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The spin-orbit assisted Mott insulator $\alpha$-RuCl3 is proximate to the coveted quantum spin liquid (QSL) predicted by the Kitaev model. In the search for the pure Kitaev QSL, reducing the dimensionality of this frustrated magnet by exfoliation has been proposed as a way to enhance magnetic fluctuations and Kitaev interactions. Here, we perform angle-dependent tunneling magnetoresistance (TMR) measurements on ultrathin $\alpha$-RuCl3 crystals with various layer numbers to probe their magnetic, electronic and crystal structure. We observe a giant change in resistance - as large as ~2500% - when the magnetic field rotates either within or out of the $\alpha$-RuCl3 plane, a manifestation of the strongly anisotropic spin interactions in this material. In combination with scanning transmission electron microscopy, this tunneling anisotropic magnetoresistance (TAMR) reveals that few-layer $\alpha$-RuCl3 crystals remain in the high-temperature monoclinic phase at low temperature. It also shows the presence of a zigzag antiferromagnetic order below the critical temperature TN ~ 14 K, which is twice the one typically observed in bulk samples with rhombohedral stacking. Our work offers valuable insights into the relation between the stacking order and magnetic properties of this material, which helps lay the groundwork for creating and electrically probing exotic magnetic phases like QSLs via van der Waals engineering.

Topological materials confined in one-dimension (1D) can transform computing technologies, such as 1D topological semimetals for nanoscale interconnects and 1D topological superconductors for fault-tolerant quantum computing. As such, understanding crystallization of 1D-confined topological materials is critical. Here, we demonstrate 1D-confined crystallization routes during template-assisted nanowire synthesis where we observe diameter-dependent phase selectivity for topological metal tungsten phosphides. A phase bifurcation occurs to produce tungsten monophosphide and tungsten diphosphide at the cross-over nanowire diameter of ~ 35 nm. Four-dimensional scanning transmission electron microscopy was used to identify the two phases and to map crystallographic orientations of grains at a few nm resolution. The 1D-confined phase selectivity is attributed to the minimization of the total surface energy, which depends on the nanowire diameter and chemical potentials of precursors. Theoretical calculations were carried out to construct the diameter-dependent phase diagram, which agrees with experimental observations. Our find-ings suggest a new crystallization route to stabilize topological materials confined in 1D., Comment: 5 figures

The charge density wave (CDW) material 1T-TaS$_2$ exhibits a pulse-induced insulator-to-metal transition, which shows promise for next-generation electronics such as memristive memory and neuromorphic hardware. However, the rational design of TaS$_2$ devices is hindered by a poor understanding of the switching mechanism, the pulse-induced phase, and the influence of material defects. Here, we operate a 2-terminal TaS$_2$ device within a scanning transmission electron microscope (STEM) at cryogenic temperature, and directly visualize the changing CDW structure with nanoscale spatial resolution and down to 300 {\mu}s temporal resolution. We show that the pulse-induced transition is driven by Joule heating, and that the pulse-induced state corresponds to nearly commensurate and incommensurate CDW phases, depending on the applied voltage amplitude. With our in operando cryo-STEM experiments, we directly correlate the CDW structure with the device resistance, and show that dislocations significantly impact device performance. This work resolves fundamental questions of resistive switching in TaS$_2$ devices critical for engineering reliable and scalable TaS$_2$ electronics.

With shrinking dimensions in integrated circuits, sensors, and functional devices, there is a pressing need to develop nanofabrication techniques with simultaneous control of morphology, microstructure, and material composition over wafer length scales. Current techniques are largely unable to meet all these conditions, suffering from poor control of morphology and defect structure or requiring extensive optimization or post-processing to achieve desired nanostructures. Recently, thermomechanical nanomolding (TMNM) has been shown to yield single-crystalline, high aspect ratio nanowires of metals, alloys, and intermetallics over wafer-scale distances. Here, we extend TMNM for wafer-scale fabrication of 2D nanostructures. Using Cu, we successfully nanomold Cu nanoribbons with widths < 50 nm, depths ~ 0.5-1 microns and lengths ~ 7 mm into Si trenches at conditions compatible with back end of line processing. Through SEM cross-section imaging and 4D-STEM grain orientation maps, we show that the grain size of the bulk feedstock is transferred to the nanomolded structures up to and including single crystal Cu. Based on the retained microstructures of molded 2D Cu, we discuss the deformation mechanism during molding for 2D TMNM., Comment: 4 figures

