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This thesis presents theoretical studies of the optical and electronic properties of defects in diamond and of the mechanisms of doping graphene. The birefringence of the four petalled defect commonly observed in CVD diamond is explained by four linear arrays of dislocations along ⟨110⟩ directions with ⟨110⟩ Burgers vectors. Such an arrangement of dislocations reproduces the extension and the features of the birefringence patterns observed experimentally. Density functional theory via the AIMPRO code was used to study the electronic and optical properties of different nitrogen-related point defects in diamond. It was found that the zero-phonon luminescence line of the NV− defects can split in the presence of a surface or other NV− defects. Since VNH and VN2 are expected to have similar optical properties, the optical transi- tions for VN2 were used to correct the transitions for VNH calculated by local density approximation. The absorption band at 2.38 eV (520 nm) observed in CVD diamond is then attributed to an internal transition of VNH. The weak zero-phonon line and broad vibronic sidebands for VN− and VN−2 and its absence for VNH− is explained by the large structural change when the defect is excited. Finally, different mechanisms for doping graphene were considered. The calculations predict the electropositive metals, such as Ti and Cr, act as donors, while molecules with strong electron affinity, such as F4-TCNQ, act as acceptors in graphene. An unexpected mechanism of doping graphene was shown by Au which dopes bilayer graphene but not single layer. In the presence of water, electrochemical reactions on the graphene can also lead to p or n-type doping.

In this thesis first-principles calculations of point and extended defects in diamond and silicon are reported. In single crystal diamond grown by chemical vapour deposition (CVD) dislocations are observed as mixed-type 45° and edge-type dislocations lying along <100> with 1/2<110> Burgers vectors. Results are presented on the core structures, core energies and electrical properties of both types of dislocations and their interaction with nitrogen is investigated. Then the focus turns to the brown diamond problem. Despite concerted research efforts, the origin of the brown colouration of diamond is still under discussion. Recently, the attention was drawn to vacancy-related defects. Experiments on type IIa diamonds indicate that the brown colour is caused by vacancy-type extended defects, however the shape and size of these defects remained unclear. In this work, the structural, electrical and optical properties of large spherical vacancy clusters and thin vacancy disks are investigated by means of density functional theory and the calculations are compared with recent experimental measurements on brown diamond. High pressure high temperature treatment (HPHT) of brown type Ia diamonds above 2000°C results in the loss of the brown colour and the formation of nitrogen-vacancy defects. The generation of such defects requires a source of mobile vacancies during the annealing process. It is suggested that the vacancy cluster model described in this thesis can explain the observed annealing behaviour since the break-up of the clusters leads to a supersaturation of mobile vacancies which readily complex with substitutional nitrogen atoms present in the material. Therefore, the effect of HPHT treatment of brown type Ia diamond is investigated by studying the formation energies of common and rare defects and estimates of their equilibrium concentrations at different annealing stages are given. Finally, an open problem also involving nitrogen, but in a different group IV semiconductor is considered. In Czochralski-silicon, nitrogen-related shallow thermal donors are formed between 500 and 750°C. Until now the exact chemical composition and atomic structure of these defects are not well established. Here, it is shown that NO and NO_2 belong to the family of nitrogen-oxygen related shallow thermal donors. Based on the law of mass action the equilibrium defect concentrations are predicted. Finally, the theoretical results are compared to recent Fourier transform infrared (FTIR) spectroscopy measurements.

Abstract Diamond is nowadays regarded as a potential semiconductor material of the future, due to its extreme and unique properties. Some of these properties, in- clude its high hardness, highest breakdown ¯eld, high Debye temperature, high thermal conductivity, high hole and electron mobilities, large bandgap and op- tical transparency, among others. These properties make diamond suitable for high-temperature, high-speed and high-power electronic applicatons, as well as in other applications. However, defects associated with ion implantation have been shown to make it rather di±cult to obtain n-type doping in diamond. As such, an understanding of the nature of defects produced during ion implanta- tion of diamond remains a subject of great importance, if not essential, for the optimization of high-temperature, high-power electronic applications in partic- ular. In this respect, this study investigates the nature of the radiation damage generated within the collision cascades of multi-implantations of carbon ions in high-pressure, high-temperature single-crystal synthetic type Ib diamond, spread over a range of energies (50-150keV) and doses. This is achieved by means of the cold-implantation-rapid-annealing (CIRA) routine, and the anal- ysis of damage caused was done by using cross sectional transmission electron microscopy techniques. More precisely, the modes used to achieve this are the bright ¯eld transmission electron microscopy (BFTEM) coupled with selected area di®raction or SAD. At low dose implantation or at sub-critical implantation doses (2.5x1015 ions/cm2), it was found that the ion-damaged diamond layer consists of some threading dislocations, not homogeneously distributed which propagate from the surface into the ion-damaged diamond. In contrast to the sub-critical implantation doses , it was found that at very high implantation doses (7.0x1015 ions/cm2), i.e., above the critical dose (where diamond transforms to graphite upon annealing), the damaged diamond layer had some unconventional defect features close to the implanted surface.

