Synthesis of Few-Layered Transition-Metal Dichalcogenides by Ion Implantation of Chalcogen and Metal Species into Sapphire.

The growth of transition-metal dichalcogenides (TMDCs) has been performed so far using most established thin-film growth techniques (e.g., vapor phase transport, chemical vapor deposition, molecular beam epitaxy, etc.). However, because there exists no self-limiting mechanism for the growth of TMDCs, none of these techniques allows precise control of the number of TMDC layers over large substrate areas. Here, we explore the ion implantation of the parent TMDC atoms into a chemically neutral substrate for the synthesis of TMDC films. The idea is that once all of the ion-implanted species have reacted together, the synthesis reaction stops, thereby effectively stopping growth. In other words, even if there is no self-limiting mechanism, growth stops when the nutrients are exhausted. We have co-implanted Mo and S ions into c-oriented sapphire substrates using various doses corresponding to 1- to 5-layer atom counts. We find that the subsurface region of the sapphire substrates is amorphized by the ion implantation process, at least for implanted doses of 2-layer atom counts and over. For all doses, we have observed the formation of MoS2 material inside the sapphire after postimplantation annealing between 800 and 850 °C. We report that the order of implantation (i.e., whether S or Mo is implanted first) is an important parameter. More precisely, samples for which S is implanted first tend to yield thin crystals with a large lateral extension (more than 200 nm for 5-layer doses) and mainly located at the interface between the amorphized and crystalline sapphire. When Mo is first implanted, the MoS2 crystals still predominantly appear at the amorphous-crystalline interface (which is much rougher), but they are much thicker, suggesting a different nucleation mechanism.

Raw and processed data used in non-covalent functionalization of single walled carbon nanotubes with Co-porphyrin and Co-phthalocyanine and its effect on field-effect transistor characteristics.

This scientific data article is related to the research work entitled "Non-Covalent functionalization of Single Walled Carbon Nanotubes with Fe-/Co-porphyrin and Co-phthalocyanine for Field-Effect Transistor Applications" published in "Organic electronics" (10.1016/j.orgel.2021.106212). In this work, we present the data of morphological, chemical and structural analyses of non-covalent functionalization of SWNTs with Co-porphyrin and Co-phthalocyanine. The analyses were performed by Raman spectroscopy, transmission electron microscopy as well as the electrical characterization of CNTFETs. This work is completed by the data of the theoretical calculations performed using Density Functional Theory (DFT).

New Schottky-Type Wire-Based Solar Cell with NiSix Nanowire Contacts.

Solar cells built with arrays of semiconductor wires have been studied for several years. They present some potential advantages over their bulk counterparts, such as (much) less use of semiconductor material, as well as improved light absorption properties. Most wire-based solar cells are fabricated with arrays of semiconductor p-n junctions, either radial or axial. Here, using a newly developed random connection process based on nickel silicide nanowires, we have built Schottky-type solar cells on interdigitated base and emitter coplanar electrodes that reach an efficiency of 6.5% when only 64% of the footprint area of the device is covered with p-type Si wire light-absorbers. To the best of our knowledge, this is the best efficiency reported so far for a Schottky-type wire-based solar cell; a simple extrapolation of the surface area suggests that an efficiency of more than 10% can be reached, which is comparable to that of single-junction hydrogenated amorphous Si cells. We also compare the Schottky-type cell with a "control" p-i-n one using the same device layout and the same nickel silicide nanowire random connection process: the efficiency of the p-i-n cell is higher (∼8%) but this is due to a higher VOC, the short-circuit current density (ISC) being very similar in both cases, close to 20 mA/cm2. The maximum temperature reached throughout the fabrication process of the cells (whether Schottky-type or p-i-n) is 550 °C, corresponding to the growth of the crystalline Si wires. Altogether, the results presented here hold promises toward cheap photovoltaics based on the use of randomly organized and randomly connected Si wire arrays.

Direct evidence of 2H hexagonal Si in Si nanowires.

Hexagonal Si (2H polytype) has attracted great interest because of its unique physical properties and wide range of potential applications. For example, it might be used in heterojunctions based on hexagonal and cubic Si. Although hexagonal Si has been reported in Si nanowires, its existence is doubted because structural defects of diamond cubic Si can produce structural signals similar to those attributed to hexagonal Si. Here, through the use of atomic resolution high-angle annular dark-field scanning transmission electron microscopy imaging, we unambiguously report the coherent intergrowth of diamond cubic (3C polytype) and 2H hexagonal Si in Si nanowires grown by chemical vapor deposition. A model describing the intergrowth of 3C and 2H Si is proposed and the reasons for the generation of 2H Si are discussed in detail.

Ultrafast-Charging Silicon-Based Coral-Like Network Anodes for Lithium-Ion Batteries with High Energy and Power Densities.

