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We explore the possibility to perform an in situ transmission electron microscopy (TEM) thermoelectric characterization of materials. A differential heating element on a custom in situ TEM microchip allows to generate a temperature gradient across the studied materials, which are simultaneously measured electrically. A thermovoltage was induced in all studied devices, whose sign corresponds to the sign of the Seebeck coefficient of the tested materials. The results indicate that in situ thermoelectric TEM studies can help to profoundly understand the interplay between the thermoelectric properties on one side and the structure/composition of the materials down to the atomic level on the other side, including grain boundaries, dopants or crystal defects. We propose an improved in situ TEM microchip design, which should facilitate a full quantitative measurement of the induced temperature gradient, the electrical and thermal conductivities, as well as the Seebeck coefficient., Comment: 12 pages, 5 figures

Layered CoO$_2$ is of great interest for its promising properties but is meta-stable in its bulk form. CoO$_2$ was synthesized by converting the quasi-one-dimensional crystal structure of bulk Ca$_3$Co$_2$O$_6$ via a hydrothermal treatment. The resulting nanostructures were predominantly nanoscrolls with very thin walls, which exhibit long-term stability. A detailed structural investigation reveals that the CoO$_2$ is found to crystallize in monoclinic form, similar to the related CaCoO$_2$-CoO$_2$ misfit structure. Individual nanoscrolls are characterized electrically and show a p-type semiconducting nature with a high current-carrying capacity of 4$\cdot$10$^5$ A cm$^{-2}$ and an extremely high breakdown voltage of up to 270 kV/cm. The results demonstrate the possibility to stabilize meta-stable materials in low-dimensional forms and a promising application of the nanoscrolls as interconnect in high-voltage electronic circuitry.

Although in-situ transmission electron microscopy (TEM) of nanomaterials has been gaining importance in recent years, difficulties in sample preparation have limited the number of studies on electrical properties. Here, a support-based preparation method of individual 1D and 2D materials is presented, which yields a reproducible sample transfer for electrical investigation by in-situ TEM. Using a mechanically rigid support grid allows the reproducible transfer and contacting to in-situ chips by focused ion beam with minimum damage and contamination. The transfer quality is assessed by exemplary studies of different nanomaterials, including a monolayer of WS2. Preliminary results from in-situ test experiments give an overview of possible studies, which concern the interplay between structural properties and electrical characteristics on the individual nanomaterial level as well as failure analysis under electrical current or studies of electromigration, Joule heating and related effects. The TEM measurements can be enriched by additional correlative microscopy techniques, which allow the study with a spatial resolution in the range of a few microns. Although developed for in-situ TEM, the present transfer method is also applicable to transferring nanomaterials to similar chips for performing further studies or even for using them in potential electrical/optoelectronic/sensing devices., Comment: 17 pages, 7 figures

The sky is the limit with regards to the societal impact nanomaterials can have on our lives. However, in this study we show that their potential is out of this world. The planet Mars has an abundant source of calcium sulfate minerals and in our work, we show that these deposits can be the basis of transformative nanomaterials to potentially support future space endeavors. Through a scalable eco-friendly liquid processing technique performed on two common terrestrial gypsum, our simple method presented a cost-efficient procedure to yield the commercially valuable intermediate phase of gypsum, known as bassanite. Through the liquid exfoliation of bassanite powders, suspensions of large aspect ratio anhydrite nanobelts with long-term stability were characterized through scanning electron microscopy and Raman spectroscopy. Transmission electron microscopy showed nanobelts to have a mesocrystal structure, with distinct nanoparticle constituents making up the lattice. Unexpectedly, anhydrite nanobelts had remarkable electronic properties, namely a bandgap that was easily tuned between semiconducting (~2.2 eV) and insulating (~4 eV) behaviors through dimensional control measured via atomic force microscopy. To demonstrate the application potential of our nanobelts; optoelectronic, electrochemical and nanocomposite measurements were made. For the hydrogen evolution reaction and mechanical reinforcement, selenite-based anhydrite nanobelts displayed superlative performances.

