Search

Understanding the phase transition mechanisms in two-dimensional (2D) materials is a key to precisely tailor their properties at the nanoscale. Molybdenum ditelluride (MoTe2) exhibits multiple phases at room temperature, making it a promising candidate for phase-change applications. Here, we fabricate lateral 2H-Td interfaces with laser irradiation and probe their phase transitions from micro- to atomic scales with in situ heating in the transmission electron microscope (TEM). By encapsulating the MoTe2 with graphene protection layers, we create an in situ reaction cell compatible with atomic resolution imaging. We find that the Td-to-2H phase transition initiates at phase boundaries at low temperatures (200-225 degree C) and propagates anisotropically along the b-axis in a layer-by-layer fashion. We also demonstrate a fully reversible 2H-Td-2H phase transition cycle, which generates a coherent 2H lattice containing inversion domain boundaries. Our results provide insights on fabricating 2D hetero-phase devices with atomically sharp and coherent interfaces., Comment: 38 pages, 5 figures, 9 supplementary figures, and supplementary information

In this paper, we report a facile process to fabricate CuO/Au core/shell nanowires, where CuO core and Au shell were prepared by thermal oxidation and sputtering, respectively. The as-prepared CuO/Au nanowires are highly sensitive surface-enhanced-Raman-scattering (SERS) substrates, which can detect methylene blue down to a very low concentration of 10−13 M. The major advantages of SERS substrates based on CuO/Au core/shell nanowires compared with others SERS substrates are the high sensitivity, uniformity, and purity due to the absence of any organic surfactants in the synthesis process.

We investigated temperature-dependent nanoscale conduction in an epitaxial VO2 film grown on an Al2O3 substrate using conductive-atomic force microscopy and deep data analysis.

HxRuO2 acts as a standalone catalyst exhibiting selective hydrogenation under mild conditions. Mobile protons embedded in the oxide lattice play an important role in stabilizing the distorted structure, and facile proton dynamics is key to improving catalytic properties.

We performed polarized Raman spectroscopy on mechanically exfoliated few-layer MoTe2 samples and observed both 1T' and Td phases at room temperature. Few-layer 1T' and Td MoTe2 exhibited a significant difference especially in interlayer vibration modes, from which the interlayer coupling strengths were extracted using the linear chain model: strong in-plane anisotropy was observed in both phases. Furthermore, temperature-dependent Raman measurements revealed a peculiar phase transition behavior in few-layer 1T' MoTe2. In contrast to bulk 1T' MoTe2 crystals where the phase transition to the Td phase occurs at ~250 K, the temperature-driven phase transition to the Td phase is increasingly suppressed as the thickness is reduced, and the transition and the critical temperature varied dramatically from sample to sample even for the same thickness. Raman spectra of intermediate phases that correspond to neither 1T' nor Td phase with different interlayer vibration modes were observed, which suggests that several metastable phases exist with similar total energies., Comment: 58 pages (32 pages of main text, 26 pages of Supporting Information), to be published in ACS Nano

An exciton is the bosonic quasiparticle of electron–hole pairs bound by the Coulomb interaction1. Bose–Einstein condensation of this exciton state has long been the subject of speculation in various model systems2,3, and examples have been found more recently in optical lattices and two-dimensional materials4–9. Unlike these conventional excitons formed from extended Bloch states4–9, excitonic bound states from intrinsically many-body localized states are rare. Here we show that a spin–orbit-entangled exciton state appears below the Neel temperature of 150 kelvin in NiPS3, an antiferromagnetic van der Waals material. It arises intrinsically from the archetypal many-body states of the Zhang–Rice singlet10,11, and reaches a coherent state assisted by the antiferromagnetic order. Using configuration-interaction theory, we determine the origin of the coherent excitonic excitation to be a transition from a Zhang–Rice triplet to a Zhang–Rice singlet. We combine three spectroscopic tools—resonant inelastic X-ray scattering, photoluminescence and optical absorption—to characterize the exciton and to demonstrate an extremely narrow excitonic linewidth below 50 kelvin. The discovery of the spin–orbit-entangled exciton in antiferromagnetic NiPS3 introduces van der Waals magnets as a platform to study coherent many-body excitons. A spin–orbit-entangled exciton state in the van der Waals material NiPS3 is observed, and found to arise from many-body states of a Zhang–Rice singlet.

