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In this tutorial review, we present the use of electron energy loss spectroscopy (EELS) and cathodoluminescence (CL) spectroscopy for surface plasmon mapping within metallic nanoparticles. We put a special emphasis on particles that are much smaller than the wavelength of visible light. We start by introducing the concept of surface plasmons, keeping the formalism as simple as possible by focusing on the quasi-static approximation. We then make a link between optical cross-sections, EELS and CL probabilities, and the surface plasmons' physical properties. A short survey of simulation tools is given. We then present typical experimental set-ups and describe some problems frequently encountered with spectrometers. Experimental conditions for improved signal to noise ratio are discussed. Analysis techniques are discussed, especially those related to the spectral imaging mode, which is extremely useful in EELS and CL experiments. Finally, the specific range of applications of EELS and CL with respect to other nano-optic techniques is discussed, as well as the strengths and weaknesses of EELS as compared with CL. [ABSTRACT FROM AUTHOR] more...

Abstract: Over the past ten years, Scanning Transmission Electron Microscopes (STEM) fitted with Electron Energy Loss Spectroscopy (EELS) and/or Cathodoluminescence (CL) spectroscopy have demonstrated to be essential tools for probing the optical properties of nano-objects at sub-wavelength scales. Thanks to the possibility of measuring them at a nanometer scale in parallel to the determination of the structure and morphology of the object of interest, new challenging experimental and theoretical horizons have been unveiled. As regards optical properties of metallic nanoparticles, surface plasmons have been mapped at a scale unimaginable only a few years ago, while the relationship between the energy levels and the size of semiconducting nanostructures a few atomic layers thick could directly be measured. This paper reviews some of these highly stimulating recent developments. [Copyright &y& Elsevier] more...

Highlights: [•] Original Ti(O,N) nanoparticles with a TiO FCC structure were synthesized by laser pyrolysis. [•] EELS and XAS allows to demonstrate that the nanoparticles are a solid solution of N and O in Ti. [•] Upon heat treatment, oxidation occurs from the surface with survival of FCC contribution till 400°C. [•] Optical properties (absorption in the visible range) can be adjusted through the control of oxidation state. [ABSTRACT FROM AUTHOR] more...

Understanding how light interacts with matter at the nanometre scale is a fundamental issue in optoelectronics and nanophotonics. In particular, many applications (such as bio-sensing, cancer therapy and all-optical signal processing) rely on surface-bound optical excitations in metallic nanoparticles. However, so far no experimental technique has been capable of imaging localized optical excitations with sufficient resolution to reveal their dramatic spatial variation over one single nanoparticle. Here, we present a novel method applied on silver nanotriangles, achieving such resolution by recording maps of plasmons in the near-infrared/visible/ultraviolet domain using electron beams instead of photons. This method relies on the detection of plasmons as resonance peaks in the energy-loss spectra of subnanometre electron beams rastered on nanoparticles of well-defined geometrical parameters. This represents a significant improvement in the spatial resolution with which plasmonic modes can be imaged, and provides a powerful tool in the development of nanometre-level optics. [ABSTRACT FROM AUTHOR] more...

Thin film properties are strongly influenced by strain and low dimensionality effects, especially when the film thickness is about a few unit cells, which corresponds to the thicknesses targeted in most of contemporary studies. In oxides, these effects are responsible for the dramatic modification of the physical properties that sometimes can change the nature of a material. Nevertheless, it is not always possible to distinguish the contribution of the strain to the changes in physical properties from the contribution due to low dimensional effects. In the present study, bismuth iron garnet Bi3Fe5O12 (BIG) is chosen to separate both effects. This material possesses, among other outstanding physical properties, the giant Faraday rotation that allows investigating films with the thickness below a few unit cells. Three series of BIG films of various thicknesses were grown on three isostructural substrates with different lattice parameters: Y3Al5O12(001), Gd3Ga5O12(001), and (GdCa)3(GaMgZr)5O12(001). The structural, magnetic, and magneto-optic properties were studied as a function of film thickness and strain. Furthermore, critical behavior of the BIG films was investigated in the vicinity of the Curie temperature. The obtained results allowed distinguishing between the low dimensional effects and the strain due to the epitaxial growth. While the size reduction is mostly responsible for the decrease of the magnetic characteristics of the films, the strain influences rather the critical thickness below which the material starts to behave as a low dimensional system. [ABSTRACT FROM AUTHOR] more...