The layer stacking order in 2D materials strongly affects functional properties and holds promise for next generation electronic devices. In bulk, octahedral MoTe$_2$ possesses two stacking arrangements, the Weyl semimetal T$_d$ phase, and the higher-order topological insulator 1T' phase; however, it remains unclear if thin exfoliated flakes of MoTe$_2$ follow the T$_d$, 1T', or an alternative stacking sequence. Here, we resolve this debate using atomic-resolution imaging within the transmission electron microscope. We find that the layer stacking in thin flakes of MoTe$_2$ is highly disordered and pseudo-random, which we attribute to intrinsic confinement effects. Conversely, WTe$_2$, which is isostructural and isoelectronic to MoTe$_2$, displays ordered stacking even for thin exfoliated flakes. Our results are important for understanding the quantum properties of MoTe$_2$ devices, and suggest that thickness may be used to alter the layer stacking in other 2D materials., Comment: 6 figures, 2 tables

Reduced dimensionality leads to emergent phenomena in quantum materials and there is a need for accelerated materials discovery of nanoscale quantum materials in reduced dimensions. Thermomechanical nanomolding is a rapid synthesis method that produces high quality single-crystalline quantum nanowires with controlled dimensions over wafer-scale sizes. Herein, we apply nanomolding to fabricate nanowires from bulk feedstock of MoP, a triple-point topological metal with extremely high conductivity that is promising for low-resistance interconnects. Surprisingly, we obtained single-crystalline Mo$_{4}$P$_{3}$ nanowires, a metastable phase at room temperature in atmospheric pressure. We thus demonstrate nanomolding can create metastable phases inaccessible by other nanomaterial syntheses and can explore a previously inaccessible synthesis space at high temperatures and pressures. Furthermore, our results suggest that the current understanding of interfacial solid diffusion for nanomolding is incomplete, providing opportunities to explore solid-state diffusion at high-pressure and high-temperature regimes in confined dimensions., Comment: 3 figures

The increasing resistance of Cu interconnects for decreasing dimensions is a major challenge in continued downscaling of integrated circuits beyond the 7-nm technology node as it leads to unacceptable signal delays and power consumption in computing. The resistivity of Cu increases due to electron scattering at surfaces and grain boundaries of the interconnects at the nanoscale. Topological semimetals, owing to their topologically protected surface states and suppressed electron backscattering, are promising material candidates to potentially replace current Cu interconnects as low-resistance interconnects. Here, we report the attractive resistivity scaling of topological metal MoP nanowires and show that the resistivity values are comparable to those of Cu interconnects below 500 nm$^2$ cross-section areas. More importantly, we demonstrate that the dimensional scaling of MoP nanowires, in terms of line resistance versus total cross-sectional area, is superior to those of effective Cu and barrier-less Ru interconnects, suggesting MoP is an attractive solution to the current scaling challenge of Cu interconnects., Comment: 4 figures

The Weyl semimetal WTe$_{2}$ has shown several correlated electronic behaviors, such as the quantum spin Hall effect, superconductivity, ferroelectricity, and a possible exciton insulator state, all of which can be tuned by various physical and chemical approaches. Here, we discover a new electronic phase in WTe$_{2}$ induced by lithium intercalation. The new phase exhibits an increasing resistivity with decreasing temperature and its carrier density is almost two orders of magnitude lower than the carrier density of the semi-metallic T$_{d}$ phase, probed by in situ Hall measurements as a function of lithium intercalation. Our theoretical calculations predict the new lithiated phase to be a charge density wave (CDW) phase with a bandgap of ~ 0.14 eV, in good agreement with the in situ transport data. The new phase is structurally distinct from the initial T$_{d}$ phase, characterized by polarization angle-dependent Raman spectroscopy, and large lattice distortions close to 6 % are predicted in the new phase. Thus, we report the first experimental evidence of CDW in T$_{d}$-WTe$_{2}$, projecting WTe$_{2}$ as a new playground for studying the interplay between CDW and superconductivity. Our finding of a new gapped phase in a two-dimensional (2D) semi-metal also demonstrates electrochemical intercalation as a powerful tuning knob for modulating electron density and phase stability in 2D materials., Comment: 6 figures