The evolution of the optical phonons in layered semiconductor alloys SnSe1-xSx is studied as a function of the composition by using polarized Raman spectroscopy with six different excitation wavelengths (784.8, 632.8, 532, 514.5, 488, and 441.6 nm). The polarization dependences of the phonon modes are compared with transmission electron diffraction measurements to determine the crystallographic orientation of the samples. Some of the Raman modes show significant variation in their polarization behavior depending on the excitation wavelengths. It is established that the maximum intensity direction of the Ag2 mode of SnSe1-xSx (0, X

The family of group IV-VI monochalcogenides has an atomically puckered layered structure, and their atomic bond configuration suggests the possibility for the realization of various polymorphs. Here, we report the synthesis of the first hexagonal polymorph from the family of group IV-VI monochalcogenides, which is conventionally orthorhombic. Recently predicted four-atomic-thick hexagonal GeSe, so-called {\gamma}-GeSe, is synthesized and clearly identified by complementary structural characterizations, including elemental analysis, electron diffraction, high-resolution transmission electron microscopy imaging, and polarized Raman spectroscopy. The electrical and optical measurements indicate that synthesized {\gamma}-GeSe exhibits high electrical conductivity of 3x10^5 S/m, which is comparable to those of other two-dimensional layered semimetallic crystals. Moreover, {\gamma}-GeSe can be directly grown on h-BN substrates, demonstrating a bottom-up approach for constructing vertical van der Waals heterostructures incorporating {\gamma}-GeSe. The newly identified crystal symmetry of {\gamma}-GeSe warrants further studies on various physical properties of {\gamma}-GeSe., Comment: 24 pages, 5 figures

As a 3D topological insulator, bismuth selenide (Bi2Se3) has potential applications for electrically and optically controllable magnetic and optoelectronic devices. Understanding the coupling with its topological phase requires studying the interactions of carriers with the lattice on time scales down to the subpicosecond regime. Here, we investigate the ultrafast carrier-induced lattice contractions and interlayer modulations in Bi2Se3 thin films by time-resolved diffraction using an X-ray free-electron laser. The lattice contraction depends on the carrier concentration and is followed by an interlayer expansion accompanied by oscillations. Using density functional theory and the Lifshitz model, the initial contraction can be explained by van der Waals force modulation of the confined free carrier layers. Our theoretical calculations suggest that the band inversion, related to a topological phase transition, is modulated by the expansion of the interlayer distance. These results provide insights into the topological phase control by light-induced structural change on ultrafast time scales.

Multiple quantum wells based on 2D semiconductors are realized by monolithic bandgap engineering and van der Waals stacking., Quantum wells (QWs), enabling effective exciton confinement and strong light-matter interaction, form an essential building block for quantum optoelectronics. For two-dimensional (2D) semiconductors, however, constructing the QWs is still challenging because suitable materials and fabrication techniques are lacking for bandgap engineering and indirect bandgap transitions occur at the multilayer. Here, we demonstrate an unexplored approach to fabricate atomic–layer–confined multiple QWs (MQWs) via monolithic bandgap engineering of transition metal dichalcogenides and van der Waals stacking. The WOX/WSe2 hetero-bilayer formed by monolithic oxidation of the WSe2 bilayer exhibited the type I band alignment, facilitating as a building block for MQWs. A superlinear enhancement of photoluminescence with increasing the number of QWs was achieved. Furthermore, quantum-confined radiative recombination in MQWs was verified by a large exciton binding energy of 193 meV and a short exciton lifetime of 170 ps. This work paves the way toward monolithic integration of band-engineered heterostructures for 2D quantum optoelectronics.

