Coexistence of intrinsic ferrovalley (FV) and nontrivial band topology attracts intensive interest both for its fundamental physics and for its potential applications, namely valley-polarized quantum anomalous Hall insulator (VQAHI). Here, based on first-principles calculations by using generalized gradient approximation plus $U$ (GGA+$U$) approach, the VQAHI induced by electronic correlation or strain can occur in monolayer $\mathrm{RuBr_2}$. For perpendicular magnetic anisotropy (PMA), the ferrovalley (FV) to half-valley-metal (HVM) to quantum anomalous Hall (QAH) to HVM to FV transitions can be driven by increasing electron correlation $U$. However, there are no special QAH states and valley polarization for in-plane magnetic anisotropy. By calculating actual magnetic anisotropy energy (MAE), the VQAHI indeed can exist between two HVM states due to PMA, a unit Chern number/a chiral edge state and spontaneous valley polarization. The increasing $U$ can induce VQAHI, which can be explained by sign-reversible Berry curvature or band inversion between $d_{xy}$/$d_{x^2-y^2}$ and $d_{z^2}$ orbitals. Even though the real $U$ falls outside the range, the VQAHI can be achieved by strain. Taking $U$$=$2.25 eV as a concrete case, the monolayer $\mathrm{RuBr_2}$ can change from a common ferromagentic (FM) semiconductor to VQAHI under about 0.985 compressive strain. It is noted that the edge states of VQAHI are chiral-spin-valley locking, which can achieve complete spin and valley polarizations for low-dissipation electronics devices. Both energy band gap and valley splitting of VQAHI in monolayer $\mathrm{RuBr_2}$ are higher than the thermal energy of room temperature (25 meV), which is key at room temperature for device applications.
Theoretical and experimental studies present that metal halogens in MX$_3$ forms can show very interesting electronic and magnetic properties in their bulk and monolayer phases. Many MX$_3$ materials have layered structures in their bulk phases, while RuBr$_3$ and RuI$_3$ have one-dimensional chains in plane. In this paper, we show that these metal halogens can also form two-dimensional layered structures in the bulk phase similar to other metal halogens, and cleavage energy values confirm that the monolayers of RuX$_3$ can be possible to be synthesised. We also find that monolayers of RuX$_3$…
In this letter we study the valley degeneracy splitting of the transition-metal dichalcogenides monolayer by first-principles calculations. The local magnetic moments are introduced into the system when the transition-metal atoms are adsorbed to the monolayer surface. Zeeman effect arising from the local magnetic moment at transition-metal atom sites lifts the valley degeneracy. Anomalous charge, spin and valley Hall Effects can be accessed due to valley splitting when we can only excite carriers of one valley. The valley splitting depends on the direction of magnetization and thus can be tune…
For a long time, two-dimensional (2D) hexagonal MoS2 was proposed as a promising material for valleytronic system. However, the limited size of growth and low carrier motilities in MoS2 restrict its further application. Very recently, a new kind of hexagonal 2D MXene, MoSi2N4, was successfully synthesized with large size, excellent ambient stability, and considerable hole mobility. In this paper, based on the first-principles calculations, we predict that the valley-contrast properties can be realized in monolayer MoSi2N4 and its derivative MoSi2As4. Beyond the traditional two-level valleys, t…
We investigate the effect on disorder potential on exciton valley polarization and valley coherence in monolayer WSe2. By analyzing polarization properties of photoluminescence, the valley coherence (VC) and valley polarization (VP) is quantified across the inhomogeneously broadened exciton resonance. We find that disorder plays a critical role in the exciton VC, while minimally affecting VP. For different monolayer samples with disorder characterized by their Stokes Shift (SS), VC decreases in samples with higher SS while VP again remains unchanged. These two methods consistently demonstrate …
In a recent work, new two-dimensional materials, the monolayer MoSi$_{2}$N$_{4}$ and WSi$_{2}$N$_{4}$, have been successfully synthesized in experiment, and several other monolayer materials with the similar structure, such as MoSi$_{2}$As$_{4}$, have been predicted [{\color{blue}Science 369, 670-674 (2020)}]. Here, based on first-principles calculations and theoretical analysis, we investigate the electronic and optical properties of monolayer MoSi$_{2}$N$_{4}$, WSi$_{2}$N$_{4}$ and MoSi$_{2}$As$_{4}$. We show that these materials are semiconductors, with a pair of Dirac-type valleys located …
We report polarization resolved photoluminescence from monolayer MoS2, a two-dimensional, non-centrosymmetric crystal with direct energy gaps at two different valleys in momentum space. The inherent chiral optical selectivity allows exciting one of these valleys and close to 90% polarized emission at 4K is observed with 40% polarization remaining at 300K. The high polarization degree of the emission remains unchanged in transverse magnetic fields up to 9T indicating robust, selective valley excitation.
