Amorphous Carbon Nitride Films: Surface and Subsurface Composition and Bonding.

To obtain quantitative information about the composition and bonding of atoms located at and beyond the analyzed solid surface nondestructively, we applied angle-resolved X-ray photoelectron spectroscopy aided by the maximum entropy method to air-exposed amorphous carbon nitride films deposited by pulsed laser deposition of diamond-like carbon modified by low-energy nitrogen ion bombardment during film growth. We demonstrate that the composition, chemical bonding, and mass density vary significantly from the top surface to a shallow subsurface region. The analyzed samples, in a shallow surface region of ∼1 nm, are composed of oxygen, nitrogen, hydrogen, and mostly carbon in sp2 hybridization. In a deeper region, the C sp3 content increases substantially going to a maximum, whereas the nitrogen percentage decreases to a minimum, then increases, and tends to saturate. Special attention has been paid to in-depth distributions of carbon atoms in trigonal and tetragonal arrangements because they specify numerous physical and chemical properties of carbon-based materials. These results indicate that the interaction of DLC:N surfaces with surroundings can be influenced, barring oxygen and nitrogen, by sp2-bonded carbon atoms located near the surface of the samples. The obtained results can be useful for developing a deeper understanding of the interaction between DLC:N layer surfaces and their surroundings and particularly with living tissue.

The Effects of Ultrasound Treatment of Graphite on the Reversibility of the (De)Intercalation of an Anion from Aqueous Electrolyte Solution.

Low cycling stability is one of the most crucial issues in rechargeable batteries. Herein, we study the effects of a simple ultrasound treatment of graphite for the reversible (de)intercalation of a ClO4- anion from a 2.4 M Al(ClO4)3 aqueous solution. We demonstrate that the ultrasound-treated graphite offers the improved reversibility of the ClO4- anion (de)intercalation compared with the untreated samples. The ex situ and in situ Raman spectroelectrochemistry and X-ray diffraction analysis of the ultrasound-treated materials shows no change in the interlayer spacing, a mild increase in the stacking order, and a large increase in the amount of defects in the lattice accompanied by a decrease in the lateral crystallite size. The smaller flakes of the ultrasonicated natural graphite facilitate the improved reversibility of the ClO4- anion electrochemical (de)intercalation and a more stable electrochemical performance with a cycle life of over 300 cycles.

High-Temperature Fire Resistance and Self-Extinguishing Behavior of Cellular Graphene.

The ability to protect materials from fire is vital to many industrial applications and life safety systems. Although various chemical treatments and protective coatings have proven effective as flame retardants, they provide only temporary prevention, as they do not change the inherent flammability of a given material. In this study, we demonstrate that a simple change of the microstructure can significantly boost the fire resistance of an atomically thin material well above its oxidation stability temperature. We show that free-standing graphene layers arranged in a three-dimensional (3D) cellular network exhibit completely different flammability and combustion rates from a graphene layer placed on a substrate. Covalently cross-linked cellular graphene aerogels can resist flames in air up to 1500 °C for a minute without degrading their structure or properties. In contrast, graphene on a substrate ignites immediately above 550 °C and burns down in a few seconds. Raman spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric studies reveal that the exceptional fire-retardant and self-extinguishing properties of cellular graphene originate from the ability to prevent carbonyl defect formation and capture nonflammable carbon dioxide gas in the pores. Our findings provide important information for understanding graphene's fire-retardant mechanism in 3D structures/assemblies, which can be used to enhance flame resistance of carbon-based materials, prevent fires, and limit fire damage.

Long-term changes in Al thin-film extreme ultraviolet filters.

Thin-film Al filters are very popular owing to their high transmittance in the wavelength range of 17-67 nm and low transmittance in the visible and near-UV regions; however, they are prone to oxidation. The amorphous Al2O3 layers on the Al surfaces have much smaller transmittance than the bulk Al material; therefore, they strongly influence the total transmittance of the filter. This paper not only provides the transmittance of very old Al filters but also maps the transmittance development of Al filters over two years since their delivery (in 2016) in an uncontrolled atmosphere.

On the Origin of Reduced Cytotoxicity of Germanium-Doped Diamond-Like Carbon: Role of Top Surface Composition and Bonding.

This work attempts to understand the behaviour of Ge-induced cytotoxicity of germanium-doped hydrogen-free diamond-like carbon (DLC) films recently thoroughly studied and published by Jelinek et al. At a low doping level, the films showed no cytotoxicity, while at a higher doping level, the films were found to exhibit medium to high cytotoxicity. We demonstrate, using surface-sensitive methods-two-angle X-ray-induced core-level photoelectron spectroscopy (ARXPS) and Low Energy Ion Scattering (LEIS) spectroscopy, that at a low doping level, the layers are capped by a carbon film which impedes the contact of Ge species with tissue. For higher Ge content in the DLC films, oxidized Ge species are located at the top surface of the layers, provoking cytotoxicity. The present results indicate no threshold for Ge concentration in cell culture substrate to avoid a severe toxic reaction.