Van der Waals epitaxy on the surface of two-dimensional (2D) layered crystals has gained significant research interest for the assembly of well-ordered nanostructures and fabrication of vertical heterostructures based on 2D crystals. Although van der Waals epitaxial assembly on the hexagonal phase of transition metal dichalcogenides (TMDCs) has been relatively well characterized, a comparable study on the distorted octahedral phase (1T' or Td) of TMDCs is largely lacking. Here we investigate the assembly behavior of one-dimensional (1D) AgCN microwires on various distorted TMDC crystals, namely 1T'-MoTe2, Td-WTe2, and 1T'-ReS2. The unidirectional alignment of AgCN chains is observed on these crystals, reflecting the symmetry of underlying distorted TMDCs. Polarized Raman spectroscopy and transmission electron microscopy directly confirm that AgCN chains display the remarkable alignment behavior along the distorted chain directions of underlying TMDCs. The observed unidirectional assembly behavior can be attributed to the favorable adsorption configurations of 1D chains along the substrate distortion, which is supported by our theoretical calculations and observation of similar assembly behavior from different cyanide chains. The aligned AgCN microwires can be harnessed as facile markers to identify polymorphs and crystal orientations of TMDCs., 23 pages, 6 main figures

The behavior of 2-dimensional (2D) van der Waals (vdW) layered magnetic materials in the 2D limit of the few-layer thickness is an important fundamental issue for the understanding of the magnetic ordering in lower dimensions. The antiferromagnetic transition temperature TN of the Heisenberg-type 2D magnetic vdW material MnPS3 was estimated as a function of the number of layers. The antiferromagnetic transition was identified by temperature-dependent Raman spectroscopy, from the broadening of a phonon peak at 155 cm−1, accompanied by an abrupt redshift and an increase of its spectral weight. TN is found to decrease only slightly from ~78 K for bulk to ~66 K for 3L. The small reduction of TN in thin MnPS3 approaching the 2D limit implies that the interlayer vdW interaction is playing an important role in stabilizing magnetic ordering in layered magnetic materials.

The evolution of the optical phonons in layered semiconductor alloys SnSe(1–x)Sx is studied as a function of the composition by using polarized Raman spectroscopy with six different excitation wavelengths (784.8, 632.8, 532, 514.5, 488, and 441.6 nm). The polarization dependences of the phonon modes are compared with transmission electron diffraction measurements to determine the crystallographic orientation of the samples. Some of the Raman modes show significant variation in their polarization behavior depending on the excitation wavelengths. It is established that the maximum intensity direction of the Ag2 mode of SnSe(1−x)Sx (0 ≤ x ≤ 1) does not depend on the excitation wavelength and corresponds to the armchair direction. It is additionally found that the lower-frequency Raman modes of Ag1, Ag2 and B3g1 in the alloys show the typical one-mode behavior of optical phonons, whereas the higher-frequency modes of B3g2, Ag3 and Ag4 show two-mode behavior.

Gallium selenide (GaSe) is one of layered group-III metal monochalcogenides, which has an indirect bandgap in monolayer and direct bandgap in bulk unlike other conventional transition metal dichalcogenides (TMDs) such as MoX2 and WX2 (X=S and Se). Four polytypes of bulk GaSe, designated as beta-, epsilon-, gamma-, and delta-GaSe, have been reported. Since different polytypes result in different optical and electrical properties even for the same thickness, identifying the polytype is essential in utilizing this material for various optoelectronic applications. We performed polarized Raman measurement on GaSe and found different ultra-low-frequency Raman spectra of inter-layer vibrational modes even for the same thickness due to different stacking sequences of the polytypes. By comparing the ultra-low-frequency Raman spectra with theoretical calculations and high-resolution electron microscopy measurements, we established the correlation between the ultra-low-frequency Raman spectra and the stacking sequences for trilayer GaSe. We further found that the AB-type stacking is more stable than the AA'-type stacking in GaSe.

