skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Mending cracks atom-by-atom in rutile TiO2 with electron beam radiolysis
Abstract Rich electron-matter interactions fundamentally enable electron probe studies of materials such as scanning transmission electron microscopy (STEM). Inelastic interactions often result in structural modifications of the material, ultimately limiting the quality of electron probe measurements. However, atomistic mechanisms of inelastic-scattering-driven transformations are difficult to characterize. Here, we report direct visualization of radiolysis-driven restructuring of rutile TiO2under electron beam irradiation. Using annular dark field imaging and electron energy-loss spectroscopy signals, STEM probes revealed the progressive filling of atomically sharp nanometer-wide cracks with striking atomic resolution detail. STEM probes of varying beam energy and precisely controlled electron dose were found to constructively restructure rutile TiO2according to a quantified radiolytic mechanism. Based on direct experimental observation, a “two-step rolling” model of mobile octahedral building blocks enabling radiolysis-driven atomic migration is introduced. Such controlled electron beam-induced radiolytic restructuring can be used to engineer novel nanostructures atom-by-atom.  more » « less
Award ID(s):
2309431 2011401
PAR ID:
10465345
Author(s) / Creator(s):
; ; ; ;
Publisher / Repository:
Nature Publishing Group
Date Published:
Journal Name:
Nature Communications
Volume:
14
Issue:
1
ISSN:
2041-1723
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract The ability to probe and control matter at the picometer scale is essential for advancing quantum and energy technologies. Scanning transmission electron microscopy offers powerful capabilities for materials analysis and modification, but sample damage, drift, and scan distortions hinder single atom analysis and deterministic manipulation. Materials analysis and modification via electron–solid interactions can be transformed by precise delivery of electrons to a specified atomic location, maintaining the beam position despite drift, and minimizing collateral dose. Here a fast, low‐dose, sub‐20‐pm precision electron beam positioning technique is developed, “atomic lock‐on,” (ALO), which offers the ability to position the beam on a specific atomic columnwithoutpreviously irradiating that column. This technique is used to lock onto a single selected atomic location to repeatedly measure its weak electron energy loss signal despite sample drift. Moreover, electron beam‐matter interactions in single atomic events are measured with time resolution. This enables observation of single‐atom dynamics, such as atomic bistability, revealing partially bonded atomic configurations and recapture phenomena. This opens prospects for using electron microscopy for high‐precision measurements and deterministic control of matter for quantum technologies. 
    more » « less
  2. Environmental transmission electron microscopy (E-TEM) enables direct observation of nanoscale chemical processes crucial for catalysis and materials design. However, the high-energy electron probe can dramatically alter reaction pathways through radiolysis, the dissociation of molecules under electron beam irradiation. While extensively studied in liquid-cell TEM, the impact of radiolysis in gas phase reactions remains unexplored. Here, we present a numerical model elucidating radiation chemistry in both gas and liquid E-TEM environments. Our findings reveal that while gas phase E-TEM generates radiolytic species with lower reactivity than liquid phase systems, these species can accumulate to reaction-altering concentrations, particularly at elevated pressures. We validate our model through two case studies: the radiation-promoted oxidation of aluminum nanocubes and disproportionation of carbon monoxide. In both cases, increasing the electron beam dose rate directly accelerates their reaction kinetics, as demonstrated by enhanced AlOx growth and carbon deposition. Based on these insights, we establish practical guidelines for controlling radiolysis in closed-cell nanoreactors. This work not only resolves a fundamental challenge in electron microscopy but also advances our ability to rationally design materials with subÅngstrom resolution. 
    more » « less
  3. A majority of ultracold atom experiments utilize resonant absorption imaging techniques to obtain the atomic density. To make well-controlled quantitative measurements, the optical intensity of the probe beam must be precisely calibrated in units of the atomic saturation intensityIsat. In quantum gas experiments, the atomic sample is enclosed in an ultra-high vacuum system that introduces loss and limits optical access; this precludes a direct determination of the intensity. Here, we use quantum coherence to create a robust technique for measuring the probe beam intensity in units ofIsatvia Ramsey interferometry. Our technique characterizes the ac Stark shift of the atomic levels due to an off-resonant probe beam. Furthermore, this technique gives access to the spatial variation of the probe intensity at the location of the atomic cloud. By directly measuring the probe intensity just before the imaging sensor our method in addition yields a direct calibration of imaging system losses as well as the quantum efficiency of the sensor. 
    more » « less
  4. Abstract Traditional mechanochemically controlled reversible‐deactivation radical polymerization (RDRP) utilizes ultrasound or ball milling to regenerate activators, which induce side reactions because of the high‐energy and high‐frequency stimuli. Here, we propose a facile approach for tribochemically controlled atom transfer radical polymerization (tribo‐ATRP) that relies on contact‐electro‐catalysis (CEC) between titanium oxide (TiO2) particles and CuBr2/tris(2‐pyridylmethylamine (TPMA), without any high‐energy input. Under the friction induced by stirring, the TiO2particles are electrified, continuously reducing CuBr2/TPMA into CuBr/TPMA, thereby conversing alkyl halides into active radicals to start ATRP. In addition, the effect of friction on the reaction was elucidated by theoretical simulation. The results indicated that increasing the frequency could reduce the energy barrier for the electron transfer from TiO2particles to CuBr2/TPMA. In this study, the design of tribo‐ATRP was successfully achieved, enabling CEC (ca. 10 Hz) access to a variety of polymers with predetermined molecular weights, low dispersity, and high chain‐end fidelity. 
    more » « less
  5. Abstract Controlled fabrication of nanopores in 2D materials offer the means to create robust membranes needed for ion transport and nanofiltration. Techniques for creating nanopores have relied upon either plasma etching or direct irradiation; however, aberration‐corrected scanning transmission electron microscopy (STEM) offers the advantage of combining a sub‐Å sized electron beam for atomic manipulation along with atomic resolution imaging. Here, a method for automated nanopore fabrication is utilized with real‐time atomic visualization to enhance the mechanistic understanding of beam‐induced transformations. Additionally, an electron beam simulation technique, Electron‐Beam Simulator (E‐BeamSim) is developed to observe the atomic movements and interactions resulting from electron beam irradiation. Using the MXene Ti3C2Tx, the influence of temperature on nanopore fabrication is explored by tracking atomic transformations and find that at room temperature the electron beam irradiation induces random displacement and results in titanium pileups at the nanopore edge, which is confirmed by E‐BeamSim. At elevated temperatures, after removal of the surface functional groups and with the increased mobility of atoms results in atomic transformations that lead to the selective removal of atoms layer by layer. This work can lead to the development of defect engineering techniques within functionalized MXene layers and other 2D materials. 
    more » « less