We investigate the vibrational properties and Raman spectra of two-dimensional Ga$_2$O$_3$ monolayer, using density functional theory. Two ferroelectric (FE) phases of Ga$_2$O$_3$ monolayer with wurtzite(WZ) and zincblende(ZB) structures( FE-WZ and FE-ZB, respectively ) are considered. The Raman tensor and angle-dependent Raman intensities of two major Raman peak ($A^1_1$ and $A^2_1$) in both FE-WZ (497, and 779 cm$^{-1}$) and FE-ZB (481, and 772 cm$^{-1}$) Ga$_2$O$_3$ monolayers are calculated for the polarizations of scattered light parallel and perpendicular to that of the incident light. The characteristics of angle-dependent Raman intensities are analyzed. The averaged non-resonant Raman spectra of minor peaks in FE-WZ($E^1$) and FE-BZ($E^1$ and $E^2$) are compared with that of major peaks $A^1_1$ and $A^2_1$ . These predictions on Raman spectra of Ga$_2$O$_3$ monolayer may guide rational design of two-dimensional optical devices.
Since double resonance Raman (DRR) spectra are laser-energy dependent, the first-principles calculations of DRR for two-dimensional materials are challenging. Here, the DRR spectrum of monolayer MoTe$_2$ is calculated by home-made program, in which we combine {\em ab-initio} density-functional-theory calculations with the electron-phonon Wannier (EPW) method. Within the fourth-order perturbation theory, we are able to quantify not only the electron-photon matrix elements within the dipole approximation, but also the electron-phonon matrix elements using the Wannier functions. The reasonable ag…
Monolayers of hexagonal boron nitride (h-BN) can in principle be identified by a Raman signature, consisting of an upshift in the frequency of the E2g vibrational mode with respect to the bulk value, but the origin of this shift (intrinsic or support-induced) is still debated. Herein we use density functional theory calculations to investigate whether there is an intrinsic Raman shift in the h-BN monolayer in comparison with the bulk. There is universal agreement among all tested functionals in predicting the magnitude of the frequency shift upon a variation in the in-plane cell parameter. It …
Orhorhombic $α$-MoO$_3$ is a layered oxide with various applications and with excellent potential to be exfoliated as a 2D ultrathin film or monolayer. In this paper, we present a first-principles computational study of its vibrational properties. Our focus is on the zone center modes which can be measured by a combination of infared and Raman spectroscopy. The polarization dependent spectra are simulated. Calculations are also performed for a monolayer form in which "double layers" of Mo$_2$O$_6$ which are weakly van der Waals bonded in the $α$-structure are isolated. Shift in phonon frequenc…
Janus transition metal dichalcogenides (TMDs) lose the horizontal mirror symmetry of ordinary TMDs, leading to the emergence of additional features, such as native piezoelectricity, Rashba effect, and enhanced catalytic activity. While Raman spectroscopy is an essential nondestructive, phase- and composition-sensitive tool to monitor the synthesis of materials, a comprehensive study of the Raman spectrum of Janus monolayers is still missing. Here, we discuss the Raman spectra of WSSe and MoSSe measured at room and cryogenic temperatures, near and off resonance. By combining polarization-resolv…
The weakly screened electron-hole interactions in an atomically thin semiconductor not only downshift its excitation spectrum from a quasiparticle one, but also redistribute excitation energies and wavefunction characters with profound effects on diverse modes of material response, including the exciton-phonon scattering processes accessible to resonant Raman measurements. Here we develop a first-principles framework to calculate frequency-dependent resonant Raman intensities that includes excitonic effects and goes beyond the Placzek approximation. We show how excitonic effects in MoS2 strong…
We report a comprehensive temperature dependent Raman measurements on three different phases of monolayer WS2 from 4K to 330K in a wide spectral range. Our studies revels the anomalous nature of the first as well as the higher order combination modes reflected in the disappearance of the few modes and anomalous temperature evaluation of the phonon self-energy parameters attributed to the detuning of resonance condition and development of strain due to thermal expansion mismatch with the underlying substrate. Our detailed temperature dependence studies also decipher the ambiguity about assignme…