Many properties of layered materials change as they are thinned from their bulk forms down to single layers, with examples including indirect-to-direct band gap transition in 2H semiconducting transition metal dichalcogenides as well as thickness-dependent changes in the valence band structure in post-transition metal monochalcogenides and black phosphorus. Here, we use angle-resolved photoemission spectroscopy to study the electronic band structure of monolayer ReSe$_{2}$, a semiconductor with a distorted 1T structure and in-plane anisotropy. By changing the polarization of incoming photons, we demonstrate that for ReSe$_{2}$, in contrast to the 2H materials, the out-of-plane transition metal $d_{z^{2}}$ and chalcogen $p_{z}$ orbitals do not contribute significantly to the top of the valence band which explains the reported weak changes in the electronic structure of this compound as a function of layer number. We estimate a band gap of 1.7 eV in pristine ReSe$_{2}$ using scanning tunneling spectroscopy and explore the implications on the gap following surface-doping with potassium. A lower bound of 1.4 eV is estimated for the gap in the fully doped case, suggesting that doping-dependent many-body effects significantly affect the electronic properties of ReSe$_{2}$. Our results, supported by density functional theory calculations, provide insight into the mechanisms behind polarization-dependent optical properties of rhenium dichalcogenides and highlight their place amongst two-dimensional crystals., Comment: 37 pages (including Supporting Information), 7 figures in the main text

The origin of the variation of photoluminescence (PL) spectra of monolayer tungsten disulfide (WS2) is investigated systematically. Dependence of the PL spectrum on the excitation power show that the relatively sharp component corresponds to excitons whereas the broader component at slightly lower energy corresponds to negatively charged trions. PL imaging and second harmonic generation measurements show that the trion signals are suppressed more than the exciton signals near the edges, thereby relatively enhancing the excitonic feature in the PL spectrum and that such relative enhancement of the exciton signals is more pronounced near approximately armchair edges. This effect is interpreted in terms of depletion of free electrons near the edges caused by structural defects and adsorption of electron acceptors such as oxygen atoms., 13 pages, 4 figures

An exciton is the bosonic quasiparticle of electron-hole pairs bound by the Coulomb interaction

Layered materials such as graphite and transition metal dichalcogenides have extremely anisotropic mechanical properties owing to orders of magnitude difference between in-plane and out-of-plane interatomic interaction strengths. Although effects of mechanical perturbations on either intra- or inter-layer interactions have been extensively investigated, mutual correlations between them have rarely been addressed. Here we show that layered materials have an inevitable coupling between in-plane uniaxial strain and interlayer shear. Because of this, the uniaxial in-plane strain induces an anomalous splitting of the degenerate interlayer shear phonon modes such that the split shear mode along the tensile strain is not softened but hardened contrary to the case of intralayer phonon modes. We confirm the effect by measuring Raman shifts of shear modes of bilayer MoS2 under strain. Moreover, by analyzing the splitting, we obtain an unexplored off-diagonal elastic constant, demonstrating that Raman spectroscopy can determine almost all mechanical constants of layered materials., Comment: 36 pages, 10 figures

How a certain ground state of complex physical systems emerges, especially in two-dimensional materials, is a fundamental question in condensed-matter physics. A particularly interesting case is systems belonging to the class of XY Hamiltonian where the magnetic order parameter of conventional nature is unstable in two-dimensional materials leading to a Berezinskii−Kosterlitz−Thouless transition. Here, we report how the XXZ-type antiferromagnetic order of a magnetic van der Waals material, NiPS3, behaves upon reducing the thickness and ultimately becomes unstable in the monolayer limit. Our experimental data are consistent with the findings based on renormalization-group theory that at low temperatures a two-dimensional XXZ system behaves like a two-dimensional XY one, which cannot have a long-range order at finite temperatures. This work provides the experimental examination of the XY magnetism in the atomically thin limit and opens opportunities of exploiting these fundamental theorems of magnetism using magnetic van der Waals materials., Exploring the ground state of two-dimensional (2D) magnetic systems enriches the fundamental understanding of magnetism and boosts the applications. The authors here show the suppression of magnetic order and 2D XY behavior in XXZ-type antiferromagnet NiPS3 when approaching the monolayer limit by Raman spectroscopy.