Fast charging rate and large energy storage are becoming key elements for the development of next-generation batteries, targeting high-performance electric vehicles. Developing electrodes with high volumetric and gravimetric capacity that could be operated at a high rate is the most challenging part of this process. Using silicon as the anode material, which exhibits the highest theoretical capacity as a lithium-ion battery anode, we report a binder-free electrode that interconnects carbon-sheathed porous silicon nanowires into a coral-like network and shows fast charging performance coupled to high energy and power densities when integrated into a full cell with a high areal capacity loading. The combination of interconnected nanowires, porous structure, and a highly conformal carbon coating in a single system strongly promotes the reaction kinetics of the electrode. This leads to fast-charging capability while maintaining the integrity of the electrode without structural collapse and, thus, stable cycling performance without using binder and conductive additives. Specifically, this anode shows high specific capacities (over 1200 mAh g-1) at an ultrahigh charging rate of 7 C over 500 charge-discharge cycles. When coupled with a commercial LiCoO2 or LiFePO4 cathode in a full cell, it delivers a volumetric energy density of 1621 Wh L-1 with a LiCoO2 cathode and a power density of 7762 W L-1 with a LiFePO4 cathode.

Graphene-Coated Aluminum Thin Film Anodes for Lithium-Ion Batteries.

We present a detailed study on graphene-coated aluminum thin films for Li-ion battery anode applications. The best electrode ageing behavior is obtained for Al films encapsulated with four porous graphene layers. Graphene encapsulation prevents "crushed" Al nanoparticles from detaching from the anode, thus allowing prolonged charge-discharge cycling. Graphene also provides surface conduction paths for electrons as well as diffusion paths for Li atoms. For the first time, we report the electrochemical room temperature formation of phases such as Li3Al2 and even Li9Al4, with a higher Li content than ß-LiAl. More interestingly, we observe a progressive change of the composite thin film electrode, switching from a pure galvanic to a pseudocapacitive behavior as the size of the Al grains decreases from ∼100 to 5-10 nm due to repeated Li alloying-dealloying. The capacity values of ∼900 and 780 mAh/g are obtained after, respectively, 500 and 1000 charge-discharge cycles at 0.1C. Our results may refocus the interest of the battery community on Al-based thin film anodes, since they are potentially very simple to fabricate, particularly if porous graphene is replaced in the future by reduced graphite oxide.

Electron-Driven Metal Oxide Effusion and Graphene Gasification at Room Temperature.

Metal oxide nanoparticles decorating graphene have attracted abundant interest in the scientific community owing to their significant application in various areas such as batteries, gas sensors, and photocatalysis. In addition, metal and metal oxide nanoparticles are of great interest for the etching of graphene, for example, to form nanoribbons, through gasification reactions. Hence it is important to have a good understanding of how nanoparticles interact with graphene. In this work we examine, in situ, the behavior of CuO and ZnO nanoparticles on graphene at room temperature while irradiated by electrons in a transmission electron microscope. ZnO is shown to etch graphene through gasification. In the gasification reaction C from graphene is released as CO or CO2. We show that the reaction can occur at room temperature. Moreover, CuO and ZnO particles trapped within a graphene fold are shown to effuse out of a fold through small ruptures. The mass transport in the effusion process between the CuO and ZnO particles is fundamentally different. Mass transport for CuO occurs in an amorphous phase, while for ZnO mass transport occurs through the short-lived gliding of vacancies and dislocations. The work highlights the potential and wealth of electron beam driven chemical reactions of nanomaterials, even at room temperature.

Significant enhancement of the electrical transport properties of graphene films by controlling the surface roughness of Cu foils before and during chemical vapor deposition.

We have studied the influence of the surface roughness of copper foils on the sheet resistance of graphene sheets grown by chemical vapor deposition. The surface roughness of the copper foils was reproducibly controlled by electropolishing. We have found that the graphene sheet resistance monotonically decreases as the surface roughness of the copper foils decreases. We show that a pre-annealing treatment combined with an optimized electropolishing process of the Cu foils and a fast CVD growth prevents the evolution of the Cu surface roughness during graphene synthesis. This combination of fabrication conditions produces small grain polycrystalline graphene films with a sheet resistance of 210 Ω â–¡(-1) and carrier mobility values as high as 5450 cm(2) V(-1) s(-1) after transfer onto SiO2/Si.

Hot electron field emission via individually transistor-ballasted carbon nanotube arrays.

We present electronically controlled field emission characteristics of arrays of individually ballasted carbon nanotubes synthesized by plasma-enhanced chemical vapor deposition on silicon-on-insulator substrates. By adjusting the source-drain potential we have demonstrated the ability to controllable limit the emission current density by more than 1 order of magnitude. Dynamic control over both the turn-on electric field and field enhancement factor have been noted. A hot electron model is presented. The ballasted nanotubes are populated with hot electrons due to the highly crystalline Si channel and the high local electric field at the nanotube base. This positively shifts the Fermi level and results in a broad energy distribution about this mean, compared to the narrow spread, lower energy thermalized electron population in standard metallic emitters. The proposed vertically aligned carbon nanotube field-emitting electron source offers a viable platform for X-ray emitters and displays applications that require accurate and highly stable control over the emission characteristics.

Negative and positive persistent photoconductance in graphene.

