Non-invasive nanoscale potentiometry and ballistic transport in epigraphene nanoribbons

The recent observation of non-classical electron transport regimes in two-dimensional materials has called for new high-resolution non-invasive techniques to locally probe electronic properties. We introduce a novel hybrid scanning probe technique to map the local resistance and electrochemical potential with nm- and $\mu$V resolution, and we apply it to study epigraphene nanoribbons grown on the sidewalls of SiC substrate steps. Remarkably, the potential drop is non uniform along the ribbons, and $\mu$m-long segments show no potential variation with distance. The potential maps are in excellent agreement with measurements of the local resistance. This reveals ballistic transport in ambient condition, compatible with micrometer-long room-temperature electronic mean free paths

An epigraphene platform for coherent 1D nanoelectronics

Exceptional edge state ballistic transport, first observed in graphene nanoribbons grown on the sidewalls of trenches etched in electronics grade silicon carbide even at room temperature, is shown here to manifest in micron scale epigraphene structures that are conventionally patterned on single crystal silicon carbide substrates. Electronic transport is dominated by a single electronic mode, in which electrons travel large distances without scattering, much like photons in an optical fiber. In addition, robust quantum coherence, non-local transport, and a ground state with half a conductance quantum are also observed. These properties are explained in terms of a ballistic edge state that is pinned at zero energy. The epigraphene platform allows interconnected nanostructures to be patterned, using standard microelectronics methods, to produce phase coherent 1D ballistic networks. This discovery is unique, providing the first feasible route to large scale quantum coherent graphene nanoelectronics, and a possible inroad towards quantum computing

Protected transport in the epigraphene edge state

The graphene edge state has long been predicted to be a zero energy, one-dimensional electronic waveguide mode that dominates transport in neutral graphene nanostructures, with potential application to graphene devices. However, its exceptional properties have been observed in only a few cases, each employing novel fabrication methods without a clear path to large-scale integration. We show here that interconnected edge-state networks can be produced using non-conventional facets of electronics grade silicon carbide wafers and scalable lithography, which cuts the epitaxial graphene and apparently fuses its edge atoms to the silicon carbide substrate. Measured epigraphene edge state (EGES) conduction is ballistic with mean free paths exceeding tens of microns, thousands of times greater than for the diffusive 2D bulk. It is essentially independent of temperature, decoupled from the bulk and substantially immune to disorder. Remarkably, EGES transport involves a non-degenerate conductance channel that is pinned at zero energy, yet it does not generate a Hall voltage, implying balanced electron and hole components. These properties, observed at all tested temperatures, magnetic fields, and charge densities, are not predicted by present theories, and point to a zero-energy spin one-half quasiparticle, composed of half an electron and a half a hole moving in opposite directions

