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With polarized and angle-resolved Raman spectroscopy studies on single two-dimensional layered perovskites (2DLP) flakes with different ammonium molecules as organic cations, in 2020 we revealed the very rich phonon spectra in the low-frequency regime. Although the phonon bands at low frequency can generally be attributed to the vibrations of the inorganic lattice, we found very different phonon spectra for the same lead-bromide octahedra composition by only changing the type of the organic cations. In addition, the intensity of the different phonon modes depended strongly on the angle of the linearly polarized excitation beam with respect to the in-plane axes of the octahedra lattice. In 2022, we mapped this angular dependence of the phonon modes, which enabled to identify the directionality of the different lattice vibrations. By correlating the phonon spectra with the temperature-dependent emission for a set of 2DLPs that featured very different STE emission, we demonstrated that the exciton relaxation cannot be related to coupling with a single (longitudinal optical) phonon band, and that several phonon bands should be involved in the emission process. We performed angle-resolved polarized emission and Raman spectroscopy on the same two-dimensional lead iodide perovskite microcrystals, which revealed the impact of the organic cations on the linear polarization of the emission, and corroborated our interpretation that multiple phonon bands should be involved in the radiative recombination process. Our studies revealed a wealth of highly directional low-frequency phonons in 2DLPs from which several bands are involved in the emission process, which leads to diverse optical and vibrational properties depending on the type of organic cation in the material., Comment: 36 pages, 8 figures and 1 table

Interface engineered ferroelectricity in van der Waals heterostructures is of broad interest both fundamentally and technologically for the applications in neuromorphic computing and so on. In particular, the moir\'e ferroelectricity in graphene/hexagonal boron nitride (hBN) heterostructures driven by charge ordering instead of traditional lattice displacement has drawn considerable attention because of its fascinating properties and promising high-frequency programmable electrical polarization switching. Yet, the underlying mechanism of the electronic ferroelectricity is still under debate. On the other hand, combining the interface engineered ferroelectricity and strong correlations in moir\'e heterostructures could enable the realization of novel quantum states such as ferroelectric superconductivity and multiferroicity. Here we study the electronic transport properties of twisted double bilayer graphene (TDBLG), aligned with one of the neighbouring hBN. We observe a strong gating hysteresis and ferroelectric-like behaviour, as well as the electronic ratchet effect. We find that the top gate is anomalously screened. On the contrary, the back gate is anomalously doubly efficient in injecting charges into graphene, that is, the effective back gate capacitance is two times larger than its geometry capacitance. This unexpected gate-tunable capacitance causes a dramatic change of electric fields between forward and backward scans. The asymmetric gating behaviours and anomalous change in capacitance could be explained with a simple model involved with a spontaneous electric polarization between top hBN and graphene. Our work provides more insights into the mysterious ferroelectricity in graphene/hBN moir\'e heterostructures and paves the way to the understanding of the underlying mechanism., Comment: 20 pages, 13 figures

Two-dimensional metal-halide perovskites are highly versatile for light-driven applications due to their exceptional variety in material composition, which can be exploited for tunability of mechanical and optoelectronic properties. The band edge emission is defined by structure and composition of both organic and inorganic layers, and electron-phonon coupling plays a crucial role in the recombination dynamics. However, the nature of the electron-phonon coupling and which kind of phonons are involved is still under debate. Here we investigate the emission, reflectance and phonon response from single two-dimensional lead-iodide microcrystals with angle-resolved polarized spectroscopy. We find an intricate dependence of the emission polarization with the vibrational directionality in the materials, which reveals that several bands of the low-frequency phonons with non-orthogonal directionality contribute to the band edge emission. Such complex electron-phonon coupling requires adequate models to predict the thermal broadening of the emission and provides opportunities to design its polarization properties., Comment: 22 pages, 4 figures

In-plane anisotropic layered materials (ALMs), such as black phosphorus (BP), exhibit unique angle-resolved polarized Raman (ARPR) spectroscopy characteristics, as attributed to birefringence, linear dichroism and complex Raman tensor. Moreover, the ARPR intensity profiles of BP flakes deposited on multilayer dielectrics are notably sensitive to their thickness, owing to interference effects. The intricate anisotropic effects present challenges in accurately predicting the ARPR intensity of BP flakes. In this study, we propose a comprehensive strategy for predicting the ARPR intensity of BP flakes by explicitly considering optical anisotropy, encompassing birefringence, linear dichroism, and anisotropic cavity interference effects within multilayered structures. Through this approach, we have identified the intrinsic complex Raman tensors for phonon modes, independent of the BP flake thickness. By leveraging this methodology, we have elucidated the flake thickness-dependent effective complex Raman tensor elements, allowing for precise prediction of the observed ARPR intensity profile for the BP flake. This work provides a profound understanding of ARPR behaviors for ALM flakes., Comment: 6 pages, 4 figures

