From a fundamental science perspective, black phosphorus (BP) is a canonical example of a material that possesses fascinating surface and electronic properties. It has extraordinary in-plane anisotropic electrical, optical, and vibrational states, as well as a tunable band gap. However, instability of the surface due to chemical degradation in ambient conditions remains a major impediment to its prospective applications. Early studies were limited by the degradation of black phosphorous surfaces in air. Recently, several robust strategies have been developed to mitigate these issues, and these novel developments can potentially allow researchers to exploit the extraordinary properties of this material and devices made out of it. Here, the fundamental chemistry of BP degradation and the tremendous progress made to address this issue are extensively reviewed. Device performances of encapsulated BP are also compared with nonencapsulated BP. In addition, BP possesses sensitive anisotropic photophysical surface properties such as excitons, surface plasmons/phonons, and topologically protected and Dirac semi-metallic surface states. Ambient degradation as well as any passivation method used to protect the surface could affect the intrinsic surface properties of BP. These properties and the extent of their modifications by both the degradation and passivation are reviewed.
Metasurfaces control light propagation at the nanoscale for applications in both free-space and surface-confined geometries. However, dynamically changing the properties of metasurfaces can be a major challenge. Here we demonstrate a reconfigurable hyperbolic metasurface comprised of a heterostructure of isotopically enriched hexagonal boron nitride (hBN) in direct contact with the phase-change material (PCM) single-crystal vanadium dioxide (VO2). Metallic and dielectric domains in VO2 provide spatially localized changes in the local dielectric environment, enabling launching, reflection, and transmission of hyperbolic phonon polaritons (HPhPs) at the PCM domain boundaries, and tuning the wavelength of HPhPs propagating in hBN over these domains by a factor of 1.6. We show that this system supports in-plane HPhP refraction, thus providing a prototype for a class of planar refractive optics. This approach offers reconfigurable control of in-plane HPhP propagation and exemplifies a generalizable framework based on combining hyperbolic media and PCMs to design optical functionality.
Active heat flow control is essential for broad applications of heating, cooling, and energy conversion. Like electronic devices developed for the control of electric power, it is very desirable to develop advanced all-thermal solid-state devices that actively control heat flow without consuming other forms of energy.Here we demonstrate temperature-gated thermal rectification using vanadium dioxide beams in which the environmental temperature actively modulates asymmetric heat flow. In this three terminal device, there are two switchable states, which can be regulated by global heating. In the "Rectifier" state, we observe up to 28% thermal rectification. In the "Resistor" state, the thermal rectification is significantly suppressed (<1%). To the best of our knowledge, this is the first demonstration of solid-state active-thermal devices with a large rectification in the Rectifier state. This temperature-gated rectifier can have substantial implications ranging from autonomous thermal management of heating and cooling systems to efficient thermal energy conversion and storage.
Hyperbolic phonon polaritons (HPhPs) are generated when infrared photons couple to polar optic phonons in anisotropic media, confining long-wavelength light to nanoscale volumes. However, to realize the full potential of HPhPs for infrared optics, it is crucial to
Reconfigurable devices offer the ability to program electronic circuits on demand. In this work, we demonstrated on-demand creation of artificial neurons, synapses, and memory capacitors in post-fabricated perovskite NdNiO 3 devices that can be simply reconfigured for a specific purpose by single-shot electric pulses. The sensitivity of electronic properties of perovskite nickelates to the local distribution of hydrogen ions enabled these results. With experimental data from our memory capacitors, simulation results of a reservoir computing framework showed excellent performance for tasks such as digit recognition and classification of electrocardiogram heartbeat activity. Using our reconfigurable artificial neurons and synapses, simulated dynamic networks outperformed static networks for incremental learning scenarios. The ability to fashion the building blocks of brain-inspired computers on demand opens up new directions in adaptive networks.
Point defects, such as oxygen vacancies, control the physical properties of complex oxides, relevant in active areas of research from superconductivity to resistive memory to catalysis. In most oxide semiconductors, electrons that are associated with oxygen vacancies occupy the conduction band, leading to an increase in the electrical conductivity. Here we demonstrate, in contrast, that in the correlated-electron perovskite rare-earth nickelates, RNiO3 (R is a rare-earth element such as Sm or Nd), electrons associated with oxygen vacancies strongly localize, leading to a dramatic decrease in the electrical conductivity by several orders of magnitude. This unusual behavior is found to stem from the combination of crystal field splitting and filling-controlled Mott–Hubbard electron–electron correlations in the Ni 3d orbitals. Furthermore, we show the distribution of oxygen vacancies in NdNiO3 can be controlled via an electric field, leading to analog resistance switching behavior. This study demonstrates the potential of nickelates as testbeds to better understand emergent physics in oxide heterostructures as well as candidate systems in the emerging fields of artificial intelligence.
Infrared absorption spectroscopy is a powerful and widely used tool for analyzing the chemical composition and structure of materials. Because of the diffraction limit, however, it cannot be applied for studying individual nanostructures. Here we demonstrate that the phase contrast in substrate-enhanced scattering-type scanning near-field optical microscopy (s-SNOM) provides a map of the infrared absorption spectrum of individual nanoparticles with nanometer-scale spatial resolution. We succeeded in the chemical identification of silicon nitride nanoislands with heights well below 10 nm, by infrared near-field fingerprint spectroscopy of the Si-N stretching bond. Employing a novel theoretical model, we show that the near-field phase spectra of small particles correlate well with their far-field absorption spectra. On the other hand, the spectral near-field contrast does not scale with the volume of the particles. We find a nearly linear scaling law, which we can attribute to the near-field coupling between the near-field probe and the substrate. Our results provide fundamental insights into the spectral near-field contrast of nanoparticles and clearly demonstrate the capability of s-SNOM for nanoscale chemical mapping based on local infrared absorption.
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