Pulsed-beam transmission electron microscopy and radiation damage.

We review the use of pulsed electron-beams in transmission electron microscopes (TEMs) for the purpose of mitigating specimen damage. We begin by placing the importance of TEMs with respect to materials characterization into proper context, and we provide a brief overview of established methods for reducing or eliminating the deleterious effects of beam-induced damage. We then introduce the concept of pulsed-beam TEM, and we briefly describe the basic methods and instrument configurations used to create so-called temporally structured electron beams. Following a brief overview of the use of high-dose-rate pulsed-electron beams in cancer radiation therapy, we review historical speculations and more recent compelling but mostly anecdotal findings of a pulsed-beam TEM damage effect. This is followed by an in-depth technical review of recent works seeking to establish cause-and-effect relationships, to conclusively uncover the presence of an effect, and to explore the practicality of the approach. These studies, in particular, provide the most compelling evidence to date that using a pulsed electron beam in the TEM is indeed a viable way to mitigate damage. Throughout, we point out current gaps in understanding, and we conclude with a brief perspective of current needs and future directions.

Low repetition-rate, high-resolution femtosecond transmission electron microscopy.

The spatial and energy resolutions of state-of-the-art transmission electron microscopes (TEMs) have surpassed 50 pm and 5 meV. However, with respect to the time domain, even the fastest detectors combined with the brightest sources may only be able to reach the microsecond timescale. Thus, conventional methods are incapable of resolving the myriad fundamental ultrafast (i.e., attosecond to picosecond) atomic-scale dynamics. The successful demonstration of femtosecond (fs) laser-based (LB) ultrafast electron microscopy (UEM) nearly 20 years ago provided a means to span this nearly 10-order-of-magnitude temporal gap. While nanometer-picosecond UEM studies of dynamics are now well established, ultrafast Å-scale imaging has gone largely unrealized. Further, while instrument development has rightly been an emphasis, and while new modalities and uses of pulsed-beam TEM continue to emerge, the overall chemical and materials application space has been only modestly explored to date. In this Perspective, we argue that these apparent shortfalls can be attributed to a simple lack of data and detail. We speculate that present work and continued growth of the field will ultimately lead to the realization that Å-scale fs dynamics can indeed be imaged with minimally modified UEM instrumentation and with repetition rates (frep) below-and perhaps even well below-1 MHz. We further argue that the use of low frep, whether for LB UEM or for chopped/bunched beams, significantly expands the accessible application space. This calls for systematically establishing modality-specific limits so that especially promising technologies can be pursued, thus, ultimately facilitating broader adoption as individual instrument capabilities expand.

Mitigating Damage to Hybrid Perovskites Using Pulsed-Beam TEM.

Using a pulsed-beam transmission electron microscope, we discover a reduction in damage to methylammonium lead iodide (MAPbI3) as compared to conventional beams delivered at the same dose rates. For rates as low as 0.001 e·Å-2·s-1, we find up to a 17% reduction in damage at a total dose of 10 e·Å-2. We systematically study the effects of number of electrons in each pulse and the duration between pulse arrival. Damage increases for both, though the number of electrons per pulse has a larger effect. A crossover is identified, where a pulsed beam causes more damage than a conventional one. Although qualitatively similar to previous findings, the degree to which damage is reduced in MAPbI3 is less than that observed for other materials (e.g., C36H74), supporting the hypothesis that the effects are material- and damage-mechanism-dependent. Despite this, the observation here of damage reduction for relatively large electron packets (up to 200 electrons per pulse) suggests that MAPbI3 is in fact less susceptible to irradiation than C36H74, which may be related to reported self-healing effects. This work provides insights into damage processes and durability in hybrid perovskites and also illustrates the viability of using pulsed-beam TEM to explore the associated molecular-level routes to degradation, analogous to laser-accelerated energetic pulsed electron beams and the study of damage to biomolecules, cells, and tissues in radiobiology.

High-resolution analogue of time-domain phonon spectroscopy in the transmission electron microscope.