A contrastive investigation of the symmetry aspects of phonons in monolayer chromium trihalides and their Janus structures Y$_3$-Cr$_2$-X$_3$ (X, Y = F, Cl, Br, I) by group theory is presented. We first classify all phonons at the Brillouin-zone center ($Γ$) into the irreducible representation. Then the infrared and Raman activity of optic phonons, Raman tensors, and the possible polarization assignments of R active phonons are predicted. Base on these results, we clarify the the discrepancy about the Raman activity o optic modes in monolayer CrI$_3$. Besides, we find that the Raman and infrar…
The electrical and thermal behavior of nanoscale devices based on two-dimensional (2D) materials is often limited by their contacts and interfaces. Here we report the temperature-dependent thermal boundary conductance (TBC) of monolayer MoS$_2$ with AlN and SiO$_2$, using Raman thermometry with laser-induced heating. The temperature-dependent optical absorption of the 2D material is crucial in such experiments, which we characterize here for the first time above room temperature. We obtain TBC ~ 15 MWm$^-$$^2$K$^-$$^1$ near room temperature, increasing as ~ T$^0$$^.$$^6$$^5$ in the range 300 -…
Resonant Raman signatures of bright and momentum-dark exciton coupled by intervalley phonon scattering in monolayer WSe2
University of Münster（明斯特大学）；Center for Soft Nanoscience (SoN), University of Münster（明斯特大学软纳米科学中心）；Technical University of Munich（慕尼黑工业大学）；Walter Schottky Institut and Physics Department, Technical University of Munich（慕尼黑工业大学沃尔特·肖特基研究所与物理系）；MCQST, München（慕尼黑量子科学与技术中心）
Atomically thin layer transition metal dichalcogenides have been intensively investigated for their rich optical properties and potential applications in nano-electronics. In this work, we study the incoherent optical phonon and exciton population dynamics in monolayer WS2 by time-resolved spontaneous Raman scattering spectroscopy. Upon excitation of the exciton transition, both the Stokes and anti-Stokes optical phonon scattering strength exhibit a large reduction. Based on the detailed balance, the optical phonon population is retrieved, which shows an instant build-up and a relaxation lifet…
The effect of bis(trifluoromethane) sulfonimide (TFSI, superacid) treatment on the optical properties of MoS$_2$ monolayers is investigated by means of photoluminescence, reflectance contrast and Raman scattering spectroscopy employed in a broad temperature range. It is shown that when applied multiple times, the treatment results in progressive quenching of the trion emission/absorption and in the redshift of the neutral exciton emission/absorption associated with both the A and B excitonic resonances. Based on this evolution, a trion complex related to the B exciton in monolayer MoS$_2$ is u…
Raman spectroscopy is frequently used to identify composition, structure and layer thickness of 2D materials. Here, we describe an efficient first-principles workflow for calculating resonant first-order Raman spectra of solids within third-order perturbation theory employing a localized atomic orbital basis set. The method is used to obtain the Raman spectra of 733 different monolayers selected from the computational 2D materials database (C2DB). We benchmark the computational scheme against available experimental data for 15 known monolayers. Furthermore, we propose an automatic procedure fo…
In recent years, two-dimensional (2D) layered semiconductors have received much attention for their potential in next-generation electronics and optoelectronics. Wide-bandgap 2D semiconductors are especially important in blue and ultraviolet wavelength region, while there are very few 2D materials in this region. Here, monolayer \b{eta}-type zirconium nitride chloride (\b{eta}-ZrNCl) is isolated for the first time, which is an air-stable layered material with a bandgap of ~3.0 eV in bulk. Systematical investigation of layer-dependent Raman scattering of ZrNCl from monolayer, bilayer, to bulk r…
Electron-phonon(e-ph) interaction in Ca2N monolayer, the first electrene material with two-dimensional(2D) electron gas floating in free space, is expected to be very weak and such a character can be used to design weak-scattering transport channels. Therefore, it is highly desirable to quantitatively evaluate the carrier mobility of electrene. In this study, e-ph interaction in Ca2N monolayer is investigated using a precise Wannier interpolation-based first principles technique. The calculated e-ph coupling matrix elements of Ca2N monolayer are indeed small compared to other 2D materials such…
