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.

Optimizing cathodoluminescence microscopy of buried interfaces through nanoscale heterostructure design.

Mapping the optical response of buried interfaces with nanoscale spatial resolution is crucial in several systems where an active component is embedded within a buffer layer for structural or functional reasons. Here, we demonstrate that cathodoluminescence microscopy is not only an ideal tool for visualizing buried interfaces, but can be optimized through heterostructure design. We focus on the prototypical system of monolayers of semiconducting transition metal dichalcogenide sandwiched between hexagonal boron nitride layers. We leverage the encapsulating layers to tune the nanoscale spatial resolution achievable in cathodoluminescence mapping while also controlling the brightness of the emission. Thicker encapsulation layers result in a brighter emission while thinner ones enhance the spatial resolution at the expense of the signal intensity. We find that a favorable trade-off between brightness and resolution is achievable up to about ∼100 nm of total encapsulation. Beyond this value, the brightness gain is marginal, while the spatial resolution enters a regime that is achievable by diffraction-limited optical microscopy. By preparing samples of varying encapsulation thickness, we are able to determine a surprisingly isotropic exciton diffusion length of >200 nm within the hexagonal boron nitride which is the dominant factor that determines spatial resolution. We further demonstrate that we can overcome the exciton diffusion-limited spatial resolution by using spectrally distinct signals, which is the case for nanoscale inhomogeneities within monolayer transition metal dichalcogenides.

Ag-Diamond Core-Shell Nanostructures Incorporated with Silicon-Vacancy Centers.

Silicon-vacancy (SiV) centers in diamond have attracted attention as highly stable fluorophores for sensing and as possible candidates for quantum information science. While prior studies have shown that the formation of hybrid diamond-metal structures can increase the rates of optical absorption and emission, many practical applications require diamond plasmonic structures that are stable in harsh chemical and thermal environments. Here, we demonstrate that Ag nanospheres, produced both in quasi-random arrays by thermal dewetting and in ordered arrays using electron-beam lithography, can be completely encapsulated with a thin diamond coating containing SiV centers, leading to hybrid core-shell nanostructures exhibiting extraordinary chemical and thermal stability as well as enhanced optical properties. Diamond shells with a thickness on the order of 20-100 nm are sufficient to encapsulate and protect the Ag nanostructures with different sizes ranging from 20 nm to hundreds of nanometers, allowing them to withstand heating to temperatures of 1000 °C and immersion in harsh boiling acid for 24 h. Ultrafast photoluminescence lifetime and super-resolution optical imaging experiments were used to study the SiV properties on and off the core-shell structures, which show that the SiV on core-shell structures have higher brightness and faster decay rate. The stability and optical properties of the hybrid Ag-diamond core-shell structures make them attractive candidates for high-efficiency imaging and quantum-based sensing applications.

Methods for tuning plasmonic and photonic optical resonances in high surface area porous electrodes.

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.

Electrically driven photon emission from individual atomic defects in monolayer WS2.

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.

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.

Adapting the Electron Beam from SEM as a Quantitative Heating Source for Nanoscale Thermal Metrology.

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.

Resolving Enhanced Mn2+ Luminescence near the Surface of CsPbCl3 with Time-Resolved Cathodoluminescence Imaging.

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.

Large Spin-Orbit Splitting of Deep In-Gap Defect States of Engineered Sulfur Vacancies in Monolayer WS_{2}.

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.

How Substitutional Point Defects in Two-Dimensional WS2 Induce Charge Localization, Spin-Orbit Splitting, and Strain.

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.

Bright sub-20-nm cathodoluminescent nanoprobes for electron microscopy.

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.

Fundamental understanding of chemical processes in extreme ultraviolet resist materials.

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.

Visualizing the bidirectional optical transfer function for near-field enhancement in waveguide coupled plasmonic transducers.

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.

Noninvasive Cathodoluminescence-Activated Nanoimaging of Dynamic Processes in Liquids.

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.

