Plasmonics is a rapidly developing field at the boundary of physical optics and condensed matter physics. It studies phenomena induced by and associated with surface plasmons-elementary polar excitations bound to surfaces and interfaces of nanostructured good metals. This Roadmap is written collectively by prominent researchers in the field of plasmonics. It encompasses selected aspects of nanoplasmonics. Among them are fundamental aspects such as quantum plasmonics based on quantum-mechanical properties of both underlying materials and plasmons themselves (such as their quantum generator, spaser), plasmonics in novel materials, ultrafast (attosecond) nanoplasmonics, etc. Selected applications of nanoplasmonics are also reflected in this Roadmap, in particular, plasmonic waveguiding, practical applications of plasmonics enabled by novel materials, thermo-plasmonics, plasmonic-induced photochemistry and photo-catalysis. This Roadmap is a concise but authoritative overview of modern plasmonics. It will be of interest to a wide audience of both fundamental physicists and chemists and applied scientists and engineers.

Photoelectrochemical (PEC) water splitting is a promising approach for producing hydrogen without greenhouse gas emissions. Despite decades of unceasing efforts, the efficiency of PEC devices based on earth-abundant semiconductors is still limited by their low light absorption, low charge mobility, high charge-carrier recombination, and reduced diffusion length. Plasmonics has recently emerged This article is protected by copyright. All rights reserved.2 as an effective approach for overcoming these limitations, although a full understanding of the involved physical mechanisms remains elusive. Here, the reported plasmonic effects are outlined such as resonant energy transfer, scattering, hot electron injection, guided modes and photonic effects, as well as the less investigated catalytic and thermal effects used in PEC water splitting. In each section, the fundamentals are reviewed and the most representative examples are discussed, illustrating possible future developments for achieving improved efficiency of plasmonic photoelectrodes.

Radiation patterns and the resonance wavelength of a plasmonic antenna are significantly influenced by its local environment, particularly its substrate. Here, we experimentally explore the role of dispersive substrates, such as aluminum-or gallium-doped zinc oxide in the near infrared and 4H-silicon carbide in the mid-infrared, upon Au plasmonic antennas, extending from dielectric to metal-like regimes, crossing through epsilon-near-zero (ENZ) conditions. We demonstrate that the vanishing index of refraction within this transition induces a "slowing down" of the rate of spectral shift for the antenna resonance frequency, resulting in an eventual "pinning" of the resonance near the ENZ frequency. This condition corresponds to a strong backward emission with near-constant phase. By comparing heavily doped semiconductors and undoped, polar dielectric substrates with ENZ conditions in the nearand mid-infrared, respectively, we also demonstrate the generality of the phenomenon using both surface plasmon and phonon polaritons, respectively. Furthermore, we also show that the redirected antenna radiation induces a Fano-like interference and an apparent stimulation of optic phonons within SiC.

Tuning of electronic state of correlated materials is key to their eventual use in advanced electronics and photonics. The prototypical correlated oxide VO 2 is insulating at room temperature and transforms to a metallic state when heated up to 67 °C (340 K). We report the emergence of a metallic state that is preserved down to 1.8 K by annealing thin films of VO 2 at an ultra-low oxygen partial pressure (P O2~1 0-24 atm). The films can be reverted back to their original state by annealing in oxygen, and this process can be iterated multiple times. The metallic phase created by oxygen deficiency has a tetragonal rutile structure and contains a large number of oxygen vacancies far beyond the solubility at equilibrium (greater than ~50X). The oxygen starvation reduces the oxidation state of vanadium from V 4+ to V 3+ and leads to the metallization. The extent of resistance reduction (concurrent with tuning of optical properties) can be controlled by the time-temperature envelope of the annealing conditions since the process is diffusionally driven. This experimental platform which can extensively tune oxygen vacancies in correlated oxides provides a new approach to study emergent phases and defect-mediated adaptive electronic and structural phase boundary crossovers.

Metal-semiconductor heterostructures have attracted a lot of attention due to their ability to enhance photovoltaic and photocatalytic processes via plasmonic effects. Thus far, most of the proposed heterostructures are designed with noble metals and the potential of alternative plasmonic materials, such as titanium nitride (TiN), is not yet well explored. In this work, TiN@TiO 2 core-shell nanoparticles (NPs) are synthesized and proposed as