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H. Kuzmany

Publications and source records attributed to H. Kuzmany.

15 recordsLinked to original sources

Linearly controlled arrangement of $^{13}$C isotopes in single-wall carbon nanotubes

The growth of single wall carbon nanotubes (SWCNT) inside host SWCNTs remains a compelling alternative to the conventional catalyst induced growth processes. It not only provides a catalyst free process but the ability to control the constituents of the inner tube if appropriate starting molecules are used. We report herein the growth of inner SWCNTs from $^{13}$C labeled toluene and natural carbon C$_{60}$. The latter molecule is essentially a stopper which acts to retain the smaller toluene. The Raman spectrum of the inner nanotubes is anomalous as it contains a highly isotope shifted "tail", which cannot be explained by assuming a homogeneous distribution of the isotopes. {\color{black}Semi-empirical} calculations of the Raman modes indicate that this unsual effect is explicable if small clusters of $^{13}$C are assumed. This indicates the absence of carbon diffusion during the inner tube growth. When combined with appropriate molecular recognition, this may enable a molecular engineering of the atomic and isotope composition of the inner tubes.

cond-mat.mes-hall

Indirect Exchange Interaction in Fully Metal-Semiconductor Separated SWCNTs Revealed by ESR

The ESR response from highly metal-semiconductor(M-SC) separated SWCNTs for temperatures T between 0.39 and 200 K is characteristically different for the two systems. The signal originates from defect spins but interaction with free electrons leads to a larger line width for M tubes. The latter decreases with increasing T whereas it increases with T for SC tubes. The spins undergo a ferromagnetic phase transition below around 10 K. Indirect exchange is suggested to be responsible for the spin-spin interaction, supported by RKKY interaction in the case of M tubes. For SC tubes spin-lattice relaxation via an Orbach process is suggested to determine the line width.

cond-mat.mtrl-sci

Inter-shell interaction in double walled carbon nanotubes: charge transfer and orbital mixing

Recent nuclear magnetic resonance measurements on isotope engineered double walled carbon nanotubes (DWCNTs) surprisingly suggest a uniformly metallic character of all nanotubes, which can only be explained by the interaction between the layers. Here we study the inter-shell interaction in DWCNTs by density functional theory and inter-molecular Hückel model. We find charge transfer between the layers using both methods. We show that not only does the charge transfer appear already at the fundamental level of the inter-molecular Hückel model, but also that the spatial distribution of the change in the electron density is well described already at this level of theory. We find that the charge transfer between the walls is on the order of 0.001 e/atom and that the inner tube is always negatively charged. We also observe orbital mixing between the states of the layers. We find that these two effects combined can in some cases lead to a semiconductor--to--metal transition of the double walled tube, but not necessarily in all cases.

cond-mat.mtrl-sci

Superposition of Quantum and Classical Rotational Motions in Sc2C2@C84 Fullerite

The superposition of the quantum rotational motion (tunneling) of the encapsulated Sc2C2 complex with the classical rotational motion of the surrounding C84 molecule in a powder crystal of Sc2C2@C84 fullerite is investigated by theory. Since the quantum rotor is dragged along by the C84 molecule, any detection method which couples to the quantum rotor (in casu the C2 bond of the Sc2C2 complex also probes the thermally excited classical motion (uniaxial rotational diffusion and stochastic meroaxial jumps) of the surrounding fullerene. The dynamic rotation-rotation response functions in frequency space are obtained as convolutions of quantum and classical dynamic correlation functions. The corresponding Raman scattering laws are derived, the overall shape of the spectra and the width of the resonance lines are studied as functions of temperature. The results of the theory are confronted with experimental low-frequency Raman spectra on powder crystals of Sc2C2@C84 [M. Krause et al., Phys. Rev. Lett. 93, 137403 (2004)]. The agreement of theory with experiment is very satisfactory in a broad temperature range.

cond-mat.mtrl-sci

Magnetic fullerenes inside single-wall carbon nanotubes

C59N magnetic fullerenes were formed inside single-wall carbon nanotubes by vacuum annealing functionalized C59N molecules encapsulated inside the tubes. A hindered, anisotropic rotation of C59N was deduced from the temperature dependence of the electron spin resonance spectra near room temperature. Shortening of spin-lattice relaxation time, T_1, of C59N indicates a reversible charge transfer toward the host nanotubes above $\sim 350$ K. Bound C59N-C60 heterodimers are formed at lower temperatures when C60 is co-encapsulated with the functionalized C59N. In the 10-300 K range, T_1 of the heterodimer shows a relaxation dominated by the conduction electrons on the nanotubes.

cond-mat.str-el

Encapsulating C59N azafullerene derivatives inside single-wall carbon nanotubes

Filling of single-wall carbon nanotubes with C59N azafullerene derivatives is reported from toluene solvent at ambient temperature. The filling is characterized by high resolution transmission electron microscopy and Raman spectroscopy. The filling efficiency is the same as for C60 fullerenes and the tube-azafullerene interaction is similar to the tube-C60 interaction. Vacuum annealing of the encapsulated azafullerene results in the growth of inner tubes, however no spectroscopic signature of nitrogen built in the inner walls is detected.

cond-mat.mtrl-sci

NMR Evidence for Gapped Spin Excitations in Metallic Carbon Nanotubes

We report on the spin dynamics of 13C isotope enriched inner-walls in double-wall carbon nanotubes (DWCNT) using 13C nuclear magnetic resonance (NMR). Contrary to expectations, we find that our data set implies that the spin-lattice relaxation time (T1) has the same temperature (T) and magnetic field (H) dependence for most of the innerwall nanotubes detected by NMR. In the high temperature regime (T > 150 K), we find that the T and H dependence of 1/T1T is consistent with a 1D metallic chain. For T < 150 K, we find a significant increase in 1/T1T with decreasing T, followed by a sharp drop below 20 K. The data clearly indicates the formation of a gap in the spin excitation spectrum, where the gap value 2 Delta = 40 K (= 3.7 meV) is H independent.

