Engineering topics

Lingerfelt, David B.

Publications and source records attributed to Lingerfelt, David B..

6 records

DOE OSTI2024

First-Principles Simulation of Beam-Induced Processes Underlying Atomic Manipulation in Electron Microscopes

The development of experimental methods and apparatuses capable of promoting atomically precise material manipulations holds great promise for realizing the ultimate limit of feature miniaturization in materials and devices. The ability to modify materials atom by atom is anticipated to usher in new technologies in areas as diverse as separation science, medicine, and quantum information science. Historically, scanning probe-based techniques have been the most prominent approaches in this space. However, these methods are best suited for the manipulation of surface-exposed regions of materials, as the strong perturbations required for bond scission are delivered most effectively to atoms in the near-proximity to the scanning probe. In contrast, convergent electron beams with energies tuned slightly below the threshold for inducing irreversible knock-on damage have recently been employed (within scanning transmission electron microscopy) to promote atomic-scale bond rearrangements in various beam-stable solids. Currently, however, the efficiency and selectivity of beam-induced atomic manipulation processes with focused electron beams are such that long irradiation times are required to induce a desired atomic rearrangement. With a better understanding of the underlying physics dictating the outcome of a given irradiation event, methods can be devised to improve the efficiency of these techniques so that their promise can be fully realized through widespread adoption.To this end, this Account details our recent efforts to develop and apply tractable first-principles simulation approaches for studying the response of materials to electric beam-like external electric potentials applied in real space. We briefly review the concepts and capabilities in the area of atomically precise materials manipulation and review the early demonstrations of accomplishments in this area, focusing on studies using scanned convergent electron beam probes in particular. We expound upon the depth of the challenge and identify critical shortcomings of theoretical methods that have previously been employed in the simulation of beam-induced processes. We then describe the computational methods that we have generalized from the concepts and tools most commonly applied to the study of molecular photochemistry and how our adaptations of these methods can be employed to capture the relevant dynamical phenomena for beam-induced processes ranging from the initial electron scattering to the ensuing multistate reactions. Here, we contextualize these methods within the current state of the art in this area, which has historically focused primarily on the simulation of inelastic image formation in the electron microscope for the purpose of interpreting the results of quantitative electron microscopy experiments. We demonstrate that the spatial distribution of state-specific excitation rates due to the presence of an external (probe) electric charge is inhomogeneous, such that irradiation at particular locations in materials can favor specific electronic transitions (and disallow others). In addition to the potential for excited-state reaction pathways to be accessed through the initial inelastic scattering of the tightly focused electron beam from the targeted atoms, we also identify favorable conditions for the electronically nonadiabatic evolution of the highly vibrationally excited system to open complex multistate reaction pathways. Implications of the early results for understanding the mechanisms and potential routes to improved efficiency and selectivity in beam-induced reactions are discussed. We conclude with a summary of the current state of theory and modeling capabilities in this area and provide our perspective on future directions for theoretical and experimental developments that we view as crucial to advancing the use of convergent electron beams in mode-specific, atomically precise platforms for direct-write materials modifications.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Imaging Strain-Localized Single-Photon Emitters in Layered GaSe below the Diffraction Limit

Nanoscale strain control of exciton funneling is an increasingly critical tool for the scalable production of single photon emitters (SPEs) in two-dimensional materials. However, conventional far-field optical microscopies remain constrained in spatial resolution by the diffraction limit and thus can provide only a limited description of nanoscale strain localization of SPEs. Here, we quantify the effects of nanoscale heterogeneous strain on the energy and brightness of GaSe SPEs on nanopillars with correlative cathodoluminescence, photoluminescence, and atomic force microscopy, supported by density functional theory simulations. We report the strain-localized SPEs have a broad range of emission wavelengths from 620 to 900 nm. We reveal substantial strain-controlled SPE wavelength tunability over a ~100 nm spectral range and 2 orders of magnitude enhancement in the SPE brightness at the pillar center due to Type-I exciton funneling. In addition, we show that radiative biexciton cascade processes contribute to observed CL photon superbunching. Also, the GaSe SPEs show excellent stability, where their properties remain unchanged after electron beam exposure. Importantly, we anticipate that this comprehensive study on the nanoscale strain control of two-dimensional SPEs will provide key insights to guide the development of truly deterministic quantum photonics.