Lifting the valley degeneracy is an efficient way to achieve valley polarization for further valleytronics operations. In this work, we demonstrate that a large valley splitting can be obtained in monolayer transition metal dichalcogenides by magnetic proximity coupling to an insulating antiferromagnetic substrate. As an example, we perform first-principles calculations to investigate the electronic structures of monolayer WS$_2$ on the MnO(111) surface. Our calculation results suggest that a large valley splitting of 214 meV, which corresponds to a Zeeman magnetic field of 1516 T, is induced …
Inspired by the successful synthesis of two-dimensional (2D) V-based Janus dichloride monolayers with intrinsic ferromagnetism and high Curie temperature (T$_{c}$), the electronic structure, spin-valley splitting and magnetic anisotropy of Janus 2H-VSeS monolayers are investigated in detailed using first-principles calculations. The results show that the Janus 2H-VSeS monolayer exhibits a large valley splitting of 105meV, high T$_{c}$ of 278K and good magnetocrystalline anisotropy (0.31meV) contributed by the in-plane d$_{x^{2}-y^{2}}$/d$_{xy}$ orbitals of V atoms. The biaxial strain ($-$8%<$\…
We study the effect of point-defect chalcogen vacancies on the optical properties of monolayer transition metal dichalcogenides using ab initio GW and Bethe-Salpeter equation calculations. We find that chalcogen vacancies introduce unoccupied in-gap states and occupied resonant defect states within the quasiparticle continuum of the valence band. These defect states give rise to a number of strongly-bound defect excitons and hybridize with excitons of the pristine system, reducing the valley-selective circular dichroism. Our results suggest a pathway to tune spin-valley polarization and other …
We have fabricated a high-quality monolayer WSe2 film on bilayer graphene by epitaxial growth, and revealed the electronic states by spin- and angle-resolved photoemission spectroscopy. We observed a direct energy gap at the Brillounin-zone corner in contrast to the indirect nature of gap in bulk WSe2, which is attributed to the lack of interlayer interaction and the breaking of space-inversion symmetry in monolayer film. A giant spin splitting of ~0.5 eV, which is the largest among known monolayer transition-metal dichalcogenides, is observed in the energy band around the zone corner. The pre…
Group-IV monochalcogenides are a family of two-dimensional puckered materials with an orthorhombic structure that is comprised of polar layers. In this article, we use first principles calculations to show the multistability of monolayer SnS and GeSe, two prototype materials where the direction of the puckering can be switched by application of tensile stress or electric field. Furthermore, the two inequivalent valleys in momentum space, which are dictated by the puckering orientation, can be excited selectively using linearly polarized light, and this provides an additional tool to identify t…
Strain-tunable multipiezo effects in Janus monolayer Cr2SSe: Selective reversal of valley polarization and single-spin-channel anomalous valley Hall effect
One of the key problems in valleytronics is to realize valley polarization. Ferrovalley (FV) semiconductor and half-valley-metal (HVM) have been proposed, which possess intrinsic spontaneous valley polarization. Here, we propose the concept of quasi-half-valley-metal (QHVM), including electron and hole carriers with only a type of carriers being valley polarized. The QHVM may realize separation function of electron and hole. A concrete example of $\mathrm{VGe_2P_4}$ monolayer is used to illustrate our proposal through the first-principle calculations. To better realize QHVM, the electric field…
Large bulk band gap is critical for application of the quantum spin Hall (QSH) insulator or two dimensional (2D) topological insulator (TI) in spintronic device operating at room temperature (RT). Based on the first-principles calculations, here we predict a group of 2D topological insulators BiX/SbX (X = H, F, Cl, and Br) monolayers with extraordinarily large bulk gaps from 0.32 to a record value of 1.08 eV. These giant-gaps are entirely due to the result of strong spin-orbit interaction related to px and py orbitals of Bi/Sb atoms around the two valley K and K' of honeycomb lattice, which is…
Electron-hole liquids(EHLs), a correlated state of matter and a thermodynamic liquid, have recently been found to exist at room temperature in suspended monolayers of MoS2. Appreciably higher rates of radiative recombination inside the liquid as compared to free excitons hold promise for optoelectronic applications such as broadband lasing. In this paper, we show that leveraging the valley physics in MoS2 may be a route towards achieving tunability of specific characteristics of an EHL, such as emission wavelength, linewidth, and most importantly, the liquid density. The conditions under which…
Two-dimensional rare-earth Janus 2$\textit{H}$-Gd$\textit{XY}$ ($\textit{X}$,$\textit{Y}$=Cl, Br, I, $\textit{X}$$\neq$$\textit{Y}$) monolayers: Bipolar ferro-magnetic semiconductors with high Curie temperature and large valley polarization
