A new (N2H4)WO3 compound has been obtained by mixing WO3 and aqueous hydrazine solution at room temperature for 24 h. The reaction is catalyzed by the presence of lithium. X-ray, synchrotron and neutron diffraction techniques have shown that the material crystallizes in trigonal space group P3221 (No. 154). Chains of distorted WO4 tetrahedra extend along the a axis of the unit cell, linked by a corner-sharing oxygen atom: the N2H4 are in the voids between them. The thermal characterization shows that this new compound is stable up to 220°C, greatly beyond the boiling point of N2H4 (114°C); thus making it a promising candidate for catalysis or trapping applications.

We have used energy-filtered photoemission electron microscopy (PEEM) at the photoemission threshold to carry out a microscopic scale characterization of the surface charge and domain structure of the (001) surface in BaTiO 3 . Signatures of ferroelectric and ferroelastic domains, and tweed, dominate the surface structure of BaTiO 3 at room temperature. The surface ferroic signatures are maintained on heating to temperature (~550 K), well above the transition temperature (393 K). This surface proximity effect provides the mechanism for memory of the bulk ferroelectric domain arrangement up to 150 K above T C and thus can be considered as a robust fingerprint of the ferroelectric state near the surface. Self-reversal of polarization is observed for the tweed below T C and for the surface domains above T C . Annealing at higher temperature triggers the dynamic tweed which in turn allows a full reorganization of the ferroic domain configuration.

Ferroic domain walls could play an important role in microelectronics, given their nanometric size and often distinct functional properties. Until now, devices and device concepts were mostly based on mobile domain walls in ferromagnetic and ferroelectric materials. A less explored path is to make use of polar domain walls in nonpolar ferroelastic materials. Indeed, while the polar character of ferroelastic domain walls has been demonstrated, polarization control has been elusive. Here, we report evidence for the electrostatic signature of the domain-wall polarization in nonpolar calcium titanate (CaTiO3). Macroscopic mechanical resonances excited by an ac electric field are observed as a signature of a piezoelectric response caused by polar walls. On the microscopic scale, the polarization in domain walls modifies the local surface potential of the sample. Through imaging of surface potential variations, we show that the potential at the domain wall can be controlled by electron injection. This could enable devices based on nondestructive information readout of surface potential.

Significant progress in the understanding of surfaces and interfaces of materials for new technologies requires operando studies, i.e., measurement of chemical, electronic, and magnetic properties under external stimulus (such as mechanical strain, optical illumination, or electric fields) applied in situ in order to approach real operating conditions. Electron microscopy attracts much interest, thanks to its ability to determine semiconductor doping at various scales in devices. Spectroscopic photoelectron emission microscopy (PEEM) is particularly powerful since it combines high spatial and energy resolution, allowing a comprehensive analysis of local work function, chemistry, and electronic structure using secondary, core level, and valence band electrons, respectively. Here we present the first operando spectroscopic PEEM study of a planar Si p-n junction under forward and reverse bias. The method can be used to characterize a vast range of materials at near device scales such as resistive oxides, conducting bridge memories and domain wall arrays in ferroelectrics photovoltaic devices.

The understanding of domain structures, specifically domain walls, currently attracts a significant attention in the field of (multi)-ferroic materials. In this article, we analyze contrast formation in full field electron microscopy applied to domains and domain walls in the uniaxial ferroelectric lithium niobate, which presents a large 3.8 eV band gap and for which conductive domain walls have been reported. We show that the transition from Mirror Electron Microscopy (MEM – electrons reflected) to Low Energy Electron Microscopy (LEEM – electrons backscattered) gives rise to a robust contrast between domains with upwards (P up ) and downwards (P down ) polarization, and provides a measure of the difference in surface potential between the domains. We demonstrate that out-of-focus conditions of imaging produce contrast inversion, due to image distortion induced by charged surfaces, and also carry information on the polarization direction in the domains. Finally, we show that the intensity profile at domain walls provides experimental evidence for a local stray, lateral electric field.

