Probing Defects and Electronic Processes on Gadolinia-doped Ceria Surfaces Using Electron Stimulated Desorption Haiyan Chen 133 Pages Directed by Professor Thomas M. Orlando Polycrystalline gadolinia-doped ceria (GDC) has been widely investigated as a promising low temperature solid oxide fuel cell (SOFC) electrolyte and as part of composite electrodes. In this thesis, electron stimulated desorption (ESD) has been used to probe the defect related electronic properties of GDC surfaces and the interactions of water and molecular oxygen with these surfaces. In particular, the electron irradiation induced surface charging of GDC has been found to be dependent on the incident electron energy: negative at lower energy and positive at higher energy. Trapping of electrons and holes by the gadolinium aggregated, oxygen vacancy rich grain boundaries has been considered as the origin of surface charging. Depending on the sample treatment, there can be various defects, hydroxyl groups, chemically adsorbed water molecules, or water dimers on GDC surfaces. Water and molecular oxygen interact primarily with defect sites. Systematic investigations of electron stimulated O+ desorption have yielded activation energies relevant to oxygen vacancy production on ceria surfaces, and to surface positive charge dissipation related to ionic conduction of GDC. Highly efficient electron stimulated O+ desorption from GDC surfaces has been attributed to the lowered charge density on oxygen ions coordinated with oxygen vacancy clusters and thus may be used as a probe for surface defect types. Electron stimulated desorption of O2+ from GDC surfaces during molecular oxygen adsorption has shown the ability of ESD to detect chemically adsorbed O2. The velocity distributions of O2+ can be used to probe intermediate adsorption species such as O2, as well as the positive charge of the surface. Overall, this thesis has demonstrated that ESD can provide important information on the kinetics and dynamics of surface charging, charge transport, adsorption and reactions occurring at defective insulating metal oxides materials. The abilities to probe the defects and their roles in surface processes make ESD a valuable technique for surface chemistry and catalysis studies.

Because the surface plays an important role in the electrical and optical properties of GaN devices, an improved understanding of surface effects should help optimize device performance. In this work, atomic force microscopy (AFM) and related techniques have been used to characterize three unique sets of n-type GaN samples. The sample sets comprised freestanding bulk GaN with Ga polar and N polar surfaces, epitaxial GaN films with laterally patterned Ga- and N-polar regions on a common surface, and truncated, hexagonal GaN microstructures containing Ga-polar mesas and semipolar facets. Morphology studies revealed that bulk Ga-polar surfaces treated with a chemical-mechanical polish (CMP) were the flattest of the entire set, with rms values of only 0.4 nm. Conducting AFM (CAFM) indicated unexpected insulating behavior for N-polar GaN bulk samples, but showed expected forward and reverse-bias conduction for periodically patterned GaN samples. Using scanning Kelvin probe microscopy, these same patterned samples demonstrated surface potential differences between the two polarities of up to 0.5 eV, where N-polar showed the expected higher surface potential. An HCl cleaning procedure used to remove the surface oxide decreased this difference between the two regions by 0.2 eV. It is possible to locally inject surface charge and measure the resulting change in surface potential using CAFM in conjunction with SKPM. After injecting electrons using a 10 V applied voltage between sample and tip, the patterned polarity samples reveal that the N-polar regions become significantly more negatively charged as compared to Ga-polar regions, with up to a 2 eV difference between charged and uncharged N polar regions. This result suggests that the N-polar regions have a thicker surface oxide that effectively stores charge. Removal of this oxide layer using HCl results in significantly decreased surface charging behavior. A phenomenological model was then developed to fit the discharging behavior of N-polar GaN with good agreement to experimental data. Surface photovoltage (SPV) measurements obtained using SKPM further support the presence of a thicker surface oxide for N polar GaN based on steady state and restoration SPV behaviors. Scanning probe microscopy techniques have therefore been used to effectively discriminate between the surface morphological and electrical behaviors of Ga- vs. N-polar GaN.

In this work Scanning Kelvin Probe Microscopy (SKPM) was used to characterize surface states and device surface charging in nitride materials. Samples grown by Molecular Beam Epitaxy (MBE), Metal Organic Chemical Vapor Deposition (MOCVD) and Hydride Vapor Phase Epitaxy (HVPE) typically show a high surface band bending of about 1 eV. In an n-type sample with 3X1017 cm-3 carrier concentration, 1 eV upward band bending corresponds to 1.7X1012 cm-2 trapped charge density in the surface states. Under continuous ultraviolet (UV) illumination up to 0.6 eV surface photo voltage effect could be observed in some samples, which further indicates that surface band bending is very likely larger than 0.6 eV, i.e. close to 1 eV. Reactive Ion Etching (RIE)damage was observed to increase surface band bending by about 0.4 eV where as surface treatments in organic solvents and inorganic acids did not affect surface band bending significantly. These results indicate presence of high density of surface states in devices fabricated in nitride materials. Surface potential measurements immediately after turning off a reverse bias to the Schottky contact of a GaN Schottky diode as well as an AlGaN/GaN Hetero-junction Field Effect Transistor (HFET) show an increase of band bending near the Schottky contact edge. For an applied reverse bias of 4 V, about 0.5 eV increase of band bending was observed. This increase of band bending was caused by tunneling of electrons from the Schottky contact and their subsequent capture by surface states near the contact edge. In case of the HFET, the increase of band bending for a bias that caused no current flow through the device was similar to a bias that did. This showed that hot electron injection from the channel did not play a significant role in increasing surface band bending. The accumulated charge near the gate edge of a HFET can deplete the channel, which would cause the drain current to decrease. The total times of accumulation and dissipation of excess surface charge near the gate edge of the HFET were comparable to the time scales of drain current transients of current collapse and recovery. From this observation we attributed current collapse phenomena to charge accumulation near the edge of the reverse biased gate contact of a HFET.