The Zeeman effect offers unique opportunities for magnetic manipulation of the spin degree of freedom (DOF). Recently, valley Zeeman splitting, referring to the lifting of valley degeneracy, has been demonstrated in two-dimensional transition metal dichalcogenides (TMDs) at liquid helium temperature. However, to realize the practical applications of valley pseudospins, the valley DOF must be controllable by a magnetic field at room temperature, which remains a significant challenge. Magnetic doping in TMDs can enhance the Zeeman splitting, however, to achieve this experimentally is not easy. H…
Electron valleys in transition-metal dichalcogenide monolayers drive novel physics and allow designing multifunctional architectures for applications. We propose to manipulate the electron valleys in these systems for spin/valley filter and valve devices through band engineering. Instead of the magnetic proximity effect that has been extensively used in previous studies, in our strategy, the electron valleys are directly coupled to the spin-polarized states of the two-dimensional ferromagnets. We find that this coupling results in a valley-selective gap opening due to the spin-momentum locking…
The optical selection rules obeyed by two-dimensional materials with spin-valley coupling enable the selective excitation of carriers. We show that six members of the monolayer MA2Z4 (M = Mo and W; A = C, Si, and Ge; Z = N, P, and As) family are direct band-gap semiconductors with protected valley states and that circularly polarized infrared light can induce valley-selective inter-band transitions. Our optovalleytronic device demonstrates a close to 100% valley- and spin-polarized current under in-plane bias and circularly polarized infrared light, which can be exploited to encode, process, a…
In monolayer hexagonal lattices, two inequivalent valleys appear in the Brillouin zone. With inversion symmetry breaking, we find chiral phonons with valley contrasting circular polarization and ionic magnetic moment. At valley centers, there is a three-fold rotational symmetry endowing phonons with a quantized pseudo angular momentum, which includes spin and orbital parts. From conservation of the pseudo angular momentum, crystal momentum and energy, selection rules in intervalley scattering of electrons by phonons are obtained. The chiral valley phonons are verified and the selection rules a…
Valleytronics is a rising topic to explore the emergent degree of freedom for charge carriers in energy band edges and has attracted a great interest due to many intriguing quantum phenomena and potential application in information processing industry. Creation of permanent valley polarization, i.e. unbalanced occupation at different valleys, is a chief challenge and also urgent question to be solved in valleytronics. Here we predict that the spin-orbit coupling and magnetic ordering allow spontaneous valley Zeeman-type splitting in pristine monolayer of VAgP2Se6 by using first-principles calc…
Modern electronic devices heavily rely on the accurate control of charge and spin of electrons. The emergence of controllable valley degree of freedom brings new possibilities and presents a promising prospect towards valleytronics. Recently, valley excitation selected by chiral optical pumping has been observed in monolayer MoS2. In this work, we report polarized photoluminescence (PL) measurements for monolayer MoSe2, another member of the family of transition-metal-dichalcogenides (MX2), and observe drastic difference from the outcomes of MoS2. In particular, we identify a valley polarizati…
We propose a new family of the d0 orbital XY (X = K, Rb, Cs; Y = N, P, As, Sb, Bi) monolayers with abundant and novel topology and valley properties. The KN, RbN, RbP, RbAs, CsP, CsAs, and CsSb monolayers possess remarkable quantum anomalous Hall effect (QAHE). CsSb monolayer also exhibits extraordinary valley QAHE with giant splitting. Moreover, the topological properties of XY monolayers can be effciently tuned by the in-plane strain, owing to the strain-induced band inversion between the px;y and pz orbitals. Our findings suggest that the d0 orbital XY monolayers can be good candidates for …
Ferrovalley materials can achieve manipulation of the valley degree of freedom with intrinsic spontaneous valley polarization introduced by their intrinsic ferromagnetism. A good ferrovalley material should possess perpendicular magnetic anisotropy (PMA), valence band maximum (VBM)/conduction band minimum (CBM) at valley points, strong ferromagnetic (FM) coupling and proper valley splitting. In this work, the monolayer $\mathrm{GdCl_2}$ is proposed as a potential candidate material for valleytronic applications by the first-principles calculations. It is proved that monolayer $\mathrm{GdCl_2}$…