Production and processing of graphene and related materials

We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a 'hands-on' approach, providing practical details and procedures as derived from literature as well as from the authors' experience, in order to enable the reader to reproduce the results. Section I is devoted to 'bottom up' approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section II covers 'top down' techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers' and modified Hummers' methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by employing a theoretical data-mining approach. The exfoliation of LMs usually results in a heterogeneous dispersion of flakes with different lateral size and thickness. This is a critical bottleneck for applications, and hinders the full exploitation of GRMs produced by solution processing. The establishment of procedures to control the morphological properties of exfoliated GRMs, which also need to be industrially scalable, is one of the key needs. Section III deals with the processing of flakes. (Ultra)centrifugation techniques have thus far been the most investigated to sort GRMs following ultrasonication, shear mixing, ball milling, microfluidization, and wet-jet milling. It allows sorting by size and thickness. Inks formulated from GRM dispersions can be printed using a number of processes, from inkjet to screen printing. Each technique has specific rheological requirements, as well as geometrical constraints. The solvent choice is critical, not only for the GRM stability, but also in terms of optimizing printing on different substrates, such as glass, Si, plastic, paper, etc, all with different surface energies. Chemical modifications of such substrates is also a key step. Sections IV–VII are devoted to the growth of GRMs on various substrates and their processing after growth to place them on the surface of choice for specific applications. The substrate for graphene growth is a key determinant of the nature and quality of the resultant film. The lattice mismatch between graphene and substrate influences the resulting crystallinity. Growth on insulators, such as SiO2, typically results in films with small crystallites, whereas growth on the close-packed surfaces of metals yields highly crystalline films. Section IV outlines the growth of graphene on SiC substrates. This satisfies the requirements for electronic applications, with well-defined graphene-substrate interface, low trapped impurities and no need for transfer. It also allows graphene structures and devices to be measured directly on the growth substrate. The flatness of the substrate results in graphene with minimal strain and ripples on large areas, allowing spectroscopies and surface science to be performed. We also discuss the surface engineering by intercalation of the resulting graphene, its integration with Si-wafers and the production of nanostructures with the desired shape, with no need for patterning. Section V deals with chemical vapour deposition (CVD) onto various transition metals and on insulators. Growth on Ni results in graphitized polycrystalline films. While the thickness of these films can be optimized by controlling the deposition parameters, such as the type of hydrocarbon precursor and temperature, it is difficult to attain single layer graphene (SLG) across large areas, owing to the simultaneous nucleation/growth and solution/precipitation mechanisms. The differing characteristics of polycrystalline Ni films facilitate the growth of graphitic layers at different rates, resulting in regions with differing numbers of graphitic layers. High-quality films can be grown on Cu. Cu is available in a variety of shapes and forms, such as foils, bulks, foams, thin films on other materials and powders, making it attractive for industrial production of large area graphene films. The push to use CVD graphene in applications has also triggered a research line for the direct growth on insulators. The quality of the resulting films is lower than possible to date on metals, but enough, in terms of transmittance and resistivity, for many applications as described in section V. Transfer technologies are the focus of section VI. CVD synthesis of graphene on metals and bottom up molecular approaches require SLG to be transferred to the final target substrates. To have technological impact, the advances in production of high-quality large-area CVD graphene must be commensurate with those on transfer and placement on the final substrates. This is a prerequisite for most applications, such as touch panels, anticorrosion