A wealth of structures for the Ge2H2+ radical cation: comparison of theory and experiment.

Five structures of Ge2H2 and Ge2H2+ are investigated in this study. Optimized geometries at the CCSD(T)/cc-pwCVQZ-PP level of theory were obtained. Focal point analyses were performed on these optimized geometries to determine relative energies using the CCSD(T) method with polarized basis sets up to quintuple-zeta. Energy corrections include full T and pertubative (Q) coupled-cluster effects plus anharmonic corrections to the zero-point vibrational energy. Relative ordering in energy from lowest to highest of the five Ge2H2+ structures is butterfly, germylidene, monobridged, trans, then linear. In neutral Ge2H2, the monobridged structure lies lower in energy than the germylidene structure. Fundamental vibrational frequencies and IR intensities were computed for the minima at the CCSD(T)/cc-pwCVTZ-PP level of theory to compare with experimental research. Partial atomic charges and natural bonding orbital analyses indicated that the positive charge of Ge2H2+ is contained in the region of the Ge-Ge bond.

Neuromorphic learning with Mott insulator NiO.

Habituation and sensitization (nonassociative learning) are among the most fundamental forms of learning and memory behavior present in organisms that enable adaptation and learning in dynamic environments. Emulating such features of intelligence found in nature in the solid state can serve as inspiration for algorithmic simulations in artificial neural networks and potential use in neuromorphic computing. Here, we demonstrate nonassociative learning with a prototypical Mott insulator, nickel oxide (NiO), under a variety of external stimuli at and above room temperature. Similar to biological species such as Aplysia, habituation and sensitization of NiO possess time-dependent plasticity relying on both strength and time interval between stimuli. A combination of experimental approaches and first-principles calculations reveals that such learning behavior of NiO results from dynamic modulation of its defect and electronic structure. An artificial neural network model inspired by such nonassociative learning is simulated to show advantages for an unsupervised clustering task in accuracy and reducing catastrophic interference, which could help mitigate the stability-plasticity dilemma. Mott insulators can therefore serve as building blocks to examine learning behavior noted in biology and inspire new learning algorithms for artificial intelligence.

Carrier localization in perovskite nickelates from oxygen vacancies.

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.

Self-Assembled Periodic Nanostructures Using Martensitic Phase Transformations.

We describe a novel approach for the rational design and synthesis of self-assembled periodic nanostructures using martensitic phase transformations. We demonstrate this approach in a thin film of perovskite SrSnO3 with reconfigurable periodic nanostructures consisting of regularly spaced regions of sharply contrasted dielectric properties. The films can be designed to have different periodicities and relative phase fractions via chemical doping or strain engineering. The dielectric contrast within a single film can be tuned using temperature and laser wavelength, effectively creating a variable photonic crystal. Our results show the realistic possibility of designing large-area self-assembled periodic structures using martensitic phase transformations with the potential of implementing "built-to-order" nanostructures for tailored optoelectronic functionalities.

Strongly correlated perovskite lithium ion shuttles.

Solid-state ion shuttles are of broad interest in electrochemical devices, nonvolatile memory, neuromorphic computing, and biomimicry utilizing synthetic membranes. Traditional design approaches are primarily based on substitutional doping of dissimilar valent cations in a solid lattice, which has inherent limits on dopant concentration and thereby ionic conductivity. Here, we demonstrate perovskite nickelates as Li-ion shuttles with simultaneous suppression of electronic transport via Mott transition. Electrochemically lithiated SmNiO3 (Li-SNO) contains a large amount of mobile Li+ located in interstitial sites of the perovskite approaching one dopant ion per unit cell. A significant lattice expansion associated with interstitial doping allows for fast Li+ conduction with reduced activation energy. We further present a generalization of this approach with results on other rare-earth perovskite nickelates as well as dopants such as Na+ The results highlight the potential of quantum materials and emergent physics in design of ion conductors.

Refractive Index-Based Control of Hyperbolic Phonon-Polariton Propagation.

