arXiv subjects

Cinzia Casiraghi

Publications and source records attributed to Cinzia Casiraghi.

12 recordsLinked to original sources

arXiv2025

Wettability and sp2/sp3 ratio effects on supercapacitor performance of N-doped hydrogenated amorphous Carbon Nanofoam

Pulsed laser-deposited amorphous carbon nanofoams are potential candidate for electrochemical energy storage applications due to ultra-light weight, large volumetric void fractions, and co-existence of sp, sp2 and sp3 carbon hybridization. It is known that charge storage in carbon nanostructures containing disordered sp2-domains is determined by their wettability, surface area, and porosity. However, their charge-storage performance is limited to the areal capacitance of the order of a few mF/cm2. We enhanced the supercapacitor performance of nitrogen-doped amorphous carbon nanofoam by engineering its wettability and sp2-C/sp3-C ratio by vacuum annealing. The specific capacitance was enhanced by about fifty times and the device voltage increased from 0.8 to 1.1 V compared to as-grown carbon nanofoam. In addition, we examined for the first time the initial increase in specific capacitance of the aqueous symmetric supercapacitor with respect to the scan rate, employing in-situ measurements coupling Raman spectroscopy and electrochemistry. We attribute this effect, observed but generally not explained in previous works in the literature, to the electrochemical activation induced by structural changes during the charge storage performance. This optimization of pulsed laser deposited carbon nanofoam may open an avenue for fabricating lightweight and porous nanostructures for advanced macro-to-micro-supercapacitor devices.

cond-mat.mtrl-sci↗

arXiv2020

Low-voltage 2D materials-based printed field-effect transistors for integrated digital and analog electronics on paper

Paper is the ideal substrate for the development of flexible and environmentally sustainable ubiquitous electronic systems, which, combined with two-dimensional materials, could be exploited in many Internet-of-Things applications, ranging from wearable electronics to smart packaging. Here we report high-performance MoS2 field-effect transistors on paper fabricated with a channel-array approach, combining the advantages of two large-area techniques: chemical vapor deposition and inkjet-printing.The first allows the pre-deposition of a pattern of MoS2; the second, the printing of dielectric layers, contacts, and connections to complete transistors and circuits fabrication. Average ION/IOFF of 8 x 10^3 (up to 5 x 10^4) and mobility of 5.5 cm2 V-1 s-1 (up to 26 cm2 V-1 s-1) are obtained. Fully functional integrated circuits of digital and analog building blocks, such as logic gates and current mirrors, are demonstrated, highlighting the potential of this approach for ubiquitous electronics on paper.

physics.app-ph↗

arXiv2020

Raman Fingerprints of Graphene Produced by Anodic Electrochemical Exfoliation

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 different 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 post-processing. Under specific conditions, 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.

physics.app-ph↗

arXiv2019

Multi-wavelength Raman Spectroscopy of Ultra-narrow Nanoribbons Made by Solution-mediated Bottom-up Approach

Here we present a combined experimental and theoretical study of graphene nanoribbons (GNRs), where detailed multi-wavelength Raman measurements are integrated by accurate ab initio simulations. Our study covers several ultra-narrow GNRs, obtained by means of solution-based bottom-up synthetic approach, allowing to rationalize the effect of edge morphology, position and type of functional groups as well as the length on the GNR Raman spectrum. We show that the low-energy region, especially in presence of bulky functional groups is populated by several modes, and a single radial breathing-like mode cannot be identified. In the Raman optical region, we find that, except for the fully-brominated case, all GNRs functionalized at the edges with different side groups show a characteristic dispersion of the D peak (8-22 cm-1/eV). This has been attributed to the internal degrees of freedom of these functional groups, which act as dispersion-activating defects. The G peak shows small to negligible dispersion in most of the cases, with larger values only in presence of poor control of the edges functionalization, exceeding the values reported for highly defected graphene. In conclusion, we have shown that the characteristic dispersion of the G and D peaks offer further insight on the GNR structure and functionalization, by making Raman spectroscopy an important tool for the characterization of GNRs.

cond-mat.mtrl-sci↗

arXiv2019

Water-based and Inkjet Printable Inks made by Electrochemically Exfoliated Graphene

Inkjet printable graphene inks are very attractive for applications in flexible and foldable electronics, such as wearable electronics and the Internet of Things. However, the ink preparation is still very time consuming as high concentrations can be achieved only with prolonged sonication (>24 hours) or with expensive setups. Here we demonstrate a water-based inkjet printable ink made from electrochemically exfoliated graphene. A printable and stable (> 1 month) ink with concentration of ~2.25 mg mL-1 was formulated in less than 5 hrs, using two successive steps: first exfoliation and dispersion of large graphene flakes (> 5 um) followed by 1 hour tip-sonication to reduce the flake size below 1 um, as required for the material to be ejected by the nozzle. The formulated ink contains more than 75% single- and few-layers (i.e. less than 2 nm in thickness) graphene flakes with an average lateral size of 740 nm. Thermal annealing allows to achieve high C/O ratio (>10), which translates into one of the highest electrical conductivity (~3.91 x 104 S m-1) reported so far for solution-processed graphene, without the use of any harsh chemical processing.

physics.app-ph↗

arXiv2018

All-2D Material Inkjet-Printed Capacitors: Towards Fully-Printed Integrated Circuits