Graphene is an ideal platform to study the coherence of quantum interference pathways by tuning doping or laser excitation energy. The latter produces a Raman excitation profile that provides direct insight into the lifetimes of intermediate electronic excitations and, therefore, on quantum interference, which has so far remained elusive. Here, we control the Raman scattering pathways by tuning the laser excitation energy in graphene doped up to 1.05eV, above what achievable with electrostatic doping. The Raman excitation profile of the G mode indicates its position and full width at half maximum are linearly dependent on doping. Doping-enhanced electron-electron interactions dominate the lifetime of Raman scattering pathways, and reduce Raman interference. This paves the way for engineering quantum pathways in doped graphene, nanotubes and topological insulators., Comment: 18 pages, 4 figures

The atomically thin MnBi2Te4 crystal is a novel magnetic topological insulator, exhibiting exotic quantum physics. Here we report a systematic investigation of ultrafast carrier dynamics and coherent interlayer phonons in few-layer MnBi2Te4 as a function of layer number using time-resolved pump-probe reflectivity spectroscopy. Pronounced coherent phonon oscillations from the interlayer breathing mode are directly observed in the time domain. We find that the coherent oscillation frequency, the photocarrier and coherent phonon decay rates all depend sensitively on the sample thickness. The time-resolved measurements are complemented by ultralow-frequency Raman spectroscopy measurements, which both confirm the interlayer breathing mode and additionally enable observation of the interlayer shear mode. The layer dependence of these modes allows us to extract both the out-of-plane and in-plane interlayer force constants. Our studies not only reveal the interlayer van der Waals coupling strengths, but also shed light on the ultrafast optical properties of this novel two-dimensional material.

Structural and superconducting transitions of layered van der Waals (vdW) hydrogenated germanene (GeH) were observed under high-pressure compression and decompression processes. GeH possesses a superconducting transition at critical temperature (Tc) of 5.41 K at 8.39 GPa. A crystalline to amorphous transition occurs at 16.80 GPa while superconductivity remains. An abnormally increased Tc up to 6.1 K has been observed in the decompression process while the GeH remained amorphous. Thorough in-situ high-pressure synchrotron X-ray diffraction and in-situ high-pressure Raman spectroscopy with the density functional theory simulations suggest that the superconductivity of GeH should be attributed to the increased density of states at the Fermi level as well as the enhanced electron-phonon coupling effect under high pressure. The decompression-driven superconductivity enhancement arises from pressure-induced phonon softening related to an in-plane Ge-Ge phonon mode. As an amorphous metal hydride superconductor, GeH provides a platform to study amorphous hydride superconductivity in layered vdW materials., Comment: 22 Pages, 4 Figures

Materials with ultralow thermal conductivity are of great interest for efficient energy conversion and thermal barrier coating. Copper-based semiconductors such as copper chalcogenides and copper halides are known to possess extreme low thermal conductivity, whereas the fundamental origin of the low thermal conductivity observed in the copper-based materials remains elusive. Here, we reveal that s-d coupling induced giant phonon anharmonicity is the fundamental mechanism responsible for the ultralow thermal conductivity of copper compounds. The symmetry controlled strong coupling of high-lying occupied copper 3d orbital with the unoccupied 4s state under thermal vibration remarkably lowers the lattice potential barrier, which enhances anharmonic scattering between phonons. This understanding is confirmed by temperature-dependent Raman spectra measurements. Our study offers an insight at atomic level connecting electronic structures with phonon vibration modes, and thus sheds light on materials properties that rely on electron-phonon coupling, such as thermoelectricity and superconductivity.

