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Electrochemical exfoliation is one of the most promising methods for scalable production of graphene. However, limited understanding of its Raman spectrum as well as lack of measurement standards for graphene strongly limit its industrial applications. In this work, we show a systematic study of the Raman spectrum of electrochemically exfoliated graphene, produced using different electrolytes and types of solvents in varying amounts. We demonstrate that no information on the thickness can be extracted from the shape of the 2D peak as this type of graphene is defective. Furthermore, the number of defects and the uniformity of the samples strongly depend on the experimental conditions, including postprocessing. Under specific conditions, the formation of short conductive trans-polyacetylene chains has been observed. Our Raman analysis provides guidance for the community on how to get information on defects coming from electrolyte, temperature, and other experimental conditions, by making Raman spectroscopy a powerful metrology tool.
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MoTe2 has two stable solid phases. 2H-MoTe2 is semiconducting while 1T' is semimetallic. The selective synthesis of pure-phase thin films is still challenging. In this study, we have investigated the growth temperature dependence of MoTe2 synthesized by molecular beam epitaxy and have identified the optimum temperature for growing the stoichiometric films. It is confirmed that the crystalline quality of MoTe2 strongly depends on the substrate temperature. Post-growth annealing of grown layers at 400 °C stabilizes the semiconducting phase. The structural properties and the phase change in our materials are analyzed in details by reflection high energy electron diffraction, low energy electron diffraction, auger electron spectroscopy, x-ray photoemission spectroscopy, and scanning tunneling microscopy.
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When coherent charge carriers cross micron-scale cavities, their dynamics can be governed by a few resonant states, also called "quantum scars", determined by the cavity geometry. Quantum scars can be described using theoretical tools but have also been directly imaged in the case of high-quality semiconductor cavities as well as in disordered graphene devices, thanks to scanning gate microscopy (SGM). Here, we discuss spatially resolved SGM images of low-temperature charge transport through a mesoscopic ring fabricated from high-quality monolayer graphene lying on top of hexagonal boron nitride. SGM images are decorated with a pattern of radial scars in the ring area, which is found to evolve smoothly and reappear when varying the charge-carrier energy. The energies separating recurrent patterns are found to be directly related to geometric dimensions of the ring. Moreover, a recurrence is also observed in simulations of the local density of states of a model graphene quantum ring. The observed recurrences are discussed in the light of recent predictions of relativistic quantum scars in mesoscopic graphene cavities.
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Graphene is of increasing interest for optoelectronic applications exploiting light detection, light emission and light modulation. Intrinsically, the light-matter interaction in graphene is of a broadband type. However, by integrating graphene into optical micro-cavities narrow-band light emitters and detectors have also been demonstrated. These devices benefit from the transparency, conductivity and processability of the atomically thin material. To this end, we explore in this work the feasibility of replacing graphene with nanocrystalline graphene, a material which can be grown on dielectric surfaces without catalyst by graphitization of polymeric films. We have studied the formation of nanocrystalline graphene on various substrates and under different graphitization conditions. The samples were characterized by resistance, optical transmission, Raman and x-ray photoelectron spectroscopy, atomic force microscopy and electron microscopy measurements. The conducting and transparent wafer-scale material with nanometer grain size was also patterned and integrated into devices for studying light-matter interaction. The measurements show that nanocrystalline graphene can be exploited as an incandescent emitter and bolometric detector similar to crystalline graphene. Moreover the material exhibits piezoresistive behavior which makes nanocrystalline graphene interesting for transparent strain sensors.
