Christian Kramberger

Raman spectroscopy of fullerenes and fullerene-nanotube composites

The discovery of fullerenes in 1985 opened a completely new field of materials research. Together with the single–wall carbon nanotubes (SWCNTs) discovered later, these curved carbon networks are a playground for pure as well as applied science. We present a review of Raman spectroscopy of fullerenes, SWCNTs and composite materials. Beginning with pristine C60, we discuss intercalated C60 compounds and polymerized C60, as well as higher and endohedral fullerenes. Concerning SWCNTs, we show how the diameter distribution can be obtained from the Raman spectra and how doping modifies the spectra. Finally, the Raman response of C60 encapsulated into SWCNTs (C60 peapods) is discussed.

Direct probe of linearly dispersing 2D interband plasmons in a free-standing graphene monolayer

In low-dimensional systems, a detailed understanding of plasmons and their dispersion relation is crucial for applying their optical response in the field of plasmonics. Electron energy-loss spectroscopy is a direct probe of these excitations. Here we report on electron energy-loss spectroscopy results on the dispersion of the ? plasmons in free-standing graphene monolayers at the momentum range of 0?|q|?0.5???1 and parallel to the ?-M direction of the graphene Brillouin zone. In contrast to the parabolic dispersion in graphite and in good agreement with theoretical predictions of a 2D electron gas of Dirac electrons, linear ? plasmon dispersion is observed. As with previous EELS results obtained from single-wall carbon nanotubes, this can be explained by local-field effects in the anisotropic 2D system yielding a significant contribution of the low-energy band structure on the high-energy ? plasmon response.

Effects of the reaction atmosphere composition on the synthesis of single and multiwalled nitrogen-doped nanotubes

Single and multiwalled nitrogen-doped carbon nanotubes were grown by chemical vapor deposition varying the feedstock composition between pure acetonitrile and ethanol/acetonitrile mixtures. The advantage of using CN sources that develop close vapor pressure values has been used in order to elucidate the effects of the reaction atmosphere in the synthesis of N-doped nanotubes. Our findings show that the morphology of the nanotube material depends strongly on the composition of the reaction atmosphere. When carrying out the experiments in an atmosphere solely determined by the vapor pressure of the feedstock components, improved homogeneity is achieved with pure CN sources or low concentration of the foreign solute. Under these conditions the temperature has strong influence in the diameter distribution.

Catalyst and Chirality Dependent Growth of Carbon Nanotubes Determined Through Nano‐Test Tube Chemistry

[*] Dr. Hidetsugu Shiozawa, Prof. S. Ravi P. Silva Advanced Technology Institute, University of Surrey, Guildford, GU2 7XH (UK) Email: h.shiozawa@surrey.ac.uk; s.silva@surrey.ac.uk Dr. Christian Kramberger, Dr. Rudolf Pfeiffer, Prof. Hans Kuzmany, Prof. Thomas Pichler Faculty of Physics, University of Vienna, Strudlhofgasse 4, 1090 Vienna (Austria) Dr. Zheng Liu, Dr. Kazu Suenaga Research Center for Advanced Carbon Materials, AIST, Tsukuba 305-8565 (Japan) Dr. Hiromichi Kataura Nanotechnology Research Institute, AIST, Tsukuba 305-8562 and JST, CREST (Japan)

Diameter selective reaction processes of single-wall carbon nanotubes

A method is presented which allows the study of diameter selective reactions in single-wall carbon nanotubes with an unprecedented accuracy. It is based on the transformation of fullerene peapods into double-wall carbon nanotubes and the study of the resulting diameter distribution of the inner nanotubes with Raman spectroscopy. This yields a spectral resolution increase of about 40 for the modes of different tubes. The method is demonstrated for the diameter selective healing of nanotube defects and yield from C70 peapod samples. The growth of very small diameter inner tubes from C70 peapods is demonstrated, which challenges the models of inner nanotube formation. An anomalous absence of middiameter inner tubes is explained by the suppressed amount of C70 peapods in the transition region between standing and lying C70 configurations.

