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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 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

A key challenge in the development of two-dimensional (2D) devices is the fabrication of metal–semiconductor junctions with minimal contact resistance and depinned energy levels. An ideal solution for practical applications is to make contacts between 2D van der Waals semiconductors and 2D van der Waals metals. Here we report the wafer-scale production of patterned layers of metallic transition metal ditellurides on different substrates. Our tungsten ditelluride and molybdenum ditelluride layers, which are grown using a tellurization process applied to a precursor transition metal layer, have an electronic performance comparable to that of mechanically exfoliated flakes and can be combined with the 2D semiconductor molybdenum disulfide. The resulting metal–semiconductor junctions are free from significant disorder effects and Fermi-level pinning, and are used to create monolayer molybdenum disulfide field-effect transistors. The Schottky barrier heights of the devices also largely follow the trend of the Schottky–Mott limit. Two-dimensional metallic WTe2 and MoTe2 layers can be combined with a semiconducting MoS2 monolayer to create metal–semiconductor junctions that are free from substantial disorder effects and Fermi-level pinning.

Spin–phonon coupling is one of the fundamental interactions in functional materials, indispensable for understanding their unexpected magnetic ground states. Ferromagnetic SrRuO3 is a correlated metal with the potential for utilization in novel spintronic devices and serves as a promising platform for studying spin–phonon interactions. In this study, we used Raman spectroscopy to identify spin–phonon coupling in SrRuO3 heterostructures. We deliberately decreased the exchange interactions within SrRuO3 by reducing system dimensions, which was coherently observed in both temperature-dependent magnetization measurements and phonon spectra. To collect the Raman signals from the very thin (quasi-2D) SrRuO3 layers while maintaining the layer thickness, we fabricated epitaxial oxide superlattices with 50 repetitions of the layers. We also present polarization-dependent Raman spectra of SrRuO3, with accurate identification of the Raman modes. These results show that the phonon dynamics of SrRuO3 is strongly influenced by the spin ordering, which can be efficiently tailored via atomically controlled epitaxial heterostructuring.

For scalable perovskite solar cells (PSCs), deposition of a homogeneous and high-quality perovskite film on a large area (>100 cm2) is a prerequisite. Conventional solutions for spin-coating on small areas usually contain polar aprotic solvents with high boiling point, which is difficult to adopt for large-area bar coating because of the uncontrollable and slow drying process due to the strong interaction between polar aprotic solvent and Lewis acidic PbI2 or perovskite. Thus, the precursor solution plays a vital role in the success of large-area coating. Here we report a coating solution suitable for large-area perovskite films. The coating solutions prepared via gas-mediated solid–liquid conversion contain preformed perovskite clusters as confirmed by rotational mode of methylammonium cation in the PbI3– framework from Raman spectroscopy. CH3NH3PbI3 (MAPbI3) films formed by D-bar coating within 20 s on the area over 100 cm2 exhibit tetragonal/cubic superlattice structure with highly preferred orientatio...

Lattice matching has been supposed to play an important role in the coupling between two materials in a vertical heterostructure (HS). To investigate this role, we fabricated a heterojunction device with a few layers of p-type WSe2 and n-type MoSe2 with different crystal orientation angles. The crystal orientations of WSe2 and MoSe2 were estimated using high-resolution X-ray diffraction. Heterojunction devices were fabricated with twist angles of 0, 15, and 30°. The I–V curve of the sample with the twist angle of 0° under the dark condition showed a diodelike behavior. The strong coupling due to lattice matching caused a well-established p–n junction. In cases of 15 and 30° samples, the van der Waals gap was built because of lattice mismatching, which resulted in the formation of a potential barrier. However, when the light-emitting diode light of 365 nm (3.4 eV) was illuminated, it was possible for excited electrons and holes to jump beyond the potential barrier and the current flowed well in both forwar...

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.

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.

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.

We report on the thickness-dependent Raman spectroscopy of ultrathin silicon (Si) nanomembranes (NMs), whose thicknesses range from 2 to 18 nm, using several excitation energies. We observe that the Raman intensity depends on the thickness and the excitation energy due to the combined effects of interference and resonance from the band-structure modulation. Furthermore, confined acoustic phonon modes in the ultrathin Si NMs were observed in ultralow-frequency Raman spectra, and strong thickness dependence was observed near the quantum limit, which was explained by calculations based on a photoelastic model. Our results provide a reliable method with which to accurately determine the thickness of Si NMs with thicknesses of less than a few nanometers.

