Single-atom Sensitivity Research Articles

Low-voltage single-atom electron microscopy with carbon-based nanomaterials

The properties of materials are strongly correlated with their atomic scale structures. Achieving a comprehensive understanding of the atomic-scale structure-property relationship requires advancements of imaging and spectroscopy techniques. Aberration-corrected scanning transmission electron microscopy (STEM) has seen rapid development over the past decades and is now routinely employed for atomic-scale characterization. However, quantitative STEM imaging and spectroscopy analysis at the single-atom level is challenging due to the extremely weak signals generated from individual atom, thus imposing stringent requirements for analysis sensitivity. This review discusses the development and application of low-voltage STEM techniques with single-atom sensitivity, primarily based on recent research presented on an invited talk at the 5th 2D23 SALVE Symposium, including annular dark-field (ADF) imaging, functional imaging and electron energy-loss spectroscopy (EELS) analysis. Carbon-based nanomaterials were chosen as model systems for demonstrating the capabilities of single-atom STEM imaging and EELS analysis, due to their structural stability under low accelerating voltages and their rich physical and chemical properties. Moreover, this review summarizes recent advancements and applications of low-voltage single-atom STEM imaging and spectroscopy in the study of functional materials and discusses prospects for future developments.

Benchmarking of X-Ray Fluorescence Microscopy with Ion Beam Implanted Samples Showing Detection Sensitivity of Hundreds of Atoms.

Single impurities in insulators are now often used for quantum sensors and single photon sources, while nanoscale semiconductor doping features are being constructed for electrical contacts in quantum technology devices, implying that new methods for sensitive, non-destructive imaging of single- or few-atom structures are needed. X-ray fluorescence (XRF) can provide nanoscale imaging with chemical specificity, and features comprising as few as 100000 atoms have been detected without any need for specialized or destructive sample preparation. Presently, the ultimate limits of sensitivity of XRF are unknown - here, gallium dopants in silicon are investigated using a high brilliance, synchrotron source collimated to a small spot. It is demonstrated that with a single-pixel integration time of 1 s, the sensitivity is sufficient to identify a single isolated feature of only 3000Ga impurities (a mass of just 350 zg). With increased integration (25 s), 650 impurities can be detected. The results are quantified using a calibration sample consisting of precisely controlled numbers of implanted atoms in nanometer-sized structures. The results show that such features can now be mapped quantitatively when calibration samples are used, and suggest that, in the near future, planned upgrades to XRF facilities might achieve single-atom sensitivity.

Probing a Defect-Site-Specific Electronic Orbital in Graphene with Single-Atom Sensitivity.

Visualization of individual electronic states ascribed to specific unoccupied orbitals at the atomic scale can reveal fundamental information about chemical bonding, but it is challenging since bonding often results in only subtle variations in the whole density of states. Here, we utilize atomic-resolution energy-loss near-edge fine structure (ELNES) spectroscopy to map out the electronic states attributed to specific unoccupied p_{z} orbital around a fourfold coordinated silicon point defect in graphene, which is further supported by theoretical calculations. Our results illustrate the power of atomic-resolution ELNES towards the probing of defect-site-specific electronic orbitals in monolayer crystals, providing insights into understanding the effect of chemical bonding on the local properties of defects in solids.

Accelerating error correction in tomographic reconstruction

Spurred by recent advances in detector technology and X-ray optics, upgrades to scanning-probe-based tomographic imaging have led to an exponential growth in the amount and complexity of experimental data and have created a clear opportunity for tomographic imaging to approach single-atom sensitivity. The improved spatial resolution, however, is highly susceptible to systematic and random experimental errors, such as center of rotation drifts, which may lead to imaging artifacts and prevent reliable data extraction. Here, we present a model-based approach that simultaneously optimizes the reconstructed specimen and sinogram alignment as a single optimization problem for tomographic reconstruction with center of rotation error correction. Our algorithm utilizes an adaptive regularizer that is dynamically adjusted at each alternating iteration step. Furthermore, we describe its implementation in a software package targeting high-throughput workflows for execution on distributed-memory clusters. We demonstrate the performance of our solver on large-scale synthetic problems and show that it is robust to a wide range of noise and experimental drifts with near-ideal throughput.

