In-Plane Anisotropy in the Layered Topological Insulator Ta2Ni3Te5 Investigated via TEM and Polarized Raman Spectroscopy.

Layered Ta2M3Te5 (M = Pd, Ni) has emerged as a platform to study 2D topological insulators, which have exotic properties such as spin-momentum locking and the presence of Dirac fermions for use in conventional and quantum-based electronics. In particular, Ta2Ni3Te5 has been shown to have superconductivity under pressure and is predicted to have second-order topology. Despite being an interesting material with fascinating physics, the detailed crystalline and phononic properties of this material are still unknown. In this study, we use transmission electron microscopy (TEM) and polarized Raman spectroscopy (PRS) to reveal the anisotropic properties of exfoliated few-layer Ta2Ni3Te5. An electron diffraction and TEM study reveals structural anisotropy in the material, with a preferential crystal orientation along the [010] direction. Through Raman spectroscopy, we discovered 15 vibrational modes, 3 of which are ultralow-frequency modes, which show anisotropic response with sample orientation varying with the polarization of the incident beam. Using angle-resolved PRS, we assigned the vibrational symmetries of 11 modes to Ag and two modes to B3g. We also found that linear dichroism plays a role in understanding the Raman signature of this material, which requires the use of complex elements in the Raman tensors. The anisotropy of the Raman scattering also depends on the excitation energies. Our observations reveal the anisotropic nature of Ta2Ni3Te5, establish a quick and nondestructive Raman fingerprint for determining sample orientation, and represent a significant advance in the fundamental understanding of the two-dimensional topological insulator (2DTI) Ta2Ni3Te5 material.

Enhanced Magnetism and Anomalous Hall Transport through Two-Dimensional Tungsten Disulfide Interfaces.

The magnetic proximity effect (MPE) has recently been explored to manipulate interfacial properties of two-dimensional (2D) transition metal dichalcogenide (TMD)/ferromagnet heterostructures for use in spintronics and valleytronics. However, a full understanding of the MPE and its temperature and magnetic field evolution in these systems is lacking. In this study, the MPE has been probed in Pt/WS2/BPIO (biphase iron oxide, Fe3O4 and α-Fe2O3) heterostructures through a comprehensive investigation of their magnetic and transport properties using magnetometry, four-probe resistivity, and anomalous Hall effect (AHE) measurements. Density functional theory (DFT) calculations are performed to complement the experimental findings. We found that the presence of monolayer WS2 flakes reduces the magnetization of BPIO and hence the total magnetization of Pt/WS2/BPIO at T > ~120 K-the Verwey transition temperature of Fe3O4 (TV). However, an enhanced magnetization is achieved at T < TV. In the latter case, a comparative analysis of the transport properties of Pt/WS2/BPIO and Pt/BPIO from AHE measurements reveals ferromagnetic coupling at the WS2/BPIO interface. Our study forms the foundation for understanding MPE-mediated interfacial properties and paves a new pathway for designing 2D TMD/magnet heterostructures for applications in spintronics, opto-spincaloritronics, and valleytronics.

Emergent magnetism and exchange bias effect in iron oxide nanocubes with tunable phase and size.

We report a systematic investigation of the magnetic properties including the exchange bias (EB) effect in an iron oxide nanocube system with tunable phase and average size (10, 15, 24, 34, and 43 nm). X-ray diffraction and Raman spectroscopy reveal the presence of Fe3O4, FeO, andα-Fe2O3phases in the nanocubes, in which the volume fraction of each phase varies depending upon particle size. While the Fe3O4phase is dominant in all and tends to grow with increasing particle size, the FeO phase appears to coexist with the Fe3O4phase in 10, 15, and 24 nm nanocubes but disappears in 34 and 43 nm nanocubes. The nanocubes exposed to air resulted in anα-Fe2O3oxidized surface layer whose thickness scaled with particle size resulting in a shell made ofα-Fe2O3phase and a core containing Fe3O4or a mixture of both Fe3O4and FeO phases. Magnetometry indicates that the nanocubes undergo Morin (of theα-Fe2O3phase) and Verwey (of the Fe3O4phase) transitions at ∼250 K and ∼120 K, respectively. For smaller nanocubes (10, 15, and 24 nm), the EB effect is observed below 200 K, of which the 15 nm nanocubes showed the most prominent EB with optimal antiferromagnetic (AFM) FeO phase. No EB is reported for larger nanocubes (34 and 43 nm). The observed EB effect is ascribed to the strong interfacial coupling between the ferrimagnetic (FiM) Fe3O4phase and AFM FeO phase, while its absence is related to the disappearance of the FeO phase. The Fe3O4/α-Fe2O3(FiM/AFM) interfaces are found to have negligible influence on the EB. Our findings shed light on the complexity of the EB effect in mixed-phase iron oxide nanosystems and pave the way to design exchange-coupled nanomaterials with desirable magnetic properties for biomedical and spintronic applications.