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

Raman spectroscopy is broadly used in the studies of transition metal dichalcogenides to determine the number of layers or other structural parameters. However, unlike the case of graphene, the Raman spectrum varies greatly depending on the excitation energy, and many unusual effects have been reported. The optical absorption spectrum has many features related to exciton states due to the strong coulomb interaction in these materials, and dramatic resonance effects occur when the excitation energy matches one of these exciton states. Several forbidden Raman modes and some unexplained peaks appear near resonance, and Davydov splitting of some Raman modes is observed. Furthermore, the polarization dependence of the some Raman modes also shows excitation energy dependence. In this review, recent progress in resonance Raman studies on transition metal dichalcogenides and some unresolved issues are reviewed. Copyright © 2017 John Wiley & Sons, Ltd.

Interlayer excitons were observed at the heterojunctions in van der Waals heterostructures (vdW HSs). However, it is not known how the excitonic phenomena are affected by the stacking order. Here, we report twist-angle-dependent interlayer excitons in MoSe2/WSe2 vdW HSs based on photoluminescence (PL) and vdW-corrected density functional theory calculations. The PL intensity of the interlayer excitons depends primarily on the twist angle: It is enhanced at coherently stacked angles of 0° and 60° (owing to strong interlayer coupling) but disappears at incoherent intermediate angles. The calculations confirm twist-angle-dependent interlayer coupling: The states at the edges of the valence band exhibit a long tail that stretches over the other layer for coherently stacked angles; however, the states are largely confined in the respective layers for intermediate angles. This interlayer hybridization of the band edge states also correlates with the interlayer separation between MoSe2 and WSe2 layers. Furthermo...

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

The resonance Raman effects in two dimensional materials including transition metal dichalcogenides and black phosphorus are reviewed. The Raman intensities of high-frequency intra-layer vibration modes are enhanced near resonance with exciton states. Some Raman peaks that are either forbidden or weak in non-resonant cases show strong enhancement near resonances. In the low-frequency Raman spectra, some unusual features, in addition to shear and breathing modes, appear near resonance with exciton states. Some intra-layer vibration modes exhibit Davydov splitting due to inter-layer interactions when the excitation energy is close to resonances. The polarization behaviors of some Raman modes in anisotropic two-dimensional materials have peculiar dependences on the excitation energy, which is related to the resonance effect.

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.

We found a clear correlation between the solar conversion efficiency and the distribution of the ZnS secondary phase in Cu 2 ZnSnS 4 (CZTS) solar cells. Five CZTS solar cells were prepared by the two-step process in which sputtered precursor multilayers were sulfurized at different temperatures. In higher efficiency solar cells, the ZnS secondary phase was found to accumulate near the interface between CZTS and MoS 2 formed on top of the Mo layer. It was also found that a solar cell with a higher efficiency showed weaker ZnS Raman signal in the MoS 2 layer. The highest conversion efficiency of 7.5% was obtained from a solar cell prepared at a sulfurization temperature of 570 °C, in which no ZnS was detected in the MoS 2 layer. We suggest that in order to obtain a high efficiency CZTS solar cell, it is critical to find a condition that keeps ZnS from the MoS 2 layer.

We report a new way to enhance the electrical performances of large area CVD-grown graphene through controlling the ripple density and heights after transfer onto SiO2/Si substrates by employing different cooling rates during fabrication. We find that graphene films prepared with a high cooling rate have reduced ripple density and heights and improved electrical characteristics such as higher electron/hole mobilities as well as reduced sheet resistance. The corresponding Raman analysis also shows a significant decrease of the defects when a higher cooling rate is employed. We suggest a model that explains the improved morphology of the graphene film obtained with higher cooling rates. From these points of view, we can suggest a new pathway toward a relatively lower density and heights of ripples in order to reduce the flexural phonon-electron scattering effect, leading to higher lateral carrier mobilities.