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An experimental study on the interaction between the top and bottom layer of a chemically functionalized graphene bilayer by mild oxygen plasma is reported. Structural, chemical, and electrical properties are monitored using Raman spectroscopy, transport measurements, conductive atomic force microscopy and X-ray photoelectron spectroscopy. Single- and double-sided chemical functionalization are found to give very different results: single-sided modified bilayers show relatively high mobility (200-600 cm(2) V(-1) s(-1) at room temperature) and a stable structure with a limited amount of defects, even after long plasma treatment (>60 s). This is attributed to preferential modification and limited coverage of the top layer during plasma exposure, while the bottom layer remains almost unperturbed. This could eventually lead to decoupling between top and bottom layers. Double-sided chemical functionalization leads to a structure containing a high concentration of defects, very similar to graphene oxide. This opens the possibility to use plasma treatment not only for etching and patterning of graphene, but also to make heterostructures (through single-sided modification of bilayers) for sensors and transistors and new graphene-derivatives materials (through double-sided modification).
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Raman spectroscopy is able to probe disorder in graphene through defect-activated peaks. It is of great interest to link these features to the nature of disorder. Here we present a detailed analysis of the Raman spectra of graphene containing different type of defects. We found that the intensity ratio of the D and D' peak is maximum (â¼13) for sp(3)-defects, it decreases for vacancy-like defects (â¼7), and it reaches a minimum for boundaries in graphite (â¼3.5). This makes Raman Spectroscopy a powerful tool to fully characterize graphene.
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Book production by medieval scriptoria have gained growing interest in recent studies. In this context, identifying ink compositions and parchment animal species from illuminated manuscripts is of great importance. Here, we introduce time-of-flight secondary ion mass spectrometry (ToF-SIMS) as a non-invasive tool to identify both inks and animal skins in manuscripts, at the same time. For this purpose, both positive and negative ion spectra in inked and non-inked areas were recorded. Chemical compositions of pigments (decoration) or black inks (text) were determined by searching for characteristic ion mass peaks. Animal skins were identified by data processing of raw ToF-SIMS spectra using principal component analysis (PCA). In illuminated manuscripts from the fifteenth to sixteenth century, malachite (green), azurite (blue), cinnabar (red) inorganic pigments, as well as iron-gall black ink, were identified. Carbon black and indigo (blue) organic pigments were also identified. Animal skins were identified in modern parchments of known animal species by a two-step PCA procedure. We believe the proposed method will find extensive application in material studies of medieval manuscripts, as it is non-invasive, highly sensitive and able to identify both inks and animal skins at the same time, even from traces of pigments and tiny scanned areas.
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Many active principles belong to the second class of the Biopharmaceutics Classification System due to their low aqueous solubility. Elaboration of new solid oral forms by hot-melt extrusion and fused deposition modeling appears as a promising tool to increase the dissolution rate of these drugs. Indeed, hot-melt extrusion allows the amorphisation of drugs and forms with complex geometries are built by 3D printing. Therefore, the goal of this work is to enhance the dissolution rate of poorly soluble drugs using hot-melt extrusion coupled with fused deposition modeling. Four formulations containing Affinisol® 15LV, Kollidon® VA64 and a challenging amount of itraconazole (25 % (wt.)) were successfully printed into forms of 20, 50 and 80 % infill densities. Differential scanning calorimetry analysis has shown that itraconazole remained amorphous during 52 weeks. The drug release rate was highly improved compared to itraconazole in a crystalline form. The dissolution rate was influenced by the infill density and the polymer composition of printed forms which could modify respectively the surface to volume ratio and the distribution of the components in the printed forms. One formulation printed with 20 % infill density even had a solubility profile similar to that of Sporanox®, the commercialized drug product in Belgium.
