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The newly developed two-dimensional layered materials provide a 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 WSe2 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 WSe2 is determined. Valley relaxation time of the free exciton in monolayer WSe2 is confirmed to be several picoseconds. A slow valley polarization relaxation process is observed to be associated with the trions, showing that the valley lifetime for trions is one order of magnitude longer than that of free excitons. This finding suggests that trion can be a good candidate for valleytronics applications.

Raman spectroscopy is the prime non-destructive characterization tool for graphene and related layered materials. The shear (C) and layer breathing modes (LBMs) are due to relative motions of the planes, either perpendicular or parallel to their normal. This allows one to directly probe the interlayer interactions in multilayer samples. Graphene and other two-dimensional (2d) crystals can be combined to form various hybrids and heterostructures, creating materials on demand with properties determined by the interlayer interaction. This is the case even for a single material, where multilayer stacks with different relative orientation have different optical and electronic properties. In twisted multilayer graphene samples there is a significant enhancement of the C modes due to resonance with new optically allowed electronic transitions, determined by the relative orientation of the layers. Here we show that this applies also to the LBMs, that can be now directly measured at room temperature. We find that twisting does not affect LBMs, quite different from the case of the C modes. This implies that the periodicity mismatch between two twisted layers mostly affects shear interactions. Our work shows that Raman spectroscopy is an ideal tool to uncover the interface coupling of 2d hybrids and heterostructures., ACS Nano, 2015, 9(7), 7440-7449

Graphene and other two-dimensional crystals can be combined to form various hybrids and heterostructures, creating materials on demand with properties determined by the interlayer interaction. This is the case even for a single material, where multilayer stacks with different relative orientation have different optical and electronic properties. Probing and understanding the interface coupling is thus of primary importance for fundamental science and applications. Here we study twisted multilayer graphene flakes with multi-wavelength Raman spectroscopy. We find a significant intensity enhancement of the interlayer coupling modes (C peaks) due to resonance with new optically allowed electronic transitions, determined by the relative orientation of the layers. The interlayer coupling results in a Davydov splitting of the C peak in systems consisting of two equivalent graphene multilayers. This allows us to directly quantify the interlayer interaction, which is much smaller compared with Bernal-stacked interfaces. This paves the way to the use of Raman spectroscopy to uncover the interface coupling of two-dimensional hybrids and heterostructures.

Stacking order of layered materials strongly influences their electronic properties. Bernal (AB) and rhombohedral (ABC) stacking are much common in few-layer graphenes. Here, we found that AB- and ABC-stacked few-layer graphenes can be well distinguished by whether their highest-frequency shear modes are observed or not in the Raman spectra at room temperature. This method can be expanded to Raman characterization of the stacking order in other two-dimensional layered materials.

Two-dimensional (2D) transition metal dichalcogenide (TMD) nanosheets exhibit remarkable electronic and optical properties. The 2D features, sizable bandgaps, and recent advances in the synthesis, characterization, and device fabrication of the representative MoS$_2$, WS$_2$, WSe$_2$, and MoSe$_2$ TMDs make TMDs very attractive in nanoelectronics and optoelectronics. Similar to graphite and graphene, the atoms within each layer in 2D TMDs are joined together by covalent bonds, while van der Waals interactions keep the layers together. This makes the physical and chemical properties of 2D TMDs layer dependent. In this review, we discuss the basic lattice vibrations of monolayer, multilayer, and bulk TMDs, including high-frequency optical phonons, interlayer shear and layer breathing phonons, the Raman selection rule, layer-number evolution of phonons, multiple phonon replica, and phonons at the edge of the Brillouin zone. The extensive capabilities of Raman spectroscopy in investigating the properties of TMDs are discussed, such as interlayer coupling, spin--orbit splitting, and external perturbations. The interlayer vibrational modes are used in rapid and substrate-free characterization of the layer number of multilayer TMDs and in probing interface coupling in TMD heterostructures. The success of Raman spectroscopy in investigating TMD nanosheets paves the way for experiments on other 2D crystals and related van der Waals heterostructures., 30 pages, 23 figures

An SiO2/Si substrate has been widely used to support two-dimensional (2d) flakes grown by chemical vapor deposition or prepared by micromechanical cleavage. The Raman intensity of the vibration modes of 2d flakes is used to identify the layer number of 2d flakes on the SiO2/Si substrate, however, such an intensity is usually dependent on the flake quality, crystal orientation and laser polarization. Here, we used graphene flakes, a prototype system, to demonstrate how to use the intensity ratio between the Si peak from SiO2/Si substrates underneath graphene flakes and that from bare SiO2/Si substrates for the layer-number identification of graphene flakes up to 100 layers. This technique is robust, fast and nondestructive against sample orientation, laser excitation and the presence of defects in the graphene layers. The effect of relevant experimental parameters on the layer-number identification was discussed in detail, such as the thickness of the SiO2 layer, laser excitation wavelength and numerical aperture of the used objective. This paves the way to use Raman signals from dielectric substrates for layer-number identification of ultrathin flakes of various 2d materials.

