Engineering the Structural and Electronic Phases of MoTe2 through W Substitution.

MoTe2 is an exfoliable transition metal dichalcogenide (TMD) that crystallizes in three symmetries: the semiconducting trigonal-prismatic 2H- or α-phase, the semimetallic and monoclinic 1T'- or ß-phase, and the semimetallic orthorhombic γ-structure. The 2H-phase displays a band gap of ∼1 eV making it appealing for flexible and transparent optoelectronics. The γ-phase is predicted to possess unique topological properties that might lead to topologically protected nondissipative transport channels. Recently, it was argued that it is possible to locally induce phase-transformations in TMDs, through chemical doping, local heating, or electric-field to achieve ohmic contacts or to induce useful functionalities such as electronic phase-change memory elements. The combination of semiconducting and topological elements based upon the same compound might produce a new generation of high performance, low dissipation optoelectronic elements. Here, we show that it is possible to engineer the phases of MoTe2 through W substitution by unveiling the phase-diagram of the Mo1-xWxTe2 solid solution, which displays a semiconducting to semimetallic transition as a function of x. We find that a small critical W concentration xc ∼ 8% stabilizes the γ-phase at room temperature. This suggests that crystals with x close to xc might be particularly susceptible to phase transformations induced by an external perturbation, for example, an electric field. Photoemission spectroscopy, indicates that the γ-phase possesses a Fermi surface akin to that of WTe2.

Quasiparticle interference, quasiparticle interactions, and the origin of the charge density wave in 2H-NbSe2.

We show that a small number of intentionally introduced defects can be used as a spectroscopic tool to amplify quasiparticle interference in 2H-NbSe2 that we measure by scanning tunneling spectroscopic imaging. We show, from the momentum and energy dependence of the quasiparticle interference, that Fermi surface nesting is inconsequential to charge density wave formation in 2H-NbSe2. We demonstrate that, by combining quasiparticle interference data with additional knowledge of the quasiparticle band structure from angle resolved photoemission measurements, one can extract the wave vector and energy dependence of the important electronic scattering processes thereby obtaining direct information both about the fermiology and the interactions. In 2H-NbSe2, we use this combination to confirm that the important near-Fermi-surface electronic physics is dominated by the coupling of the quasiparticles to soft mode phonons at a wave vector different from the charge density wave ordering wave vector.

Visualizing moiré ferroelectricity via plasmons and nano-photocurrent in graphene/twisted-WSe2 structures.

Ferroelectricity, a spontaneous and reversible electric polarization, is found in certain classes of van der Waals (vdW) materials. The discovery of ferroelectricity in twisted vdW layers provides new opportunities to engineer spatially dependent electric and optical properties associated with the configuration of moiré superlattice domains and the network of domain walls. Here, we employ near-field infrared nano-imaging and nano-photocurrent measurements to study ferroelectricity in minimally twisted WSe2. The ferroelectric domains are visualized through the imaging of the plasmonic response in a graphene monolayer adjacent to the moiré WSe2 bilayers. Specifically, we find that the ferroelectric polarization in moiré domains is imprinted on the plasmonic response of the graphene. Complementary nano-photocurrent measurements demonstrate that the optoelectronic properties of graphene are also modulated by the proximal ferroelectric domains. Our approach represents an alternative strategy for studying moiré ferroelectricity at native length scales and opens promising prospects for (opto)electronic devices.

Nano-spectroscopy of excitons in atomically thin transition metal dichalcogenides.

