The electronic properties of ultrathin crystals of molybdenum disulfide consisting of N = 1, 2, ... 6 S-Mo-S monolayers have been investigated by optical spectroscopy. Through characterization by absorption, photoluminescence, and photoconductivity spectroscopy, we trace the effect of quantum confinement on the material's electronic structure. With decreasing thickness, the indirect band gap, which lies below the direct gap in the bulk material, shifts upwards in energy by more than 0.6 eV. This leads to a crossover to a direct-gap material in the limit of the single monolayer. Unlike the bulk material, the MoS 2 monolayer emits light strongly. The freestanding monolayer exhibits an increase in luminescence quantum efficiency by more than a factor of 1000 compared with the bulk material.

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 1-4 . Such valley polarization has been demonstrated by using strain 5,6 and magnetic fields 7-10 , but neither of these approaches allow for dynamic control. Here we demonstrate that optical pumping with circularly-polarized light can achieve complete dynamic valley polarization in monolayer MoS 2 11,12 , a twodimensional (2D) non-centrosymmetric crystal with direct energy gaps at two valleys [13][14][15][16] . Moreover, this polarization is retained for longer than 1 ns. Our results, and similar results by Zeng et al. 17 , demonstrate the viability of optical valley control and valley-based electronic and optoelectronic applications in MoS 2 monolayers.Since optical photons do not carry significant momentum, they cannot selectively populate different valleys based on this attribute. For appropriate materials, however, carriers in different valleys are associated with well-defined, but different angular momenta. This suggests the possibility of addressing different valleys by control of the photon angular momentum, i.e., by the helicity (circular polarization state) of light. Indeed, just such valley-specific circular dichroism of interband transitions has been predicted in non-centrosymmetric materials 3,4,11,12 . Graphene with its two prominent K and K' valleys has been considered theoretically in this context 3,4 . For this approach to be applicable, however, the inherent inversion symmetry of the single-and bilayer graphene must be broken 3,4 , and the effect has not yet been realized experimentally. Monolayer MoS 2 , on the other hand, is a direct band gap semiconductor [13][14][15][16] that possesses a structure similar to graphene, but with explicitly broken inversion symmetry. It has recently been proposed as a suitable material for valleytronics 11,12 .Monolayer MoS 2 consists of a single layer of Mo atoms sandwiched between two layers of S atoms in a trigonal prismatic structure 18 (Fig. 1a). Inversion symmetry is broken since the two sublattices are occupied, respectively, by one Mo and two S atoms. At the K and K' valleys in momentum space, the highest energy valence bands (VB) and the lowest energy conduction bands (CB) are mainly of Mo d-orbital character 18 . Because of the broken inversion symmetry, spin-orbit (SO) interactions split the VBs by about 160 meV 11,19,20 (Fig. 1b). The spin projection along the c-axis of the crystal, S z , is well defined and the two bands are of spin down (! ↓ ) and spin up (! ↑ ) in character. This broken spin degeneracy, in combination with time reversal symmetry (! ↓ (!) = ! ↑ (−!), where ! is crystal momentum) implies tha...

Two-dimensional (2D) atomic crystals, such as graphene and transition-metal dichalcogenides, have emerged as a new class of materials with remarkable physical properties 1 . In contrast to graphene, monolayer MoS 2 is a non-centrosymmetric material with a direct energy gap 2-5 . Strong photoluminescence 2,3 , a current on-off ratio exceeding 10 8 in field-effect transistors 6 , and efficient valley and spin control by optical helicity 7-9 have recently been demonstrated in this material. Here we report the spectroscopic identification in doped monolayer MoS 2 of tightly bound negative trions, a quasi-particle composed of two electrons and a hole. These quasiparticles, which can be created with valley and spin polarized holes, have no analogue in other materials. They also possess a large binding energy (~ 20 meV), rendering them significant even at room temperature. Our results open up new avenues both for fundamental studies of many-body interactions and for optoelectronic and valleytronic applications in 2D atomic crystals.The trion binding energy that we observe in monolayer MoS 2 is nearly an order of magnitude larger than that found in conventional quasi-2D systems, such as semiconductor quantum wells (QWs) [10][11][12][13] . This is a consequence of the greatly enhanced Coulomb interactions in monolayer MoS 2 , arising from reduced dielectric screening in gapped 2D crystals and the relatively heavy carrier band masses associated with the Mo d-manifolds 4,5,14 . For an electron density as high as n = 10 11 cm -2 , for instance, the dimensionless interaction parameter r s is ~60 in monolayer MoS 2 (Supplementary Information S1). This value is significantly larger than that for carriers in QWs even at very low doping levels 15 . Monolayer MoS 2 is a strongly interacting system even in the presence of relatively high carrier densities; it thus presents an ideal laboratory for exploring many-body phenomena, such as carrier multiplication and Wigner crystallization 16 .The atomic structure of MoS 2 consists of hexagonal planes of S and Mo atoms in a trigonal prismatic structure (Fig. 1a) 17 . The two sublattices of the hexagonal MoS 2 structure are occupied, respectively, by one Mo and two S atoms (Fig. 1b). Monolayer MoS 2 is a direct gap semiconductor with energy gaps located at the K and K' points of the Brillouin zone (Fig. 1c). Both the highest valence bands and the lowest conduction bands are formed primarily from the Mo d-orbitals 4,17 . The large spin-orbit interaction 2 splits the highest valence bands at the K (K') point by ~ 160 meV 2,3,7,14,18 . The valley and spin (VS) degrees are coupled because of the lack of inversion symmetry in monolayer MoS 2 . As has been recently shown experimentally, this allows optical pumping of a single valley (and spin) with circularly polarized light 7-9 .Here we investigate the optical response of monolayer MoS 2 as a function of carrier density by means of absorption and photoluminescence (PL) spectroscopy. In our investigations we have made use of MoS 2 monolayers p...