(Invited) Atom Probe Tomography: A New Tool For the Analysis of Solid Liquid Interfaces?

Atom probe tomography is an established method for the microsocopic analysis of hard materials, which stands out by combining single-atom sensitivity with a 3D volume reconstruction. The method is based on laser-assisted field evaporation from nanometric emitter tips. In solid state reactions it delivered decisive information to understand the detailed conditions of nucleation and growth of product phases. In recent efforts, we desire to break the materials limitations aiming for application to liquids, softmatter and polymeric materials. To this end, a new instrument has been constructed that joins cryogenic ion beam preparation with a flexible transfer into an atom probe chamber. Meanwhile, we are able to produce nanometric needles from frozen liquids, even from pure water [1]. Studies are performed with aqueous solutions [2], liquids of short alkanes [3], self-assembling monolayers [4]. The talk discusses the field desorption of complex materials and presents time of flight mass spectra and their dependence on field or laser intensity. The complex mechanisms of field desorption from frozen water surfaces are further elucidated by DFT and Monte-Carlo simulation. Finally, by evaluating evaporation probabilities and event correlations, even insight in bonding strength and the stability of molecules in strong electrical fields may be provided.[1] T. M. Schwarz, E. M. Weikum, K. Meng, E. Hadjixenophontos, C. A. Dietrich, J. Kästner, P. Stender, G. Schmitz, Field evaporation and atom probe tomography of pure water tips, Nature Scientific Reports (2020) 10:20271 | (DOI: 10.1038/s41598-020-77130-x[2] T. M. Schwarz, C. A. Dietrich, J. Ott, E. M. Weikum, R. Lawitzki, H. Solodenko, E. Hadjixenophontos, B. Gault, J. Kästner, G. Schmitz, P. Stender, 3D Sub-Nanometer Analysis of Glucose in an Aqueous Solution by Cryo-Atom Probe Tomography, Scientific reports 11 (2021) 11607 (DOI: 10.1038/s41598-021-90862-8)[3] Kuan Meng, Tim Schwarz, Eric Weikum, Patrick Stender, Guido Schmitz, Frozen n-Tetradecane investigated by cryo-Atom Probe Tomography, J. Microsc. Microanal. (2021), 1-11; (DOI:10.1017/S14319276210125)[4] Helena Solodenko, Patrick Stender, Guido Schmitz, “Atom Probe Study of 1-octadecanethiol self-assembled Monolayers on Platinum (111) and (200) surfaces”, J. Microsc. Microanal. (2021), 1–10. (DOI: 10.1017/S1431927621012654)

Atomic mechanisms of gold nanoparticle growth in ionic liquids studied by in situ scanning transmission electron microscopy.

Elementary atomic mechanisms underlying nanoparticle growth in liquids are largely unexplored and mostly a subject of conjectures based on theory and indirect experimental insights. Direct, experimental observation of such processes at an atomic level requires imaging with single-atom sensitivity and control over kinetics. Although conventional liquid-cell (scanning) transmission electron microscopy ((S)TEM) enables nanoscale studies of dynamic processes, the visualization of atomic processes in the liquid phase is inhibited owing to the liquid film thickness and its encapsulation, both limiting the achievable spatial resolution. In contrast, by using thin, free-standing ionic liquid nanoreactors, this work shows that the mechanisms controlling and triggering particle growth can be uncovered at an atom-by-atom level. Our observations of growing particle ensembles reveal that diverse growth pathways proceed simultaneously. We record Ostwald ripening and oriented particle coalescence tracked at the atomic scale, which confirm the mechanisms suggested by theory. However, we also identify unexpected growth phenomena and more intricate coalescence events which show competing mechanisms. The diversity of the observed growth processes thus illustrates that growth reactions in liquids, on the atomic scale, are much more complex than predicted by theory. Furthermore, this work demonstrates that free-standing ionic liquids enable (sub-)Ångström resolution imaging of dynamic processes in liquids with single-atom sensitivity, thus providing a powerful alternative approach to conventional liquid-cell (S)TEM.

