Non-volatile electric-field control of inversion symmetry.

Competition between ground states at phase boundaries can lead to significant changes in properties under stimuli, particularly when these ground states have different crystal symmetries. A key challenge is to stabilize and control the coexistence of symmetry-distinct phases. Using BiFeO3 layers confined between layers of dielectric TbScO3 as a model system, we stabilize the mixed-phase coexistence of centrosymmetric and non-centrosymmetric BiFeO3 phases at room temperature with antipolar, insulating and polar semiconducting behaviour, respectively. Application of orthogonal in-plane electric (polar) fields results in reversible non-volatile interconversion between the two phases, hence removing and introducing centrosymmetry. Counterintuitively, we find that an electric field 'erases' polarization, resulting from the anisotropy in octahedral tilts introduced by the interweaving TbScO3 layers. Consequently, this interconversion between centrosymmetric and non-centrosymmetric phases generates changes in the non-linear optical response of over three orders of magnitude, resistivity of over five orders of magnitude and control of microscopic polar order. Our work establishes a platform for cross-functional devices that take advantage of changes in optical, electrical and ferroic responses, and demonstrates octahedral tilts as an important order parameter in materials interface design.

Near-Field Coupling with a Nanoimprinted Probe for Dark Exciton Nanoimaging in Monolayer WSe2.

Tip-enhanced photoluminescence (TRPL) is a powerful technique for spatially and spectrally probing local optical properties of 2-dimensional (2D) materials that are modulated by the local heterogeneities, revealing inaccessible dark states due to bright state overlap in conventional far-field microscopy at room temperature. While scattering-type near-field probes have shown the potential to selectively enhance and reveal dark exciton emission, their technical complexity and sensitivity can pose challenges under certain experimental conditions. Here, we present a highly reproducible and easy-to-fabricate near-field probe based on nanoimprint lithography and fiber-optic excitation and collection. The novel near-field measurement configuration provides an ∼3 orders of magnitude out-of-plane Purcell enhancement, diffraction-limited excitation spot, and subdiffraction hyperspectral imaging resolution (below 50 nm) of dark exciton emission. The effectiveness of this high spatial XD mapping technique was then demonstrated through reproducible hyperspectral mapping of oxidized sites and bubble areas.

Nature of the Electrical Double Layer on Suspended Graphene Electrodes.

The structure of interfacial water near suspended graphene electrodes in contact with aqueous solutions of Na2SO4, NH4Cl, and (NH4)2SO4 has been studied using confocal Raman spectroscopy, sum frequency vibrational spectroscopy, and Kelvin probe force microscopy. SO42- anions were found to preferentially accumulate near the interface at an open circuit potential (OCP), creating an electrical field that orients water molecules below the interface, as revealed by the increased intensity of the O-H stretching peak of H-bonded water. No such increase is observed with NH4Cl at the OCP. The intensity of the dangling O-H bond stretching peak however remains largely unchanged. The degree of orientation of the water molecules as well as the electrical double layer strength increased further when positive voltages are applied. Negative voltages on the other hand produced only small changes in the intensity of the H-bonded water peaks but affected the intensity and frequency of dangling O-H bond peaks. The TOC figure is an oversimplified representation of the system in this work.

py4DSTEM: A Software Package for Four-Dimensional Scanning Transmission Electron Microscopy Data Analysis.

Scanning transmission electron microscopy (STEM) allows for imaging, diffraction, and spectroscopy of materials on length scales ranging from microns to atoms. By using a high-speed, direct electron detector, it is now possible to record a full two-dimensional (2D) image of the diffracted electron beam at each probe position, typically a 2D grid of probe positions. These 4D-STEM datasets are rich in information, including signatures of the local structure, orientation, deformation, electromagnetic fields, and other sample-dependent properties. However, extracting this information requires complex analysis pipelines that include data wrangling, calibration, analysis, and visualization, all while maintaining robustness against imaging distortions and artifacts. In this paper, we present py4DSTEM, an analysis toolkit for measuring material properties from 4D-STEM datasets, written in the Python language and released with an open-source license. We describe the algorithmic steps for dataset calibration and various 4D-STEM property measurements in detail and present results from several experimental datasets. We also implement a simple and universal file format appropriate for electron microscopy data in py4DSTEM, which uses the open-source HDF5 standard. We hope this tool will benefit the research community and help improve the standards for data and computational methods in electron microscopy, and we invite the community to contribute to this ongoing project.

