High Capacitance Porous Ruthenium Nitride Films with High Rate Capability for Micro-Supercapacitors.

The demand for high-performance energy storage devices to power Internet of Things applications has driven intensive research on micro-supercapacitors (MSCs). In this study, RuN films made by magnetron sputtering as an efficient electrode material for MSCs are investigated. The sputtering parameters are carefully studied in order to maximize film porosity while maintaining high electrical conductivity, enabling a fast charging process. Using a combination of advanced techniques, the relationships among the morphology, structure, and electrochemical properties of the RuN films are investigated. The films are shown to have a complex structure containing a mixture of crystallized Ru and RuN phases with an amorphous oxide layer. The combination of high electrical conductivity and pseudocapacitive charge storage properties enabled a 16 µm-thick RuN film to achieve a capacitance value of 0.8 F cm-2 in 1 m KOH with ultra-high rate capability.

Distinguishing cellular from abiotic spheroidal microstructures in the ca. 3.4 Ga Strelley Pool Formation.

The morphogenesis of most carbonaceous microstructures that resemble microfossils in Archean (4-2.5 Ga old) rocks remains debated. The associated carbonaceous matter may even-in some cases-derive from abiotic organic molecules. Mineral growths associated with organic matter migration may mimic microbial cells, some anatomical features, and known microfossils-in particular those with simple spheroid shapes. Here, spheroid microstructures from a chert of the ca. 3.4 Ga Strelley Pool Formation (SPF) of the Pilbara Craton (Western Australia) were imaged and analyzed with a combination of high-resolution in situ techniques. This provides new insights into carbonaceous matter distributions and their relationships with the crystallographic textures of associated quartz. Thus, we describe five new types of spheroids and discuss their morphogenesis. In at least three types of microstructures, wall coalescence argues for migration of carbonaceous matter onto abiotic siliceous spherulites or diffusion in poorly crystalline silica. The nanoparticulate walls of these coalescent structures often cut across multiple quartz crystals, consistent with migration in/on silica prior to quartz recrystallization. Sub-continuous walls lying at quartz boundaries occur in some coalescent vesicles. This weakens the "continuous carbonaceous wall" criterion proposed to support cellular inferences. In contrast, some clustered spheroids display wrinkled sub-continuous double walls, and a large sphere shows a thick sub-continuous wall with pustules and depressions. These features appear consistent with post-mortem cell alteration, although abiotic morphogenesis remains difficult to rule out. We compared these siliceous and carbonaceous microstructures to coalescent pyritic spheroids from the same sample, which likely formed as "colloidal" structures in hydrothermal context. The pyrites display a smaller size and only limited carbonaceous coatings, arguing that they could not have acted as precursors to siliceous spheroids. This study revealed new textural features arguing for abiotic morphogenesis of some Archean spheroids. The absence of these features in distinct types of spheroids leaves open the microfossil hypothesis in the same rock. Distinction of such characteristics could help addressing further the origin of other candidate microfossils. This study calls for similar investigations of metamorphosed microfossiliferous rocks and of the products of in vitro growth of cell-mimicking structures in presence of organics and silica.

3D LiMn2 O4 Thin Film Deposited by ALD: A Road toward High-Capacity Electrode for 3D Li-Ion Microbatteries.

Miniaturized electronics suffer from a lack of energy autonomy. In that context, the fabrication of lithium-ion solid-state microbatteries with high performance is mandatory for powering the next generation of portable electronic devices. Here, the fabrication of a thin film positive electrode for 3D Li-ion microbatteries made by the atomic layer deposition (ALD) method and in situ lithiation step is demonstrated. The 3D electrodes based on spinel LiMn2 O4 films operate at high working potential (4.1 V vs Li/Li+ ) and are capable of delivering a remarkable surface capacity (≈180 µAh cm-2 ) at low C-rate while maintaining more than 40 µAh cm-2 at C/2 (time constant = 2 h). Both the thickness of the electrode material and the 3D gain of the template are carefully tuned to maximize the electrode performance. Advanced characterization techniques such as transmission electron and X-ray transmission microscopies are proposed as perfect tools to study the conformality of the deposited films and the interfaces between each layer: no interdiffusion or segregation are observed. This work represents a major issue towards the fabrication of 3D-lithiated electrode by ALD-without any prelithiation step by electrochemical technique-making it an attractive solution for the fabrication of 3D Li-ion solid-state microbatteries with semiconductor processing methods.