A Mina de diamantes de Romaria está localizada no perímetro urbano da cidade de Romaria, na região oeste de Minas Gerais. Durante os trabalhos de mineração executados nos últimos cem anos, foi lavrada uma área de aproximadamente 1 km2 de sedimentos. O local está situado na borda NE da Bacia do Paraná, na margem direita do Rio Bagagem, entre os Ribeirões Água Suja e Marrecos. Neste local vem sendo lavrado um conglomerado polimítico da Formação Uberaba, Grupo Bauru, pertencente ao Cretáceo Superior. Ele é constituído por clastos de micaxistos, anfibolitos, filitos e veios pegmatóides do Pré-Cambriano; arenitos da Formação Botucatu e basaltos da Formação Serra Geral. Possui matriz areno-argilosa onde foram identificadas as fases caulinita, illita e quartzo por difratometria. Sua espessura na área da mina oscila em torno de 6 m. Os minerais pesados separados do conglomerado diamantífero amostrado nas Frentes de Lavra 2 (Ferraria), 6 (Mangueiras) e na Cata exploratória do Sarkis, situada fora da área minerada, são constituídos em sua maior parte por fases opacas, entre as quais se destaca a magnetita, representando 50% em volume do concentrado. Outras fases opacas incluem hematita, ilmenita e fragmentos de lateritos. Entre as fases transparentes, destacase a granada que ocorre nas cores vermelha clara, vermelha escura, roxa, violeta e laranja, além de outros minerais derivados de rochas do embasamento cristalino. Análises químicas realizadas pela microssonda eletrônica revelaram que a ilmenita contém teores de MgO (7,4 - 11,4 % em peso) e de Cr2O3 (0,0 - 2,9 % em peso) típicos de rochas kimberlíticas. Da mesma forma, as granadas correspondem a piropos ricos em Cr2O3 (0,2 - 6,7 % em peso) correspondendo aos grupos G9 (lherzolitos), G5 e G4 (piroxenitos) e G10 (harzburgitos), sendo semelhantes a granadas das principais províncias kimberlíticas conhecidas. O diamante, por sua vez, contém microestruturas típicas semelhantes a diamantes de outras localidades. Foram identificadas trígonos em faces octaédricas, bem como microestruturas de simetria senária semelhantes às observadas em diamantes do lamproíto Argyle, na Austrália. Foram descritas microestruturas quadráticas nos cristais cúbicos, e degraus resultantes da dissolução de planos de crescimento cristalino em superfícies curvas de cristais rombododecaédricos. Atualmente a mina está paralisada desde 1984 devido a uma dívida contraída pela Extratífera de Diamantes do Brasil (EXDIBRA) com o Banco Nacional de Desenvolvimento Social. Apesar do potencial mineral existente no local, qualquer tentava de lavra só poderá ser executada mediante a quitação desta dívida. / The diamond Mine of Romaria is located in the northeast border of the Paraná Sedimentary Basin, nearby the town of Romaria, in western Minas Gerais State, Brazil. The mining place is situated on the right side of the Bagagem River, comprising an area of 1 km2 between the Água Suja and Marrecos streams. At this place diamonds have been washed from a Cretaceous polimictic conglomerate of the Uberaba Formation, Bauru Group, since the end of the nineteen century. This heterogeneous diamond-bearing conglomerate contains large conglomerate blocks of several lithologies with dimensions up to 0.80 m, set in an arenous-clayish matrix where kaolinite, illite and quartz have identified among the clasts such as mica and staurolite schists, phyllites and amphibolites of the Araxá Group, quartzites of the Canastra Group, arenites of the Botucatu Formation and basalts of the Serra Geral Formation. The concentrates obtained by washing the conglomerate contains large amounts of opaques phases mainly magnetite which may reach up to 50% in volume. Other opaques are represented by hematite, ilmenite, rutile, limonite as well as rock fragments of mica schists and complex intergrowths of laterites. The mineralogical assemblages of the transparent phases include staurolite, amphibole, epidote, kyanite, monazite, tourmaline, zircon and diamond as well. Electron micro probe analyses revealed that the ilmenites contain MgO (7.4-11.4 wt%) and Cr2O3 (0.0-2.9 wt%) contents similar to their counterparts of kimberlites from worldwide localities. Moreover, garnets are chromium rich pyropes with Cr2O3 ranging from 0.2 up to 6.7 wt %. The use discriminating diagrams revealed that most of the analysed sampled plot in the fields G9 and G3-G5 corresponding to lherzolitic and pyroxenitic parageneses, respectively. The plots include some rare G10 (harzbugitic) and G0 (unclassified) samples corresponding to garnets derived from rocks of the crystalline basement. Although diamonds have not been mined in the last years a small parcel produced by local diggers (garimpeiros) was available for physical studies including color and crystalline morphology. Several microstructures have been observed in octahedral crystal such as trigons and a pseudo-hexagonal microstructure observed in diamonds from lamproites. Cubic crystals showing the combination of the cube and dodecahedral revealed microstructures of square symmetry. Concerning dodecahedral crystal hillocks produced by dissolution were observed on the rounded faces of the samples. Presently the Mine of Romaria is closed since 1984 due to an old debt contracted by late owner Extratífera de Diamantes do Brasil (EXDIBRA) with the Brazilian Federal Agency of the Banco Nacional de Desenvolvimento Social (BNDES).