In this study, CZTSSe precursors (Se/Cu/SnS/ZnS) were deposited by sputtering and evaporation and then annealed without added chalcogen substances in an argon-filled atmospheric chamber using rapid thermal processing (RTP). A low-temperature pre-annealing treatment (PAT) was applied to induce a pre-reaction between Se and Cu/SnS/ZnS. It was found that the PAT leads to the formation of CuSe and Cu2−xSe and enhances Se incorporation during RTP chalcogenization. Scanning electron microscopy (SEM), X-ray diffractometry, Raman analysis and scanning transmission electron microscopy with energy dispersive spectroscopy (STEM-EDS) were applied to investigate the differences between the absorber with the PAT and the one without the PAT. Better morphologies on the surface and in the cross section were obtained for the CZTSSe absorber annealed using the PAT compared with the absorber annealed without the PAT. Both absorbers showed nearly pure kesterite phases in their upper regions, as confirmed by Raman analysis. However, STEM-EDS maps revealed that when the absorber was prepared without the PAT, Zn- and S-rich secondary phases and voids were easily formed near the back contact. The electrical characteristics and efficiencies of the CZTSSe thin films showed drastic changes; the CZTSSe solar cell without the PAT showed no diode response, but the cell with the PAT showed an efficiency of 6.77% with an open-circuit voltage (Voc), short-circuit current density (Jsc) and fill factor (FF) of 376 mV, 31.39 mA/cm2 and 57%, respectively.

Raman spectroscopy has been established as one of the core experimental tools to study two-dimensional materials (2DMs) including graphene, black phosphorus, transitional metal chalcogenides, and other layered materials. If the polarization of the incident photons and the scattered photons are carefully controlled, the selection rules for the Raman scattering from phonon modes allow accurate mode assignments, which is not always possible in Raman scattering measurements using unpolarized light. Furthermore, polarized Raman spectroscopy can be used to determine the crystallographic orientation of isotropic 2DMs with in-plane strain or anisotropic 2DMs. This review explains the basics of polarized Raman spectroscopy, especially in the context of 2DMs research, and survey some of the most important applications of polarized Raman spectroscopy in isotropic and anisotropic 2DMs studies.

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.

Surface enhanced-Raman spectroscopy (SERS) is greatly affected by the substrate where excitation of the localized metal surface plasmon resonance enhances the scattering signals. This report presents the results of preparation of CuO/Ag nanowires by thermal oxidation and sputtering method. The nanowires were coated with a layer of Ag by sputtering. The samples were investigated with different characterization techniques including X-ray diffraction, scanning electron microscopy, X-ray energy dispersive spectroscopy, X-ray photoemission spectroscopy, and Raman spectroscopy. The effect of the coating layer thickness, ranging from 20 to 240 nm, on SERS efficiency was studied. The results show that the CuO/Ag nanowires are very sensitive SERS substrates, which can detect the signal of Methylene Blue at low concentration of 10-10 M. The reason for high sensitivity of the as-prepared CuO/Ag nanowires is believed to be the surface plasmon resonance in silver layer, which is further enhanced due to the charge transfer transition from Ag shell to CuO core.

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.

Following the celebrated discovery of graphene, considerable attention has been directed toward the rich spectrum of properties offered by van der Waals crystals. However, studies have been largely limited to their 2D properties due to lack of 1D structures. Here, the growth of high-yield, single-crystalline 1D nanobelts composed of transition metal ditellurides at low temperatures (T ≤ 500 °C) and in short reaction times (t ≤ 10 min) via the use of tellurium-rich eutectic metal alloys is reported. The synthesized semimetallic 1D products are highly pure, stoichiometric, structurally uniform, and free of defects, resulting in high electrical performances. Furthermore, complete compositional tuning of the ternary ditelluride nanobelts is achieved with suppressed phase separation, applicable to the creation of unprecedented low-dimensional materials/devices. This approach may inspire new growth/fabrication strategies of 1D layered nanostructures, which may offer unique properties that are not available in other materials.

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.

Variously shaped graphene domains are of significant interest since the electronic properties of pristine graphene are strongly dependent on its size, shape, and edge structures. With the consideration that the reactivity of graphene is governable by the p-electron structure at its edge, a number of attempts have been made to grow variously shaped graphene domains and to define their edge structures. In this work, we explored the anisotropic behavior of hydrogen in the formation of graphene domains during atmospheric pressure chemical vapor deposition. As increasing the hydrogen or reducing the methane partial pressure, the formation of pentagonal graphene domains was accelerated through anisotropic growth and etching. Their edge structures were characterized using polarization-dependent D and G peak Raman spectroscopy. This work contributes significantly to improving graphene-based engineering by allowing graphene shapes and domain edges to be tuned, and also provides greater insight into the electronic properties of graphene devices.