The acoustic modes of diamond not only are of profound significance for studying its thermal conductivity, mechanical properties and optical properties, but also play a determined role in the performance of high-frequency and high-power acoustic wave devices. Here we report the bulk acoustic waves (BAWs) and surface acoustic waves (SAWs) of single crystal diamond by using the angle-resolved Brillouin light scattering (BLS) spectroscopy. We identify two high-velocity surface skimming bulk waves, with sound velocities of 1.277x10^6 and 1.727x10^6 cm/s, respectively. Furthermore, we conduct the relationship among the refractive index, incident angle and the velocities of BAWs propagating along an arbitrary direction. Our results may provide a valuable reference for fundamental researches and devices engineering in the community of diamond-based acoustic study.

Quantum spin liquid (QSL) represents a new class of condensed matter states characterized by the long-range many-body entanglement of topological orders. The most prominent feature of the elusive QSL state is the existence of fractionalized spin excitations. Subject to the strong quantum fluctuations, the spin-1/2 antiferromagnetic system on a kagome lattice is the promising candidate for hosting a QSL ground state, but the structurally ideal realization is rare. Here, we report Raman scattering on the single crystalline Cu$_3$Zn(OH)$_6$FBr, and confirm that the ideal kagome structure remains down to low temperatures without any lattice distortion by the angle-resolved polarized Raman responses and second-harmonic-generation measurements. Furthermore, at low temperatures the Raman scattering reveals a continuum of the spin excitations in Cu$_3$Zn(OH)$_6$FBr, in contrast to the sharp magnon peak in the ordered kagome antiferromagnet EuCu$_3$(OH)$_6$Cl$_3$. Such magnetic Raman continuum, in particular, the substantial low-energy one-pair spinon excitation serves as strong evidence for fractionalized spin excitations in Cu$_3$Zn(OH)$_6$FBr., Comment: 4+13 figures

In moir\'e crystals formed by stacking van der Waals (vdW) materials, surprisingly diverse correlated electronic phases and optical properties can be realized by a subtle change in the twist angle. Here, we discover that phonon spectra are also renormalized in MoS$_2$ twisted bilayers, adding a new perspective to moir\'e physics. Over a range of small twist angles, the phonon spectra evolve rapidly due to ultra-strong coupling between different phonon modes and atomic reconstructions of the moir\'e pattern. We develop a new low-energy continuum model for phonons that overcomes the outstanding challenge of calculating properties of large moir\'e supercells and successfully captures essential experimental observations. Remarkably, simple optical spectroscopy experiments can provide information on strain and lattice distortions in moir\'e crystals with nanometer-size supercells. The newly developed theory promotes a comprehensive and unified understanding of structural, optical, and electronic properties of moir\'e superlattices., Comment: 21 pages, 4 figures

The electronic Raman scattering (ERS) features of single-walled carbon nanotubes (SWNTs) can reveal a wealth of information about their electronic structures, but have previously been thought to appear exclusively in metallic (M-) but not in semiconducting (S-) SWNTs. We report the experimental observation of the ERS features with an accuracy of 1 meV in suspended S-SWNTs, the processes of which are accomplished via the available high-energy electron-hole pairs. The ERS features can facilitate further systematic studies on the properties of SWNT, both metallic and semiconducting, with defined chirality., Comment: 12 pages, 4 figures and 1 table

Magneto-optical effect refers to a rotation of polarization plane, which has been widely studied in traditional ferromagnetic metal and insulator films and scarcely in two-dimensional layered materials. Here we uncover a new nonreciprocal magneto-inelastic light scattering effect in ferromagnetic few-layer CrI3. We observed a rotation of the polarization plane of inelastic light scattering between -20o and +60o that are tunable by an out-of-plane magnetic field from -2.5 to 2.5 T. It is experimentally observed that the degree of polarization can be magnetically manipulated between -20% and 85%. This work raises a new magneto-optical phenomenon and could create opportunities of applying 2D ferromagnetic materials in Raman lasing, topological photonics, and magneto-optical modulator for information transport and storage.