Under pressure small molecular systems exhibit a remarkable degree of polymorphism and unexpected behaviours. Two previously unexplored binary systems, those of niobium{hydrogen and water{oxygen, are explored and their phase diagrams mapped. In the case of water and oxygen, two hitherto unknown clathrate structures are found. A wide study of dense nitrogen at and above room temperature is also reported. The phase diagram of nitrogen is exceptionally complex for a single element and exhibits considerable metastability of phases. Current theoretical understanding of nitrogen has many disagreements with experimental observation. High quality structural data on various previously known phases are reported as well as a novel molecular phase. This new phase, λ-N2, has been studied using Raman spectroscopy and powder x-ray diffrraction. Combining experimental and theoretical results gives a layered structure with intermolecular interactions playing an important role and an apparently weakened intramolecular bond. The dissociation of the nitrogen triple bond is also examined. The amorphous η state is studied via Raman spectroscopy and optical and IR absorbance methods before laser heating at 255 GPa. After heating the sample becomes very much more transparent and shows signs that the nature of the bandgap has changed suggesting that the nitrogen may be in a crystalline atomic phase hitherto unknown. An effort to take nitrogen to considerably higher pressures is reported. A two stage diamond anvil cell was developed using focused ion beam micromachining. Although ultimately unsuccessful, to the author's knowledge this was the first ever attempt at designing such a system to be compatible with small molecular samples and Raman spectroscopy and various conclusions are as to how best to proceed with such developments.

This thesis presents work undertaken using Synchrotron and Laboratory based techniques in parallel on the Chemical State and Luminescence Imaging of Natural and Synthetic Diamond. X-ray absorption spectroscopy (XAS) techniques have revealed information on the chemical structure and bonding within brown and variegated type Ia, IIa, CVD and high-pressure, high-temperature (HPHT) treated diamonds. XAS, Raman, X-ray Excited Optical Luminescence (XEOL) and Photoluminescence (PL) are some of the techniques that have been applied to characterise and investigate the cause of the brown colouration. The XAS measurements have been undertaken in imaging mode with the capabilities of correlating the luminescence image with the brown regions in partial luminescence yield (PLY) and total luminescence yield (TLY). OD-XAS spectrums have been obtained at non-brown and brown regions and have revealed a higher concentration of sp2-bonded carbon present at the brown sites. Raman spectroscopy utilized in imaging mode also supports this discovery.