Excitons play a dominant role in the optoelectronic properties of atomically thin van der Waals (vdW) semiconductors. These excitons are amenable to on-demand engineering with diverse control knobs, including dielectric screening, interlayer hybridization, and moiré potentials. However, external stimuli frequently yield heterogeneous excitonic responses at the nano- and meso-scales, making their spatial characterization with conventional diffraction-limited optics a formidable task. Here, we use a scattering-type scanning near-field optical microscope (s-SNOM) to acquire exciton spectra in atomically thin transition metal dichalcogenide microcrystals with previously unattainable 20 nm resolution. Our nano-optical data revealed material- and stacking-dependent exciton spectra of MoSe2, WSe2, and their heterostructures. Furthermore, we extracted the complex dielectric function of these prototypical vdW semiconductors. s-SNOM hyperspectral images uncovered how the dielectric screening modifies excitons at length scales as short as few nanometers. This work paves the way towards understanding and manipulation of excitons in atomically thin layers at the nanoscale.

Nanoscale lattice dynamics in hexagonal boron nitride moiré superlattices.

Twisted two-dimensional van der Waals (vdW) heterostructures have unlocked a new means for manipulating the properties of quantum materials. The resulting mesoscopic moiré superlattices are accessible to a wide variety of scanning probes. To date, spatially-resolved techniques have prioritized electronic structure visualization, with lattice response experiments only in their infancy. Here, we therefore investigate lattice dynamics in twisted layers of hexagonal boron nitride (hBN), formed by a minute twist angle between two hBN monolayers assembled on a graphite substrate. Nano-infrared (nano-IR) spectroscopy reveals systematic variations of the in-plane optical phonon frequencies amongst the triangular domains and domain walls in the hBN moiré superlattices. Our first-principles calculations unveil a local and stacking-dependent interaction with the underlying graphite, prompting symmetry-breaking between the otherwise identical neighboring moiré domains of twisted hBN.

Sensitivity of the superconducting state in thin films.

For more than two decades, there have been reports on an unexpected metallic state separating the established superconducting and insulating phases of thin-film superconductors. To date, no theoretical explanation has been able to fully capture the existence of such a state for the large variety of superconductors exhibiting it. Here, we show that for two very different thin-film superconductors, amorphous indium oxide and a single crystal of 2H-NbSe2, this metallic state can be eliminated by adequately filtering external radiation. Our results show that the appearance of temperature-independent, metallic-like transport at low temperatures is sufficiently described by the extreme sensitivity of these superconducting films to external perturbations. We relate this sensitivity to the theoretical observation that, in two dimensions, superconductivity is only marginally stable.

Unconventional scaling of the superfluid density with the critical temperature in transition metal dichalcogenides.

We report on muon spin rotation experiments probing the magnetic penetration depth λ(T) in the layered superconductors in 2H-NbSe2 and 4H-NbSe2. The current results, along with our earlier findings on 1T'-MoTe2 (Guguchia et al.), demonstrate that the superfluid density scales linearly with T c in the three transition metal dichalcogenide superconductors. Upon increasing pressure, we observe a substantial increase of the superfluid density in 2H-NbSe2, which we find to correlate with T c. The correlation deviates from the abovementioned linear trend. A similar deviation from the Uemura line was also observed in previous pressure studies of optimally doped cuprates. This correlation between the superfluid density and T c is considered a hallmark feature of unconventional superconductivity. Here, we show that this correlation is an intrinsic property of the superconductivity in transition metal dichalcogenides, whereas the ratio T c/T F is approximately a factor of 20 lower than the ratio observed in hole-doped cuprates. We, furthermore, find that the values of the superconducting gaps are insensitive to the suppression of the charge density wave state.

Magnetism in semiconducting molybdenum dichalcogenides.