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.

Structural and transport properties of high performance SmBa2Cu3O7−x coated conductors produced by a dual-chamber co-evaporation are presented. The 5 μm-thick SmBCO coated conductors grown on IBAD-MgO based Hastelloy metal templates show critical currents larger than 1020–1560 A/cm at 77 K and self-field. The current transport characteristics of the conductors are investigated by room-temperature thermoelectric microscopy and low-temperature bolometric microscopy. The local thermoelectric images show the tilted grains, grain boundaries, and microstructural defects on the surface of the coated conductors. The bias current-dependent bolometric response at low temperature displays the current of the local flux flow dissipation as an increasing bias. Furthermore, we measured micro-Raman scattering microscopic imaging on oxygen-related peaks of the conductors. Comparing the Raman signal images with the low temperature optical scanning maps, it is remarkable that the structural disorders represented by oxygen-related Raman peaks are closely related to the low temperature bolometric abnormalities. From this result, a nature of the dissipative current distribution in coated conductors is revealed. The scanning optical microscopic study will provide a promising method for quality assurance of coated conductors.

Raman scattering and atomic force microscopy measurements on Cu 2 ZnSnS 4 thin films prepared by a direct solution method revealed that metal sulfates of various morphologies (dense clusters or separated particles) were partially embedded on the surface of the Cu 2 ZnSnS 4 layer. This residue was removed during the subsequent chemical bath deposition of the CdS buffer layer. However, the removal of the residue led to poor crystallinity and reduced photocurrent near the location of the residue, which suggests that controlling the formation of the sulfates during the fabrication of the absorber layer would be critical for obtaining high efficiency solar cells by the solution method.

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

Compositional and structural studies of Cu 2 ZnSnSe 4 (CZTSe) thin films were carried out by X-ray diffraction, energy dispersive X-ray spectroscopy (EDS), particle induced X-ray emission (PIXE), photoluminescence, and Raman spectroscopy. CZTSe thin films with different compositions were deposited on sodalime glass by co-evaporation. The composition of the films measured by two different methods, EDS and PIXE, showed significant differences. Generally, the Zn/Sn ratio measured by EDS is larger than that measured by PIXE. Both the micro-PIXE and the micro-Raman imaging results indicated the compositional and structural inhomogeneity of the sample.

The CdTe thin and thick films were obtained by the close spaced vacuum sublimation technique on a glass substrate under the following growth conditions: the evaporator temperature was 620 °C; and the substrate temperature was varied in the range from 250 °C to 550 °C. High purity CdTe powder was used as a charge for evaporation. The Raman spectra were measured using TRIAX 320 and TRIAX 550 spectrometers at room temperature. The 488-nm line and 514.5-nm line of an Ar+ laser and a 785-nm diode laser were used as excitation sources. The signal was collected by the liquid nitrogen cooled charge-coupled-device (CCD) detector. A number of intense Raman peaks at 140, 167, 190, 271, 332 and 493 cm-1 were observed and were interpreted as TO (140 cm-1), 1LO (167 cm-1), 2LO (332 cm-1), 3LO (493 cm-1) phonon modes and plasmon-phonon mode (190 cm-1). The presence of several phonon replicas in the Raman spectra confirms high crystal quality of the samples. (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

The mechanical properties of ZnO microwires have been studied using three different methods: quasi-static flexural measurements using atomic force microscopy, static measurements using a nano indenter, and dynamic flexural measurements using optical interferometry. ZnO microwires were synthesized by chemical vapor deposition method, and the crystal structure and quality were examined using x-ray diffraction and photoluminescence spectroscopy. The Young's moduli were estimated using the measurement results from the three methods, and they showed consistent values in the range 67.5–79.4 GPa for microwires with diameters of 1.8 μm ± 100 nm.

Two-dimensional magnetic van der Waals (vdW) materials have attracted much interest recently. Magnetism in two dimensions is one of the most fascinating topics in condensed matter physics whereas atomically thin magnetic materials present new opportunities for novel spintronic devices. Raman spectroscopy has been established as an invaluable tool in the studies of such magnetic vdW materials as it has been found that the magnetic ordering, which is often difficult to probe directly in atomically thin samples, can be reliably monitored by Raman spectroscopy. Here, we review recent progress in using Raman spectroscopy for the study of magnetic vdW materials with the examples of Ising-type ferromagnet CrI3, Ising-type antiferromagnet FePS3, and XY-type antiferromagnet NiPS3. By monitoring characteristic spectroscopic signatures of magnetic ordering, one can probe various aspects of magnetic ordering.

