconductors lead to condensation and light amplification. The much stronger Coulomb interaction in transition metal dichalcogenides such as WSe$_2$ monolayers combined with the presence of the valley degree of freedom is expected to provide new opportunities for controlling excitonic effects. But so far the bosonic character of exciton scattering processes remains largely unexplored in these two-dimensional (2D) materials. Here we show that scattering between B-excitons and A-excitons pre…
The variety of excitonic states in tungsten-based dichalcogenide monolayers stems from unique interplay between the spin and valley degrees of freedom. One of the exciton species is the indirect exciton (momentum or valley dark), which is responsible to a series of resonances when the monolayer is charge neutral. We investigate the short-range electron-hole exchange interaction of the indirect exciton, as well as its recombination mechanism mediated by impurities. The analysis provides thorough understanding of the energy and polarization of the zero-phonon indirect exciton resonance in the em…
Experimental signature of layer skyrmions and implications for band topology in twisted WSe2 bilayers
University of Texas at Austin（德克萨斯大学奥斯汀分校）；The University of Hong Kong（香港大学）；National Yang Ming Chiao Tung University（阳明交通大学）；Pennsylvania State University（宾夕法尼亚州立大学）；National Institute for Materials Science（日本物质材料研究机构）
With the both spin and valley degrees of freedom, the low-lying excitonic spectra of photo-excited transition-metal dichalcogenide monolayers (TMDC-MLs) are featured by rich fine structures, comprising the intra-valley bright exciton states as well as various intra- and inter-valley dark ones. The latter states can be classified as those of the spin- and momentum-forbidden dark excitons according to the violated optical selection rules. Because of the optical invisibility, the two types of the dark states are in general hardly observed and even distinguished in conventional spectroscopies alth…
Single-photon emitters play a key role in present and emerging quantum technologies. Several recent measurements have established monolayer WSe$_2$ as a promising candidate for a reliable single photon source. The origin and underlying microscopic processes have remained, however, largely elusive. We present a multi-scale tight-binding simulation for the optical spectra of WSe$_2$ under non-uniform strain and in the presence of point defects employing the Bethe-Salpeter equation. Strain locally shifts excitonic energy levels into the band gap where they overlap with localized intra-gap defect …
Spin-valley 0.7 anomaly in bilayer graphene/WSe$_2$ quantum point contacts
Solid State Physics Laboratory, ETH Zürich（苏黎世联邦理工学院固态物理实验室）；Research Center for Materials Nanoarchitectonics, National Institute for Materials Science（国立材料研究所材料纳米结构研究中心）；Research Center for Electronic and Optical Materials, National Institute for Materials Science（国立材料研究所电子与光学材料研究中心）；Department of Physics, Ben-Gurion University of the Negev（内盖夫本-古里安大学物理系）
Monolayers and multilayers of semiconducting transition metal dichalcogenides (TMDCs) offer an ideal platform to explore valley-selective physics with promising applications in valleytronics and information processing. Here we manipulate the energetic degeneracy of the $\mathrm{K}^+$ and $\mathrm{K}^-$ valleys in few-layer TMDCs. We perform high-field magneto-reflectance spectroscopy on WSe$_2$, MoSe$_2$, and MoTe$_2$ crystals of thickness from monolayer to the bulk limit under magnetic fields up to 30 T applied perpendicular to the sample plane. Because of a strong spin-layer locking, the gro…
We present a comprehensive optical study of the excitonic Zeeman effects in transition metal dichalcogenide monolayers, which are discussed comparatively for selected materials: MoSe$_2$, WSe$_2$ and WS$_2$. We introduce a simple semi-phenomenological description of the magnetic field evolution of individual electronic states in fundamental sub-bands by considering three additive components: valley, spin and orbital terms. We corroborate the validity of the proposed description by inspecting the Zeeman-like splitting of neutral and charged excitonic resonances in absorption-type spectra. The v…