Tip-Enhanced Photoluminescence of Freestanding Lateral Heterobubbles.

Two-dimensional (2D) semiconducting materials have promising applications in flexible optoelectronics, nanophotonics, and sensing based on the broad tunability of their optical and electronic properties. 2D nanobubbles form exciton funnels due to localized strain that can be used as local emitters for information processing. Their nanoscale optical characterization requires the use of near-field scanning probe microscopy (SPM). However, previous near-field studies of 2D materials were performed on SiO2/Si and metallic substrates using the plasmonic gap mode to increase the signal-to-noise ratio. Another challenge is the deterministic control of bubble size and location. We addressed these challenges by investigating the photoluminescence (PL) signals of freestanding monolayer lateral WSe2-MoSe2 heterostructures under the influence of strain exerted by a plasmonic SPM tip. For first time, we performed tip-enhanced PL imaging of freestanding 2D materials and studied the competition between the PL enhancement mechanisms by nanoindentation as a function of the tip-sample distance. We observed the tunability of PL as a function of bubble size, which opens new possibilities to design optoelectronic nanodevices.

Bandgap Engineering in 2D Lateral Heterostructures of Transition Metal Dichalcogenides via Controlled Alloying.

2D heterostructures made of transition metal dichalcogenides (TMD) have emerged as potential building blocks for new-generation 2D electronics due to their interesting physical properties at the interfaces. The bandgap, work function, and optical constants are composition dependent, and the spectrum of applications can be expanded by producing alloy-based heterostructures. Herein, the successful synthesis of monolayer and bilayer lateral heterostructures, based on ternary alloys of MoS2(1- x ) Se2 x -WS2(1- x ) Se2 x , is reported by modifying the ratio of the source precursors; the bandgaps of both materials in the heterostructure are continuously tuned in the entire range of chalcogen compositions. Raman and photoluminescence (PL) spatial maps show good intradomain composition homogeneity. Kelvin probe measurements in different heterostructures reveal composition-dependent band alignments, which can further be affected by unintentional electronic doping during the growth. The fabrication of sequential multijunction lateral heterostructures with three layers of thickness, composed of quaternary and ternary alloys, is also reported. These results greatly expand the available tools kit for optoelectronic applications in the 2D realm.

Single-Pore versus Dual-Pore Bipyridine-Based Covalent-Organic Frameworks: An Insight into the Heterogeneous Catalytic Activity for Selective CH Functionalization.

Exponential growth in the field of covalent-organic frameworks (COFs) is emanating from the direct correlation between designing principles and desired properties. The comparison of catalytic activity between single-pore and dual-pore COFs is of importance to establish structure-function relationship. Herein, the synthesis of imine-linked dual-pore [(BPyDC)]x % -ETTA COFs (x = 0%, 25%, 50%, 75%, 100%) with controllable bipyridine content is fulfilled by three-component condensation of 4,4',4″,4'″-(ethene-1,1,2,2-tetrayl)tetraaniline (ETTA), 4,4'-biphenyldialdehyde, and 2,2'-bipyridyl-5,5'-dialdehyde in different stoichiometric ratio. The strong coordination of bipyridine moieties of [(BPyDC)]x % -ETTA COFs with palladium imparts efficient catalytic active sites for selective functionalization of sp2 CH bond to CX (X = Br, Cl) or CO bonds in good yield. To broaden the scope of regioselective CH functionalization, a wide range of electronically and sterically substituted substrates under optimized catalytic condition are investigated. A comparison of the catalytic activity of palladium decorated dual-pore frameworks with single-pore imine-linked Pd(II) @ Py-2,2'-BPyDC framework  is undertaken. The finding of this work provides a sporadic example of chelation-assisted CH functionalization and disclosed an in-depth comparison of the relationship between superior catalytic activity and core properties of rationally designed imine linked frameworks.

