Boron carbide-aromatic composites, formed by plasma-enhanced co-deposition of carboranes and aromatic precursors, present enhanced electron-hole separation as neutron detector. This is achieved by aromatic coordination to the carborane icosahedra and results in improved neutron detection efficiency. Photoemission (XPS) and FTIR suggest that chemical bonding between B atoms in icosahedra and aromatic contents with preservation of π system during plasma process. XPS, UPS, density functional theory (DFT) calculations, and variable angle spectroscopic ellipsometery (VASE) demonstrate that for orthocarborane/pyridine and orthocarborane/aniline films, states near the valence band maximum are aromatic in character, while states near the conduction band minimum include those of either carborane or aromatic character. Thus, excitation across the band gap results in electrons and holes on carboranes and aromatics, respectively. Further such aromatic-carborane interaction dramatically shrinks the indirect band gap from 3 eV (PECVD orthocarborane) to ~ 1.6 eV (PECVD orthocarborane/pyridine) to ~1.0 eV (PECVD orthocarborane/aniline), with little variation in such properties with aromatic/orthocarborane stoichiometry. The narrowed band gap indicate the potential for greatly enhanced charge generation relative to PECVD orthocarborane films, as confirmed by zero-bias neutron voltaic studies. The results indicate that the enhanced electron-hole separation and band gap narrowing observed for aromatic/orthocarborane films relative to PECVD orthocarborane, has significant potential for a range of applications, including neutron detection, photovoltaics, and photocatalysis. Acknowledgements: This work was supported by the Defense Threat Reduction Agency (Grant No.HDTRA1-14-1-0041). James Hilfiker is also gratefully acknowledged for stimulating discussions.

No description available.

A transparent conductive electrode (TCE) is an important component in many of our modern optoelectronic devices like photovoltaics, light emitting diodes and touch screens. These devices require good current injection and spreading as well as a high transparency. In this thesis we explore the use of graphene as an alternative to the current widely used indium tin oxide (ITO) as TCE in gallium nitride (GaN) based light emitting diodes (LEDs). Monolayer crystalline graphene can be produced on copper foils using chemical vapor deposition (CVD), where metals (especially copper) has a catalysing effect on the formation of graphene. However, transfer of graphene from copper foils is not suitable for an industrial scale and it results in a poor contact with the target substrate. We investigate the possibility of directly integrating graphene on GaN-based LEDs by using plasma-enhanced chemical vapor deposition (PECVD). We try to obtain the optimal conditions under these catalyst-free circumstances and propose a recipe adapted for the setup that we used. We will also study ideas of using a metal (we tried copper and nickel) to assist the direct growth that could help to increase the fraction of sp2 carbon bonds and reduce the sheet resistance. The metals are evaporated onto our samples either before or after we grow a carbon film to either assist the growth or rearrange the carbon respectively. The focus was not on trying to optimize the conditions for one metal treatment but rather to briefly explore multiple methods to find a suitable path for further studies. The direct grown pristine carbon films shows indications from Raman measurements of being nanocrystalline graphene with a sheet resistance ranging from about 20-50 kΩ/sq having a transmittance of approximately 96 % at 550 nm. A transmittance at this level is closely related to the value of an ideal monolayer graphene, which indicates that our carbon films could be close to one atom in thickness while being visually homogeneous and complete in coverage. Due to the use of a temperature close to the melting point of copper we struggled to keep the assisting copper from evaporating too fast or staying homogeneous after the treatment. Nickel has a higher melting temperature, but it appears as if this metal might be diffusing into the GaN substrate which changes the properties of both the GaN and carbon film. Even though the metal treatments that we tested did not provide any noticeable improvements, there is need for further investigations to obtain suitable treatment conditions. We suggest that the treatments involving copper are a more promising path to pursue as nickel seem to cause unavoidable intermixing problems.

Zugl.: Hagen, Univ., Diss., 2009

Zugl.: Chemnitz, Techn. Univ., Diss., 2008

Zugl.: Aachen, Techn. Hochsch., Diss., 2008.

Universiẗat, Diss., 2001--Kaiserslautern.

