Synthesis and characterization of new discotic polycyclic aromatic hydrocarbons and related pyrolytic nanostructures

Diskotische Hexa-peri-hexabenzocoronene (HBC) als molekulare, definierte graphitische Substrukturen sind bereits seit langem Gegenstand von Untersuchungen zu der Delokalisierung von π-Elektronen. In dieser Arbeit wurden zusätzlich Platin-Komplexe in das periphere Substitutionsmuster von HBC eingeführt. Dies führte zu einer Verbesserung der Emission von dem angeregten Triplett-Zustand in den Singulett-Grundzustand mit einer zusätzlichen Verlängerung der Lebensdauer des angeregten Zustandes. Zusätzlich erlaubte diese Konfiguration ein schnelles Intersystem-Crossing mittels einer verstärkten Spin-Orbit Kopplung, die sowohl bei tiefen Temperaturen, als auch bei Raumtemperatur exklusiv zu Phosphoreszenz (T1→S0) führte. Das Verständniss über solche Prozesse ist auch essentiell für die Entwicklung verbesserter opto-elektronischer Bauteile. Die Erstellung von exakt definierten molekularen Strukturen, die speziell für spezifische Interaktionen hergestellt wurden, machten eine Inkorporation von hydrophoben-hydrophilen, wasserstoffverbrückten oder elektrostatischen funktionalisierten Einheiten notwendig, um damit den supramolekularen Aufbau zu kontrollieren. Mit Imidazolium-Salzen funktionalisierte HBC Derivate wurden zu diesem Zwecke hergestellt. Eine interessante Eigenschaft dieser Moleküle ist ihre Amphiphilie. Dies gestattete die Untersuchung ihrer Eigenschaften in einem polaren Solvens und sowohl der Prozessierbarkeit als auch der Faserbildung auf Siliziumoxid-Trägern. Abhängig vom Lösungsmittel und der gewählten Konditionen konnten hochkristalline Fasern erhalten werden. Durch eine Substitution der HBCs mit langen, sterisch anspruchsvollen Seitenketten, konnte durch eine geeignete Prozessierung eine homöotrope Ausrichtung auf Substraten erreicht werden, was dieses Material interessant für photovoltaische Applikationen macht. Neuartige Polyphenylen-Metall-Komplexe mit diskotischen, linearen und dendritischen Geometrien wurden mittels einer einfachen Reaktion zwischen Co2(CO)8 und Ethinyl-Funktionalitäten in Dichlormethan hergestellt. Nach der Pyrolyse dieser Komplexe ergaben sich unterschiedliche Kohlenstoff-Nanopartikel, inklusive Nanoröhren, graphitischen Nanostäben und Kohlenstoff/Metall Hybrid Komplexe, die durch Elektronenmikroskopie untersucht wurden. Die resultierenden Strukturen waren dabei abhängig von der Zusammensetzung und Struktur der Ausgangssubstanzen. Anhand dieser Resultate ergeben sich diverse Möglichkeiten, um den Mechanismus, der zur Herstellung graphitischer Nanopartikel führt, besser zu verstehen.

Field-free control of magnetism in nanostructured materials probed with high resolution X-ray microscopy