Facile Morphological Qualification of Transferred Graphene by Phase-Shifting Interferometry.

Post-growth graphene transfer to a variety of host substrates for circuitry fabrication has been among the most popular subjects since its successful development via chemical vapor deposition in the past decade. Fast and reliable evaluation tools for its morphological characteristics are essential for the development of defect-free transfer protocols. The implementation of conventional techniques, such as Raman spectroscopy, atomic force microscopy (AFM), and transmission electron microscopy in production quality control at an industrial scale is difficult because they are limited to local areas, are time consuming, and their operation is complex. However, through a one-shot measurement within a few seconds, phase-shifting interferometry (PSI) successfully scans ≈1 mm2 of transferred graphene with a vertical resolution of ≈0.1 nm. This provides crucial morphological information, such as the surface roughness derived from polymer residues, the thickness of the graphene, and its adhesive strength with respect to the target substrates. Graphene samples transferred via four different methods are evaluated using PSI, Raman spectroscopy, and AFM. Although the thickness of the nanomaterials measured by PSI can be highly sensitive to their refractive indices, PSI is successfully demonstrated to be a powerful tool for investigating the morphological characteristics of the transferred graphene for industrial and research purposes.

Biexcitons in monolayer transition metal dichalcogenides tuned by magnetic fields.

We present time-integrated four-wave mixing measurements on monolayer MoSe2 in magnetic fields up to 25 T. The experimental data together with time-dependent density function theory calculations provide interesting insights into the biexciton formation and dynamics. In the presence of magnetic fields the coherence at negative and positive time delays is dominated by intervalley biexcitons. We demonstrate that magnetic fields can serve as a control to enhance the biexciton formation and help search for more exotic states of matter, including the creation of multiple exciton complexes and excitonic condensates.

Strong room-temperature ferromagnetism in VSe2 monolayers on van der Waals substrates.

Reduced dimensionality and interlayer coupling in van der Waals materials gives rise to fundamentally different electronic 1 , optical 2 and many-body quantum3-5 properties in monolayers compared with the bulk. This layer-dependence permits the discovery of novel material properties in the monolayer regime. Ferromagnetic order in two-dimensional materials is a coveted property that would allow fundamental studies of spin behaviour in low dimensions and enable new spintronics applications6-8. Recent studies have shown that for the bulk-ferromagnetic layered materials CrI3 (ref. 9 ) and Cr2Ge2Te6 (ref. 10 ), ferromagnetic order is maintained down to the ultrathin limit at low temperatures. Contrary to these observations, we report the emergence of strong ferromagnetic ordering for monolayer VSe2, a material that is paramagnetic in the bulk11,12. Importantly, the ferromagnetic ordering with a large magnetic moment persists to above room temperature, making VSe2 an attractive material for van der Waals spintronics applications.

One-pot growth of two-dimensional lateral heterostructures via sequential edge-epitaxy.

Two-dimensional heterojunctions of transition-metal dichalcogenides have great potential for application in low-power, high-performance and flexible electro-optical devices, such as tunnelling transistors, light-emitting diodes, photodetectors and photovoltaic cells. Although complex heterostructures have been fabricated via the van der Waals stacking of different two-dimensional materials, the in situ fabrication of high-quality lateral heterostructures with multiple junctions remains a challenge. Transition-metal-dichalcogenide lateral heterostructures have been synthesized via single-step, two-step or multi-step growth processes. However, these methods lack the flexibility to control, in situ, the growth of individual domains. In situ synthesis of multi-junction lateral heterostructures does not require multiple exchanges of sources or reactors, a limitation in previous approaches as it exposes the edges to ambient contamination, compromises the homogeneity of domain size in periodic structures, and results in long processing times. Here we report a one-pot synthetic approach, using a single heterogeneous solid source, for the continuous fabrication of lateral multi-junction heterostructures consisting of monolayers of transition-metal dichalcogenides. The sequential formation of heterojunctions is achieved solely by changing the composition of the reactive gas environment in the presence of water vapour. This enables selective control of the water-induced oxidation and volatilization of each transition-metal precursor, as well as its nucleation on the substrate, leading to sequential edge-epitaxy of distinct transition-metal dichalcogenides. Photoluminescence maps confirm the sequential spatial modulation of the bandgap, and atomic-resolution images reveal defect-free lateral connectivity between the different transition-metal-dichalcogenide domains within a single crystal structure. Electrical transport measurements revealed diode-like responses across the junctions. Our new approach offers greater flexibility and control than previous methods for continuous growth of transition-metal-dichalcogenide-based multi-junction lateral heterostructures. These findings could be extended to other families of two-dimensional materials, and establish a foundation for the development of complex and atomically thin in-plane superlattices, devices and integrated circuits.

