Nanoscale Cathodoluminescence Thermometry with a Lanthanide-Doped Heavy-Metal Oxide in Transmission Electron Microscopy.

When navigated by the available energy of a system, often provided in the form of heat, physical processes or chemical reactions fleet on a free-energy landscape, thus changing the structure. In in situ transmission electron microscopy (TEM), where material structures are measured and manipulated inside the microscope while being subjected to external stimuli such as electrical fields, laser irradiation, or mechanical stress, it is necessary to precisely determine the local temperature of the specimen to provide a comprehensive understanding of material behavior and to establish the relationship among energy, structure, and properties at the nanoscale. Here, we propose using cathodoluminescence (CL) spectroscopy in TEM for in situ measurement of the local temperature. Gadolinium oxide particles doped with emissive europium ions present an opportunity to utilize them as a temperature probe in CL measurements via a ratiometric approach. We show the thermometric performance of the probe and demonstrate a precision of ±5 K in the temperature range from 113 to 323 K with the spatial resolution limited by the size of the particles, which surpasses other methods for temperature determination. With the CL-based thermometry, we further demonstrate measuring local temperature under laser irradiation.

Microsecond melting and revitrification of cryo samples: protein structure and beam-induced motion.

A novel approach to time-resolved cryo-electron microscopy (cryo-EM) has recently been introduced that involves melting a cryo sample with a laser beam to allow protein dynamics to briefly occur in the liquid, before trapping the particles in their transient configurations by rapidly revitrifying the sample. With a time resolution of just a few microseconds, this approach is notably fast enough to study the domain motions that are typically associated with the activity of proteins but which have previously remained inaccessible. Here, crucial details are added to the characterization of the method. It is shown that single-particle reconstructions of apoferritin and Cowpea chlorotic mottle virus from revitrified samples are indistinguishable from those from conventional samples, demonstrating that melting and revitrification leaves the particles intact and that they do not undergo structural changes within the spatial resolution afforded by the instrument. How rapid revitrification affects the properties of the ice is also characterized, showing that revitrified samples exhibit comparable amounts of beam-induced motion. The results pave the way for microsecond time-resolved studies of the conformational dynamics of proteins and open up new avenues to study the vitrification process and to address beam-induced specimen movement.

Photoluminescence and Energy Transfer in Double- and Triple-Lanthanide-Doped YVO4 Nanoparticles.

Optical materials doped with several lanthanides are unique in their properties and are widely used in various fields of science and technology. The study of these systems provides solutions for noncontact thermometry, bioimaging, sensing technology, and others. In this paper, we report on the demonstration of YVO4 nanoparticles doped with one, two, and three different rare earth ions (Tm3+, Er3+, and Nd3+). We discuss the morphology, structural properties, and luminescence behavior of particles. Luminescence decay kinetics reveal the energy transfer efficiency (up to 78%) for different ions under the selective excitation of individual ions. Thus, we found that the energy transition from Tm3+ is more favorable than from Er3+ while we did not observe any significant energy rearrangement in the samples under the excitation of Nd3+. The observed strong variation of REI lifetimes makes the suggested nanoparticles promising for luminescent labeling, anticounterfeiting, development of data storage systems, etc.

Visualizing Nanoscale Dynamics with Time-resolved Electron Microscopy.

The large number of interactions in nanoscale systems leads to the emergence of complex behavior. Understanding such complexity requires atomic-resolution observations with a time resolution that is high enough to match the characteristic timescale of the system. Our laboratory's method of choice is time-resolved electron microscopy. In particular, we are interested in the development of novel methods and instrumentation for high-speed observations with atomic resolution. Here, we present an overview of the activities in our laboratory.

Microsecond melting and revitrification of cryo samples.

The dynamics of proteins that are associated with their function typically occur on the microsecond timescale, orders of magnitude faster than the time resolution of cryo-electron microscopy. We have recently introduced a novel approach to time-resolved cryo-electron microscopy that affords microsecond time resolution. It involves melting a cryo sample with a heating laser, so as to allow dynamics of the proteins to briefly occur in the liquid phase. When the laser is turned off, the sample rapidly revitrifies, trapping the particles in their transient configurations. Precise control of the temperature evolution of the sample is crucial for such an approach to succeed. Here, we provide a detailed characterization of the heat transfer occurring under laser irradiation as well as the associated phase behavior of the cryo sample. While areas close to the laser focus undergo melting and revitrification, surrounding regions crystallize. In situ observations of these phase changes therefore provide a convenient approach for assessing the temperature reached in each melting and revitrification experiment and for adjusting the heating laser power on the fly.

The fragmentation mechanism of gold nanoparticles in water under femtosecond laser irradiation.