The observation of the Higgs boson solidified the standard model of particle physics. However, explanations of anomalies (e.g. dark matter) rely on further symmetry breaking calling for an undiscovered axial Higgs mode. In condensed matter the Higgs was seen in magnetic, superconducting and charge density wave(CDW) systems. Uncovering a low energy mode's vector properties is challenging, requiring going beyond typical spectroscopic or scattering techniques. Here, we discover an axial Higgs mode in the CDW system RTe3 using the interference of quantum pathways. In RTe3 (R=La,Gd), the electronic ordering couples bands of equal or different angular momenta. As such, the Raman scattering tensor associated to the Higgs mode contains both symmetric and antisymmetric components, which can be excited via two distinct, but degenerate pathways. This leads to constructive or destructive interference of these pathways, depending on the choice of the incident and Raman scattered light polarization. The qualitative behavior of the Raman spectra is well-captured by an appropriate tight-binding model including an axial Higgs mode. The elucidation of the antisymmetric component provides direct evidence that the Higgs mode contains an axial vector representation (i.e. a pseudo-angular momentum) and hints the CDW in RTe3 is unconventional. Thus we provide a means for measuring collective modes quantum properties without resorting to extreme experimental conditions.

Surface functionalization of two-dimensional (2D) materials with organic electron donors (OEDs) is a powerful method to modulate the electronic properties of the material. However, our fundamental understanding of the doping mechanism is largely limited to the categorization of molecular dopants as n- or p-type based on the relative position of the molecule's redox potential in relation to the Fermi level of the 2D host. Our limited knowledge about the impact of factors other than the redox properties of the molecule on doping makes it challenging to controllably use molecules to dope 2D materials and design new OEDs. Here, we functionalize monolayer MoS$_2$ using two molecular dopants, Me- and $^t$Bu-OED, which have the same redox potential but different steric properties to probe the effects of molecular size on the doping level of MoS$_2$. We show that, for the same functionalization conditions, the doping powers of Me- and $^t$Bu-OED are 0.22 - 0.44 and 0.11 electrons per molecule, respectively, demonstrating that the steric properties of the molecule critically affect doping levels. Using the stronger dopant, Me-OED, a carrier density of 1.10 +/- 0.37 x 10$^{14}$ cm$^{-2}$ is achieved in MoS$_2$, the highest doping level to date for MoS$_2$ using surface functionalization. Overall, we establish that tuning of the steric properties of the dopant is essential in the rational design of molecular dopants., Comment: 5 figures and 1 table

Phase transitions of two-dimensional materials and their heterostructures enable many applications including electrochemical energy storage, catalysis, and memory; however, the nucleation pathways by which these transitions proceed remain underexplored, prohibiting engineering control for these applications. Here, we demonstrate that the lithium intercalation-induced 2H-1T' phase transition in MoS2 proceeds via nucleation of the 1T' phase at a heterointerface by monitoring the phase transition of MoS2/graphene and MoS2/hexagonal boron nitride (hBN) heterostructures with Raman spectroscopy in situ during intercalation. We observe that graphene-MoS2 heterointerfaces require an increase of 0.8 V in applied electrochemical potential to nucleate the 1T' phase in MoS2 compared to hBN-MoS2 heterointerfaces. The increased nucleation barrier at graphene-MoS2 heterointerfaces is due to the reduced charge transfer from lithium to MoS2 at the heterointerface as lithium also dopes graphene based on ab initio calculations. Further, we show that the growth of the 1T' domain propagates along the heterointerface, rather than through the interior of MoS2. Our results provide the first experimental observations of the heterogeneous nucleation and growth of intercalation-induced phase transitions in two-dimensional materials and heterointerface effects on their phase transition., Comment: 5 figures

We investigate the electronic structure of tungsten ditelluride (WTe$_2$) flakes with different thicknesses in magneto-transport studies. The temperature-dependent resistance and magnetoresistance (MR) measurements both confirm the breaking of carrier balance induced by thickness reduction, which suppresses the `turn-on' behavior and large positive MR. The Shubnikov-de-Haas oscillation studies further confirm the thickness-dependent change of electronic structure of WTe$_2$ and reveal a possible temperature-sensitive electronic structure change. Finally, we report the thickness-dependent anisotropy of Fermi surface, which reveals that multi-layer WTe$_2$ is an electronic 3D material and the anisotropy decreases as thickness decreases.