Highly sensitive phototransistors based on two-dimensional (2D) GaTe nanosheet have been demonstrated. The performance (photoresponsivity, detectivity) of the GaTe nanosheet phototransistor can be efficiently adjusted by using the applied gate voltage. The devices exhibit an ultrahigh photoresponsivity of 274.3 AW−1. The detectivity of 2D GaTe devices is ∼1012 Jones, which surpasses that of currently-exploited InGaAs photodetectors (1011−1012 Jones). To reveal the origin of the enhanced photocurrent in GaTe nanosheets, theoretical modeling of the electronic structures was performed to show that GaTe nanosheets also have a direct bandgap structure, which contributes to the promotion of photon absorption and generation of excitons. This work shows that GaTe nanosheets are promising materials for high performance photodetectors.

Anisotropic two-dimensional (2D) van der Waals (vdW) layered materials, with both scientific interest and application potential, offer one more dimension than isotropic 2D materials to tune their physical properties. Various physical properties of 2D multi-layer materials are modulated by varying their stacking orders owing to significant interlayer vdW coupling. Multilayer rhenium disulfide (ReS2), a representative anisotropic 2D material, was expected to be randomly stacked and lack interlayer coupling. Here, we demonstrate two stable stacking orders, namely isotropic-like (IS) and anisotropic-like (AI) N layer (NL, N1) ReS2 are revealed by ultralow- and high-frequency Raman spectroscopy, photoluminescence and first-principles density functional theory calculation. Two interlayer shear modes are observed in AI-NL-ReS2 while only one shear mode appears in IS-NL-ReS2, suggesting anisotropic- and isotropic-like stacking orders in IS- and AI-NL-ReS2, respectively. This explicit difference in the observed frequencies identifies an unexpected strong interlayer coupling in IS- and AI-NL-ReS2. Quantitatively, the force constants of them are found to be around 55-90% of those of multilayer MoS2. The revealed strong interlayer coupling and polytypism in multi-layer ReS2 may stimulate future studies on engineering physical properties of other anisotropic 2D materials by stacking orders.

Transition-metal dichalcogenide (TMD) semiconductors have been widely studied due to their distinctive electronic and optical properties. The property of TMD flakes is a function of its thickness, or layer number (N). How to determine N of ultrathin TMDs materials is of primary importance for fundamental study and practical applications. Raman mode intensity from substrates has been used to identify N of intrinsic and defective multilayer graphenes up to N=100. However, such analysis is not applicable for ultrathin TMD flakes due to the lack of a unified complex refractive index ($\tilde{n}$) from monolayer to bulk TMDs. Here, we discuss the N identification of TMD flakes on the SiO$_2$/Si substrate by the intensity ratio between the Si peak from 100-nm (or 89-nm) SiO$_2$/Si substrates underneath TMD flakes and that from bare SiO$_2$/Si substrates. We assume the real part of $\tilde{n}$ of TMD flakes as that of monolayer TMD and treat the imaginary part of $\tilde{n}$ as a fitting parameter to fit the experimental intensity ratio. An empirical $\tilde{n}$, namely, $\tilde{n}_{eff}$, of ultrathin MoS$_{2}$, WS$_{2}$ and WSe$_{2}$ flakes from monolayer to multilayer is obtained for typical laser excitations (2.54 eV, 2.34 eV, or 2.09 eV). The fitted $\tilde{n}_{eff}$ of MoS$_{2}$ has been used to identify N of MoS$_{2}$ flakes deposited on 302-nm SiO$_2$/Si substrate, which agrees well with that determined from their shear and layer-breathing modes. This technique by measuring Raman intensity from the substrate can be extended to identify N of ultrathin 2D flakes with N-dependent $\tilde{n}$ . For the application purpose, the intensity ratio excited by specific laser excitations has been provided for MoS$_{2}$, WS$_{2}$ and WSe$_{2}$ flakes and multilayer graphene flakes deposited on Si substrates covered by 80-110 nm or 280-310 nm SiO$_2$ layer., Comment: 10 pages, 4 figures. Accepted by Nanotechnology

We have systematically examined the circular polarization of monolayer WSe2 at different temperature, excitation energy and exciton density. The valley depolarization in WSe2 is experimentally confirmed to be governed by the intervalley electron-hole exchange interaction. More importantly, a non-monotonic dependence of valley circular polarization on the excitation power density has been observed, providing the experimental evidence for the non-monotonic dependence of exciton intervalley scattering rate on the excited exciton density. The physical origination of our experimental observations has been proposed to be in analogy to the D′yakonov-Perel′ mechanism that is operative in conventional GaAs quantum well systems. Our experimental results are fundamentally important for well understanding the valley pseudospin relaxation in atomically thin transition metal dichalcogenides.

