Self-assembled photonic cavities with atomic-scale confinement.

Despite tremendous progress in research on self-assembled nanotechnological building blocks, such as macromolecules1, nanowires2 and two-dimensional materials3, synthetic self-assembly methods that bridge the nanoscopic to macroscopic dimensions remain unscalable and inferior to biological self-assembly. By contrast, planar semiconductor technology has had an immense technological impact, owing to its inherent scalability, yet it seems unable to reach the atomic dimensions enabled by self-assembly. Here, we use surface forces, including Casimir-van der Waals interactions4, to deterministically self-assemble and self-align suspended silicon nanostructures with void features well below the length scales possible with conventional lithography and etching5, despite using only conventional lithography and etching. The method is remarkably robust and the threshold for self-assembly depends monotonically on all the governing parameters across thousands of measured devices. We illustrate the potential of these concepts by fabricating nanostructures that are impossible to make with any other known method: waveguide-coupled high-Q silicon photonic cavities6,7 that confine telecom photons to 2 nm air gaps with an aspect ratio of 100, corresponding to mode volumes more than 100 times below the diffraction limit. Scanning transmission electron microscopy measurements confirm the ability to build devices with sub-nanometre dimensions. Our work constitutes the first steps towards a new generation of fabrication technology that combines the atomic dimensions enabled by self-assembly with the scalability of planar semiconductors.

Electron Beam Induced Enhancement and Suppression of Oxidation in Cu Nanoparticles in Environmental Scanning Transmission Electron Microscopy.

We have investigated the effects of high-energy electron irradiation on the oxidation of copper nanoparticles in environmental scanning transmission electron microscopy (ESTEM). The hemispherically shaped particles were oxidized in 3 mbar of O2 in a temperature range 100-200 °C. The evolution of the particles was recorded with sub-nanometer spatial resolution in situ in ESTEM. The oxidation encompasses the formation of outer and inner oxide shells on the nanoparticles, arising from the concurrent diffusion of copper and oxygen out of and into the nanoparticles, respectively. Our results reveal that the electron beam actively influences the reaction and overall accelerates the oxidation of the nanoparticles when compared to particles oxidized without exposure to the electron beam. However, the extent of this electron beam-assisted acceleration of oxidation diminishes at higher temperatures. Moreover, we observe that while oxidation through the outward diffusion of Cu+ cations is enhanced, the electron beam appears to hinder oxidation through the inward diffusion of O2- anions. Our results suggest that the impact of the high-energy electrons in ESTEM oxidation of Cu nanoparticles is mostly related to kinetic energy transfer, charging, and ionization of the gas environment, and the beam can both enhance and suppress reaction rates.

Creation of Boron Vacancies in Hexagonal Boron Nitride Exfoliated from Bulk Crystals for Quantum Sensing.

Boron vacancies (VB-) in hexagonal boron -nitride (hBN) have sparked great interest in recent years due to their optical and spin properties. Since hBN can be readily integrated into devices where it interfaces a huge variety of other 2D materials, boron vacancies may serve as a precise sensor which can be deployed at very close proximity to many important materials systems. Boron vacancy defects may be produced by a number of existing methods, the use of which may depend on the final application. Any method should reproducibly generate defects with controlled density and desired pattern. To date, however, detailed studies of such methods are missing. In this paper, we study various techniques for the preparation of hBN flakes from bulk crystals and relevant postprocessing treatments, namely, focused ion beam (FIB) implantation, for creation of VB-s as a function of flake thickness and defect concentrations. We find that flake thickness plays an important role when optimizing implantation parameters, while careful sample cleaning proved important to achieve consistent results.

In Situ TEM under Optical Excitation for Catalysis Research.

In situ characterization of materials in their operational state is a highly active field of research. Investigating the structure and response of materials under stimuli that simulate real working environments for technological applications can provide new insight and unique input to the synthesis and design of novel materials. Over recent decades, experimental setups that allow different stimuli to be applied to a sample inside an electron microscope have been devised, built, and commercialized. In this review, we focus on the in situ investigation of optically active materials using transmission electron microscopy. We illustrate two different approaches for exposing samples to light inside the microscope column, explaining the importance of different aspects of their mechanical construction and choice of light source and materials. We focus on the technical challenges of the setups and provide details of the construction, providing the reader with input on deciding which setup will be more useful for a specific experiment. The use of these setups is illustrated using examples from the literature of relevance to photocatalysis and nanoparticle synthesis.

Stacking and Twisting of Freestanding Complex Oxide Thin Films.

