Optical and electronic properties of amorphous diamond

The optical and electronic properties of highly tetrahedral amorphous diamond-like carbon (amorphous diamond, a-D) films were investigated. The structure of the films grown on silicon and glass substrates, under similar deposition conditions using a compact filtered cathodic vacuum arc system, are compared using electron energy loss spectroscopy (EELS). Results from hydrogenation of the films are also reported. The hydrogenated films show two prominent IR absorption peaks centered at 2920 and 2840 cm-1, which are assigned to the stretch mode of the C-H bond in the sp3 configuration on the C-H3 and C-H sites respectively. The high loss EELS spectra show no reduction in the high sp3 content in the hydrogenated films. UV and visible transmission spectra of a-D thin films are also presented. The optical band gap of 2.0-2.2 eV for the a-D films is found to be consistent with the electronic bandgap. The relationship between the intrinsic compressive stress in the films and the refractive index is also presented. The space charge limited current flow is analyzed and coupled with the optical absorption data to give an estimate of 1018 cm-3 eV-1 for the valence band edge density of states.

Defect and disorder reduction by annealing in hydrogenated tetrahedral amorphous carbon

Hydrogenated tetrahedral amorphous carbon (ta-C:H) is a form of diamond-like carbon with a high sp3 content (>60%), grown here using a plasma beam source. Information on the behaviour of hydrogen upon annealing is obtained from effusion measurements, which show that hydrogen does not effuse significantly at temperatures less than 500 °C in films grown using methane and 700 °C in films grown using acetylene. Raman measurements show no significant structural changes at temperatures up to 300 °C. At higher temperatures, corresponding to the onset of effusion, the Raman spectra show a clustering of the sp2 phase. The density of states of ta-C:H is directly measured using scanning tunnelling spectroscopy. The measured gradients of the conduction and valence band tails increase up to 300 °C, confirming the occurrence of band tail sharpening. Examination of the photoluminescence background in the Raman spectra shows an increase in photoluminescence intensity with decreasing defect density, providing evidence that paramagnetic defects are the dominant non-radiative recombination centres in ta-C:H.

Bonding regimes of nitrogen in amorphous carbon

Nitrogen can have numerous effects on diamond-like carbon: it can dope, it can form the hypothetical superhard compound C3N4, or it can create fullerene-like bonding structures. We studied amorphous carbon nitrogen films deposited by a filtered cathodic vacuum arc as a function of nitrogen content, ion energy and deposition temperature. The incorporation of nitrogen from 10-2 to 10 at% was measured by secondary ion mass spectrometry and elastic recoil detection analysis and was found to vary slightly sublinearly with N2 partial pressure during deposition. In the doping regime from 0 to about 0.4% N, the conductivity changes while the sp3 content and optical gap remain constant. From 0.4 to approximately 10% N, existing sp2 sites condense into clusters and reduce the band gap. Nitrogen contents over 10% change the bonding from mainly sp3 to mainly sp2. Ion energies between 20 and 250 eV do not greatly modify this behaviour. Deposition at higher temperatures causes a sudden loss of sp3 bonding above about 150 °C. Raman spectroscopy and optical gap data show that existing sp2 sites begin to cluster below this temperature, and the clustering continues above this temperature. This transition is found to vary only weakly with nitrogen addition, for N contents below 10%.

Influence of ion energy and deposition temperature on the surface morphology of carbon films deposited by ion beams

Carbon films were deposited by mass-selected ion beam technique with ion energies 50-200eV at a substrate temperature from room temperature to 80 degreesC,. For the energies used, smooth diamond-like carbon films were deposited at room temperature. When the substrate temperature was 600 degreesC,rough graphitic films were produced. But highly oriented carbon tubes were observed when the energies were larger than 140eV at 800 degreesC. They were perpendicular to the surface and parallel to each other. preferred orientation of graphite basic plane was observed by high-resolution electron microscopy. Shallow ion implantation and stress are responsible for this orientation.

