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This numerical study investigates the effects of adding a small amount of ignition promoters for controlling the wedge-induced oblique shock wave (OSW) to oblique detonation wave (ODW) transition in a premixed hydrogen–air mixture at hypersonic speeds. The time-dependent two-dimensional compressible Euler equations for multiple thermally perfect species with a reactive source term are solved using adaptive mesh refinement and detailed chemical kinetics. The wedge with a fixed angle of 26 ◦ exhibits abrupt to smooth transitions for freestream Mach numbers 7–9 (speeds 2.8–3.2 km/s) at a pressure of 20 kPa and a temperature of 300 K. The small amount (1000 PPM by vol.) of H 2O 2 and O 3 is found to be effective at significantly reducing the initiation length for the oblique detonation transition for all Mach numbers, which suggests a practical approach to increase the operating flight range for oblique detonation wave engine with a finite length wedge. At Mach number 8, the abrupt OSW to ODW transition turns towards a smooth transition with a small amount of H 2O 2 and O 3 addition. Comparatively, O 3 addition was found to be effective in reducing the ODW initiation length by promoting reactivity behind even a weaker oblique shock at low Mach number 7, for abrupt transition, while H 2O 2 addition was more effective than O 3 at high Mach numbers 8 and 9, during a smooth transition. The maximum 73% and 80% reduction in initiation length of ODW was observed with 10,000 PPM H 2O 2 and O 3 addition, respectively, during an abrupt OSW to ODW transition at Mach 7.

International audience; The formation of nanopores under electron irradiation is an ideal process to quantify chemical bonds in 2D materials. Nowadays, High Resolution Transmission Electron Microscopy (HRTEM) allows investigating such nucleation and growth phenomena with incomparable spatial and temporal resolution. Moreover, theoretical calculations are usually exploited to confirm characteristic features of these atomic-scale observations. Nevertheless, the full understanding of the ejection mechanisms of atoms requires studying in details the interplay between the very dynamic edge structure of expanding nanopores and the displacement energy of edge atoms (E D). Here, the dynamics of triangular nanopores in hexagonal boron nitride (h-BN) under various electron dose rates was followed by aberration-corrected HRTEM with high 2 temporal resolution to provide new in situ insights into their growth processes. We notably reveal that the ejection of atomic pairs is an elemental mechanisms that considerably speeds up the expansion of nanopores. Atomic-scale calculations were exploited to quantify the structure-dependent E D of all the ejected edge atoms. They revealed strong variations of this threshold energy during the growth processes. This quantitative study reconciles theoretical and experimental measurements of the ejection rate of atoms in h-BN under electron irradiation which is essential for nanopore engineering in this atomically-thin membrane.

Optical modulators are essential components in optical communication and photonic neuromorphic networks. Graphene on silicon waveguides have been proposed for optical modulation but the modulation depth is limited to 0.1 dB/ $\mu$ m. Higher modulation depth and shorter modulators can be achieved with plasmonic modes; however, due to its transverse magnetic nature, they weakly interact with graphene. In this contribution, a plasmonic Bloch mode supported by a plasmonic waveguide is used to overcome this problem. Its high in-plane electric field strongly interacts with graphene. Numerical results show modulation depths of 4 dB/ $\mu$ m at 1.65 $\mu$ m with 2.6 dB loss. A subwavelength footprint of 0.5 $\mu$ m $^2$ allows a modulation speed of up to 39 GHz and an energy consumption of 21.2 fJ/b. This sub- $\lambda$ size modulator is a promising candidate for optical communication and neuromorphic circuits.

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International audience; Variations of the lattice parameter can significantly change the properties of a material, and, in particular, its electronic behaviour. In the case of graphene, however, variations of the lattice constant with respect to graphite have been limited to less than 2.5% due to its well-established high in-plane stiffness. Here, through systematic electronic and lattice structure studies, we report regions where the lattice constant of graphene monolayers grown on copper by chemical vapour deposition increases up to ~7.5% of its relaxed value. Density functional theory calculations confirm that this expanded phase is energetically metastable and driven by the enhanced interaction between the substrate and the graphene adlayer. We also prove that this phase possesses distinctive chemical and electronic properties. The inherent phase complexity of graphene grown on copper foils revealed in this study may inspire the investigation of possible metastable phases in other seemingly simple heterostructure systems.