Ultrathin Free-Standing Oxide Membranes for Electron and Photon Spectroscopy Studies of Solid-Gas and Solid-Liquid Interfaces.

Free-standing ultrathin (∼2 nm) films of several oxides (Al2O3,TiO2, and others) have been developed, which are mechanically robust and transparent to electrons with Ekin ≥ 200 eV and to photons. We demonstrate their applicability in environmental X-ray photoelectron and infrared spectroscopy for molecular level studies of solid-gas (≥1 bar) and solid-liquid interfaces. These films act as membranes closing a reaction cell and as substrates and electrodes for electrochemical reactions. The remarkable properties of such ultrathin oxides membranes enable atomic/molecular level studies of interfacial phenomena, such as corrosion, catalysis, electrochemical reactions, energy storage, geochemistry, and biology, in a broad range of environmental conditions.

Ultralow-threshold, continuous-wave upconverting lasing from subwavelength plasmons.

Miniaturized lasers are an emerging platform for generating coherent light for quantum photonics, in vivo cellular imaging, solid-state lighting and fast three-dimensional sensing in smartphones1-3. Continuous-wave lasing at room temperature is critical for integration with opto-electronic devices and optimal modulation of optical interactions4,5. Plasmonic nanocavities integrated with gain can generate coherent light at subwavelength scales6-9, beyond the diffraction limit that constrains mode volumes in dielectric cavities such as semiconducting nanowires10,11. However, insufficient gain with respect to losses and thermal instabilities in nanocavities has limited all nanoscale lasers to pulsed pump sources and/or low-temperature operation6-9,12-15. Here, we show continuous-wave upconverting lasing at room temperature with record-low thresholds and high photostability from subwavelength plasmons. We achieve selective, single-mode lasing from Yb3+/Er3+-co-doped upconverting nanoparticles conformally coated on Ag nanopillar arrays that support a single, sharp lattice plasmon cavity mode and greater than wavelength λ/20 field confinement in the vertical dimension. The intense electromagnetic near-fields localized in the vicinity of the nanopillars result in a threshold of 70 W cm-2, orders of magnitude lower than other small lasers. Our plasmon-nanoarray upconverting lasers provide directional, ultra-stable output at visible frequencies under near-infrared pumping, even after six hours of constant operation, which offers prospects in previously unrealizable applications of coherent nanoscale light.

Optically Discriminating Carrier-Induced Quasiparticle Band Gap and Exciton Energy Renormalization in Monolayer MoS_{2}.

Optoelectronic excitations in monolayer MoS_{2} manifest from a hierarchy of electrically tunable, Coulombic free-carrier and excitonic many-body phenomena. Investigating the fundamental interactions underpinning these phenomena-critical to both many-body physics exploration and device applications-presents challenges, however, due to a complex balance of competing optoelectronic effects and interdependent properties. Here, optical detection of bound- and free-carrier photoexcitations is used to directly quantify carrier-induced changes of the quasiparticle band gap and exciton binding energies. The results explicitly disentangle the competing effects and highlight longstanding theoretical predictions of large carrier-induced band gap and exciton renormalization in two-dimensional semiconductors.

Uncovering Single-Molecule Photophysical Heterogeneity of Bright, Thermally Activated Delayed Fluorescence Emitters Dispersed in Glassy Hosts.

Recently developed all-organic emitters used in display applications achieve high brightness by harvesting triplet populations via thermally activated delayed fluorescence. The photophysical properties of these emitters therefore involve new inherent complexities and are strongly affected by interactions with their host material in the solid state. Ensemble measurements occlude the molecular details of how host-guest interactions determine fundamental properties such as the essential balance of singlet oscillator strength and triplet harvesting. Therefore, using time-resolved fluorescence spectroscopy, we interrogate these emitters at the single-molecule level and compare their properties in two distinct glassy polymer hosts. We find that nonbonding interactions with aromatic moieties in the host appear to mediate the molecular configurations of the emitters, but also promote nonradiative quenching pathways. We also find substantial heterogeneity in the time-resolved photoluminescence of these emitters, which is dominated by static disorder in the polymer. Finally, since singlet-triplet cycling underpins the mechanism for increased brightness, we present the first room-temperature measurement of singlet-triplet equilibration dynamics in this family of emitters. Our observations present a molecular-scale interrogation of host-guest interactions in a disordered film, with implications for highly efficient organic light-emitting devices. Combining a single-molecule experimental technique with an emitter that is sensitive to triplet dynamics, yet read out via fluorescence, should also provide a complementary approach to performing fundamental studies of glassy materials over a large dynamic range of time scales.

