Nanographene oxide particles (NGO) were produced via oxidative exfoliation of graphite. Three different sizes of NGO (300 nm, 200 nm and 100 nm) have been separated by using probe sonication and sucrose density gradient centrifugation. There is great interest in functionalized NGO as a nanocarrier for in vitro and in vivo drug delivery, in order to improve dispersibility and stability of the nanocarrier platforms in physiological media. In this study, the NGO particles were covalently functionalized with zero generation polyamidoamide (PAMAM-G0) and with gelatin via noncovalent interaction. Spectroscopic techniques have been used to discriminate the chemical states of NGO prior and after functionalization. The X-ray photoelectron spectroscopy (XPS) revealed a clear change in the chemical state of NGO after functionalization, for both covalent and noncovalent approaches. Raman spectroscopy gave obvious insight after oxidation of graphite and functionalization of NGO particles depending on the variation of intensity ratios between D, G and 2D bands. The Fourier transform infrared spectroscopy (FTIR) exhibited the presence of oxygen containing functional groups distributed onto graphene sheets after oxidation of graphite. Furthermore, the FTIR is complementary with the XPS which performed a strong reduction in the oxygen contents after functionalization. UV visible spectroscopy was used to understand the binding capacity of gelatin coated NGO particles. The Microscopy tools, scanning electron microscopy (SEM) and atomic force microscopy (AFM) are used to estimate the dimensions of NGO particles (thickness and lateral width). The nanohybrid systems (NGO-PAMAM and Gelatin-NGO) loaded with carboplatin (CP) were sought for anticancer activity investigation in HeLa and neuroblastoma cancer cells respectively. Mesenchymal stem cells (hMSCs) were used as a model of normal cells. On HeLa cells, the pristine NGO particles with average widths of 200 nm and 300 nm showed a cytotoxic effect at low (50 g.ml−1) and high (100 g.ml−1) concentrations. While the pristine NGO sample with an average width of 100 nm revealed no significant cytotoxicity at 50 g.ml−1, and only recorded a 10% level at 100 g.ml−1. The mesenchymal stem cells showed less than 35% viability for all size distributions. After functionalization with PAMAM, the carrier was found to be able to deliver carboplatin to the cancer cells, by enhancing the drug anticancer efficiency. Moreover, the carboplatin loaded NGO carrier shows no significant effect on the viability of hMSCs even at high concentration (100 g.ml−1). On neuroblastoma cells, the cell viability assay validated gelatin-NGO nanohybrids as a useful nanocarrier for CP release and delivery, without obvious signs of toxicity. The nano-sized NGO (200 nm and 300 nm) did not enable CP to kill the cancer cells efficiently, whilst the CP loaded gelatin-NGO 100 nm resulted in a synergistic activity through increasing the local concentration of CP inside the cancer cells.