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International audience; We propose a semiconductor–insulator–semiconductor (SIS) heterojunction diode consisting of monolayer (1-L) MoS2, hexagonal boron nitride (h-BN), and epitaxial p-GaN that can be applied to high-performance nanoscale optoelectronics. The layered materials of 1-L MoS2 and h-BN, grown by chemical vapor deposition, were vertically stacked by a wet-transfer method on a p-GaN layer. The final structure was verified by confocal photoluminescence and Raman spectroscopy. Current–voltage (I–V) measurements were conducted to compare the device performance with that of a more classical p–n structure. In both structures (the p–n and SIS heterojunction diode), clear current-rectifying characteristics were observed. In particular, a current and threshold voltage were obtained for the SIS structure that was higher compared to that of the p–n structure. This indicated that tunneling is the predominant carrier transport mechanism. In addition, the photoresponse of the SIS structure induced by the illumination of visible light was observed by photocurrent measurements.

International audience; Electronic structure describes the distribution of electronic states in reciprocal space, being one of the most fundamental concepts in condensed matter physics, since it determines the electrical, optical and magnetic behaviours of materials. Due to its two-dimensional honeycomb lattice with covalent bonding, pristine graphene exhibits unsurpassed in-plane stiffness and stable structural properties. Here by employing angle-resolved photoemission spectroscopy with spatial resolution ∼ 100 nm (Nano-ARPES), we discuss in detail the structural and electronic properties of graphene grown on cooper by chemical vapour deposition (CVD). Our results reveal the spatial inhomogeneity of graphene film, demonstrating the power of Nano-ARPES to detect the microscopic inhomogeneity of electronic structure for different materials.

International audience; We report on the optical and electrical excitation of the modes of a “hybrid” waveguide consisting of a single organic nanofiber on a thin gold film. In the first set of experiments, light is used to excite the photoluminescence of an organic nanofiber on a thin gold film and the resulting emission is analyzed using Fourier-space leakage radiation microscopy. Two guided modes and the dispersion relations of this hybrid waveguide are thus determined. From numerical calculations, both a fundamental and excited mode of mixed photonic–plasmonic character are identified. In a second experiment, a local electrical nanosource of surface plasmon polaritons (SPPs) is coupled to the hybrid waveguide. The SPP nanosource consists of the inelastic electron tunnel current between the tip of a scanning tunneling microscope (STM) and the gold film. We show that the electrically excited SPPs couple to the fundamental mode and that the coupling efficiency is highest when the SPP nanosource is aligned with the nanofiber axis. Moreover, the electrically excited SPPs strongly scatter into out-of-plane light at the nanofiber end. This light from scattered SPPs measured in the substrate is phase shifted by about π with respect to the direct light emission from beneath the STM tip. These experiments lead to a better understanding of the processes that must be optimized in order to exploit such hybrid waveguide structures.

International audience; A Hot Wire assisted Chemical Vapor Deposition (HWCVD) process has been developed for producing highdensity arrays of parallel, straight and organized silicon nanowires (SiNWs) inside vertical Porous Anodic Alumina (PAA) templates, exploring temperatures ranging from 430 °C to 600 °C, and pressures varying between 2.5 and 7.5 mbar. In order to prevent parasitic amorphous silicon (a-Si) deposit and to promote the crystalline SiNWs growth, we used a tungsten hot wire to partially crack H2 into atomic hydrogen, which acts like a selective etchant regarding a-Si. Here we describe the optimization route we followed to limit the deposit of a-Si onto the surface of the porous membrane and on the walls of the pores, which led to the possibility to grow SiNWs inside the PAA membranes. Such an approach has high potentialities for device realization, like PIN junctions, FETs or electrodes for Li-ion batteries.

The effects of an atomic hydrogen ( H at ) pretreatment of the catalyst layer on the low temperature growth of single-walled carbon nanotubes (SWCNTs) have been investigated using a modified catalytic chemical vapor deposition system. Well-defined and isolated individual Fe nanoparticles as a catalyst are successfully formed on the defects with high trapping energy which are created on the Al 2 O 3 surface by H at pretreatment, yielding highly dense SWCNTs. The pretreatment mechanism of H at , compared to H 2 , is also discussed. It was also found that the quality of SWCNTs can be enhanced when H at is flowed with CH 4 during nanotubes growth at low temperature. In this case, the undesired carbon products and defects on catalyst seeds and nanotube walls can be selectively removed by H at . Therefore it is essential to use H at in the pretreatment stage for increasing catalytic activity and to keep the size of nanoparticles in the nm range. H at can also be employed in growth stage for enhancing SWCNTs quality and density at low temperature.