Gold-mediated exfoliation of MoS2 has attracted considerable interest in the recent years. A strong interaction between MoS2 and Au facilitates preferential production of centimeter-sized monolayer MoS2 with near-unity yield and provides a heterostructure system noteworthy from a fundamental standpoint. However, little is known about the detailed nature of the MoS2-Au interaction and its evolution with the MoS2 thickness. Here, we identify specific vibrational and binding energy fingerprints of such strong interaction using Raman and X-ray photoelectron spectroscopy, which indicate substantial…
The deposition of a monolayer by direct self-assembly from solution of an active spin-crossover (SCO) complex via chemisorption has been achieved starting from the perchlorate salt of Co(II) bis(4-(4-carboxyphenyl)-2,2:6,2-terpyridine). MALDI-TOF MS, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) confirm the presence of an intact monolayer of SCO molecules grafted through carboxylate groups to the Ag surface. Three different spectroscopic techniques (Raman, XPS and X-ray Absorption spectroscopy, XAS) evidence a thermal spin transition of such monolayer of molecules. To our knowl…
Janus monolayer transition metal dichalcogenides, where one of the two chalcogen layers is substituted with a different kind of chalcogen atoms, are pushing the properties of two dimensional materials into new territories. Yet only little is known about this new kind of material class, mainly due to the challenging synthesis. In this work we propose a method to prepare high quality Janus MoSSe monolayers from as-exfoliated MoSe2 by thermal sulfurization. With this we aim to pave a way for more exotic Janus monolayers, which have been out of the experimental reach thus far. The synthesized MoSS…
Two-dimensional materials that exhibit spontaneous electric polarization are of notable interest for functional materials. However, despite many two-dimensional polar materials are predicted in theory, the number of experimentally confirmed two-dimensional ferroelectrics are still far less than bulk ferroelectrics. We provide strong evidence that the Pmn2$_1$ phase of arsenic chalcogenides As$_2$X$_3$ (X=S, Se, and Te), which include the recently isolated monolayer orpiment, are intrinsic ferroelectrics and demonstrate strong in-plane piezoelectricity. We found the calculated energy barriers f…
Laser-assisted chemical modification is demonstrated on ultra-thin transition-metal dichalcogenides (TMDs), locally replacing selenium by sulfur atoms. The photo-conversion process takes place in a controlled reactive gas environment and the heterogeneous reaction rates are monitored via in situ real-time Raman and photoluminescence spectroscopies. The spatially localized photo-conversion resulted in a heterogeneous TMD structure, with chemically distinct domains, where the initial high crystalline quality of the film is not affected during the process. This has been further confirmed via tran…
There has been a massive growth in the study of transition metal dichalcogenides (TMDs) over the past decade, based upon their interesting and unusual electronic, optical and mechanical properties, such as tuneable and strain-dependent bandgaps. Tungsten disulfide (WS2), as a typical example of TMDs, has considerable potential in applications such as strain engineered devices and the next generation multifunctional polymer nanocomposites. However, controlling the strain, or more practically, monitoring the strain in WS2 and the associated micromechanics have not been so well studied. Both phot…
Certain significant fallacies are involved in discussions of the high-Tc mechanism unsolved for over 30 years in cuprate superconductors. These fallacies are explored with the aim of unravelling this mechanism. Moreover, using polarised electronic Raman scattering in inhomogeneous underdoped cuprate superconductors, the intrinsic nonlinear Raman spectrum is obtained by subtracting the pseudogap characteristic of a nonlinear from the linear Raman spectrum measured in the B2g mode of the node area below the critical temperature. The intrinsic nonlinear behaviour implies the existence of the noda…