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Itraconazol , Povidona , Composición de Medicamentos/métodos , Liberación de Fármacos , Itraconazol/química , Polímeros/química , Povidona/química , Impresión Tridimensional , SolubilidadRESUMEN
Two-dimensional (2D) anatase titanium dioxide (TiO2) is expected to exhibit different properties as compared to anatase nanocrystallites, due to its highly reactive exposed facets. However, access to 2D anatase TiO2 is limited by the non-layered nature of the bulk crystal, which does not allow use of top-down chemical exfoliation. Large efforts have been dedicated to the growth of 2D anatase TiO2 with high reactive facets by bottom-up approaches, which relies on the use of harmful chemical reagents. Here, we demonstrate a novel fluorine-free strategy based on topochemical conversion of 2D 1T-TiS2 for the production of single crystalline 2D anatase TiO2, exposing the {001} facet on the top and bottom and {100} at the sides of the nanosheet. The exposure of these faces, with no additional defects or doping, gives rise to a significant activity enhancement in the hydrogen evolution reaction, as compared to commercially available Degussa P25 TiO2 nanoparticles. Because of the strong potential of TiO2 in many energy-based applications, our topochemical approach offers a low cost, green and mass scalable route for production of highly crystalline anatase TiO2 with well controlled and highly reactive exposed facets.
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Finely tuned: Carbon nanotubes are exposed to a CF(4) radio-frequency plasma (see picture). High-resolution photoelectron spectroscopy shows that the treatment effectively grafts fluorine atoms onto the MWCNTs, altering the valence electronic states. Fluorine surface concentration can be tuned by varying the exposure time.Multi-wall carbon nanotubes (MWCNTs) were exposed to a CF(4) radio-frequency (rf) plasma. High-resolution photoelectron spectroscopy shows that the treatment effectively grafts fluorine atoms onto the MWCNTs, altering the valence electronic states. Fluorine surface concentration can be tuned by varying the exposure time. Evaporation of gold onto MWCNTs is used to mark active site formation. High-resolution transmission electron microscopy coupled with density functional theory (DFT) modelling is used to characterise the surface defects formed, indicating that the plasma treatment does not etch the tube surface. We suggest that this combination of theory and microscopy of thermally evaporated gold atoms onto the CNT surface may be a powerful approach to characterise both surface defect density as well as defect type.
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Flúor/química , Nanotubos de Carbono/química , Oro/química , Microscopía Electrónica de Transmisión , Espectrometría por Rayos XRESUMEN
We study the interface between carbon nanotubes (CNTs) and surface-deposited titanium using electron microscopy and photoemission spectroscopy, supported by density functional calculations. Charge transfer from the Ti atoms to the nanotube and carbide formation is observed at the interface which indicates strong interaction. Nevertheless, the presence of oxygen between the Ti and the CNTs significantly weakens the Ti-CNT interaction. Ti atoms at the surface will preferentially bond to oxygenated sites. Potential sources of oxygen impurities are examined, namely oxygen from any residual atmosphere and pre-existing oxygen impurities on the nanotube surface, which we enhance through oxygen plasma surface pre-treatment. Variation in literature data concerning Ohmic contacts between Ti and carbon nanotubes is explained via sample pre-treatment and differing vacuum levels, and we suggest improved treatment routes for reliable Schottky barrier-free Ti-nanotube contact formation.
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In this study of the changes induced by exposing MWCNTs to a nitrogen plasma, it was found by HRTEM that the atomic nitrogen exposure does not significantly etch the surface of the carbon nanotube (CNT). Nevertheless, the atomic nitrogen generated by a microwave plasma effectively grafts amine, nitrile, amide, and oxime groups onto the CNT surface, as observed by XPS, altering the density of valence electronic states, as seen in UPS.
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We present a combined theoretical and experimental comparative study of the deposition of five different metals on perfect and defective graphene and multi-walled carbon nanotubes (MWNTs): Ti, Ni, Pd, Pt and Au. Atomistic modelling successfully provides a comprehensive picture of surface binding, diffusion and aggregation properties for these metals, highlighting some fundamental differences in their surface chemical and electronic behaviour. We correlate these theoretical results with experimental TEM images of metal deposited MWCNTs.