Two-dimensional (2D) transition metal dichalcogenide (TMD) nanosheets exhibit remarkable electronic and optical properties. The 2D features, sizable bandgaps and recent advances in the synthesis, characterization and device fabrication of the representative MoS2, WS2, WSe2 and MoSe2 TMDs make TMDs very attractive in nanoelectronics and optoelectronics. Similar to graphite and graphene, the atoms within each layer in 2D TMDs are joined together by covalent bonds, while van der Waals interactions keep the layers together. This makes the physical and chemical properties of 2D TMDs layer-dependent. In this review, we discuss the basic lattice vibrations of 2D TMDs from monolayer, multilayer to bulk material, including high-frequency optical phonons, interlayer shear and layer breathing phonons, the Raman selection rule, layer-number evolution of phonons, multiple phonon replica and phonons at the edge of the Brillouin zone. The extensive capabilities of Raman spectroscopy in investigating the properties of TMDs are discussed, such as interlayer coupling, spin–orbit splitting and external perturbations. The interlayer vibrational modes are used in rapid and substrate-free characterization of the layer number of multilayer TMDs and in probing interface coupling in TMD heterostructures. The success of Raman spectroscopy in investigating TMD nanosheets paves the way for experiments on other 2D crystals and related van der Waals heterostructures.

The quantum confinement in atomic scale and the presence of interlayer coupling in multilayer make the electronic and optical properties of 2D materials (2DMs) be dependent on the layer number (N) from monolayer to multilayer. Optical properties of 2DMs have been widely probed by several optical techniques, such as optical contrast, Rayleigh scattering, Raman spectroscopy, optical absorption, photoluminescence, and second harmonic generation. Here, it is reviewed how optical properties of several typical 2DMs (e.g., monolayer and multilayer graphenes, transition metal dichalcogenides) probed by these optical techniques significantly depend on N. Further, it has been demonstrated how these optical techniques service as fast and nondestructive approaches for N counting or thickness determination of these typical 2DM flakes. The corresponding approaches can be extended to the whole 2DM family produced by micromechanical exfoliations, chemical-vapor-deposition growth, or transfer processes on various substrates, which bridges the gap between the characterization and international standardization for thickness determination of 2DM flakes.

Coherent longitudinal acoustic phonon is generated and detected in multilayer Molybdenum Disulphide (MoS2) with number of layers ranging from 10 to over 1300 by femtosecond laser pulse. For thin MoS2, the excited phonon frequency exhibits a standing wave nature and shows linear dependence on the sample thickness. The frequency varies from 40 GHz to 0.2 THz (10 layers), which promises possible application in THz frequency mechanical resonators. This linear thickness dependence gradually disappears in thicker samples above about 150 layers and the oscillation period shows linear dependence on the probe wavelength. From both the oscillation period of the coherent phonon and the delay time of acoustic echo, we can deduce a consistent sound velocity of 7.11*103 m/s in MoS2. The generation mechanisms of the coherent acoustic phonon are also discussed through pump power dependent measurement.

Molybdenum disulfide (MoS2) is back in the spotlight because of the indirect-to-direct bandgap tunability and valley related physics emerging in the monolayer regime. However, rigorous control of the monolayer thickness is still a huge challenge for commonly utilized physical exfoliation and chemical synthesis methods. Herein, we have successfully grown predominantly monolayer MoS2 on an inert and nearly lattice-matching mica substrate by using a low-pressure chemical vapor deposition method. The growth is proposed to be mediated by an epitaxial mechanism, and the epitaxial monolayer MoS2 is intrinsically strained on mica due to a small adlayer-substrate lattice mismatch (~2.7%). Photoluminescence (PL) measurements indicate strong single-exciton emission in as-grown MoS2 and room-temperature PL helicity (circular polarization ~0.35) on transferred samples, providing straightforward proof of the high quality of the prepared monolayer crystals. The homogeneously strained high-quality monolayer MoS2 prepared in this study could competitively be exploited for a variety of future applications.