Plasmonic nanoparticles in aqueous solution have long been known to fragment under irradiation with intense ultrafast laser pulses, creating progeny particles with diameters of a few nanometers. However, the mechanism of this process is still intensely debated, despite numerous experimental and theoretical studies. Here, we use in situ electron microscopy to directly observe the femtosecond laser-induced fragmentation of gold nanoparticles in water, revealing that the process occurs through ejection of individual progeny particles. Our observations suggest that the fragmentation mechanism involves Coulomb fission, which occurs as the femtosecond laser pulses ionize and melt the gold nanoparticle, causing it to eject a highly charged progeny droplet. Subsequent Coulomb fission events, accompanied by solution-mediated etching and growth processes, create complex fragmentation patterns that rapidly fluctuate under prolonged irradiation. Our study highlights the complexity of the interaction of plasmonic nanoparticles with ultrafast laser pulses and underlines the need for in situ observations to unravel the mechanisms of related phenomena.

Atomic-Resolution Imaging of Fast Nanoscale Dynamics with Bright Microsecond Electron Pulses.

Atomic-resolution electron microscopy is a crucial tool to elucidate the structure of matter. Recently, fast electron cameras have added the time domain to high-resolution imaging, allowing static images to be acquired as movies from which sample drift can later be removed computationally and enabling real-time observations of atomic-scale dynamics on the millisecond time scale. Even higher time resolution can be achieved with short electron pulses, yet their potential for atomic-resolution imaging remains unexplored. Here, we generate high-brightness microsecond electron pulses from a Schottky emitter whose current we briefly drive to near its limit. We demonstrate that drift-corrected imaging with such pulses can achieve atomic resolution in the presence of much larger amounts of drift than with a continuous electron beam. Moreover, such pulses enable atomic-resolution observations on the microsecond time scale, which we employ to elucidate the crystallization pathways of individual metal nanoparticles as well as the high-temperature transformation of perovskite nanocrystals.

Characterization of a time-resolved electron microscope with a Schottky field emission gun.

The rapid growth of the field of time-resolved and ultrafast electron microscopy has been accompanied by the active development of new instrumentation. Recently, time-resolved microscopes equipped with a field emission gun have been introduced, demonstrating great potential for experiments that benefit from the high brightness and coherence of the electron source. Here, we describe a straightforward design of a time-resolved transmission electron microscope with a Schottky field emission gun and characterize its performance. At the same time, our design gives us the flexibility to alternatively operate the instrument as if it was equipped with a flat metal photocathode. We can, thus, effectively choose to sacrifice brightness in order to obtain pulses with vastly larger numbers of electrons than from the emitter if for a given application the number of electrons is a crucial figure of merit. We believe that our straightforward and flexible design will be of great practical relevance to researchers wishing to enter the field.

Real-time observation of jumping and spinning nanodroplets.

The manipulation of liquids at nanoscale dimensions is a central goal of the emergent nanofluidics field. Such endeavors extend to nanodroplets, which are ubiquitous objects involved in many technological applications. Here, we employ time-resolved electron microscopy to elucidate the formation of so-called jumping nanodroplets on a graphene surface. We flash-melt a thin gold nanostructure with a laser pulse and directly observe how the resulting nanodroplet contracts into a sphere and jumps off its substrate, a process that occurs in just a few nanoseconds. Our study provides the first experimental characterization of these morphological dynamics through real-time observation and reveals new aspects of the phenomenon. We observe that friction alters the trajectories of individual droplets. Surprisingly, this leads some droplets to adopt dumbbell-shaped geometries after they jump, suggesting that they spin with considerable angular momentum. Our experiments open up new avenues for studying and controlling the fast morphological dynamics of nanodroplets through their interaction with structured surfaces.

In Situ Observation of Coulomb Fission of Individual Plasmonic Nanoparticles.

Reshaping plasmonic nanoparticles with laser pulses has been extensively researched as a tool for tuning their properties. However, in the absence of direct observations of the processes involved, important mechanistic details have remained elusive. Here, we present an in situ electron microscopy study of one such process that involves Coulomb fission of plasmonic nanoparticles under femtosecond laser irradiation. We observe that gold nanoparticles encapsulated in a silica shell fission by emitting progeny droplets comprised of about 10-500 atoms, with ejection preferentially occurring along the laser polarization direction. Under continued irradiation, the emitted droplets coalesce into a second core within the silica shell, and the system evolves into a dual-core particle. Our findings are consistent with a mechanism in which electrons are preferentially emitted from the gold core along the laser polarization direction. The resulting anisotropic charge distribution in the silica shell then determines the direction in which progeny droplets are ejected. In addition to yielding insights into the mechanism of Coulomb fission in plasmonic nanoparticles, our experiments point toward a facile method for forming surfaces decorated with aligned dual-gold-core silica shell particles.

Coulomb explosion imaging of CH3I and CH2ClI photodissociation dynamics.