Anomalous Interlayer Exciton Diffusion in WS2/WSe2 Moiré Heterostructure.

Stacking van der Waals crystals allows for the on-demand creation of a periodic potential landscape to tailor the transport of quasiparticle excitations. We investigate the diffusion of photoexcited electron-hole pairs, or excitons, at the interface of WS2/WSe2 van der Waals heterostructure over a wide range of temperatures. We observe the appearance of distinct interlayer excitons for parallel and antiparallel stacking and track their diffusion through spatially and temporally resolved photoluminescence spectroscopy from 30 to 250 K. While the measured exciton diffusivity decreases with temperature, it surprisingly plateaus below 90 K. Our observations cannot be explained by classical models like hopping in the moiré potential. A combination of ab initio theory and molecular dynamics simulations suggests that low-energy phonons arising from the mismatched lattices of moiré heterostructures, also known as phasons, play a key role in describing and understanding this anomalous behavior of exciton diffusion. Our observations indicate that the moiré potential landscape is dynamic down to very low temperatures and that the phason modes can enable efficient transport of energy in the form of excitons.

A substitutional quantum defect in WS2 discovered by high-throughput computational screening and fabricated by site-selective STM manipulation.

Point defects in two-dimensional materials are of key interest for quantum information science. However, the parameter space of possible defects is immense, making the identification of high-performance quantum defects very challenging. Here, we perform high-throughput (HT) first-principles computational screening to search for promising quantum defects within WS2, which present localized levels in the band gap that can lead to bright optical transitions in the visible or telecom regime. Our computed database spans more than 700 charged defects formed through substitution on the tungsten or sulfur site. We found that sulfur substitutions enable the most promising quantum defects. We computationally identify the neutral cobalt substitution to sulfur (Co S 0 ) and fabricate it with scanning tunneling microscopy (STM). The Co S 0 electronic structure measured by STM agrees with first principles and showcases an attractive quantum defect. Our work shows how HT computational screening and nanoscale synthesis routes can be combined to design promising quantum defects.

Size-Induced Ferroelectricity in Antiferroelectric Oxide Membranes.

Despite extensive studies on size effects in ferroelectrics, how structures and properties evolve in antiferroelectrics with reduced dimensions still remains elusive. Given the enormous potential of utilizing antiferroelectrics for high-energy-density storage applications, understanding their size effects will provide key information for optimizing device performances at small scales. Here, the fundamental intrinsic size dependence of antiferroelectricity in lead-free NaNbO3 membranes is investigated. Via a wide range of experimental and theoretical approaches, an intriguing antiferroelectric-to-ferroelectric transition upon reducing membrane thickness is probed. This size effect leads to a ferroelectric single-phase below 40 nm, as well as a mixed-phase state with ferroelectric and antiferroelectric orders coexisting above this critical thickness. Furthermore, it is shown that the antiferroelectric and ferroelectric orders are electrically switchable. First-principle calculations further reveal that the observed transition is driven by the structural distortion arising from the membrane surface. This work provides direct experimental evidence for intrinsic size-driven scaling in antiferroelectrics and demonstrates enormous potential of utilizing size effects to drive emergent properties in environmentally benign lead-free oxides with the membrane platform.

Imaging the hidden modes of ultrathin plasmonic strip antennas by cathodoluminescence.