The intercalation-induced phase transition of MoS2 from the semiconducting 2H to the semimetallic 1T' phase has been studied in detail for nearly a decade; however, the effects of a heterointerface between MoS2 and other two-dimensional (2D) crystals on the phase transition have largely been overlooked. Here, ab initio calculations show that intercalating Li at a MoS2-hexagonal boron nitride (hBN) interface stabilizes the 1T phase over the 2H phase of MoS2 by ~ 100 mJ m-2, suggesting that encapsulating MoS2 with hBN may lower the electrochemical energy needed for the intercalation-induced phase transition. However, in situ Raman spectroscopy of hBN-MoS2-hBN heterostructures during electrochemical intercalation of Li+ shows that the phase transition occurs at the same applied voltage for the heterostructure as for bare MoS2. We hypothesize that the predicted thermodynamic stabilization of the 1T'-MoS2-hBN interface is counteracted by an energy barrier to the phase transition imposed by the steric hindrance of the heterointerface. The phase transition occurs at lower applied voltages upon heating the heterostructure, which supports our hypothesis. Our study highlights that interfacial effects of 2D heterostructures can go beyond modulating electrical properties and can modify electrochemical and phase transition behaviors., Comment: 4 figures and 1 table

Owing to the small energy differences between its polymorphs, MoTe2 can access a full spectrum of electronic states, from the 2H semiconducting state to the 1T semimetallic state, and from the Td Weyl semimetallic state to the superconducting state in the 1T and Td phase at low temperature. Thus, it is a model system for phase transformation studies as well as quantum phenomena such as the quantum spin Hall effect and topological superconductivity. Careful studies of MoTe2 and its potential applications require large area MoTe2 thin films with high crystallinity and thickness control. Here, we present cm2 scale synthesis of 2H MoTe2 thin films with layer control and large grains that span several microns. Layer control is achieved by controlling the initial thickness of the precursor MoOx thin films, which are deposited on sapphire substrates by atomic layer deposition and subsequently tellurized. Despite the van der Waals epitaxy, the precursor-substrate interface is found to critically determine the uniformity in thickness and grain size of the resulting MoTe2 films: MoTe2 grown on sapphire show uniform films while MoTe2 grown on amorphous SiO2 substrates form islands. This synthesis strategy decouples the layer control from the variabilities of growth conditions for robust growth results, and is applicable to grow other transition metal dichalcogenides with layer control., Comment: 6 figure

Topological crystalline insulator tin telluride (SnTe) provides a rich playground to examine interactions of correlated electronic states, such as ferroelectricity, topological surface states, and superconductivity. Making SnTe into nanowires further induces novel electronic states due to one-dimensional (1D) confinement effects. Thus, for transport measurements, SnTe nanowires must be made narrow in their diameters to ensure the 1D confinement and phase coherence of the topological surface electrons. This study reports a facile growth method to produce narrow SnTe nanowires with a high yield using alloy nanoparticles as growth catalysts. The average diameter of the SnTe nanowires grown using the alloy nanoparticles is 85 nm, nearly a factor of three reduction from the previous average diameter of 240 nm using gold nanoparticles as growth catalysts. Transport measurements reveal the effect of the nanowire diameter on the residual resistance ratio and magnetoresistance. Particularly, the ferroelectric transition temperature for SnTe is observed to change systematically with the nanowire diameter. In situ cryogenic cooling of narrow SnTe nanowires in a transmission electron microscope directly reveals the cubic to rhombohedral structural transition, which is associated with the ferroelectric transition. Thus, these narrow SnTe nanowires represent a model system to study electronic states arising from the 1D confinement, such as 1D topological superconductivity as well as a potential multi-band superconductivity., Comment: 5 figures

Lithium intercalation into graphite is the foundation for the lithium-ion battery, and the thermodynamics of the lithiation of graphitic electrodes have been heavily investigated. Intercalated lithium in bulk graphite undergoes structural ordering known as staging to minimize electrostatic repulsions within the crystal lattice. While this process is well-understood for bulk graphite, confinement effects become important at the nanoscale, which can significantly impact the electrochemistry of nanostructured electrodes. Therefore, graphene offers a model platform to study intercalation dynamics at the nanoscale by combining on-chip device fabrication and electrochemical intercalation with in situ characterization. We show that microscale mechanical strain significantly affects the formation of ordered lithium phases in graphene. In situ Raman spectroscopy of graphene microflakes mechanically constrained at the edge during lithium intercalation reveals a thickness-dependent increase of up to 1.26 V in the electrochemical potential that induces lithium staging. While the induced mechanical strain energy increases with graphene thickness to the fourth power, its magnitude is small compared to the observed increase in electrochemical energy. We hypothesize that the mechanical strain energy increases a nucleation barrier for lithium staging, greatly delaying the formation of ordered lithium phases. Our results indicate that electrode assembly can critically impact lithium staging dynamics important for cycling rates and power generation for batteries. We demonstrate strain engineering in two-dimensional nanomaterials as an approach to manipulate phase transitions and chemical reactivity., Comment: 4 figures