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International audience; The low temperature catalytic growth of multiwall carbon nanotubes (MWCNTs) rests on the continuous nucleation and growth of graphene layers at the surface of crystalline catalystparticles. Here, we study the atomic mechanisms at work in this phenomenon, by observing the growth of such layers in situ in the transmission electron microscope, in the case of iron-based catalysts. Graphene layers, parallel to the catalyst surface, appear by a mechanism of step flow, where the atomic layers of catalyst are "replaced" by graphene planes. Quite remarkably, catalyst facets systematically develop while this mechanism is at work. We discuss the origin of faceting in terms of equilibrium particle shape and graphene layer nucleation. Step bunching due to impeded step migration, in certain growth conditions, yields characteristic catalyst nail-head shapes. Mastering themechanisms of faceting and step bunching could open up the way to tailoring the structure of low temperature-grown MWCNTs, e.g. with highly parallel carbon walls and, ultimately, with controlled structure and chirality.

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LGEP 2014 ID = 1648; International audience; In this paper, we study the transfer of graphene onto InAs/GaAs quantum dots (QDs). The graphene is first grown on Cu foils by chemical vapor deposition and then polymer Polymethyl Methacrylate (PMMA) is deposited on the top of graphene/Cu. High quality graphene sheet has been obtained by lowering the dissolving rate of PMMA using vapor processing. Uncapped as well as capped graphene InAs/GaAs QDs have been studied using optical microscopy, scanning electron microscopy, and Raman spectroscopy. We gather from this that the average shifts Δω of QDs Raman peaks are reduced compared to those previously observed in graphene and GaAs capped QDs. The encapsulation by graphene makes the indium atomic concentration intact in the QDs by the reduction of the strain effect of graphene on QDs and the migration of In atoms towards the surface. This gives us a new hetero-structure graphene–InAs/GaAs QDs wherein the graphene plays a key role as a cap layer.

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We present a robust and versatile approach for the reproducible and controllable growth of single-walled carbon nanotubes (SWNTs) through a self-assembled mono-layer (SAM) technique coupled with an atomic hydrogen (Hat) pretreatment to control the catalytic metallic nanoparticles size and density. The nanoparticles are obtained from a self-assembled monolayer of metal complexes or salts on a SiO2 substrate using a two-step strategy. The oxide is first functionalized by silanization with a coordinating ligand leading to the formation of an anchoring SAM on the substrate. Then, metallic complexes such as ruthenium porphyrin (RuTPP) or metallic salts (FeCl3, RuCl3) are assembled by coordination bonds on the preformed organic SAM. Pyrolysis under radical hydrogen atmosphere of the as-prepared SAM yields metallic nanoparticles whose size and density are controlled and tuned. Using the as-formed nanoparticles as catalysts, SWNTs are grown by double hot-filament-assisted chemical vapor deposition (d-HFCVD). They exhibit a remarkably good crystalline quality, with a diameter (and type) strongly dependent on the nature of the initial catalyst precursor and its preparation. Field-effect transistors (FETs) with excellent characteristics were obtained using such in-place grown SWNTs. The electronic properties of the SWNTs can be tuned: the transistors obtained from Ru(TPP) and FeCl3 exhibit ION/IOFF current ratio up to ∼109, indicative of the direct growth of a high proportion of semiconducting nanotubes over than 98%. Such elevated values have been reported essentially for CNT-FETs devices based on individual semiconducting SWNTs. By contrast, devices obtained from the RuCl3 salt display ION/IOFF current ratio well below 102, indicating the direct growth of SWNTs highly enriched in metallic specimens.

International audience; Y- and comb-type carbon nanotrees formed from branched carbon nanofibres grown by plasma-enhanced chemical vapour deposition were studied by transmission electron microscopy. Different growth mechanisms are proposed for the two types of nanotrees based on the observed and reconstituted dynamic transformations of the catalyst particles during synthesis. However, the splitting of the larger catalyst particles is required for both kinds of nanotrees, whatever the involved growth mechanism. The carbon nanotrees are well crystallized and connections of the branches are continuous, which may be interesting for future applications in nanoelectronic devices and also composite materials.

The nucleation and growth of multiwall carbon nanotubes (MWCNTs) at the surface of crystalline iron-based catalysts are studied by in situ annealing and high-resolution transmission electron microscopy. Graphene planes, parallel to the catalyst surface, appear by a mechanism of step flow, where the atomic layers of catalyst are "replaced" by graphene layers. More interestingly, as the catalyst particles have curved or poly-faceted surfaces, those catalyst atomic layers correspond to no definite atomic plane. The step height may thus vary along a given step flow process. Step bunching due to impeded step migration, in certain growth conditions, yields characteristic catalyst nail-head shapes. Mastering this mechanism opens up the way to tailor the structure of MWCNTs, e.g. with highly parallel carbon walls.

