Challenges and Applications to Operando and In Situ TEM Imaging and Spectroscopic Capabilities in a Cryogenic Temperature Range.

ConspectusIn this Account, we describe the challenges and promising applications of transmission electron microscopy (TEM) imaging and spectroscopy at cryogenic temperatures. Our work focuses on two areas of application: the delay of electron-beam-induced degradation and following low-temperature phenomena in a continuous and variable temperature range. For the former, we present a study of LiMn1.5Ni0.5O4 lithium ion battery cathode material that undergoes electron beam-induced degradation when studied at room temperature by TEM. Cryogenic imaging reveals the true structure of LiMn1.5Ni0.5O4 nanoparticles in their discharged state. Improved stability under electron beam irradiation was confirmed by following the evolution of the O K-edge fine structure by electron energy-loss spectroscopy. Our results demonstrate that the effect of radiation damage on discharged LiMn1.5Ni0.5O4 was previously underestimated and that atomic-resolution imaging at cryogenic temperature has a potential to be generalized to most of the Li-based materials and beyond. For the latter, we present two studies in the imaging of low-temperature phenomena on the local scale, namely, the evolution of ferroelectric and ferromagnetic domains walls, in BaTiO3 and Y3Fe5O12 systems, respectively, in a continuous and variable temperature range. Continuous imaging of the phase transition in BaTiO3, a prototypical ferroelectric system, from the low-temperature orthorhombic phase continuously up to the centrosymmetric high-temperature phase is shown to be possible inside a TEM. Similarly, the propagation of domain walls in Y3Fe5O12, a magnetic insulator, is studied from ∼120 to ∼400 K and combined with the application of a magnetic field and electrical current pulses to mimic the operando conditions as in domain wall memory and logic devices for information technology. Such studies are promising for studying the pinning of the ferroelectric and magnetic domains versus temperature, spin-polarized current, and externally applied magnetic field to better manipulate the domain walls. The capability of combining operando TEM stimuli such as current, voltage, and/or magnetic field with in situ TEM imaging in a continuous cryogenic temperature range will allow the uncovering of fundamental phenomena on the nanometer scale. These studies were made possible using a MEMS-based TEM holder that allowed an electron-transparent sample to be transferred and electrically contacted on a MEMS chip. The six-contact double-tilt holder allows the alignment of the specimen into its zone axis while simultaneously using four electrical contacts to regulate the temperature and two contacts to apply the electrical stimuli, i.e., operando TEM imaging. This Account leads to the demonstration of (i) the high-resolution imaging and spectroscopy of nanoparticles oriented in the desired [110] zone-axis direction at cryogenic temperatures to mitigate the electron beam degradation, (ii) imaging of low-temperature transitions with accurate and continuous control of the temperature that allowed single-frame observation of the presence of both the orthorhombic and tetragonal phases in the BaTiO3 system, and (iii) magnetic domain wall propagation as a function of temperature, magnetic field, and current pulses (100 ns with a 100 kHz repetition rate) in the Y3Fe5O12 system.

Hybridized surface lattice modes in intercalated 3-disk plasmonic crystals for high figure-of-merit plasmonic sensing.

Engineering the spectral lineshape of plasmonic modes by various electromagnetic couplings and mode interferences enables significant improvements for plasmonic sensing. However, bulk and surface sensitivities remain constrained by a trade-off arising from their respective dependence on the interaction volume and decay length of the plasmonic mode, making higher bulk sensitivity realized at the expense of reduced surface sensitivity. We propose a new approach to overcome this trade-off by combining near-field and far-field coupling in an intercalated 3-disk plasmonic crystal, where ∼10× higher figure of merit (FoM) and ∼2× higher surface sensitivity can be achieved, in comparison with those achievable by localized surface plasmons. A plasmonic mode with a Q-factor up to ∼110 is demonstrated based on gold 3-disk arrays in the visible spectrum, with a bulk FoM of ∼24 and a surface sensitivity prefactor of ∼13.56. The design and fabrication simplicity of the 3-disk structure highlight its potential for a robust plasmonic sensing platform with a high figure of merit.

Demographic Representation and Collective Storytelling in the Me Too Twitter Hashtag Activism Movement.

The #MeToo movement on Twitter has drawn attention to the pervasive nature of sexual harassment and violence. While #MeToo has been praised for providing support for self-disclosures of harassment or violence and shifting societal response, it has also been criticized for exemplifying how women of color have been discounted for their historical contributions to and excluded from feminist movements. Through an analysis of over 600,000 tweets from over 256,000 unique users, we examine online #MeToo conversations across gender and racial/ethnic identities and the topics that each demographic emphasized. We found that tweets authored by white women were overrepresented in the movement compared to other demographics, aligning with criticism of unequal representation. We found that intersected identities contributed differing narratives to frame the movement, co-opted the movement to raise visibility in parallel ongoing movements, employed the same hashtags both critically and supportively, and revived and created new hashtags in response to pivotal moments. Notably, tweets authored by black women often expressed emotional support and were critical about differential treatment in the justice system and by police. In comparison, tweets authored by white women and men often highlighted sexual harassment and violence by public figures and weaved in more general political discussions. We discuss the implications of this work for digital activism research and design, including suggestions to raise visibility by those who were under-represented in this hashtag activism movement. Content warning: this article discusses issues of sexual harassment and violence.