Detection of atomic nuclear reaction products via optical imaging

In this paper we propose a new method for measuring the cross section of low yield nuclear reactions by capturing the products in a cryogenically frozen noble gas solid. Once embedded in the noble gas solid, which is optically transparent, the product atoms can be selectively identified by laser induced fluorescence and individually counted via optical imaging to determine the cross section. Single atom sensitivity by optical imaging is feasible because the surrounding lattice of noble gas atoms facilitates a large wavelength shift between the excitation and emission spectrum of the product atoms. The tools and techniques from the fields of single molecule spectroscopy and superresolution imaging in combination with an electromagnetic recoil separator, for beam and isotopic differentiation, allow for a detection scheme with near unity efficiency, a high degree of selectivity, and single atom sensitivity. This technique could be used to determine a number of astrophysically important nuclear reaction rates.

Quantitative imaging of electric surface potentials with single-atom sensitivity.

Because materials consist of positive nuclei and negative electrons, electric potentials are omnipresent at the atomic scale. However, due to the long range of the Coulomb interaction, large-scale structures completely outshine small ones. This makes the isolation and quantification of the electric potentials that originate from nanoscale objects such as atoms or molecules very challenging. Here we report a noncontact scanning probe technique which addresses this challenge. It exploits a quantum dot sensor and the joint electrostatic screening by tip and surface, thus enabling quantitative surface potential imaging across all relevant length scales down to single atoms. We apply the technique to the characterization of a nanostructured surface, thereby extracting work function changes and dipole moments for important reference systems. This authenticates the method as a versatile tool to study the building blocks of materials and devices down to the atomic scale.

Atomic electrostatic maps of 1D channels in 2D semiconductors using 4D scanning transmission electron microscopy

Defects in materials give rise to fluctuations in electrostatic fields that reflect the local charge density, but imaging this with single atom sensitivity is challenging. However, if possible, this provides information about the energetics of adatom binding, localized conduction channels, molecular functionality and their relationship to individual bonds. Here, ultrastable electron-optics are combined with a high-speed 2D electron detector to map electrostatic fields around individual atoms in 2D monolayers using 4D scanning transmission electron microscopy. Simultaneous imaging of the electric field, phase, annular dark field and the total charge in 2D MoS2 and WS2 is demonstrated for pristine areas and regions with 1D wires. The in-gap states in sulphur line vacancies cause 1D electron-rich channels that are mapped experimentally and confirmed using density functional theory calculations. We show how electrostatic fields are sensitive in defective areas to changes of atomic bonding and structural determination beyond conventional imaging.

Control of Knock-On Damage for 3D Atomic Scale Quantification of Nanostructures: Making Every Electron Count in Scanning Transmission Electron Microscopy.

Understanding nanostructures down to the atomic level is the key to optimizing the design of advanced materials with revolutionary novel properties. This requires characterization methods capable of quantifying the three-dimensional (3D) atomic structure with the highest possible precision. A successful approach to reach this goal is to count the number of atoms in each atomic column from 2D annular dark field scanning transmission electron microscopy images. To count atoms with single atom sensitivity, a minimum electron dose has been shown to be necessary, while on the other hand beam damage, induced by the high energy electrons, puts a limit on the tolerable dose. An important challenge is therefore to develop experimental strategies to optimize the electron dose by balancing atom-counting fidelity vs the risk of knock-on damage. To achieve this goal, a statistical framework combined with physics-based modeling of the dose-dependent processes is here proposed and experimentally verified. This model enables an investigator to theoretically predict, in advance of an experimental measurement, the optimal electron dose resulting in an unambiguous quantification of nanostructures in their native state with the highest attainable precision.