We show that thin layers of EuO, a ferromagnetic insulator, can be achieved by topotactic reduction under titanium of a Eu2O3 film deposited on top of a graphene template. The reduction process leads to the formation of a 7-nm thick EuO smooth layer, without noticeable structural changes in the underlying chemical vapor deposited (CVD) graphene. The obtained EuO films exhibit ferromagnetism, with a Curie temperature that decreases with the initially deposited Eu2O3 layer thickness. By adjusting the thickness of the Eu2O3 layer below 7 nm, we promote the formation of EuO at the very graphene interface: the EuO/graphene heterostructure demonstrates the anomalous Hall effect (AHE), which is a fingerprint of proximity-induced spin polarization in graphene. The AHE signal moreover persists above Tc up to 350K due to a robust super-paramagnetic phase in EuO. This original high-temperature magnetic phase is attributed to magnetic polarons in EuO: we propose that the high strain in our EuO films grown on graphene stabilizes the magnetic polarons up to room temperature. This effect is different from the case of bulk EuO in which polarons vanish in the vicinity of the Curie temperature Tc= 69K., Comment: 29 pages

The control of the magnetization inversion dynamics is one of the main challenges driving the design of new nanostructured magnetic materials for magnetoelectronic applications. Nanoparticles with onion-like architecture offer a unique opportunity to expand the possibilities allowing to combine different phases at the nanoscale and also modulate the coupling between magnetic phases by introducing spacers in the same structure. Here we report the fabrication, by a three-step high temperature decomposition method, of Fe3O4/MgO/CoFe2O4 onio-like nanoparticles and their detailed structural analysis, elemental compositional maps and magnetic response. The core/shell/shell nanoparticles present epitaxial growth and cubic shape with overall size of (29+-6) nm. These nanoparticles are formed by cubic iron oxide core of (22+-4) nm covered by two shells, the inner of magnesium oxide and the outer of cobalt ferrite of ~1 and ~2.5 nm of thickness, respectively. The magnetization measurements show a single reversion magnetization curve and the enhancement of the coercivity field, from HC~608 Oe for the Fe3O4/MgO to HC~5890 Oe to the Fe3O4/MgO/CoFe2O4 nanoparticles at T=5 K, ascribed to the coupling between both ferrimagnetic phases with a coupling constant of =2 erg/cm2. The system also exhibits exchange bias effect, where the exchange bias field increases up to HEB~2850 Oe at 5 K accompanied with the broadening of the magnetization loop of HC~6650 Oe. This exchange bias effect originates from the freezing of the surface spins below the freezing temperature TF=32 K that pinned the magnetic moment of the cobalt ferrite shell., Comment: 39 pages, 8 figures

Electrochemical reactions for hydrogen and hydrogen peroxide production are essential for energy conversion to diminish energy crisis, but still lack efficient electrocatalysts. Development of non\-noble metal bifunctional electrocatalysts for hydrogen evolution and 2e oxygen reduction reaction to ease reaction kinetics is a challenging task. Integration of single components by employing easy strategies provides a key\-step towards the realization of highly active electrocatalysts. In this vein, MoSe2 owns catalytic active sites and high specific surface area but suffers from insufficient conductivity and high catalytic performance that noble\-metals provide. Herein, MoSe2 was used as a platform for the incorporation of manganese metallated porphyrin. The developed hybrid, namely MoSe2\-MnP, by the initial metal\-ligand coordination and the subsequent grafting with MnP was fully characterized and electrochemically assessed. The bifunctional electrocatalyst lowered the overpotential toward hydrogen evolution, improved reaction kinetics and charge transfer processes and was extremely stable after 10000 ongoing cycles. Simultaneously, rotating ring disk electrode analysis showed that oxygen reduction proceeds through the 2e pathway for the selective production of hydrogen peroxide with a high yield of 97 percent. The new facile modification route can be applied in diverse transition metal dichalcogenides and will help the development of new advanced functional materials.