Impact of CT scanner location on door to imaging time for emergency department stroke evaluation.

BACKGROUND AND OBJECTIVES: Stroke is a potentially serious condition commonly diagnosed in the ED. Time to diagnosis can be crucial to maximizing outcome in a majority of ischemic stroke cases amenable to thrombolytic therapy. METHODS: An analysis of 148 consecutive adults transported by EMS to an urban emergency department with a diagnosis of cerebro-vascular accident during a 12 month period was performed to determine the impact of CT scanner location on door-to-head CT [DTCT] scan time. The CT scanner was relocated from an upper floor of the hospital to within the ER department midway through the study period. RESULTS: The rate of DTCT scan time ≤20 min increased significantly from 47% [pre-relocation] to 74% [post-relocation]; and the rate of DTCT ultra-rapid scan time ≤10 min more than doubled. CONCLUSIONS: Hospitals providing ED care for stroke patients can expedite management by ensuring CT scanner location is in closest possible proximity to the ED.

Nanobridges formed through electron beam image reversal lithography for plasmonic mid-infrared resonators with high aspect ratio nanogaps.

We present the emergence of nanobridge networks through a nanofabrication technique based on image-reversal electron beam lithography and demonstrate plasmonic structures with high aspect ratio sub-20 nm gaps capable of strong intensity enhancement in the mid-infrared range. The proposed technique, which employs the engineering of natural formations of nanobridges in predefined templates, could serve as an alternative path for realizing mid-infrared plasmonic resonators with potential applications in surface plasmon polariton-based integrated optics, and enhancement of light-matter interaction for high efficiency photodetection and nanoscale light emitters.

Combining sonicated cold development and pulsed electrodeposition for high aspect ratio sub-10 nm gap gold dimers for sensing applications in the visible spectrum.

Strong interactions between localized surface plasmons and nanoscale objects have led to the development of highly sensitive biochemical sensing in planar metallic nanostructures with sensing performance mainly dependent on the interaction volume and the local electric field. However, the sensitivity and the interaction volume of these planar structures have been limited by the achievable aspect ratios based on the standard lift-off process. We propose a new technique which involves cold sonicated development and pulsed electrodeposition to overcome this limitation, and demonstrate robust gold square dimers with sub-10 nm gaps and a gap aspect ratio of ∼8. We show that smooth gold surfaces can be achieved by growing the gold film directly on a transparent ITO substrate without a gold seed layer, and demonstrate a significant improvement in Q factors and resonance contrast in electrodeposited dimers compared to dimers fabricated by physical vapor deposition. We demonstrate that the electrodeposited dimers exhibit near 50% higher bulk refractive index sensitivity than their planar counterparts. The technique may be used to grow a variety of metals of arbitrary geometries and spatial arrangements.

Polarization invariant plasmonic nanostructures for sensing applications.

Optics-based sensing platform working under unpolarized light illumination is of practical importance in the sensing applications. For this reason, sensing platforms based on localized surface plasmons are preferred to their integrated optics counterparts for their simple mode excitation and inexpensive implementation. However, their optical response under unpolarized light excitation is typically weak due to their strong polarization dependence. Herein, the role of rotational symmetry for realizing robust sensing platform exhibiting strong optical contrast and high sensitivity is explored. Specifically, gammadion and star-shaped gold nanostructures with different internal and external rotational symmetries are fabricated and studied in detail, from which their mode characteristics are demonstrated as superposition of their constituent longitudinal plasmons that are in conductive coupling with each other. We demonstrate that introducing and increasing internal rotational symmetry would lead to the enhancement in optical contrast up to ~3x under unpolarized light illumination. Finally, we compare the sensing performances of rotationally symmetric gold nanostructures with a more rigorous figure-of-merit based on sensitivity, Q-factor, and spectral contrast.

Ultra-small v-shaped gold split ring resonators for biosensing using fundamental magnetic resonance in the visible spectrum.

Strong light localization within metal nanostructures occurs by collective oscillations of plasmons in the form of electric and magnetic resonances. This so-called localized surface plasmon resonance (LSPR) has gained much interest in the development of low-cost sensing platforms in the visible spectrum. However, demonstrations of LSPR-based sensing are mostly limited to electric resonances due to the technological limitations for achieving magnetic resonances in the visible spectrum. In this work, we report the first demonstration of LSPR sensing based on fundamental magnetic resonance in the visible spectrum using ultrasmall gold v-shaped split ring resonators. Specifically, we show the ability for detecting adsorption of bovine serum albumin and cytochrome c biomolecules at monolayer levels, and the selective binding of protein A/G to immunoglobulin G.