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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 S0 ) and fabricate it with scanning tunneling microscopy (STM). The Co S0 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.

Abstract: Point defects in two-dimensional materials are of key interest for quantum information science. However, the space of possible defects is immense, making the identification of high-performance quantum defects extremely 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$_{\rm S}^{0}$) as very promising and fabricate it with scanning tunneling microscopy (STM). The Co$_{\rm S}^{0}$ electronic structure measured by STM agrees with first principles and showcases an attractive new quantum defect. Our work shows how HT computational screening and novel defect synthesis routes can be combined to design new quantum defects.

Materials imperfections in planar superconducting quantum circuits - in particular, two-level-system (TLS) defects - contribute significantly to decoherence, ultimately limiting the performance of quantum computation and sensing. The identification of specific parasitic layers and their associated loss contributions has, however, proven elusive. Using a combination of x-ray photoemission spectroscopy (XPS) and analytical scanning transmission electron microscopy (STEM), we determine the thickness, chemical composition, and location of the oxides present in niobium-on-silicon coplanar-waveguide (CPW) resonators and quantify their respective contributions to the measured single-photon quality factor (Q). Using selective chemical etching, we reduce first the substrate-air oxide then the metal-air oxide thickness, dramatically reducing both TLS (δTLS) and non-TLS (δhi) losses, resulting in a median Q value over 5×106, with individual devices approaching 6×106. We find that silicon surface oxides host 70% of TLS losses, with a δTLS:δhi loss-density ratio near 11:1. In contrast, niobium surface oxides host 77% of non-TLS losses, uniformly distributed within the oxide layer, with a δTLS:δhi loss-density ratio of 3:4 for the superconducting circuits investigated in this work. Only 7% of losses come from other sources, including the niobium-silicon interface, which is sufficiently clean in our devices to allow epitaxial Nb nucleation on Si. As we mitigate surface losses through selective modification of the interface dielectrics, we arrive in a regime where TLS losses are no longer dominant, which will allow other types of losses in superconducting circuits to be investigated in more detail, including nonequilibrium quasiparticles.

Individual atomic defects in 2D materials impact their macroscopic functionality. Correlating the interplay is challenging, however, intelligent hyperspectral scanning tunneling spectroscopy (STS) mapping provides a feasible solution to this technically difficult and time consuming problem. Here, dense spectroscopic volume is collected autonomously via Gaussian process regression, where convolutional neural networks are used in tandem for spectral identification. Acquired data enable defect segmentation, and a workflow is provided for machine-driven decision making during experimentation with capability for user customization. We provide a means towards autonomous experimentation for the benefit of both enhanced reproducibility and user-accessibility. Hyperspectral investigations on WS2 sulfur vacancy sites are explored, which is combined with local density of states confirmation on the Au{111} herringbone reconstruction. Chalcogen vacancies, pristine WS2, Au face-centered cubic, and Au hexagonal close-packed regions are examined and detected by machine learning methods to demonstrate the potential of artificial intelligence for hyperspectral STS mapping.

Qubits made from superconducting materials are a mature platform for quantum information science application, such as quantum computing. However, material-based losses are now a limiting factor in reaching the coherence times needed for applications. In particular, knowledge of the atomistic structure and properties of the circuit materials is needed to identify, understand, and mitigate material-based decoherence channels. In this work, we characterize the atomic structure of the native oxide film formed on Nb resonators by comparing fluctuation electron microscopy experiments to density functional theory calculations, finding that an amorphous layer is consistent with an Nb2O5 stoichiometry. Comparing x-ray absorption measurements at the Oxygen K edge with first-principles calculations, we find evidence of d-type magnetic impurities in our sample, known to cause impedance in proximal superconductors. This work identifies the structural and chemical composition of the oxide layer grown on Nb superconductors and shows that soft x-ray absorption can fingerprint magnetic impurities in these superconducting systems.

Surface plasmons have found a wide range of applications in plasmonic and nanophotonic devices. The combination of plasmonics with three-dimensional photonic crystals has enormous potential for the efficient localization of light in high surface area photoelectrodes. However, the metals traditionally used for plasmonics are difficult to form into three-dimensional periodic structures and have limited optical penetration depth at operational frequencies, which limits their use in nanofabricated photonic crystal devices. The recent decade has seen an expansion of the plasmonic material portfolio into conducting ceramics, driven by their potential for improved stability, and their conformal growth via atomic layer deposition has been established. In this work, we have created three-dimensional photonic crystals with an ultrathin plasmonic titanium nitride coating that preserves photonic activity. Plasmonic titanium nitride enhances optical fields within the photonic electrode while maintaining sufficient light penetration. Additionally, we show that post-growth annealing can tune the plasmonic resonance of titanium nitride to overlap with the photonic resonance, potentially enabling coupled-phenomena applications for these three-dimensional nanophotonic systems. Through characterization of the tuning knobs of bead size, deposition temperature and cycle count, and annealing conditions, we can create an electrically- and plasmonically-active photonic crystal as-desired for a particular application of choice.