We show that inversion symmetry breaking together with spin-orbit coupling leads to coupled spin and valley physics in monolayers of MoS2 and other group-VI dichalcogenides, making possible controls of spin and valley in these 2D materials. The spin-valley coupling at the valence band edges suppresses spin and valley relaxation, as flip of each index alone is forbidden by the valley contrasting spin splitting. Valley Hall and spin Hall effects coexist in both electron-doped and hole-doped systems. Optical interband transitions have frequency-dependent polarization selection rules which allow s…
Breaking space-time symmetries in two-dimensional crystals (2D) can dramatically influence their macroscopic electronic properties. Monolayer transition-metal dichalcogenides (TMDs) are prime examples where the intrinsically broken crystal inversion symmetry permits the generation of valley-selective electron populations, even though the two valleys are energetically degenerate, locked by time-reversal symmetry. Lifting the valley degeneracy in these materials is of great interest because it would allow for valley-specific band engineering and offer additional control in valleytronic applicati…
We investigate the valley depolarization due to the electron-hole exchange interaction in monolayer MoS$_{2}$. Both the long- and short-range parts of the intra- and inter-valley electron-hole exchange interactions are calculated. We find that both the long- and short-range exchange interactions can cause the inter- and intra-valley bright exciton transitions. With the intra-valley bright exciton transition channel nearly forbidden due to the large splitting of the valence bands, the inter-valley channel due to the exchange interaction can cause the valley depolarization efficiently by the Mai…
The valley degree of freedom is a sought-after quantum number in monolayer transition-metal dichalcogenides. Similar to optical spin orientation in semiconductors, the helicity of absorbed photons can be relayed to the valley (pseudospin) quantum number of photoexcited electrons and holes. Also similar to the quantum-mechanical spin, the valley quantum number is not a conserved quantity. Valley depolarization of excitons in monolayer transition-metal dichalcogenides due to long-range electron-hole exchange typically takes a few ps at low temperatures. Exceptions to this behavior are monolayers…
Single layers of transition metal dichalcogenides are two-dimensional direct bandgap semiconductors with degenerate, but inequivalent, `valleys' in the electronic structure that can be selectively excited by polarized light. Coherent superpositions of light and matter, exciton-polaritons, have been observed when these materials are strongly coupled to photons, but these hybrid quasiparticles do not harness the valley-sensitive excitations of monolayer transition metal dichalcogenides. Here, we demonstrate evidence for valley polarized exciton-polaritons in monolayers of MoS$_2$ embedded in a d…
We investigate the optical control possibilities of spin-valley qubit carried by single electrons localized in nanostructures of monolayer TMDs, including small quantum dots formed by lateral heterojunction and charged impurities. The quantum controls are discussed when the confinement induces valley hybridization and when the valley hybridization is absent. We show that the bulk valley and spin optical selection rules can be inherited in different forms in the two scenarios, both of which allow the definition of spin-valley qubit with desired optical controllability. We also investigate nucle…
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…
Valleytronic materials, characterized by local extrema (valley) in their bands, and topological insulators have separately attracted great interest recently. However, the interplay between valleytronic and topological properties in one single system, likely to enable important unexplored phenomena and applications, has been largely overlooked so far. Here, by combining a tight-binding model with first-principles calculations, we find the large-band-gap quantum spin Hall effects (QSHEs) and valley Hall effects (VHEs) appear simultaneously in the Bi monolayers decorated with halogen elements, de…
Using time-resolved Kerr rotation, we measure the spin/valley dynamics of resident electrons and holes in single charge-tunable monolayers of the archetypal transition-metal dichalcogenide (TMD) semiconductor WSe2. In the n-type regime, we observe long (70 ns) polarization relaxation of electrons that is sensitive to in-plane magnetic fields $B_y$, indicating spin relaxation. In marked contrast, extraordinarily long (2 microsecond) polarization relaxation of holes is revealed in the p-type regime, that is unaffected by $B_y$, directly confirming long-standing expectations of strong spin-valley…
Electronic and spintronic devices rely on the fact that free charge carriers in solids carry electric charge and spin, respectively. There are, however, other properties of charge carriers that might be exploited in new families of devices. In particular, if there are two or more conduction (or valence) band extrema in momentum space, then confining charge carriers in one of these valleys allows the possibility of valleytronic devices. Such valley polarization has been demonstrated by using strain and magnetic fields, but neither of these approaches allow for dynamic control. Recently, optical…