An optical antenna can convert a propagative optical radiation into a localized excitation and the reciprocal. Although optical antennas can be readily created using resonant nanoparticles (metallic or dielectric) as elementary building blocks, the realization of antennas sustaining multiple resonances over a broad range of frequencies remains a challenging task. Here, we use aluminum self-similar, fractal-like structures as broadband optical antennas. Using electron energy loss spectroscopy, we experimentally evidence that a single aluminum Cayley tree, a simple self-similar structure, sustains multiple plasmonic resonances. The spectral position of these resonances is scalable over a broad spectral range spanning two decades, from ultraviolet to midinfrared. Such multiresonant structures are highly desirable for applications ranging from nonlinear optics to light harvesting and photodetection, as well as surface-enhanced infrared absorption spectroscopy. [ABSTRACT FROM AUTHOR] more...

Surface phonon polaritons (SPhPs) are coupled photon-phonon excitations that emerge at the surfaces of nanostructured materials. Although they strongly influence the optical and thermal behavior of nanomaterials, no technique has been able to reveal the complete three-dimensional (3D) vectorial picture of their electromagnetic density of states. Using a highly monochromated electron beam in a scanning transmission electron microscope, we could visualize varying SPhP signatures from nanoscale MgO cubes as a function of the beam position, energy loss, and tilt angle. The SPhPs’ response was described in terms of eigenmodes and used to tomographically reconstruct the phononic surface electromagnetic fields of the object. Such 3D information promises insights in nanoscale physical phenomena and is invaluable to the design and optimization of nanostructures for fascinating new uses. [ABSTRACT FROM AUTHOR] more...

The first colour photographs were created by a process introduced by Edmond Becquerel in 1848. The nature of these photochromatic images colours motivated a debate between scientists during the XIXth century, which is still not settled. We present the results of chemical analysis (EDX, HAXPES and EXAFS) and morphology studies (SEM, STEM) aiming at explaining the optical properties of the photochromatic images (UV‐visible spectroscopy and low loss EELS). We rule out the two hypotheses (pigment and interferences) that have prevailed since 1848, respectively based on variations in the oxidation degree of the compound forming the sensitized layer and periodically spaced photolytic silver planes. A study of the silver nanoparticles dispersions contained in the coloured layers showed specific localizations and sizes distributions of the nanoparticles for each colour. These results allow us to formulate a plasmonic hypothesis on the origin of the photochromatic images colours. [ABSTRACT FROM AUTHOR] more...

The first colour photographs were created by a process introduced by Edmond Becquerel in 1848. The nature of these photochromatic images colours motivated a debate between scientists during the XIXth century, which is still not settled. We present the results of chemical analysis (EDX, HAXPES and EXAFS) and morphology studies (SEM, STEM) aiming at explaining the optical properties of the photochromatic images (UV‐visible spectroscopy and low loss EELS). We rule out the two hypotheses (pigment and interferences) that have prevailed since 1848, respectively based on variations in the oxidation degree of the compound forming the sensitized layer and periodically spaced photolytic silver planes. A study of the silver nanoparticles dispersions contained in the coloured layers showed specific localizations and sizes distributions of the nanoparticles for each colour. These results allow us to formulate a plasmonic hypothesis on the origin of the photochromatic images colours. [ABSTRACT FROM AUTHOR] more...