Quantum sensing and computation can be realized with superconductingmicrowave circuits. Qubits are engineered quantum systems of capacitors andinductors with non-linear Josephson junctions. They operate in thesingle-excitation quantum regime, photons of $27 \mu$eV at 6.5 GHz. Quantumcoherence is fundamentally limited by materials defects, in particularatomic-scale parasitic two-level systems (TLS) in amorphous dielectrics atcircuit interfaces.[1] The electric fields driving oscillating charges inquantum circuits resonantly couple to TLS, producing phase noise anddissipation. We use coplanar niobium-on-silicon superconducting resonators toprobe decoherence in quantum circuits. By selectively modifying interfacedielectrics, we show that most TLS losses come from the silicon surface oxide,and most non-TLS losses are distributed throughout the niobium surface oxide.Through post-fabrication interface modification we reduced TLS losses by 85%and non-TLS losses by 72%, obtaining record single-photon resonator qualityfactors above 5 million and approaching a regime where non-TLS losses aredominant. [1]M\"uller, C., Cole, J. H. & Lisenfeld, J. Towards understandingtwo-level-systems in amorphous solids: insights from quantum circuits. Rep.Prog. Phys. 82, 124501 (2019)

Quantum dot-like single-photon sources in transition metal dichalcogenides (TMDs) exhibit appealing quantum optical properties but lack a well-defined atomic structure and are subject to large spectral variability. Here, we demonstrate electrically stimulated photon emission from individual atomic defects in monolayer WS2 and directly correlate the emission with the local atomic and electronic structure. Radiative transitions are locally excited by sequential inelastic electron tunneling from a metallic tip into selected discrete defect states in the WS2 bandgap. Coupling to the optical far field is mediated by tip plasmons, which transduce the excess energy into a single photon. The applied tip-sample voltage determines the transition energy. Atomically resolved emission maps of individual point defects closely resemble electronic defect orbitals, the final states of the optical transitions. Inelastic charge carrier injection into localized defect states of two-dimensional materials provides a powerful platform for electrically driven, broadly tunable, atomic-scale single-photon sources.

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.

The electron beam (e-beam) in the scanning electron microscopy (SEM) provides an appealing mobile heating source for thermal metrology with spatial resolution of ∼1 nm, but the lack of systematic quantification of the e-beam heating power limits such application development. Here, we systemically study e-beam heating in LPCVD silicon nitride (SiNx) thin-films with thickness ranging from 200 to 500 nm from both experiments and complementary Monte Carlo simulations using the CASINO software package. There is good agreement about the thickness-dependent e-beam energy absorption of thin-film between modeling predictions and experiments. Using the absorption results, we then demonstrate adapting the e-beam as a quantitative heating source by measuring the thickness-dependent thermal conductivity of SiNx thin-films, with the results validated to within 7% by a separate Joule heating experiment. The results described here will open a new avenue for using SEM e-beams as a mobile heating source for advanced nanoscale thermal metrology development.

Mn2+ doping of lead halide perovskites has garnered recent interest because it produces stable orange luminescence in tandem with perovskite emission. Here, we observe enhanced Mn2+ luminescence at the edges of Mn2+-doped CsPbCl3 perovskite microplates and suggest an explanation for its origin using the high spatiotemporal resolution of time-resolved cathodoluminescence (TRCL) imaging. We reveal two luminescent decay components that we attribute to two different Mn2+ populations. While each component appears to be present both near the surface and in the bulk, the origin of the intensity variation stems from a higher proportion of the longer lifetime component near the perovskite surface. We suggest that this higher emission is caused by an increased probability of electron-hole recombination on Mn2+ near the perovskite surface due to an increased trap concentration there. This observation suggests that such surface features have yet untapped potential to enhance emissive properties via control of surface-to-volume ratio.