Single-layer transition metal dichalcogenides (TMDs) provide a promising material system to explore the electron's valley degree of freedom as a quantum information carrier 1-3 . The valley degree of freedom in single-layer TMDs can be directly accessed by means of optical excitation 4-6 . The rapid valley relaxation of optically excited electron-hole pairs (excitons) 7-9 through the long-range electron-hole exchange interaction 10,11 , however, has been a major roadblock. Theoretically such a valley relaxation does not occur for the recently discovered dark excitons [12][13][14][15][16] , suggesting a potential route for long valley lifetimes 10 . Here we investigate the valley dynamics of dark excitons in single-layer WSe 2 by time-resolved photoluminescence spectroscopy. We develop a waveguide-based method to enable the detection of the dark exciton emission, which involves spin-forbidden optical transitions with an out-of-plane dipole moment. The valley degree of freedom of dark excitons is accessed through the valley-dependent Zeeman effect under an out-of-plane magnetic field. We find a short valley lifetime for the dark neutral exciton, likely due to the short-range electron-hole exchange 17,18 , but long valley lifetimes exceeding several nanoseconds for dark charged excitons.Single-layer transition metal dichalcogenides (TMDs, MX 2 : M=Mo, W; X=S, Se) are direct band-gap semiconductors with direct gaps located at the K and K' valleys of the Brillouin zone 19,20 . Both valence and conduction bands are spin-split at the two valleys by the strong spinorbit coupling. The exciton formed by Coulomb interaction from electron and hole of antiparallel spins is a bright exciton (optically active), and from electron and hole of parallel spins, a dark exciton (optically inactive). The bright exciton exhibits strong valley circular dichroism (i.e. each handedness of circularly polarized light couples only to one of the two valleys), which provides an effective means to access the valley degree of freedom 4-6 . However, the valley relaxation is very fast (order of 10 ps) for the bright neutral 7-9 and charged excitons 21-23 . The fast valley relaxation is attributed to the long-range electron-hole exchange interaction 10,11 , which mixes the two valley exciton states. On the other hand, intervalley scattering of the dark exciton would require a spin flip, which does not occur through the longrange exchange interaction 10 . A long-lived valley polarization of the dark exciton is thus possible. In tungsten-based TMDs the dark exciton has a lower energy than the bright exciton and has recently been shown long-lived 13,24 . Direct measurement of the valley lifetime of the dark exciton, however, remains challenging. This spin-forbidden exciton has an out-of-plane (OP) transition dipole moment 12,14,25 , making its detection difficult with conventional far-field optical techniques. In addition, unlike for the bright exciton, there are no valley-dependent optical selection rules for the dark exciton that can be utilized ...

The large-scale growth of semiconducting thin films forms the basis of modern electronics and optoelectronics. A decrease in film thickness to the ultimate limit of the atomic, sub-nanometre length scale, a difficult limit for traditional semiconductors (such as Si and GaAs), would bring wide benefits for applications in ultrathin and flexible electronics, photovoltaics and display technology. For this, transition-metal dichalcogenides (TMDs), which can form stable three-atom-thick monolayers, provide ideal semiconducting materials with high electrical carrier mobility, and their large-scale growth on insulating substrates would enable the batch fabrication of atomically thin high-performance transistors and photodetectors on a technologically relevant scale without film transfer. In addition, their unique electronic band structures provide novel ways of enhancing the functionalities of such devices, including the large excitonic effect, bandgap modulation, indirect-to-direct bandgap transition, piezoelectricity and valleytronics. However, the large-scale growth of monolayer TMD films with spatial homogeneity and high electrical performance remains an unsolved challenge. Here we report the preparation of high-mobility 4-inch wafer-scale films of monolayer molybdenum disulphide (MoS2) and tungsten disulphide, grown directly on insulating SiO2 substrates, with excellent spatial homogeneity over the entire films. They are grown with a newly developed, metal-organic chemical vapour deposition technique, and show high electrical performance, including an electron mobility of 30 cm(2) V(-1) s(-1) at room temperature and 114 cm(2) V(-1) s(-1) at 90 K for MoS2, with little dependence on position or channel length. With the use of these films we successfully demonstrate the wafer-scale batch fabrication of high-performance monolayer MoS2 field-effect transistors with a 99% device yield and the multi-level fabrication of vertically stacked transistor devices for three-dimensional circuitry. Our work is a step towards the realization of atomically thin integrated circuitry.