Synthesis, structural analysis, and magnetic behaviour of three fumarate bridged coordination polymers: five-fold interpenetrated diamond-like net of Ni-II, sheets of Ni-II and Co-II

The hydrothermal reactions of Ni(NO3)(2).6H(2)O, disodium fumarate (fum) and 1,2-bis(4-pyridyl)ethane (bpe)/1,3-bis(4-pyridyl) propane (bpp) in aqueous-methanol medium yield one 3-D and one 2-D metal-organic hybrid material, [Ni(fum)(bpe)] (1) and [Ni(fum)(bpp)(H2O)] (2), respectively. Complex 1 possesses a novel unprecedented structure, the first example of an "unusual mode" of a five-fold distorted interpenetrated network with metal-ligand linkages where the four six-membered windows in each adamantane-type cage are different. The structural characterization of complex 2 evidences a buckled sheet where nickel ions are in a distorted octahedral geometry, with two carboxylic groups, one acting as a bis-chelate, the other as a bis-monodentate ligand. The metal ion completes the coordination sphere through one water molecule and two bpp nitrogens in cis position. Variable-temperature magnetic measurements of complexes 1 and 2 reveal the existence of very weak antiferromagnetic intramolecular interactions and/or the presence of single-ion zero field splitting (D) of isolated Ni-II ions in both the compounds. Experimentally, both the J parameters are close, comparable and very small. Considering zero-field splitting of Ni-II, the calculated D values are in agreement with values reported in the literature for Ni-II ions. Complex 3, [{Co(phen)}(2)(fum)(2)] (phen=1,10-phenanthroline) is obtained by diffusing methanolic solution of 1,10-phenanthroline on an aqueous layer of disodium fumarate and Co(NO3)(2).6H(2)O. It consists of dimeric Co-II(phen) units, doubly bridged by carboxylate groups in a distorted syn-syn fashion. These fumarate anions act as bis-chelates to form corrugated sheets. The 2D layer has a (4,4) topology, with the nodes represented by the centres of the dimers. The magnetic data were fitted ignoring the very weak coupling through the fumarate pathway and using a dimer model.

Determination of Population Size of Glass-like Carbon Sampling Used in Weibull Analysis

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Determining the Optimum Processing Parameters of Glass-like Carbon Using Weibull Analysis of its Fracture Behaviour

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Carbon Film Coating of Abutment Surfaces: Effect on the Abutment Screw Removal Torque

Purpose: To evaluate the effect of diamond-like carbon (DLC) coating of prefabricated implant abutment on screw removal torque (RT) before and after mechanical cycling (MC).Materials and Methods: Fifty-four abutments for external-hex implants were divided among 6 groups (n = 9): S, straight abutment (control); SC, straight coated abutment; SCy, straight abutment and MC; SCCy, straight coated abutment and MC; ACy, angled abutment and MC; and ACCy, angled coated abutment and MC. The abutments were attached to the implants by a titanium screw. RT values were measured and registered. Data (in Newton centimeter) were analyzed with analysis of variance and Dunnet test (alpha = 0.05).Results: RT values were significantly affected by MC (P = 0.001) and the interaction between DLC coating and MC (P = 0.038). SCy and ACy showed the lowest RT values, statistically different from the control. The abutment coated groups had no statistical difference compared with the control. Scanning electron microscopy analysis showed DLC film with a thickness of 3 mm uniformly coating the hexagonal abutment.Conclusion: DLC film deposited on the abutment can be used as an alternative procedure to reduce abutment screw loosening.

The biocompatibility of carbon nanotubes

Carbon nanotubes (CNT) are well-ordered, high aspect ratio allotropes of carbon. The two main variants, single-walled carbon nanotubes (SWCNT) and multi-walled carbon nanotubes (MWCNT) both possess a high tensile strength, are ultra-light weight, and have excellent chemical and thermal stability. They also possess semi- and metallic-conductive properties. This startling array of features has led to many proposed applications in the biomedical field, including biosensors, drug and vaccine delivery and the preparation of unique biomaterials such as reinforced and/or conductive polymer nanocomposites. Despite an explosion of research into potential devices and applications, it is only recently that information on toxicity and biocompatibility has become available. This review presents a summary of the performance of existing carbon biomaterials and gives an outline of the emerging field of nanotoxicology, before reviewing the available and often conflicting investigations into the cytotoxicity and biocompatibility of CNT. Finally, future areas of investigation and possible solutions to current problems are proposed. (c) 2005 Elsevier Ltd. All rights reserved.