coatings, transparent electrodes and gas sensors etc. New strategies have improved the transferred graphene quality, making CVD graphene a feasible option for CMOS foundries. Methods based on complete etching of the metal substrate in suitable etchants, typically iron chloride, ammonium persulfate, or hydrogen chloride although reliable, are time- and resource-consuming, with damage to graphene and production of metal and etchant residues. Electrochemical delamination in a low-concentration aqueous solution is an alternative. In this case metallic substrates can be reused. Dry transfer is less detrimental for the SLG quality, enabling a deterministic transfer. There is a large range of layered materials (LMs) beyond graphite. Only few of them have been already exfoliated and fully characterized. Section VII deals with the growth of some of these materials. Amongst them, h-BN, transition metal tri- and di-chalcogenides are of paramount importance. The growth of h-BN is at present considered essential for the development of graphene in (opto) electronic applications, as h-BN is ideal as capping layer or substrate. The interesting optical and electronic properties of TMDs also require the development of scalable methods for their production. Large scale growth using chemical/physical vapour deposition or thermal assisted conversion has been thus far limited to a small set, such as h-BN or some TMDs. Heterostructures could also be directly grown. Section VIII discusses advances in GRM functionalization. A broad range of organic molecules can be anchored to the sp2 basal plane by reductive functionalization. Negatively charged graphene can be prepared in liquid phase (e.g. via intercalation chemistry or electrochemically) and can react with electrophiles. This can be achieved both in dispersion or on substrate. The functional groups of GO can be further derivatized. Graphene can also be noncovalently functionalized, in particular with polycyclic aromatic hydrocarbons that assemble on the sp2 carbon network by π–π stacking. In the liquid phase, this can enhance the colloidal stability of SLG/FLG. Approaches to achieve noncovalent on-substrate functionalization are also discussed, which can chemically dope graphene. Research efforts to derivatize CNMs are also summarized, as well as novel routes to selectively address defect sites. In dispersion, edges are the most dominant defects and can be covalently modified. This enhances colloidal stability without modifying the graphene basal plane. Basal plane point defects can also be modified, passivated and healed in ultra-high vacuum. The decoration of graphene with metal nanoparticles (NPs) has also received considerable attention, as it allows to exploit synergistic effects between NPs and graphene. Decoration can be either achieved chemically or in the gas phase. All LMs, can be functionalized and we summarize emerging approaches to covalently and noncovalently functionalize MoS2 both in the liquid and on substrate. Section IX describes some of the most popular characterization techniques, ranging from optical detection to the measurement of the electronic structure. Microscopies play an important role, although macroscopic techniques are also used for the measurement of the properties of these materials and their devices. Raman spectroscopy is paramount for GRMs, while PL is more adequate for non-graphene LMs (see section IX.2). Liquid based methods result in flakes with different thicknesses and dimensions. The qualification of size and thickness can be achieved using imaging techniques, like scanning probe microscopy (SPM) or transmission electron microscopy (TEM) or spectroscopic techniques. Optical microscopy enables the detection of flakes on suitable surfaces as well as the measurement of optical properties. Characterization of exfoliated materials is essential to improve the GRM metrology for applications and quality control. For grown GRMs, SPM can be used to probe morphological properties, as well as to study growth mechanisms and quality of transfer. More generally, SPM combined with smart measurement protocols in various modes allows one to get obtain information on mechanical properties, surface potential, work functions, electrical properties, or effectiveness of functionalization. Some of the techniques described are suitable for 'in situ' characterization, and can be hosted within the growth chambers. If the diagnosis is made 'ex situ', consideration should be given to the preparation of the samples to avoid contamination. Occasionally cleaning methods have to be used prior to measurement