Control of impurity concentrations in semiconducting materials is essential to device technology. Because of their intrinsic confinement, the properties of two-dimensional semiconductors such as transition metal dichalcogenides (TMDs) are more sensitive to defects than traditional bulk materials. The technological adoption of TMDs is dependent on the mitigation of deleterious defects and guided incorporation of functional foreign atoms. The first step toward impurity control is the identification of defects and assessment of their electronic properties. Here, we present a comprehensive study of point defects in monolayer tungsten disulfide (WS2) grown by chemical vapor deposition using scanning tunneling microscopy/spectroscopy, CO-tip noncontact atomic force microscopy, Kelvin probe force spectroscopy, density functional theory, and tight-binding calculations. We observe four different substitutional defects: chromium (CrW) and molybdenum (MoW) at a tungsten site, oxygen at sulfur sites in both top and bottom layers (OS top/bottom), and two negatively charged defects (CD type I and CD type II). Their electronic fingerprints unambiguously corroborate the defect assignment and reveal the presence or absence of in-gap defect states. CrW forms three deep unoccupied defect states, two of which arise from spin-orbit splitting. The formation of such localized trap states for CrW differs from the MoW case and can be explained by their different d shell energetics and local strain, which we directly measured. Utilizing a tight-binding model the electronic spectra of the isolectronic substitutions OS and CrW are mimicked in the limit of a zero hopping term and infinite on-site energy at a S and W site, respectively. The abundant CDs are negatively charged, which leads to a significant band bending around the defect and a local increase of the contact potential difference. In addition, CD-rich domains larger than 100 nm are observed, causing a work function increase of 1.1 V. While most defects are electronically isolated, we also observed hybrid states formed between CrW dimers. The important role of charge localization, spin-orbit coupling, and strain for the formation of deep defect states observed at substitutional defects in WS2 as reported here will guide future efforts of targeted defect engineering and doping of TMDs.

Structural defects in 2D materials offer an effective way to engineer new material functionalities beyond conventional doping. We report on the direct experimental correlation of the atomic and electronic structure of a sulfur vacancy in monolayer WS_{2} by a combination of CO-tip noncontact atomic force microscopy and scanning tunneling microscopy. Sulfur vacancies, which are absent in as-grown samples, were deliberately created by annealing in vacuum. Two energetically narrow unoccupied defect states followed by vibronic sidebands provide a unique fingerprint of this defect. Direct imaging of the defect orbitals, together with ab initio GW calculations, reveal that the large splitting of 252±4  meV between these defect states is induced by spin-orbit coupling.

In this letter, we demonstrate that improved low energy electron absorption is achieved by suppressing the crystallinity of chromium thin-films grown on W[110], which points to a promising route for achieving highly efficient thermionic energy converters. Using low energy electron microscopy (LEEM) and in situ film growth, we show that substrate temperature control permits well-controlled fabrication of either epitaxial Cr[110] films or nanocrystalline Cr layers. We show that the work function of cesium saturated nanocrystalline Cr thin-films is ∼0.20 eV lower than that of epitaxial Cr[110] films. Our LEEM measurements of absorbed and reflected currents as a function of electron energy demonstrate that nanocrystallinity of cesiated chromium films results in 96% electron absorption in the range up to 1 eV above the work function, compared to just 79% absorption in cesiated crystalline Cr[110] films. These results point to metal films with suppressed crystallinity as an economical and scalable means to synthesize nanoengineered surfaces with optimized properties for next generation anode materials in high performance thermionic energy converters.

Electron microscopy has been instrumental in our understanding of complex biological systems. Although electron microscopy reveals cellular morphology with nanoscale resolution, it does not provide information on the location of different types of proteins. An electron-microscopy-based bioimaging technology capable of localizing individual proteins and resolving protein-protein interactions with respect to cellular ultrastructure would provide important insights into the molecular biology of a cell. Here, we synthesize small lanthanide-doped nanoparticles and measure the absolute photon emission rate of individual nanoparticles resulting from a given electron excitation flux (cathodoluminescence). Our results suggest that the optimization of nanoparticle composition, synthesis protocols and electron imaging conditions can lead to sub-20-nm nanolabels that would enable high signal-to-noise localization of individual biomolecules within a cellular context. In ensemble measurements, these labels exhibit narrow spectra of nine distinct colours, so the imaging of biomolecules in a multicolour electron microscopy modality may be possible.