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 understand propagation and loss mechanisms on substrates suitable for applications from waveguiding to infrared sensing. We employ scattering-type scanning near-field optical microscopy (s-SNOM) and nano-Fourier transform infrared (FTIR) spectroscopy, in concert with analytical and numerical calculations, to elucidate HPhP characteristics as a function of the complex substrate dielectric function. We consider propagation on suspended, dielectric and metallic substrates to demonstrate that the thickness-normalized wavevector can be reduced by a factor of 25 simply by changing the substrate from dielectric to metallic behavior. Moreover, by incorporating the imaginary contribution to the dielectric function in lossy materials, the wavevector can be dynamically controlled by small local variations in loss or carrier density. Counterintuitively, higher-order HPhP modes are shown to exhibit the same change in the polariton wavevector as the fundamental mode, despite the drastic differences in the evanescent ranges of these polaritons. However, because polariton refraction is dictated by the fractional change in the wavevector, this still results in significant differences in polariton refraction and reduced sensitivity to substrate-induced losses for the higher-order HPhPs. Such effects may therefore be used to spatially separate hyperbolic modes of different orders and for index-based sensing schemes. Our results advance our understanding of fundamental hyperbolic polariton excitations and their potential for on-chip photonics and planar metasurface optics.

Hyperspectral time-domain terahertz nano-imaging.

Terahertz (THz) near-field microscopy has wide and unprecedented application potential for nanoscale materials and photonic-device characterization. Here, we introduce hyperspectral THz nano-imaging by combining scattering-type scanning near-field optical microscopy (s-SNOM) with THz time-domain spectroscopy (TDS). We describe the technical implementations that enabled this achievement and demonstrate its performance with a heterogeneously doped Si semiconductor sample. Specifically, we recorded a hyperspectral image of 40 by 20 pixels in 180 minutes and with a spatial resolution of about ~170 nm by measuring at each pixel with a time domain spectrum covering the range from 0.4 to 1.8 THz. Fitting the spectra with a Drude model allows for measuring-noninvasively and without the need for Ohmic contacts-the local mobile carrier concentration of the differently doped Si areas. We envision wide application potential for THz hyperspectral nano-imaging, including nanoscale carrier profiling of industrial semiconductor structures or characterizing complex and correlated electron matter, as well as low dimensional (1D or 2D) materials.

Geometric constraints on phase coexistence in vanadium dioxide single crystals.

The appearance of stripe phases is a characteristic signature of strongly correlated quantum materials, and its origin in phase-changing materials has only recently been recognized as the result of the delicate balance between atomic and mesoscopic materials properties. A vanadium dioxide (VO2) single crystal is one such strongly correlated material with stripe phases. Infrared nano-imaging on low-aspect-ratio, single-crystal VO2 microbeams decorated with resonant plasmonic nanoantennas reveals a novel herringbone pattern of coexisting metallic and insulating domains intercepted and altered by ferroelastic domains, unlike previous reports on high-aspect-ratio VO2 crystals where the coexisting metal/insulator domains appear as alternating stripe phases perpendicular to the growth axis. The metallic domains nucleate below the crystal surface and grow towards the surface with increasing temperature as suggested by the near-field plasmonic response of the gold nanorod antennas.

Temperature-gated thermal rectifier for active heat flow control.

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.

A modular platform to generate functional sympathetic neuron-innervated heart assembloids.

The technology of human pluripotent stem cell (hPSC)-based 3D organoid/assembloid cultures has become a powerful tool for the study of human embryonic development, disease modeling and drug discovery in recent years. The autonomic sympathetic nervous system innervates and regulates almost all organs in the body, including the heart. Yet, most reported organoids to date are not innervated, thus lacking proper neural regulation, and hindering reciprocal tissue maturation. Here, we developed a simple and versatile sympathetic neuron (symN)-innervated cardiac assembloid without the need for bioengineering. Our human sympathetic cardiac assembloids (hSCAs) showed mature muscle structures, atrial to ventricular patterning, and spontaneous beating. hSCA-innervating symNs displayed neurotransmitter synthesis and functional regulation of the cardiac beating rate, which could be manipulated pharmacologically or optogenetically. We modeled symN-mediated cardiac development and myocardial infarction. This hSCAs provides a tool for future neurocardiotoxicity screening approaches and is highly versatile and modular, where the types of neuron (symN or parasympathetic or sensory neuron) and organoid (heart, lung, kidney) to be innervated may be interchanged.

Infrared Nanoimaging of Hydrogenated Perovskite Nickelate Memristive Devices.