Direct electron detection is currently revolutionizing many fields of electron microscopy due to its lower noise, its reduced point-spread function, and its increased quantum efficiency. More specifically to this work, Timepix3 is a hybrid-pixel direct electron detector capable of outputting temporal information of individual hits in its pixel array. Its architecture results in a data-driven detector, also called event-based, in which individual hits trigger the data off the chip for readout as fast as possible. The presence of a pixel threshold value results in an almost readout-noise-free detector while also defining the hit time of arrival and the time the signal stays over the pixel threshold. In this work, we have performed various experiments to calibrate and correct the Timepix3 temporal information, specifically in the context of electron microscopy. These include the energy calibration, and the time-walk and pixel delay corrections, reaching an average temporal resolution throughout the entire pixel matrix of 1. 37 ± 0. 04 ns. Additionally, we have also studied cosmic rays tracks to characterize the charge dynamics along the volume of the sensor layer, allowing us to estimate the limits of the detector's temporal response depending on different bias voltages, sensor thickness, and the electron beam ionization volume. We have estimated the uncertainty due to the ionization volume ranging from about 0.8 ns for 60 keV electrons to 8.8 ns for 300 keV electrons. • Timepix3 time calibration achieves 1.37 ns temporal resolution. • Energy and time-walk can be calibrated using uniform illumination datasets. • Electron–photon temporal correlation can be used to calibrate the pixel delay. • Cosmic rays tracks provides further insights about the sensor layer. [ABSTRACT FROM AUTHOR] more...

Over the past two or three decades, nanoscience and nanotechnology have clearly established themselves as prominent domains in research in physics, not only because of the innovative concepts and properties that they display but also for their capacity to generate many important applications and commercial developments. As many of these new devices exhibit a range of properties (transport, optical, magnetic, catalysis) which are governed by local structural and electronic configurations, such as coordination and bonding at the atomic level, it is no surprise that new tools of investigation are constantly being developed for imaging, analyzing, understanding and controlling at the relevant scale. Among them, electron microscopy has recently demonstrated its ability to meet many of these requirements. In particular, Å-sized probes are nowadays generated by aberration correctors in a scanning transmission electron microscope (STEM) and they can investigate the electron excitation spectrum of the specimen (through electron energy-loss spectroscopy, EELS) with a typical energy resolution of 0.1–0.3 eV over a broad spectral band from the IR to the X ray domain. In the high energy range, characteristic signals due to the excitation of atomic core levels are quite useful because they identify the atoms in the analyzed volume (which can itself be as small as a single atom) and can therefore deliver atomically-resolved elemental maps. But the pixel-by-pixel recording of the fine structures beyond the characteristic threshold is much more informative and tells us how the excited atom is surrounded by its neighbors, what is its exact structural environment and its charge population. The present review focuses on this particularly exciting field, with a special interest in the types of information accessible and their signature. After summarizing the ingredients required for successful experiments (instrumental as well as theoretical), examples encountered in different situations, in particular in single layers of 2D materials and at the interfaces in oxide heterostructures, will demonstrate the present capabilities of this STEM-EELS technique. [ABSTRACT FROM AUTHOR] more...

To date, quantum sources in the ultraviolet (UV) spectral region have been obtained only in semiconductor quantum dots. Color centers in wide bandgap materials may represent a more effective alternative. However, the quest for UV quantum emitters in bulk crystals faces the difficulty of combining an efficient UV excitation/detection optical setup with the capability of addressing individual color centers in potentially highly defective materials. In this work we overcome this limit by employing an original experimental setup coupling cathodoluminescence within a scanning transmission electron microscope to a Hanbury-Brown-Twiss intensity interferometer. We identify a new extremely bright UV single photon emitter (4.1 eV) in hexagonal boron nitride. Hyperspectral cathodoluminescence maps show a high spatial localization of the emission (∼80 nm) and a typical zero-phonon line plus phonon replica spectroscopic signature, indicating a point defect origin, most likely carbon substitutional at nitrogen sites. An additional nonsingle-photon broad emission may appear in the same spectral region, which can be attributed to intrinsic defects related to electron irradiation. [ABSTRACT FROM AUTHOR] more...