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. Point defects in 2D semiconductors have potential for quantum computing applications, but their controlled design and synthesis remains challenging. Here, the authors identify and fabricate a promising quantum defect in 2D WS2 via high-throughput computational screening and scanning tunnelling microscopy. [ABSTRACT FROM AUTHOR]

New photoresists are needed to advance extreme ultraviolet (EUV) lithography. The tailored design of efficient photoresists is enabled by a fundamental understanding of EUV induced chemistry. Processes that occur in the resist film after absorption of an EUV photon are discussed, and a new approach to study these processes on a fundamental level is described. The processes of photoabsorption, electron emission, and molecular fragmentation were studied experimentally in the gas-phase on analogs of the monomer units employed in chemically amplified EUV resists. To demonstrate the dependence of the EUV absorption cross section on selective light harvesting substituents, halogenated methylphenols were characterized employing the following techniques. Photoelectron spectroscopy was utilized to investigate kinetic energies and yield of electrons emitted by a molecule. The emission of Auger electrons was detected following photoionization in the case of iodo-methylphenol. Mass-spectrometry was used to deduce the molecular fragmentation pathways following electron emission and atomic relaxation. To gain insight on the interaction of emitted electrons with neutral molecules in a condensed film, the fragmentation pattern of neutral gas-phase molecules, interacting with an electron beam, was studied and observed to be similar to EUV photon fragmentation. Below the ionization threshold, electrons were confirmed to dissociate iodo-methylphenol by resonant electron attachment.

Crucial to analyze phenomena as varied as plasmonic hot spots and the spreadof cancer in living tissue, nanoscale thermometry is challenging: probes areusually larger than the sample under study, and contact techniques may alterthe sample temperature itself. Many photostable nanomaterials whoseluminescence is temperature-dependent, such as lanthanide-doped phosphors, havebeen shown to be good non-contact thermometric sensors when optically excited.Using such nanomaterials, in this work we accomplished the key milestone ofenabling far-field thermometry with a spatial resolution that is notdiffraction-limited at readout. We explore thermal effects on the cathodoluminescence of lanthanide-dopedNaYF$_4$ nanoparticles. Whereas cathodoluminescence from such lanthanide-dopednanomaterials has been previously observed, here we use quantitative featuresof such emission for the first time towards an application beyond localization.We demonstrate a thermometry scheme that is based on cathodoluminescencelifetime changes as a function of temperature that achieves $\sim$ 30 mKsensitivity in sub-$\mu$m nanoparticle patches. The scheme is robust againstspurious effects related to electron beam radiation damage and opticalalignment fluctuations. We foresee the potential of single nanoparticles, of sheets of nanoparticles,and also of thin films of lanthanide-doped NaYF$_4$ to yield temperatureinformation via cathodoluminescence changes when in the vicinity of a sample ofinterest; the phosphor may even protect the sample from direct contact todamaging electron beam radiation. Cathodoluminescence-based thermometry is thusa valuable novel tool towards temperature monitoring at the nanoscale, withbroad applications including heat dissipation in miniaturized electronics andbiological diagnostics.

We report visualizations of the bidirectional near-field optical transfer function for a waveguide-coupled plasmonic transducer as a metrology technique essential for successful development for mass-fabricated near-field devices. Plasmonic devices have revolutionized the observation of nanoscale phenomena, enabling optical excitation and readout from nanoscale regions of fabricated devices instead of as limited by optical diffraction. Visualizations of the plasmonic transducer modes were acquired both by local near-field excitation of the antenna on the front facet of a waveguide using the focused electron beam of a scanning electron microscope as a probe of the near-field cathodoluminescence during far-field collection from the back facet of the waveguide, and by local mapping of the optical near-field for the same antenna design using scattering scanning near-field optical microscopy as a probe of the near-field optical mode density for far-field light focused into the back facet of the waveguide. Strong agreement between both measurement types and numerical modeling was observed, indicating that the method enables crucial metrological comparisons of as fabricated device performance to as-modeled device expectations for heat-assisted magnetic recording heads, which can be extended to successful development of future near-field-on-chip devices such as optical processor interconnects.

In situ electron microscopy provides remarkably high spatial resolution, yet electron beam irradiation often damages soft materials and perturbs dynamic processes, requiring samples to be very robust. Here, we instead noninvasively image the dynamics of metal and polymer nanoparticles in a liquid environment with subdiffraction resolution using cathodoluminescence-activated imaging by resonant energy transfer (CLAIRE). In CLAIRE, a free-standing scintillator film serves as a nanoscale optical excitation source when excited by a low energy, focused electron beam. We capture the nanoscale dynamics of these particles translating along and desorbing from the scintillator surface and demonstrate 50 ms frame acquisition and a range of imaging of at least 20 nm from the scintillator surface. Furthermore, in contrast with in situ electron microscopy, CLAIRE provides spectral selectivity instead of relying on scattering alone. We also demonstrate through quantitative modeling that the CLAIRE signal from metal nanoparticles is impacted by multiplasmonic mode interferences. Our findings demonstrate that CLAIRE is a promising, noninvasive approach for super-resolution imaging for soft and fluid materials with high spatial and temporal resolution.