We perform spectrally resolved cathodoluminescence (CL) imaging nanoscopy using a 30 keV electron beam to identify the resonant modes of an ultrathin (20 nm), laterally tapered plasmonic Ag nanostrip antenna. We resolve with deep-subwavelength resolution four antenna resonances (resonance orders m = 2-5) that are ascribed to surface plasmon polariton standing waves that are confined on the strip. We map the local density of states on the strip surface and show that it has contributions from symmetric and antisymmetric surface plasmon polariton modes, each with a very different mode index. This work illustrates the power of CL experiments that can visualize hidden modes that for symmetry reasons have been elusive in optical light scattering experiments.

Ferroelectricity in a semiconducting all-inorganic halide perovskite.

Ferroelectric semiconductors are rare materials with both spontaneous polarizations and visible light absorptions that are promising for designing functional photoferroelectrics, such as optical switches and ferroelectric photovoltaics. The emerging halide perovskites with remarkable semiconducting properties also have the potential of being ferroelectric, yet the evidence of robust ferroelectricity in the typical three-dimensional hybrid halide perovskites has been elusive. Here, we report on the investigation of ferroelectricity in all-inorganic halide perovskites, CsGeX3, with bandgaps of 1.6 to 3.3 eV. Their ferroelectricity originates from the lone pair stereochemical activity in Ge (II) that promotes the ion displacement. This gives rise to their spontaneous polarizations of ~10 to 20 µC/cm2, evidenced by both ab initio calculations and key experiments including atomic-level ionic displacement vector mapping and ferroelectric hysteresis loop measurement. Furthermore, characteristic ferroelectric domain patterns on the well-defined CsGeBr3 nanoplates are imaged with both piezo-response force microscopy and nonlinear optical microscopic method.

Electric field control of chirality.

Polar textures have attracted substantial attention in recent years as a promising analog to spin-based textures in ferromagnets. Here, using optical second-harmonic generation­based circular dichroism, we demonstrate deterministic and reversible control of chirality over mesoscale regions in ferroelectric vortices using an applied electric field. The microscopic origins of the chirality, the pathway during the switching, and the mechanism for electric field control are described theoretically via phase-field modeling and second-principles simulations, and experimentally by examination of the microscopic response of the vortices under an applied field. The emergence of chirality from the combination of nonchiral materials and subsequent control of the handedness with an electric field has far-reaching implications for new electronics based on chirality as a field-controllable order parameter.

Plasmonics for extreme light concentration and manipulation.

The unprecedented ability of nanometallic (that is, plasmonic) structures to concentrate light into deep-subwavelength volumes has propelled their use in a vast array of nanophotonics technologies and research endeavours. Plasmonic light concentrators can elegantly interface diffraction-limited dielectric optical components with nanophotonic structures. Passive and active plasmonic devices provide new pathways to generate, guide, modulate and detect light with structures that are similar in size to state-of-the-art electronic devices. With the ability to produce highly confined optical fields, the conventional rules for light-matter interactions need to be re-examined, and researchers are venturing into new regimes of optical physics. In this review we will discuss the basic concepts behind plasmonics-enabled light concentration and manipulation, make an attempt to capture the wide range of activities and excitement in this area, and speculate on possible future directions.

Tuning the color of silicon nanostructures.

Empowering silicon (Si) with optical functions constitutes a very important challenge in photonics. The scalable fabrication capabilities for this earth-abundant, environmentally friendly material are unmatched in sophistication and can be unleashed to realize a plethora of high-performance photonic functionalities that find application in information, bio-, display, camouflage, ornamental, and energy technologies. Nanofashioning represents a general strategy to turn Si into a useful optical material and Si structures have already been engineered to enable light emission, optical cloaking, waveguiding, nonlinear optics, enhanced light absorption, and sensing. Here, we demonstrate that a wide spectrum of colors can be generated by harnessing the strong resonant light scattering properties of Si nanostructures under white light illumination. The ability to engineer such colors in a predetermined fashion through a choice of the structure size, dielectric environment, and illumination conditions opens up entirely new applications of Si and puts this material in a new light.

Strongly Quantum-Confined Blue-Emitting Excitons in Chemically Configurable Multiquantum Wells.