Since their first realization, electron microscopes have demonstrated their unique ability to map with highest spatial resolution (sub-atomic in most recent instruments) the position of atoms as a consequence of the strong scattering of the incident high energy electrons by the nuclei of the material under investigation. When interacting with the electron clouds either on atomic orbitals or delocalized over the specimen, the associated energy transfer, measured and analyzed as an energy loss (Electron Energy Loss Spectroscopy) gives access to analytical properties (atom identification, electron states symmetry and localization). In the moderate energy-loss domain (corresponding to an optical spectral domain from the infrared (IR) to the rather far ultra violet (UV), EELS spectra exhibit characteristic collective excitations of the rather-free electron gas, known as plasmons. Boundary conditions, such as surfaces and/or interfaces between metallic and dielectric media, generate localized surface charge oscillations, surface plasmons (SP), which are associated with confined electric fields. This domain of research has been extraordinarily revived over the past few years as a consequence of the burst of interest for structures and devices guiding, enhancing and controlling light at the sub-wavelength scale. The present review focuses on the study of these surface plasmons with an electron microscopy-based approach which associates spectroscopy and mapping at the level of a single and well-defined nano-object, typically at the nanometer scale i.e. much improved with respect to standard, and even near-field, optical techniques. After calling to mind some early studies, we will briefly mention a few basic aspects of the required instrumentation and associated theoretical tools to interpret the very rich data sets recorded with the latest generation of (Scanning)TEM microscopes. The following paragraphs will review in more detail the results obtained on simple planar and spherical surfaces (or interfaces), extending then to more complex geometries isolated and in interaction, thus establishing basic rules from the classical to the quantum domain. A few hints towards application domains and prospective fields rich of interest will finally be indicated, confirming the demonstrated key role of electron-beam nanoplasmonics, the more as an yet-enhanced energy resolution down to the 10 meV comes on the verge of current access. [ABSTRACT FROM AUTHOR] more...

Plasmonmodes of the exact same individual gold nanoprisms are investigatedthrough combined nanometer-resolved electron energy-loss spectroscopy(EELS) and cathodoluminescence (CL) measurements. We show that CLonly probes the radiative modes, in contrast to EELS, which additionallyreveals dark modes. The combination of both techniques on the sameparticles thus provides complementary information and also demonstratesthat although the radiative modes give rise to very similar spatialdistributions when probed by EELS or CL, their resonant energies appearto be different. We trace this phenomenon back to plasmon dissipation,which affects in different ways the plasmon signatures probed by thesetechniques. Our experiments are in agreement with electromagneticnumerical simulations and can be further interpreted within the frameworkof a quasistatic analytical model. We therefore demonstrate that CLand EELS are closely related to optical scattering and extinction,respectively, with the addition of nanometer spatial resolution. [ABSTRACT FROM AUTHOR] more...

Having access to the chemical environmentat the atomic level ofa dopant in a nanostructure is crucial for the understanding of itsproperties. We have performed atomically resolved electron energy-lossspectroscopy to detect individual nitrogen dopants in single-walledcarbon nanotubes and compared with first-principles calculations.We demonstrate that nitrogen doping occurs as single atoms in differentbonding configurations: graphitic-like and pyrrolic-like substitutionalnitrogen neighboring local lattice distortion such as Stone-Thrower-Walesdefects. We also show that the largest fraction of nitrogen amountis found in poly aromatic species that are adsorbed on the surfaceof the nanotube walls. The stability under the electron beam of thesenanotubes has been studied in two different cases of nitrogen incorporationcontent and configuration. These findings provide key informationfor the applications of these nanostructures. [ABSTRACT FROM AUTHOR] more...

CsNiCr(CN)6 coordination nanoparticles with sizes ranging from 6 to 30 nm are highly diluted in an organic polymer matrix. Their static and dynamic magnetic behaviour allows unravelling of surface anisotropy and interparticle dipolar interaction effects. The single magnetic domain critical size is thus evaluated to be around 22 nm with a blocking temperature of 21 K (at ν = 1 Hz) and an effective energy barrier for the reversal of the magnetization of 426 K. [ABSTRACT FROM AUTHOR] more...