Solid-state devices made from correlated oxides, such as perovskite nickelates, are promising for neuromorphic computing by mimicking biological synaptic function. However, comprehending dopant action at the nanoscale poses a formidable challenge to understanding the elementary mechanisms involved. Here, we perform operando infrared nanoimaging of hydrogen-doped correlated perovskite, neodymium nickel oxide (H-NdNiO3, H-NNO), devices and reveal how an applied field perturbs dopant distribution at the nanoscale. This perturbation leads to stripe phases of varying conductivity perpendicular to the applied field, which define the macroscale electrical characteristics of the devices. Hyperspectral nano-FTIR imaging in conjunction with density functional theory calculations unveils a real-space map of multiple vibrational states of H-NNO associated with OH stretching modes and their dependence on the dopant concentration. Moreover, the localization of excess charges induces an out-of-plane lattice expansion in NNO which was confirmed by in situ X-ray diffraction and creates a strain that acts as a barrier against further diffusion. Our results and the techniques presented here hold great potential for the rapidly growing field of memristors and neuromorphic devices wherein nanoscale ion motion is fundamentally responsible for function.

Near-field spatial mapping of strongly interacting multiple plasmonic infrared antennas.

Near-field dipolar plasmon interactions of multiple infrared antenna structures in the strong coupling limit are studied using scattering-type scanning near-field optical microscope (s-SNOM) and theoretical finite-difference time-domain (FDTD) calculations. We monitor in real-space the evolution of plasmon dipolar mode of a stationary antenna structure as multiple resonantly matched dipolar plasmon particles are closely approaching it. Interparticle separation, length and polarization dependent studies show that the cross geometry structure favors strong interparticle charge-charge, dipole-dipole and charge-dipole Coulomb interactions in the nanometer scale gap region, which results in strong field enhancement in cross-bowties and further allows these structures to be used as polarization filters. The nanoscale local field amplitude and phase maps show that due to strong interparticle Coulomb coupling, cross-bowtie structures redistribute and highly enhance the out-of-plane (perpendicular to the plane of the sample) plasmon near-field component at the gap region relative to ordinary bowties.

Characterization of localized surface plasmon resonance transducers produced from Au(25) nanoparticle multilayers.

This article reports the preparation of gold plasmonic transducers using a nanoparticle self-assembly/heating method and the characterization of the films using scattering-type scanning near-field optical microscopy (s-SNOM). Nanoparticle-polymer multilayer films were prepared by the layer-by-layer assembly on glass slides by alternating exposures to monodisperse Au(25) nanoparticles and ionic polymer linkers. Thermal evaporation of organic matters from the nanoparticle-polymer multilayer films at 600 °C allowed the nanoparticles to coalescence and form nanostructured films. Characterization of the nanostructured films generated from Au(25) nanoparticles using atomic force microscopy (AFM) showed that the films have rounded, small, island-like morphologies (d: 30-50 nm) with a pit in the center of many islands. However, further characterizations with s-SNOM revealed that the produced nanoislands contain a single gold cluster in a pit surrounded by donut-shaped dielectric species. Formation of such a structure is thought to be resulted from the embedding of gold clusters under the reorganized polysiloxane binder coatings and glass surfaces during heat treatment of the Au(25) nanoparticle multilayer films. The nanostructured films displayed strong surface plasmon resonance bands in UV-vis spectra with a peak absorbance occurring at ~545-550 nm. The optical sensing capability of the films was examined using D-glucose-functionalized gold island films with the interaction of Concanavalin A (ConA). The result showed that the adsorption of ConA on island films causes a large change in the LSPR band intensity.

Reconfigurable hyperbolic polaritonics with correlated oxide metasurfaces.

Polaritons enable subwavelength confinement and highly anisotropic flows of light over a wide spectral range, holding the promise for applications in modern nanophotonic and optoelectronic devices. However, to fully realize their practical application potential, facile methods enabling nanoscale active control of polaritons are needed. Here, we introduce a hybrid polaritonic-oxide heterostructure platform consisting of van der Waals crystals, such as hexagonal boron nitride (hBN) or alpha-phase molybdenum trioxide (α-MoO3), transferred on nanoscale oxygen vacancy patterns on the surface of prototypical correlated perovskite oxide, samarium nickel oxide, SmNiO3 (SNO). Using a combination of scanning probe microscopy and infrared nanoimaging techniques, we demonstrate nanoscale reconfigurability of complex hyperbolic phonon polaritons patterned at the nanoscale with high resolution. Hydrogenation and temperature modulation allow spatially localized conductivity modulation of SNO nanoscale patterns, enabling robust real-time modulation and nanoscale reconfiguration of hyperbolic polaritons. Our work paves the way towards nanoscale programmable metasurface engineering for reconfigurable nanophotonic applications.