cond-mat.str-el

Fine Structure of the Radial Breathing Mode in Double-Wall Carbon Nanotubes

The analysis of the Raman scattering cross section of the radial breathing modes of double-wall carbon nanotubes allowed to determine the optical transitions of the inner tubes. The Raman lines are found to cluster into species with similar resonance behavior. The lowest components of the clusters correspond well to SDS wrapped HiPco tubes. Each cluster represents one particular inner tube inside different outer tubes and each member of the clusters represents one well defined pair of inner and outer tubes. The number of components in one cluster increases with decreasing of the inner tube diameter and can be as high as 14.

cond-mat.soft

Highly unperturbed inner tubes in CVD grown double-wall carbon nanotubes

The synthesis of double-wall carbon nanotubes (DWCNTs) with highly unperturbed inner shells is reported using the catalytic vapor deposition method. Temperature dependent and high resolution Raman measurements show an enhanced phonon life-time of the inner tubes with respect to the outer ones and similar diameter SWCNTs. This proves that the inner tubes are unperturbed similar to the inner tubes in peapod-grown DWCNTs. The presence of the outer tube is argued to protect the inner tube from interaction with impurities and also to stabilize the growth of defect free inner tubes. The current material underlines the application potential of DWCNTs.

cond-mat.mtrl-sci

Highly 13C isotope enriched azafullerene, C59N, for nuclear spin labelling

Synthesis of highly $^{13}$C isotope enriched azafullerene, C$_{59}$N embedded in C$_{60}$ is reported. $^{13}$C enriched fullerenes, produced with the Krätschmer-Huffmann process, were subject to a N$_{2}$ discharge that produces C$_{59}$N with a low probability. Raman spectroscopy indicates a homogeneous $^{13}$C distribution. Electron spin resonance measurement (ESR) proves that the C$_{59}$N concentration, 0.2 %, is similar as in non-enriched fullerenes. The ESR spectrum is simulated accurately with the known $^{14}$N and $^{13}$C hyperfine coupling constants. The material enables the nuclear spin-labelling of heterofullerene complexes with a potential for biological applications. It might also find applications as a building element for quantum computation.

cond-mat.mtrl-sci

Interaction between concentric Tubes in DWCNTs

A detailed investigation of the Raman response of the inner tube radial breathing modes (RBMs) in double-wall carbon nanotubes is reported. It revealed that the number of observed RBMs is two to three times larger than the number of possible tubes in the studied frequency range. This unexpected increase in Raman lines is attributed to a splitting of the inner tube response. It is shown to originate from the possibility that one type of inner tube may form in different types of outer tubes and the fact that the inner tube RBM frequency depends on the diameter of the enclosing tube. Finally, a comparison of the inner tube RBMs and the RBMs of tubes in bundles gave clear evidence that the interaction in a bundle is stronger than the interaction between inner and outer tubes.

cond-mat.mtrl-sci

Isotope engineering in carbon nanotube systems

We report on single-wall carbon nanotube (SWCNT) specific $^{13}$C isotope enrichment. The high temperature annealing of isotope enriched fullerenes encapsulated in SWCNTs yields double-wall carbon nanotubes (DWCNTs) with a high isotope enrichment of the inner wall. The vibrational spectra evidences that no carbon exchange occurs between the two walls. The method facilitates the identification of the Raman signal of the outer and inner tubes. Nuclear magnetic resonance proves the significant contrast of the isotope enriched SWCNTs as compared to other carbon phases, and provides information on the electronic properties of the small diameter inner tubes of the DWCNTs.

cond-mat.mtrl-sci

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 C$_{60}$, 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 C$_{60}$ 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 a reliable 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.

cond-mat.mtrl-sci

Diameter selective characterization of single-wall carbon nanotubes

A novel method is presented which allows the characterization of diameter selective phenomena in SWCNTs. It is based on the transformation of fullerene peapod materials into double-wall carbon nanotubes and studying the diameter distribution of the latter. The method is demonstrated for the diameter selective healing of nanotube defects and yield from C$_{70}$ peapod samples. Openings on small diameter nanotubes are closed first. The yield of very small diameter inner nanotubes from C$_{70}$ peapods is demonstrated. This challenges the theoretical models of inner nanotube formation. An anomalous absence of mid-diameter inner tubes is observed and explained by the suppressed amount of C$_{70}$ peapods due to the competition of the two almost equally stable standing and lying C$_{70}$ peapod configurations.

cond-mat.mtrl-sci

Low temperature fullerene encapsulation in single wall carbon nanotubes: synthesis of N@C$_{60}$@SWCNT

High filling of single wall carbon nanotubes (SWCNT) with C$_{60}$ and C$_{70}$ fullerenes in solvent is reported at temperatures as low as 69 $^{o}$C. A 2 hour long refluxing in n-hexane of the mixture of the fullerene and SWCNT results in a high yield of C$_{60}$,C$_{70}$@SWCNT, fullerene peapod, material. The peapod filling is characterized by TEM, Raman and electron energy loss spectroscopy and X-ray scattering. We applied the method to synthesize the temperature sensitive (N@C$_{60}$:C$_{60}$)@SWCNT as proved by electron spin resonance spectroscopy. The solvent prepared peapod samples can be transformed to double walled nanotubes enabling a high yield and industrially scalable production of DWCNT.

cond-mat.mtrl-sci