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Hybrid materials taking advantage of the different physical properties of materials are highly attractive for numerous applications in today's science and technology. Here, it is demonstrated that epitaxial bi‐domain III–V/Si are hybrid structures, composed of bulk photo‐active semiconductors with 2D topological semi‐metallic vertical inclusions, endowed with ambipolar properties. By combining structural, transport, and photoelectrochemical characterizations with first‐principle calculations, it is shown that the bi‐domain III–V/Si materials are able within the same layer to absorb light efficiently, separate laterally the photo‐generated carriers, transfer them to semimetal singularities, and ease extraction of both electrons and holes vertically, leading to efficient carrier collection. Besides, the original topological properties of the 2D semi‐metallic inclusions are also discussed. This comb‐like heterostructure not only merges the superior optical properties of semiconductors with good transport properties of metallic materials, but also combines the high efficiency and tunability afforded by III–V inorganic bulk materials with the flexible management of nano‐scale charge carriers usually offered by blends of organic materials. Physical properties of these novel hybrid heterostructures can be of great interest for energy harvesting, photonic, electronic or computing devices., Here, it is demonstrated that epitaxial bi‐domain III–V/Si are hybrid structures, composed of bulk photo‐active semiconductors with 2D topological semi metallic vertical inclusions, endowed with ambipolar properties. Operating III–V/Si photoelectrodes confirm that this hybrid material can by itself photogenerate and laterally separate carriers, which are efficiently extracted afterward from the photoelectric device.

The mechanisms governing the formation of Schottky barriers at graphene/hydrogen-passivated silicon interfaces where the graphene plays the role of a two-dimensional (2D) metal electrode have been investigated by means of x-ray photoemission spectroscopy and density functional theory (DFT) calculations. To control the graphene work function without altering either the structure or the band dispersion of graphene we used a method that consists in depositing small amounts of gold forming clusters on the graphene/hydrogen-passivated silicon system under an ultra-high-vacuum environment. We observe from experimental measurements that the Fermi level is mainly free from pinning at the graphene/hydrogen-silicon interface whereas for a semi-infinite metal on silicon the Fermi level is almost fully pinned. This alleviation of the Fermi level pinning observed with the graphene layer is explained by DFT calculations showing that the graphene and the semiconductor are decoupled and that the metal-induced gap states (MIGS) density at the silicon midgap at the interface is very low ($l5\ifmmode\times\else\texttimes\fi{}{10}^{10}\phantom{\rule{0.16em}{0ex}}\mathrm{states}/(\mathrm{eV}\phantom{\rule{0.28em}{0ex}}\mathrm{c}{\mathrm{m}}^{2})$]. The important conclusion that stems from the DFT results analysis is that the low MIGS density at the semiconductor midgap is related to the 2D nature of the graphene layer. More precisely, the MIGS density is low owing to the lack of propagating states perpendicular to the graphene layer. This finding brings important information to understand the mechanisms that govern the formation and the electronic properties of Schottky barriers at 2D-metal/three-dimensional-semiconductor interfaces.

International audience; Fermi level pinning at metal/semiconductor interfaces forbids a total control over the Schottky barrier height. 2D materials may be an interesting route to circumvent this problem. As they weakly interact with their substrate through Van der Waals forces, deposition of 2D materials avoids the formation of the large density of state at the semiconductor interface often responsible for Fermi level pinning. Here, we demonstrate the possibility to alleviate Fermi-level pinning and reduce the Schottky barrier height by the association of surface passivation of germanium with the deposition of 2D graphene

International audience; The control of tunnel contact resistance is of primary importance for semiconductor-based spintronic devices. This control is hardly achieved with conventional oxide-based tunnel barriers due to deposition-induced interface states. Manipulation of single 2D atomic crystals (such as graphene sheets) weakly interacting with their substrate might represent an alternative and efficient way to design new heterostructures for a variety of different purposes including spin injection into semiconductors. In the present paper, we study by x-ray photoemission spectroscopy the band alignments and interface chemistry of iron-graphene-hydrogenated passivated silicon (001) surfaces for a low and a high n-doping concentration. We find that the hydrogen passivation of the Si(001) surface remains efficient even with a graphene sheet on the Si(001) surface. For both doping concentrations, the semiconductor is close to flat-band conditions which indicates that the Fermi level is unpinned on the semiconductor side of the Graphene/Si(001):H interface. When iron is deposited on the graphene/Si(001):H structures, the Schottky barrier height remains mainly unaffected by the metallic overlayer with a very low barrier height for electrons, a sought-after property in semiconductor based spintronic devices. Finally, we demonstrate that the graphene layer intercalated between the metal and semiconductor also serves as a protection against iron-silicide formation even at elevated temperatures preventing from the formation of a Si-based magnetic dead layer. © 2016 Author(s).