The study of ultra-low energy deposition of hydrogenated amorphous carbon thin films

This thesis is dedicated to the production and analysis of thin hydrogenated amorphous carbon films. A cascaded arc plasma source was used to produce a high density plasma of hydrocarbon radicals that deposited on a substrate at ultra low energies. The work was intended to create a better understanding of the mechanisms responsible for the film formation, by an extensive analysis on the properties of the films in correlation with the conditions used in the plasma cell. Two different precursors were used: methane and acetylene. They revealed a very different picture for the mechanism of film formation and properties. Methane was less successful, and the films formed were soft, with poor adhesion to the substrate and decomposing with time. Acetylene was the better option, and the films formed in this case were harder, with better adhesion to the substrate and stable over time. The plasma parameters could be varied to change the character of films, from polymer-like to diamond-like carbon. Films deposited from methane were grown at low deposition rates, which increased with the increase in process pressure and source power and decreased with the increase in substrate temperature and in hydrogen fraction in the carrier gas. The films had similar hydrogen content, sp3 fractions, average roughness (Ra) and low hardness. Above a deposition temperature of 350°C graphitization occurred - an increase in the sp2 fraction. A deposition mechanism was proposed, based upon the reaction product of the dissociative recombination of CH4+. There were small differences between the chemistries in the plasma at low and high precursor flow rates and low and high substrate temperatures; all experimental conditions led to formation of films that were either polymer-like, soft amorphous hydrogenated carbon or graphitic-like in structure. Films deposited from acetylene were grown at much higher deposition rates on different substrates (silicon, glass and plastics). The film quality increased noticeably with the increase of relative acetylene to argon flow rate, up to a certain value, where saturation occurred. With the increase in substrate temperature and the lowering of the acetylene injection ring position further improvements in film quality were achieved. The deposition process was scaled up to large area (5 x 5 cm) substrates in the later stages of the project. A deposition mechanism was proposed, based upon the reaction products of the dissociative recombination of C2H2 +. There were large differences between the chemistry in the plasma at low and medium/high precursor flow rates. This corresponded to large differences in film properties from low to medium flow rates, when films changed their character from polymer-like to diamond-like, whereas the differences between films deposited at medium and high precursor flow rates were small. Modelling of the film growth on silicon substrates was initiated and it explained the formation of sp2 and sp3 bonds at these very low energies. However, further improvements to the model are needed.

Synthesis, characterisation and applications of diamond materials

This thesis presented a detailed research work on diamond materials. Chapter 1 is an overall introduction of the thesis. In the Chapter 2, the literature review on the physical, chemical, optical, mechanical, as well as other properties of diamond materials are summarised. Followed by this chapter, several advanced diamond growth and characterisation techniques used in experimental work are also introduced. Then, the successful installation and applications of chemical vapour deposition system was demonstrated in Chapter 4. Diamond growth on a variety of different substrates has been investigated such as on silicon, diamond-like carbon or silica fibres. In Chapter 5, the single crystalline diamond substrate was used as the substrate to perform femtosecond laser inscription. The results proved the potentially feasibility of this technique, which could be utilised in fabricating future biochemistry microfluidic channels on diamond substrates. In Chapter 6, the hydrogen-terminated nanodiamond powder was studied using impedance spectroscopy. Its intrinsic electrical properties and its thermal stability were presented and analysed in details. As the first PhD student within Nanoscience Research Group at Aston, my initial research work was focused on the installation and testing of the microwave plasma enhanced chemical vapour deposition system (MPECVD), which will be beneficial to all the future researchers in the group. The fundamental of the on MPECVD system will be introduced in details. After optimisation of the growth parameters, the uniform diamond deposition has been achieved with a good surface coverage and uniformity. Furthermore, one of the most significant contributions of this work is the successful pattern inscription on diamond substrates by femtosecond laser system. Previous research of femtosecond laser inscription on diamond was simple lines or dots, with little characterisation techniques were used. In my research work, the femtosecond laser has been successfully used to inscribe patterns on diamond substrate and fully characterisation techniques, e.g. by SEM, Raman, XPS, as well as AFM, have been carried out. After the femtosecond laser inscription, the depth of microfluidic channels on diamond film has been found to be 300~400 nm, with a graphitic layer thickness of 165~190 nm. Another important outcome of this work is the first time to characterise the electrical properties of hydrogenterminated nanodiamond with impedance spectroscopy. Based on the experimental evaluation and mathematic fitting, the resistance of hydrogen-terminated nanodiamond reduced to 0.25 MO, which were four orders of magnitude lower than untreated nanodiamond. Meanwhile, a theoretical equivalent circuit has been proposed to fit the results. Furthermore, the hydrogenterminated nanodiamond samples were annealed at different temperature to study its thermal stability. The XPS and FTIR results indicate that hydrogen-terminated nanodiamond will start to oxidize over 100ºC and the C-H bonds can survive up to 400ºC. This research work reports the fundamental electrical properties of hydrogen-terminated nanodiamond, which can be used in future applications in physical or chemical area.