In the present work, some MoS2 and WS2 nanosheets were prepared and characterized. Depending on the preparation procedures, trigonal prismatic (2H) or octahedral (1T) coordination of the metal atoms were obtained, exhibiting metallic (1T) or semiconducting (2H) character. Both MoS2 and WS2 nanosheets were found exhibiting large nonlinear optical (NLO) response, strongly dependent on their metallic (1T) or semiconducting (2H) character. So, the semiconducting character 2H-MoS2 and 2H-WS2 exhibit positive nonlinear absorption and strong self-focusing, while their metallic character counterparts exhibit strong negative nonlinear absorption and important self-defocusing. In addition, the semiconducting MoS2 and WS2 were found exhibiting important and very broadband optical limiting action extended from 450 to 1750 nm. So, by selecting the crystalline phase of the nanosheets, i.e., their semiconduction/metallic character, their NLO response can be greatly modulated. The results of the present work demonstrate unambiguously that the control of the crystalline phase of MoS2 and WS2 provides an efficient strategy for 2D nanostructures with custom made NLO properties for specific optoelectronic and photonic applications.

Morphological control at the nanoscale paves the way to fabricate nanostructures with desired plasmonic properties. We report the nanoengineering of plasmon resonances in 1D hollow nanostructures of two different AuAg nanotubes; completely hollow nanotubes and hybrid nanotubes comprising solid Ag and hollow AuAg segments. Spatially resolved plasmon mapping by electron energy loss spectroscopy (EELS) revealed the presence of high order resonator-like modes and localized surface plasmon resonance (LSPR) modes in both nanotubes. Experimental findings are accurately correlated with boundary element method (BEM) simulations, where both experiments and simulations revealed that the plasmon resonances are intensely present inside the nanotubes due to plasmon hybridization. Based on the experimental and simulated results reported, we show that the novel hybrid AuAg nanotubes possess two significant coexisting features: (i) LSPRs have been generated distinctively from the hollow and solid parts of the hybrid AuAg nanotube, which opens the way to control a broad range of plasmon resonances with one single nanostructure and (ii) the periodicity of the high-order modes are disrupted due to the plasmon hybridization by the interaction of solid and hollow parts, resulting in an asymmetrical plasmon distribution in 1D nanostructures. The asymmetry could be modulated/engineered leading to control coded plasmonic nanotubes.

Photo-rechargeable (solar) battery can be considered as an energy harvesting cum storage system, where it can charge the conventional metal-ion battery using light instead of electricity, without having other parasitic reactions. Here we demonstrate a two-electrode lithium ion solar battery with multifaceted TiS2-TiO2 hybrid sheets as cathode. Choice of TiS2-TiO2 electrode ensures the formation of a type II semiconductor heterostructure while the lateral heterostructure geometry ensures high mass/charge transfer and light interactions with the electrode. TiS2 has a higher lithium binding energy (1.6 eV) than TiO2 (1.03 eV), ensuring the possibilities of higher amount of Li ion insertion to TiS2 and hence the maximum recovery with the photocharging, as further confirmed by the experiments. Apart from the demonstration of solar solid-state batteries, the charging of lithium ion full cell with light indicates the formation of lithium intercalated graphite compounds, ensuring the charging of the battery without any other parasitic reactions at the electrolyte or electrode-electrolyte interfaces. Possible mechanisms proposed here for the charging and discharging processes of solar batteries, based on our experimental and theoretical results, indicate the potential of such systems in forthcoming era of renewable energies.

Designing electrocatalysts for HER in alkaline conditions to overcome the sluggish kinetics associated with the additional water dissociation step is a recognized challenge in promoting the hydrogen economy. To this end, delicately tuning the atomic-scale structure and surface composition of nanoparticles is a common strategy and, specifically, making use of hybrid structures, can produce synergistic effects that lead to highly active catalysts. Here, we present a core-shell catalyst of Ag@MoS$_2$ that shows promising results towards the hydrogen evolution reaction (HER) in both 0.5 M H2SO4 and 0.5 M KOH. In this hybrid structure, the MoS$_2$ shell is strained and defective, and charge transfer occurs between the conductive core and the shell, contributing to the electrocatalytic activity. The shelling process results in a large fraction of Ag$_2$S in the cores, and adjusting the relative fractions of Ag, Ag$_2$S, and MoS$_2$ leads to improved catalytic activity and fast charge-transfer kinetics. We suggest that the enhancement of alkaline HER is associated with a cooperative effect of the interfaces, where the Ag(I) sites in Ag$_2$S drive the water dissociation step, and the formed hydrogen subsequently recombines on the defective MoS$_2$ shell. This study demonstrates the benefits of hybrid structures as functional nanomaterials and provides a scheme to activate MoS$_2$ for HER in alkaline conditions.

