Detection and Visualization of Minor Irradiation-Induced Changes in Polytetrafluoroethylene (PTFE) by Raman Spectroscopy.

Exposure of polytetrafluoroethylene (PTFE) to argon plasma results in chemical modification of the polymer near the surface. Interestingly, PTFE modification can be induced by the sub-band gap ultraviolet (UV) irradiation. In the latter case, the changes in the chemical structure are very subtle, and they are practically invisible to conventional experimental techniques. Raman spectra of irradiated and raw samples show practically identical peaks. However, the baseline that is commonly considered as an unwanted spectral component contains an important information that reflects the minor structural changes. With the proper data analysis, this allows us to visualize the effects of the argon plasma and sub-band gap UV irradiation on the polymer.

Resistive Switching in Bigraphene/Diamane Nanostructures Formed on a La3Ga5SiO14 Substrate Using Electron Beam Irradiation.

Memristors, resistive switching memory devices, play a crucial role in the energy-efficient implementation of artificial intelligence. This study investigates resistive switching behavior in a lateral 2D composite structure composed of bilayer graphene and 2D diamond (diamane) nanostructures formed using electron beam irradiation. The resulting bigraphene/diamane structure exhibits nonlinear charge carrier transport behavior and a significant increase in resistance. It is shown that the resistive switching of the nanostructure is well controlled using bias voltage. The impact of an electrical field on the bonding of diamane-stabilizing functional groups is investigated. By subjecting the lateral bigraphene/diamane/bigraphene nanostructure to a sufficiently strong electric field, the migration of hydrogen ions and/or oxygen-related groups located on one or both sides of the nanostructure can occur. This process leads to the disruption of sp3 carbon bonds, restoring the high conductivity of bigraphene.

On the State of Graphene Oxide Nanosheet in a Polyurethane Matrix.

Thermally stable films were obtained from a water-based polyurethane (PU) dispersion with small (0.1-1.5 wt.%) additions of graphene oxide (GO). The films were studied through elemental analysis, X-ray photoelectron spectroscopy, differential thermogravimetry, and Raman spectroscopy. It was found that the introduction of GO into a PU matrix was accompanied by a partial reduction in graphene oxide nanosheet and an increase in the concentration of defects in GO structure. It has been also established that the [C/N]at ratio in the near-surface layer of PU/GO composite films grows with an increase in the content of graphene oxide in the composite films.

Baseline Search in Raman Spectroscopy by Modified Tikhonov Regularization with Automatic Choice of Both Parameters.

Baseline estimation in vibrational spectroscopy can be done efficiently with Tikhonov regularization. The state-of-the-art approaches, based on asymmetric weighting, require an additional parameter. Besides λ, the penalty for the second derivative, they introduce the asymmetry parameter p that sets different weights for the points above and below the baseline. To choose the parameters "once and for all" is not possible, because they always depend on the noise level and baseline flexibility. Currently, the common practice is to choose these two parameters visually, without any well-defined criteria. The present work shows how such criteria can be constructed in a form of a specific functional. This formulation makes it possible to optimize the regularization parameters for the given spectrum. The Python code is provided for the derivative-and-peak-screened ALS algorithm.

Formation of Diamane Nanostructures in Bilayer Graphene on Langasite under Irradiation with a Focused Electron Beam.

In the presented paper, we studied bilayer CVD graphene transferred to a langasite substrate and irradiated with a focused electron beam through a layer of polymethyl methacrylate (PMMA). Changes in the Raman spectra and an increase in the electrical resistance of bigraphene after irradiation indicate a local phase transition associated with graphene diamondization. The results are explained in the framework of the theory of a chemically induced phase transition of bilayer graphene to diamane, which can be associated with the release of hydrogen and oxygen atoms from PMMA and langasite due to the "knock-on" effect, respectively, upon irradiation of the structure with an electron beam. Theoretical calculations of the modified structure of bigraphene on langasite and the experimental evaluation of sp3-hybridized carbon fraction indicate the formation of diamane nanoclusters in the bigraphene irradiated regions. This result can be considered as the first realization of local tunable bilayer graphene diamondization.

Spin-Induced Switching of Electronic State Populations in Transition Metal Polyphthalocyanines.

Polyphthalocyanines (PPCs) are a new and promising class of two dimensional materials offering versatile avenues for next generation electronic devices. For organic spintronic devices, PPCs can be engineered to tailor the electric and magnetic properties. In this work, we investigate PPC's monolayers with embedded transition metal atoms (TM = Fe, Ni, Cu), utilizing first principle calculations based on spin-polarized generalized gradient approximation (SGGA). PPC sheets with central TM atoms are simulated for the dispersion curves, electronic density of states (DOS), and projected density of states (PDOS) using quantum atomistic toolkit (Quantum ATK) software. According to simulations, the FePPC supercell with four magnetic moments of Fe, aligned in a parallel ferromagnetic (FM) configuration, show the conductive FM state, while in the case of the anti-parallel antiferromagnetic (AFM) order of the magnetic moments, the material exhibits semiconducting non-magnetic behavior. FM-ordered NiPPC displays a metallic state, which is partly suppressed for AFM-ordered NiPPC. In contrast, non-magnetic CuPPC is found to be the best conductor due to its larger PDOS at the Fermi level among all considered systems.