Surface functionalization with organic electron donors (OEDs) is an effective doping strategy for two-dimensional (2D) materials, which can achieve doping levels beyond those possible with conventional electric field gating. While the effectiveness of surface functionalization has been demonstrated in many 2D systems, the doping efficiencies of OEDs have largely been unmeasured, which is in stark contrast to their precision syntheses and tailored redox potentials. Here, using monolayer MoS2 as a model system and an organic reductant based on 4,4-bipyridine (DMAP-OED) as a strong organic dopant, we establish that the doping efficiency of DMAP-OED to MoS2 is in the range of 0.63 to 1.26 electrons per molecule. We also achieve the highest doping level to date in monolayer MoS2 by surface functionalization and demonstrate that DMAP-OED is a stronger dopant than benzyl viologen, which was the previous best OED dopant. The measured range of the doping efficiency is in good agreement with the values predicted from first-principles calculations. Our work provides a basis for the rational design of OEDs for high-level doping of 2D materials., Comment: 19 pages, 4 figures, 1 table

We report electron transport studies in an encapsulated few-layer WTe$_2$ at low temperatures and high magnetic fields. The magnetoconductance reveals a temperature-induced crossover between weak antilocalization (WAL) and weak localization (WL) in quantum diffusive regime. We show that the crossover clearly manifests coexistence and competition among several characteristic lengths, including the dephasing length, the spin-flip length, and the mean free path. In addition, low temperature conductance increases logarithmically with the increase of temperature indicating an interplay of electron-electron interaction (EEI) and spin-orbit coupling (SOC). We demonstrate the existences and quantify the strengths of EEI and SOC which are considered to be responsible for gap opening in the quantum spin hall state in WTe2 at the monolayer limit.

Recently rediscovered black phosphorus is a layered semiconductor with promising electronic and photonic properties. Dynamic control of its bandgap can enable novel device applications and allow for the exploration of new physical phenomena. However, theoretical investigations and photoemission spectroscopy experiments performed on doped black phosphorus through potassium adsorption indicate that in its few-layer form, an exceedingly large electric field in the order of several volts per nanometer is required to effectively tune its bandgap, making the direct electrical control unfeasible. Here we demonstrate the tuning of bandgap in intrinsic black phosphorus using an electric field directly and reveal the unique thickness-dependent bandgap tuning properties, arising from the strong interlayer electronic-state coupling. Furthermore, leveraging a 10-nm-thick black phosphorus in which the field-induced potential difference across the film dominates over the interlayer coupling, we continuously tune its bandgap from ~300 to below 50 milli-electron volts, using a moderate displacement field up to 1.1 volts per nanometer. Such dynamic tuning of bandgap may not only extend the operational wavelength range of tunable black phosphorus photonic devices, but also pave the way for the investigation of electrically tunable topological insulators and topological nodal semimetals.

Synapses are functional links between neurons, through which "information" flows in the neural network. These connections vary significantly in strength, typically resulting from the intrinsic heterogeneity in their chemical and biological properties. Such heterogeneity is fundamental to the diversity of neural activities, which together with other features of the brain enables functions ranging from perception and recognition, to memory and reasoning. Realizing such heterogeneity in synaptic electronics is critical towards building artificial neural network with the potential for achieving the level of complexity in biological systems. However, such intrinsic heterogeneity has been very challenging to realize in current synaptic devices. Here, we demonstrate the first black phosphorus (BP) synaptic device, which offers intrinsic anisotropy in its synaptic characteristics directly resulting from its low crystal symmetry. The charge transfer between the 2-nm native oxide of BP and the BP channel is utilized to achieve the synaptic behavior. Key features of biological synapses such as long-term plasticity with heterogeneity, including long-term potentiation/depression and spike-timing-dependent plasticity, are mimicked. With the anisotropic BP synaptic devices, we also realize a simple compact heterogeneous axon-multi-synapses network. This demonstration represents an important step towards introducing intrinsic heterogeneity to artificial neuromorphic systems., Comment: 24 pages, 7 figures, Advanced Materials, In press