A wide band gap semiconducting form of graphene can be produced by growing a buckled form of graphene from a SiC(0001¯) surface randomly seeded with nitrogen. In this work, we show that the disorder observed in this form of graphene can be substantially reduced by pre-patterning the nitrogen seeded SiC surface into trenches. The result of the patterning is highly improved film thickness variations, orientational epitaxy, domain size, and electronic structure. The ordering induced by this patterned growth offers a way to take advantage of the extremely high mobilities and switching speeds in C-face graphene devices while having the thickness uniformity and fabrication scalability normally only achievable for graphene grown on the SiC(0 0 0 1) Si-face.

The discovery of ballistic transport in graphene grown on SiC(0001) sidewall trenches has sparked an intense effort to uncover the origin of this exceptional conductivity. How a ribbons edge termination, width, and topography influence its transport is not yet understood. This work presents the first structural and electronic comparison of sidewall graphene grown with different edge terminations. We show that armchair and zigzag terminated ribbons, grown from SiC, have very different topographies and interact differently with the substrate, properties that are critical to device architecture in sidewall ribbon electronics.

We report on the charge spill-out and work function of epitaxial few-layer graphene on 6 H-SiC(0 0 0 1). Experiments from high-resolution, energy-filtered x-ray photoelectron emission microscopy (XPEEM) are combined with ab initio density functional theory calculations using a relaxed interface model. The work function values obtained from theory and experiments are in qualitative agreement, reproducing the previously observed trend of increasing work function with each additional graphene plane. Electron transfer at the SiC/graphene interface through a buffer layer (BL) causes an interface dipole moment which is at the origin of the graphene work function modulation. The total charge transfer is independent of the number of graphene layers, and is consistent with the constant binding energy of the SiC component of the C 1s core-level, measured by XPEEM. Charge leakage into a vacuum depends on the number of graphene layers, explaining why the experimental, layer-dependent C 1s graphene core-level binding energy shift does not rigidly follow that of the work function. Thus, a combination of charge transfer at the SiC/graphene interface and charge spill-out into the vacuum resolves the apparent discrepancy between the experimental work function and C 1s binding energy.

We present a spatial and wave-vector resolved study of the electronic structure of micron sized ferroelectric domains at the surface of a BaTiO(3)(001) single crystal. The n-type doping of the BaTiO(3) is controlled by in situ vacuum and oxygen annealing, providing experimental evidence of a surface paraelectric-ferroelectric transition below a critical doping level. Real space imaging of photoemission threshold, core level and valence band spectra show contrast due to domain polarization. Reciprocal space imaging of the electronic structure using linearly polarized light provides unambiguous evidence for the presence of both in- and out-of-plane polarization with two- and fourfold symmetry, respectively. The results agree well with first principles calculations.

The application of PhotoEmission Electron Microscopy (PEEM) and Low Energy Electron Microscopy (LEEM) techniques to the study of the electronic and chemical structure of ferroelectric materials is reviewed. Electron optics in both techniques gives spatial resolution of a few tens of nanometres. PEEM images photoelectrons whereas LEEM images reflected and elastically backscattered electrons. Both PEEM and LEEM can be used in direct and reciprocal space imaging. Together, they provide access to surface charge, work function, topography, chemical mapping, surface crystallinity and band structure. Examples of applications for the study of ferroelectric thin films and single crystals are presented.

Graphene quantum dots, nanoribbons, and nanographene are great promising in various applications owing to the quantum confinement and edge effects. Here we evidence the presence of epitaxial nanographene on SiC. Morphology and electronic structure of the graphene layers have been analyzed by SPELEEM. Using Scanning Tunneling Microscopy, we show that the increase of relative number of clusters carbon enabled the observation of nanographene, the diameter of which was around 20 nm. This nanographene shows a honeycomb structure at atomic level. The local chemical and electronic properties of the sample have been determined by photoelectron spectroscopy using synchrotron radiation.

In alkaline aqueous medium (pH 9), potassium ferricyanide was used as an oxidizing agent on InP. This electroless process was successfully controlled by capacity measurements, AFM and XPS analyses. For the first time, the chemical stability of the oxide has been studied against the strongest reducing agent in liquid ammonia (−50°C): the solvated electron. It was obtained in two ways; an electroless process which involved the addition of metallic potassium and by cathodic galvanostatic treatment on InP in neutral medium. As a first result, the electroless process required a strong rinsing step of the surface by pure liquid ammonia. As a second result, the galvanostatic process gave also promising results. A significant decrease of the amount of oxide was evidenced by capacity measurements, AFM and XPS analyses.