2D materials↗

DOE OSTI2022

Extracting Inelastic Scattering Cross Sections for Finite and Aperiodic Materials from Electronic Dynamics Simulations

Explicit time-dependent electronic structure theory methods are increasingly prevalent in the areas of condensed matter physics and quantum chemistry, with the broad-band optical absorptivity of molecular and small condensed-phase systems nowadays routinely studied with such approaches. Here, in this paper, it is demonstrated that electronic dynamics simulations can similarly be employed to study cross sections for the scattering-induced electronic excitations probed in nonresonant inelastic X-ray scattering and momentum-resolved electron energy loss spectroscopies. A method is put forth for evaluating the electronic dynamic structure factor, which involves the application of a momentum boost-type perturbation and transformation of the resulting reciprocal space density fluctuations into the frequency domain. Good agreement is first demonstrated between the dynamic structure factor extracted from these electronic dynamics simulations and the corresponding transition matrix elements from linear response theory. The method is then applied to some extended (quasi)one-dimensional systems, for which the wave vector becomes a good quantum number in the thermodynamic limit. Finally, the dispersion of many-body excitations in a series of hydrogen-terminated graphene flakes (and twisted bilayers thereof) is investigated to highlight the utility of the presented approach for capturing morphology-dependent effects in the inelastic scattering cross sections of nanostructured and/or noncrystalline materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Strain-Induced asymmetry and on-site dynamics of silicon defects in graphene

In the last decade, the atomically-focused electron beams utilized in scanning transmission electron microscopes (STEMs) have been shown to induce a broad set of local structural transformations in materials, opening pathways for directing material synthesis and modification atom-by-atom. The mechanisms underlying these transformations remain largely unknown, due to the intractability of modeling the myriad of reaction pathways that can be accessed through high-energy electron scattering. The information on materials’ structure and dynamics that can be extracted from STEM images is similarly left underexplored. Here, we report the observation of anomalous on-site dynamics of individual silicon impurity atoms in graphene during STEM imaging. Density functional theory-based structural optimizations of anisotropically-strained molecular nanographenes reveal two distinct (but nearly degenerate) stable structures for four-fold coordinated silicon impurities, where interconversion between the two structures manifests slight changes of the silicon position within the lattice site. Implications for defect-based strain engineering in graphene are discussed.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Nonadiabatic Effects on Defect Diffusion in Silicon-Doped Nanographenes

Single atom impurities in graphene, substitutional silicon defects in particular, have been observed to diffuse under electron beam irradiation. However, the relative importance of elastic and inelastic scattering in facilitating their mobility remains unclear. Here, we employ excited-state electronic structure calculations to explore potential inelastic effects, and find an electronically nonadiabatic excited-state silicon diffusion pathway involving “softened” Si–C bonding that presents an ~2 eV lower diffusion barrier than the ground-state pathway. Beam-induced transition rates to this state indicate that the excited-state pathway is accessible through irradiation of the defect site. However, even in the limit of fully elastic scattering, upward nonadiabatic transitions are also possible along the diffusion coordinate, increasing the diffusion barrier and further demonstrating the potential for electronic nonadiabaticity to influence beam-induced atomic transformations in materials. Additionally, we also propose some experimentally testable signatures of such excited-state pathways.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

DOE OSTI2020

Reconstruction of effective potential from statistical analysis of dynamic trajectories

The broad incorporation of microscopic methods is yielding a wealth of information on the atomic and mesoscale dynamics of individual atoms, molecules, and particles on surfaces and in open volumes. Analysis of such data necessitates statistical frameworks to convert observed dynamic behaviors to effective properties of materials. Here, we develop a method for the stochastic reconstruction of effective local potentials solely from observed structural data collected from molecular dynamics simulations (i.e., data analogous to those obtained via atomically resolved microscopies). Using the silicon vacancy defect in graphene as a model, we apply the statistical framework presented herein to reconstruct the free energy landscape from the calculated atomic displacements. Evidence of consistency between the reconstructed local potential and the trajectory data from which it was produced is presented, along with a quantitative assessment of the uncertainty in the inferred parameters.

74 ATOMIC AND MOLECULAR PHYSICS↗