Production and processing of graphene and related materials

© 2020 The Author(s). We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a 'hands-on' approach, providing practical details and procedures as derived from literature as well as from the authors' experience, in order to enable the reader to reproduce the results. Section I is devoted to 'bottom up' approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section II covers 'top down' techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers' and modified Hummers' methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by employing a theoretical data-mining approach. The exfoliation of LMs usually results in a heterogeneous dispersion of flakes with different lateral size and thickness. This is a critical bottleneck for applications, and hinders the full exploitation of GRMs produced by solution processing. The establishment of procedures to control the morphological properties of exfoliated GRMs, which also need to be industrially scalable, is one of the key needs. Section III deals with the processing of flakes. (Ultra)centrifugation techniques have thus far been the most investigated to sort GRMs following ultrasonication, shear mixing, ball milling, microfluidization, and wet-jet milling. It allows sorting by size and thickness. Inks formulated from GRM dispersions can be printed using a number of processes, from inkjet to screen printing. Each technique has specific rheological requirements, as well as geometrical constraints. The solvent choice is critical, not only for the GRM stability, but also in terms of optimizing printing on different substrates, such as glass, Si, plastic, paper, etc, all with different surface energies. Chemical modifications of such substrates is also a key step. Sections IV-VII are devoted to the growth of GRMs on various substrates and their processing after growth to place them on the surface of choice for specific applications. The substrate for graphene growth is a key determinant of the nature and quality of the resultant film. The lattice mismatch between graphene and substrate influences the resulting crystallinity. Growth on insulators, such as SiO2, typically results in films with small crystallites, whereas growth on the close-packed surfaces of metals yields highly crystalline films. Section IV outlines the growth of graphene on SiC substrates. This satisfies the requirements for electronic applications, with well-defined graphene-substrate interface, low trapped impurities and no need for transfer. It also allows graphene structures and devices to be measured directly on the growth substrate. The flatness of the substrate results in graphene with minimal strain and ripples on large areas, allowing spectroscopies and surface science to be performed. We also discuss the surface engineering by intercalation of the resulting graphene, its integration with Si-wafers and the production of nanostructures with the desired shape, with no need for patterning. Section V deals with chemical vapour deposition (CVD) onto various transition metals and on insulators. Growth on Ni results in graphitized polycrystalline films. While the thickness of these films can be optimized by controlling the deposition parameters, such as the type of hydrocarbon precursor and temperature, it is difficult to attain single layer graphene (SLG) across large areas, owing to the simultaneous nucleation/growth and solution/precipitation mechanisms. The differing characteristics of polycrystalline Ni films facilitate the growth of graphitic layers at different rates, resulting in regions with differing numbers of graphitic layers. High-quality films can be grown on Cu. Cu is available in a variety of shapes and forms, such as foils, bulks, foams, thin films on other materials and powders, making it attractive for industrial production of large area graphene films. The push to use CVD graphene in applications has also triggered a research line for the direct growth on insulators. The quality of the resulting films is lower than possible to date on metals, but enough, in terms of transmittance and resistivity, for many applications as described in section V. Transfer technologies are the focus of section VI. CVD synthesis of graphene on metals and bottom up molecular approaches require SLG to be transferred to the final target substrates. To have technological impact, the advances in production of high-quality large-area CVD graphene must be commensurate with those on transfer and placement on the final substrates. This is a prerequisite for most applications, such as touch panels, anticorrosion coatings, transparent electrodes and gas sensors etc. New strategies have improved the transferred graphene quality, making CVD graphene a feasible option for CMOS foundries. Methods based on complete etching of the metal substrate in suitable etchants, typically iron chloride, ammonium persulfate, or hydrogen chloride although reliable, are time- and resourceconsuming, with damage to graphene and production of metal and etchant residues. Electrochemical delamination in a low-concentration aqueous solution is an alternative. In this case metallic substrates can be reused. Dry transfer is less detrimental for the SLG quality, enabling a deterministic transfer. There is a large range of layered materials (LMs) beyond graphite. Only few of them have been already exfoliated and fully characterized. Section VII deals with the growth of some of these materials. Amongst them, h-BN, transition metal tri- and di-chalcogenides are of paramount importance. The growth of h-BN is at present considered essential for the development of graphene in (opto) electronic applications, as h-BN is ideal as capping layer or substrate. The interesting optical and electronic properties of TMDs also require the development of scalable methods for their production. Large scale growth using chemical/physical vapour deposition or thermal assisted conversion has been thus far limited to a small set, such as h-BN or some TMDs. Heterostructures could also be directly grown

Propriétés électroniques des systèmes quasi-unidimensionnels (C60@SWCNTs et nanofils d'InAs) étudiés par le transport électronique sous champ magnétique intense