International audience; Coexistence of both edge plane and basal plane in graphite often hinders the understanding of lithium ion diffusion mechanism. In this report, two types of graphene samples were prepared by chemical vapor deposition (CVD): (i) well-defined basal plane graphene grown on Cu foil and (ii) edge plane-enriched graphene layers grown on Ni film. Electrochemical performance of the graphene electrode can be split into two regimes depending on the number of graphene layers: (i) the corrosion-dominant regime and (ii) the lithiation-dominant regime. Li ion diffusion perpendicular to the basal plane of graphene is facilitated by defects, whereas diffusion parallel to the plane is limited by the steric hindrance that originates from aggregated Li ions adsorbed on the abundant defect sites. The critical layer thickness (lc) to effectively prohibit substrate reaction using CVD-grown graphene layers was predicted to be ∼6 layers, independent of defect population. Our density functional theory calculations demonstrate that divacancies and higher order defects have reasonable diffusion barrier heights allowing lithium diffusion through the basal plane but neither monovacancies nor Stone-Wales defect.

Reactions between the tripodal hydroxytriamine, 2,2-bis(aminomethyl)-3-aminopropan-1-ol, “hytame”, and the isomeric pyridine aldehydes generate in all cases the tris(aminal) species based on a 1,3,5-triaza-adamantane skeleton. In all cases also, the product from water under basic conditions consists of an approximately 1:9 mixture of the triequatorial and monoaxial–diequatorial isomers. While all these tripyridyltriaza-adamantanes appear capable of acting as Lewis bases, in particular cases metal ion binding leads to a radical structural rearrangement. These cases involve the pyridine-2-aldehyde derivatives only and certain transition metal ions (notably Fe(II)), and result in the conversion of the tris(aminal) into its isomeric tris(imine) form. This is apparently favoured because it can act as a hexadentate ligand towards a single metal ion, although kinetic influences are clearly important in this chemistry because template reactions of the triamine, pyridine-2-aldehyde and several metal ions give much better yields of the tris(imine) complex than do analogous rearrangement reactions. For the low-spin, kinetically inert Fe(II) complex of the tris(imine), its formation is apparently so favourable that it is generated via aldehyde unit exchange when the aza-adamantanes derived from pyridine-3- and -4-aldehyde are heated with a mixture of Fe(II) and pyridine-2-aldehyde. When the kinetically labile Zn(II) complex is treated with EDTA, the metal ion is extracted but the released ligand does not undergo valence tautomerisation to what would be expected to be the triaxial isomer of the tripyridyltriaza-adamantane but instead rapidly undergoes partial hydrolysis before slowly forming the mixture of triequatorial and monoaxial–diequatorial isomers.

International audience; Iron is a widely used catalyst for the growth of carbon nanotubes (CNTs) or carbon nanofibers (CNFs) by catalytic chemical vapor deposition. However, both Fe and Fe−C compounds (generally, Fe3C) have been found to catalyze the growth of CNTs/CNFs, and a comparison study of their respective catalytic activities is still missing. Furthermore, the control of the crystal structure of iron-based catalysts, that is α-Fe or Fe3C, is still a challenge, which not only obscures our understanding of the growth mechanisms of CNTs/CNFs, but also complicates subsequent procedures, such as the removal of catalysts for better industrial applications. Here, we show a partial control of the phase of iron catalysts (α-Fe or Fe3C), obtained by varying the growth temperatures during the synthesis of carbon-based nanofibers/nanotubes in a plasma-enhanced chemical vapor deposition reactor. We also show that the structure of CNFs originating from Fe3C is bamboo-type, while that of CNFs originating from Fe is not. Moreover, we directly compare the growth rates of carbon-based nanofibers/nanotubes during the same experiments and find that CNFs/ CNTs grown by α-Fe nanoparticles are longer than CNFs grown from Fe3C nanoparticles. The influence of the type of catalyst on the growth of CNFs is analyzed and the corresponding possible growth mechanisms, based on the different phases of the catalysts, are discussed.

10 pages; International audience; Carbon nanofibres (CNFs) obtained by plasma enhanced chemical vapour deposition are made of cone-shaped graphene layers, the opening angle of which has a significant influence on their properties: the smaller the angle, the closer the properties to those of carbon nanotubes. That angle is determined by the shape of the metal nanoparticle used to catalyse the growth. We show in this paper that the shape of Ni nanoparticle catalysts, and in turn the CNF properties, can be tuned during plasma-enhanced chemical vapour deposition, by the choice of the etchant gas. We show in particular that a water-containing etchant (H2O or H2O+H2) increases the growth rate by an order of magnitude at 600°C compared to an ammonia-containing etchant (NH3 or NH3+H2), and leaves more elongated Ni particles with a cone angle three times smaller. We conclude that the cone angle and the growth rate are directly related, and propose a mechanism to explain that large difference between the two etchants.