The selection rule for angle-resolved polarized Raman (ARPR) intensity of phonons from standard group-theoretical method in isotropic materials would break down in anisotropic layered materials (ALMs) due to birefringence and linear dichroism effects. The two effects result in depth-dependent polarization and intensity of incident laser and scattered signal inside ALMs and thus make a challenge to predict ARPR intensity at any laser incidence direction. Herein, taking in-plane anisotropic black phosphorus as a prototype, we developed a so-called birefringence-linear-dichroism (BLD) model to quantitatively understand its ARPR intensity at both normal and oblique laser incidences by the same set of real Raman tensors for certain laser excitation. No fitting parameter is needed, once the birefringence and linear dichroism effects are considered with the complex refractive indexes. An approach was proposed to experimentally determine real Raman tensor and complex refractive indexes, respectively, from the relative Raman intensity along its principle axes and incident-angle resolved reflectivity by Fresnel$'$s law. The results suggest that the previously reported ARPR intensity of ultrathin ALM flakes deposited on a multilayered substrate at normal laser incidence can be also understood based on the BLD model by considering the depth-dependent polarization and intensity of incident laser and scattered Raman signal induced by both birefringence and linear dichroism effects within ALM flakes and the interference effects in the multilayered structures, which are dependent on the excitation wavelength, thickness of ALM flakes and dielectric layers of the substrate. This work can be generally applicable to any opaque anisotropic crystals, offering a promising route to predict and manipulate the polarized behaviors of related phonons., Comment: Accepted by Science Bulletin

Information technology demands high-speed optoelectronic devices, but going beyond the one terahertz (THz) barrier is challenging due to the difficulties associated with generating, detecting, and processing high-frequency signals. Here, we show that femtosecond-laser-driven phonons can be utilized to coherently manipulate the excitonic properties of semiconductors at THz frequencies. The precise control of the pump and subsequent time-delayed broadband probe pulses enables the simultaneous generation and detection processes of both periodic lattice vibrations and their couplings with electronic states. Combining ultralow frequency Raman spectroscopy with first-principles calculations, we identify the unique phonon mode-selective and probe-energy dependent features of electron-phonon interactions in layered PdSe2. Two distinctive types of coherent phonon excitations could couple preferentially to different types of electronic excitations: the intralayer (4.3 THz) mode to carriers and the interlayer (0.35 THz) mode to excitons. This work provides new insights to understand the excited-state phonon interactions of 2D materials, and to achieve future applications of optoelectronic devices operating at THz frequencies.

The interaction between excitons and phonons in semiconductor nanocrystals plays a crucial role in the exciton energy spectrum and dynamics, and thus in their optical properties. We investigate the exciton2 phonon coupling in giant-shell CdSe/CdS core-shell nanocrystals via resonant Raman spectroscopy. The Huang-Rhys parameter is evaluated by the intensity ratio of the longitudinal-optical (LO) phonon of CdS with its first multiscattering (2LO) replica. We used four different excitation wavelengths in the range from the onset of the CdS shell absorption to well above the CdS shell band edge to get insight into resonance effects of the CdS LO phonon with high energy excitonic transitions. The isotropic spherical giant-shell nanocrystals show consistently stronger exciton-phonon coupling as compared to the anisotropic rod-shaped dot-in-rod (DiR) architecture, and the 2LO/LO intensity ratio decreases for excitation wavelengths approaching the CdS band edge. The strong exciton-phonon coupling in the spherical giant-shell nanocrystals can be related to the delocalization of the electronic wave functions. Furthermore, we observe the radial breathing modes of the GS nanocrystals and their overtones by ultralow frequency Raman spectroscopy with nonresonant excitation, using laser energies well below the band gap of the heteronanocrystals, and highlight the differences between higher order, Comment: 16 pages, 3 figures

The vibrational modes in organic/inorganic layered perovskites are of fundamental importance for their optoelectronic properties. The hierarchical architecture of the Ruddlesden-Popper phase of these materials allows for distinct directionality of the vibrational modes withrespect to the main axes of the pseudocubic lattice in the octahedral plane. Here, we study the directionality of the fundamental phonon modes in single exfoliated Ruddlesden-Popper perovskite flakes with polarized Raman spectroscopy at ultralow-frequencies. A wealth of Raman bands is distinguished in the range from 15-150 cm-1 (2-15 meV), whose features depend on the organic cation species, on temperature, and on the direction of the linear polarization of the incident light. By controlling the angle of the linear polarization of the excitation laser with respect to the in-plane axes of the octahedral layer, we gain detailed information on the symmetry of the vibrational modes. The choice of two different organic moieties, phenethylammonium (PEA) and butylammonium (BA) allows to discern the influence of the linker molecules, evidencing strong anisotropy of the vibrations for the (PEA)2PbBr4 samples. Temperature dependent Raman measurements reveal that the broad phonon bands observed at room temperature consist of a series of sharp modes, and that such mode splitting strongly differs for the different organic moieties and vibrational bands., Comment: 25 pages, 4 figures