Electro-optic phase modulators play a vital role in various large-scale photonic systems including Light Detection and Ranging (LIDAR), quantum circuits, optical neural networks and optical communication links. The key requirement of these modulators include strong phase change with low modulation induced optical loss, low electrical power consumption, small device footprint and low fabrication complexity. Conventional silicon phase modulators have either high power consumption (thermo-optic effect) or high optical loss (plasma-dispersion effect). On the other hand, low-loss phase modulation can be achieved using electro-optic 𝑋² effect such as LiNbO₃ which has a large device footprint (in mm's) and requires complex fabrication. The need of the hour is a material or a device that is strongly tunable with low optical loss and capable of picosecond switching speed. Transition metal dichalcogenides (TMDs) have been widely studied for optoelectronic applications due to their strong and tunable excitonic response. In fact, TMDs have been shown to experience massive changes of upto 20 % in their refractive index with doping, but this modulation is accompanied with large absorption change (60 %), which greatly limits their utility in photonic applications. In contrast, very litte is known about the effect of doping on the electro-optic response of TMDs at energies far below the exciton resonances, where the material is transparent and therefore could be used for photonic circuits. In this work, we first probe the electro-optic properties of TMDs in the near-infrared using a dielectric SiN microring resonator platform. We measure a strong doping induced change in the refractive index (Δn) of 0.52 in WS2 with minimal induced absorption (Δk) of 0.004. The |Δn/Δk| of 125, is an order of magnitude higher than the measured |Δn/Δk| for 2D materials including graphene and TMD monolayer at excitonic resonances, and for bulk electro-refractive materials commonly employed in silicon photonics. We next utilize this strong electro-refractive response to demonstrate low power, lossless optical phase modulation based on a composite SiN-TMD platform. The WS₂ based photonic modulator achieves a modulation efficiency (V_π⋅L) of 0.8 V ⋅ cm with a RC limited bandwidth of 0.3 GHz and DC electrical power consumption of 0.64 nW. The measured index change in monolayer TMDs (∼ 15%) in TMDs is unprecedented, considering the change in index of bulk (LiNbO₃) - the 'gold standard' for photonics - is typically 0.04 %. Despite the observed strong electro-refractive effect in TMDs and the enhanced light-matter interaction, the change in effective index of the propagating mode is 6.5 × 10⁻⁴ RIU, thereby requiring WS₂ phase modulators that are 1.3 mm long. This is due to the low optical mode overlap of 0.03 % with the monolayer that necessitates long phase shifter length. There is an urgent need for a compact, low-loss and high-speed optical phase shifter. Conventional phase modulators with low optical loss require long lengths to achieve strong phase change. On the contrary, traditional intensity modulators leverage compact high-finesse ring resonators to modulate output intensity. However, such cavities with conventional electro-refractive materials such as silicon where Δn/Δk = -20 cannot be used for phase modulation, owing to the high insertion loss associated with the phase change. Here, we show that we can leverage high-finesse ring resonators to achieve strong phase change with low optical loss. We achieve this by simultaneously modulating both the real and imaginary part of the effective index in the cavity to the same extent i.e. Δn/Δk ≈1. We design a hybrid SiN-2D platform that modulates the complex effective index of the propagating mode, by tuning the loss and index in monolayer graphene (Gr) and WSe₂ embedded on a SiN waveguide, respectively. We engineer the Gr-WSe₂ capacitor design to achieve a linear phase change of (0.50 ± 0.05)π radians with a low transmission modulation of 1.73 ± 0.20 dB and insertion loss of 2.96 ± 0.34 dB. We measure a 3 dB electro-optic bandwidth of 14.9 ± 0.1 GHz in the SiN-2D hybrid platform. We measure a phase modulation efficiency (V_(π/2)⋅L) of 0.045 V ⋅ cm with an insertion loss of 4.7 dB for a phase change of π/2 radians in the 25 μm SiN-2D platform. We show that the V_(π/2)⋅L for our SiN-2D hybrid platform is significantly lower than V_(π/2)⋅L of electro-refractive phase modulators based on silicon PN, PIN and MOS capacitors with comparable insertion loss. The TMD or TMD-graphene capacitor is incorporated as a post-fabrication process, transforming any passive substrate into an active photonic platform. The demonstrated enhanced light-matter interaction in monolayer TMDs could open up routes to a range of novel applications with these 2D materials and enable highly reconfigurable photonic circuits with low optical loss and power dissipation. We estimate that the efficiency of our TMD platform can be improved by optimizing the optical mode overlap with the monolayer through photonic mode optimization or reducing the dielectric thickness. For large-scale photonic systems, wafer-scale integration of TMD materials with silicon photonics can be done either as a direct TMD growth process on silicon wafers or a post-processing step where large wafer-scale TMD films are transferred onto a silicon photonics platform fabricated in a standard foundry.

The structural and electronic properties of graphene and graphene-related materials have been intensively investigated using the plane wave based periodic density func- tional theory (DFT). The Vienna ab initio simulation package (VASP) code employing the generalized gradient approximation (GGA) for the exchange correlation potential was used. In all calculations, the geometry optimization option was employed in allow- ing the structure to fully relax. Hydrogen adatoms were adsorbed on C, Si and SiC in the graphene structure in-volving (1x1),(2x2),(3x3) and (4x4) two dimensional unit cells. The density of states reveals that the adsorption of 50% hydrogen makes the system metallic but 100% coverage at the on top sites generates a band gap. Our results show that SiC in the graphene structure is a plausible structure with a wide band gap. For adsoption of lithium adatoms, we considered various configurations involving the (1x1), (2x1) and (2x2) two-dimensional unit cells, and we consider the isolated Li dimer on graphene. We consider more detailed configurations than have been studied before, and our results compare favourably with previously calculated results where such results exist. For 100% coverage, we have new results for Li on the on-top site, which suggests a staggered configuration for the lowest energy structure for which the Li adatoms are alternately pushed into and pulled out of the graphene layer. For 50% coverage, Li favours the hollow site. We discovered that a careful relaxation of the system also shows a staggered configuration, a result that has not been investigated before. / Dissertation (MSc)--University of Pretoria, 2011. / Physics / unrestricted