The effect of oxygen adsorption on the local structure and electronic properties of monolayer graphene grown on SiC (0001) has been studied by means of low-energy electron microscopy (LEEM), microprobe low-energy electron diffraction (μLEED), and microprobe angle resolved photoemission (μARPES). We show that the buffer layer of epitaxial graphene on SiC (0001) is partially decoupled after oxidation. The monitoring of the oxidation process demonstrates that the oxygen saturates the Si dangling bonds, breaks some Si–C bonds at the interface, and intercalates the graphene layer. Accurate control over the oxidation parameters enables us to tune the charge density modulation in the layer.

In this letter we report on transport measurements of epitaxial graphene on SiC(0001) with oxygen adsorption. In a $50\times 50 \mu\mathrm{m^2}$ size Hall bar we observe the half-integer quantum Hall effect with a transverse resistance plateau quantized at filling factor around $\nu = 2$, an evidence of monolayer graphene. We find low electron concentration of $9\times 10^{11} \textrm{cm}^{-2}$ and we show that a doping of $10^{13}\textrm{cm}^{-2}$ which is characteristic of intrinsic epitaxial graphene can be restored by vacuum annealing. The effect of oxygen adsorption on carrier density is confirmed by local angle-resolved photoemission spectroscopy measurements. These results are important for understanding oxygen adsorption on epitaxial graphene and for its application to metrology and mesoscopic physics where a low carrier concentration is required.

This paper is focused on a new route to synthesize Mn3O4 nanoparticles by alkalisation by sodium hydroxide on a manganeous solution at room temperature. The precipitates obtained at different pH values have been characterized by XRD and TEM. Since the first addition of sodium hydroxide, a white Mn(OH)2 precipitate appears. At pH=7, γ-MnOOH phase is predominant with needle like shaped particles. At pH=10, hausmanite nanoparticles, which exhibits well defined cubic shape in the range 50–120nm are obtained. This new precipitation route is a fast and easy environmentally friendly process to obtain well crystallized hausmanite nanoparticles.

An anodic photo-galvanostatic treatment at low current density (1μA·cm−2) is carried out on n-InP semiconductor in liquid ammonia (223K). The gradual chemical evolution of the surface is studied as a function of the anodic charge. Proof and reproducibility of the chemical transformation of the surface are clearly evidenced by X-ray photoelectron spectroscopy (XPS) analyses. Like by cyclic voltammetry, the perfect coverage of the InP surface by a thin phosphazene like film is also revealed by XPS data. However, a low anodic charge (≈0.5mC·cm−2) is required by photo-galvanostatic treatment while a higher anodic charge (≈7mC·cm−2) is involved by cyclic voltammetry. The excess of charge could be related to ammonia oxidation during the formation of the passivating film. This result proves the electrochemical oxidation of the solvent as a determinant step of the mechanism film formation.

The imaging of surfaces using the PhotoElectron Emission Microscopy (PEEM) technique has recently received considerable interest, mainly thanks to the use of high brilliance synchrotron radiation which facilitates the study of surface properties and chemical selectivity. By inserting a transfer lens in the optical column of a high transmission and full energy-filtering PEEM, it is possible to image the back focal plane, named k-PEEM imaging mode. Hence, the corresponding image shows the angular distribution of the emitted photoelectrons for a given kinetic energy. By varying the kinetic energy, the complete energy filtering provides full 2D cuts of the band structure in reciprocal space. In this paper, we present the principles and the capabilities of this new imaging mode, and compare it to the standard ARPES technique. Then, we present results obtained on a model sample: Ag(100), and on a technological sample, epitaxial graphene on SiC(0001), highlighting the potential of this new imaging mode for the spatially resolved characterization of the electronic structure of monocrystalline materials in devices.

A protective monolayer "phosphazene" like film on InP has been already successfully evidenced by a controlled anodic process in liquid ammonia (NH3 Liq.). In order to understand the formation mechanism of this passivating film, in-situ comparisons of electrochemical interface responses are performed as well on InP as GaAs. Current-voltage and interfacial capacity measurements are explored on both semiconductors. Similarities of electrochemical behaviours between these two semiconductors are striking. But contrary to InP, the initial surface state is electrochemically recovered by an in-situ cathodic treatment on GaAs. This absolute reversible electrochemical behaviour is definitively significant for GaAs.