Atomic scale engineering of carbon nanotubes

Carbon nanotubes, seamless cylinders made from carbon atoms, have outstanding characteristics: inherent nano-size, record-high Young’s modulus, high thermal stability and chemical inertness. They also have extraordinary electronic properties: in addition to extremely high conductance, they can be both metals and semiconductors without any external doping, just due to minute changes in the arrangements of atoms. As traditional silicon-based devices are reaching the level of miniaturisation where leakage currents become a problem, these properties make nanotubes a promising material for applications in nanoelectronics. However, several obstacles must be overcome for the development of nanotube-based nanoelectronics. One of them is the ability to modify locally the electronic structure of carbon nanotubes and create reliable interconnects between nanotubes and metal contacts which likely can be used for integration of the nanotubes in macroscopic electronic devices. In this thesis, the possibility of using ion and electron irradiation as a tool to introduce defects in nanotubes in a controllable manner and to achieve these goals is explored. Defects are known to modify the electronic properties of carbon nanotubes. Some defects are always present in pristine nanotubes, and naturally are introduced during irradiation. Obviously, their density can be controlled by irradiation dose. Since different types of defects have very different effects on the conductivity, knowledge of their abundance as induced by ion irradiation is central for controlling the conductivity. In this thesis, the response of single walled carbon nanotubes to ion irradiation is studied. It is shown that, indeed, by energy selective irradiation the conductance can be controlled. Not only the conductivity, but the local electronic structure of single walled carbon nanotubes can be changed by the defects. The presented studies show a variety of changes in the electronic structures of semiconducting single walled nanotubes, varying from individual new states in the band gap to changes in the band gap width. The extensive simulation results for various types of defect make it possible to unequivocally identify defects in single walled carbon nanotubes by combining electronic structure calculations and scanning tunneling spectroscopy, offering a reference data for a wide scientific community of researchers studying nanotubes with surface probe microscopy methods. In electronics applications, carbon nanotubes have to be interconnected to the macroscopic world via metal contacts. Interactions between the nanotubes and metal particles are also essential for nanotube synthesis, as single walled nanotubes are always grown from metal catalyst particles. In this thesis, both growth and creation of nanotube-metal nanoparticle interconnects driven by electron irradiation is studied. Surface curvature and the size of metal nanoparticles is demonstrated to determine the local carbon solubility in these particles. As for nanotube-metal contacts, previous experiments have proved the possibility to create junctions between carbon nanotubes and metal nanoparticles under irradiation in a transmission electron microscope. In this thesis, the microscopic mechanism of junction formation is studied by atomistic simulations carried out at various levels of sophistication. It is shown that structural defects created by the electron beam and efficient reconstruction of the nanotube atomic network, inherently related to the nanometer size and quasi-one dimensional structure of nanotubes, are the driving force for junction formation. Thus, the results of this thesis not only address practical aspects of irradiation-mediated engineering of nanosystems, but also contribute to our understanding of the behaviour of point defects in low-dimensional nanoscale materials.

Electronic excitations in solids studied using inelastic x-ray scattering

Inelastic x-ray scattering can be used to study the electronic structure of matter. The x rays scattered from the target both induce and carry information on the electronic excitations taking place in the system. These excitations are the manifestations of the electronic structure and the physics governing the many-body system. This work presents results of non-resonant inelastic x-ray scattering experiments on a range of materials including metallic, insulating and semiconducting compounds as well as an organic polymer. The experiments were carried out at the National Synchrotron Light Source, USA and at the European Synchrotron Radiation Facility, France. The momentum transfer dependence of the experimental valence- and core-electron excitation spectra is compared with the results of theoretical first principles computations that incorporate the electron-hole interaction. A recently developed method for analyzing the momentum transfer dependence of core-electron excitation spectra is studied in detail. This method is based on real space multiple scattering calculations and is used to extract the angular symmetry components of the local unoccupied density of final states.

