The interconnect fabric that provides electrical connectivity to active devices is an essential component to modern semiconductor chips. As the dimensions of these devices are scaled to improve performance and keep pace with Moore's Law, the local Cu interconnects must scale in parallel. Intrinsic material properties of Cu result in spiking electrical resistivity with scaling and present a looming bottleneck to chip performance. In this thesis, we introduce graphene as a replacement material to Cu interconnects in support of future chip scaling. In particular we focus on experimentally establishing fundamental mechanisms of chemically doping graphene via the basal plane and edge passivation, with broad contributions that extend beyond the focus of local interconnects.

Thesis (Ph. D.)--University of Missouri-Columbia, 2003. / Typescript. Vita. Includes bibliographical references (leaves 107-109). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 2003. / Typescript. Vita. Includes bibliographical references (leaves 107-109). Also available on the Internet.

Graphene is a two-dimensional sp2 hybridized carbon lattice that is also the fundamental building block of graphite. Graphene has attracted significant interest recently due to its distinctive electrical, optical and mechanical properties. These properties have spurred research directed at modifying graphene for use in a variety of electronic, optoelectronic, and sensor technologies. However, before graphene can be used in products, it is necessary to find methods to tune, modify, grow and integrate graphene features while substantially boosting device performance and maintaining current processing compatibility and ease of integration with existing manufacturing infrastructure. This dissertation focuses on developing techniques for controllably doping the graphene layer through scalable, industry friendly and simple chemical doping; using self-assembled monolayer compounds, photo-acid and photo-base generators, polymers and metal-organic species. We have, in fact, demonstrated simple p-n junctions fabricated in this manner. Characteristic I-V curves indicate the superposition of two separate Dirac points from the p and n regions, confirming an energy separation of neutrality points within the complementary regions; Raman studies of these methods have shown that these processes result in extremely low defect levels in the graphene. Our simple methods for producing patterned doping profiles in graphene films and devices open up a variety of new possibilities for forming complex doping profiles in a simple manner in graphene. This work can enable rapid testing, such as controlled work function tuning, complex doping profiles and simple post-fabrication tuning, of concepts for graphene that may be useful in both interconnect and transparent conductor applications. In addition to graphene doping, we also investigated approaches to the synthesis of few-layer graphene flakes, since current techniques still produce inferior materials. Exfoliation of Graphene Sheets by an Electron Donor Surfactant was demonstrated to generate few-layers graphene flakes that rival the electrical quality of reduce graphene-oxide (rGO) flakes. Last but not least, Diels-Alder adducts on silica were explored as a controllable carbon precursor for pristine graphene; these allow for a rational direct-growth-of-graphene-on-surface reaction mediated by copper catalyst, without the use of flammable precursors, such as methane, that are used in current methods of chemical vapor deposition synthesis of graphene.

Applications of zinc oxide (ZnO) for optoelectronic devices, including light emitting diodes, semiconductor lasers, and solar cells have not yet been realized due to the lack of high-quality p-type ZnO. In the research presented herein, pulsed laser deposition is employed to grow Ag-doped ZnO thin films, which are characterized in an attempt to understand the ability of Ag to act as a p-type dopant. By correlating the effects of the substrate temperature, oxygen pressure, and laser energy on the electrical and microstructural properties of Ag-doped ZnO films grown on c-cut sapphire substrates, p-type conductivity is achieved under elevated substrate temperatures. Characteristic stacking fault features have been continuously observed by transmission electron microscopy in all of the p-type films. Photoluminescence studies on n-type and p-type Ag-doped ZnO thin films demonstrate the role of stacking faults in determining the conductivity of the films. Exciton emission attributed to basal plane stacking faults suggests that the acceptor impurities are localized nearby the stacking faults in the n-type films. The photoluminescence investigation provides a correlation between microstructural characteristics and electrical properties of Ag- doped ZnO thin films; a link that enables further understanding of the doping nature of Ag impurities in ZnO. Under optimized deposition conditions, various substrates are investigated as potential candidates for ZnO thin film growth, including r -cut sapphire, quartz, and amorphous glass. Electrical results indicated that despite narrow conditions for obtaining p-type conductivity at a given substrate temperature, flexibility in substrate choice enables improved electrical properties. In parallel, N+-ion implantation at elevated temperatures is explored as an alternative approach to achieve p-type ZnO. The ion implantation fluence and temperature have been optimized to achieve p-type conductivity. Transmission electron microscopy reveals that characteristic stacking fault features are present throughout the p-type films, however in n-type N-doped films high-density defect clusters are observed. These results suggest that the temperature under which ion implantation is performed plays a critical role in determining the amount of dynamic defect re- combination that can take place, as well as defect cluster formation processes. Ion implantation at elevated temperatures is shown to be an effective method to introduce increased concentrations of p-type N dopants while reducing the amount of stable post-implantation disorder. Finally, the fabrication and properties of p-type Ag-doped ZnO/n-type ZnO and p-type N-doped ZnO/n-type ZnO thin film junctions were reported. For the N-doped sample, a rectifying behavior was observed in the I-V curve, consistent with N-doped ZnO being p-type and forming a p-n junction. The turn-on voltage of the device was ∼2.3 V under forward bias. The Ag-doped samples did not result in rectifying behavior as a result of conversion of the p-type layer to n-type behavior under the n- type layer deposition conditions. The systematic studies in this dissertation provide possible routes to grow p-type Ag-doped ZnO films and in-situ thermal activation of N-implanted dopant ions, to overcome the growth temperature limits, and to push one step closer to the future integration of ZnO-based devices.