Opto-spintronics is an emerging field where ultra-thin magnetic-semiconductors having high spin-valley coupling play an important role. Here, we demonstrate substitutional vanadium (V) doping in MoS$_2$ lattice in different extent, leading to the coexistence of photoluminescence (PL), valleypolarization (~32%), and valley splitting (~28 meV shift in PL with helicity $\sigma^+$ and $\sigma^-$ of light excitation). A large V doping causes semiconductor to metal transition in MoS$_2$ but with medium level causing the existence of photoluminescence with high spin polarization. The ambipolar nature of medium level V doped MoS$_2$ is shown here indicating its potential as an opto-electronic material. The presence of V-dopants and their different level of content are proven by both spectroscopic and microscopic methods.A detailed temperature and power dependent photoluminescence studies along with density functional theory-based calculations in support unravels the emergence of the co-existence of spin-valley coupling and photoluminescence. This study shows the potential of doping MoS$_2$ for deriving new materials for next generation room temperature opto-spintronics.

We explore the possibility of applying physical phase plates (PPs) in combination with aberration-corrected transmission electron microscopy. Phase-contrast transfer characteristics are calculated and compared for a thin-film based Zernike PP, a hole-free (HF) or Volta PP and an electrostatic Zach PP, considering their phase-shifting properties in combination with partial spatial coherence. The effect of slightly converging illumination conditions, often used in high-resolution applications, on imaging with PPs is discussed. Experiments with an unheated Zernike PP applied to various nanomaterial specimens and a qualitative analysis clearly demonstrates the general compatibility of PPs and aberration-corrected transmission electron microscopy. Calculations and experiments show the benefits of the approach, among which is a strong phase-contrast enhancement of a large range of spatial frequencies. This allows the simultaneous imaging of atomic-resolution structures and morphological features at the nanometer scale, with maximum phase contrast. The calculations can explain why the HFPP damps contrast transfer at higher spatial frequencies., Comment: Revised version submitted to Ultramicroscopy 21 pages, 14 figures

Nanoparticles (NPs) which combine several magnetic phases offer wide perspectives for cutting edge applications because of the high modularity of their magnetic properties. Besides the addition of the magnetic characteristics intrinsic to each phase, the interface that results from core-shell and, further, from onion structures leads to synergistic properties such as magnetic exchange coupling. Such a phenomenon is of high interest to overcome the superparamagnetic limit of iron oxide NPs which hampers potential applications. In this manuscript, we report on the design of NPs with an onion-like structure which have been scarcely reported yet. These NPs consist in a Fe(3_delta)O4 core covered by a first shell of CoFe2O4 and a second shell of Fe(3-delta)O4. They were synthesized by a multi-step seed mediated growth approach. Although TEM micrographs clearly show the growth of each shell from the iron oxide core, core sizes and shell thicknesses markedly differ from what is suggested by the size increase. We investigated very precisely the structure of NPs in performing high resolution (scanning) TEM imaging and GPA. The chemical composition and spatial distribution of atoms were studied by EELS. The chemical environment and oxidation state of cations were investigated by M\"ossbauer spectrometry, soft XAS and XMCD. These techniques allowed us to estimate the increase of Fe2+ content in the iron oxide core of the core@shell structure and the increase of the cobalt ferrite shell thickness in the core@shell@shell one, while the iron oxide shell appears to be much thinner than expected. Thus, the modification of the chemical composition as well as the size of the Fe(3-delta)O4 core and the thickness of the cobalt ferrite shell have a high impact on the magnetic properties. Furthermore, the growth of the iron oxide shell also markedly modifies the magnetic properties of the core-shell NPs.