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Ion beam depth profiling is increasingly used to investigate layers and interfaces in complex multilayered devices, including solar cells. This approach is particularly challenging on hybrid perovskite layers and perovskite solar cells because of the presence of organic/inorganic interfaces requiring the fine optimization of the sputtering beam conditions. The ion beam sputtering must ensure a viable sputtering rate on hard inorganic materials while limiting the chemical (fragmentation), compositional (preferential sputtering) or topographical (roughening and intermixing) modifications on soft organic layers. In this work, model (Csx(MA0.17FA0.83)100-xPb(I0.83Br0.17)3/cTiO2/Glass) samples and full mesoscopic perovskite solar cells are profiled using low-energy (500 and 1000 eV) monatomic beams (Ar⺠and Csâº) and variable-size argon clusters (Arnâº, 75 < n < 4000) with energy up to 20 keV. The ion beam conditions are optimized by systematically comparing the sputtering rates and the surface modifications associated with each sputtering beam. X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, and in-situ scanning probe microscopy are combined to characterize the interfaces and evidence sputtering-related artifacts. Within monatomic beams, 500 eV Cs⺠results in the most intense and stable ToF-SIMS molecular profiles, almost material-independent sputtering rates and sharp interfaces. Large argon clusters (n > 500) with insufficient energy (E < 10 keV) result in the preferential sputtering of organic molecules and are highly ineffective to sputter small metal clusters (Pb and Au), which tend to artificially accumulate during the depth profile. This is not the case for the optimized cluster ions having a few hundred argon atoms (300 < n < 500) and an energy-per-atom value of at least 20 eV. In these conditions, we obtain (i) the low fragmentation of organic molecules, (ii) convenient erosion rates on soft and hard layers (but still different), and (iii) constant molecular profiles in the perovskite layer, i.e., no accumulation of damages.
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The growth of single-layer graphene (SLG) by chemical vapor deposition (CVD) on copper surfaces is very popular because of the self-limiting effect that, in principle, prevents the growth of few-layer graphene (FLG). However, the reproducibility of the CVD growth of homogeneous SLG remains a major challenge, especially if one wants to avoid heavy surface treatments, monocrystalline substrates and expensive equipment to control the atmosphere inside the growth system. We demonstrate here that backside tungsten coating of copper foils allows for the exclusive growth of SLG with full coverage by atmospheric pressure CVD implemented in a vacuum-free furnace. We show that the absence of FLG patches is related to the suppression of carbon diffusion through copper. In the perspective of large-scale production of graphene, this approach constitutes a significant improvement to the traditional CVD growth process since (1) a tight control of the hydrocarbon flow is no longer required to avoid FLG formation and, consequently, (2) the growth duration necessary to reach full coverage can be drastically shortened.
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The polarization dependence (linear dichroism) of the C 1s X-ray absorption spectrum of individual multi-walled carbon nanotubes (MWCNTs) is measured using scanning transmission X-ray microscopy. A very strong dichroic effect is found in the C 1s --> pi* transition, with almost complete disappearance of this transition when the electric-field (E)-vector is aligned parallel to high-quality (low-defect) MWCNTs and maximum intensity when the E-vector is orthogonal to the tube axis. In contrast, there is very little dichroism in the C 1s --> sigma* transitions. The origin of this polarization effect is explained. The magnitude of the polarization dependence is found to differ in MWCNTs synthesized by different methods (arc discharge versus chemical vapor deposition). This is ascribed to differences in densities of sp(2)-type defects. The potential for use of this signal to characterize defects in single-carbon-nanotube devices is discussed.