Magnetic memories are a backbone of today's digital data storage technology, where the digital information is stored as the magnetic configuration of nanostructured ferromagnetic bits. Currently, the writing of the digital information on the magnetic memory is carried out with the help of magnetic fields. This approach, while viable, is not optimal due to its intrinsically high energy consumption and relatively poor scalability. For this reason, the research for different mechanisms that can be used to manipulate the magnetic configuration of a material is of interest. In this thesis, the control of the magnetization of different nanostructured materials with field-free mechanisms is investigated. The magnetic configuration of these nanostructured materials was imaged directly with high resolution x-ray magnetic microscopy. rnFirst of all, the control of the magnetic configuration of nanostructured ferromagnetic Heusler compounds by fabricating nanostructures with different geometries was analyzed. Here, it was observed that the magnetic configuration of the nanostructured elements is given by the competition of magneto-crystalline and shape anisotropy. By fabricating elements with different geometries, we could alter the point where these two effects equilibrate, allowing for the possibility to tailor the magnetic configuration of these nanostructured elements to the required necessities.rnThen, the control of the magnetic configuration of Ni nanostructures fabricated on top of a piezoelectric material with the magneto-elastic effect (i.e. by applying a piezoelectric strain to the Ni nanostructures) was investigated. Here, the magneto-elastic coupling effect gives rise to an additional anisotropy contribution, proportional to the strain applied to the magnetic material. For this system, a reproducible and reversible control of the magnetic configuration of the nanostructured Ni elements with the application of an electric field across the piezoelectric material was achieved.rnFinally, the control of the magnetic configuration of La0.7Sr0.3MnO3 (LSMO) nanostructures with spin-polarized currents was studied. Here, the spin-transfer torque effect was employed to achieve the displacement of magnetic domain walls in the LSMO nanostructures. A high spin-transfer torque efficiency was observed for LSMO at low temperatures, and a Joule-heating induced hopping of the magnetic domain walls was observed at room temperatures, allowing for the analysis of the energetics of the domain walls in LSMO.rnThe results presented in this thesis give thus an overview on the different field-free approaches that can be used to manipulate and tailor the magnetization configuration of a nanostructured material to the various technological requirements, opening up novel interesting possibilities for these materials.

Comparison between femtosecond laser and fusion-arc inscribed long period gratings in photonic crystal fibre

The use of high intensity femtosecond laser sources for inscribing fibre gratings has attained significant interest. The principal advantage of high-energy pulses is their ability for grating inscription in any material type without preprocessing or special core doping. In the field of fibre optical sensing LPGs written in photonic crystal fibre have a distinct advantage of low temperature sensitivity over gratings written in conventional fibre and thus minimal temperature cross-sensitivity. Previous studies have indicated that LPGs written by a point-by-point inscription scheme using a low repetition femtosecond laser exhibit post-fabrication evolution leading to temporal instabilities at room temperatures with respect to spectral location, strength and birefringence of the attenuation bands. These spectral instabilities of LPGs are studied in photonic crystal fibres (endlessly single mode microstructure fibre) to moderately high temperatures 100°C to 200°C and their performance compared to fusion-arc fabricated LPG. Initial results suggest that the fusion-arc fabricated LPG demonstrate less spectral instability for a given constant and moderate temperature, and are similar to the results obtained when inscribed in a standard single mode fibre.

Quantum dot materials for terahertz generation applications

Compact and tunable semiconductor terahertz sources providing direct electrical control, efficient operation at room temperatures and device integration opportunities are of great interest at the present time. One of the most well-established techniques for terahertz generation utilises photoconductive antennas driven by ultrafast pulsed or dual wavelength continuous wave laser systems, though some limitations, such as confined optical wavelength pumping range and thermal breakdown, still exist. The use of quantum dot-based semiconductor materials, having unique carrier dynamics and material properties, can help to overcome limitations and enable efficient optical-to-terahertz signal conversion at room temperatures. Here we discuss the construction of novel and versatile terahertz transceiver systems based on quantum dot semiconductor devices. Configurable, energy-dependent optical and electronic characteristics of quantum-dot-based semiconductors are described, and the resonant response to optical pump wavelength is revealed. Terahertz signal generation and detection at energies that resonantly excite only the implanted quantum dots opens the potential for using compact quantum dot-based semiconductor lasers as pump sources. Proof-of-concept experiments are demonstrated here that show quantum dot-based samples to have higher optical pump damage thresholds and reduced carrier lifetime with increasing pump power.

Flexural and torsional rigidity of colonoscope at room and body temperatures

A series of experiments have been conducted to determine the flexural, EI, and torsional, GJ, rigidity of an Olympus colonoscope CF‐140S and torsional rigidity of a Pentax colonoscope EC‐3870 and the dependency of these properties on temperature and on the presence of loops. Along the length of the colonoscope, the Olympus colonoscope flexural rigidity varied between 260 and 400 Ncm2 and torsional rigidity varied between 68 and 88 Ncm2/deg, with an average of 76 Ncm2/deg for tests involving 0.86 Nm of anti‐clockwise torque. Results show a significant decrease of 10% in torsional rigidity between clockwise and anti‐clockwise torque. For the Pentax colonoscope flexural rigidity was not tested; its torsional rigidity varied between 34 and 76 Ncm2/deg, with an average of 46 Ncm2/deg for tests involving 0.43 Nm of anti‐clockwise torque. An increase in temperature of the Olympus colonoscope from 24°C to 37°C reduces EI by an average of 17% and GJ by an average of 7%. A right‐handed loop caused a significant increase in flexural rigidity, but other looping configurations had no significant influence.