Femtosecond photoexcitation of semiconducting materials leads to the generation of coherent acoustic phonons (CAPs), the behaviours of which are linked to intrinsic and engineered electronic, optical and structural properties. While often studied with pump-probe spectroscopic techniques, the influence of nanoscale structure and morphology on CAP dynamics can be challenging to resolve with these all-optical methods. Here, we used ultrafast electron microscopy (UEM) to resolve variations in CAP dynamics caused by differences in the degree of crystallinity in as-prepared and annealed GaAs lamellae. Following in situ femtosecond photoexcitation, we directly imaged the generation and propagation dynamics of hypersonic CAPs in a mostly amorphous and, following an in situ photothermal anneal, a mostly crystalline lamella. Subtle differences in both the initial hypersonic velocities and the asymptotic relaxation behaviours were resolved via construction of space-time contour plots from phonon wavefronts. Comparison to bulk sound velocities in crystalline and amorphous GaAs reveals the influence of the mixed amorphous-crystalline morphology on CAP dispersion behaviours. Further, an increase in the asymptotic velocity following annealing establishes the sensitivity of quantitative UEM imaging to both structural and compositional variations through differences in bonding and elasticity. Implications of extending the methods and results reported here to elucidating correlated electronic, optical and structural behaviours in semiconducting materials are discussed. This article is part of a discussion meeting issue 'Dynamic in situ microscopy relating structure and function'.

Reducing Radiation Damage in Soft Matter with Femtosecond-Timed Single-Electron Packets.

Despite the development of a myriad of mitigation methods, radiation damage continues to be a major limiting factor in transmission electron microscopy. Intriguing results have been reported using pulsed-laser driven and chopped electron beams for modulated dose delivery, but the underlying relationships and effects remain unclear. Indeed, delivering precisely timed single-electron packets to the specimen has yet to be systematically explored, and no direct comparisons to conventional methods within a common parameter space have been made. Here, using a model linear saturated hydrocarbon (n-hexatriacontane, C36H74), we show that precisely timed delivery of each electron to the specimen, with a well-defined and uniform time between arrival, leads to a repeatable reduction in damage compared to conventional ultralow-dose methods for the same dose rate and the same accumulated dose. Using a femtosecond pulsed laser to confine the probability of electron emission to a 300 fs temporal window, we find damage to be sensitively dependent on the time between electron arrival (controlled with the laser repetition rate) and on the number of electrons per packet (controlled with the laser-pulse energy). Relative arrival times of 5, 20, and 100 µs were tested for electron packets comprised of, on average, 1, 5, and 20 electrons. In general, damage increased with decreasing time between electrons and, more substantially, with increasing electron number. Further, we find that improvements relative to conventional methods vanish once a threshold number of electrons per packet is reached. The results indicate that precise electron-by-electron dose delivery leads to a repeatable reduction in irreversible structural damage, and the systematic studies indicate this arises from control of the time between sequential electrons arriving within the same damage radius, all else being equal.

Sources of error in Debye-Waller-effect measurements relevant to studies of photoinduced structural dynamics.

We identify and quantify several practical effects likely to be present in both static and ultrafast electron-scattering experiments that may interfere with the Debye-Waller (DW) effect. Using 120-nm thick, small-grained, polycrystalline aluminum foils as a test system, we illustrate the impact of specimen tilting, in-plane translation, and changes in z height on Debye-Scherrer-ring intensities. We find that tilting by less than one degree can result in statistically-significant changes in diffracted-beam intensities for large specimen regions containing > 105 nanocrystalline grains. We demonstrate that, in addition to effective changes in the field of view with tilting, slight texturing of the film can result in deviations from expected DW-effect behavior. Further, we find that in-plane translations of as little as 20 nm also produce statistically-significant intensity changes, while normalization to total image counts eliminates such effects arising from changes in z height. The results indicate that the use of polycrystalline films in ultrafast electron-scattering experiments can greatly reduce the negative impacts of these effects as compared to single-crystal specimens, though it does not entirely eliminate them. Thus, it is important to account for such effects when studying thin-foil specimens having relatively short reciprocal-lattice rods.