The fundamental momentum conservation requirement q ~ 0 for the Raman process is relaxed in the nanocrystallites (NCs), and phonons away from the Brillouin-zone center will be involved in the Raman scattering, which is well-known as the phonon confinement effect in NCs. This usually gives a downshift and asymmetric broadening of the Raman peak in various NCs. Recently, the A'1 mode of 1L MoS2 NCs is found to exhibit a blue shift and asymmetric broadening toward the high-frequency side [Chem. Soc. Rev. 44 (2015) 2757 and Phys. Rev. B 91 (2015) 195411]. In this work, we carefully check this issue by studying Raman spectra of 1L MoS2 NCs prepared by the ion implantation technique in a wide range of ion-implanted dosage. The same confinement coefficient is used for both E' and A'1 modes in 1L MoS2 NCs since the phonon uncertainty in an NC is mainly determined by its domain size. The asymmetrical broadening near the A'1 and E' modes is attributed to the appearance of defect-activated phonons at the zone edge and the intrinsic asymmetrical broadening of the two modes, where the anisotropy of phonon dispersion curves along Γ–K and Γ–M is also considered. The photoluminescence spectra confirm the formation of small domain size of 1L MoS2 nanocrystallites in the ion-implanted 1L MoS2. This study provides not only an approach to quickly probe phonon dispersion trends of 2D materials away from Γ by the Raman scattering of the corresponding NCs, but also a reference to completely understand the confinement effect of different modes in various nanomaterials.

Defects strongly modify optical properties in pristine and nanostructured two-dimensional (2D) materials. The ion implantation technique can be used to gradually introduce defects in semiconductor to obtain nanocrystallites (NCs) with different domain sizes. Here, we present a detailed study on the Raman and photoluminescence spectra of 2D NCs of monolayer WS2 (1L WS2) and 1L WSe2 prepared by ion implantation. With increasing ion dosages, both and modes of 1L WS2 exhibit a downshift in frequency and an asymmetrical broadening toward lower frequency, while the mode in 1L WSe2 NCs exhibits an opposite behavior, showing asymmetrical broadening and peak shift toward higher frequency. This behavior is well understood by phonon quantum confinement of the out-of-plane optical branch whose frequency displays a minimum at Γ in pristine 1L WSe2. After the ion implantation, phonons from the Brillouin zone boundary are revealed in the Raman spectra, and the corresponding assignments are identified by resonant Raman spectra at low temperature. The defects can act as trapping centers of free carriers, which result in a sharp decrease of photoluminescence (PL) emission from A exciton with increasing ion dosage. The PL peak from A-exciton in both 1L WS2 and 1L WSe2 NCs blueshifts with increasing the ion dosage due to the quantum confinement effect of smaller NC size. The ion-implantation results in a new emission peak of defect-bound neutral excitons below the A-exciton peak in both 1L WS2 and 1L WSe2 NCs. Its relative intensity to the A exciton increases with increasing the ion dosage and finally vanishes along with the A exciton. These results offer a route toward tailoring the optical properties of 2D materials by controlling the size of 2D NCs.

Any of two or more two-dimensional (2D) materials with similar properties can be alloyed into a new layered material, namely, 2D alloy. Individual monolayer in 2D alloys are kept together by Van der Waals interactions. The property of multilayer alloys is a function of their layer number. Here, we studied the shear (C) and layer-breathing (LB) modes of Mo$_{0.5}$W$_{0.5}$S$_2$ alloy flakes and their link to the layer number of alloy flakes. The study reveals that the disorder effect is absent in the C and LB modes of 2D alloys, and the monatomic chain model can be used to estimate the frequencies of the C and LB modes. We demonstrated how to use the C and LB mode frequency to identify the layer number of alloy flakes deposited on different substrates. This technique is independent of the substrate, stoichiometry, monolayer thickness and complex refractive index of 2D materials, offering a robust and substrate-free approach for layer-number identification of 2D materials., Comment: 5 pages, 4 figures

We report the nonlinear optical (NLO) properties of vertically stood WS2 nanoplates excited by 532-nm picosecond laser light. The nanoplates were synthesized by a no-catalyst thermal evaporation process. Raman spectroscopy and x-ray diffraction pattern indicate that the nanoplates are of high crystal quality. The nanoplates exhibit large nonlinear saturable absorption but negligible nonlinear refraction. Mechanisms of the NLO response are proposed.

In this work, comprehensive temperature and excitation power dependent photoluminescence and time-resolved photoluminescence studies are carried out on monolayer WSe2 to reveal its properties of exciton emissions and related excitonic dynamics. Competitions between the localized and delocalized exciton emissions, as well as the exciton and trion emissions are observed, respectively. These competitions are suggested to be responsible for the abnormal temperature and excitation intensity dependent photoluminescence properties. The radiative lifetimes of both excitons and trions exhibit linear dependence on temperature within the temperature regime below 260 K, providing further evidence for two-dimensional nature of monolayer material.