The Concentration of C(sp3) Atoms and Properties of an Activated Carbon with over 3000 m2/g BET Surface Area.

The alkaline activation of a carbonized graphene oxide/dextrin mixture yielded a carbon-based nanoscale material (AC-TR) with a unique highly porous structure. The BET-estimated specific surface area of the material is 3167 m2/g, which is higher than the specific surface area of a graphene layer. The material has a density of 0.34 g/cm3 and electrical resistivity of 0.25 Ω·cm and its properties were studied using the elemental analysis, transmission electron microscopy (TEM), electron diffraction (ED), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray induced Auger electron spectroscopy (XAES), and electron energy loss spectroscopy (EELS) in the plasmon excitation range. From these data, we derive an integral understanding of the structure of this material. The concentration of sp3 carbon atoms was found to be relatively low with an absolute value that depends on the measurement method. It was shown that there is no graphite-like (002) peak in the electron and X-ray diffraction pattern. The characteristic size of a sp2-domain in the basal plane estimated from the Raman spectra was 7 nm. It was also found that plasmon peaks in the EELS spectrum of AC-TR are downshifted compared to those of graphite.

Reduced Graphene Oxide Aerogel inside Melamine Sponge as an Electrocatalyst for the Oxygen Reduction Reaction.

A graphene oxide aerogel (GOA) was formed inside a melamine sponge (MS) framework. After reduction with hydrazine at 60 °C, the electrical conductive nitrogen-enriched rGOA-MS composite material with a specific density of 20.1 mg/cm3 was used to fabricate an electrode, which proved to be a promising electrocatalyst for the oxygen reduction reaction. The rGOA-MS composite material was characterized by elemental analysis, scanning electron microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. It was found that nitrogen in the material is presented by different types with the maximum concentration of pyrrole-like nitrogen. By using Raman scattering it was established that the rGOA component of the material is graphene-like carbon with an average size of the sp2-domains of 5.7 nm. This explains a quite high conductivity of the composite obtained.

Phonon propagation scale and nanoscale order in vitreous silica from Raman spectroscopy.

For nanoscale systems such as nanoparticles and 3D-bonded networks, the range of spatial coherence is well reflected in the Raman spectral pattern. For confined, or localized, phonons, the range of q-points contributing to the spectrum depends on the phonon confinement length, which makes it possible to derive size information from the spectra. In this work, the Raman spectrum of vitreous silica is described as localized phonons of an SiO2 network. The convergence of the spectral pattern with the confinement size is studied. It is shown that the phonon propagation scale in vitreous silica is within the 0.5-2 nm range.

Phonon confinement and size effect in Raman spectra of ZnO nanoparticles.

We study Raman spectra of ZnO nanoparticles of 5-12 nm size in the whole range of the first-order phonon bands. We apply the 3D phonon confinement model (PCM) for the interpretation of the observed Raman spectra. It is found that PCM is well applicable to the acoustic modes as well as to the optical ones, despite the fact that PCM has been thought not to be suitable for acoustic phonons. We show that the asymptotic behavior of PCM for the small-size limit is more consistent with the observation than that of the elastic sphere model (ESM). Furthermore, PCM gives detailed information on the complex size-dependent shapes of the phonon bands.

An asymmetric fitting function for condensed-phase Raman spectroscopy.

Asymmetric lineshapes are experimentally observed in the Raman spectra of different classes of condensed matter. Determination of the peak parameters, typically done with symmetric pseudo-Voigt functions, in such situations yields unreliable results. While a wide choice of asymmetric fitting functions is possible, for the function to be practically useful, it should satisfy several criteria: simple analytic form, minimum parameters, description of the symmetric shape as "zero case", estimation of the desired peak parameters in a straightforward way and, above all, adequate description of the experimental data. In this work we formulate the asymmetric pseudo-Voigt function by damped perturbation of the original symmetric shapes with one asymmetry-related parameter. The damped character of the perturbation ensures by construction consistent behavior of the line tails. We test the asymmetric function by fitting the experimental Raman spectra. The results show that the function is able to describe a wide range of experimentally observed asymmetries for different natures of asymmetric broadening, including 3D and 2D crystals, nanoparticles, polymers, and molecular solids and liquids.

Communication: three-dimensional model for phonon confinement in small particles: quantitative bandshape analysis of size-dependent Raman spectra of nanodiamonds.

Raman spectroscopy of nano-scale materials is facing a challenge of developing a physically sound quantitative approach for the phonon confinement effect, which profoundly affects the phonon Raman band shapes of small particles. We have developed a new approach based on 3-dimensional phonon dispersion functions. It analyzes the Raman band shapes quantitatively in terms of the particle size distributions. To test the model, we have successfully obtained good fits of the observed phonon Raman spectra of diamond nanoparticles in the size range from 1 to 100 nm.

Vapor-phase synthesis of indium (III) oxide nanocrystals.

A new way for chemical vapor deposition of indium (111) oxide is presented. It can be used to obtain both polycrystalline films and different arrays of nanocrystals. Used as a catalyst, In or Au thin films can afford selective deposition on an arbitrary spot of surface. The obtained materials were characterized electron microscopy, X-ray diffraction and cathodoluminescence methods.