Reversible Diameter Modulation of Single-Walled Carbon Nanotubes by Acetonitrile-Containing Feedstock

Changing the carbon feedstock from pure ethanol to a 5 vol % mixture of acetonitrile in ethanol during the growth of vertically aligned single-walled carbon nanotubes (SWNTs) reduces the mean diameter of the emerging SWNTs from approximately 2 to 1 nm. We show this feedstock-dependent change is reversible and repeatable, as demonstrated by multilayered vertically aligned SWNT structures. The reversibility of this process and lack of necessity for catalyst modification provides insight into the role of nitrogen in reducing the SWNT diameter.

Unraveling the 3D Atomic Structure of a Suspended Graphene/hBN van der Waals Heterostructure

In this work we demonstrate that a free-standing van der Waals heterostructure, usually regarded as a flat object, can exhibit an intrinsic buckled atomic structure resulting from the interaction between two layers with a small lattice mismatch. We studied a freely suspended membrane of well-aligned graphene on a hexagonal boron nitride (hBN) monolayer by transmission electron microscopy (TEM) and scanning TEM (STEM). We developed a detection method in the STEM that is capable of recording the direction of the scattered electron beam and that is extremely sensitive to the local stacking of atoms. A comparison between experimental data and simulated models shows that the heterostructure effectively bends in the out-of-plane direction, producing an undulated structure having a periodicity that matches the moiré wavelength. We attribute this rippling to the interlayer interaction and also show how this affects the intralayer strain in each layer.

A broadband and high throughput single-monochromator Raman spectrometer: Application for single-wall carbon nanotubes

We present a high sensitivity single-monochromator Raman spectrometer which allows operation with a tunable laser source. The instrument is based on the modification of a commercial Raman spectrometer; such instruments operate with interference Rayleigh filters which also act as laser mirrors and are usually considered as inherently narrow band. In our design, the two tasks are separated and the filter can be freely rotated without much effect on the light alignment. Since rotation shifts the filter passband, this modification allows tunable operation with efficient stray light filtering down to 150 cm(-1). The design is optimized for single-wall carbon nanotubes, for which the performance is demonstrated using a tunable dye laser source. The spectrometer thus combines the high sensitivity with the broadband characteristics of usual triple monochromator systems.

A Fourier transform Raman spectrometer with visible laser excitation

We present the development and performance of a Fourier transformation (FT)-based Raman spectrometer working with visible laser (532 nm) excitation. It is generally thought that FT-Raman spectrometers are not viable in the visible range where shot noise limits the detector performance and therein they are outperformed by grating based, dispersive ones. We show that contrary to this common belief, the recent advances of high-performance interference filters makes the FT-Raman design a valid alternative to dispersive Raman spectrometers for samples which do not luminesce. We critically compare the performance of our spectrometer to two dispersive ones: a home-built single channel and a state-of-the-art charge coupled device-based instruments. We demonstrate a similar or even better sensitivity than the charge coupled device-based dispersive spectrometer particularly when the laser power density is considered. The instrument possesses all the known advantages of the FT principle of spectral accuracy, high throughput, and economic design. We also discuss the general considerations, which helps the community reassess the utility of the different Raman spectrometer designs. Copyright

The Raman Response of Double Wall Carbon Nanotubes

Raman spectroscopy on carbon nanotubes (CNT) yields a rich variety of information owing to the close interplay between electronic and vibrational properties. In this paper, we review the properties of double wall carbon nanotubes (DWCNTs). In particular, it is shown that SWCNT encapsulating C60, so-called peapods, are transformed into DWCNTs when subject to a high temperature treatment. The inner tubes are grown in a catalyst free environment and do not suffer from impurities or defects that are usually encountered for as-grown SWCNTs or DWCNTs. As a consequence, the inner tubes are grown with a high degree of perfection as deduced from the unusually narrow radial breathing mode (RBM) lines. This apostrophizes the interior of the SWCNTs as a nano-clean room. The mechanism of the inner nanotube production from C60 is discussed. We also report recent studies aimed at the simplification and industrial scaling up of the DWCNT production process utilizing a low temperature peapod synthesis method. A splitting of the RBMs of inner tubes is observed. This is related to the interaction between the two shells of the DWCNTs as the same inner tube type can be encapsulated in different outer ones. The sharp appearance of the inner tube RBMs allows an assignment of the tube modes to (n,m) indexes and thus provides a precise determination of the relation between the tube diameter and the RBM frequencies.