Persistent photoconductance, a prolonged light-induced conducting behavior that lasts several hundred seconds, has been observed in semiconductors. Here we report persistent negative photoconductance and consecutive prominent persistent positive photoconductance in graphene. Unusually large yields of negative PC (34%) and positive PC (1652%) and remarkably long negative transient response time (several hours) were observed. Such high yields were reduced in multilayer graphene and were quenched under vacuum conditions. Two-dimensional metallic graphene strongly interacts with environment and/or substrate, causing this phenomenon, which is markedly different from that in three-dimensional semiconductors and nanoparticles.

Influence of copper morphology in forming nucleation seeds for graphene growth.

We report that highly crystalline graphene can be obtained from well-controlled surface morphology of the copper substrate. Flat copper surface was prepared by using a chemical mechanical polishing method. At early growth stage, the density of graphene nucleation seeds from polished Cu film was much lower and the domain sizes of graphene flakes were larger than those from unpolished Cu film. At later growth stage, these domains were stitched together to form monolayer graphene, where the orientation of each domain crystal was unexpectedly not much different from each other. We also found that grain boundaries and intentionally formed scratched area play an important role for nucleation seeds. Although the best monolayer graphene was grown from polished Cu with a low sheet resistance of 260 Ω/sq, a small portion of multilayers were also formed near the impurity particles or locally protruded parts.

Synthesis of few-layered graphene by ion implantation of carbon in nickel thin films.

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.

Stable field emission from arrays of vertically aligned free-standing metallic nanowires.

We present a fully elaborated process to grow arrays of metallic nanowires with controlled geometry and density, based on electrochemical filling of nanopores in track-etched templates. Nanowire growth is performed at room temperature, atmospheric pressure and is compatible with low cost fabrication and large surfaces. This technique offers an excellent control of the orientation, shape and nanowires density. It is applied to fabricate field emission arrays with a good control of the emission site density. We have prepared Co, Ni, Cu and Rh nanowires with a height of 3 µm, a diameter of 80 nm and a density of ∼10(7) cm(-2). The electron field emission measurements and total energy distributions show that the as-grown nanowires exhibit a complex behaviour, first with emission activation under high field, followed by unstable emission. A model taking into account the effect of an oxide layer covering the nanowire surface is developed to explain this particular field emission behaviour. Finally, we present an in situ cleaning procedure by ion bombardment that collectively removes this oxide layer, leading to a stable and reproducible emission behaviour. After treatment, the emission current density is ∼1 mA cm(-2) for a 30 V µm(-1) applied electric field.

Carbon nanotube based photocathodes.

This paper describes a novel photocathode which is an array of vertically aligned multi-walled carbon nanotubes (MWCNTs), each MWCNT being associated with one p-i-n photodiode. Unlike conventional photocathodes, the functions of photon-electron conversion and subsequent electron emission are physically separated. Photon-electron conversion is achieved with p-i-n photodiodes and the electron emission occurs from the MWCNTs. The current modulation is highly efficient as it uses an optically controlled reconfiguration of the electric field at the MWCNT locations. Such devices are compatible with high frequency and very large bandwidth operation and could lead to their application in compact, light and efficient microwave amplifiers for satellite telecommunication. To demonstrate this new photocathode concept, we have fabricated the first carbon nanotube based photocathode using silicon p-i-n photodiodes and MWCNT bunches. Using a green laser, this photocathode delivers 0.5 mA with an internal quantum efficiency of 10% and an I(ON)/I(OFF) ratio of 30.

Electroactive superelongation of carbon nanotube aggregates in liquid crystal medium.

We report an effect of superelongation of carbon nanotube (CNT) aggregates driven by the electric field in a liquid crystal (LC) medium. The CNT aggregates started to elongate above a certain threshold field and sustained the elongation up to nearly 400% in the linear region with a large electroactive constant of 70 (V/microm)-1. The original morphology of the CNT aggregates was restored upon removal of the field. The elongation was fully reversible below a certain breakdown field, irrespective of the nematic or isotropic phase of the LC medium. The overall process involved (i) the alignment of CNT aggregates to increase the dipole energy of aggregates in the presence of the bias voltage, (ii) stretching of the CNTs by sliding-out from the bundles, and (iii) the entropic elasticity that restores the randomly entangled CNT network of the original aggregates after suppression of the bias voltage.

Conformal anodic oxidation of aluminum thin films.

Membrane-based synthesis, also called template synthesis, is a very general approach used to prepare arrays of nanomaterials with monodispersed geometrical features. The most commonly used porous templates are track-etched polycarbonate and porous anodic alumina membranes. Common to all these templates is the fact that the pores are perpendicular to the surface of the membrane. Here, a novel approach is presented, where the pores are synthesized parallel to the surface of the membrane. For the first time, the anodic oxidation of an aluminum thin film is performed laterally, i.e., parallel to the surface of the substrate, instead of perpendicular as usually done. For low anodic oxidation voltages (between 3 and 5 V) we obtain highly regular and ordered pore arrays, at least over a few hundred nanometers length, with a minimum pore size of approximately 3 to 4 nm. With such porous alumina structures, the controlled in-plane organization of arrays of template-grown nanowires and carbon nanotubes for reproducible device fabrication should be much easier.