We report a method to characterize z-directional surface roughness of chemical vapor deposition-grown graphene monolayers with the aid of surface-enhanced Raman scattering spectral signatures of “out-of-plane” phonon modes observed at Au nanoparticle (NP)–graphene–Au thin film junctions. This method reveals that intensities of the out-of-plane mode (Radial Breathing Like Mode) are strongly correlated with the Full Width at Half Maximum (FWHM) of the de-convoluted 2D peak. On the basis of our findings, in-plane 2D peak shape can be used as a straightforward, quantitative indicator in estimating surface roughness of graphene without loading Au NPs by calculating the FWHM [2D−]/FWHM [2D+] value. Furthermore, we examine the different ripple (RP) shapes on graphene by employing atomic force microscopy-correlated Raman microscopy to identify “threading” and “surrounded” RP types for further investigation on the relationship between spectral features and structural aspects. Electrostatic force microscopy (EFM)-based investigation further substantiates that threading-type RPs in graphene show higher EFM amplitude, indicating that the threading domains tend to be more neutral with a few more sp3 type defects than the surroundings.

We investigated the transport and photovoltaic properties of Cu-deficient Cu(In1 − xGax)Se2 (CIGS) thin-film solar cells containing ordered vacancy compound (OVC) layers. Raman spectra clearly revealed that the CIGS thin films with lower Cu concentrations contained larger volumes of OVC layers. The temperature-dependent inverse ideality factor showed that the CIGS film containing more (less) OVC layers exhibited tunneling-mediated bulk (interface)-dominated recombination. The capacitance–voltage characteristics and admittance spectra showed that the CIGS cells containing more OVC layers had more uniform carrier concentration near the junction and less interfacial trap states compared with cells with less OVC layers. These results suggested that the Cu-deficiency and the resulting OVC layer formation reduced the interfacial defect density and suppressed the interface recombination processes of the CIGS solar cells.

We measured the polarization dependence of the photocurrent in symmetric Pd-graphene-Pd photodevices. The photocurrent is maximum when the polarization angle of the incident light is parallel to the edge of an electrode. On the other hand, when the polarization direction is parallel to the graphene channel, the photocurrent is minimum. This polarization dependence of the photocurrent is similar to what has been observed in an asymmetric Pd-graphene-Ti device and results from an anisotropic electron-photon interaction in graphene, which generates photocarriers with momenta predominantly in the direction perpendicular to the polarization direction.

We investigated the structural and optical properties of Cu-poor CuGaSe2 (CGSe) films depending on the use of different substrates: indium-doped tin oxide (ITO) coated soda-lime glass (SLG) and fluorine-doped tin oxide (FTO) coated SLG as back contacts, widely used Mo-coated SLG, and pure SLG. The Cu-poor phase is chosen as a counterpart of Cu-poor Cu(In,Ga)Se2 to show the highest efficiency in this class of materials, and also give a test board for parasitic phases which might influence on device properties. Although the Cu-poor CGSe thin-films were deposited on the four substrates at the same time in an identical condition, they showed differences in the morphology and grain size due to different CGSe/substrate interfaces and growth mechanisms depending on the substrates. These surface properties of the CGSe films were identified clearly by atomic force microscopy (AFM) measurements. X-ray diffraction (XRD) measurement also supported the result of the AFM analysis and showed that the preferred orientation of CGSe is (112), independent of the substrates. The existence of parasitic phases was examined by Raman and photoluminescence spectroscopic techniques. While defect compounds such as CuGa3Se5 and CuGa5Se8 were identified for all films, the signals related to these parasitic phases are strongest for the films on the pure SLG substrate. Furthermore, the absorption property was investigated by spectroscopic ellipsometry in a photon energy range of 0.7–5 eV. We found that the absorption coefficient values for the CGSe films are about 104–105 cm−1 in the visible region. The absorption coefficient is also changed according to the use of different substrates. This difference comes from the parasitic phase formation, which leads to an increase of the bandgap and suppression of the optical absorption strength. Our systematic study suggests clearly that the difference in distribution of parasitic phases in the CGSe films could originate primarily from the different substrates used for the film deposition.