International audience; In the field of organic and molecular electronics at monolayer coverage, the need for abrupt and well-controlled top metal contacts is a key point. A general method which provides reliable molecular junctions with most metals remains to be found. In this paper we show that reliable molecular junctions Au/hexadecanethiol/n-GaAs(100) are obtained using buffer-layer-assisted growth (BLAG). They show in hot electron transport measurements at the nanoscale a tunnel regime through the organic monolayer with a full spatial uniformity. Using ballistic electron emission microscopy (BEEM) in the spectroscopic mode as well as photoemission and C(V)-transport measurements, we draw a coherent band alignment scheme of the whole heterostructure at the nanoscale and at the macroscopic scale. Through this study, the BLAG method appears as a general method that should work for contacting organic monolayers with most metals. © 2016 American Chemical Society.

International audience; We present an experimental investigation of the interface electronic structure of thin MgO films epitaxially grown on Ag(001) by x-ray and ultraviolet photoemission spectroscopy as a function of the oxide growth conditions. It is shown that the Schottky barrier height at MgO/metal interface can be tuned over 0.7 eV by a modification of the oxygen partial pressure or the sample temperature. These experimental results are explained in the framework of the extended Schottky-Mott model and the MgO-induced polarization effect by Mg enrichment of the silver surface region.

International audience; The transport mechanisms through MgO ultrathin layers (0.5-1.2 nm) deposited on n-type doped GaAs(001) layers have been studied. In order to favor field emission (FE) across the junctions, a high doping concentration layer in vicinity of the semiconductor surfaces has been included. Varying doping concentration of the underlying GaAs layer we find that the dominant transport mechanism is either the variable-range hopping mechanism or a thermionic emission-like process instead of the FE process. The observation of such mechanisms can be explained by the fact that during the MgO deposition, defect states are introduced in the semiconductor band gap.

International audience; The electronic band structure and the work function of MgO thin films epitaxially grown on Ag(001) have been investigated using x-ray and ultraviolet photoelectron spectroscopy for various oxide thicknesses. The deposition of thin MgO films on Ag(001) induces a strong diminution in the metal work function. The p-type Schottky barrier height is constant at 3.85+/-0.10 eV above two MgO monolayers and the experimental value of the ionization potential is 7.15+/-0.15 eV. Our results are well consistent with the description of the Schottky barrier height in terms of the Schottky-Mott model corrected by an MgO-induced polarization effect.

International audience; We report on ballistic electron-emission spectroscopy on high-quality Au(110)/GaAs(001) and Fe(001)/GaAs(001) Schottky contacts. For the Au(110)/GaAs(001) interface, the ballistic current is characterized by a strong electron injection in the L valley of the GaAs conduction band. This remarkable spectroscopic feature is absent for the Fe(001)/GaAs(001) interface. These observations are explained by the different electronic structures in the two metal layers, assuming conservation of the electron transverse momentum at the metal/semiconductor epitaxial interfaces. Conversely, this comparative study suggests that the technique can be used for the analysis of local electronic states propagating in the metal films.

International audience; The spatially resolved electronic structure of the epitaxial Au/MgO/GaAs(001) tunnel junction has been studied by ballistic electron emission microscopy. The Schottky barrier height of Au on the MgO/GaAs heterostructure is determined to be 3.90 eV, in good agreement with spatially averaged x-ray photoelectron spectroscopy measurements. Locally, two well-defined conduction channels are observed for electrons energies of 2.5 and 3.8 eV, i.e., below the conduction band minimum of the oxide layer. These conduction channels are attributed to band of defect states in the band-gap of the tunnel barrier related to oxygen vacancies in the MgO layer. These defect states are responsible for the low barrier height measured on magnetic tunnel junctions with epitaxial MgO(001) tunnel barriers.

International audience; The electrical properties of Au/MgO/n-GaAs(001) tunnel structures have been investigated with capacitance-voltage and current-voltage measurements at room temperature with various MgO thicknesses between 0.5 and 6.0nm. For an oxide thickness higher than 2nm and for low bias voltages, the voltage essentially drops across the oxide and the structure progressively enters the high-current mode of operation with increasing reverse bias voltage, the property sought in spin injection devices. In this mode, we demonstrate that a large amount of charge accumulates at the MgO/GaAsinterface in interface traps located in the semiconductor band gap.