Environmental stability of 2D anisotropic tellurium containing nanomaterials: anisotropic to isotropic transition.

We report on the vibrational (Raman) spectrum and structural transformation of semiconducting pseudo-1D GaTe and ZrTe3 nanomaterials driven by ambient molecular interactions at the nanoscale by angle-resolved Raman spectroscopy, atomic force microscopy (AFM), and environmental X-ray photoelectron (XPS) measurements. The results show that tellurium containing pseudo-1D materials undergo drastic structural and physical changes within a week. During this process, new Raman peaks start to emerge and surface roughness increases substantially. Surprisingly, aged Raman spectra of GaTe, ZrTe3, and α-TeOx show striking similarities suggesting that oxidation of tellurium takes place. Careful, environmental tests reveal that the interaction between GaTe and H2O molecules forms Te-O bonds at the outermost layers of GaTe which leads to newly emerging Raman peaks, a much reduced Schottky junction current density, and an anisotropic to isotropic structural transition. These findings offer fresh interpretation of the aging mechanisms for these material systems, provide new interpretation of the Raman spectrum of aged GaTe which was previously presumed to be of the hexagonal phase, and introduce an anisotropic to isotropic transformation effect induced by molecular interactions on the surface.

The importance of inner-shell electronic structure for enhancing the EUV absorption of photoresist materials.

In order to increase computation power and efficiency, the semiconductor industry continually strives to reduce the size of features written using lithographic techniques. The planned switch to a shorter wavelength extreme ultraviolet (EUV) source presents a challenge for the associated photoresists, which in their current manifestation show much poorer photoabsorption cross sections for the same dose. Here we consider the critical role that an inner-shell electronic structure might play in enhancing photoabsorption cross sections, which one can control by the choice of substituent elements in the photoresist. In order to increase the EUV sensitivity of current photoresists, it is critical to consider the inner-shell atomic structure of the elements that compose the materials. We validate this hypothesis using a series of halogenated organic molecules, which all have similar valence structures, but differ in the character of their semi-core and deep valence levels. Using various implementations of time-dependent density functional theory, the absorption cross sections are computed for the model systems of CH3X, X = H, OH, F, Cl, Br, I, as well as a representative polymer fragment: 2-methyl-phenol and its halogenated analogues. Iodine has a particularly high cross section in the EUV range, which is due to delayed absorption by its 4d electrons. The computational results are compared to standard database values and experimental data when available. Generally we find that the states that dominate the EUV oscillator strength are generated by excitations of deep valence or semi-core electrons, which are primarily atomic-like and relatively insensitive to the specific molecular structure.

Origin of Reversible Photoinduced Phase Separation in Hybrid Perovskites.

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.

Ultrasensitive photodetectors exploiting electrostatic trapping and percolation transport.

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.

Revealing Optical Properties of Reduced-Dimensionality Materials at Relevant Length Scales.

Reduced-dimensionality materials for photonic and optoelectronic applications including energy conversion, solid-state lighting, sensing, and information technology are undergoing rapid development. The search for novel materials based on reduced-dimensionality is driven by new physics. Understanding and optimizing material properties requires characterization at the relevant length scale, which is often below the diffraction limit. Three important material systems are chosen for review here, all of which are under investigation at the Molecular Foundry, to illustrate the current state of the art in nanoscale optical characterization: 2D semiconducting transition metal dichalcogenides; 1D semiconducting nanowires; and energy-transfer in assemblies of 0D semiconducting nanocrystals. For each system, the key optical properties, the principal experimental techniques, and important recent results are discussed. Applications and new developments in near-field optical microscopy and spectroscopy, scanning probe microscopy, and cathodoluminescence in the electron microscope are given detailed attention. Work done at the Molecular Foundry is placed in context within the fields under review. A discussion of emerging opportunities and directions for the future closes the review.

Visualizing nanoscale excitonic relaxation properties of disordered edges and grain boundaries in monolayer molybdenum disulfide.

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.