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Nanotubos de Carbono/química , Absorciometría de FotónRESUMEN
Graphitization of a polymer layer provides a convenient route to synthesize nanocrystalline graphene on dielectric surfaces. The transparent and conducting wafer scale material is of interest as a membrane and a coating, and for the generation and detection of light, or strain sensing. In this work, we study the formation of nanocrystalline graphene on germanium, a surface which promotes the CVD synthesis of monocrystalline graphene. The surprising result that we obtained through graphitization is the formation of cavities in germanium, over which nanocrystalline graphene is suspended. Depending on the crystallographic orientation of the germanium surface, either trenches in (110)-Ge or pits in (111)-Ge are formed, and their dimensions depend on the graphitization temperature. Using Raman spatial imaging, we can show that nanocrystalline graphene is formed across the entire wafer in spite of the cavity formation. Interestingly, the Raman intensity is suppressed when the material is supported by germanium and is enhanced when the material is suspended. Through simulations, we can show that these effects are induced by the high refractive index of germanium and by interferences of the light field depending on the spacing between graphene and germanium. Using atomic force and scanning electron microscopy, we determined that ripples in the suspended material are induced by the mismatch of thermal expansion coefficients. Our results provide a new route to lithography-free fabrication of suspended membranes.
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Tin monosulfide (SnS) is an emerging thin-film absorber material for photovoltaics. An outstanding challenge is to improve carrier lifetimes to >1 ns, which should enable >10% device efficiencies. However, reported results to date have only demonstrated lifetimes at or below 100 ps. In this study, we employ defect modeling to identify the sulfur vacancy and defects from Fe, Co, and Mo as most recombination-active. We attempt to minimize these defects in crystalline samples through high-purity, sulfur-rich growth and experimentally improve lifetimes to >3 ns, thus achieving our 1 ns goal. This framework may prove effective for unlocking the lifetime potential in other emerging thin-film materials by rapidly identifying and mitigating lifetime-limiting point defects.
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The sensing properties of carbon nanotubes (CNTs) decorated with gold nanoparticles have been investigated by means of combined theoretical and experimental approaches. On one hand, first-principles and nonequilibrium Green's functions techniques give access to the microscopic features of the sensing mechanisms in individual nanotubes, such as electronic charge transfers and quantum conductances. On the other hand, drop coating deposition of carbon nanotubes decorated with gold nanoparticles onto sensor substrates and their characterization in the detection of pollutants such as NO(2), CO, and C(6)H(6) provide insight into the sensing ability of nanotube mats. Using the present combined approaches, the improvement in the detection of some specific gases (NO(2) and CO) using Au-functionalized nanotubes is explained. However, for other gases such as C(6)H(6), the Au nanoparticles do not seem to play a crucial role in the sensing process when compared with pristine CNTs functionalized with oxygen plasma. Indeed, these different situations can be explained by identifying the relationship between the change of resistance (macroscopic feature) and the shift of the Fermi level (microscopic feature) after gas adsorption. The understanding of the sensing ability at the atomic level opens the way to design new gas sensors and to tune their selectivity by predicting the nature of the metal that is the most appropriate to detect specific molecular species.
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Oro/química , Nanotecnología/métodos , Nanotubos de Carbono/química , Adsorción , Contaminantes Atmosféricos/química , Carbono/química , Dióxido de Carbono/química , Gases , Nanopartículas del Metal/química , Microscopía Electrónica de Rastreo/métodos , Microscopía Electrónica de Transmisión/métodos , Oxígeno/química , Teoría Cuántica , Espectrometría por Rayos X/métodos , TemperaturaRESUMEN
The presence of defects in carbon nanotubes strongly modifies their electrical, mechanical, and chemical properties. It was long thought undesirable, but recent experiments have shown that introduction of structural defects using ion or electron irradiation can lead to novel nanodevices. We demonstrate a method for detecting and quantifying point defect density in individual carbon nanotubes (CNTs) based on measuring the polarization dependence (linear dichroism) of the C 1s --> pi* transition at specific locations along individual CNTs with a scanning transmission X-ray microscope (STXM). We show that STXM can be used to probe defect density in individual CNTs with high spatial resolution. The quantitative relationship between ion dose, nanotube diameter, and defect density was explored by purposely irradiating selected sections of nanotubes with kiloelectronvolt (keV) Ga(+) ions. Our results establish polarization-dependent X-ray microscopy as a new and very powerful characterization technique for carbon nanotubes and other anisotropic nanostructures.