The scope of this thesis is related to the electronic properties of quasi 1D systems probed by highfield magnetotransport. Two different systems exhibiting quasi-1D confinement have beenconsidered: carbon C60 peapods (C60@SWCNTs) and InAs semiconductor nanowires. Themagnetotransport measurements on single nano-objets have been used to investigate the specificelectronic structure of these 1D systems. In both cases, the high magnetic fields experimentshave been supported by structural characterisation and conductance measurements at zero field.The encapsulation of various molecules inside carbon nanotubes (CNTs), as for instance C60fullerenes encapsulated in SWCNT, constitutes promising routes towards the tunability of theCNT conductance. Among the wide variety of filled CNTs, peapods represent a pioneer hybridstructure discovered in 1998. Since that time, their electronic structure has been subjected tointense and controversial theoretical studies together with a limited number of experimentalrealizations. In this thesis the electronic properties of individual fullerene peapods have beeninvestigated by combining micro-Raman spectroscopy and magnetotransport measurements onthe same devices. We bring evidence that the encapsulated C60 strongly modify the electronicband structure of semiconducting nanotubes in the vicinity of the charge neutrality point,including a rigid shift and a partial filling of the energy gap. In addition by playing with aselective UV excitation of the fullerene, we demonstrate that the electronic coupling between theC60 and the CNT is strongly modified by the partial coalescence of the C60 and their distributioninside the tube. The experimental results are supported by numerical simulations of the Densityof States and the conductance of CNTs with coalesced fullerenes inside (K. Katin, M. Maslov).Semiconductor nanowires (sc-NWs) are being the subject of intense researches started a decadeago. They represent model systems for the exploration of the electronic properties inerrant to thequasi1-D confinement. Moreover they offer the possibility to play with band structure tailoringand carrier doping. In this direction III-V sc-NWs such as InAs NWs have played a particularrole due to the small electron effective mass. We have studied the high magnetic fieldconductance of single nanowires. Prior to the high field measurements, the zero and low fieldinvestigations have demonstrated a weakly diffusive regime of the carrier transport in thesewires. The high field investigations have revealed a drastic conductance drop above a criticalfield, which clearly rises with the Fermi energy. This effect is interpreted by the loss ofconducting channels once all the magneto-electric subbands, shifted toward the high energyrange by the magnetic field, have crossed the Fermi energy. Preliminary band structurecalculations (Y-M. Niquet), taking into account the lateral and magnetic confinements, are infairly good qualitative agreement with the observed result in the high field regime. This result isthe first observation of band structure effects in magneto-transport experiments on sc-NWs.Cette thèse présente des mesures de transport électronique dans des systèmes quasi-unidimensionnels (quasi-1D) sous champ magnétique intense. Deux systèmes différents présentant un confinement électrique quasi-1D ont été considérés: les peapods de carbone (C60@SWCNTs) et les nanofils d'InAs. L’objectif de ces travaux consiste à sonder les propriétés électroniques spécifiques de ces systèmes quasi-1D par les mesures de magnétotransport sur les nano-objets uniques. Dans les deux cas, les expériences sous champs magnétiques intenses ont été accompagnée par des caractérisations structurales et des mesures de conductance à champ magnétique nul.L'encapsulation de diverses molécules à l'intérieur de nanotubes de carbone (CNTs), comme par exemple les fullerènes C60, constitue une des voies prometteuses vers l'accordabilité de la conductance des CNTs. Parmi la grande variété des nanotubes de carbone remplis, les peapods représentent une structure hybride pionnière découvert en 1998. Depuis lors, leur structure électronique a fait l’objet d’études théoriques controversées avec un nombre limité de réalisations expérimentales. Dans cette thèse, les propriétés électroniques des peapods individuels ont été étudiés en combinant les mesures de spectroscopie micro-Raman et de magnétotransport sur les mêmes échantillons. Nous avons constaté que les C60 encapsulés modifient fortement la structure de bande électronique des nanotubes semi-conducteurs au voisinage du point de neutralité de charge. Cette modification comprend un déplacement rigide de la structure électronique et un remplissage partiel de la bande interdite. Nous avons aussi montré que l’excitation UV sélective des fullerènes conduit à une forte modification du couplage électronique entre les C60 et le CNT induite par la coalescence partielle des C60 et de leur distribution à l'intérieur du tube. Les résultats expérimentaux sont supportés par des simulations numériques de la densité d'états et de la conductance des nanotubes de carbone avec des fullerènes fusionnés à l'intérieur (K. Katin, M. Maslov).Les nanofils semiconducteurs (sc-NWs) font l'objet de recherches actives depuis ces dix dernières années. Ils représentent des systèmes modèles pour l’étude des propriété électronique objet quasi-1D. Ils représentent en outre des possibilités de modulation de la structure de bande aussi que de contrôle de la densité de porteurs. Dans ce domaine de recherche, les nanofils semi-conducteurs à base de composes III-V tel que InAs, ont une place particulière en raison de la faible masse effective des porteurs de charge. Nous avons étudié la conductance de nanofils individuels dans une large gamme de champs magnétiques (jusqu'à 60T). Les mesures en champ nul et en champ faible ont démontré un transport faiblement diffusif dans ces nanofils. Les mesures de transport sous champ magnétique intense ont révélé une forte chute de la conductance au dessus d'un champ critique qui s'élève clairement avec l'énergie de Fermi. Cet effet est interprété par la perte de canaux de conduction une fois que toutes les sous-bandes magnéto-électriques, décalés vers les hautes énergies par le champ magnétique, ont traversé l'énergie de Fermi. Les calculs de structure de bande préliminaires (Y-M. Niquet), en prenant en compte les confinements latéraux et magnétiques, sont en bon accord qualitatif avec les résultats observés dans le régime de champ magnétique intense. Ce résultat est la première observation des effets de structure de bande dans les expériences de magnéto-transport sur les sc-NW