International audience; Lateral porous anodic alumina (PAA) templates were used to organize carbon nanotubes (CNTs) grown by a hot-filament assisted chemical vapor deposition (HFCVD) process. For the CNT growth, we used a modified "home-made" HFCVD system with two independently powered filaments which are fitted respectively on the methane (CH4) gas line, which serves as a carbon precursor and on the hydrogen (H2) gas line, which acts as an etching agent for the parasitic amorphous carbon. Various activation powers of the hot filaments were used to directly or indirectly decompose the gas mixtures at relatively low substrate temperatures. A parametric study of the HFCVD process has been carried out for optimizing the confined CNTs growth inside the lateral PAA templates.

International audience; The synthesis of few-layered graphene is performed by ion implantation of carbon species in thin nickel films, followed by high temperature annealing and quenching. Although ion implantation enables a precise control of the carbon content and of the uniformity of the in-plane carbon concentration in the Ni films before annealing, we observe thickness non-uniformities in the synthesized graphene layers after high temperature annealing. These non-uniformities are probably induced by the heterogeneous distribution/topography of the graphene nucleation sites on the Ni surface. Taken altogether, our results indicate that the number of graphene layers on top of Ni films is controlled by the nucleation process on the Ni surface rather than by the carbon content in the Ni film.

International audience; Growth on transition metal substrates is becoming a method of choice to prepare large-area graphene foils. In the case of nickel, where carbon has a significant solubility, such a growth process includes at least two elementary steps: (1) carbon dissolution into the metal, and (2) graphene precipitation at the surface. Here, we dissolve calibrated amounts of carbon in nickel films, using carbon ion implantation, and annealing at 725 °C or 900 °C. We then use transmission electron microscopy to analyse the precipitation process in detail: the latter appears to imply carbon diffusion over large distances and at least two distinct microscopic mechanisms.

Graphene is perhaps the most promising material ever discovered for microelectronics applications, but its preparation includes either high-temperature processing or film transfer, and sometimes both of them, which forbids for the moment its introduction into fabrication lines. In this communication we report a synthesis route involving exposure of nickel thin films deposited on silicon oxide to a mixture of methane and hydrogen activated by DC plasma at 450°C. In addition of the awaited graphene film formed at the surface of catalyst layer, we observed the formation of a second graphene film at the catalyst/silicon oxide interface. To our knowledge, no other team have yet reported graphene synthesis directly on a dielectric substrate at low temperature. With the idea of increasing the graphene structural quality, we studied the effect of additional post growth high temperature annealing. The films synthesized were characterized using Raman spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM).

8 pages; International audience; Vertically aligned multi-walled carbon nanofibers (CNFs) were grown by plasma-enhanced chemical vapor deposition with Ni catalysts on the top of nanofibers. Transmission electron microscopy was used to study the morphology and crystallography of Ni catalysts, which are essential for the nucleation and growth of CNFs. A model for the faceted shape of Ni catalytic particles is proposed. It is shown that the exposed polyhedral surfaces of Ni catalytic particles for vertically aligned CNFs are composed of {111}, {110}, and {100}, a faceting that appears to be characteristic of the growth atmosphere.

International audience; Large-area graphene film doped with nitrogen is of great interest for a wide spectrum of nanoelectronics applications, such as field effect devices, super capacitors, and fuel cells among many others. Here, we report on the structural and electronic properties of nitrogen doped trilayer graphene on 4H-SiC (0001) grown under atmospheric pressure. The trilayer nature of the growth is evidenced by scanning transmission electron microscopy. X-ray photoelectron spectroscopy shows the incorporation of 1.2% of nitrogen distributed in pyrrolic-N, and pyridinic-N configurations as well as a graphitic-N contribution. This incorporation causes an increase in the D band on the Raman signature indicating that the nitrogen is creating defects. Ultraviolet photoelectron spectroscopy shows a decrease of the work function of 0.3 eV due to the N-type doping of the nitrogen atoms in the carbon lattice and the edge defects. A top gate field effect transistor device has been fabricated and exhibits carrier mobilities up to 1300 cm2/V s for holes and 850 cm2/V s for electrons at room temperature.