This thesis reports on ultrafast linear and nonlinear optical probing of nanometer thick films. Exfoliated graphene and few-layer graphite are probed through optical second harmonic generation (SHG) with 800 nm, 150 fs pulses. Samples of varying thickness from 1 carbon layer to bulk graphite are deposited onto an oxidized silicon substrate. SHG measurements are taken as a function of azimuthal rotation angle of the films. It is found that the SHG from graphene is much weaker than that from bilayer graphene, and has a qualitatively different azimuthal pattern. As the sample thickness increases from bilayer graphene to bulk graphite, the SHG yield generally decreases. Both of these effects are explained in terms of the symmetry of graphene and graphite, and modeled using multilayer optical transfer matrices, and an identical set of nonlinear susceptibility tensor elements for the front and back surfaces. These tensors are independent of sample thickness. MnAs films of 150 and 190 nm thickness on (001)GaAs are optically excited with 775 nm, 200 fs pump pulses. Specular SHG at 388 nm and first order optical diffraction at ∼ 400 nm are used to probe the samples on timescales up to 2 μs. It is found that the SHG probes the temperature-dependent, spatially averaged, surface strain. This strain reaches a maximum deviation in ∼ 6–100 ps after optical excitation depending on the pump fluence and initial temperature. The strain then recovers in hundreds of picoseconds, a timescale consistent with heat diffusion. The optical diffraction probes the first Fourier component of the paramagnetic–ferromagnetic stripes inherent to MnAs films in the 10–40◦C temperature range. After optical excitation, the diffraction data show highly nonthermal behaviour in the MnAs films. If a sample is excited from the coexistence phase, the diffraction signal shows decaying oscillations with a period of ∼ 335±4 (408±4) ps for the 150 (190) nm films; this is consistent with the release of a standing acoustic wave. Decay occurs on a timescale of ∼ 2 ns consistent with local diffusion through the films. The stripes are restored on a timescale of hundreds of nanoseconds, with a temporal behavior consistent with a diffusion process, possibly thermal in origin.

This thesis reports on ultrafast linear and nonlinear optical probing of nanometer thick films. Exfoliated graphene and few-layer graphite are probed through optical second harmonic generation (SHG) with 800 nm, 150 fs pulses. Samples of varying thickness from 1 carbon layer to bulk graphite are deposited onto an oxidized silicon substrate. SHG measurements are taken as a function of azimuthal rotation angle of the films. It is found that the SHG from graphene is much weaker than that from bilayer graphene, and has a qualitatively different azimuthal pattern. As the sample thickness increases from bilayer graphene to bulk graphite, the SHG yield generally decreases. Both of these effects are explained in terms of the symmetry of graphene and graphite, and modeled using multilayer optical transfer matrices, and an identical set of nonlinear susceptibility tensor elements for the front and back surfaces. These tensors are independent of sample thickness. MnAs films of 150 and 190 nm thickness on (001)GaAs are optically excited with 775 nm, 200 fs pump pulses. Specular SHG at 388 nm and first order optical diffraction at ∼ 400 nm are used to probe the samples on timescales up to 2 μs. It is found that the SHG probes the temperature-dependent, spatially averaged, surface strain. This strain reaches a maximum deviation in ∼ 6–100 ps after optical excitation depending on the pump fluence and initial temperature. The strain then recovers in hundreds of picoseconds, a timescale consistent with heat diffusion. The optical diffraction probes the first Fourier component of the paramagnetic–ferromagnetic stripes inherent to MnAs films in the 10–40◦C temperature range. After optical excitation, the diffraction data show highly nonthermal behaviour in the MnAs films. If a sample is excited from the coexistence phase, the diffraction signal shows decaying oscillations with a period of ∼ 335±4 (408±4) ps for the 150 (190) nm films; this is consistent with the release of a standing acoustic wave. Decay occurs on a timescale of ∼ 2 ns consistent with local diffusion through the films. The stripes are restored on a timescale of hundreds of nanoseconds, with a temporal behavior consistent with a diffusion process, possibly thermal in origin.