Polarized Raman spectroscopy on few-layer ReS2 and ReSe2 was carried out to determine the crystallographic orientations. Since monolayer ReX2 (X=S or Se) has a distorted trigonal structure with only an inversion center, there is in-plane anisotropy and the two faces of a monolayer crystal are not equivalent. Since many physical properties vary sensitively depending on the crystallographic orientation, it is important to develop a reliable method to determine the crystal axes of ReX2. By comparing the relative polarization dependences of some representative Raman modes measured with three different excitation laser energies with high-resolution scanning transmission electron microscopy, we established a reliable procedure to determine the all three principal directions of few-layer ReX2 including a way to distinguish the two types of faces: a 2.41-eV laser for ReS2 or a 1.96-eV laser for ReSe2 should be chosen as the excitation source of polarized Raman measurements; then the relative directions of the maximum intensity polarization of the Raman modes at 151 and 212 cm-1 (124 and 161 cm-1) of ReS2 (ReSe2) can be used to determine the face types and the Re-chain direction unambiguously., Comment: 22 pages, 4 figures, supplementary information 9 pages

State Fund for Fun- damental Research; Ministry of Education and Science of Ukraine; New&Renew- able Energy of the Korea Institute of Energy Technology Evaluation and Planning

Raman spectra of few-layer MoSe2 were measured with 8 excitation energies. New peaks that appear only near resonance with various exciton states are analyzed, and the modes are assigned. The resonance profiles of the Raman peaks reflect the joint density of states for optical transitions, but the symmetry of the exciton wave functions leads to selective enhancement of the A1g mode at the A exciton energy and the shear mode at the C exciton energy. We also find Davydov splitting of intra-layer A1g, E1g, and A2u modes due to inter-layer interaction for some excitation energies near resonances. Furthermore, by fitting the spectral positions of inter-layer shear and breathing modes and Davydov splitting of intra-layer modes to a linear chain model, we extract the strength of the inter-layer interaction. We find that the second-nearest-neighbor inter-layer interaction amounts to about 30% of the nearest-neighbor interaction for both in-plane and out-of-plane vibrations., 45 pages, 19 figures, ACS Nano published (2016)

To observe the superconducting current and structural properties of high critical temperature ( T c ) superconductors (HTS), we suggest the following imaging methods: Room temperature imaging (RTI) through thermal heating, low-temperature bolometric microscopy (LTBM) and Raman scattering imaging. RTI and LTBM images visualize thermal-electric voltages as different thermal gradients at room temperature (RT) and superconducting current dissipation at near- T c , respectively. Using RTI, we can obtain structural information about the surface uniformity and positions of impurities. LTBM images show the flux flow in two dimensions as a function of the local critical currents. Raman imaging is transformed from Raman survey spectra in particular areas, and the Raman vibration modes can be combined. Raman imaging can quantify the vibration modes of the areas. Therefore, we demonstrate the spatial transport properties of superconducting materials by combining the results. In addition, this enables visualization of the effect of current flow on the distribution of impurities in a uniform superconducting crystalline material. These imaging methods facilitate direct examination of the local properties of superconducting materials and wires.