Controlled synthesis and transfer of large-area WS2 sheets: from single layer to few layers.

The isolation of few-layered transition metal dichalcogenides has mainly been performed by mechanical and chemical exfoliation with very low yields. In this account, a controlled thermal reduction-sulfurization method is used to synthesize large-area (~1 cm(2)) WS2 sheets with thicknesses ranging from monolayers to a few layers. During synthesis, WOx thin films are first deposited on Si/SiO2 substrates, which are then sulfurized (under vacuum) at high temperatures (750-950 °C). An efficient route to transfer the synthesized WS2 films onto different substrates such as quartz and transmission electron microscopy (TEM) grids has been satisfactorily developed using concentrated HF. Samples with different thicknesses have been analyzed by Raman spectroscopy and TEM, and their photoluminescence properties have been evaluated. We demonstrated the presence of single-, bi-, and few-layered WS2 on as-grown samples. It is well known that the electronic structure of these materials is very sensitive to the number of layers, ranging from indirect band gap semiconductor in the bulk phase to direct band gap semiconductor in monolayers. This method has also proved successful in the synthesis of heterogeneous systems of MoS2 and WS2 layers, thus shedding light on the controlled production of heterolayered devices from transition metal chalcogenides.

Progress, challenges, and opportunities in two-dimensional materials beyond graphene.

Graphene's success has shown that it is possible to create stable, single and few-atom-thick layers of van der Waals materials, and also that these materials can exhibit fascinating and technologically useful properties. Here we review the state-of-the-art of 2D materials beyond graphene. Initially, we will outline the different chemical classes of 2D materials and discuss the various strategies to prepare single-layer, few-layer, and multilayer assembly materials in solution, on substrates, and on the wafer scale. Additionally, we present an experimental guide for identifying and characterizing single-layer-thick materials, as well as outlining emerging techniques that yield both local and global information. We describe the differences that occur in the electronic structure between the bulk and the single layer and discuss various methods of tuning their electronic properties by manipulating the surface. Finally, we highlight the properties and advantages of single-, few-, and many-layer 2D materials in field-effect transistors, spin- and valley-tronics, thermoelectrics, and topological insulators, among many other applications.

Extraordinary room-temperature photoluminescence in triangular WS2 monolayers.

Individual monolayers of metal dichalcogenides are atomically thin two-dimensional crystals with attractive physical properties different from those of their bulk counterparts. Here we describe the direct synthesis of WS2 monolayers with triangular morphologies and strong room-temperature photoluminescence (PL). The Raman response as well as the luminescence as a function of the number of S-W-S layers is also reported. The PL weakens with increasing number of layers due to a transition from direct band gap in a monolayer to indirect gap in multilayers. The edges of WS2 monolayers exhibit PL signals with extraordinary intensity, around 25 times stronger than that at the platelet's center. The structure and chemical composition of the platelet edges appear to be critical for PL enhancement.

Evidence for ambient-temperature reversible catalytic hydrogenation in Pt-doped carbons.

In situ high-pressure Raman spectroscopy, with corroborating density functional calculations, is used to probe C-H chemical bonds formed when dissociated hydrogen diffuses from a platinum nanocatalyst to three distinct graphenic surfaces. At ambient temperature, hydrogenation and dehydrogenation are reversible in the combined presence of an active catalyst and oxygen heteroatoms. Hydrogenation apparently occurs through surface diffusion in a chemisorbed state, while dehydrogenation requires diffusion of the chemisorbed species back to an active catalyst.

Nitrogen-doped graphene: beyond single substitution and enhanced molecular sensing.

