No description available.

No description available.

Metal-semiconductor contacts are of fundamental importance to the operation of all semiconductor devices. There are many competing theories of Schottky barrier formation but as yet no quantitative predictive model exists to adequately explain metal-semiconductor interfaces. The II-VI compound semiconductors CdTe, CdS and ZnSe have recently come to the fore with the advent of high efficiency photovoltaic cells and short wavelength light emitters. Major problems still exist however in forming metal contacts to these materials with the desired properties. This work presents results which make a significant contribution to the theory of metal/II-VI interface behaviour in terms of Schottky barriers to n-type CdTe, CdS and ZnSe. Predominantly aqueous based wet chemical etchants were applied to the surfaces of CdTe, CdS and ZnSe which were subsequently characterised by X-ray photoelectron spectroscopy. The ionic nature of these II-VI compounds meant that they behaved as insoluble salts of strong bases and weak acids. Acid etchants induced a stoichiometric excess of semiconductor anion at the surface which appeared to be predominantly in the elemental or hydrogenated state. Alkaline etchants conversely induced a stoichiometric excess of semiconductor cation at the surface which appeared to be in an oxidised state. Metal contacts were vacuum-evaporated onto these etched surfaces and characterised by current-voltage and capacitance-voltage techniques. The surface preparation was found to have a clear influence upon the electrical properties of Schottky barriers formed to etched surfaces. Reducing the native surface oxide produced near ideal Schottky diodes. An extended study of Au, Ag and Sb contacts to [mathematical formula] substrates again revealed the formation of several discrete Schottky barriers largely independent of the metal used; for [mathematical formula]. Deep levels measured within this study and those reported in the literature led to the conclusion that Fermi level pinning by native defects is a dominant mechanism in Schottky barrier formation in these systems.

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The purpose of this thesis is to probe microscopic compositions and electronic structures at the high-£edielectric-semiconductor interfaces. The samples are prepared by electron beam evaporation, including Y2O3/Si, (Ga2O3-Gd2O3)/GaAs, Gd2O3/GaAs, Gd2O3/GaN and (Ga2O3-Gd2O3)/GaN. The thermal annealing effects on the interfacial properties have been investigated by depth-profiling X-ray photoelectron spectroscopy (XPS) with synchrotron radiation beam. The depth-profiling XPS data show the O-H bonding in all the measured oxide layers. For Y2O3/Si, the hydroxide can be removed by surface desorption at 300¢J, while a Y-Si-O-H state maintained at the interface. The data suggests that the Y-Si-O-H state is possibly formed in the deposition process. For (Ga2O3-Gd2O3)/GaAs, the hydroxide can be removed by surface desorption at 100¢J, and GaOx and GaOy intermediary states have been observed. For Gd2O3/GaAs, the hydroxide can be removed by surface desorption at 250¢J, and a GaOx intermediary state has been observed, and no arsenic oxides have been detected. For Gd2O3/GaN and (Ga2O3-Gd2O3)/GaN, a GaOx intermediary state and little N-O bonding have been observed. Comparing the XPS relative intensity of the N 1s states, (Ga2O3-Gd2O3)/GaN shows a more stable interface than Gd2O3/GaN.

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No description available.

No description available.

The growth of atomically flat silver films on Si(111) usually requires a two-step growth, including deposition at low temperature (≈100 K) followed by slowly annealing to room temperature. In addition, flat silver films are usually only obtained on Si(111) for film thicknesses larger than the critical thickness of 6 monolayer. In this work, Ag thin film formation at ambient temperature on Sn/Si(111)-√3×√3 has been investigated experimentally using a combination of scanning tunneling microscopy, scanning tunneling spectroscopy and low-energy electron diffraction. The first buffer layer, probably consisting of both Ag and Sn, formed a partially ordered structure consisting of atomic rows which mainly followed the high-symmetry directions of the underlying Si(111) lattice. From 3 ML coverage, an atomically flat Ag film was formed. Low-energy electron diffraction confirmed that the films grew in the [111]-direction. This shows that atomically flat Ag films as thin as 3 ML can be grown on Sn/Si(111)-√3×√3 by conventional deposition at room temperature. The electronic structures of the films were studied for a range of different coverages by scanning tunneling spectroscopy. The normalized tunneling conductance showed quantum well states in the occupied electronic states, which moved towards the Fermi energy with increasing film thicknesses.