Giant photoinduced optical bleaching at room and liquid helium temperatures in Sb/As(2)S(3) multilayered films

We report the observation of giant photo induced optical bleaching in Sb/As(2)S(3) multilayered film at room and liquid He temperatures, when irradiated with 532 nm laser at moderate intensities. The experimental results show a dramatic increase in transmittance near the band gap regime at both the temperatures; however the rates at which transmission change occurs are rather slow at low temperature. The huge change in transmission is due to the photo induced intermixing of As(2)S(3) layer with Sb. Our XPS measurements show that photo induced intermixing occurs through the wrong homopolar bonds, which under actinic light illumination are converted into energetically favored hetropolar bonds. (C) 2011 Elsevier B.V. All rights reserved.

FT-Raman studies of a range of polyimides subjected to high-energy Radiations at room and elevated temperatures

A range of polyimides have been subjected to electron beam radiolysis at different temperatures. These polyimides were chemically designed to suit space applications, being either transparent or having groups which provide oxidation resistance. The structural changes that occur in the polyimides, when subjected to electron beam irradiation doses up to 18.5 MGy and up to temperatures close to their glass transition temperatures, were studied using FT-Raman spectroscopy. The range of polyimides studied included a series of perfluoropolyimides, a silicon-modified polyimide, and Ultem. The changes in the Raman peak intensities of the different groups indicated scission reactions involving the imide rings and ether linkages. (c) 2006 Wiley Periodicals, Inc.

Analytical electron microscope investigation of boron carbide microstructures at elevated temperatures

The microstructures of hot-pressed B4C were monitored during in situ heating experiments from room temperature to 1000C by analytical electron microscopy (AEM). Variations in the microstructure of B4C were not observed. However, during heating, secondary phases formed in voids and on the surfaces of the specimen.

Harnessing the influence of reactive edges and defects of graphene substrates for achieving complete cycle of room-temperature molecular sensing

Molecular doping and detection are at the forefront of graphene research, a topic of great interest in physical and materials science. Molecules adsorb strongly on graphene, leading to a change in electrical conductivity at room temperature. However, a common impediment for practical applications reported by all studies to date is the excessively slow rate of desorption of important reactive gases such as ammonia and nitrogen dioxide. Annealing at high temperatures, or exposure to strong ultraviolet light under vacuum, is employed to facilitate desorption of these gases. In this article, the molecules adsorbed on graphene nanoflakes and on chemically derived graphene-nanomesh flakes are displaced rapidly at room temperature in air by the use of gaseous polar molecules such as water and ethanol. The mechanism for desorption is proposed to arise from the electrostatic forces exerted by the polar molecules, which decouples the overlap between substrate defect states, molecule states, and graphene states near the Fermi level. Using chemiresistors prepared from water-based dispersions of single-layer graphene on mesoporous alumina membranes, the study further shows that the edges of the graphene flakes (showing p-type responses to NO2 and NH3) and the edges of graphene nanomesh structures (showing n-type responses to NO2 and NH3) have enhanced sensitivity. The measured responses towards gases are comparable to or better than those which have been obtained using devices that are more sophisticated. The higher sensitivity and rapid regeneration of the sensor at room temperature provides a clear advancement towards practical molecule detection using graphene-based materials.