In Situ Liquid Electrochemical TEM Investigation of LiMn1.5 Ni0.5 O4 Thin Film Cathode for Micro-Battery Applications.

Micro-batteries are attractive miniaturized energy devices for new Internet of Things applications, but the lack of understanding of their degradation process during cycling hinders improving their performance. Here focused ion beam (FIB)-lamella from LiMn1.5 Ni0.5 O4 (LMNO) thin-film cathode is in situ cycled in a liquid electrolyte inside an electrochemical transmission electron microscope (TEM) holder to analyze structural and morphology changes upon (de)lithiation processes. A high-quality electrical connection between the platinum (Pt) current collector of FIB-lamella and the microchip's Pt working electrode is established, as confirmed by local two-probe conductivity measurements. In situ cyclic voltammetry (CV) experiments show two redox activities at 4.41 and 4.58/4.54 V corresponding to the Ni2+/3+ and Ni3+/4+ couples, respectively. (S)TEM investigations of the cycled thin-film reveal formation of voids and cracks, loss of contact with current collector, and presence of organic decomposition products. The 4D STEM ASTAR technique highlights the emergence of an amorphization process and a decrease in average grain size from 20 to 10 nm in the in situ cycled electrode. The present findings, obtained for the first time through the liquid electrochemical TEM study, provide several insights explaining the capacity fade of the LMNO thin-film cathode typically observed upon cycling in a conventional liquid electrolyte.

Fast X-ray Nanotomography with Sub-10 nm Resolution as a Powerful Imaging Tool for Nanotechnology and Energy Storage Applications.

In the last decade, transmission X-ray microscopes (TXMs) have come into operation in most of the synchrotrons worldwide. They have proven to be outstanding tools for non-invasive ex and in situ 3D characterization of materials at the nanoscale across varying range of scientific applications. However, their spatial resolution has not improved in many years, while newly developed functional materials and microdevices with enhanced performances exhibit nanostructures always finer. Here, optomechanical breakthroughs leading to fast 3D tomographic acquisitions (85 min) with sub-10 nm spatial resolution, narrowing the gap between X-ray and electron microscopy, are reported. These new achievements are first validated with 3D characterizations of nanolithography objects corresponding to ultrahigh-aspect-ratio hard X-ray zone plates. Then, this powerful technique is used to investigate the morphology and conformality of nanometer-thick film electrodes synthesized by atomic layer deposition and magnetron sputtering deposition methods on 3D silicon scaffolds for electrochemical energy storage applications.

Engineering a Robust Flat Band in III-V Semiconductor Heterostructures.

Electron states in semiconductor materials can be modified by quantum confinement. Adding to semiconductor heterostructures the concept of lateral geometry offers the possibility to further tailor the electronic band structure with the creation of unique flat bands. Using block copolymer lithography, we describe the design, fabrication, and characterization of multiorbital bands in a honeycomb In0.53Ga0.47As/InP heterostructure quantum well with a lattice constant of 21 nm. Thanks to an optimized surface quality, scanning tunnelling spectroscopy reveals the existence of a strong resonance localized between the lattice sites, signature of a p-orbital flat band. Together with theoretical computations, the impact of the nanopatterning imperfections on the band structure is examined. We show that the flat band is protected against the lateral and vertical disorder, making this industry-standard system particularly attractive for the study of exotic phases of matter.

NanoSIMS Imaging of D/H Ratios on FIB Sections.