Catalysis using nanostructures has been a topic of substantial interest for fundamental studies and for practical applications in energy and environmental sectors. The growing demand for production of energy and in the cleaning of polluting hazardous vehicles/industrial wastes has led to several studies in catalysis. Despite the substantial growth of heterogeneous catalytic technologies in last decade, they are still far from reaching their full potential in terms of efficiency, selectivity as well as durability. It is often difficult to simultaneously tackle all the mentioned issues with single component catalysts. Most of these challenges are being overcome with heterostructures/supported hybrid catalysts by modifying their interfaces. The properties of heterostructures hybrids arises not only from the individual contributions of the individual components but also from strong synergetic effect arising from the interface. Engineering the interfaces provides pathways to promote the catalytic performance and hence has been explored. In this regard, we have focused on the progress in investigating the active interfaces that affect the performance of metal oxide-metal, semiconductor-metal and coupled semiconductor nanocatalyst hybrids. We explored a wide spectrum of their applications in photo catalytic, electrocatalytic as well as gas-phase reactions and highlighted the importance of the interface for overall performance. The entire study reported in the thesis is organized as follows: Chapter 1 is a general introduction of hybrid nanocatalyst and their role in wide spectra of catalytic reactions in photo/electro catalysis as well as gas-phase reactions. This chapter describes the motivation behind modulating the interface between two or more nanostructures to obtain multifunctional nanocatalysts. Nan catalysts to achieve high throughput with active interfaces are elaborated while indicating the role of morphology, internal induced state, charge transfer, geometric, support, as well as electronic effect for enhanced performance. Motivation behind specific nanocatalyst hybrid, synthesis routes as well as characterization techniques are detailed in the respective chapters. Specific details for different hybrids are described in the following chapters. Chapter 2 describes the synthesis of high dense ultrathin Au wires on ZnO nanorods for electrocatalytic oxidation of ethanol, where the prerequisite step is the formation of amine-modified support. Oleylamine modification not only serves to anchor Au nanowires on ZnO but also passivates surface defects of ZnO, which in turn enhances the photocurrent. In addition to the stability, the support induces electronic effect on Au nanowires, which facilitates redox process at low potential. Most importantly, the support promotes the activity of Au nanowires upon photoirradiation, and thus leading to synergy between electro and photooxidation current. This is of immense importance for photofuel cell technologies. Moreover, the method enabled the first time electrocatalysis on these nanowires that revealed ultrathin nanowires are potentially interesting systems for catalysis applications provided they are stabilized by a suitable support. Chapter 3 deals with the growth of ultrathin Au nanowires on metal oxide (TiO2) coupled with graphene hybrid support in order to overcome the low conductivity of metal oxide. Oleylamine, used for growth of Au nanowires simultaneously functionalizes the support and leads to room temperature GO reduction. With respect to catalytic activity, we also synthesized the binary counterparts (rGO/Au, TiO2/Au ultrathin nanowires) to delineate the contribution of each of the components to the overall electrocatalytic oxidation of ethanol. Comparative analysis of photo and electrocatalytic activity between the different binary and ternary hybrids provides interesting information. Both, electronic effect of TiO2 and electrical conductivity of rGO add their specific beneficial to the nanowires, leading to superior ternary system. Chapter 4 rGO supported ultrathin Au nanowires exhibits high electrocatalytic performance for oxidation of borohydride with a lower onset potential compared to rGO/Au nanoparticles. Electrochemical impedance spectroscopy measurements display abnormal inductive behavior of the synthesized hybrids, indicative of Au surface reactivation. DFT calculations indicate that the origin of the high activity stems from the shift in the position of the Au d-band center. Chapter 5 Different aspect ratio ZnO nanostructures are obtained by varying the solvothermal reaction time. We observed a direct correlation between observed photocatalytic activity, measured photocurrent and length of the ZnO nanorods. Furthermore, photoresponse of the high aspect ratio ZnO nanorods are improved by attaching Au nanoparticles, intimate contact of two components leads to band bending. Thus, the synthesized ZnO/Au heterostructure favors for prominent separation of photogenerated charge carriers. Chapter 6 TiO2 and PbO/TiO2 hybrids are synthesized via non–hydrolytic sol–gel combustion method. Hybrid exhibits higher photocatalytic activity for the degradation of dye than TiO2. The estimated photogenerated species reveals that the origin of enhanced activity stems from the direct oxidization of dye via photogenerated hole rather than radicals. The semiconductors are matched based on their band edge positions, for the formation of energetic radicals to degrade the pollutants. Based on this study, we infer that semiconductors should not neglected (for example Si) based on calculated mismatch of their valence band edges position for photooxidation reaction via radicals. Chapter 7 describes the Pd dopant associated band engineering, a strategy for tuning the optoelectronic properties of ZnO towards enhanced photocatalytic activity. Incorporated Pd heterocation induces internal energy states within the ZnO band gap. The created energy level leads to trends mismatch between photocatalytic activity and measured photocurrent. Formed energy level arrests the photogenerated electrons, which make them not contribute for the photocurrent generation. Hence, the isolated photogenerated hole efficiently oxidizes the pollutants through hydroxyl radicals, and thus leads to enhanced photocatalytic activity. Chapter 8 employed Pd-substituted zinc stannate for CO oxidation as heterogeneous catalyst for the first time. Compared with SnO2 support, zinc stannate based materials exhibits abnormal sudden light-off profiles at selective temperatures. On the basis of DRIFT studies under relevant conditions, we find that the initially formed product gets adsorbed over the catalyst surface. It leads to the accumulation of carbonates as a consequence, both lattice oxygen mobility and further CO interactions are disabled. As soon as Sn redox nature dominates over the accumulated carbonates, this leads to sudden release of lattice oxygen, and thus leads to a sudden full conversion. Therefore, choosing the suitable support material greatly influences the nature of the light-off CO oxidation profile. Chapter 9 Although, reducible oxide supported gold nanostructures exhibits the highest CO oxidation activity; they still suffer from problems such as limited selectivity towards CO in the presence of H2. Both ex-situ and in-situ experiments demonstrate that, Au nanoparticles supported on Zn2SnO4 matrix selectively oxidizes CO. DRIFT experiments revealed that the involvement of OH groups leads to the formation of hydroxycarbonyl under PROX conditions. Chapter 10 This chapter discusses the conclusions for the previous chapters and highlights the possibilities for future scope for the developed nanocatalysts hybrids for energy and environmental applications.