Nanoscale tomography reveals the deactivation of automotive copper-exchanged zeolite catalysts

Copper-exchanged zeolite chabazite (Cu-SSZ-13) was recently commercialized for the selective catalytic reduction of NOX with ammonia in vehicle emissions as it exhibits superior reaction performance and stability compared to all other catalysts, notably Cu-ZSM-5. Herein, the 3D distributions of Cu as well as framework elements (Al, O, Si) in both fresh and aged Cu-SSZ-13 and Cu-ZSM-5 are determined with nanometer resolution using atom probe tomography (APT), and correlated with catalytic activity and other characterizations. Both fresh catalysts contain a heterogeneous Cu distribution, which is only identified due to the single atom sensitivity of APT. After the industry standard 135,000 mile simulation, Cu-SSZ-13 shows Cu and Al clustering, whereas Cu-ZSM-5 is characterized by severe Cu and Al aggregation into a copper aluminate phase (CuAl2O4 spinel). The application of APT as a sensitive and local characterization method provides identification of nanometer scale heterogeneities that lead to catalytic activity and material deactivation.

Observation of metal nanoparticles at atomic resolution in Pt-based cancer chemotherapeutics.

The chemotherapeutics cisplatin and oxaliplatin are important tools in the fight against cancer. Both compounds are platinum complexes. Aberration-corrected scanning transmission electron microscopy using the annular dark-field imaging mode now routinely provides single-atom sensitivity with atomic number contrast. Here, this imaging mode is used to directly image the platinum within the two drugs in their dried form on an amorphous carbon support film. The oxaliplatin is found to have wetted the supporting amorphous carbon, forming disordered clusters suggesting that the platinum has remained within the complex. Conversely, the cisplatin sample reveals 1.8-nm-diameter metallic platinum clusters. The size and shape of the clusters do not appear to be dependent on drying rate nor formed by beam damage, which may suggest that they were present in the original drug solution.

Electric field imaging of single atoms

In scanning transmission electron microscopy (STEM), single atoms can be imaged by detecting electrons scattered through high angles using post-specimen, annular-type detectors. Recently, it has been shown that the atomic-scale electric field of both the positive atomic nuclei and the surrounding negative electrons within crystalline materials can be probed by atomic-resolution differential phase contrast STEM. Here we demonstrate the real-space imaging of the (projected) atomic electric field distribution inside single Au atoms, using sub-Å spatial resolution STEM combined with a high-speed segmented detector. We directly visualize that the electric field distribution (blurred by the sub-Å size electron probe) drastically changes within the single Au atom in a shape that relates to the spatial variation of total charge density within the atom. Atomic-resolution electric field mapping with single-atom sensitivity enables us to examine their detailed internal and boundary structures.

Interfaces in Heterogeneous Catalysts: Advancing Mechanistic Understanding through Atomic-Scale Measurements.