Previous studies have suggested that the material graphene might transition into an electron-electron interaction driven, unconventional, time-reversal-symmetry-breaking, (d+id)wave superconducting state upon either significant electron or hole doping, and, in particular, upon doping to the Van Hove singularity. As defects are likely to be introduced in the doping process, we are, in this text, concerned with the effects of defects on this superconducting state near the Van Hove singularity doping. To investigate the effects we use a mean-field treatment of a phenomenological resonant-valence-bond model. We find that the resonant-valence-bond amplitudes, which in the defect free graphene sheet are proportional to the superconducting pairing-potential, are suppressed near the defects, and that the recovery is well described by an exponential, yet anisotropic, recovery. In general, we find that the (d+id)-wave, superconducting state is quite resilient, and that even for strong defects, such as a vacancy, the recovery length is of the order of one lattice constant when extrapolated to weak pairing-potentials; this is compared to a conventional superconducting state of an attractive Hubbard model for which the same decay length is found to be of the order of a half lattice constant. For the defect free graphene sheet the (d+id)-wave state is a completely gapped state. The introduction of vacancies is, however, found to be accompanied by the appearance of midgap states. These states are shown to be localized around the vacancies. In accordance with the nature of this text, we will, for the benefit of students and non-experts, include an introductory section on the fundamental methods and concepts used. It gives a short and hopefully pedagogical introduction to the rudimentary concepts of solid state theory and the microscopic BCS theory of superconductivity.

Diamond is a unique material with excellent properties. As a result of the development within the area of CVD synthesis, doping and surface functionalization, diamond has become a strong candidate for use in electrochemical, electronic and biomedical applications. In this thesis, theoretical calculations have been used with the purpose to investigate various properties of the diamond surfaces. The effect of doping elements (N and B) on the stability of different surface terminations with X (where X = H, OH, Oontop or Obridge) has been investigated for a diamond (100) surface. As a result, the adsorption energy for all termination types was shown to decrease from the situation with a non-doped diamond surface, to the scenario with a N- (or B-doped) diamond thin film.. This result was found to correlate well with the changes of the calculated Csurface-X bond lengths. Furthermore, the spin density has been calculated and used to show the local distribution of the unpaired electron, which is the consequence of the introduction of dopants into the diamond slab. As a result, the spin density was found to be localized in the vicinity to the dopants for H- (or OH-) terminated diamond (100) surfaces. On the other hand, a delocalised spin density over the Oadsorbate and Csurface layer for Oontop- and Obridge-terminated surfaces, has also been observed. Moreover, the results of the pDOS calculations indicate the electron donating ability of N, and the hole donating ability of B. The Fermi level was shifted towards the lower conduction band edge for N-doped diamond, and towards the upper edge of the valence band edge for B-doped diamond. Hence, N-doped diamond will render n-type conductivity, and B-doped diamond will show p-type conductivity. In addition, an interesting observation was made for Oontop –terminated diamond surfaces. Localized electron conductivity, involving only this type of termination situation,, was also observed for N- (or B-) doped and completely  Oontop-terminated diamond surfaces. With the purpose of applying diamond substrates in the formation of epitaxial graphene, the annealing process of an ideal diamond (111) surface has also been simulated in the present work. It was thereby shown that high temperatures (over 2000 K) will be required for the epitaxial formation of graphene ontop of the diamond (111) surface. However, in the presence of hydrogen radicals (by saturating the radical sites in the system), the required temperature was observed to decrease to 1000 K. In addition to these MD simulations, by using an interlayer iron ontop of the diamond (111) surface, the adhesion energies between the graphene and the Fe//diamond slab, as well as the adhesion energy between the graphene//Fe layer and the diamond (111) surface, have been calculated. Thereby, the interaction between the graphene and Fe layer was obtained to be very weak, and of an electrostatic type. On the other hand, the interaction between the Fe interlayer and the diamond substrate was calculated as a moderately strong covalent bond. Moreover, the changes in these interactions, correlating to the changes in the pDOS spectra of graphene, Fe and diamond, gave a tendency of one-dimensional quantum size effect, depending on the thickness of Fe interlayer.