The discovery of strongly correlated electronic phases in twisted bilayer graphene has led to an enormous interest in twisted van der Waals (vdW) heterostructures. While twisting vdW layers provides a new control knob and never before seen functionalities, it also leads to large spatial variations in the electronic properties. Scanning probe experiments are therefore necessary to fully understand the properties of twisted vdW heterostructures. In this thesis, we studied twisted bilayer graphene (TBG) with two scanning probe techniques at two twist angle regimes. At small twist angles, our nano-infrared images resolved the spatial variations of the electronic structure occurring within a Moiré unit cell and uncovered a quantum photonic crystal. Meanwhile, with nano-photocurrent experiments, we resolved DC Seebeck coefficient changes occurring in domain walls on nanometer length scales. At larger twist angles, we mapped the twist angle variations naturally occurring in our device with a combination of nano-photocurrent and nano-infrared imaging. Finally, we also investigated different materials for use as nano-optics compatible top gates in future experiments on TBG. Our results demonstrate the power of nano-optics techniques in uncovering the rich, spatially inhomogeneous physics of twisted vdW heterostructures.

Silicon photonics accelerated the advent of complex integrated photonic systems where multiple devices and elements of the circuits synchronize to perform advanced functions such as beam formation for range detection, quantum computation, spectroscopy, and high-speed communication links. The key ingredient for silicon's growing dominance in integrated photonics is scalability: the ability to monolithically integrate large number of devices. There are emerging device designs and material platforms compatible with silicon photonics that offer performances superior to silicon alone, yet their lack of scalability often limits the demonstrations to device-level. Here we discuss two of such platforms, suspended air-cladded microresonators and graphene modulators. In this thesis, we demonstrate methods to scale these devices and enable more complex applications and higher performance than a single device can ever acheive. We present an effective method to thermally tune optical properties of suspended and air-cladded devices. We utilize released MEMs-like wire structures and integrated heaters and demonstrate efficient thermo-optic tuning of suspended microdisk resonators without affecting optical performance of the device. We further scale this method to a system of two evanescently coupled resonators and demonstrate on-demand control of their coupling dynamics. We present an approach to achieve large yield of high bandwidth graphene modulators to enable Tbits/s data transmission. Despite their high performance, graphene modulators have been demonstrated at single device-level primarily due to low yield, ultimately limiting their total data transmission capacity. We achieve large yield by minimizing performance variation of graphene modulators due to random inhomogeneous doping in graphene by optimizing device design and leveraging state-of-the-art electrochemical delamination graphene transfer. We present for the first time, to the best of our knowledge, a statistical analysis of graphene photonic devices. Finally, we present a graphene modulator that is versatile for photonic links at cryogenic temperature. We demonstrate the operation of high bandwidth graphene modulator at 4.9 K, a feat that is fundamentally challenging other electro-optic materials. We describe its performance enhancement at cryogenic temperature compared to ambient environment unlike modulators based on other electro-optic materials whose performance degrades at cryogenic temperature.

This thesis explores the substrate-dependent charge carrier dynamics of large area graphene fi lms. Using terahertz spectroscopy, we measure conductivity spectra of graphene supported by seven distinct substrates, and extract their transport properties (carrier scattering time, doping density, and carrier mobility) within the Drude model. We find that graphene supported by distinct substrates exhibit signi cantly different transport properties. We propose that graphene fi lms supported by substrates with less charged impurities exhibit longer scattering times, and enhanced carrier mobilities, emphasizing the importance of the graphene-substrate interaction for optimization of device performance. These results will be signi cant for the effective integration of graphene into future technologies where an optimal carrier mobility is desired.