Developing novel catalysts with high efficiency and selectivity is critical for enabling future clean energy conversion technologies. Interfaces in catalyst systems have long been considered the most critical factor in controlling catalytic reaction mechanisms. Interfaces include not only the catalyst surface but also interfaces within catalyst particles and those formed by constructing heterogeneous catalysts. The atomic and electronic structures of catalytic surfaces govern the kinetics of binding and release of reactant molecules from surface atoms. Interfaces within catalysts are introduced to enhance the intrinsic activity and stability of the catalyst by tuning the surface atomic and chemical structures. Examples include interfaces between the core and shell, twin or domain boundaries, or phase boundaries within single catalyst particles. In supported catalyst nanoparticles (NPs), the interface between the metallic NP and support serves as a critical tuning factor for enhancing catalytic activity. Surface electronic structure can be indirectly tuned and catalytically active sites can be increased through the use of supporting oxides. Tuning interfaces in catalyst systems has been identified as an important strategy in the design of novel catalysts. However, the governing principle of how interfaces contribute to catalyst behavior, especially in terms of interactions with intermediates and their stability during electrochemical operation, are largely unknown. This is mainly due to the evolving nature of such interfaces. Small changes in the structural and chemical configuration of these interfaces may result in altering the catalytic performance. These interfacial arrangements evolve continuously during synthesis, processing, use, and even static operation. A technique that can probe the local atomic and electronic interfacial structures with high precision while monitoring the dynamic interfacial behavior in situ is essential for elucidating the role of interfaces and providing deeper insight for fine-tuning and optimizing catalyst properties. Scanning transmission electron microscopy (STEM) has long been a primary characterization technique used for studying nanomaterials because of its exceptional imaging resolution and simultaneous chemical analysis. Over the past decade, advances in STEM, that is, the commercialization of both aberration correctors and monochromators, have significantly improved the spatial and energy resolution. Imaging atomic structures with subangstrom resolution and identifying chemical species with single-atom sensitivity are now routine for STEM. These advancements have greatly benefitted catalytic research. For example, the roles of lattice strain and surface elemental distribution and their effect on catalytic stability and reactivity have been well documented in bimetallic catalysts. In addition, three-dimensional atomic structures revealed by STEM tomography have been integrated in theoretical modeling for predictive catalyst NP design. Recent developments in stable electronic and mechanical devices have opened opportunities to monitor the evolution of catalysts in operando under synthesis and reaction conditions; high-speed direct electron detectors have achieved sub-millisecond time resolutions and allow for rapid structural and chemical changes to be captured. Investigations of catalysts using these latest microscopy techniques have provided new insights into atomic-level catalytic mechanisms. Further integration of new microscopy methods is expected to provide multidimensional descriptions of interfaces under relevant synthesis and reaction conditions. In this Account, we discuss recent insights on understanding catalyst activity, selectivity, and stability using advanced STEM techniques, with an emphasis on how critical interfaces dictate the performance of precious metal-based heterogeneous catalysts. The role of extended interfacial structures, including those between core and shell, between separate phases and twinned grains, between the catalyst surface and gas, and between metal and support are discussed. We also provide an outlook on how emerging electron microscopy techniques, such as vibrational spectroscopy and electron ptychography, will impact future catalysis research.

Many-body interferometry of a Rydberg-dressed spin lattice

Ultracold atoms are an ideal platform to study strongly correlated phases of matter in and out of equilibrium. Much of the experimental progress in this field crucially relies on the control of the contact interaction between two atoms. Control of strong long-range interactions between distant ground state atoms has remained a long standing goal, opening the path towards the study of fundamentally new quantum many-body systems including frustrated or topological magnets and supersolids. Optical dressing of ground state atoms by near-resonant laser coupling to Rydberg states has been proposed as a versatile method to engineer such interactions. However, up to now the great potential of this approach for interaction control in a many-body setting has eluded experimental confirmation. Here we report the realisation of coherent Rydberg-dressing in an ultracold atomic lattice gas and directly probe the induced interaction potential using an interferometric technique with single atom sensitivity. We use this approach to implement a two-dimensional synthetic spin lattice and demonstrate its versatility by tuning the range and anisotropy of the effective spin interactions. Our measurements are in remarkable agreement with exact solutions of the many-body dynamics, providing further evidence for the high degree of accurate interaction control in these systems. Finally, we identify a collective many-body decay process, and discuss possible routes to overcome this current limitation of coherence times. Our work marks the first step towards the use of laser-controlled Rydberg interactions for the study of exotic quantum magnets in optical lattices.

In-line Holography with Single Atom Sensitivity: Challenges and Achievements

In-line Holography with Single Atom Sensitivity: Challenges and Achievements

Advanced electron crystallography through model-based imaging.