The Raman selection rules arise from the crystal symmetry and then determine the Raman activity and polarization of scattered phonon modes. However, these selection rules can be broken in resonant process due to the strong electron-phonon coupling effect. Here we reported the observation of breakdown of Raman selection rules in few-layer WS$_2$ by using resonant Raman scattering with dark A exciton. In this case, not only the infrared active modes and backscattering forbidden modes are observed, but the intensities of all observed phonon modes become strongest under paralleled-polarization and independent on the Raman tensors of phonons. We attributed this phenomenon to the interaction between dark A exciton and the scatted phonon, the so-called intraband Fr\"{o}hlich interaction, where the Raman scattering possibility is totally determined by the symmetry of exciton rather than the phonons due to strong electron-phonon coupling. Our results not only can be used to easily detect the optical forbidden excitonic and phononic states but also provide a possible way to manipulate optical transitions between electronic levels., Comment: 3 Figures

A stable single-photon source working at high temperatures with high brightness and covering full band emission from one host material is critically important for quantum technologies. Here, we find that the certain hBN single-photon emissions (SPEs) can be significantly enhanced by lasers with special wavelengths, which largely broaden the wavelength range of the hBN emitters, down to ultraviolet (357 nm) and up to near-infrared (912 nm). Importantly, these hBN SPEs are still stable even at the temperature up to 1100 Kelvin. The decoupling between single-photon and acoustic phonon is observed at high temperatures. Our work suggests that hBN can be a good host material for generating single-photon sources with ultrabroad wavelength range., Comment: 4 Figures

Anisotropic photonic materials with linear dichroism are crucial components in many sensing, imaging and communication applications. Such materials play an important role as polarizers, filters and wave-plates in photonic devices and circuits. Conventional crystalline materials with optical anisotropy typically show unidirectional linear dichroism over a broad wavelength range. The linear dichroism conversion phenomenon has not been observed in crystalline materials. Here, we report the investigation of the unique linear dichroism conversion phenomenon in quasi-one-dimensional (quasi-1D) hexagonal perovskite chalcogenide BaTiS3. The material shows record level of optical anisotropy within the visible wavelength range. In contrast to conventional anisotropic optical materials, the linear dichroism polarity in BaTiS3 makes an orthogonal change at an optical wavelength corresponding to the photon energy of 1.78 eV. First principle calculations reveal that this anomalous linear dichroism conversion behavior originates from different selection rules of the optical transitions from the parallel bands in the BaTiS3 material. Wavelength dependent polarized Raman spectroscopy further confirms this phenomenon. Such material with linear dichroism conversion property can facilitate new ability to control and sense the energy and polarization of light, and lead to novel photonic devices such as polarization-wavelength selective detectors and lasers for multispectral imaging, sensing and optical communication applications.

We report the observations of unexpected layer-dependent, strong, and anisotropic second harmonic generations (SHGs) in atomically thin ReS2. Appreciable (negligible) SHGs are obtained from even (odd) numbers of ReS2 layers, which is opposite to the layer-dependence of SHGs in group VI transition metal dichalcogenides, such as MoS2 and WS2. The results are analyzed from ReS2's crystal structure, implying second harmonic polarizations generated from the interlayer coupling. Pumped by a telecomband laser, SHG from the bilayer ReS2 is almost one order of magnitude larger than that from the monolayer WS2. The estimated second-order nonlinear susceptibility of 900 pm/V is remarkably high among those reported in two-dimensional materials. The laser polarization dependence of ReS2's SHG is strongly anisotropic and indicates its distorted lattice structure with more unequal and non-zero second-order susceptibility elements.

Pentagon is one of the most beautiful geometric structures in nature, but it is rarely seen simply because five-fold symmetry is mathematically forbidden in a 2D or 3D periodic lattices. Fortunately, pentagon as a structural element is allowed in 1D or 0D systems, since translational symmetry is not necessary there. However, in these systems pentagons only compose a small portion of the structure. So far, 1D or 0D systems consisting of purely pentagons are still rare. Here, combing high resolution non-contact atomic force microscopy and tip-enhanced Raman spectroscopy, we have directly visualized the pentagon-ring structure in self-assembled Si nanoribbons and magic clusters on Ag(110) substrate. Moreover, chemical fingerprint of Si pentagon was detected in individual Si nanoribbon and clusters by tip-enhanced Raman spectroscopy. This work demonstrates that Si pentagon can be an important element in building silicon nanostructures, which may find potential applications in future nanoelectronics based on silicon., Comment: 4 figures