The distinct physical properties of hybrid organic-inorganic materials can lead to unexpected nonequilibrium phenomena that are difficult to characterize due to the broad range of length and time scales involved. For instance, mixed halide hybrid perovskites are promising materials for optoelectronics, yet bulk measurements suggest the halides reversibly phase separate upon photoexcitation. By combining nanoscale imaging and multiscale modeling, we find that the nature of halide demixing in these materials is distinct from macroscopic phase separation. We propose that the localized strain induced by a single photoexcited charge interacting with the soft, ionic lattice is sufficient to promote halide phase separation and nucleate a light-stabilized, low-bandgap, ∼8 nm iodide-rich cluster. The limited extent of this polaron is essential to promote demixing because by contrast bulk strain would simply be relaxed. Photoinduced phase separation is therefore a consequence of the unique electromechanical properties of this hybrid class of materials. Exploiting photoinduced phase separation and other nonequilibrium phenomena in hybrid materials more generally could expand applications in sensing, switching, memory, and energy storage.

We provide direct evidence for the existence of isolated, one-dimensional charge density waves at mirror twin boundaries (MTBs) of single-layer semiconducting MoSe 2. Such MTBs have been previously observed by transmission electron microscopy and have been predicted to be metallic in MoSe 2 and MoS 2. Our low-temperature scanning tunnelling microscopy/spectroscopy measurements revealed a substantial bandgap of 100 meV opening at the Fermi energy in the otherwise metallic one-dimensional structures. We found a periodic modulation in the density of states along the MTB, with a wavelength of approximately three lattice constants. In addition to mapping the energy-dependent density of states, we determined the atomic structure and bonding of the MTB through simultaneous high-resolution non-contact atomic force microscopy. Density functional theory calculations based on the observed structure reproduced both the gap opening and the spatially resolved density of states.

The sensitivity of semiconductor photodetectors is limited by photocarrier recombination during the carrier transport process. We developed a new photoactive material that reduces recombination by physically separating hole and electron charge carriers. This material has a specific detectivity (the ability to detect small signals) of 5 × 10(17) Jones, the highest reported in visible and infrared detectors at room temperature, and 4-5 orders of magnitude higher than that of commercial single-crystal silicon detectors. The material was fabricated by sintering chloride-capped CdTe nanocrystals into polycrystalline films, where Cl selectively segregates into grain boundaries acting as n-type dopants. Photogenerated electrons concentrate in and percolate along the grain boundaries-a network of energy valleys, while holes are confined in the grain interiors. This electrostatic field-assisted carrier separation and percolation mechanism enables an unprecedented photoconductive gain of 10(10) e(-) per photon, and allows for effective control of the device response speed by active carrier quenching.

Photovoltaic devices based on hybrid perovskite materials have exceeded 22% efficiency due to high charge-carrier mobilities and lifetimes. Properties such as photocurrent generation and open-circuit voltage are influenced by the microscopic structure and orientation of the perovskite crystals, but are difficult to quantify on the intra-grain length scale and are often treated as homogeneous within the active layer. Here, we map the local short-circuit photocurrent, open-circuit photovoltage, and dark drift current in state-of-the-art methylammonium lead iodide solar cells using photoconductive atomic force microscopy. We find, within individual grains, spatially correlated heterogeneity in short-circuit current and open-circuit voltage up to 0.6 V. These variations are related to different crystal facets and have a direct impact on the macroscopic power conversion efficiency. We attribute this heterogeneity to a facet-dependent density of trap states. These results imply that controlling crystal grain and facet orientation will enable a systematic optimization of polycrystalline and single-crystal devices for photovoltaic and lighting applications.

Two-dimensional monolayer transition metal dichalcogenide semiconductors are ideal building blocks for atomically thin, flexible optoelectronic and catalytic devices. Although challenging for two-dimensional systems, sub-diffraction optical microscopy provides a nanoscale material understanding that is vital for optimizing their optoelectronic properties. Here we use the 'Campanile' nano-optical probe to spectroscopically image exciton recombination within monolayer MoS2 with sub-wavelength resolution (60 nm), at the length scale relevant to many critical optoelectronic processes. Synthetic monolayer MoS2 is found to be composed of two distinct optoelectronic regions: an interior, locally ordered but mesoscopically heterogeneous two-dimensional quantum well and an unexpected ∼300-nm wide, energetically disordered edge region. Further, grain boundaries are imaged with sufficient resolution to quantify local exciton-quenching phenomena, and complimentary nano-Auger microscopy reveals that the optically defective grain boundary and edge regions are sulfur deficient. The nanoscale structure-property relationships established here are critical for the interpretation of edge- and boundary-related phenomena and the development of next-generation two-dimensional optoelectronic devices.