Effects of temperature and ammonia flow rate on the chemical vapour deposition growth of nitrogen-doped graphene.

We doped graphene in situ during synthesis from methane and ammonia on copper in a low-pressure chemical vapour deposition system, and investigated the effect of the synthesis temperature and ammonia concentration on the growth. Raman and X-ray photoelectron spectroscopy was used to investigate the quality and nitrogen content of the graphene and demonstrated that decreasing the synthesis temperature and increasing the ammonia flow rate results in an increase in the concentration of nitrogen dopants up to ca. 2.1% overall. However, concurrent scanning electron microscopy studies demonstrate that decreasing both the growth temperature from 1000 to 900 °C and increasing the N/C precursor ratio from 1/50 to 1/10 significantly decreased the growth rate by a factor of six overall. Using scanning tunnelling microscopy we show that the nitrogen was incorporated mainly in substitutional configuration, while current imaging tunnelling spectroscopy showed that the effect of the nitrogen on the density of states was visible only over a few atom distances.

Structure-color-species correlation in photonic nanoarchitectures occurring in blue lycaenid butterfly scales.

The blue colored males of nine Polyommatine butterfly species were investigated under the aspect of color-structure-species correlation. A large number of individuals from museum collections (in total more than 100) were used to obtain average reflectance spectra to reduce the effect of individual variations as much as possible. Structural characteristics were investigated by scanning electron microscopy and transmission electron microscopy. The relevant structural data were extracted using the Biophot Analyzer software. It was found that the position of the main reflectance peak is decided primarily by the nearest neighbor distance of holes in the perforated layers constituting the pepper-pot type structure. However, very different value of the 2D filling factor may have a large enough effect on the spectral position and the width and asymmetry of the peak to overrule the classification on taking into account only the nearest neighbor distance. The comparison of the structural and spectral data may indicate that the species Polyommatus amandus may constitute an evolutionary link between different groups of species. The examined pepper-pot type nanoarchitectures show that with the alteration of the structural parameters (first neighbor distance, 2D filling factor) the tuning of the reflectance of such nanoarchitectures may be achieved. These type of nanoarchitectures may be attractive for practical applications as their large scale manufacturing may require less strict conditions as compared with fully regular nanoarchitectures.

Scanning tunneling microscopy and spectroscopy of nitrogen doped multi-walled carbon nanotubes produced by the pyrolysis of ferrocene and benzylamine.

In this work, carbon nanotube samples were produced by aerosol chemical vapour deposition from a solution of ferrocene in benzylamine. The multi-walled nanotubes produced by this method were investigated by TEM, SEM/EDS, scanning tunneling microscopy (STM) and tunneling spectroscopy (STS). The dl/dV curves obtained from the STS measurements showed asymmetric density of states (DOS) in nanotubes, with higher DOS above the Fermi energy. These STS measurements and the EDS analysis indicate successful doping with nitrogen originating from the decomposition of benzylamine.

Apparent diameter of carbon nanotubes in scanning tunnelling microscopy measurements.

Geometric effects influencing scanning tunnelling microscopy (STM) image formation of single wall carbon nanotubes (SWCNTs) were studied within the framework of a simple model potential. We focused on the geometrical effects which may influence the tunnelling probabilities and lead to discrepancies between the apparent height of the nanotubes measured by STM and their real geometrical diameter. We found that there are two main factors responsible for the underestimation of nanotubes diameter by measuring their height in STM images: (1) the curvature of the nanotube affects the cross sectional shape of the tunnelling channel; (2) the decay rate of tunnelling probabilities inside the tunnel gap increases with increasing curvature of the electrodes. For a nanotube with 1 nm diameter an apparent flattening of about 10%, due to these geometry-related effects, is predicted. Furthermore these effects are found to be dependent on the diameter of the tubes and tip-sample distances: an increasing flattening of the tubes is predicted for decreasing tube diameter and increasing tip-sample distance.

The structure and properties of graphene on gold nanoparticles.

Graphene covered metal nanoparticles constitute a novel type of hybrid material, which provides a unique platform to study plasmonic effects, surface-enhanced Raman scattering (SERS), and metal-graphene interactions at the nanoscale. Such a hybrid material is fabricated by transferring graphene grown by chemical vapor deposition onto closely spaced gold nanoparticles produced on a silica wafer. The morphology and physical properties of nanoparticle-supported graphene are investigated by atomic force microscopy, optical reflectance spectroscopy, scanning tunneling microscopy and spectroscopy (STM/STS), and confocal Raman spectroscopy. This study shows that the graphene Raman peaks are enhanced by a factor which depends on the excitation wavelength, in accordance with the surface plasmon resonance of the gold nanoparticles, and also on the graphene-nanoparticle distance which is tuned by annealing at moderate temperatures. The observed SERS activity is correlated with the nanoscale corrugation of graphene. STM and STS measurements show that the local density of electronic states in graphene is modulated by the underlying gold nanoparticles.

A model for the hillock formation on graphite surfaces by 246 MeV Kr+ ions.

Scanning tunnelling microscopy has been used to study the effect of ion bombardment at different angles of incidence on a graphite surface. The 246 MeV energy of Kr+ ions was selected in the medium energy range, where the electronic and nuclear stopping is nearly balanced. The low dose (1 x 10(12)/cm2) of ions allows the characterization of single features caused by bombardment in perpendicular, at 30 degrees and at 60 degrees incidence. The density of hillocks caused by the ion bombardment is significantly lower than the ion dose and this density depends on the angle of incidence. The hillocks are attributed to knocked-on atoms leaving the sample surface. A simple model for the scattering process is presented to enlighten the hillock density differences. Other features produced by the ion bombardment, such as elongated traces and (square root of 3 x square root of 3) R30 superstructures are also reported.