The room temperature epitaxial growth of Fe films on the As-rich GaAs(001)-(2×4) surface is studied using x-ray photoelectron spectroscopy as well as reflection high-energy electron diffraction and photoelectron diffraction. Interdiffusion mechanisms take place between Fe and GaAs during the deposition of the first 4 ML (0.7nm) Fe. The authors find that an Fe-based substitutional alloy with a body-centered-cubic structure confined on several atomic planes and containing 30% of foreign species (Ga and As atoms) sits at the Fe∕GaAs(001) interface. This intermixed layer is then buried by an almost pure Fe layer.

International audience; The electronic band structure in the epitaxial Fe∕MgO∕GaAs(001) tunnel junction has been studied by x-ray and ultraviolet photoelectron spectroscopy measurements. The Schottky barrier height (SBH) of Fe on MgO∕GaAs heterostructure is determined to be 3.3±0.1eV, which sets the Fe Fermi level at about 0.3eV above the GaAs valence band maximum. This SBH is also exactly the same as that measured from Fe on MgO monocrystal. After Fe deposition, no band bending change is observed in MgO and GaAs underlayers. On the contrary, Au and Al depositions led to clear variation of the band bending in both MgO and GaAs layers. This effect is analyzed as a fingerprint of defect states at the MgO∕GaAs interface.

The electronic band structure at the interface of the MgO-GaAs(001) tunnel contact has been experimentally studied. X-ray photoelectron spectroscopy has been used to measure the valence-band offset at the MgO-GaAs(001) heterojunction interface. The valence-band offset ΔEV is determined to be 4.2±0.1eV. As a consequence, a nested “type-I” band alignment with a conduction-band offset of ΔEC=2.2±0.1eV is found. The accurate determination of the valence and conduction band offsets is important for the fundamental understanding of the tunnel spin injection in GaAs.

International audience; We show that in agreement with the ternary Fe–Ga–As phase diagram, the solid-state interdiffusions in epitaxial Fe/GaAs(0 0 1) heterostructures lead, at a temperature of approximately 500 °C, to the formation of thermodynamically stable Fe3GaAs/GaAs(0 0 1) contacts quite similar to the well-known silicide/Si ones. The Fe3GaAs films are made of grains epitaxial on GaAs with a well-defined interface. Their magnetic and electrical properties make Fe3GaAs on GaAs an attractive metallization scheme for future magnetoelectronic devices. The results we report concern (25 or 80 nm Fe)/GaAs(0 0 1) heterostructures annealed at 480 and 500 °C for 10 min and characterized ex situ by He+ Rutherford backscattering and ion channeling, X-ray diffraction, transmission electron microscopy and alternating gradient field magnetometry.

Fe films have been grown on cubic GaN(0 0 1) layers by molecular beam epitaxy. They were studied in situ by reflection high-energy electron diffraction, X-ray photoemission spectroscopy and X-ray photoelectron diffraction and ex situ by Rutherford backscattering spectrometry (RBS), X-ray diffraction and alternating gradient field magnetometry. Despite the large lattice mismatch between Fe and cubic GaN [Δa/a=(2aFe−aGaN)/aGaN=+26%], the growth of Fe on GaN was found to be epitaxial with the orientation relationship (0 0 1)[1 0 0]Fe∥(0 0 1)[1 1 0]GaN i.e. with a 45° rotation of the Fe unit cell with respect to the GaN one. The mosaic spread of the Fe film does not exceed 1°. In such conditions we observed that the magnetic hysteresis loops show a cubic anisotropy with the easy axes along 〈1 0 0〉, as for bulk bcc Fe.

The epitaxial growth of ultrathin Fe films on InAs(0 0 1)-(2×4) and -(4×2) surfaces at room temperature is studied using reflection high-energy electron diffraction as well as ultraviolet and X-ray photoelectron spectroscopy. The InAs(0 0 1)-(2×4) and -(4×2) surfaces are obtained either by ion bombardment and annealing or by molecular beam epitaxy. For the different surfaces a detailed analysis of the In 4d core-level line shape leads to the same conclusion. The deposition of Fe onto InAs(0 0 1) induces a substrate disruption and a surface segregation: in a first step In atoms are released in the metallic overlayer and with increasing the Fe coverage these In atoms continue to segregate at the surface. At the same time, some In atoms are trapped in the Fe overlayer. A small amount of As surface segregation is also observed. Finally, the position of the Fermi level (independent of the surface reconstruction and the preparation method) at the Fe/InAs(0 0 1) interfaces is found ∼0.2 eV above the conduction band minimum.