For topological insulators and topological crystalline insulators (TCIs), their exotic surface states are promising for fundamental condensed matter physics research as well as future electronics such as low-dissipation electronics and spintronics. However, the high bulk carrier density that often dominates the transport property is the major materials challenge, critically hindering our ability to study and manipulate the surface states. In this manuscript, we demonstrate an alloying strategy, SnSexTe1-x, to effectively reduce the bulk carrier density. As long as SnSexTe1-x remains in the cubic crystal structure, it is predicted to be a TCI. We show systematic decrease of the bulk carrier density with the increasing Se concentration, demonstrating that the alloying principle works. In addition, we map out the phase diagram of the cubic to the orthorhombic structural transition as a function of the Se concentration. This was made possible by studying alloy nanoplates which remain single-crystalline and is either in the cubic or the orthorhombic phase, in contrast to bulk alloys that would exhibit polycrystalline grains. Lastly, we investigate systematically the ferroelectric transition associated with the structural transition from the cubic to the rhombohedral phase for SnSexTe1-x. This is the first ferroelectric transition study of the alloy system SnSexTe1-x., Comment: 25 pages, 4 figures

Topological crystalline insulators are topological insulators whose surface states are protected by the crystalline symmetry, instead of the time reversal symmetry. Similar to the first generation of three-dimensional topological insulators such as Bi2Se3 and Bi2Te3, topological crystalline insulators also possess surface states with exotic electronic properties such as spin-momentum locking and Dirac dispersion. Experimentally verified topological crystalline insulators to date are SnTe, Pb1-xSnxSe, and Pb1-xSnxTe. Because topological protection comes from the crystal symmetry, magnetic impurities or in-plane magnetic fields are not expected to open a gap in the surface states in topological crystalline insulators. Additionally, because they are cubic structure instead of layered structure, branched structures or strong coupling with other materials for large proximity effects are possible, which are difficult with layered Bi2Se3 and Bi2Te3. Thus, additional fundamental phenomena inaccessible in three-dimensional topological insulators can be pursued. In this review, topological crystalline insulator SnTe nanostructures will be discussed. For comparison, experimental results based on SnTe thin films will be covered. Surface state properties of topological crystalline insulators will be discussed briefly., Comment: Accepted Manuscript Nanoscale, 2014

Indium (In) doping in topological crystalline insulator SnTe induces superconductivity, making In-doped SnTe a candidate for a topological superconductor. SnTe nanostructures offer well-defined nanoscale morphology and high surface-to-volume ratios to enhance surface effects. Here, we study In-doped SnTe nanoplates, InxSn1-xTe, with x ranging from 0 to 0.1 and show they superconduct. More importantly, we show that In doping reduces the bulk mobility of InxSn1-xTe such that the surface states are revealed in magnetotransport despite the high bulk carrier density. This is manifested by two-dimensional linear magnetoresistance in high magnetic fields, which is independent of temperature up to 10 K. Aging experiments show that the linear magnetoresistance is sensitive to ambient conditions, further confirming its surface origin. We also show that the weak antilocalization observed in InxSn1-xTe nanoplates is a bulk effect. Thus, we show that nanostructures and reducing the bulk mobility are effective strategies to reveal the surface states and test for topological superconductors.

SnTe is a topological crystalline insulator that possesses spin-polarized, Dirac-dispersive surface states protected by crystal symmetry. Multiple surface states exist on the {100}, {110}, and {111} surfaces of SnTe, with the band structure of surface states depending on the mirror symmetry of a particular surface. Thus, to access surface states selectively, it is critical to control the morphology of SnTe such that only desired crystallographic surfaces are present. Here, we grow SnTe nanostructures using vapor-liquid-solid and vapor-solid growth mechanisms. Previously, SnTe nanowires and nanocrystals have been grown.1-4 In this report, we demonstrate synthesis of SnTe nanoplates with lateral dimensions spanning tens of microns and thicknesses of a hundred nanometers. The top and bottom surfaces are either (100) or (111), maximizing topological surface states on these surfaces. Magnetotransport on these SnTe nanoplates shows high bulk carrier density, consistent with bulk SnTe crystals arising due to defects such as Sn vacancies. In addition, we observe a structural phase transition in these nanoplates from the high temperature rock salt to low temperature rhombohedral structure. For nanoplates with very high carrier density, we observe a slight upturn in resistance at low temperatures, indicating electron-electron interactions., Comment: Nano Lett., Article ASAP,2014