On the growth mechanism of single-walled carbon nanotubes by catalytic carbon vapor deposition on supported metal catalysts.

A comprehensive kinetic study was performed to throw light on the formation mechanism of single walled carbon nanotubes (SWNTs) in chemical vapor deposition processes. SWNTs were synthesized by catalytic decomposition of methane or ethylene on supported transition metal catalysts. Kinetic curves (the amount of SWNT as a function of time) were obtained as a function of the nature and the preparation of the supported catalysts, temperature, the fluxes of the gases (the reagent hydrocarbon and the carrying gas), and the partial pressure of the hydrocarbon. The final products were characterized by transmission electron microscopy, Raman spectroscopy, chemical analysis, and thermogravimetric measurements. The fundamental factors determining the SWNT formation are discussed in detail, taking into consideration several observations from the literature as well.

Role of photonic-crystal-type structures in the thermal regulation of a Lycaenid butterfly sister species pair.

One of the possible functions of the photonic-crystal structure found on the wing scales of some butterflies is investigated. The optical and electron microscopic investigation of two male butterflies-blue (colored) and brown (discolored)-representing a sister species pair and originating from different altitudes, revealed that the blue color can be attributed unambiguously to the fine, spongelike medium, called "pepper-pot structure," present between the ridges and the cross ribs in the scales of the colored butterfly. Only traces of this structure can be found on the scales of the discolored butterfly. Other physical measurements, mainly optical reflectivity, transmission, and thermal measurements, are correlated with structural data and simulation results. The thermal measurements reveal that under identical illumination conditions the high-altitude butterfly reaches a temperature 1.3-1.5 times the temperature reached by the low-altitude butterfly. This is attributed to the photonic-crystal-like behavior of the pepper-pot structure, which significantly reduces the penetration of light with wavelength in the blue region of the spectrum into the body of the scales. This sheds some light on the adaptation that enhances the survival chance of the butterfly in a cold environment rich in blue and UV radiation.

Temperature and saturation dependence in the vapor sensing of butterfly wing scales.

The sensing of gasses/vapors in the ambient air is the focus of attention due to the need to monitor our everyday environment. Photonic crystals are sensing materials of the future because of their strong light-manipulating properties. Natural photonic structures are well-suited materials for testing detection principles because they are significantly cheaper than artificial photonic structures and are available in larger sizes. Additionally, natural photonic structures may provide new ideas for developing novel artificial photonic nanoarchitectures with improved properties. In the present paper, we discuss the effects arising from the sensor temperature and the vapor concentration in air during measurements with a photonic crystal-type optical gas sensor. Our results shed light on the sources of discrepancy between simulated and experimental sensing behaviors of photonic crystal-type structures. Through capillary condensation, the vapors will condensate to a liquid state inside the nanocavities. Due to the temperature and radius of curvature dependence of capillary condensation, the measured signals are affected by the sensor temperature as well as by the presence of a nanocavity size distribution. The sensing materials used are natural photonic nanoarchitectures present in the wing scales of blue butterflies.

Controlling the nanoscale rippling of graphene with SiO2 nanoparticles.

The electronic properties of graphene can be significantly influenced by mechanical strain. One practical approach to induce strain in graphene is to transfer atomically thin membranes onto pre-patterned substrates with specific corrugations. The possibility of using nanoparticles to impart extrinsic rippling to graphene has not been fully explored yet. Here we study the structure and elastic properties of graphene grown by chemical vapour deposition and transferred onto a continuous layer of SiO2 nanoparticles with diameters of around 25 nm, prepared on a Si substrate by the Langmuir-Blodgett technique. We show that the corrugation of the transferred graphene, and thus the membrane strain, can be modified by annealing at moderate temperatures. The membrane parts bridging the nanoparticles are suspended and can be reversibly lifted by the attractive forces between an atomic force microscope tip and graphene. This allows the dynamic control of the local morphology of graphene nanomembranes.

Bioinspired artificial photonic nanoarchitecture using the elytron of the beetle Trigonophorus rothschildi varians as a 'blueprint'.

An unusual, intercalated photonic nanoarchitecture was discovered in the elytra of Taiwanese Trigonophorus rothschildi varians beetles. It consists of a multilayer structure intercalated with a random distribution of cylindrical holes normal to the plane of the multilayer. The nanoarchitectures were characterized structurally by scanning electron microscopy and optically by normal incidence, integrated and goniometric reflectance measurements. They exhibit an unsaturated specular and saturated non-specular component of the reflected light. Bioinspired, artificial nanoarchitectures of similar structure and with similar properties were realized by drilling holes of submicron size in a multilayer structure, showing that such photonic nanoarchitectures of biological origin may constitute valuable blueprints for artificial photonic materials.

Wing scale microstructures and nanostructures in butterflies--natural photonic crystals.

The aim of our study was to investigate the correlation between structural colour and scale morphology in butterflies. Detailed correlations between blue colour and structure were investigated in three lycaenid subfamilies, which represent a monophylum in the butterfly family Lycaenidae (Lepidoptera): the Coppers (Lycaeninae), the Hairstreaks (Theclinae) and the Blues (Polyommatinae). Complex investigations such as spectral measurements and characterization by means of light microscopy, scanning electron microscopy and transmission electron microscopy enabled us to demonstrate that: (i) a wide array of nanostructures generate blue colours; (ii) monophyletic groups use qualitatively similar structures; and (iii) the hue of the blue colour is characteristic for the microstructure and nanostructure of the body of the scales.