Graphene is a two-dimensional network in which sp(2)-hybridized carbon atoms are arranged in two different triangular sub-lattices (A and B). By incorporating nitrogen atoms into graphene, its physico-chemical properties could be significantly altered depending on the doping configuration within the sub-lattices. Here, we describe the synthesis of large-area, highly-crystalline monolayer N-doped graphene (NG) sheets via atmospheric-pressure chemical vapor deposition, yielding a unique N-doping site composed of two quasi-adjacent substitutional nitrogen atoms within the same graphene sub-lattice (N(2)(AA)). Scanning tunneling microscopy and spectroscopy (STM and STS) of NG revealed the presence of localized states in the conduction band induced by N(2)(AA)-doping, which was confirmed by ab initio calculations. Furthermore, we demonstrated for the first time that NG could be used to efficiently probe organic molecules via a highly improved graphene enhanced Raman scattering.

Polarized Rayleigh back-scattering from individual semiconductor nanowires.

A complete understanding of the interaction between electromagnetic radiation and semiconductor nanowires (NWs) is required in order to further develop a new generation of opto-electronic and photonic devices based on these nanosystems. The reduced dimensionality and high aspect ratio of nanofilaments can induce strong polarization dependence of the light absorption, emission and scattering, leading in some cases to the observation of optical antenna effects. In this work we present the first systematic study of polarized Rayleigh back-scattering from individual crystalline semiconductor NWs with known crystalline structure, orientation and diameters. To explain our experimental Rayleigh polar patterns, we propose a simple theory that relies on a secondary calculation of the volume-averaged internal electromagnetic fields inside the NW. These results revealed that the internal and emitted field can be enhanced depending on the polarization with respect to the NW axis; we also show that this effect strongly depends on the NW diameter.

Structural, electronic, optical and vibrational properties of nanoscale carbons and nanowires: a colloquial review.

This review addresses the field of nanoscience as viewed through the lens of the scientific career of Peter Eklund, thus with a special focus on nanocarbons and nanowires. Peter brought to his research an intense focus, imagination, tenacity, breadth and ingenuity rarely seen in modern science. His goal was to capture the essential physics of natural phenomena. This attitude also guides our writing: we focus on basic principles, without sacrificing accuracy, while hoping to convey an enthusiasm for the science commensurate with Peter's. The term 'colloquial review' is intended to capture this style of presentation. The diverse phenomena of condensed matter physics involve electrons, phonons and the structures within which excitations reside. The 'nano' regime presents particularly interesting and challenging science. Finite size effects play a key role, exemplified by the discrete electronic and phonon spectra of C(60) and other fullerenes. The beauty of such molecules (as well as nanotubes and graphene) is reflected by the theoretical principles that govern their behavior. As to the challenge, 'nano' requires special care in materials preparation and treatment, since the surface-to-volume ratio is so high; they also often present difficulties of acquiring an experimental signal, since the samples can be quite small. All of the atoms participate in the various phenomena, without any genuinely 'bulk' properties. Peter was a master of overcoming such challenges. The primary activity of Eklund's research was to measure and understand the vibrations of atoms in carbon materials. Raman spectroscopy was very dear to Peter. He published several papers on the theory of phonons (Eklund et al 1995a Carbon 33 959-72, Eklund et al 1995b Thin Solid Films 257 211-32, Eklund et al 1992 J. Phys. Chem. Solids 53 1391-413, Dresselhaus and Eklund 2000 Adv. Phys. 49 705-814) and many more papers on measuring phonons (Pimenta et al 1998b Phys. Rev. B 58 16016-9, Rao et al 1997a Nature 338 257-9, Rao et al 1997b Phys. Rev. B 55 4766-73, Rao et al 1997c Science 275 187-91, Rao et al 1998 Thin Solid Films 331 141-7). His careful sample treatment and detailed Raman analysis contributed greatly to the elucidation of photochemical polymerization of solid C(60) (Rao et al 1993b Science 259 955-7). He developed Raman spectroscopy as a standard tool for gauging the diameter of a single-walled carbon nanotube (Bandow et al 1998 Phys. Rev. Lett. 80 3779-82), distinguishing metallic versus semiconducting single-walled carbon nanotubes, (Pimenta et al 1998a J. Mater. Res. 13 2396-404) and measuring the number of graphene layers in a peeled flake of graphite (Gupta et al 2006 Nano Lett. 6 2667-73). For these and other ground breaking contributions to carbon science he received the Graffin Lecture award from the American Carbon Society in 2005, and the Japan Carbon Prize in 2008. As a material, graphite has come full circle. The 1970s renaissance in the science of graphite intercalation compounds paved the way for a later explosion in nanocarbon research by illuminating many beautiful fundamental phenomena, subsequently rediscovered in other forms of nanocarbon. In 1985, Smalley, Kroto, Curl, Heath and O'Brien discovered carbon cage molecules called fullerenes in the soot ablated from a rotating graphite target (Kroto et al 1985 Nature 318 162-3). At that time, Peter's research was focused mainly on the oxide-based high-temperature superconductors. He switched to fullerene research soon after the discovery that an electric arc can prepare fullerenes in bulk quantities (Haufler et al 1990 J. Phys. Chem. 94 8634-6). Later fullerene research spawned nanotubes, and nanotubes spawned a newly exploding research effort on single-layer graphene. Graphene has hence evolved from an oversimplified model of graphite (Wallace 1947 Phys. Rev. 71 622-34) to a new member of the nanocarbon family exhibiting extraordinary electronic properties. Eklund's career spans this 35-year odyssey.