Propriétés électroniques des systèmes quasi-unidimensionnels (C60@SWCNTs et nanofils d'InAs) étudiés par le transport électronique sous champ magnétique intense

Cette thèse présente des mesures de transport électronique dans des systèmes quasi-unidimensionnels (quasi-1D) sous champ magnétique intense. Deux systèmes différents présentant un confinement électrique quasi-1D ont été considérés: les peapods de carbone (C60@SWCNTs) et les nanofils d'InAs. L objectif de ces travaux consiste à sonder les propriétés électroniques spécifiques de ces systèmes quasi-1D par les mesures de magnétotransport sur les nano-objets uniques. Dans les deux cas, les expériences sous champs magnétiques intenses ont été accompagnée par des caractérisations structurales et des mesures de conductance à champ magnétique nul.L'encapsulation de diverses molécules à l'intérieur de nanotubes de carbone (CNTs), comme par exemple les fullerènes C60, constitue une des voies prometteuses vers l'accordabilité de la conductance des CNTs. Parmi la grande variété des nanotubes de carbone remplis, les peapods représentent une structure hybride pionnière découvert en 1998. Depuis lors, leur structure électronique a fait l objet d études théoriques controversées avec un nombre limité de réalisations expérimentales. Dans cette thèse, les propriétés électroniques des peapods individuels ont été étudiés en combinant les mesures de spectroscopie micro-Raman et de magnétotransport sur les mêmes échantillons. Nous avons constaté que les C60 encapsulés modifient fortement la structure de bande électronique des nanotubes semi-conducteurs au voisinage du point de neutralité de charge. Cette modification comprend un déplacement rigide de la structure électronique et un remplissage partiel de la bande interdite. Nous avons aussi montré que l excitation UV sélective des fullerènes conduit à une forte modification du couplage électronique entre les C60 et le CNT induite par la coalescence partielle des C60 et de leur distribution à l'intérieur du tube. Les résultats expérimentaux sont supportés par des simulations numériques de la densité d'états et de la conductance des nanotubes de carbone avec des fullerènes fusionnés à l'intérieur (K. Katin, M. Maslov).Les nanofils semiconducteurs (sc-NWs) font l'objet de recherches actives depuis ces dix dernières années. Ils représentent des systèmes modèles pour l étude des propriété électronique objet quasi-1D. Ils représentent en outre des possibilités de modulation de la structure de bande aussi que de contrôle de la densité de porteurs. Dans ce domaine de recherche, les nanofils semi-conducteurs à base de composes III-V tel que InAs, ont une place particulière en raison de la faible masse effective des porteurs de charge. Nous avons étudié la conductance de nanofils individuels dans une large gamme de champs magnétiques (jusqu'à 60T). Les mesures en champ nul et en champ faible ont démontré un transport faiblement diffusif dans ces nanofils. Les mesures de transport sous champ magnétique intense ont révélé une forte chute de la conductance au dessus d'un champ critique qui s'élève clairement avec l'énergie de Fermi. Cet effet est interprété par la perte de canaux de conduction une fois que toutes les sous-bandes magnéto-électriques, décalés vers les hautes énergies par le champ magnétique, ont traversé l'énergie de Fermi. Les calculs de structure de bande préliminaires (Y-M. Niquet), en prenant en compte les confinements latéraux et magnétiques, sont en bon accord qualitatif avec les résultats observés dans le régime de champ magnétique intense. Ce résultat est la première observation des effets de structure de bande dans les expériences de magnéto-transport sur les sc-NWsThe scope of this thesis is related to the electronic properties of quasi 1D systems probed by high field magnetotransport. Two different systems exhibiting quasi-1D confinement have been considered: carbon C60 peapods (C60@SWCNTs) and InAs semiconductor nanowires. The magnetotransport measurements on single nano-objets have been used to investigate the specific electronic structure