The optical properties of the two-dimensional (2D) crystals are dominated by tightly bound electron-hole pairs (excitons) and lattice vibration modes (phonons). The exciton-phonon interaction is fundamentally important to understand the optical properties of 2D materials and thus help develop emerging 2D crystal based optoelectronic devices. Here, we presented the excitonic resonant Raman scattering (RRS) spectra of few-layer WS$_2$ excited by 11 lasers lines covered all of A, B and C exciton transition energies at different sample temperatures from 4 to 300 K. As a result, we are not only able to probe the forbidden phonon modes unobserved in ordinary Raman scattering, but also can determine the bright and dark state fine structures of 1s A exciton. In particular, we also observed the quantum interference between low-energy discrete phonon and exciton continuum under resonant excitation. Our works pave a way to understand the exciton-phonon coupling and many-body effects in 2D materials., Comment: 14 pages, 11 figures

Multilayer graphene (MLG) grown by chemical vapor deposition (CVD) is a promising material for electronic and optoelectronic devices. Understanding the stacking configuration and interlayer coupling of MLGs is technologically relevant and of importance for the device applications. Here, we reported a kind of twisted MLGs (tMLGs), which are formed by stacking one graphene monolayer on the top of AB-stacked MLG by rotating a certain angle between them. The twist angle of tMLGs are identified by the twist-related modes, R and R'. With increasing the total layer number of N, the observed interlayer shear modes in the tMLG flake always follow those of AB-stacked (N-1)LG, while the observed interlayer breathing modes always follow those of AB-stacked NLG, independent of its twist angle. The layer breathing coupling of the tMLGs is almost identical to that of mechanically-exfoliated tMLGs, which demonstrates the high quality of MLGs grown by CVD. This study provides an applicable approach to probe the stacking configuration and interlayer coupling of MLGs grown by CVD or related methods. This work also demonstrates the possibility to grow MLG flakes with a fixed stacking configuration, $e.g.$, t(1+$n$)LG, by the CVD method., Comment: 11 pages, 5 figure, accepted by Carbon

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

The anisotropic two-dimensional (2D) van der Waals (vdW) layered materials, with both scientific interest and potential application, have one more dimension to tune the properties than the isotropic 2D materials. The interlayer vdW coupling determines the properties of 2D multi-layer materials by varying stacking orders. As an important representative anisotropic 2D materials, multilayer rhenium disulfide (ReS2) was expected to be random stacking and lack of interlayer coupling. Here, we demonstrate two stable stacking orders (aa and a-b) of N layer (NL, N>1) ReS2 from ultralow-frequency and high-frequency Raman spectroscopy, photoluminescence spectroscopy and first-principles density functional theory calculation. Two interlayer shear modes are observed in aa-stacked NL-ReS2 while only one interlayer shear mode appears in a-b-stacked NL-ReS2, suggesting anisotropic-like and isotropic-like stacking orders in aa- and a-b-stacked NL-ReS2, respectively. The frequency of the interlayer shear and breathing modes reveals unexpected strong interlayer coupling in aa- and a-b-NL-ReS2, the force constants of which are 55-90% to those of multilayer MoS2. The observation of strong interlayer coupling and polytypism in multi-layer ReS2 stimulate future studies on the structure, electronic and optical properties of other 2D anisotropic materials.

Two-dimensional Molybdenum Disulfide (MoS2) has shown promising prospects for the next generation electronics and optoelectronics devices. The monolayer MoS2 can be patterned into quasi-one-dimensional anisotropic MoS2 nanoribbons (MNRs), in which theoretical calculations have predicted novel properties. However, little work has been carried out in the experimental exploration of MNRs with a width of less than 20 nm where the geometrical confinement can lead to interesting phenomenon. Here, we prepared MNRs with width between 5 nm to 15 nm by direct helium ion beam milling. High optical anisotropy of these MNRs is revealed by the systematic study of optical contrast and Raman spectroscopy. The Raman modes in MNRs show strong polarization dependence. Besides that the E' and A'1 peaks are broadened by the phonon-confinement effect, the modes corresponding to singularities of vibrational density of states are activated by edges. The peculiar polarization behavior of Raman modes can be explained by the anisotropy of light absorption in MNRs, which is evidenced by the polarized optical contrast. The study opens the possibility to explore quasione-dimensional materials with high optical anisotropy from isotropic 2D family of transition metal dichalcogenides.