Studies of electronic structure by x-ray Raman and emission spectroscopy: applications to MgB2 superconductors and high pressure physics

X-ray Raman scattering and x-ray emission spectroscopies were used to study the electronic properties and phase transitions in several condensed matter systems. The experimental work, carried out at the European Synchrotron Radiation Facility, was complemented by theoretical calculations of the x-ray spectra and of the electronic structure. The electronic structure of MgB2 at the Fermi level is dominated by the boron σ and π bands. The high density of states provided by these bands is the key feature of the electronic structure contributing to the high critical temperature of superconductivity in MgB2. The electronic structure of MgB2 can be modified by atomic substitutions, which introduce extra electrons or holes into the bands. X ray Raman scattering was used to probe the interesting σ and π band hole states in pure and aluminum substituted MgB2. A method for determining the final state density of electron states from experimental x-ray Raman scattering spectra was examined and applied to the experimental data on both pure MgB2 and on Mg(0.83)Al(0.17)B2. The extracted final state density of electron states for the pure and aluminum substituted samples revealed clear substitution induced changes in the σ and π bands. The experimental work was supported by theoretical calculations of the electronic structure and x-ray Raman spectra. X-ray emission at the metal Kβ line was applied to the studies of pressure and temperature induced spin state transitions in transition metal oxides. The experimental studies were complemented by cluster multiplet calculations of the electronic structure and emission spectra. In LaCoO3 evidence for the appearance of an intermediate spin state was found and the presence of a pressure induced spin transition was confirmed. Pressure induced changes in the electronic structure of transition metal monoxides were studied experimentally and were analyzed using the cluster multiplet approach. The effects of hybridization, bandwidth and crystal field splitting in stabilizing the high pressure spin state were discussed. Emission spectroscopy at the Kβ line was also applied to FeCO3 and a pressure induced iron spin state transition was discovered.

Nickel(II) meso-hydroxyporphyrin complexes revisited: Palladium-catalysed synthesis, electronic structures of derived oxy radicals, and oxidative coupling to a dioxoporphodimethene dyad

We report the synthesis and characterisation of new examples of meso-hydroxynickel(II) porphyrins with 5,15-diphenyl and 10-phenyl-5,15-diphenyl/diaryl substitu- tion. The OH group was introduced by using carbonate or hydroxide as nucleophile by using palladium/phosphine cat- alysis. The NiPor OHs exist in solution in equilibrium with the corresponding oxy radicals NiPor OC. The 15-phenyl group stabilises the radicals, so that the 1H NMR spectra of {NiPor OH} are extremely broad due to chemical exchange with the paramagnetic species. The radical concentration for the diphenylporphyrin analogue is only 1%, and its NMR line-broadening was able to be studied by variable-tempera- ture NMR spectroscopy. The EPR signals of NiPor OC are con- sistent with somewhat delocalised porphyrinyloxy radicals, and the spin distributions calculated by using density func- tional theory match the EPR and NMR spectroscopic obser- vations. Nickel(II) meso-hydroxy-10,20-diphenylporphyrin was oxidatively coupled to a dioxo-terminated porphodimethene dyad, the strongly red-shifted electronic spectrum of which was successfully modelled by using time-dependent DFT calculations.

Electronic structure and bonding of beta-rhombohedral boron using cluster fragment approach

Theoretical studies using density functional theory are carried out to understand the electronic structure and bonding and electronic properties of elemental beta-rhombohedral boron. The calculated band structure of ideal beta-rhombohedral boron (B-105) shows valence electron deficiency and depicts metallic behavior. This is in contrast to the experimental result that it is a semiconductor. To understand this ambiguity we discuss the electronic structure and bonding of this allotrope with cluster fragment approach using our recently proposed mno rule. This helps us to comprehend in greater detail the structure of B-105 and materials which are closely related to beta-rhombohedral boron. The molecular structures B12H12-2, B28H21+1, BeB27H21, LiB27H21-1, CB27H21+2, B57H36+3, Be3B54H36, and Li2CB54H36, and corresponding solids Li8Be3B102 and Li10CB102 are arrived at using these ideas and studied using first principles density functional theory calculations.

Flow driven electronic transport in carbon nan otubes

The flow of a liquid on single-walled carbon nanotube bundles induces an electrical signal (voltage/current) in the sample along the direction of the flow. The electrical response is found to be logarithmic in the flow speed over a wide range. The magnitude of the flow induced electrical signal generated depends sensitively on the ionic conductivity and the polar nature of the liquid, and electrical biasing of the nanotubes can control its direction. Our measurements suggest that the dominant mechanism responsible for this highly sub-linear response should involve a direct forcing of the free charge carriers in the nanotubes by the fluctuating Coulombic field of the liquid flowing past it.