The realization of novel heterostructures arising from the combination of nanomaterials is an effective way to modify their physicochemical and electrocatalytic properties, giving them enhanced characteristics stemming from their individual constituents. Interfacing carbon nanohorns (CNHs) possessing high porosity, large specific surface area and good electrical conductivity, with MoS2 owning multiple electrocatalytic active sites but lacking significant conductivity, robust interactions and effective structure, can be a strategy to boost the electrocatalytic reduction of protons to molecular hydrogen. Herein, we covalently introduce, in a stepwise approach, complementary functional groups at the conical tips and sidewalls of CNHs, along with the basal plane of MoS2, en route the construction of 3D-2D CNH-MoS2 heterostructures. The increased MoS2 loading onto CNHs, improving and facilitating charge delocalization and transfer in neighboring CNHs, along with the plethora of active sites, results in excellent electrocatalytic activity for protons reduction same to that of commercial Pt/C. We have registered minute overpotential, low Tafel slope and small charge-transfer resistance for electrocatalyzing the evolution of hydrogen from the newly prepared heterostructure of 0.029 V, 71 mV/dec and 34.5 {\Omega}, respectively. Furthermore, the stability of the 3D-2D CNH-MoS2 heterostructure was validated after performing 10,000 ongoing electrocatalytic cycles.

The development of noble-metal free electrocatalysts is of high importance for clean energy conversion applications. MoS$_2$ has been considered as a promising low cost catalyst for the hydrogen evolution reaction (HER), however its activity is limited by poor conductivity and low abundance of active sites. Moreover, its suitability as an effective catalyst for other reactions, in particluar the oxygen reduction reaction (ORR), was hardly explored to date. Herein, we show hybrid nanostructures of shelled CuS particles with MoS$_2$ layers, which produces several outcomes: The MoS$_2$ shell is strained and defective, and charge transfer from the core to MoS$_2$ occurs, enabling activation of the basal plane of MoS$_2$. Changing the feed ratio of the precursors led to control over morphology, such that the wrapping of the cores with the shell was continuously varied and characterized. We found an optimal hybrid structure, which provided high electrochemical active surface area and fast charge transfer kinetics, leading to improved activity not only towards HER (overpotential of 225 mV at 10 mA cm$^{-1}$), but also for the sluggish ORR (onset potential 0.87 V vs RHE)., Comment: 26 pages

Numerous physical phase plates (PP) for phase-contrast enhancement in transmission electron microscopy (TEM) have been proposed and studied with the hole-free or Volta PP having a high impact and interest in recent years. This study is concerned with comparative TEM image simulations considering realistic descriptions of various PP approaches and samples from three different fields of application covering a large range of object sizes. The simulated images provide an illustrative characterization of the typical image appearance and common artifacts of the dfferent PPs and the influence of simulation parameters especially important for PP simulations. A quantitative contrast analysis shows the superior phase-shifting properties of the hole-free phase plate for biological applications and the benefits of adjustable phase plates. The application of PPs in high-resolution TEM imaging, especially of weak-phase objects such as (atomically thin) 2D materials, is shown to increase image interpretability. The software with graphical user interface written and used for the presented simulations is available for free usage.

Graphene oxide (GO) is reduced by Joule heating using in-situ transmission electron microscopy (TEM). The approach allows the simultaneous study of GO conductivity by electrical measurements and of its composition and structural properties throughout the reduction process by TEM, electron diffraction and electron energy-loss spectroscopy. The small changes of GO properties observed at low applied electric currents are attributed to the promotion of diffusion processes. The actual reduction process starts from an applied power density of about 2 1014 Wm-3 and occurs in a highly uniform and localized manner. The conductivity increases more than 4 orders of magnitude reaching a value of 3 103 Sm-1 with a final O content of less than 1%. We discuss differences between the reduction by thermal annealing and Joule heating.

This study reports on the plasmon-mediated remote Raman sensing promoted by specially designed coaxial nanowires. This unusual geometry for Raman study is based on the separation, by several micrometres, of the excitation laser spot, on one tip of the nanowire, and the Raman detection at the other tip. The very weak efficiency of Raman emission makes it challenging in a remote configuration. For the proof-of-concept, we designed coaxial nanowires consisting in a gold core to propagate the surface plasmon polaritons and a Raman-emitting shell of poly(3,4-ethylene-dioxythiophene). The success of the fabrication was demonstrated by correlating, for the same single nanowire, a morphological analysis by electron microscopy and Raman spectroscopy analysis. Importantly for probing remote-Raman effect, the original hard template-based process allows to control the location of the polymer shell all along the nanowire, or only close to one or the two nanowire tips. Such all-in-one single nanowires could have applications in the remote detection of photo-degradable substances and for exploring 1D nanosources for integrated photonic and plasmonic systems., Comment: 8 pages, 6 figures, Supplementary Information available