The integration of dissimilar materials in heterostructures has long been a cornerstone of modern materials science-seminal examples are 2D materials and van der Waals heterostructures. Recently, new methods have been developed that enable the realization of ultrathin freestanding oxide films approaching the 2D limit. Oxides offer new degrees of freedom, due to the strong electronic interactions, especially the 3d orbital electrons, which give rise to rich exotic phases. Inspired by this progress, a new platform for assembling freestanding oxide thin films with different materials and orientations into artificial stacks with heterointerfaces is developed. It is shown that the oxide stacks can be tailored by controlling the stacking sequences, as well as the twist angle between the constituent layers with atomically sharp interfaces, leading to distinct moiré patterns in the transmission electron microscopy images of the full stacks. Stacking and twisting is recognized as a key degree of structural freedom in 2D materials but, until now, has never been realized for oxide materials. This approach opens unexplored avenues for fabricating artificial 3D oxide stacking heterostructures with freestanding membranes across a broad range of complex oxide crystal structures with functionalities not available in conventional 2D materials.

Competing oxidation mechanisms in Cu nanoparticles and their plasmonic signatures.

Chemical reactions involving nanoparticles often follow complex processes. In this respect, real-time probing of single nanoparticles under reactive conditions is crucial for uncovering the mechanisms driving the reaction pathway. Here, we have captured in situ the oxidation of single Cu nanoparticles to unravel a sequential competitive activation of different mechanisms at temperatures 50-200 °C. Using environmental scanning transmission electron microscopy, we monitor the evolution of oxide formation with sub-nanometre spatial resolution, and show how the prevalence of oxide island nucleation, Cabrera-Mott, Valensi-Carter and Kirkendall mechanisms under different conditions determines the morphology of the particles. Moreover, using in situ electron energy-loss spectroscopy, we probe the localised surface plasmons of individual particles during oxidation, and with the aid of finite-difference time-domain electrodynamic simulations investigate the signature of each mechanism in their plasmonic response. Our results shed light on the rich and intricate processes involved in the oxidation of nanoparticles, and provide in-depth insight into how these processes govern their morphology and optical response, beneficial for applications in catalysis, sensing, nanomedicine and plasmonics.

Self-supported Pt-CoO networks combining high specific activity with high surface area for oxygen reduction.

Several concepts for platinum-based catalysts for the oxygen reduction reaction (ORR) are presented that exceed the US Department of Energy targets for Pt-related ORR mass activity. Most concepts achieve their high ORR activity by increasing the Pt specific activity at the expense of a lower electrochemically active surface area (ECSA). In the potential region controlled by kinetics, such a lower ECSA is counterbalanced by the high specific activity. At higher overpotentials, however, which are often applied in real systems, a low ECSA leads to limitations in the reaction rate not by kinetics, but by mass transport. Here we report on self-supported platinum-cobalt oxide networks that combine a high specific activity with a high ECSA. The high ECSA is achieved by a platinum-cobalt oxide bone nanostructure that exhibits unprecedentedly high mass activity for self-supported ORR catalysts. This concept promises a stable fuel-cell operation at high temperature, high current density and low humidification.

Monolithic integration of InP on Si by molten alloy driven selective area epitaxial growth.

We report a new approach for monolithic integration of III-V materials into silicon, based on selective area growth and driven by a molten alloy in metal-organic vapor epitaxy. Our method includes elements of both selective area and droplet-mediated growths and combines the advantages of the two techniques. Using this approach, we obtain organized arrays of high crystalline quality InP insertions into (100) oriented Si substrates. Our detailed structural, morphological and optical studies reveal the conditions leading to defect formation. These conditions are then eliminated to optimize the process for obtaining dislocation-free InP nanostructures grown directly on Si and buried below the top surface. The PL signal from these structures exhibits a narrow peak at the InP bandgap energy. The fundamental aspects of the growth are studied by modeling the InP nucleation process. The model is fitted by our X-ray diffraction measurements and correlates well with the results of our transmission electron microscopy and optical investigations. Our method constitutes a new approach for the monolithic integration of active III-V materials into Si platforms and opens up new opportunities in active Si photonics.

Electron inelastic mean free path in water.

Liquid phase transmission electron microscopy (LPTEM) is rapidly developing as a powerful tool for probing processes in liquid environments with close to atomic resolution. Knowledge of the water thickness is needed for reliable interpretation and modelling of analytical studies in LPTEM, and is particularly essential when using thin liquid layers, required for achieving the highest spatial resolutions. The log-ratio method in electron energy-loss spectroscopy (EELS) is often applied in TEM to quantify the sample thickness, which is measured relative to the inelastic mean free path (λIMFP). However, λIMFP itself is dependent on sample material, the electron energy, and the convergence and divergence angles of the microscope electronoptics. Here, we present a detailed quantitative analysis of the λIMFP of water as functions of the EELS collection angle (ß) at 120 keV and 300 keV in a novel nanochannel liquid cell. We observe good agreement with earlier studies conducted on ice, but find that the most widely used theoretical models significantly underestimate λIMFP of water. We determine an adjusted average energy-loss term Em, water, and characteristic scattering angle θE, water that improve the accuracy. The results provide a comprehensive knowledge of the λIMFP of water (or ice) for reliable interpretation and quantification of observations in LPTEM and cryo-TEM studies.