The acquisition of a hyperspectral image is nowadays a standard technique used in the scanning transmission electron microscope. It relates the spatial position of the electron probe to the spectral data associated with it. In the case of electron energy loss spectroscopy (EELS), frame-based hyperspectral acquisition is much slower than the achievable rastering time of the scan unit (SU), which sometimes leads to undesirable effects in the sample, such as electron irradiation damage, that goes unperceived during frame acquisition. In this work, we have developed an event-based hyperspectral EELS by using a Timepix3 application-specific integrated circuit detector with two supplementary time-to-digital (TDC) lines embedded. In such a system, electron events are characterized by their positional and temporal coordinates, but TDC events only by temporal ones. By sending reference signals from the SU to the TDC line, it is possible to reconstruct the entire spectral image with SU-limited scanning pixel dwell time and thus acquire, with no additional cost, a hyperspectral image at the same rate as that of a single channel detector, such as annular dark-field. To exemplify the possibilities behind event-based hyperspectral EELS, we have studied the decomposition of calcite (CaCO 3) into calcium oxide (CaO) and carbon dioxide (CO 2) under the electron beam irradiation. • 3D datacubes acquiring up to 10 6 spectrum/s can be obtained. • EELS spectral-imaging is acquired with the scanning rate used in regular imaging. • 512x512 EELS spectral-images can be acquired every tens of milliseconds. • Principal component analysis denoise datasets with sub-ms pixel acquisition time. [ABSTRACT FROM AUTHOR] more...

Based on nickel hexacyanidochromate and cobalt hexacyanidoferrate Prussian blue analogues, two series of photomagnetic/ferromagnetic sub-50 nm core multishell coordination nanoparticles have been synthesized in a surfactant-free one-pot multistep procedure with good control over the dispersity (1096 standard deviation) and good agreement with the targeted size at each step. The composition and the valence state of each shell have been probed by different techniques that have revealed the predominance of CoII-NC-FIII pairs in a series synthesized without alkali while CoIII-NC-FII photoswitchable pairs have been successfully obtained in the photoactive coordination nanoparticles by control of Cs+insertion. When compared, the photoinduced behavior of the latter compound is in good agreement with that of the model one. Exchange coupling favors a uniform reversal of the magnetization of the heterostructured nanoparticles, with a large magnetization brought by a soft ferromagnetic shell and a large coercivity due to a harder photomagnetic shell. Moreover, a persistent increase of the photoinduced magnetization is observed for the first time up to the ordering temperature (60 K) of the ferromagnetic component because of a unique synergy. [ABSTRACT FROM AUTHOR] more...

We report on the identification and nanometer scale characterization over a large energy range of random, disorder-driven, surface plasmons in silver semicontinuous films embedded in silicon nitride. By performing spatially resolved electron energy loss spectroscopy experiments, we experimentally demonstrate that these plasmons eigenmodes arise when the films become fractal, leading to the emergence of strong electrical fields ("hot spots") localized over few nanometers. We show that disorder-driven surface plasmons strongly depart from those usually found in nanoparticles, being strongly confined and randomly and densely distributed in space and energy. Beyond that, we show that they have no obvious relation with the local morphology of the films, in stark contrast with surface plasmon eigenmodes of nanoparticles. [ABSTRACT FROM AUTHOR] more...

New, ultrasmall nanoparticles with sizes below 5 nm have been obtained. These small rigid platforms (SRP) are composed of a polysiloxane matrix with DOTAGA (1,4,7,10-tetraazacyclododecane-1-glutaric anhydride-4,7,10-triacetic acid)-Gd3+ chelates on their surface. They have been synthesised by an original top-down process: 1) formation of a gadolinium oxide Gd2O3 core, 2) encapsulation in a polysiloxane shell grafted with DOTAGA ligands, 3) dissolution of the gadolinium oxide core due to chelation of Gd3+ by DOTAGA ligands and 4) polysiloxane fragmentation. These nanoparticles have been fully characterised using photon correlation spectroscopy (PCS), transmission electron microscopy (TEM), a superconducting quantum interference device (SQUID) and electron paramagnetic resonance (EPR) to demonstrate the dissolution of the oxide core and by inductively coupled plasma mass spectrometry (ICP-MS), mass spectrometry, fluorescence spectroscopy, 29Si solid-state NMR, 1H NMR and diffusion ordered spectroscopy (DOSY) to determine the nanoparticle composition. Relaxivity measurements gave a longitudinal relaxivity r1 of 11.9 s−1 m M−1 per Gd at 60 MHz. Finally, potentiometric titrations showed that Gd3+ is strongly chelated to DOTAGA (complexation constant log β110=24.78) and cellular tests confirmed the that nanoconstructs had a very low toxicity. Moreover, SRPs are excreted from the body by renal clearance. Their efficiency as contrast agents for MRI has been proved and they are promising candidates as sensitising agents for image-guided radiotherapy. [ABSTRACT FROM AUTHOR] more...