Cu 2 ZnSnSe 4 photovoltaic absorber layers were prepared by the vapor selenization of stacked Cu/Sn/CuZn/Mo/glass precursor films with different Cu/(Zn + Sn) compositional ratios (CZT = 0.8, 0.85 and 0.9). The absorber was ZnSe-free at CZT = 0.9 but the films obtained from CZT = 0.85 or 0.8 contained a ZnSe phase mainly at the bottom or top of the absorber film, respectively. Although the solar cell fabricated from the CZT = 0.9 absorber showed poor-shunt characteristics (efficiency = 1.94%), that produced from CZT = 0.85 exhibited significantly distorted current–voltage characteristics (efficiency = 4.23%). The CZT = 0.8 ratio showed the highest efficiency of 5.8% and normal pn diode behavior. This suggests that the existence or location of the ZnSe phase within the absorber is not related directly to the solar cell performance. Instead, the ZnSe phase may alter the defect distribution near the space charge region. Several aspects of the device behavior depending on the CZT ratio are discussed with respect to the relative position of the ZnSe phase.

Three types of carbon nanoscroll (CNS) structures that are formed when scrolling up graphene sheets are investigated using Raman spectroscopy and atomic force microscopy (AFM). The CNSs were produced from exfoliated monolayer graphene deposited on a Si chip by applying a droplet of isopropyl alcohol (IPA) solution. The three types of CNS are classified as single-elliptical-core, double-elliptical-core (both with large internal volumes) and collapsed ribbon-like, based on AFM surface profile measurements. We discuss the structure and formation of CNS with much larger hollow cores than is commonly assumed and relate this to the large effective 2D bending stiffness of graphene in the IPA solution. The large elliptical core structures show Raman spectra similar to those previously reported for CNS and indicate little interaction between the scrolled layers. The Raman spectra from ribbon-like structures show additional features that are similar to that of folded graphene. These new features can be related to layer breathing modes combined with some resonance enhancement at specific regions of the ribbon-like CNSs that are due to specific twist angles produced when the structure folds/collapses.

Correction for ‘Anomalous polarization dependence of Raman scattering and crystallographic orientation of black phosphorus’ by Jungcheol Kim et al., Nanoscale, 2015, 7, 18708–18715, DOI: 10.1039/C5NR04349B.

The atomic or molecular assembly on 2D materials through the relatively weak van der Waals interaction is quite different from the conventional heteroepitaxy and may result in unique growth behaviors. Here, it is shown that straight 1D cyanide chains display universal epitaxy on hexagonal 2D materials. A universal oriented assembly of cyanide crystals (AgCN, AuCN, and Cu0.5Au0.5CN) is observed, where the chains are aligned along the three zigzag lattice directions of various 2D hexagonal crystals (graphene, h‐BN, WS2, MoS2, WSe2, MoSe2, and MoTe2). The potential energy landscape of the hexagonal lattice induces this preferred alignment of 1D chains along the zigzag lattice directions, regardless of the lattice parameter and surface elements as demonstrated by first‐principles calculations and parameterized surface potential calculations. Furthermore, the oriented microwires can serve as crystal orientation markers, and stacking‐angle‐controlled vertical 2D heterostructures are successfully fabricated by using them as markers. The oriented van der Waals epitaxy can be generalized to any hexagonal 2D crystals and will serve as a unique growth process to form crystals with orientations along the zigzag directions by epitaxy., 1D cyanide chains show universal oriented van der Waals epitaxy on various hexagonal 2D crystals. The chain directions are always aligned along the zigzag lattice directions of the 2D substrates, regardless of differing lattice parameters and surface elements. Stacking‐angle‐controlled vertical 2D heterostructures can also be fabricated using cyanide microwire markers for identification of crystal orientations.

