The surface chemistry of GeH[subscript x] with dielectric surfaces is relevant to the application of germanium (Ge) nanocrystals for nanocrystal flash memory devices. GeH[subscript x] surface chemistry was first explored for thermally-grown SiO₂ revealing that GeH[subscript x] undergoes two temperature dependent reactions that remove Ge from the SiO₂ surface as GeH₄ and Ge, respectively. Ge only accumulates due to reactions between GeH[subscript x] species that form stable Ge clusters on the SiO₂ surface. Next, a Si-etched SiO₂ surface is probed by GeH[subscript x] revealing that the Si-etching defect activates the surface toward Ge deposition. The activation involves two separate reactions involving, first, the capture of GeH[subscript x] by the defect and second, a reaction between the captured Ge and remaining GeH[subscript x] species leading to the formation of Ge clusters. Reacting the defect with diborane, deactivates it toward GeH[subscript x] and also deactivates intrinsic hydroxyl groups toward GeH[subscript x] adsorption. A structure is proposed for the Si-etching defect. The surface chemistry of GeHx with HfO₂ is studied showing that the hafnium germinate that forms beneath the Ge nanocrystals exists as islands and not a continuous film. Annealing the hafnium germinate under a silane atmosphere will reduce it to Ge while leading to the deposition of hafnium silicate (HfSiO[subscript x]) and silicon (Si). Treating the HfO₂ with silane prior to Ge nanocrystal growth yields a surface with hafnium silicate islands on which Si also deposits. Ge deposition on this surface leads to the suppression of hafnium germinate formation. Electrical testing of capacitors made from Ge nanocrystals and HfO₂ shows that Ge nanocrystals encapsulated in Si/HfSiO[subscript x] layers have greatly improved retention characteristics. / text

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This thesis focuses on understanding the influence of defect sites in titanium dioxide that drive many types of thermal and photochemical reactions. Two of the most common defects in vacuum are titanium interstitials and oxygen vacancies. Molecular oxygen fills oxygen vacancies and creates oxygen adatoms. We broadly investigate reduction and oxidation reactions of oxygenates driven by titanium interstitials and oxygen adatoms. First, we focus on the thermal chemistry of oxygen adatoms with butyrophenone and find that it reacts with the adatoms to form a strongly bound complex. The large difference in mobility between complexed and uncomplexed butyrophenone, and the corrugated nature of the \(TiO_2(110)\) surface plane, allows a confined one-dimensional gas to persist, which is characterized by scanning tunneling microscopy (STM). Next, we focus on the reductive coupling of benzaldehyde to stilbene that is driven by titanium interstitials. The diolate intermediate of the reaction is identified by STM and the thermodynamic preference of molecular oxygen to interact with titanium interstitials is exploited to selectively reverse the benzaldehyde diolate intermediates. Additionally, we investigate the photo-oxidative coupling of methanol to methyl formate, the photo-oxidation of butyrophenone and the photo-stability of benzoate. Finally, we identify a water splitting mechanism on reduced titania that creates oxygen adatoms. We demonstrate that the photo-generated oxygen adatoms thermally react with titanium interstitials to make TiOx islands and drive the photo-oxidation of formaldehyde and butyrophenone. Methods used include temperature programmed reaction spectroscopy, STM, and density functional theory. / Chemistry and Chemical Biology

Two different interfaces were the focus of study: 1) the interface between disordered amorphous carbon and inorganic materials (metal nanostructures and silicon), and 2) the interface between partially ordered graphene (graphene oxide) and synthetic polymer matrix. Specifically, the uniqueness of this study can be summarized through the following novel findings, fabrication processes, and characterization techniques: • A simple and efficient process for faster, greener, less-expensive, and highly localized transformation of amorphous carbon nanostructures into graphitic nanostructures using low temperature heat and light treatments was developed for the fabrication of low-resistance interfaces between carbon nanomaterials and inorganic metal surfaces. • A new protocol for high resolution mapping the charge distribution and electronic properties of nanoscale chemically heterogeneous domains on non-homogeneous surfaces such as graphene oxide was established. • High strength laminated mechanical nanocomposites based on high interfacial stress transfer between polymer matrices and large area, flat, and non-wrinkled graphene oxide sheets were suggested and demonstrated. • Scanning Thermal Twist Microscopy – a thermal microscopy based technique was developed and demonstrated for characterizing the thermal properties of homogeneous and heterogeneous interfaces with nanoscale spatial resolution and high thermal sensitivity unachievable using traditional techniques.

No description available.