Reconfigurable perovskite nickelate electronics for artificial intelligence.

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 NdNiO3 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.

Nanoscale subsurface- and material-specific identification of single nanoparticles.

We report on high resolution subsurface and material specific differentiation of silica, Au and silica-capped Au nanoparticles using scattering-type scanning near-field optical microscopy (s-SNOM) in the visible (λ=633 nm) and mid-infrared (λ=10.7 µm) frequencies. Strong optical contrast is observed in the visible wavelength, mainly because of the dipolar plasmon resonance of the embedded Au nanoparticles which is absent in the infrared. We show that the use of small tapping amplitude improves the apparent image contrast in nanoparticles by causing increased tip-particle and reduced tip-substrate interactions. Experimental results are in excellent agreement with extended dipole model calculations modified to include the capping layer characterized by its refractive index.

Photodegradation Protection in 2D In-Plane Heterostructures Revealed by Hyperspectral Nanoimaging: The Role of Nanointerface 2D Alloys.

Single-layer heterostructures exhibit striking quasiparticle properties and many-body interaction effects that hold promise for a range of applications. However, their properties can be altered by intrinsic and extrinsic defects, thus diminishing their applicability. Therefore, it is of paramount importance to identify defects and understand 2D materials' degradation over time using advanced multimodal imaging techniques. Here we implemented a liquid-phase precursor approach to synthesize 2D in-plane MoS2-WS2 heterostructures exhibiting nanoscale alloyed interfaces and map exotic interface effects during photodegradation using a combination of hyperspectral tip-enhanced photoluminescence and Raman and near-field nanoscopy. Surprisingly, 2D alloyed regions exhibit thermal and photodegradation stability providing protection against oxidation. Coupled with surface and interface strain, 2D alloy regions create stable localized potential wells that concentrate excitonic species via a charge carrier funneling effect. These results demonstrate that 2D alloys can withstand extreme degradation effects over time and could enable stable 2D device engineering.

Recent Progress on Stability and Passivation of Black Phosphorus.

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.

Probing structural changes in single enveloped virus particles using nano-infrared spectroscopic imaging.

Enveloped viruses, such as HIV, Ebola and Influenza, are among the most deadly known viruses. Cellular membrane penetration of enveloped viruses is a critical step in the cascade of events that lead to entry into the host cell. Conventional ensemble fusion assays rely on collective responses to membrane fusion events, and do not allow direct and quantitative studies of the subtle and intricate fusion details. Such details are accessible via single particle investigation techniques, however. Here, we implement nano-infrared spectroscopic imaging to investigate the chemical and structural modifications that occur prior to membrane fusion in the single archetypal enveloped virus, influenza X31. We traced in real-space structural and spectroscopic alterations that occur during environmental pH variations in single virus particles. In addition, using nanospectroscopic imaging we quantified the effectiveness of an antiviral compound in stopping viral membrane disruption (a novel mechanism for inhibiting viral entry into cells) during environmental pH variations.

Nanoscopy of Phase Separation in InxGa1-xN Alloys.

Phase separations in ternary/multinary semiconductor alloys is a major challenge that limits optical and electronic internal device efficiency. We have found ubiquitous local phase separation in In1-xGaxN alloys that persists to nanoscale spatial extent by employing high-resolution nanoimaging technique. We lithographically patterned InN/sapphire substrates with nanolayers of In1-xGaxN down to few atomic layers thick that enabled us to calibrate the near-field infrared response of the semiconductor nanolayers as a function of composition and thickness. We also developed an advanced theoretical approach that considers the full geometry of the probe tip and all the sample and substrate layers. Combining experiment and theory, we identified and quantified phase separation in epitaxially grown individual nanoalloys. We found that the scale of the phase separation varies widely from particle to particle ranging from all Ga- to all In-rich regions and covering everything in between. We have found that between 20 and 25% of particles show some level of Ga-rich phase separation over the entire sample region, which is in qualitative agreement with the known phase diagram of In1-xGaxN system.