We investigated interlayer phonon modes of mechanically exfoliated few-layer 2H-SnS2 samples by using room temperature low-frequency micro-Raman spectroscopy. Raman measurements were performed using laser wavelengths of 441.6, 514.4, 532 and 632.8 nm with power below 100 μW and inside a vacuum chamber to avoid photo-oxidation. The intralayer Eg and A1g modes are observed at ~206 cm−1 and 314 cm−1, respectively, but the Eg mode is much weaker for all excitation energies. The A1g mode exhibits strong resonant enhancement for the 532 nm (2.33 eV) laser. In the low-frequency region, interlayer vibrational modes of shear and breathing modes are observed. These modes show characteristic dependence on the number of layers. The strengths of the interlayer interactions are estimated by fitting the interlayer mode frequencies using the linear chain model and are found to be 1.64 × 1019 N · m−3 and 5.03 × 1019 N · m−3 for the shear and breathing modes, respectively.

We investigated interlayer phonon modes of mechanically exfoliated few-layer 2H-SnS2 samples by using room temperature low-frequency micro-Raman spectroscopy. Raman measurements were performed using laser wavelengths of 441.6, 514.4, 532 and 632.8 nm with power below 100 μW and inside a vacuum chamber to avoid photo-oxidation. The intralayer Eg and A1g modes are observed at ~206 cm−1 and 314 cm−1, respectively, but the Eg mode is much weaker for all excitation energies. The A1g mode exhibits strong resonant enhancement for the 532 nm (2.33 eV) laser. In the low-frequency region, interlayer vibrational modes of shear and breathing modes are observed. These modes show characteristic dependence on the number of layers. The strengths of the interlayer interactions are estimated by fitting the interlayer mode frequencies using the linear chain model and are found to be 1.64 × 1019 N · m−3 and 5.03 × 1019 N · m−3 for the shear and breathing modes, respectively.

Nanocrystalline ZnO films were deposited onto glass substrates in the temperature range of 473–673 K using pulsed spray pyrolysis. The structural, substructural, and optical properties of the films were investigated by means of X-ray diffraction analysis, Raman scattering, and Fourier transform infrared (FTIR) spectroscopy. The effect of the substrate temperature (Ts) on the coherent scattering domain (CSD) sizes L, microstrains ϵ, and microstress σ grades, and the average density of dislocations ρ in the films were estimated through the broadening of X-ray lines using the Cauchy and Gauss approximations and the threefold function convolution method. The ZnO films grown at Ts = 623–673 K possessed the highest values of L, and the lowest of ϵ, σ, and ρ, indicating high-crystalline quality. The Raman spectra showed peaks located at 95–98, 333–336, 415, 439–442, 572, and 578–584 cm−1, which were interpreted as E2low(Zn), (E2high−E2low), E1(TO), E2high(O), A1(LO) and E1(LO) phonon modes of the ZnO wurtzite phase. The FTIR spectra showed relatively weak signals at 856, 1405, and 1560 cm−1, corresponding to the C–H and C–O stretching modes, in addition to the main Zn–O mode at 475 cm−1, indicating a low content of precursor residues.

ZnSe thin films were deposited on well-cleaned glass substrates by the close-spaced vacuum sublimation technique. Various structural, sub-structural and optical properties have been investigated through scanning electron microscopy (SEM), X-ray diffraction (XRD), spectral photometry, Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy. Electro-physical studies were performed using an ITO/ZnSe/In “sandwich” structure. The correlation between the films structure and their optical and electro-physical properties was estimated. The evaluated films were fine-crystalline, with their grain size depending on the substrate temperature. The optical band gap was estimated through optical measurements and the high optical qualities of the ZnSe films were confirmed by Raman and FTIR analyses.