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 …
Achieving combination of spin and valley polarized states with topological insulating phase is pregnant to promote the fantastic integration of topological physics, spintronics and valleytronics. In this work, a spin-valley-coupled quantum spin Hall insulator (svc-QSHI) is predicted in Janus monolayer $\mathrm{CSb_{1.5}Bi_{1.5}}$ with dynamic, mechanical and thermal stabilities. The inequivalent valleys have opposite Berry curvature and spin moment, which can produce a spin-valley Hall effect. In the center of Brillouin zone, a Rashba-type spin splitting can be observed due to missing horizont…
Exciton dispersion as a function of center-of-mass momentum, \textbf{Q}, is essential to the understanding of exciton dynamics. We use the ab-initio GW-Bethe Salpeter equation method to calculate the dispersion of excitons in monolayer MoS$_2$ and find a nonanalytic light-like dispersion. This behavior arises from an unusual $|Q|$ term in both the intra- and inter-valley exchange of the electron-hole interaction, which concurrently gives rise to a valley quantum phase of winding number two. A simple effective Hamiltonian to $Q^2$ order with analytic solutions is derived to describe quantitativ…
Carrier-doped transition metal dichalcogenide (TMD) monolayers are of great interest in valleytronics due to the large Zeeman response (g-factors) in these spin-valley-locked materials, arising from many-body interactions. We develop an \textit{ab initio} approach based on many-body perturbation theory to compute the interaction-enhanced g-factors in carrier-doped materials. We show that the g-factors of doped WSe$_2$ monolayers are enhanced by screened exchange interactions resulting from magnetic-field-induced changes in band occupancies. Our interaction-enhanced g-factors $g^*$ agree well w…
By enabling control of valley degrees of freedom in transition-metal dichalcogenides, valley-selective circular dichroism has become a key concept in valleytronics. In this manuscript, we show that valley excitons -- bound electron-hole pairs formed at either the K or K' valleys upon absorption of circularly-polarized light -- are chiral quasiparticles characterized by a finite orbital angular momentum (OAM). We further formulate an ab-initio many-body theory of valley-selective circular dichroism and valley excitons based on the Bethe-Salpeter equation. Beside governing the interaction with c…
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…
We investigate with polarized microphotoluminescence the optical pumping of the valley degree of freedom in charge-tunable MoS2 monolayers encapsulated with hexagonal boron nitride at cryogenic temperatures. We report a large steady state valley polarization of the different excitonic complexes following circularly-polarized laser excitation 25 meV above the neutral exciton transition. For the first time in this material we reveal efficient valley pumping of positively-charged trions, which were so far elusive in non-encapsulated monolayers due to defect and laser-induced large electron doping…
Monolayers of transition metal dichalcogenides are ideal materials to control both spin and valley degrees of freedom either electrically or optically. Nevertheless, optical excitation mostly generates excitons species with inherently short lifetime and spin/valley relaxation time. Here we demonstrate a very efficient spin/valley optical pumping of resident electrons in n-doped WSe2 and WS2 monolayers. We observe that, using a continuous wave laser and appropriate doping and excitation densities, negative trion doublet lines exhibit circular polarization of opposite sign and the photoluminesce…
We investigate the valley related carrier dynamics in monolayer MoS2 using helicity resolved non-degenerate ultrafast pump-probe spectroscopy at the vicinity of the high-symmetry K point under the temperature down to 78 K. Monolayer MoS2 shows remarkable transient reflection signals, in stark contrast to bilayer and bulk MoS2 due to the enhancement of many-body effect at reduced dimensionality. The helicity resolved ultrafast time-resolved result shows that the valley polarization is preserved for only several ps before scattering process makes it undistinguishable. We suggest that the dynamic…
Valley pseudospin in two-dimensional (2D) transition-metal dichalcogenides (TMDs) allows optical control of spin-valley polarization and intervalley quantum coherence. Defect states in TMDs give rise to new exciton features and theoretically exhibit spin-valley polarization; however, experimental achievement of this phenomenon remains challenges. Here, we report unambiguous valley pseudospin of defect-bound localized excitons in CVD-grown monolayer MoS2; enhanced valley Zeeman splitting with an effective g-factor of -6.2 is observed. Our results reveal that all five d-orbitals and the increase…