A pH-sensitive carrier based-on modified hollow mesoporous carbon nanospheres with calcium-latched gate for drug delivery.

A novel nanocarrier based-on hollow mesoporous carbon nanospheres (HMCNs) with primary amines on its surface, a large cavity, and good hydrophilicity was synthesized by a hydrothermal reaction. The primary amine functionalities on the mesoporous carbon were used as the initiation sites for growing poly (epichlorohydrin) (PCH) chains. The chlorine groups in the side chain of PCH were replaced with imidazole as the pendant groups. Calcium chloride (CaCl2) was applied as a capping agent. The coordination bonding was formed between pendant imidazole groups and calcium ions. Doxorubicin (DOX) was selected as a model of hydrophilic anticancer drug and was loaded onto the nanocarrier and released through the cleavage of the pH-sensitive coordination bonding. The gating mechanism enables the nanocarrier to store and release the calcium ions and the DOX molecules trapped in the pores. MTT assay toward HeLa cells indicated that the nanocarrier had low toxicity because of the surface modification with the oxygen-rich polymer. The cellular uptake of the pH-sensitive nanocarrier for HeLa cancer cell lines was confirmed by CLSM images and flow cytometry. So, the novel pH-sensitive nanocarrier can be applicable to carry and release both DOX drug and calcium ions for cancer treatment.

Nanoscale-Induced Formation of Silicide around Gold Nanoparticles Encapsulated in a-Si.

Decorating thin-film solar cells with plasmonic nanoparticles is being pursued in order to improve device efficiency through increased scattering and local field enhancement. Gold nanoparticles are particularly interesting due to their chemical inertness and plasmon resonance in the visible range of the spectrum. In this work, gold nanoparticles fabricated by a gas aggregation nanoparticle source and embedded in a-Si (a commercial solar cell material) are studied using X-ray photoelectron spectroscopy, transmission electron microscopy, electron energy-loss spectroscopy, and energy-dispersive X-ray spectroscopy. The formation of gold silicide around the nanoparticles is investigated, as it has important consequences for the optical and electronic properties of the structures. Different from previous studies, in which the silicide formation is observed for gold nanoparticles and thin films grown on top of crystalline silicon or silica, it is found that silicide formation is largely enhanced around the nanoparticles, owing to their increased surface/volume ratio. A detailed gold silicide formation mechanism is presented based on the results, and strategies for optimizing the design of plasmonically enhanced solar cells with gold nanoparticles encapsulated in a-Si are discussed.

Rationally Designed PdAuCu Ternary Alloy Nanoparticles for Intrinsically Deactivation-Resistant Ultrafast Plasmonic Hydrogen Sensing.

Hydrogen sensors are a prerequisite for the implementation of a hydrogen economy due to the high flammability of hydrogen-air mixtures. They are to comply with the increasingly stringent requirements set by stakeholders, such as the automotive industry and manufacturers of hydrogen safety systems, where sensor deactivation is a severe but widely unaddressed problem. In response, we report intrinsically deactivation-resistant nanoplasmonic hydrogen sensors enabled by a rationally designed ternary PdAuCu alloy nanomaterial, which combines the identified best intrinsic attributes of the constituent binary Pd alloys. This way, we achieve extraordinary hydrogen sensing metrics in synthetic air and poisoning gas background, simulating real application conditions. Specifically, we find a detection limit in the low ppm range, hysteresis-free response over 5 orders of magnitude hydrogen pressure, subsecond response time at room temperature, long-term stability, and, as the key, excellent resistance to deactivating species like carbon monoxide, notably without application of any protective coatings. This constitutes an important step forward for optical hydrogen sensor technology, as it enables application under demanding conditions and provides a blueprint for further material and performance optimization by combining and concerting intrinsic material assets in multicomponent nanoparticles. In a wider context, our findings highlight the potential of rational materials design through alloying of multiple elements for gas sensor development, as well as the potential of engineered metal alloy nanoparticles in nanoplasmonics and catalysis.

Metal-polymer hybrid nanomaterials for plasmonic ultrafast hydrogen detection.

Hydrogen-air mixtures are highly flammable. Hydrogen sensors are therefore of paramount importance for timely leak detection during handling. However, existing solutions do not meet the stringent performance targets set by stakeholders, while deactivation due to poisoning, for example by carbon monoxide, is a widely unsolved problem. Here we present a plasmonic metal-polymer hybrid nanomaterial concept, where the polymer coating reduces the apparent activation energy for hydrogen transport into and out of the plasmonic nanoparticles, while deactivation resistance is provided via a tailored tandem polymer membrane. In concert with an optimized volume-to-surface ratio of the signal transducer uniquely offered by nanoparticles, this enables subsecond sensor response times. Simultaneously, hydrogen sorption hysteresis is suppressed, sensor limit of detection is enhanced, and sensor operation in demanding chemical environments is enabled, without signs of long-term deactivation. In a wider perspective, our work suggests strategies for next-generation optical gas sensors with functionalities optimized by hybrid material engineering.