Transition metal dichalcogenides (TMDs) are interesting for understanding the fundamental physics of two-dimensional (2D) materials as well as for applications to many emerging technologies, including spin electronics. Here, we report the discovery of long-range magnetic order below T M = 40 and 100 K in bulk semiconducting TMDs 2H-MoTe2 and 2H-MoSe2, respectively, by means of muon spin rotation (µSR), scanning tunneling microscopy (STM), and density functional theory (DFT) calculations. The µSR measurements show the presence of large and homogeneous internal magnetic fields at low temperatures in both compounds indicative of long-range magnetic order. DFT calculations show that this magnetism is promoted by the presence of defects in the crystal. The STM measurements show that the vast majority of defects in these materials are metal vacancies and chalcogen-metal antisites, which are randomly distributed in the lattice at the subpercent level. DFT indicates that the antisite defects are magnetic with a magnetic moment in the range of 0.9 to 2.8 µB. Further, we find that the magnetic order stabilized in 2H-MoTe2 and 2H-MoSe2 is highly sensitive to hydrostatic pressure. These observations establish 2H-MoTe2 and 2H-MoSe2 as a new class of magnetic semiconductors and open a path to studying the interplay of 2D physics and magnetism in these interesting semiconductors.

Author Correction: Signatures of the topological s+- superconducting order parameter in the type-II Weyl semimetal T d -MoTe2.

The original version of this article omitted the following from the Acknowledgements: "CAM and AL were supported by the NSF MRSEC program through Columbia in the Center for Precision Assembly of Superstratic and Superatomic Solids (DMR-1420634). Additionally, this research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under 'Contract No. DE-AC02-05CH11231'." This has now been corrected in both the PDF and HTML versions of the article.

Signatures of the topological s +- superconducting order parameter in the type-II Weyl semimetal T d-MoTe2.

In its orthorhombic T d polymorph, MoTe2 is a type-II Weyl semimetal, where the Weyl fermions emerge at the boundary between electron and hole pockets. Non-saturating magnetoresistance and superconductivity were also observed in T d-MoTe2. Understanding the superconductivity in T d-MoTe2, which was proposed to be topologically non-trivial, is of eminent interest. Here, we report high-pressure muon-spin rotation experiments probing the temperature-dependent magnetic penetration depth in T d-MoTe2. A substantial increase of the superfluid density and a linear scaling with the superconducting critical temperature T c is observed under pressure. Moreover, the superconducting order parameter in T d-MoTe2 is determined to have 2-gap s-wave symmetry. We also exclude time-reversal symmetry breaking in the superconducting state with zero-field µSR experiments. Considering the strong suppression of T c in MoTe2 by disorder, we suggest that topologically non-trivial s +- state is more likely to be realized in MoTe2 than the topologically trivial s ++ state.

Mechanical control of spin states in spin-1 molecules and the underscreened Kondo effect.

The ability to make electrical contact to single molecules creates opportunities to examine fundamental processes governing electron flow on the smallest possible length scales. We report experiments in which we controllably stretched individual cobalt complexes having spin S = 1, while simultaneously measuring current flow through the molecule. The molecule's spin states and magnetic anisotropy were manipulated in the absence of a magnetic field by modification of the molecular symmetry. This control enabled quantitative studies of the underscreened Kondo effect, in which conduction electrons only partially compensate the molecular spin. Our findings demonstrate a mechanism of spin control in single-molecule devices and establish that they can serve as model systems for making precision tests of correlated-electron theories.

Vibration-assisted electron tunneling in C140 transistors.

We measure electron tunneling in transistors made from C(140), a molecule with a mass-spring-mass geometry chosen as a model system to study electron-vibration coupling. We observe vibration-assisted tunneling at an energy corresponding to the stretching mode of C(140). Molecular modeling provides explanations for why this mode couples more strongly to electron tunneling than to the other internal modes of the molecule. We make comparisons between the observed tunneling rates and those expected from the Franck-Condon model.

Magnetic anisotropy variations and nonequilibrium tunneling in a cobalt nanoparticle.

We present detailed measurements of the discrete electron-tunneling level spectrum within nanometer-scale cobalt particles as a function of magnetic field and gate voltage, in this way probing individual quantum many-body eigenstates inside ferromagnetic samples. Variations among the observed levels indicate that different quantum states within one particle are subject to different magnetic anisotropy energies. Gate-voltage studies demonstrate that the low-energy tunneling spectrum is affected dramatically by the presence of nonequilibrium spin excitations.