Few- and single-layer MoS2 host substantial densities of defects. They are thought to influence the doping level, the crystal structure, and the binding of electron-hole pairs. We disentangle the concomitant spectroscopic expression of all three effects and identify to what extent they are intrinsic to the material or extrinsic to it, i.e., related to its local environment. We do so by using different sources of MoS2 -- a natural one and one prepared at high pressure and high temperature -- and different substrates bringing varying amounts of charged impurities and by separating the contributions of internal strain and doping in Raman spectra. Photoluminescence unveils various optically active excitonic complexes. We discover a defect-bound state having a low binding energy of 20 meV that does not appear sensitive to strain and doping, unlike charged excitons. Conversely, the defect does not significantly dope or strain MoS2. Scanning tunneling microscopy and density functional theory simulations point to substitutional atoms, presumably individual nitrogen atoms at the sulfur site. Our work shows the way to a systematic understanding of the effect of external and internal fields on the optical properties of two-dimensional materials.

We propose an innovative, easy-to-implement approach to synthesize large-area singlecrystalline graphene sheets by chemical vapor deposition on copper foil. This method doubly takes advantage of residual oxygen present in the gas phase. First, by slightly oxidizing the copper surface, we induce grain boundary pinning in copper and, in consequence, the freezing of the thermal recrystallization process. Subsequent reduction of copper under hydrogen suddenly unlocks the delayed reconstruction, favoring the growth of centimeter-sized copper (111) grains through the mechanism of abnormal grain growth. Second, the oxidation of the copper surface also drastically reduces the nucleation density of graphene. This oxidation/reduction sequence leads to the synthesis of aligned millimeter-sized monolayer graphene domains in epitaxial registry with copper (111). The as-grown graphene flakes are demonstrated to be both single-crystalline and of high quality., Comment: Main text (18 pages, 6 figures) + supplementary information (26 pages, 15 figures)

The optical and morphological properties of hollow gold nanoparticles (HGNPs) can be finely modified by employing Poly-L-Lysine hydrobromide (PLL), an homo poly aminoacid of the L-lysine, used as reducer and stabilizer. We investigate locally the plasmonic response of these nanostructures by electron energy loss spectroscopy (EELS). The plasmon excitations are interpreted by discrete dipolar approximation (DDA) simulations. We demonstrate that this controlled top-down morphological modification a fine tuning of the optical response is possible. Unlike the traditional lithographic techniques, this has been achieved in a controlled manner using wet chemistry, enabling the potential use of these nanostructures for a broad range of plasmonic applications, including biomedicine, catalysis and quantum communications.

Having access to the chemical environment at the atomic level of a dopant in a nanostructure is crucial for the understanding of its properties. We have performed atomically-resolved electron energy-loss spectroscopy to detect individual nitrogen dopants in single-walled carbon nanotubes and compared with first principles calculations. We demonstrate that nitrogen doping occurs as single atoms in different bonding configurations: graphitic-like and pyrrolic-like substitutional nitrogen neighbouring local lattice distortion such as Stone-Thrower-Wales defects. The stability under the electron beam of these nanotubes has been studied in two extreme cases of nitrogen incorporation content and configuration. These findings provide key information for the applications of these nanostructures., Comment: 25 pages, 13 figures

Carbon nanotubes are the focus of considerable research efforts due to their fascinating physical properties. They provide an excellent model system for the study of one dimensional materials and molecular electronics. The chirality of nanotubes can lead to very different electronic behaviours, either metallic or semiconducting. Their electronic spectrum consists of a series of Van Hove singularities defining a bandgap for semiconducting tubes and molecular orbitals at the corresponding energies. A promising way to tune the nanotubes electronic properties for future applications is to use doping by heteroatoms. Here we report on experimental investigation of the role of many-body interactions in nanotube bandgaps, the visualization in direct space of the molecular orbitals of nanotubes and the properties of nitrogen doped nanotubes using scanning tunneling microscopy and transmission electron microscopy as well as electron energy loss spectroscopy.