Interactions of colloidal particles with surfaces occur in natural and engineered systems, and they influence the transport of contaminants through diffusion, aggregation, filtration, and sedimentation. To quantify the transport and fate of colloidal particles and their influence on environmental systems, it is important to understand their interactions with surfaces. These interactions are influenced by physical and chemical surface properties such as hydrophobicity, charge density, and roughness, as well as environmental conditions such as relative humidity (RH). In atmospheric systems, RH induces the capillary force and also influences the contributions of van der Waals and electrostatic forces. To investigate the role of surface properties and RH in the interaction of colloidal particles with surfaces, atomic force microscopy was employed to measure the adhesion and friction forces of colloidal particles including Bacillus thuringiensis spores, silica, and gold at various experimental conditions with several types of surfaces including mica, silica, and radioactive gold. Contributions to the adhesion force by van der Waals, capillary, and electrostatic forces were theoretically calculated and compared to measured forces. Through experimental results and theoretical studies, it was identified how surface properties of interacting surfaces and experimental conditions influence the interfacial interactions of colloidal particles in atmospheric systems. The role of RH in adhesion and friction depends on the hydrophobicity or contact angles of interacting surfaces and surface roughness. Relative humidity also influences the contribution of electrostatic force to the total adhesion force by screening the strength of surface potential or providing a passage for charge leakage. The results of this thesis provide a better understanding of particulate processes that are influenced by the interactions of colloidal particles with surfaces and can be useful in monitoring and control of contamination in atmospheric systems.

This work describes the functionalization and testing of Si$_3$N$_4$-based photonic crystal slabs (PCS) for label-free biosensing. PCS support optical resonance modes that are sensitive to the local refractive index. Knowing that surface binding events change the local RI, analyte binding to the activated sensor can be detected. Various functionalization recipes were tried, and one was preferred for the biosensing experiments due to its higher yield and uniformity. Additionally, thickness of the topmost sensor layer was studied to assess biosensor performance quantified through sensitivity metrics. On the systems level, a reusable clamping system and customized microfluidic channels were designed, fabricated, and implemented on the PCS biosensors to enable device refurbishment. Proof-of-principle biodetection experiments were carried out using the established functionalization protocol on the in-house fabricated PCS. Conjugation of streptavidin and bovine serum albumin to the sensor surface was observed through wavelength shifts of the resonant modes.

This work describes the functionalization and testing of Si$_3$N$_4$-based photonic crystal slabs (PCS) for label-free biosensing. PCS support optical resonance modes that are sensitive to the local refractive index. Knowing that surface binding events change the local RI, analyte binding to the activated sensor can be detected. Various functionalization recipes were tried, and one was preferred for the biosensing experiments due to its higher yield and uniformity. Additionally, thickness of the topmost sensor layer was studied to assess biosensor performance quantified through sensitivity metrics. On the systems level, a reusable clamping system and customized microfluidic channels were designed, fabricated, and implemented on the PCS biosensors to enable device refurbishment. Proof-of-principle biodetection experiments were carried out using the established functionalization protocol on the in-house fabricated PCS. Conjugation of streptavidin and bovine serum albumin to the sensor surface was observed through wavelength shifts of the resonant modes.

iv The recovery of lactic acid from its dilute aqueous solutions is a major problem. The ester of lactic acid, namely, methyl lactate has a wide range of applications. The esterification of an aqueous solution of lactic acid with methanol is a reversible reaction. As excess of amount water is present in the reaction mixture, the conversion is greatly restricted by the chemical reaction equilibrium limitations. In this study the esterification kinetics of lactic acid with methanol both in the absence and presence of an ion exchange resin as a heterogeneous acid catalyst was investigated with isothermal batch experiments between 40 - 70 0 C and at atmospheric pressure. Self-polymerization of lactic acid was enlightened by considering the hydrolysis reaction of lactoyllactic acid at the reaction temperatures and at various initial concentrations. Both homogeneous and heterogeneous reaction rate constants were evaluated. Methyl lactate process development was also investigated. The process was based on the recovery of 10% lactic acid by reaction with methanol in a absorption column using ion-exchange resin Lewatit SPC-112 H+. The effect of various parameters including lactic acid concentration or reactant molar ratio, lactic acid feed flow rate, methanol and inert carrier rate on reactor performance were studied. The reaction of methyl lactate formation over the ion exchange resin catalyst was observed to be slower than the mass transfer rate whereas mass transfer of methanol in gas phase was the limiting step for methanol transfer to the liquid mixture. Mass transfer of water from liquid phase to the gas phase was controlled by the mass transfer resistance of liquid phase. Thus, it can be concluded that the counter-current gas-liquid reactors with acidic solid catalysts can be used as simultaneous reaction and separation equipment.

Solid-liquid contact angle is an important parameter in many particulate processes of the mineral, ceramic and chemical industries. In particular, modification of the contact angle through surface active agents plays a crucial role in froth flotation of minerals. In the case of flat solid surfaces, direct measurement of the contact angle is possible. However, such flat surfaces can not be obtained with finely divided solids typically encountered in flotation applications. Then, indirect methods based on powder beds as thin layers of powders deposited on glass plates or packed columns are used for the determination of apparent contact angles. This thesis presents an alternative novel method based on the capillaric dewatering of filter cakes for the measurement of the receding contact angle and correlates the contact angles measured as such with column wicking and micro-flotation test results of zircon and rutile mineral particles. The experimental procedure is simple and fast. The results have proven that the proposed method is reliable and give a good measure of the contact angle in the absence and presence of surface active non-wetting agents.