Dans ce travail avons mis en évidence l’influence de la puissance radio-fréquence (RF) sur les différentes propriétés microstructurales, optiques, électriques, paramagnétiques ainsi que la morphologie des films minces polymérisés par PECVD capacitive, en utilisant la vapeur du cyclohexane comme précurseur.A faible puissance RF les surfaces de nos films sont poreuses et fortement hydrogénées. Elles possèdent un caractère hydrophile. L’augmentation de la puissance RF (à partir de 120 W) engendre une microstructure moins hydrogénée des couches et favorise les réarrangements atomiques entre les atomes de carbone et notamment, la formation de liaisons de type C=C (C-sp²). Dans cette gamme de puissance nous avons réussi à augmenter le caractère conducteur de nos films polymérisés. Ces résultats sont en bon accord avec les mesures optiques qui montrent qu'à forte puissance RF les films obtenus sont plus durs (augmentation de n avec la puissance) et leur gap optique est de plus en plus faible. Cette diminution du gap optique a été interprétée en termes de distorsions, de graphitisation et de réorganisation des sites C-sp2 pour former des amas plus grands et mieux organisés. Il apparaît, en combinant ces mesures avec celles obtenues sur la microstructure (Raman et Infrarouge), que l’augmentation de la conductivité électrique et la diminution du gap optique correspondent à une augmentation du nombre des doubles liaisons C=C, c’est-à-dire, une « graphitisation » du film favorisant ainsi le caractère conducteur.Néanmoins, la conductivité électrique reste faible, ce qui est expliqué par les mesures de résonance paramagnétique électronique (RPE), qui montrent qu’il existe des défauts au sein des sites C-sp2 et que la densité de spins augmente avec la puissance RF, indiquant que la densité de défauts augmente dans les films minces déposés à forte puissance RF. De plus le rétrécissement des raies RPE lorsque la puissance RF augmente, indique la diminution de l’interaction d’échange entre les spins suite à leur délocalisation dans les structures des liaisons . / In this work we have shown the influence of the radio frequency (RF) power on the microstructural, optical, electrical, electronic and morphological properties of thin films polymerized by capacitive PECVD using cyclohexane as precursor gas.At low RF power, the surfaces of our films are porous and highly hydrogenated. They have a hydrophilic character. The increase in the RF power (above 120 W) generates less hydrogenated microstructure and promotes atomic rearrangements between the carbon atoms, including the formation of C = C (C-sp²) bonds. In this RF power range we observed an increase of the conductor character of our polymerized films. These results are in good agreement with optical measurements, show that high RF power induces harder deposited films (increase of n with RF power) and a decrease in the optical gap. This decrease in the optical gap was interpreted in terms of distortions, graphitization and reorganization of the C-sp2 sites, which form larger and better organized clusters. It appears, by combining these measurements with those obtained on the microstructure (Raman and FTIR), that the increase in the electrical conductivity and the decrease of the optical gap is associated with the increase in the number of C = C double bonds, that is to say a "graphitization" of the film, promoting the conductive nature.However, the electrical conductivity values are still a little low, which is explained by the electron paramagnetic resonance (EPR) measurements, which showed the presence of defects within the C-sp2 sites, and that the spin density increases with RF power, suggesting an increase in the defect density in the thin films deposited at high RF power. Furthermore, the narrowing of the EPR lines when the RF power increases indicates a decrease in the exchange interaction between spins as a result of delocalization phenomena in the  bond structures.

No description available.

<p>Silicon oxide films (oxygen-rich or silicon-rich) doped with various rare-earth (RE) [cerium (Ce), terbium (Tb), europium (Eu) and erbium (Er)] elements have been by deposited by electron cyclotron resonance plasma-enhanced chemical vapour deposition (ECR-PECVD). The successful in-situ incorporation of high concentrations of RE elements has been confirmed by Rutherford backscattering spectrometry (RBS), and the optical properties of the films were analyzed by Photoluminescence (PL) spectroscopy.</p><p> Ce, Tb, Eu and Er related emission was observed from the films with corresponding doping and was found to be sensitive to RE concentration, the presence of Si nanoclusters (Si-ncs) and annealing induced structural evolution. The significant enhancement of Ce^3 + emission in Ce-doped oxygen-rich films under annealing in flowing N2 at 1200 °C was found to be related to the formation of cerium silicate whose presence was confirmed by Fourier transform infra-red (FTIR) spectra and high-resolution transmission electron microscopy (HR-TEM) images. The observation of intense Tb^3+ emission from Tb-doped oxygen-rich films under nonresonant excitation revealed the presence of indirect excitation processes. The organic ligands introduced from the Tb(tmhd)3 precursor during deposition was considered as the possible sensitizer. The presence of Si-ncs in Ce or Eu-doped silicon-rich films resulted in the quenching of both RE and Si-ncs PL, while in Tb or Er-doped silicon-rich films the coupling between Si-nes and RE ions can excite RE-related emission efficiently. The formation of Si-ncs with sizes of 2-3 nm in Tb-doped silicon-rich films under annealing in flowing N2 at 1100 and 1200 °C was revealed by HR-TEM images.</p> / Thesis / Master of Applied Science (MASc)