Nanoscale Near-Field Tomography of Surface States on (Bi0.5Sb0.5)2Te3.

Three-dimensional topological insulators (TIs) have attracted tremendous interest for their possibility to host massless Dirac Fermions in topologically protected surface states (TSSs), which may enable new kinds of high-speed electronics. However, recent reports have outlined the importance of band bending effects within these materials, which results in an additional two-dimensional electron gas (2DEG) with finite mass at the surface. TI surfaces are also known to be highly inhomogeneous on the nanoscale, which is masked in conventional far-field studies. Here, we use near-field microscopy in the mid-infrared spectral range to probe the local surface properties of custom-tailored (Bi0.5Sb0.5)2Te3 structures with nanometer precision in all three spatial dimensions. Applying nanotomography and nanospectroscopy, we reveal a few-nanometer-thick layer of high surface conductivity and retrieve its local dielectric function without assuming any model for the spectral response. This allows us to directly distinguish between different types of surface states. An intersubband transition within the massive 2DEG formed by quantum confinement in the bent conduction band manifests itself as a sharp, surface-bound, Lorentzian-shaped resonance. An additional broadband background in the imaginary part of the dielectric function may be caused by the TSS. Tracing the intersubband resonance with nanometer spatial precision, we observe changes of its frequency, likely originating from local variations of doping or/and the mixing ratio between Bi and Sb. Our results highlight the importance of studying the surfaces of these novel materials on the nanoscale to directly access the local optical and electronic properties via the dielectric function.

Femtosecond photo-switching of interface polaritons in black phosphorus heterostructures.

The possibility of hybridizing collective electronic motion with mid-infrared light to form surface polaritons has made van der Waals layered materials a versatile platform for extreme light confinement and tailored nanophotonics. Graphene and its heterostructures have attracted particular attention because the absence of an energy gap allows plasmon polaritons to be tuned continuously. Here, we introduce black phosphorus as a promising new material in surface polaritonics that features key advantages for ultrafast switching. Unlike graphene, black phosphorus is a van der Waals bonded semiconductor, which enables high-contrast interband excitation of electron-hole pairs by ultrashort near-infrared pulses. Here, we design a SiO2/black phosphorus/SiO2 heterostructure in which the surface phonon modes of the SiO2 layers hybridize with surface plasmon modes in black phosphorus that can be activated by photo-induced interband excitation. Within the Reststrahlen band of SiO2, the hybrid interface polariton assumes surface-phonon-like properties, with a well-defined frequency and momentum and excellent coherence. During the lifetime of the photogenerated electron-hole plasma, coherent hybrid polariton waves can be launched by a broadband mid-infrared pulse coupled to the tip of a scattering-type scanning near-field optical microscopy set-up. The scattered radiation allows us to trace the new hybrid mode in time, energy and space. We find that the surface mode can be activated within ∼50 fs and disappears within 5 ps, as the electron-hole pairs in black phosphorus recombine. The excellent switching contrast and switching speed, the coherence properties and the constant wavelength of this transient mode make it a promising candidate for ultrafast nanophotonic devices.

Tracking the ultrafast motion of a single molecule by femtosecond orbital imaging.

Watching a single molecule move on its intrinsic timescale has been one of the central goals of modern nanoscience, and calls for measurements that combine ultrafast temporal resolution with atomic spatial resolution. Steady-state experiments access the requisite spatial scales, as illustrated by direct imaging of individual molecular orbitals using scanning tunnelling microscopy or the acquisition of tip-enhanced Raman and luminescence spectra with sub-molecular resolution. But tracking the intrinsic dynamics of a single molecule directly in the time domain faces the challenge that interactions with the molecule must be confined to a femtosecond time window. For individual nanoparticles, such ultrafast temporal confinement has been demonstrated by combining scanning tunnelling microscopy with so-called lightwave electronics, which uses the oscillating carrier wave of tailored light pulses to directly manipulate electronic motion on timescales faster even than a single cycle of light. Here we build on ultrafast terahertz scanning tunnelling microscopy to access a state-selective tunnelling regime, where the peak of a terahertz electric-field waveform transiently opens an otherwise forbidden tunnelling channel through a single molecular state. It thereby removes a single electron from an individual pentacene molecule's highest occupied molecular orbital within a time window shorter than one oscillation cycle of the terahertz wave. We exploit this effect to record approximately 100-femtosecond snapshot images of the orbital structure with sub-ångström spatial resolution, and to reveal, through pump/probe measurements, coherent molecular vibrations at terahertz frequencies directly in the time domain. We anticipate that the combination of lightwave electronics and the atomic resolution of our approach will open the door to visualizing ultrafast photochemistry and the operation of molecular electronics on the single-orbital scale.