The discovery of three-dimensional (3D) topological insulators opens a gateway to generate unusual phases and particles made of the helical surface electrons, proposing new applications using unusual spin nature. Demonstration of the helical electron transport is a crucial step to both physics and device applications of topological insulators. Topological insulator nanowires, of which spin-textured surface electrons form 1D band manipulated by enclosed magnetic flux, offer a unique nanoscale platform to realize quantum transport of spin-momentum locking nature. Here, we report an observation of a topologically protected 1D mode of surface electrons in topological insulator nanowires existing at only two values of half magnetic quantum flux ($\pm$h/2e) due to a spin Berry's phase ($\pi$). The helical 1D mode is robust against disorder but fragile against a perpendicular magnetic field breaking time-reversal-symmetry. This result demonstrates a device with robust and easily accessible 1D helical electronic states from 3D topological insulators, a unique nanoscale electronic system to study topological phenomena., Comment: 5 figures

A topological insulator is a new state of matter, possessing gapless spin-locking surface states across the bulk band gap which has created new opportunities from novel electronics to energy conversion. However, the large concentration of bulk residual carriers has been a major challenge for revealing the property of the topological surface state via electron transport measurement. Here we report surface state dominated transport in Sb-doped Bi2Se3 nanoribbons with very low bulk electron concentrations. In the nanoribbons with sub-10nm thickness protected by a ZnO layer, we demonstrate complete control of their top and bottom surfaces near the Dirac point, achieving the lowest carrier concentration of 2x10^11/cm2 reported in three-dimensional (3D) topological insulators. The Sb-doped Bi2Se3 nanostructures provide an attractive materials platform to study fundamental physics in topological insulators, as well as future applications., Comment: 5 pages, 4 figures, 1 table

Topological insulators represent a new state of quantum matter attractive to both fundamental physics and technological applications such as spintronics and quantum information processing. In a topological insulator, the bulk energy gap is traversed by spin-momentum locked surface states forming an odd number of surface bands that possesses unique electronic properties. However, transport measurements have often been dominated by residual bulk carriers from crystal defects or environmental doping which mask the topological surface contribution. Here we demonstrate (BixSb1-x)2Te3 as a tunable topological insulator system to manipulate bulk conductivity by varying the Bi/Sb composition ratio. (BixSb1-x)2Te3 ternary compounds are confirmed as topological insulators for the entire composition range by angle resolved photoemission spectroscopy (ARPES) measurements and ab initio calculations. Additionally, we observe a clear ambipolar gating effect similar to that observed in graphene using nanoplates of (BixSb1-x)2Te3 in field-effect-transistor (FET) devices. The manipulation of carrier type and concentration in topological insulator nanostructures demonstrated in this study paves the way for implementation of topological insulators in nanoelectronics and spintronics., Comment: 7 pages, 4 figures

Bi2Se3 is a topological insulator with metallic surface states residing in a large bulk bandgap. It is believed that Bi2Se3 gets additional n-type doping after exposure to atmosphere, thereby reducing the relative contribution of surface states in total conductivity. In this letter, transport measurements on Bi2Se3 nanoribbons provide additional evidence of such environmental doping process. Systematic surface composition analyses by X-ray photoelectron spectroscopy reveal fast formation and continuous growth of native oxide on Bi2Se3 under ambient conditions. In addition to n-type doping at the surface, such surface oxidation is likely the material origin of the degradation of topological surface states. Appropriate surface passivation or encapsulation may be required to probe topological surface states of Bi2Se3 by transport measurements.

Ultra-thin topological insulator nanostructures, in which coupling between top and bottom surface states takes place, are of great intellectual and practical importance. Due to the weak Van der Waals interaction between adjacent quintuple layers (QLs), the layered bismuth selenide (Bi2Se3), a single Dirac-cone topological insulator with a large bulk gap, can be exfoliated down to a few QLs. In this paper, we report the first controlled mechanical exfoliation of Bi2Se3 nanoribbons (> 50 QLs) by an atomic force microscope (AFM) tip down to a single QL. Microwave impedance microscopy is employed to map out the local conductivity of such ultra-thin nanoribbons, showing drastic difference in sheet resistance between 1~2 QLs and 4~5 QLs. Transport measurement carried out on an exfoliated (\leq 5 QLs) Bi2Se3 device shows non-metallic temperature dependence of resistance, in sharp contrast to the metallic behavior seen in thick (> 50 QLs) ribbons. These AFM-exfoliated thin nanoribbons afford interesting candidates for studying the transition from quantum spin Hall surface to edge states.