Cavity-enhanced stimulated raman scattering from short GaP nanowires.

We report the first observation of stimulated Raman scattering (SRS) from semiconductor nanowires (SNWs). Using continuous wave (CW) excitation (514.5 nm), very strong nonlinear SRS was observed in backscattering from short segments of crystalline GaP NWs with diameter d = 210 nm when the wire length L < 1.1 microm. The SRS intensity was found to increase dramatically with decreasing L down to 270 nm. The effective threshold pump power P(T) needed to observe the SRS is quite small. Indeed, we observe values of P(T) 3 orders of magnitude smaller than reported for bulk crystals of strongly nonlinear LiIO(3) and Ba(NO(3))(2) and 2 orders of magnitude smaller than that reported recently for SRS from "top-down" fabricated silicon microwaveguides. P(T) was observed to decrease linearly with decreasing L. Our data are discussed in terms of theoretical results developed for dielectric cavities. The quality factors Q for the short GaP cylindrical cavities studied here are estimated to be approximately 15,000. Our results suggest that SNWs may find applications as Raman lasers.

Adsorption of ammonia on graphene.

We report on experimental studies of NH3 adsorption/desorption on graphene surfaces. The study employs bottom-gated graphene field effect transistors supported on Si/SiO2 substrates. Detection of NH3 occurs through the shift of the source-drain resistance maximum ('Dirac peak') with the gate voltage. The observed shift of the Dirac peak toward negative gate voltages in response to NH3 exposure is consistent with a small charge transfer (f approximately 0.068 +/- 0.004 electrons per molecule at pristine sites) from NH3 to graphene. The desorption kinetics involves a very rapid loss of NH3 from the top surface and a much slower removal from the bottom surface at the interface with the SiO2 that we identify with a Fickian diffusion process.

Probing graphene edges via Raman scattering.

We present results of a Raman scattering study from the region near the edges of n-graphene layer films. We find that a Raman band (D) located near 1344 cm(-1) (514.5 nm excitation) originates from a region next to the edge with an apparent width of approximately 70 nm (upper bound). The D-band was found to exhibit five important characteristics: (1) a single Lorentzian component for n = 1, and four components for n = 2-4, (2) an intensity I(D) approximately cos(4) theta, where theta is the angle between the incident polarization and the average edge direction, (3) a local scattering efficiency (per unit area) comparable to the G-band, (4) dispersive behavior ( approximately 50 cm(-1)/eV for n = 1), consistent with the double resonance (DR) scattering mechanism, and (5) a scattering efficiency that is almost independent of the crystallographic orientation of the edge. High-resolution transmission electron microscope images reveal that our cleaved edges exhibit a sawtooth-like roughness of approximately 3 nm (i.e., approximately 20 times the C-C bond length). We propose that in the double resonance Raman scattering process the photoelectron scatters diffusely from our edges, obscuring the recently proposed strong variation in the scattering from armchair versus zigzag symmetry edges based on theoretical arguments.