Graphene, a layer of carbon atoms arranged in a honeycomb-type structure, has attracted enormous interest since it was first isolated in 2004. Chemical vapor deposition (CVD) is one of the most common techniques to produce graphene but questions remain on how best to standardize its growth. Different designs of reactors, numerous sub-types of CVD (plasma-enhanced, low pressure…), catalytic metal foils that vary in surface chemistry and texture… these are all variables that are abundantly scrutinized in the literature. Despite the scattering of procedures and observations, it is rare to find comparative studies of graphene growth. In this thesis, two thermal CVD reactors were explored to grow single–layer graphene (SLG) on a 50 μm copper foil. These set–ups were very different, one being a “showerhead” cold–wall type whereas the other one had a tubular hot-wall chamber. Their inner volume, gas flow limits, and heating rates were other differentiating factors. The work had three critical steps: pre–growth treatment of the metal foil, growth step and SLG transfer. All required absolute control to obtain high quality, uniform and cm2–scale SLG placed on a SiO2 substrate. Overall, and after standardizing the surface of the metal foil, it was possible to design a CVD recipe for the two reactors that differed only on the gas flow rates used. Thus, and contrary to an often-used argument in the literature, SLG growth recipes can be transferred amongst thermal CVD reactors.

Photonic crystals are media with periodically varying optical properties. Photonic crystals enable exquisite control of light propagation in integrated optical circuits and also emulate advanced physical concepts. However, common photonic crystals directly pattern the optical medium and thus are unfit for in-operando on/off controls. In this dissertation, we introduced, fabricated, and studied the properties of graphene polaritonic crystals. Our polaritonic crystal system consists of a pristine sheet of graphene in a back-gated platform with nano-structured gate insulators. We employed scattering-type scanning near-field optical microscopy (s-SNOM) to study the novel properties of polaritons propagating in the polaritonic crystal. We demonstrated the formation of a polaritonic bandgap, variations of the polaritonic local density of states, and the emergence of polaritonic domain wall states. We also revealed the programmable control of the polariton propagation direction and reconstructed the polaritonic bandstructure from real-space polariton images. The exploration of topological polaritonic phenomena in the polaritonic crystal relies on the selective excitation of topologically non-trivial modes using a chiral polariton launcher. We searched for the design of an efficient chiral polariton launcher. Throughout the journey, we visualized the polaritonic vortex mode of hBN phonon-polaritons. We discovered that the optical spin angular momentum of hBN phonon-polaritons resembles nano-scale meron spin textures. The meron spin texture possesses a half-integer topological charge determined by the handedness of the incident beam. The polaritonic crystal platform studied in this dissertation sheds light on the exploration of topologically non-trivial polaritonic states, such as valley plasmons and topological edge states. In addition, our electrostatically-tunable polaritonic crystals are derived from standard metal oxide semiconductor field-effect transistor technology and pave a way for practical on-chip light manipulation.

No description available.

The objective of this research is to develop a scalable manufacturing process for high-volume production of low-cost graphene materials from lignin. The process includes preparation of catalyst-lignin precursors, pretreatment of precursors, and catalytic graphitization of kraft lignin to graphene materials. A growth concept, “catalytic thermal molecular welding (CTMW)” technique is proposed and validated to produce graphene materials from solid carbon resources. CTMW technique is a single process with two stages, i.e., the carbon-encapsulated metal nanostructures are first prepared. Then in the second stage these core-shell structures are opened by “scissoring molecules”, the cracked carbon shell units are welded and reconstructed to multilayer graphene materials under high temperature with selected “welding reagent gases” like light hydrocarbons (methane, natural gas, etc.) and hydrogen. Multi-layer nano-shell structure-based graphene materials, such as fluffy graphene, graphene chains, multi-layer graphene nanoplatelets, flatten or curved sheet-like graphene can be produced through altering fabrication conditions. The effects of transitional metal catalysts (Ni, Cu, Fe, and Mo) on the yields and structures of multi-layer nano-shell structure-based graphene materials from lignin are compared. The effects of the iron chemical resources (Fe(NO3)3, FeCl2, FeCl3, and Fe2O3 (nano)), iron loading on the yields and structures of multi-layer graphene materials from lignin are also examined. The influences of temperature, heating rate, heating time, metal-lignin precursor particle size, and welding reagent gas types on the yield of multi-layer graphene materials from lignin resources are investigated. Welding temperatures are optimized as1,000°C or above, with heating rates of 10°C or above. Welding gases including, argon (Ar), hydrogen (H2), methane (CH4), natural gas (NG), and mixed of these gases, are used at flow rates from 20 to 300 mL/min. Heating time is controlled between 0 to 5 hours. The effect of precursor particle size on final products is examined between 44 to 426 microns (Delta-m).