Topological insulator (TI) represents an unconventional quantum phase of matter with insulating bulk bandgap and metallic surface states. Recent theoretical calculations and photoemission spectroscopy measurements show that Group V-VI materials Bi2Se3, Bi2Te3 and Sb2Te3 are TI with a single Dirac cone on the surface. These materials have anisotropic, layered structures, in which five atomic layers are covalently bonded to form a quintuple layer, and quintuple layers interact weakly through van der Waals interaction to form the crystal. A few quintuple layers of these materials are predicted to exhibit interesting surface properties. Different from our previous nanoribbon study, here we report the synthesis and characterizations of ultrathin Bi2Te3 and Bi2Se3 nanoplates with thickness down to 3 nm (3 quintuple layers), via catalyst-free vapor-solid (VS) growth mechanism. Optical images reveal thickness-dependant color and contrast for nanoplates grown on oxidized silicon (300nm SiO2/Si). As a new member of TI nanomaterials, ultrathin TI nanoplates have an extremely large surface-to-volume ratio and can be electrically gated more effectively than the bulk form, potentially enhancing surface states effects in transport measurements. Low temperature transport measurements of a single nanoplate device, with a high-k dielectric top gate, show decrease in carrier concentration by several times and large tuning of chemical potential., Comment: 6 figures

Relativistic electrons in a structured medium generate radiative losses such as Cherenkov and transition radiation that act as a virtual light source, coupling to the photonic densities of states. The effect is most pronounced when the imaginary part of the dielectric function is zero, a regime where in a non-retarded treatment no loss or coupling can occur. Maps of the resultant energy losses as a sub-5nm electron probe scans across finite waveguide structures reveal spatial distributions of optical modes in a spectral domain ranging from near-infrared to far ultraviolet., Comment: 18 pages, 4 figures

A simple surface band structure and a large bulk band gap have allowed Bi2Se3 to become a reference material for the newly discovered three-dimensional topological insulators, which exhibit topologically-protected conducting surface states that reside inside the bulk band gap. Studying topological insulators such as Bi2Se3 in nanostructures is advantageous because of the high surface-to-volume ratio, which enhances effects from the surface states; recently reported Aharonov-Bohm oscillation in topological insulator nanoribbons by some of us is a good example. Theoretically, introducing magnetic impurities in topological insulators is predicted to open a small gap in the surface states by breaking time-reversal symmetry. Here, we present synthesis of magnetically-doped Bi2Se3 nanoribbons by vapor-liquid-solid growth using magnetic metal thin films as catalysts. Although the doping concentration is less than ~ 2%, low-temperature transport measurements of the Fe-doped Bi2Se3 nanoribbon devices show a clear Kondo effect at temperatures below 30 K, confirming the presence of magnetic impurities in the Bi2Se3 nanoribbons. The capability to dope topological insulator nanostructures magnetically opens up exciting opportunities for spintronics., Comment: 16 pages, 4 figures

Recent theoretical calculations and photoemission spectroscopy measurements on the bulk Bi2Se3 material show that it is a three-dimensional topological insulator possessing conductive surface states with nondegenerate spins, attractive for dissipationless electronics and spintronics applications. Nanoscale topological insulator materials have a large surface-to-volume ratio that can manifest the conductive surface states and are promising candidates for devices. Here we report the synthesis and characterization of high quality single crystalline Bi2Se3 nanomaterials with a variety of morphologies. The synthesis of Bi2Se3 nanowires and nanoribbons employs Au-catalyzed vapor-liquid-solid (VLS) mechanism. Nanowires, which exhibit rough surfaces, are formed by stacking nanoplatelets along the axial direction of the wires. Nanoribbons are grown along [11-20] direction with a rectangular cross-section and have diverse morphologies, including quasi-one-dimensional, sheetlike, zigzag and sawtooth shapes. Scanning tunneling microscopy (STM) studies on nanoribbons show atomically smooth surfaces with ~ 1 nm step edges, indicating single Se-Bi-Se-Bi-Se quintuple layers. STM measurements reveal a honeycomb atomic lattice, suggesting that the STM tip couples not only to the top Se atomic layer, but also to the Bi atomic layer underneath, which opens up the possibility to investigate the contribution of different atomic orbitals to the topological surface states. Transport measurements of a single nanoribbon device (four terminal resistance and Hall resistance) show great promise for nanoribbons as candidates to study topological surface states., Comment: Nano Letters, Article ASAP