The present project has made a comprehensive assessment of the effect of Nb doping on various charge-transfer related properties of TiO2. Of particular focus, the electrical properties of Nb-doped TiO2 (0.65 at %) have been investigated using the simultaneous measurement of electrical conductivity and thermoelectric power. This investigation was undertaken at elevated temperatures (1073 K -- 1298 K) in equilibrium with a gas phase of controlled oxygen activity (10-10 Pa < p(O2) < 75 kPa). In addition, the effect of segregation on the surface versus bulk composition of Nb-doped TiO2 was also investigated at a function of temperature and oxygen activity. Specifically, the following determinations were undertaken: The effect of oxygen activity, p(O2) and temperature on both electrical conductivity and thermoelectric power The effect of Nb on the defect disorder and related electrical properties of TiO2 The determination of equilibration kinetics and the associated chemical diffusion data for Nb-doped TiO2 The determination of Nb bulk diffusion in TiO2 The effect of p(O2), temperature and dopant content on Nb segregation and the related surface composition of Nb-doped TiO2 The obtained electrical properties enable the determination of a defect disorder model for Nb-doped TiO2, which may be considered within the following p(O2) regimes: Strongly Reduced Regime. In this regime, the predominant ionic defect was anticipated to be oxygen vacancies compensated electronically by electrons. While the transition to this regime (from higher p(O2)) was clearly observed, the predominant defect disorder existing beyond this transition was not confirmed due to an inability to obtain sufficiently low oxygen activity. Metallic-type conductivity behaviour was observed within this transition region. Reduced Regime I. In this regime, the predominate defect disorder defined by the electronic compensation of incorporated Nb ions by electrons was clearly observed. Reduced Regime II. In this regime, the predominate defect disorder defined by the ionic compensation of incorporated Nb ions by quadruply-charged titanium vacancies, was clearly observed. The present project included the determination of diffusion data which included: Temperature dependence of 93Nb tracer diffusion in single crystal TiO2 over the temperature range 1073 K -- 1573 K Chemical diffusion coefficient over the temperature range 1073 K -- 1298 K and oxygen activity range, 10-10 Pa < p(O2) < 75 kPa These pioneering studies are significant as they enable the prediction of the processing conditions required to reliably 1) incorporate Nb into the TiO2 lattice, and 2) achieve equilibrium with the gas phase. Finally, the present project included investigations on the effect of Nb segregation on the surface composition of Nb-doped TiO2, with the following outcomes: Due to segregation, the surface can be significantly enriched in Nb compared to the bulk The extent of enrichment increases as the bulk Nb content or the oxygen activity is decreased Following enrichment, the surface Nb concentration could be sufficiently high to assume a unique surface phase The outcomes of the present project are significant as they can enable the processing of TiO2 with enhanced charge transport and controlled surface properties.

Thesis (Ph. D.)--West Virginia University, 2007. / Title from document title page. Document formatted into pages; contains xv, 145 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 138-145).

Thesis (Ph.D.)--McMaster University (Canada), 1989. / Source: Dissertation Abstracts International, Volume: 62-13, Section: A, page: 0000.

Thesis (Ph. D.)--Ohio University, 2001. / Title from PDF t.p.

Thesis (M.S.)--Ohio University, November, 2003. / Title from PDF t.p. Includes bibliographical references (leaves 58-62).