Visible light-driven cross-coupling reactions at lower temperatures using a photocatalyst of palladium and gold alloy nanoparticles

Palladium (Pd)-catalyzed cross-coupling reactions are among the most important methods in organic synthesis. We report the discovery of highly efficient and green photocatalytic processes by which cross-coupling reactions, including Sonogashira, Stille, Hiyama, Ullmann, and Buchwald–Hartwig reactions, can be driven with visible light at temperatures slightly above room temperature using alloy nanoparticles of gold and Pd on zirconium oxide, thus achieving high yields. The alloy nanoparticles absorb visible light, and their conduction electrons gain energy, which is available at the surface Pd sites. Results of the density functional theory calculations indicate that transfer of the light excited electrons from the nanoparticle surface to the reactant molecules adsorbed on the nanoparticle surface activates the reactants. When the light intensity was increased, a higher reaction rate was observed, because of the increased population of photoexcited electrons. The irradiation wavelength also has an important impact on the reaction rates. Ultraviolet irradiation can drive some reactions with the chlorobenzene substrate, while visible light irradiation failed to, and substantially improve the yields of the reactions with the bromobenzene substrate. The discovery reveals the possibility of using low-energy and -density sources such as sunlight to drive chemical transformations.

Direct photocatalytic conversion of aldehydes to esters using supported gold nanoparticles under visible light irradiation at room temperature

Visible light can drive esteri fi cation from aldehydes and alcohols using supported gold nanoparticles (Au/Al 2 O 3 ) as photo- catalysts at ambient temperatures. The gold nanoparticles (AuNPs) absorb visible light due to the localized surface plasmon resonance (LSPR) e ff ect, and the conduction electrons of the AuNPs gain the energy of the incident light. The energetic electrons, which concentrate at the NP surface, facilitate the activation of a range of aldehyde and alcohol substrates. The photocatalytic e ffi ciencies strongly depend on the Au loading, particle sizes of the AuNPs, irradiance, and wavelength of the light irradiation. Finally, a plausible reaction mechanism was proposed, and the Au/Al 2 O 3 catalysts can be reused several times without signi fi cantly losing activity. The knowledge acquired in this study may inspire further studies in new e ffi cient recyclable photocatalysts and a wide range of organic synthesis driven by sunlight.

Highly Monodisperse Colloidal Magnesium Nanoparticles by Room Temperature Digestive Ripening

Nanoclusters of 25 nm sized Mg-THF have been prepared by the solvated metal atom dispersion method. Room-temperature digestive ripening of these nanoclusters in the presence of hexadecylamine (HDA) resulted in highly monodisperse colloidal Mg-HDA nanoparticles of 2.8 ± 0.2 nm. An insight into the room-temperature digestive ripening process was obtained by studying the disintegration of clusters for various Mg:HDA ratios. The Mg colloids are quite stable with respect to precipitation of particles under Ar atmosphere. Using this procedure, pure Mg(0) nanopowders were obtained in gram scale quantities. The Mg powder precipitated from the colloid was fully hydrided at 33 bar and 118 °C. Initial desorption of H2 from samples of MgH2 was achieved at a remarkably low temperature, 115 °C compared to >350 °C in bulk Mg, demonstrating the importance of the size on the desorption temperatures.

Room temperature giant magnetoresistance in La1-xPbxMnO3

Oxides of the La1-xPbxMnO3 system show giant magnetoresistance around 300 K. In La1-xPbxMnO3 the magnitude of the magnetoresistance (MR) at 320 K is 85% at 6 T and it is nearly temperature independent over a temperature range 40-320 K. All the compositions (0.1 less than or equal to x less than or equal to 0.5) show a peak in resistivity around 300-340 K and the magnitude of the MR also shows a peak around the same temperatures. This investigation suggests how to hole dope LaMnO3 in order to achieve maximum MR around 300 K so that these materials can have practical applications.

Crystal packing and melting temperatures of small oxalate esters: the role of C-H center dot center dot center dot O hydrogen bonding

The simple dialkyl oxalates are generally liquids at room temperature except for dimethyl and di-tert-butyl oxalate which melt at 327 and 343 K. The crystal structures of diethyl, di-iso-propyl, di-n-butyl, di-tert-butyl and methyl ethyl oxalates were determined. The liquid esters were crystallized using the cryocrystallization technique. A comparison of the intermolecular interactions and packing features in these crystal structures was carried out. The crystal structure of dimethyl oxalate was redetermined at various temperatures. The other compounds were also studied at several temperatures in order to assess the attractive nature of the hydrogen bonds therein. A number of moderate to well defined C-H center dot center dot center dot O interactions account for the higher melting points of the two solid esters. Additionally, a diminished entropic contribution Delta S(m) in di-tert-butyl oxalate possibly increases the melting point of this compound further.