Surface enhanced Raman scattering (SERS) in the visible range on scalable aluminum-coated platforms.

We demonstrate the potential of combining plasmonic Bragg grating structures, with the scattering effect of a rough Al layer to tune SERS enhancement in the visible region. Novel Al-based substrates with good analytical reproducibility and enhancement factors in the range of 107-109 are produced by a scalable procedure which meets the development of producing sustainable SERS platforms.

Probing the Chemistry of Adhesion between a 316L Substrate and Spin-on-Glass Coating.

Hydrogen silsesquioxane ([HSiO3/2] n)-based "spin-on-glass" has been deposited on a 316L substrate and cured in Ar/H2 gas atmosphere at 600 °C to form a continuous surface coating with submicrometer thickness. The coating functionality depends primarily on the adhesion to the substrate, which is largely affected by the chemical interaction at the interface between the coating and the substrate. We have investigated this interface by transmission electron microscopy and electron energy loss spectroscopy. The analysis identified a 5-10 nm thick interaction zone containing signals from O, Si, Cr, and Fe. Analysis of the energy loss near edge structure of the present elements identified predominantly signal from [SiO4]4- units together with Fe2+, Cr2+, and traces of Cr3+. High-resolution transmission electron microscopy images of the interface region confirm a crystalline Fe2SiO4 interfacial region. In agreement with computational thermodynamics, it is proposed that the spin-on-glass forms a chemically bonded silicate-rich interaction zone with the substrate. It was further suggested that this zone is composed of a corundum-type oxide at the substrate surface, followed by an olivine-structure intermediate phase and a spinel-type oxide in the outer regions of the interfacial zone.

Multipole plasmons and their disappearance in few-nanometre silver nanoparticles.

Electron energy-loss spectroscopy can be used for detailed spatial and spectral characterization of optical excitations in metal nanoparticles. In previous electron energy-loss experiments on silver nanoparticles with radii smaller than 20 nm, only the dipolar surface plasmon resonance was assumed to play a role. Here, applying electron energy-loss spectroscopy to individual silver nanoparticles encapsulated in silicon nitride, we observe besides the usual dipole resonance an additional surface plasmon resonance corresponding to higher angular momenta for nanoparticle radii as small as 4 nm. We study the radius and electron beam impact position dependence of both resonances separately. For particles smaller than 4 nm in radius the higher-order surface plasmon mode disappears, in agreement with generalized non-local optical response theory, while the dipole resonance blueshift exceeds our theoretical predictions. Unlike in optical spectra, multipole surface plasmons are important in electron energy-loss spectra even of ultrasmall metallic nanoparticles.

Extremely confined gap surface-plasmon modes excited by electrons.

High-spatial and energy resolution electron energy-loss spectroscopy (EELS) can be used for detailed characterization of localized and propagating surface-plasmon excitations in metal nanostructures, giving insight into fundamental physical phenomena and various plasmonic effects. Here, applying EELS to ultra-sharp convex grooves in gold, we directly probe extremely confined gap surface-plasmon (GSP) modes excited by swift electrons in nanometre-wide gaps. We reveal the resonance behaviour associated with the excitation of the antisymmetric GSP mode for extremely small gap widths, down to ~5 nm. We argue that excitation of this mode, featuring very strong absorption, has a crucial role in experimental realizations of non-resonant light absorption by ultra-sharp convex grooves with fabrication-induced asymmetry. The occurrence of the antisymmetric GSP mode along with the fundamental GSP mode exploited in plasmonic waveguides with extreme light confinement is a very important factor that should be taken into account in the design of nanoplasmonic circuits and devices.

Surface-enhanced Raman scattering on aluminum using near infrared and visible excitation.

We observed strong surface-enhanced Raman scattering on discontinuous nanostructured aluminum films using 785 nm excitation even though dielectric constants of this metal suggest plasmon supported spectroscopy in the ultraviolet range. The excitation of SERS correlates with plasmon resonances in the 1.3-2.5 eV range identified in electron energy loss spectra.

High resolution STEM of quantum dots and quantum wires.

This article reviews the application of high resolution scanning transmission electron microscopy (STEM) to semiconductor quantum dots (QDs) and quantum wires (QWRs). Different imaging and analytical techniques in STEM are introduced and key examples of their application to QDs and QWRs are presented. In addition, the benefits offered by aberration correction are discussed and an outlook for future developments of high resolution STEM analysis of QDs and QWRs is given.