Atomically resolved scanning tunneling microscopy on perovskite manganite single crystals

Atomically resolved scanning tunneling microscopy was conducted on cleaved single crystals of the cubic perovskite Pr0.68Pb0.32MnO3.Several different surface configurations could be resolved including a frequent square arrangement with atomic distances in excellent agreement to the bulk lattice constant of the cubic structure. We also observed stripe formation and a surface reconstruction. The latter is likely related to a polar rare earth-oxygen terminated surface. (C) 2010 American Institute of Physics.

Spectrophotometric and potentiometric investigations of copper (II)-Ethanolamine complexes - Part III. diethanolamine (Gaussian analysis of electronic spectra in mono and diethanolamine systems)

Spectrophotometric and potentiometric investigations have been carried out on copper-diethanolamine system. Job plots at 900, 900 and 580 mμ have indicated the formation of CuD++, CuD2++ and CuD3++. The n- pA curves obtained indicate the formation of CuD++, CuD2++, CuD3++, CuDOH+, CuD2OH+ and CuD3OH+. The n- pA curves have been analyzed to obtain the stability constants of these complexes. Absorption curves of pure complexes have been computed by a graphical method. Gaussian analysis of the absorption curves of pure and hydroxy complexes show the presence of a second band, indicating that the structure is that of a distorted octahedron.

Electronic Document Management in Construction – Research Issue and Results

Electronic document management (EDM) technology has the potential to enhance the information management in construction projects considerably, without radical changes to current practice. Over the past fifteen years this topic has been overshadowed by building product modelling in the construction IT research world, but at present EDM is quickly being introduced in practice, in particular in bigger projects. Often this is done in the form of third party services available over the World Wide Web. In the paper, a typology of research questions and methods is presented, which can be used to position the individual research efforts which are surveyed in the paper. Questions dealt with include: What features should EMD systems have? How much are they used? Are there benefits from use and how should these be measured? What are the barriers to wide-spread adoption? Which technical questions need to be solved? Is there scope for standardisation? How will the market for such systems evolve?

The Electronic Journal of Information Technology in Construction (ITcon): An Open Access Journal Using an Un-paid, Volunteer-Based Organization

Introduction This case study is based on the experiences with the Electronic Journal of Information Technology in Construction (ITcon), founded in 1995. Development This journal is an example of a particular category of open access journals, which use neither author charges nor subscriptions to finance their operations, but rely largely on unpaid voluntary work in the spirit of the open source movement. The journal has, after some initial struggle, survived its first decade and is now established as one of half-a-dozen peer reviewed journals in its field. Operations The journal publishes articles as they become ready, but creates virtual issues through alerting messages to “subscribers”. It has also started to publish special issues, since this helps in attracting submissions, and also helps in sharing the work-load of review management. From the start the journal adopted a rather traditional layout of the articles. After the first few years the HTML version was dropped and papers are only published in PDF format. Performance The journal has recently been benchmarked against the competing journals in its field. Its acceptance rate of 53% is slightly higher and its average turnaround time of seven months almost a year faster compared to those journals in the sample for which data could be obtained. The server log files for the past three years have also been studied. Conclusions Our overall experience demonstrates that it is possible to publish this type of OA journal, with a yearly publishing volume equal to a quarterly journal and involving the processing of some fifty submissions a year, using a networked volunteer-based organization.

PEDOT-PSSA as an alternative support for Pt electrodes in PEFCs

Poly (3,4-ethylenedioxythiophene) (PEDOT) and poly (styrene sulphonic acid) (PSSA) supported platinum (Pt) electrodes for application in polymer electrolyte fuel cells (PEFCs) are reported. PEDOT-PSSA support helps Pt particles to be uniformly distributed on to the electrodes, and facilitates mixed electronic and ionic (H+-ion) conduction within the catalyst, ameliorating Pt utilization. The inherent proton conductivity of PEDOT-PSSA composite also helps reducing Nation content in PEFC electrodes. During prolonged operation of PEFCs, Pt electrodes supported onto PEDOT-PSSA composite exhibit lower corrosion in relation to Pt electrodes supported onto commercially available Vulcan XC-72R carbon. Physical properties of PEDOT-PSSA composite have been characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and transmission electron microscopy. PEFCs with PEDOT-PSSA-supported Pt catalyst electrodes offer a peak power-density of 810 mW cm(-2) at a load current-density of 1800 mA cm(-2) with Nation content as low as 5 wt.% in the catalyst layer. Accordingly, the present study provides a novel alternative support for platinized PEFC electrodes.