There is a growing interest for relying on cleaner and more sustainable energy sources due to the negative side-effects of the dominant fossil-fuel based energy storage and conversion systems. Cleaner, electrochemical energy storage through lithium-ion batteries has gained considerable interest and market value for applications such as electric vehicles and renewable energy storage. However, capacity and rate (power) limitations of current lithium-ion battery technology hinder its ability to meet the high energy demands in a competitive and reliable fashion. Silicon is an element with very high capacity to Li-ion storage although commercially impractical due to its poor stability and rate capabilities. Nevertheless, it has been heavily researched with more novel electrode nanostructures to improve its stability and rate capability. It was found that silicon nanomaterials such as silicon nanowires have inherently higher stability due to mitigation of cracking and higher rate capability due to the short Li-ion diffusion distance. However, electrode compositions based only on silicon nanowires without additional structural features and a high conductive support do not have enough stability and rate capability for successful commercialization. One structural and conductive support of silicon materials studied in literature is graphene. Graphene-based electrodes have been reported as material capable of rapid electron transport enabling new strides in rate capabilities for Li ion batteries. This thesis presents a novel electrode nanostructure with a simple, inexpensive, scalable method of silicon nanwire synthesis on graphene nanosheets via nickel catalyst. The research herein shows the different electrode compositions and variables studied to yield the highest achievable capacity, stability and rate capability performance. The carbon coating methodology in addition to enhancing the 3D conductivity of the electrode by replacing typical binders with pyrolyzed polyacrylonitrile provided the highest performance results.

Graphene is a single layer of carbon atoms, laid out in a hexagonal lattice. The material has remarkable properties that opened up several new research areas since its discovery in 2004. One promising field is graphene based biosensors, where researchers hope to create new devices that are smaller, cheaper and more reliable than those based on today’s technology. Among several manufacturing methods, graphene grown on silicon carbide is one of the promising ones for biosensing. A chip design has been developed in order to support research into graphene on silicon carbide as a base material for biosensors. Along with the chip, a holder for electrochemical measurements has been designed and an investigation into the requirements of a custom measurement device for the sensor has been undertaken.

Ubiquitous concerns in device fabrication are nanoscale positioning and the integration of complex combinations of diverse materials, many of which are extremely fragile. Frequently the completed device requires one or more of the constituent materials to be synthesized under suboptimal conditions, thus compromising the performance of the final structure. We have developed a platform to fabricate multi-component electrode cross-bar structures, where each material can be synthesized under its own ideal conditions. Furthermore, surface treatments and procedures that may otherwise be incompatible can be performed without concern of damage to the other constituent materials. We demonstrate our approach by fabricating an all carbon cross-bar electrode structure comprised of a graphene-graphite heterojunction. Initially, a graphene field effect transistor is fabricated using electron beam and optical lithography. The top graphite electrode is sculpted from a bulk piece of highly oriented pyrolytic graphite with the aid of a focused ion beam (FIB) and integrated micromanipulator system. This requires real-time shaping, cutting, accurate positioning (circa 100 nm precision) and wiring of the graphite top electrode. Electron transport characteristics of each electrode component and the final heterostructure have been measured. We show that this process is effective for the production of micron and submicron-scale multi-layer device structures including other materials such as gold. This fabrication scheme could be extended to produce novel structures such as mechanical resonators, and provide a foundation for combining fragile materials that have otherwise been incompatible with traditional fabrication techniques. / Graduate