The local structural distortions in polydomain ferroelectric PbTiO3/SrTiO3 superlattices are investigated by means of high spatial and energy resolution electron-energy-loss spectroscopy combined with high-angle annular dark field imaging. Local structural variations across the interfaces have been identified with unit-cell resolution through the analysis of the energy-loss near-edge structure of the Ti L2, 3 and O K edges. Ab initio and multiplet calculations of the Ti L2, 3 edges provide unambiguous evidence for an inhomogeneous polarization profile associated with the observed structural distortions across the superlattice. [ABSTRACT FROM AUTHOR] more...

The article highlights a research on using controlled ultrasensitive surface-enhanced Raman scattering (SERS) to allow zeptomole detection. The study shows that sparse distribution of 15NAT molecules can resolve SERS signal from individual hot spots using Raman spectroscopy. However, zeptomole detection with nanospheres is unattainable while results in SERS count rate is below the noise level. more...

Transmission Electron Microscopy (TEM), X-ray Absorption Near Edge Spectroscopy (XANES), Electron Energy-Loss Spectroscopy (EELS), Small-Angle X-ray Scattering (SAXS), and SQUID magnetic studies were performed in a batch of horse spleen ferritins from which iron had been gradually removed, yielding samples containing 2200, 1200, 500, and 200 iron atoms. Taken together, findings obtained demonstrate that the ferritin iron core consists of a polyphasic structure (ferrihydrite, magnetite, hematite) and that the proportion of phases is modified by iron removal. Thus, the relative amount of magnetite in ferritin containing 2200 to 200 iron atoms rose steadily from ~20% to ~70% whereas the percentage of ferrihydrite fell from ~60% to ~20%. These results indicate a ferrihydrite-magnetite core-shell structure. It was also found that the magnetite in the ferritin iron core is not a source of free toxic ferrous iron, as previously believed. Therefore, the presence of magnetite in the ferritin cores of patients with Alzheimer's disease is not a cause of their increased brain iron(II) concentration. [ABSTRACT FROM AUTHOR] more...

This paper reviews transmission electron microscopy studies, combining high resolution imaging and electron energy loss spectroscopy, of the nucleation and growth of carbon single wall nanotubes with a particular emphasis on the nanotubes obtained from the evaporation-based elaboration techniques. Inspection of samples obtained from different synthesis routes shows that in all cases nanotubes are found to emerge from catalyst particles and that they have grown perpendicular or parallel to the surface according to whether they have been synthesized via evaporation-based methods or CCVD methods. Whereas the latter case corresponds to the well-known situation of carbon filaments growth, the former case strongly suggests another formation and growth process, which is described and its different steps discussed in detail. In this model, formation of the nanotubes proceeds via solvation of carbon into liquid metal droplets, followed by precipitation, at the surface of the particles, of excess carbon in the form of nanotubes through a nucleation and root growth process. It is argued that the nucleation of the nanotubes, which compete with the formation of graphene sheets wrapping the surface of the particle, necessarily results from a surface instability induced by the conditions of segregation. The nature and the origin of this instability was studied in the case of the class of catalyst Ni–R.E. (R.E.=Y, La, Ce, …) in order to identify the influence of the nature of the catalyst. The respective roles played by Ni and R.E. have been identified. It is shown that carbon and rear-earth co-segregate and self-assemble at the surface of the particle in order to form a surface layer destabilizing the formation of graphene sheets and providing nucleation sites for nanotubes growing perpendicular to the surface. To cite this article: A. Loiseau et al., C. R. Physique 4 (2003). [Copyright &y& Elsevier] more...