This study focuses on fabrication of dry adhesives mimicking gecko adhesion. We also look into the origin of the supreme adhesion of geckos, which have inspired the fabrication of fibrillar dry adhesives during the last decade or so. In principle, the superior material properties of ??-keratin (the main material comprising the fibrillar feature on gecko toe pads) along with the hierarchical high aspect-ratio fibrillar structure of geckos??? foot pad have enabled geckos to stick readily and rapidly to almost any surface in both dry and wet conditions. In this research, non-sticky fluoropolymer (Teflon AF) resembling ??-keratin rigidity and having an extremely low surface energy and dielectric constant was applied to fabricate a novel dry adhesive consisting of extremely high aspect-ratio nanopillars (200 nm in diameter) terminated with a fluffy top nanolayer. Both the nanopillars and the terminating layer were fabricated concurrently by replica-molding using a nanoporous anodic aluminum oxide membrane as the mold. In particular, upon infiltration of Teflon AF melt into the anodic aluminum oxide nanopores, the polymer melt fingered over the pore walls. The fingerlike structure formed during infiltration, subsequently collapsed after removal of the mold, developing a unique sheet-like nanostructure on top of the base nanopillars. Concurrent fabrication of the terminating nanostructure helps the fabrication of extremely high aspect-ratio (27.5???225) nanopillars which, up to an aspect-ratio of 185, neither collapse at the tip nor bundle. In order to fabricate nanopillars of different topographical properties, in our first approach, the height of the nanopillars as well as the size and density of the terminating nanostructure are carefully controlled by adjusting the processing temperature. Following that, a novel replica-molding technique for fabrication of bi-level Teflon AF nanopillars is reported. The developed technique relies on the concurrent heating and cooling of the Teflon AF melt which filled vertically-aligned alumina nanochannels. Unlike conventional polymer infiltration methods which consist of filling the mold by only heating the polymer above its glass transition temperature, in our novel method, the polymer melt is also simultaneously cooled down during the infiltration process. Concurrent cooling of the Teflon AF melt allows control over the interfacial instabilities of the polymer thin film, which forms ahead of the polymer melt upon its infiltration into the alumina nanochannels. Doing so, the geometrical properties of the subsequently developed peculiar fluffy nanostructure ??? after removal of the mold ??? on top of the extremely high aspect-ratio Teflon AF nanopillars (~25 ??m tall) are modified. In this project, we have also shown that the adhesion of the fabricated dry adhesives for the most part arises from electrostatic interactions of the applied polymer. In other words, Teflon AF, having an exceptional potential for developing electric charges at its surface upon contact with other materials via the so-called contact electrification phenomenon, can develop significant electrostatic interactions at its surface upon contact. In the current thesis, tribological results were discussed in detail to clarify the contribution of the structural properties of the fabricated dry adhesives toward their remarkable adhesion and friction forces generated via contact electrification. Nanopillars of specific geometrical properties have achieved remarkable adhesion and friction strengths, up to ~2.1 N/cm2 and 17 N/cm2, respectively (up to ~2.1 and 1.7 times larger than those of a gecko toe pad). It is commonly accepted that the adhesive performance of other synthetic bio-inspired dry adhesives is due to the formation of van der Waals interactions at the tip or side of the dry adhesives fibrils with the substrate they are brought into contact with. However, what has been usually neglected in this connection is that electrostatic interactions may also be developed at the contact between any two materials via the familiar contact electrification phenomenon. Although contact electrification is common and can have a large influence on interfacial interaction forces, its impact on adhesive properties of synthetic dry adhesives has been overlooked. Our results on adhesion of bi-level Teflon AF nanopillars, which can generate strong adhesion forces relying on electrostatic interactions arising from contact electrification, have brought to light again the idea that charging the surface of dry adhesives, specifically polymeric ones, can play a very crucial role in their adhesive behavior. From this perspective, the main reasons that have caused this lack of attention to this concept and the possible contributions of contact electrification to interfacial interactions of polymeric dry adhesives, other than bi-level Teflon AF nanopillars, are also thoroughly discussed in this thesis. Besides synthetic fibrillar dry adhesives, the possibility of the occurrence of contact electrification and its contribution to the supreme dry adhesion of geckos have also been overlooked for several decades. In this research, by the simultaneous measurement of electric charges and adhesion forces that gecko toe pads develop on two distinct substrates (a sticky and a non-sticky one), we have shown that the toe pads generate significantly large amounts of electric charge on both substrates. More importantly, we have found that there is a direct correlation between the contact electrification-driven electrostatic forces and the measured adhesion forces. Otherwise stated, we have shown that what makes the difference that geckos stick strongly to one surface and not to the other are the electrostatic interactions arising from contact electrification, and not van der Waals interactions, which have been considered as the prime source of adhesion of geckos for many years.