The increasing need for precise determination of the atomic arrangement of non-periodic structures in materials design and the control of nanostructures explains the growing interest in quantitative transmission electron microscopy. The aim is to extract precise and accurate numbers for unknown structure parameters including atomic positions, chemical concentrations and atomic numbers. For this purpose, statistical parameter estimation theory has been shown to provide reliable results. In this theory, observations are considered purely as data planes, from which structure parameters have to be determined using a parametric model describing the images. As such, the positions of atom columns can be measured with a precision of the order of a few picometres, even though the resolution of the electron microscope is still one or two orders of magnitude larger. Moreover, small differences in average atomic number, which cannot be distinguished visually, can be quantified using high-angle annular dark-field scanning transmission electron microscopy images. In addition, this theory allows one to measure compositional changes at interfaces, to count atoms with single-atom sensitivity, and to reconstruct atomic structures in three dimensions. This feature article brings the reader up to date, summarizing the underlying theory and highlighting some of the recent applications of quantitative model-based transmisson electron microscopy.

Imaging and addressing of individual fermionic atoms in an optical lattice

We demonstrate fluorescence microscopy of individual fermionic potassium atoms in a 527-nm-period optical lattice. Using electromagnetically induced transparency (EIT) cooling on the 770.1-nm D$_1$ transition of $^{40}$K, we find that atoms remain at individual sites of a 0.3-mK-deep lattice, with a $1/e$ pinning lifetime of $67(9)\,\rm{s}$, while scattering $\sim 10^3$ photons per second. The plane to be imaged is isolated using microwave spectroscopy in a magnetic field gradient, and can be chosen at any depth within the three-dimensional lattice. With a similar protocol, we also demonstrate patterned selection within a single lattice plane. High resolution images are acquired using a microscope objective with 0.8 numerical aperture, from which we determine the occupation of lattice sites in the imaging plane with 94(2)\% fidelity per atom. Imaging with single-atom sensitivity and addressing with single-site accuracy are key steps towards the search for unconventional superfluidity of fermions in optical lattices, the initialization and characterization of transport and non-equilibrium dynamics, and the observation of magnetic domains.

Measuring strain and rotation fields at the dislocation core in graphene

Strain fields, dislocations and defects may be used to control electronic properties of graphene. By using advanced imaging techniques with high-resolution transmission electron microscopes, we have measured the strain and rotation fields about dislocations in monolayer graphene with single-atom sensitivity. These fields differ qualitatively from those given by conventional linear elasticity. However, atom positions calculated from two dimensional (2D) discrete elasticity and three dimensional discrete periodized F\"oppl-von K\'arm\'an equations (dpFvKEs) yield fields close to experiments when determined by geometric phase analysis. 2D theories produce symmetric fields whereas those from experiments exhibit asymmetries. Numerical solutions of dpFvKEs provide strain and rotation fields of dislocation dipoles and pairs that also exhibit asymmetries and, compared with experiments, may yield information on out-of-plane displacements of atoms. While discrete theories need to be solved numerically, analytical formulas for strains and rotation about dislocations can be obtained from 2D Mindlin's hyperstress theory. These formulas are very useful for fitting experimental data and provide a template to ascertain the importance of nonlinear and nonplanar effects. Measuring the parameters of this theory, we find two characteristic lengths between three and four times the lattice spacings that control dilatation and rotation about a dislocation. At larger distances from the dislocation core, the elastic fields decay to those of conventional elasticity. Our results may be relevant for strain engineering in graphene and other 2D materials of current interest.

Observing Atoms at Work by Controlling Beam-Sample Interactions.

Functional behavior can be initiated and captured in series of images with previously unknown details using a successful effort to effectively control beam-sample interactions in high-resolution transmission electron microscopy. The approach uses tunable electron dose rates that can be chosen to be as low as attoamperes per square-Ångstrom to delay sample degradation to an unexplored end. Dose rates can be systematically increased to stimulate and observe dynamic object responses. Observations can be made in real time with deep sub-Ångstrom resolution and single-atom sensitivity, even if radiation-sensitive matter is probed and either pressure or temperature is raised in the electron microscope.