The D/H ratio imaging of weakly hydrated minerals prepared as focused ion beam (FIB) sections is developed in order to combine isotopic imaging by nanoscale secondary ion mass spectrometry (NanoSIMS) of micrometer-sized grains with other nanoscale imaging techniques, such as transmission electron microscopy. In order to maximize the accuracy, sensitivity, precision, and reproducibility of D/H ratios at the micrometer size, while minimizing the surface contamination at the same time, we explored all instrumental parameters known to influence the measurement of D/H ratios in situ. Optimal conditions were found to be obtained with the use of (i) a Cs+ ion source and detection of H- and D- at low mass resolving power, (ii) a primary beam intensity of 100 pA, and (iii) raster sizes in the range of 8-15 µm. Nominally anhydrous minerals were used to evaluate the detection limits and indicate a surface contamination level of ∼200 ppm equivalent H2O under these conditions. With the high primary intensity used here, the dwell time is not a parameter as critical as found in previous studies and a dwell time of 1 ms/px is used to minimize dynamic contamination during analysis. Analysis of FIB sections was found to reduce significantly static contamination due to sample preparation and improved accuracy compared to using polished sections embedded not only in epoxy but in indium as well. On amphiboles, the typical overall uncertainty including reproducibility is ∼20 ‰ on bulk FIB sections and ∼50 ‰ at the 1.5 µm scale using image processing (1σ).

Size and shape control of a variety of metallic nanostructures using tilted, rotating evaporation and lithographic lift-off techniques.

Here, we demonstrate a simple top-down method for nanotechnology whereby electron beam (ebeam) lithography can be combined with tilted, rotated thermal evaporation to control the topography and size of an assortment of metallic objects at the nanometre scale. In order to do this, the evaporation tilt angle is varied between 1 and 24°. The technique allows the 3-dimensional tailoring of a range of metallic object shapes from sharp, flat bottomed spikes to hollow cylinders and rings-all of which have rotational symmetry and whose critical dimensions are much smaller than the lithographic feature size. The lithographic feature size is varied from 400 nm down to 40 nm. The nanostructures are characterized using electron microscopy techniques-the specific shape can be predicted using topographic modelling of the deposition. Although individual nanostructures are studied here, the idea can easily be extended to fabricate arrays for e.g. photonics and metamaterials. Being a generic technique-depending on easily controlled lithographic and evaporation parameters-it can be readily incorporated into any standard planar process and could be adapted to suit other thin-film materials deposited using physical means.

Trap-Free Heterostructure of PbS Nanoplatelets on InP(001) by Chemical Epitaxy.

Semiconductor nanocrystalline heterostructures can be produced by the immersion of semiconductor substrates into an aqueous precursor solution, but this approach usually leads to a high density of interfacial traps. In this work, we study the effect of a chemical passivation of the substrate prior to the nanocrystalline growth. PbS nanoplatelets grown on sulfur-treated InP (001) surfaces at temperatures as low as 95 °C exhibit abrupt crystalline interfaces that allow a direct and reproducible electron transfer to the InP substrate through the nanometer-thick nanoplatelets with scanning tunnelling spectroscopy. It is in sharp contrast with the less defined interface and the hysteresis of the current-voltage characteristics found without the passivation step. Based on a tunnelling effect occurring at energies below the bandgap of PbS, we show the formation of a type II, trap-free, epitaxial heterointerface, with a quality comparable to that grown on a nonreactive InP (110) substrate by molecular beam epitaxy. Our scheme offers an attractive alternative to the fabrication of semiconductor heterostructures in the gas phase.

Bottom-up fabrication of InAs-on-nothing MOSFET using selective area molecular beam epitaxy.

In this paper we report on the fabrication and electrical characterization of InAs-on-nothing metal-oxide-semiconductor field-effect transistor composed of a suspended InAs channel and raised InAs n+ contacts. This architecture is obtained using 3D selective and localized molecular beam epitaxy on a lattice mismatched InP substrate. The suspended InAs channel and InAs n+ contacts feature a reproducible and uniform shape with well-defined 3D sidewalls. Devices with 1 µm gate length present a saturation drain current (I Dsat) of 300 mA mm-1 at V DS = 0.8 V and a trans-conductance (GM ) of 120 mS mm-1 at V DS = 0.5 V. In terms of electrostatic control, the devices display a minimal subthreshold swing of 110 mV dec-1 at V DS = 0.5 V and a small drain induced barrier lowering of 50 mV V-1.

Morphology and valence band offset of GaSb quantum dots grown on GaP(001) and their evolution upon capping.