Light matter interactions are greatly enhanced in two-dimensional (2D) semiconductors because of strong excitonic effects. Many optoelectronic applications would benefit from creating stacks of atomically thin 2D semiconductors separated by insulating barrier layers, forming multiquantum-well structures. However, most 2D transition metal chalcogenide systems require serial stacking to create van der Waals multilayers. Hybrid metal organic chalcogenolates (MOChas) are self-assembling hybrid materials that combine multiquantum-well properties with scalable chemical synthesis and air stability. In this work, we use spatially resolved linear and nonlinear optical spectroscopies over a range of temperatures to study the strongly excitonic optical properties of mithrene, that is, silver benzeneselenolate, and its synthetic isostructures. We experimentally probe s-type bright excitons and p-type excitonic dark states formed in the quantum confined 2D inorganic monolayers of silver selenide with exciton binding energy up to ∼0.4 eV, matching recent theoretical predictions of the material class. We further show that mithrene's highly efficient blue photoluminescence, ultrafast exciton radiative dynamics, as well as flexible tunability of molecular structure and optical properties demonstrate great potential of MOChas for constructing optoelectronic and quantum excitonic devices.

An infrared spectral biomarker accurately predicts neurodegenerative disease class in the absence of overt symptoms.

Although some neurodegenerative diseases can be identified by behavioral characteristics relatively late in disease progression, we currently lack methods to predict who has developed disease before the onset of symptoms, when onset will occur, or the outcome of therapeutics. New biomarkers are needed. Here we describe spectral phenotyping, a new kind of biomarker that makes disease predictions based on chemical rather than biological endpoints in cells. Spectral phenotyping uses Fourier Transform Infrared (FTIR) spectromicroscopy to produce an absorbance signature as a rapid physiological indicator of disease state. FTIR spectromicroscopy has over the past been used in differential diagnoses of manifest disease. Here, we report that the unique FTIR chemical signature accurately predicts disease class in mouse with high probability in the absence of brain pathology. In human cells, the FTIR biomarker accurately predicts neurodegenerative disease class using fibroblasts as surrogate cells.

The role of chalcogen vacancies for atomic defect emission in MoS2.

For two-dimensional (2D) layered semiconductors, control over atomic defects and understanding of their electronic and optical functionality represent major challenges towards developing a mature semiconductor technology using such materials. Here, we correlate generation, optical spectroscopy, atomic resolution imaging, and ab initio theory of chalcogen vacancies in monolayer MoS2. Chalcogen vacancies are selectively generated by in-vacuo annealing, but also focused ion beam exposure. The defect generation rate, atomic imaging and the optical signatures support this claim. We discriminate the narrow linewidth photoluminescence signatures of vacancies, resulting predominantly from localized defect orbitals, from broad luminescence features in the same spectral range, resulting from adsorbates. Vacancies can be patterned with a precision below 10 nm by ion beams, show single photon emission, and open the possibility for advanced defect engineering of 2D semiconductors at the ultimate scale.

Anisotropic 2D excitons unveiled in organic-inorganic quantum wells.

Two-dimensional (2D) excitons arise from electron-hole confinement along one spatial dimension. Such excitations are often described in terms of Frenkel or Wannier limits according to the degree of exciton spatial localization and the surrounding dielectric environment. In hybrid material systems, such as the 2D perovskites, the complex underlying interactions lead to excitons of an intermediate nature, whose description lies somewhere between the two limits, and a better physical description is needed. Here, we explore the photophysics of a tuneable materials platform where covalently bonded metal-chalcogenide layers are spaced by organic ligands that provide confinement barriers for charge carriers in the inorganic layer. We consider self-assembled, layered bulk silver benzeneselenolate, [AgSePh]∞, and use a combination of transient absorption spectroscopy and ab initio GW plus Bethe-Salpeter equation calculations. We demonstrate that in this non-polar dielectric environment, strongly anisotropic excitons dominate the optical transitions of [AgSePh]∞. We find that the transient absorption measurements at room temperature can be understood in terms of low-lying excitons confined to the AgSe planes with in-plane anisotropy, featuring anisotropic absorption and emission. Finally, we present a pathway to control the exciton behaviour by changing the chalcogen in the material lattice. Our studies unveil unexpected excitonic anisotropies in an unexplored class of tuneable, yet air-stable, hybrid quantum wells, offering design principles for the engineering of an ordered, yet complex dielectric environment and its effect on the excitonic phenomena in such emerging materials.