In this work, we report on the structural and optical properties of ZnO films deposited by pulsed spray pyrolysis at relatively low temperatures, compatiblewith a large variety of substrates and processing technologies. Crystalline ZnO films were deposited onto glass substrates using zinc acetate dihydrate dissolved in distilled water with concentration of 0.2M. The temperature of the substrate was varied in the range Ts = 473–673K with ΔТ = 50 K. Effect of Ts were investigated by scanning electron microscopy, x-ray diffraction and energy dispersive x-ray, and optical spectroscopies. Also, the influence of Ts on the grain size, phase composition, texture quality, coherent scattering domain size, crystal lattice parameters, chemical composition, ransmission coefficient, and the bang gap of the ZnO films were studied. X-ray diffraction analysis revealed that films were polycrystalline with hexagonal phase and showed as preferential orientation (101) at Ts573 K. Scanning electron microscopy (SEM) measurements showed that the substrate temperature has a strong effect on morphology of the films. Energy dispersive analysis revealed that ZnO films consisted of the non-stoichiometric compounds. Optical measurements showed ZnO films to be highly transparent in the visible region, and optical band gap is shifting from 3.18 eV to 3.30 eV. This research was supported by the Ministry of Education and Science of Ukraine (Grant Numbers 0113U000131, 0112U000772, and the individual grant for D.O.).

Few-layer tungsten diselenide (WSe2) is investigated using circularly polarized Raman spectroscopy with up to eight excitation energies. The main E2g1 and A1g modes near 250 cm-1 appear as a single peak in the Raman spectrum taken without consideration of polarization but are resolved by using circularly polarized Raman scattering. The resonance behaviors of the E2g1 and A1g modes are examined. Firstly, both the E2g1 and A1g modes are enhanced near resonances with the exciton states. The A1g mode exhibits Davydov splitting for trilayers or thicker near some of the exciton resonances. The low-frequency Raman spectra show shear and breathing modes involving rigid vibrations of the layers and also exhibit strong dependence on the excitation energy. An unidentified peak at ~19 cm-1 that does not depend on the number of layers appears near resonance with the B exciton state at 1.96 eV (632.8 nm). The strengths of the intra- and inter-layer interactions are estimated by comparing the mode frequencies and Davydov splitting with the linear chain model, and the contribution of the next-nearest-neighbor interaction to the inter-layer interaction turns out to be about 34% of the nearest-neighbor interaction. Fano resonance is observed for 1.58-eV excitation, and its origin is found to be the interplay between two-phonon scattering and indirect band transition., 45 pages, 20 figures (including Supplementary Information)

Raman spectra of few-layer WS2 have been measured with up to seven excitation energies, and peculiar resonance effects are observed. The two-phonon acoustic phonon scattering signal close to the main E2g1 peak is stronger than the main peaks for excitations near the A or B exciton states. The low-frequency Raman spectra show a series of shear and layer-breathing modes that are useful for determining the number of layers. In addition, hitherto unidentified peaks (X1 and X2), which do not seem to depend on the layer thickness, are observed near resonances with exciton states. The polarization dependences of the two peaks are different: X1 vanishes in cross polarization, but X2 does not. At the resonance with the A exciton state, the Raman-forbidden, lowest-frequency shear mode for odd number of layers appears as strong as that for the allowed case of even number of layers. This mode also exhibits a strong Breit-Wigner-Fano line shape and an anomalous polarization behavior at this resonance., Comment: 35 pages, 16 figures

Graphene and related two-dimensional materials are promising candidates for atomically thin, flexible, and transparent optoelectronics. In particular, the strong light-matter interaction in graphene has allowed for the development of state-of-the-art photodetectors, optical modulators, and plasmonic devices. In addition, electrically biased graphene on SiO2 substrates can be used as a low-efficiency emitter in the mid-infrared range. However, emission in the visible range has remained elusive. Here we report the observation of bright visible-light emission from electrically biased suspended graphenes. In these devices, heat transport is greatly minimised; thus hot electrons (~ 2800 K) become spatially localised at the centre of graphene layer, resulting in a 1000-fold enhancement in the thermal radiation efficiency. Moreover, strong optical interference between the suspended graphene and substrate can be utilized to tune the emission spectrum. We also demonstrate the scalability of this technique by realizing arrays of chemical-vapour-deposited graphene bright visible-light emitters. These results pave the way towards the realisation of commercially viable large-scale, atomically-thin, flexible and transparent light emitters and displays with low-operation voltage, and graphene-based, on-chip ultrafast optical communications., Comment: 63 page