This work presents a detailed study of GaSb quantum dot (QD) epitaxy on (001) GaP substrates by means of molecular beam epitaxy. Despite the large mismatch between GaP and GaSb, we show that in the nucleation-diffusion regime, the QD size distribution follows the predictions of the scaling theory. Scanning transmission electron microscopy analysis of grown QDs reveal that they are plastically relaxed by 60° pairs of misfit dislocations and the valence band offset measured by x-ray photoelectron spectroscopy on such QDs amounts to 0.5 eV. After capping, the QD morphology is strongly modified with a large P/Sb exchange-segregation reaction, which even leads to the formation of core-shell nanostructures. Remarkably the resulting QD layer is coherent to the substrate without any remaining misfit dislocation and exhibits still strong composition modulations.

3D silicon shapes through bulk nano structuration by focused ion beam implantation and wet etching.

The work presented in this paper concerns the synthesis of silicon (Si) 2D and 3D nanostructures using the delayed effect, caused by implanted Ga ions, on the dissolution of Si in aqueous solutions of tetramethylammonium hydroxide (TMAH). The crystalline silicon substrates (100) are first cleaned and then hydrogenated by immersion in an aqueous solution of hydrofluoric acid. The ion implantation is then carried out by a focused ion beam by varying the dose and the exposure time. Chemical etching in aqueous solutions of TMAH at 80 °C leads to the selective dissolution of the Si planes not exposed to the ions. The preliminary results obtained in the laboratory made it possible to optimize the experimental conditions for the synthesis of 2D and 3D nanoobjects of controlled shape and size. Analysis by transmission electron microscopy and energy dispersive x-ray showed the amorphous nature of the nanostructures obtained and the presence of 5%-20% Ga in these nanoobjects. The first experiments of recrystallization by rapid thermal annealing allowed to reconstitute the crystal structure of these nanoobjects.

Iron minerals within specific microfossil morphospecies of the 1.88 Ga Gunflint Formation.

Problematic microfossils dominate the palaeontological record between the Great Oxidation Event 2.4 billion years ago (Ga) and the last Palaeoproterozoic iron formations, deposited 500-600 million years later. These fossils are often associated with iron-rich sedimentary rocks, but their affinities, metabolism, and, hence, their contributions to Earth surface oxidation and Fe deposition remain unknown. Here we show that specific microfossil populations of the 1.88 Ga Gunflint Iron Formation contain Fe-silicate and Fe-carbonate nanocrystal concentrations in cell interiors. Fe minerals are absent in/on all organically preserved cell walls. These features are consistent with in vivo intracellular Fe biomineralization, with subsequent in situ recrystallization, but contrast with known patterns of post-mortem Fe mineralization. The Gunflint populations that display relatively large cells (thick-walled spheres, filament-forming rods) and intra-microfossil Fe minerals are consistent with oxygenic photosynthesizers but not with other Fe-mineralizing microorganisms studied so far. Fe biomineralization may have protected oxygenic photosynthesizers against Fe2+ toxicity during the Palaeoproterozoic.

Nonstoichiometric Low-Temperature Grown GaAs Nanowires.

The structural and electronic properties of nonstoichiometric low-temperature grown GaAs nanowire shells have been investigated with scanning tunneling microscopy and spectroscopy, pump-probe reflectivity, and cathodoluminescence measurements. The growth of nonstoichiometric GaAs shells is achieved through the formation of As antisite defects, and to a lower extent, after annealing, As precipitates. Because of the high density of atomic steps on the nanowire sidewalls, the Fermi level is pinned midgap, causing the ionization of the subsurface antisites and the formation of depleted regions around the As precipitates. Controlling their incorporation offers a way to obtain unique electronic and optical properties that depart from the ones found in conventional GaAs nanowires.

Quantitative impedance characterization of sub-10 nm scale capacitors and tunnel junctions with an interferometric scanning microwave microscope.