of these 1D systems. In both cases, the high magnetic fields experiments have been supported by structural characterisation and conductance measurements at zero field.The encapsulation of various molecules inside carbon nanotubes (CNTs), as for instance C60 fullerenes encapsulated in SWCNT, constitutes promising routes towards the tunability of the CNT conductance. Among the wide variety of filled CNTs, peapods represent a pioneer hybrid structure discovered in 1998. Since that time, their electronic structure has been subjected to intense and controversial theoretical studies together with a limited number of experimental realizations. In this thesis the electronic properties of individual fullerene peapods have been investigated by combining micro-Raman spectroscopy and magnetotransport measurements on the same devices. We bring evidence that the encapsulated C60 strongly modify the electronic band structure of semiconducting nanotubes in the vicinity of the charge neutrality point, including a rigid shift and a partial filling of the energy gap. In addition by playing with a selective UV excitation of the fullerene, we demonstrate that the electronic coupling between the C60 and the CNT is strongly modified by the partial coalescence of the C60 and their distribution inside the tube. The experimental results are supported by numerical simulations of the Density of States and the conductance of CNTs with coalesced fullerenes inside (K. Katin, M. Maslov).Semiconductor nanowires (sc-NWs) are being the subject of intense researches started a decade ago. They represent model systems for the exploration of the electronic properties inerrant to the quasi1-D confinement. Moreover they offer the possibility to play with band structure tailoring and carrier doping. In this direction III-V sc-NWs such as InAs NWs have played a particular role due to the small electron effective mass. We have studied the high magnetic field conductance of single nanowires. Prior to the high field measurements, the zero and low field investigations have demonstrated a weakly diffusive regime of the carrier transport in these wires. The high field investigations have revealed a drastic conductance drop above a critical field, which clearly rises with the Fermi energy. This effect is interpreted by the loss of conducting channels once all the magneto-electric subbands, shifted toward the high energy range by the magnetic field, have crossed the Fermi energy. Preliminary band structure calculations (Y-M. Niquet), taking into account the lateral and magnetic confinements, are in fairly good qualitative agreement with the observed result in the high field regime. This result is the first observation of band structure effects in magneto-transport experiments on sc-NWsTOULOUSE-INSA-Bib. electronique (315559905) / SudocSudocFranceF

A bottom-up approach for controlled deformation of carbon nanotubes through blistering of supporting substrate surface

International audienceTuning the band structure and, in particular, gap opening in 1D and 2D materials through their deformation is a promising approach for their application in modern semiconductor devices. However, there is an essential breach between existing laboratory scale methods applied for deformation of low-dimensional materials and the needs of large-scale production. In this work, we propose a novel method which is potentially well compatible with high end technological applications: single-walled carbon nanotubes (SWCNTs) first deposited on the flat surface of a supporting wafer, which has been pre-implanted with H + and He + ions, are deformed in a controlled and repetitive manner over blisters formed after subsequent thermal annealing. By using resonant Raman spectroscopy, we demonstrate that the SWCNTs clamped by metallic stripes at their ends are deformed over blisters to an average tensile strain of 0.15±0.03%, which is found to be in a good agreement with the value calculated taking into account blister's dimensions. The principle of the technique may be applied to other 1D and 2D materials in perspective