The photodissociation dynamics of CH3I and CH2ClI at 272 nm were investigated by time-resolved Coulomb explosion imaging, with an intense non-resonant 815 nm probe pulse. Fragment ion momenta over a wide m/z range were recorded simultaneously by coupling a velocity map imaging spectrometer with a pixel imaging mass spectrometry camera. For both molecules, delay-dependent pump-probe features were assigned to ultraviolet-induced carbon-iodine bond cleavage followed by Coulomb explosion. Multi-mass imaging also allowed the sequential cleavage of both carbon-halogen bonds in CH2ClI to be investigated. Furthermore, delay-dependent relative fragment momenta of a pair of ions were directly determined using recoil-frame covariance analysis. These results are complementary to conventional velocity map imaging experiments and demonstrate the application of time-resolved Coulomb explosion imaging to photoinduced real-time molecular motion.

Ultrafast Excited-State Dynamics of Ligand-Field and Ligand-to-Metal Charge-Transfer States of CuCl42- in Solution: A Detailed Transient Absorption Study.

Ultrafast excited-state dynamics of CuCl42- in acetonitrile is studied by femtosecond broadband transient absorption spectroscopy following excitation of the complex into all ligand-field (LF or d-d) states and into the two ligand-to-metal charge transfer (LMCT) states corresponding to the most intense steady-state absorption bands. The LF excited states are found to be nonreactive. The lowest-lying 2E LF excited state has a lifetime less than 150 fs, and the lifetimes of the second (2B1) and the third (2A1) LF excited states are 1 and 5 ps, respectively. All three LF states decay directly into the ground 2B2 state. Such significant differences in excited-state decay time constants were rationalized computationally through time-dependent density functional theory (TD-DFT) computations. TD-DFT mapping of the relaxation pathway along the symmetric Cl-Cu-Cl umbrella bending vibration gives evidence for a conical intersection between the 2E excited state and the ground 2B2 state. The LMCT states decay within 200 fs with the primary deactivation mode consistent to be Cu-Cl stretch. A fraction of the CuCl42- complexes excited into the LMCT states undergoes ionic dissociation to form products that survive longer than 1 ns. The remaining fraction undergoes internal conversion, which can be viewed as back electron transfer, populating the lower vibrationally hot LF states. The LF states populated from the LMCT states exhibit the same lifetimes as the Franck-Condon LF states and likewise decay directly into the ground state.

Ultrafast Photochemistry of Copper(II) Monochlorocomplexes in Methanol and Acetonitrile by Broadband Deep-UV-to-Near-IR Femtosecond Transient Absorption Spectroscopy.

Photochemistry of copper(II) monochlorocomplexes in methanol and acetonitrile solutions is studied by UV-pump/broadband deep-UV-to-near-IR probe femtosecond transient absorption spectroscopy. Upon 255 and 266 nm excitation, the complexes in acetonitrile and methanol, respectively, are promoted to the excited ligand-to-metal charge transfer (LMCT) state, which has a short (sub-250 fs) lifetime. From the LMCT state, the complexes decay via internal conversion to lower-lying ligand field (LF) d-d excited states or the vibrationally hot ground electronic state. A minor fraction of the excited complexes relaxes to the LF electronic excited states, which are relatively long-lived with lifetimes >1 ns. Also, in methanol solutions, about 3% of the LMCT-excited copper(II) monochlorocomplexes dissociate forming copper(I) solvatocomplexes and chlorine atoms, which then further react forming long-lived photoproducts. In acetonitrile, about 50% of the LMCT-excited copper(II) monochlorocomplexes dissociate forming radical and ionic products in a ratio of 3:2. Another minor process observed following excitation only in methanol solutions is the re-equilibration between several forms of the copper(II) ground-state complexes present in solutions. This re-equilibration occurs on a time scale from sub-nanoseconds to nanoseconds.

Mechanism of Formation of Copper(II) Chloro Complexes Revealed by Transient Absorption Spectroscopy and DFT/TDDFT Calculations.

Copper(II) complexes are extremely labile with typical ligand exchange rate constants on the order of 10(6)-10(9) M(-1) s(-1). As a result, it is often difficult to identify the actual formation mechanism of these complexes. In this work, using UV-vis transient absorption when probing in a broad time range (20 ps to 8 µs) in conjunction with DFT/TDDFT calculations, we studied the dynamics and underlying reaction mechanisms of the formation of extremely labile copper(II) CuCl4(2-) chloro complexes from copper(II) CuCl3(-) trichloro complexes and chloride ions. These two species, produced via photochemical dissociation of CuCl4(2-) upon 420 nm excitation into the ligand-to-metal-charge-transfer electronic state, are found to recombine into parent complexes with bimolecular rate constants of (9.0 ± 0.1) × 10(7) and (5.3 ± 0.4) × 10(8) M(-1) s(-1) in acetonitrile and dichloromethane, respectively. In dichloromethane, recombination occurs via a simple one-step addition. In acetonitrile, where [CuCl3](-) reacts with the solvent to form a [CuCl3CH3CN](-) complex in less than 20 ps, recombination takes place via ligand exchange described by the associative interchange mechanism that involves a [CuCl4CH3CN](2-) intermediate. In both solvents, the recombination reaction is potential energy controlled.