We present a method to characterize sub-10 nm capacitors and tunnel junctions by interferometric scanning microwave microscopy (iSMM) at 7.8 GHz. At such device scaling, the small water meniscus surrounding the iSMM tip should be reduced by proper tip tuning. Quantitative impedance characterization of attofarad range capacitors is achieved using an 'on-chip' calibration kit facing thousands of nanodevices. Nanoscale capacitors and tunnel barriers were detected through variations in the amplitude and phase of the reflected microwave signal, respectively. This study promises quantitative impedance characterization of a wide range of emerging functional nanoscale devices.

Novel heterostructured Ge nanowires based on polytype transformation.

We report on a strain-induced phase transformation in Ge nanowires under external shear stresses. The resulted polytype heterostructure may have great potential for photonics and thermoelectric applications. ⟨111⟩-oriented Ge nanowires with standard diamond structure (3C) undergo a phase transformation toward the hexagonal diamond phase referred as the 2H-allotrope. The phase transformation occurs heterogeneously on shear bands along the length of the nanowire. The structure meets the common phenomenological criteria of a martensitic phase transformation. This point is discussed to initiate an on going debate on the transformation mechanisms. The process results in unprecedented quasiperiodic heterostructures 3C/2H along the Ge nanowire. The thermal stability of those 2H domains is also studied under annealing up to 650 °C by in situ TEM.

Peptidic ligands to control the three-dimensional self-assembly of quantum rods in aqueous media.

The use of peptidic ligands is validated as a generic chemical platform allowing one to finely control the organization in solid phase of semiconductor nanorods originally dispersed in an aqueous media. An original method to generate, on a macroscopic scale and with the desired geometry, three-dimensional supracrystals composed of quantum rods is introduced. In a first step, nanorods are transferred in an aqueous phase thanks to the substitution of the original capping layer by peptidic ligands. Infrared and nuclear magnetic resonance spectroscopy data prove that the exchange is complete; fluorescence spectroscopy demonstrates that the emitter optical properties are not significantly altered; electrophoresis and dynamic light scattering experiments assess the good colloidal stability of the resulting aqueous suspension. In a second step, water evaporation in a microstructured environment yields superstructures with a chosen geometry and in which nanorods obey a smectic B arrangement, as shown by electron microscopy. Incidentally, bulk drying in a capillary tube generates a similar local order, as evidenced by small angle X-ray scattering.

Vertical "III-V" V-shaped nanomembranes epitaxially grown on a patterned Si[001] substrate and their enhanced light scattering.

We report on a new form of III-V compound semiconductor nanostructures growing epitaxially as vertical V-shaped nanomembranes on Si(001) and study their light-scattering properties. Precise position control of the InAs nanostructures in regular arrays is demonstrated by bottom-up synthesis using molecular beam epitaxy in nanoscale apertures on a SiO(2) mask. The InAs V-shaped nanomembranes are found to originate from the two opposite facets of a rectangular pyramidal island nucleus and extend along two opposite <111> B directions, forming flat {110} walls. Dark-field scattering experiments, in combination with light-scattering theory, show the presence of distinctive shape-dependent optical resonances significantly enhancing the local intensity of incident electromagnetic fields over tunable spectral regions. These new nanostructures could have interesting potential in nanosensors, infrared light emitters, and nonlinear optical elements.

Large array of sub-10-nm single-grain Au nanodots for use in nanotechnology.

A uniform array of single-grain Au nanodots, as small as 5-8 nm, can be formed on silicon using e-beam lithography. The as-fabricated nanodots are amorphous, and thermal annealing converts them to pure Au single crystals covered with a thin SiO(2) layer. These findings are based on physical measurements, such as atomic force microscopy (AFM), atomic-resolution scanning transmission electron microscopy, and chemical techniques using energy dispersive X-ray spectroscopy. A self-assembled organic monolayer is grafted on the nanodots and characterized chemically with nanometric lateral resolution. The extended uniform array of nanodots is used as a new test-bed for molecular electronic devices.

100 nm period grating by high-index phase-mask immersion lithography.

The interferogram of a high index phase mask of 200 nm period under normal incidence of a collimated beam at 244 nm wavelength with substantially suppressed zeroth order produces a 100 nm period grating in a resist film under immersion. The paper describes the phase mask design, its fabrication, the effect of electron-beam lithographic stitching errors and optical assessment of the fabricated sub-cutoff grating.