Adhesion and differentiation of Saos-2 osteoblast-like cells on chromium-doped diamond-like carbon coatings.

Diamond-like carbon (DLC) thin films are promising for use in coating orthopaedic, dental and cardiovascular implants. The problem of DLC layers lies in their weak layer adhesion to metal implants. Chromium is used as a dopant for improving the adhesion of DLC films. Cr-DLC layers were prepared by a hybrid technology, using a combination of pulsed laser deposition (PLD) from a graphite target and magnetron sputtering. Depending on the deposition conditions, the concentration of Cr in the DLC layers moved from zero to 10.0 at.%. The effect of DLC layers with 0.0, 0.9, 1.8, 7.3, 7.7 and 10.0 at.% Cr content on the adhesion and osteogenic differentiation of human osteoblast-like Saos-2 cells was assessed in vitro. The DLC samples that contained 7.7 and 10.0 at.% of Cr supported cell spreading on day 1 after seeding. On day three after seeding, the most apparent vinculin-containing focal adhesion plaques were also found on samples with higher concentrations of chromium. On the other hand, the expression of type I collagen and alkaline phosphatase at the mRNA and protein level was the highest on Cr-DLC samples with a lower concentration of Cr (0-1.8 at.%). We can conclude that higher concentrations of chromium supported cell adhesion; however DLC and DLC doped with a lower concentration of chromium supported osteogenic cell differentiation.

Thiol-yne reaction on boron-doped diamond electrodes: application for the electrochemical detection of DNA-DNA hybridization events.

Boron-doped diamond (BDD) interfaces were chemically functionalized through the catalyst free thiol-yne reaction. Different thiolated precursors (e.g., perfluorodecanethiol, 6-(ferrocenyl)-hexanethiol, DNA) were successfully "clicked" to alkynyl-terminated BDD by irradiating the interface at 365 nm for 30 min. Thiolated oligonucleotide strands were immobilized using the optimized reaction conditions, and the surface concentration was tuned to obtain a surface coverage of 3.1 × 10(12) molecules cm(-2). Electrochemical impedance spectroscopy (EIS) was employed to follow the kinetics of hybridization and dehybridization events. The sensitivity of the oligonucleotide modified BDD interface was assayed, and a detection limit of 1 nM was obtained.

Nanomolar hydrogen peroxide detection using horseradish peroxidase covalently linked to undoped nanocrystalline diamond surfaces.

In this article, we report on the low-level detection of hydrogen peroxide, a key player in the redox signaling pathway and a toxic product in the cellular system, using a colorimetric solution assay. Amine-terminated undoped nanocrystalline diamond thin films were grown on glass using a linear-antenna microwave plasma CVD process. The diamond surface consists mainly of -NH(2) termination. The aminated diamond surface was decorated with horseradish peroxidase (HRP) enzyme using carbodiimide coupling chemistry. The success of the HRP immobilization was confirmed by X-ray photoelectron spectroscopy (XPS). The enzymatic activity of immobilized HRP was determined with a colorimetric test based on the HRP-catalyzed oxidation of 2,2'-azino-bis(3-ethylbenzothiazoline-6-sufonic acid (ABTS) in the presence of hydrogen peroxide. The surface coverage of active HRP was estimated to be Γ = 7.3 × 10(13) molecules cm(-2). The use of the functionalized diamond surface as an optical sensor for the detection of hydrogen peroxide with a detection limit of 35 nM was demonstrated.

Electron spectra line shape analysis of highly oriented pyrolytic graphite and nanocrystalline diamond.

The X-ray excited Auger electron spectroscopy (XAES), X-ray photoelectron spectroscopy (XPS) and elastic peak electron spectroscopy (EPES) methods were applied in investigating samples of nanocrystalline diamond and highly oriented pyrolytic graphite of various C sp(2)/sp(3) ratios, crystallinity conditions and grain sizes. The composition at the surface was estimated from the XPS. The C sp(2)/sp(3) ratio was evaluated from the width of the XAES first derivative C KLL spectra and from fitting of XPS C 1s spectra into components. The pattern recognition (PR) method applied for analyzing the spectra line shapes exhibited high accuracy in distinguishing different carbon materials. The PR method was found to be a potentially useful approach for identification, especially important for technological applications in fields of materials engineering and for controlling the chemical reaction products during synthesis.