A well-defined insulating layer is of primary importance in the fabrication of passive (e.g. capacitors) and active (e.g. transistors) components in integrated circuits. One of the most widely known 2-Dimensional (2D) dielectric materials is hexagonal boron nitride (hBN). Solution-based techniques are cost-effective and allow simple methods to be used for device fabrication. In particular, inkjet printing is a low-cost, non-contact approach, which also allows for device design flexibility, produces no material wastage and offers compatibility with almost any surface of interest, including flexible substrates. In this work we use water-based and biocompatible graphene and hBN inks to fabricate all-2D material and inkjet-printed capacitors. We demonstrate an areal capacitance of 2.0 \pm 0.3 nF cm^(-2) for a dielectric thickness of \sim 3 μm and negligible leakage currents, averaged across more than 100 devices. This gives rise to a derived dielectric constant of 6.1 \pm 1.7. The inkjet printed hBN dielectric has a breakdown field of 1.9 \pm 0.3 MV cm^(-1). Fully printed capacitors with sub-/mu m hBN layer thicknesses have also been demonstrated. The capacitors are then exploited in two fully printed demonstrators: a resistor-capacitor (RC) low-pass filter and a graphene-based field effect transistor.

physics.app-ph↗

arXiv2016

Raman fingerprints of atomically precise graphene nanoribbons

Bottom-up approaches allow the production of ultra-narrow and atomically precise graphene nanoribbons (GNRs), with electronic and optical properties controlled by the specific atomic structure. Combining Raman spectroscopy and ab-initio simulations, we show that GNR width, edge geometry and functional groups all influence their Raman spectra. The low-energy spectral region below 1000 cm-1 is particularly sensitive to edge morphology and functionalization, while the D peak dispersion can be used to uniquely fingerprint the presence of GNRs, and differentiates them from other sp2 carbon nanostructures.

cond-mat.mes-hall↗

arXiv2012

Probing the Nature of Defects in Graphene by Raman Spectroscopy

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 (~ 13) for sp3-defects, it decreases for vacancy-like defects (~ 7) and reaches a minimum for boundaries in graphite (~3.5).

cond-mat.mes-hall↗

arXiv2012

Raman spectroscopy of graphene and bilayer under biaxial strain: bubbles and balloons

In this letter we use graphene bubbles to study the Raman spectrum of graphene under biaxial (e.g. isotropic) strain. Our Gruneisen parameters are in excellent agreement with the theoretical values. Discrepancy in the previously reported values is attributed to the interaction of graphene with the substrate. Bilayer balloons (intentionally pressurized membranes) have been used to avoid the effect of the substrate and to study the dependence of strain on the inter-layer interactions.

cond-mat.mes-hall↗

arXiv2011

Electrochemical behaviour of monolayer and bilayer graphene

Results of a study on the electrochemical properties of exfoliated single and multilayer graphene flakes are presented. Graphene flakes were deposited on silicon/silicon oxide wafers to enable fast and accurate characterization by optical microscopy and Raman spectroscopy. Conductive silver paint and silver wires were used to fabricate contacts; epoxy resin was employed as masking coating in order to expose a stable, well defined area of graphene. Both multilayer and monolayer graphene microelectrodes showed quasi-reversible behavior during voltammetric measurements in potassium ferricyanide. However, the standard heterogeneous charge transfer rate constant, k°, was estimated to be higher for mono-layer graphene flakes.

cond-mat.mes-hall↗

arXiv2011

High-Yield Production and Transfer of Graphene Flakes Obtained by Anodic Bonding

We report large-yield production of graphene flakes on glass by anodic bonding. Under optimum conditions, we counted several tens of flakes with lateral size around 20-30 μm and few tens of flakes with larger size. 60-70% of the flakes have negligible D peak. We show that it is possible to easily transfer the flakes by wedging technique. The transfer on silicon does not damage graphene and lowers the doping. The charge mobility of the transferred flakes on silicon is of the order of 6000 cm^2/V s (at carrier concentration of 10^12 cm^-2), which is typical for devices prepared on this substrate with exfoliated graphene.

cond-mat.mes-hall↗

arXiv2006

Born-Oppenheimer Breakdown in Graphene

The Born-Oppenheimer approximation (BO) has proven effective for the accurate determination of chemical reactions, molecular dynamics and phonon frequencies in a wide range of metallic systems. Graphene, recently discovered in the free state, is a zero band-gap semiconductor, which becomes a metal if the Fermi energy is tuned applying a gate-voltage Vg. Graphene electrons near the Fermi energy have twodimensional massless dispersions, described by Dirac cones. Here we show that a change in Vg induces a stiffening of the Raman G peak (i.e. the zone-center E2g optical phonon), which cannot be described within BO. Indeed, the E2g vibrations cause rigid oscillations of the Dirac-cones in the reciprocal space. If the electrons followed adiabatically the Dirac-cone oscillations, no change in the phonon frequency would be observed. Instead, since the electron-momentum relaxation near the Fermi level is much slower than the phonon motion, the electrons do not follow the Dirac-cone displacements. This invalidates BO and results in the observed phonon stiffening. This spectacular failure of BO is quite significant since BO has been the fundamental paradigm to determine crystal vibrations from the early days of quantum mechanics.

cond-mat.mes-hall↗