The aim of DNA sequencing is to obtain the order of DNA composition comprising the base pairs A (adenine) T (thymine), and C (cytosine) G (guanine). The fast development of DNA sequencing technology allows us to better understand the relationships among diseases, inheritance, and individuality. Solid state nanopores have been recommended as the next generation platform for DNA sequencing due to its low-cost and high-throughput. In particular, nanopores fabricated from graphene sheets are extremely thin and structurally robust and have been extensively used in DNA detection in recent years. In DNA sequencing, the translocation of a DNA molecule through a nanopore is known to be a very complicated issue and is affected by many factors, such as ion concentration, thickness of the nanopore, and the nanopore diameter. The technique of molecular dynamic simulations has been a complementary tool to study DNA translocation through nanopores.       In this thesis, I summarize my work of computational studies of DNA sequencing using graphene nanopores. These studies include: DNA translocation through single-layer graphene nanopores of different diameters under conditions of various ion concentrations and applied voltages; DNA translocation through multilayer graphene nanopores varied from a single to a few layers; pulling out single strand DNA molecules from small graphene nanopores of different geometries. The major contributions of this work include: 1. Effects of bias voltage on DNA translocation time were investigated leading to the insight that lower applied voltages can extend the time of DNA translocation through monolayer graphene nanopores. The effect of salt concentration on the corresponding ionic current was studied. At a low ionic concentration (&lt; 0.3M), the current increases as DNA translocates through a nanopore. However, at a high ionic concentration (&gt;0.5M), the current decreases as DNA translocates through the nanopore. A theoretical model was proposed to explore the relationship between the current and the occupied nanopore area. We demonstrated that the DNA translocation time can be prolonged by narrowing the diameter of a nanopore properly and the reduction of the blockade current depends on the ratio of the unoccupied nanopore area to the total nanopore area. 2.  DNA translocation through multilayer graphene nanopores was studied by molecular dynamics simulations with the aim to achieve single-base resolution. We show that the DNA translocation time can be extended by increasing the graphene layers up to a moderate number (7) and that the current in DNA translocation undergoes a stepwise change upon DNA going through an multi-layer graphene (MLG) nanopore. A model was built to account for the relationship between the current change and the unoccupied volume of the MLG nanopore. We demonstrate that the blockade current is closely related to the unoccupied volume. The dynamics of DNA translocation depends specifically on the interaction of nucleotides with the graphene sheet. Thus, our study indicates that the resolution of DNA detection can be improved by increasing the number of graphene layers in a certain range and by modifying the surface of graphene nanopores. 3. The effect of graphene nanopore geometry on DNA sequencing has been assessed by steered molecular dynamics simulations. DNA fragments including A, T, C, G and 5-methylcytosine (MC) were pulled through graphene nanopores of different geometries with diameters down to ~1nm by steered molecular dynamics simulations. We demonstrated that the bases (A, T, C, G, and MC) can be indentified in single-base resolution by the characteristic force peak values in a circular graphene nanopore but not in graphene nanopores of other geometries. Symmetric nanopores are thus better suited to DNA sequence detection via force curves than asymmetric nanopores. This implies that the graphene nanopore surface should be modified as symmetric as possible to sequence DNA by an atomic force microscope or optical tweezers. This helps us to understand low-cost and time-efficient DNA sequencing in narrow nanopores. 4. The translocation time for different nucleotides to pass through graphene nanopores with certain diameters was investigated. It was found that the translocation times are different for different bases under a low electric field. The results indicate that DNA can be sequenced by the translocation time to pass through a graphene nanopore. 5. Inspired by the structure of K+ channel proteins, a series of oxygen doped graphene nanopores of different size were designed to discriminate the transport of K+ and Na+ ions. The results indicate that the ion selectivity of such biomimetic graphene nanopores can be simply controlled by the size of the nanopore.  Compared to K+, the smaller radius of Na+ leads to a much higher free energy barrier in the nanopore of a certain size. / <p>QC 20141212</p>

The understanding of nucleation and growth of metals on a planar support at the atomic level is critical for both surface science research and heterogeneous catalysis studies. In this dissertation, two planar substrates, including graphene and ultra-thin silica film were employed for supported model catalysts studies. The structure and stability of several catalytically important metals supported on these two substrates were thoroughly investigated using scanning tunneling microscopy (STM) coupled with other traditional surface science techniques. In the study of the graphene/Ru(0001) system, the key factors that govern the growth and distribution of metals on the graphene have been studied based on different behaviors of five transition metals, namely Pt, Rh, Pd, Co, and Au supported on the template of a graphene moire pattern formed on Ru(0001). Both metal-carbon (M-C) bond strength and metal cohesive energies play significant roles in the cluster formation process and the M-C bond strength is the most important factor that affects the morphology of clusters at the initial stages of growth. Interestingly, Au exhibits two-dimensional (2-D) structures that span several moire unit cells. Preliminary data obtained by dosing molecular oxygen onto CO pre-covered Au islands suggest that the 2-D Au islands catalyze the oxidation of CO. Moreover, graphene/Ru(0001) system was modified by introducing transition metals, oxygen or carbon at the interface between the graphene and Ru(0001). Our STM results reveal that the geometric and/or electronic structure of graphene can be adjusted correspondingly. In the study of the silica thin film system, the structure of silica was carefully investigated and our STM images favor for the [SiO4] cluster model rather than the network structure. The nucleation and adsorption of three metals, namely Rh, Pt and Pd show that the bond strength between the metal atom and Si is the key factor that determines the nucleation sites at the initial stages of metal deposition. The annealing effect studies reveal that Rh and Pt atoms diffuse beneath the silica film and form the 2-D islands that are covered with a silica thin film. In contrast, the formation of Pd silicide was observed upon annealing to high temperatures.

Thesis (M.S.)--Texas State University--San Marcos, 2008. / Vita. Includes bibliographical references (leaves 61-63). Also available on microfilm.