Ultrafast Sub-100 fs All-Optical Modulation and Efficient Third-Harmonic Generation in Weyl Semimetal Niobium Phosphide Thin Films.

Since their experimental discovery in 2015, Weyl semimetals have generated a large amount of attention due their intriguing physical properties that arise from their linear electron dispersion relation and topological surface states. In particular, in the field of nonlinear (NL) optics and light harvesting, Weyl semimetals have shown outstanding performances and achieved record NL conversion coefficients. In this context, the first steps toward Weyl semimetal nanophotonics are performed here by thoroughly characterizing the linear and NL optical behavior of epitaxially grown niobium phosphide (NbP) thin films, covering the visible to the near-infrared regime of the electromagnetic spectrum. Despite the measured high linear absorption, third-harmonic generation studies demonstrate high conversion efficiencies up to 10-4 % that can be attributed to the topological electron states at the surface of the material. Furthermore, nondegenerate pump-probe measurements with sub-10 fs pulses reveal a maximum modulation depth of ≈1%, completely decaying within 100 fs and therefore suggesting the possibility of developing all-optical switching devices based on NbP. Altogether, this work reveals the promising NL optical properties of Weyl semimetal thin films, which outperform bulk crystals of the same material, laying the grounds for nanoscale applications, enabled by top-down nanostructuring, such as light-harvesting, on-chip frequency conversion, and all-optical processing.

Large Fermi-Energy Shift and Suppression of Trivial Surface States in NbP Weyl Semimetal Thin Films.

Weyl semimetals, a class of 3D topological materials, exhibit a unique electronic structure featuring linear band crossings and disjoint surface states (Fermi-arcs). While first demonstrations of topologically driven phenomena have been realized in bulk crystals, efficient routes to control the electronic structure have remained largely unexplored. Here, a dramatic modification of the electronic structure in epitaxially grown NbP Weyl semimetal thin films is reported, using in situ surface engineering and chemical doping strategies that do not alter the NbP lattice structure and symmetry, retaining its topological nature. Through the preparation of a dangling-bond-free, P-terminated surface which manifests in a surface reconstruction, all the well-known trivial surface states of NbP are fully suppressed, resulting in a purely topological Fermi-arc dispersion. In addition, a substantial Fermi-energy shift from -0.2 to 0.3 eV across the Weyl points is achieved by surface chemical doping, unlocking access to the hitherto unexplored n-type region of the Weyl spectrum. These findings constitute a milestone toward surface-state and Fermi-level engineering of topological bands in Weyl semimetals, and, while there are still challenges in minimizing doping-driven disorder and grain boundary density in the films, they do represent a major advance to realize device heterostructures based on Weyl physics.

Realization of Epitaxial NbP and TaP Weyl Semimetal Thin Films.

Weyl semimetals (WSMs) exhibit an electronic structure governed by linear band dispersions and degenerate (Weyl) points that lead to exotic physical phenomena. While WSMs were established in bulk monopnictide compounds several years ago, the growth of thin films remains a challenge. Here, we report the bottom-up synthesis of single-crystalline NbP and TaP thin films, 9 to 70 nm thick, by means of molecular beam epitaxy. The as-grown epitaxial films feature a phosphorus-rich stoichiometry, a tensile-strained unit cell, and a homogeneous surface termination, unlike their bulk crystal counterparts. These properties result in an electronic structure governed by topological surface states as directly observed using in situ momentum photoemission microscopy, along with a Fermi-level shift of -0.2 eV with respect to the intrinsic chemical potential. Although the Fermi energy of the as-grown samples is still far from the Weyl points, carrier mobilities close to 103 cm2/(V s) have been measured at room temperature in patterned Hall-bar devices. The ability to grow thin films of Weyl semimetals that can be tailored by doping or strain, is an important step toward the fabrication of functional WSM-based devices and heterostructures.