Anisotropic nanoparticles of the Fe(pyrazine)Pt(CN)4network were prepared embedded in various matrices that revealed to have a dramatic effect on the cooperative spin crossover phenomena. By a judicious choice of the nature of the matrix and the control of interparticle distances, a hysteresis of 15 K was achieved close to room temperature for such nano-objects. [ABSTRACT FROM AUTHOR] more...

Anisotropic coordination nanoparticles of the photomagnetic network CsI2CuII7[MoIV(CN)8]4are obtained through a surfactant-free high-yield synthetic procedure in water. These particles are organised as Langmuir–Blodgett films with a preferential orientation of the nano-objects within the film that exhibit a magnetic bistability below 20 K with a very large coercivity due to an efficient photo-transformation. [ABSTRACT FROM AUTHOR] more...

Spin-crossover coordination nanoparticles of the cyanide-badged three-dimensional network Fe(pyrazine){Pt(CN)4} were prepared at three different sizes using a microemulsion. The 14 nm particles present a transition centered around 265 K with a hysteresis of 6 K. [ABSTRACT FROM AUTHOR] more...

• A random scan operating mode in STEM achieved at the hardware level is presented. • Random sparse hyperspectral images can be extracted in any acquisition time window. • Randomization of pixel acquisition order can reduce dose accumulation effects. • Spatial and spectral dynamics can be followed in STEM hyperspectral imaging. • Proof of concepts for EELS and nano-cathodoluminescence are provided. The evolution of the scanning modules for scanning transmission electron microscopes (STEM) allows now to generate arbitrary scan pathways, an approach currently explored to improve acquisition speed and to reduce electron dose effects. In this work, we present the implementation of a random scan operating mode in STEM achieved at the hardware level via a custom scan control module. A pre-defined pattern with fully shuffled raster order is used to sample the entire region of interest. Subsampled random sparse images can then be extracted at successive time frames, to which suitable image reconstruction techniques can be applied. With respect to the conventional raster scan mode, this method permits to limit dose accumulation effects, but also to decouple the spatial and temporal information in hyperspectral images. We provide some proofs of concept of the flexibility of the random scan operating mode, presenting examples of its applications in different spectro-microscopy contexts: atomically-resolved elemental maps with electron energy loss spectroscopy and nanoscale-cathodoluminescence spectrum images. By employing adapted post-processing tools, it is demonstrated that the method allows to precisely track and correct for sample instabilities and to follow spectral diffusion with a high spatial resolution. [ABSTRACT FROM AUTHOR] more...

Nanocrystals of semiconducting, highly-doped metal oxides present localized surface plasmon resonance properties responsible for intense optical absorption in the near-infrared (NIR) spectral range. These features make them strong candidates for designing "new generation", spectrally-selective electrochromic smart windows and other optoelectronic devices. In the present study, nanocrystals of tin-doped indium oxide (ITO) are solvothermally-synthesized in benzyl alcohol. Their structure, morphology and composition are assessed by X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy, while their optical plasmonic behavior is evidenced by means of VIS-NIR spectrometry and electron energy loss spectroscopy coupled to scanning transmission electron microscopy. Remarkably, the latter setup allows for the value-added acquisition of high-resolution mappings and quantifications of the nanocrystals individual plasmon responses at both surface and bulk levels. Inks of ITO nanocrysals are then spray-coated onto glass to act as NIR-modulating plasmonic electrochromic layers. ITO dispersions are straightforwardly deposited from low toxic media (isopropanol) according to a room-temperature procedure implying no harsh chemical or thermal post-treatment – only a mild drying step at 100 °C for 10 min. Finally, in situ spectroelectrochemical measurements completed on the films immersed in liquid electrolyte show appreciable NIR contrasts (up to 40%) upon electrochemical charge/discharge, together with a >80% VIS transmittance. Image 1 • Plasmonic ITO nanocrystals are synthesized from a solvothermal protocol. • Their LSPR signature is characterized by VIS-NIR and STEM-EELS measurements. • Isopropanol dispersions of ITO nanocrystals are spray-coated onto glass at RT. • Sprayed layers act as NIR-modulating electrochromic coatings with up to 40% contrast. [ABSTRACT FROM AUTHOR] more...