Thesis (Ph. D.)--Chemistry and Biochemistry, Georgia Institute of Technology, 2010. / Committee Chair: Orlando, Thomas; Committee Member: El-Sayed, Mostafa; Committee Member: First, Phillip; Committee Member: Lackey, Jack; Committee Member: Tolbert, Laren. Part of the SMARTech Electronic Thesis and Dissertation Collection.

Thesis (Ph. D.)--University of Washington, 2002. / Vita. Includes bibliographical references (leaves 78-83).

CdTe is one of the most promising absorbers for use in inexpensive semiconductor solar cells having achieved a high efficiency of 16.4% in small area cells [1]. One of the most important technological problems in obtaining high efficiencies is to have a good ohmic contact on the CdTe, which is characterized by a very high work function [2]. Cu is used as a dopant in CdTe at the contact to promote quantum mechanical tunneling [3]. But the oversupply of Cu causes the diffusion of Cu through CdTe to the underlying CdS layer resulting in the degradation of the cell performance. It has been reported that Cu was segregated near the CdS/CdTe junction. To avoid the Cu segregation at the junction, Cu supply should be minimized while the ohmic characteristics of p-CdTe contact are maintained [4]. In this thesis, the main objective is to understand the role of Cu at the CdS/CdTe interface. Here the Cu is added at the CdS/CdTe interface and is avoided at the back contact.

This research project investigated physical aging and carbon dioxide plasticization behavior of glassy polymer films. Recent studies have shown that thin glassy polymer films undergo physical aging more rapidly than thick films. This suggests that thickness may also play a role in the plasticization and conditioning responses of thin glassy films in the presence of highly-sorbing penetrants such as CO₂. The effect of film thickness on CO₂ permeation and sorption was studied extensively through carefully defined and controlled methods that provide a basis for future study of plasticization behavior. Thin films are found to be more sensitive than thick films to CO₂ exposure, undergoing more extensive and rapid plasticization at any pressure. The response of glassy polymers films to CO₂ is not only dependent on thickness, but also on aging time, CO₂ pressure, exposure time, and prior history. Thin films experiencing constant CO₂ exposure for longer periods of time exhibit an initial large increase in CO₂ permeability, which eventually reaches a maximum, followed by a significant decrease in permeability for the duration of the experiment. Thick films, in contrast, do not seem to exhibit this trend for the range of conditions explored. For a series of different polymers, the extent of plasticization response tracks with CO₂ solubility. There is little data available for gas sorption in thin glassy polymer films. In this work, a novel method involving spectroscopic ellipsometry is used to obtain simultaneously the film thickness and CO₂ sorption capacity for thin glassy polymer films. This allows a more comprehensive look at CO₂ permeability, sorption, and diffusivity as a function of both CO₂ pressure and exposure time. Like the gas permeation data, these experiments suggest that thin film sorption behavior is substantially different than that of thick film counterparts. Dynamic ellipsometry experiments show that refractive index minima, fractional free volume maxima, and CO₂ diffusivity maxima correlate well with observed CO₂ permeability maxima observed for thin Matrimid® films. These experiments demonstrate that plasticization and physical aging are competing processes. Aging, however, dominates over long time scales. Over time, CO₂ diffusivity is most affected by these competing effects, and the evolution of CO₂ diffusivity is shown to be the main contributing factor to changes in CO₂ permeability at constant pressure. / text

Motivated by the need for a Ge surface passivation layer, chemical vapor deposition of thin (< 10 nm) films of amorphous boron carbo-nitride (BCxNy) on Ge(100) surfaces were studied to assess film continuity, interface bonding, Ge oxidation prevention, and electrical passivation. BCxNy nominally 2.5-5 nm thick continuously covers Ge(100), as determined by ion scattering spectroscopy and two angle resolved x-ray photoelectron spectroscopy (ARXPS) techniques. ARXPS analysis reveals no evidence of an interfacial layer due to elemental intermixing at the BCxNy-Ge(100) interface. High resolution transmission electron microscopy images of HfO₂ / BCxNy / Ge(100) cross-sections reveal abrupt BCxNy-Ge(100) interfaces. XPS was used to track Ge oxidation of BCxNy-covered Ge(100) upon exposure to ambient, 50 °C deionized water, and a 250 °C atomic layer deposition HfO₂ process. If the BCxNy layer is continuous ([greater-than or equal to] ~ 4 nm), the underlying Ge(100) surface is not oxidized despite incorporation of O into BCxNy. Thinner films ([less than or equal to] 3.2 nm) permitted Ge(100) oxidation in each oxidizing environment studied. Ge nanowires with a 5.7 nm BCxNy coating were resistant to oxidation for at least 5 months of ambient exposure. C-V and I-V measurements were made for metal-insulator-semiconductor (MIS) structures fabricated from n-Si(100) and n-Ge(100) wafers passivated with 4.5-5 nm BCxNy. C-rich BC0.61N0.08 films studied up to this point exhibited large amounts of hysteresis and fixed negative charge, so they were abandoned in favor of N-rich BCxNy (0.09 [less than or equal to] x [less than or equal to] 0.15, 0.38 [less than or equal to] y [less than or equal to] 0.52). N-rich BCxNy grown at 275-400 °C showed that lower deposition temperatures resulted in improved electrical characteristics, including decreased hysteresis, lower VFB shift, lower leakage current, and less C-V stretch-out. The electrical improvement is attributed to decreased bulk and interfacial defects in BCxNy deposited at lower temperatures. Even for the lowest growth temperature studied (275 °C), BCxNy-passivated Ge(100) devices had considerable hysteresis and electrical characteristics worsened after a post-metallization anneal. BCxNy-passivated Si(100) devices outperformed similar Ge(100) devices, likely due to the higher interface state densities at the BCxNy-Ge(100) interface associated with the higher relative inertness of Ge(100) to thermal nitridation. / text

Lead zirconate titantate (PZT) is an electroceramic material with many important technological applications in sensing and computer memory. Some of these applications require the PZT based devices to operate in radiation fields where they will be exposed to a high flux of energetic, heavy and light, charged and uncharged particles. The risk to any device exposed to ionizing radiation is the accumulation of displacement and ionization damage. Significant damage accumulation over time can lead to property drifts and, in some cases, failure of the device to perform properly. The goal of the undertaking recounted in this dissertation was to study changes in the ferroelectric properties of PZT exposed to the neutron field of a research nuclear reactor and to help develop an understanding for the type of radiation induced defects that play a dominant role in the degradation process. Thin film PZT capacitors were prepared using a wet chemical technique. The capacitors were then irradiated in a 1 MW TRIGA research nuclear reactor at the University of Texas at Austin up to a maximum 1 MeV equivalent neutron flux of 5.2 x 10¹⁵ cm⁻². Following irradiation, electronic characterization of polarization-electric field hysteresis loops, first order reversal curves, and small-signal permittivity were performed to ascertain tendencies between irradiation dose and ferroelectric properties. The measurements indicate a drop in remanent polarization, a loss of domain wall mobility, shifts in local switching fields and the formation of dipolar defects. These effects are all attributed to the introduction of defects into the material through displacement damage cascades. Numerical models of the damage cascades were performed to determine the displacement concentration. Comparison of those values and the primary recoil spectrum with typical survival rates found in the literature suggest that both free point defects as well as defect clusters are produced in comparable if not larger concentrations. It is proposed that defect clusters play a more significant role in ferroelectric property change than previously believed. / text

This dissertation presents the development of methods based on microfabricated devices for combined structure and thermoelectric characterizations of individual nanowire and thin film materials. These nanostructured materials are being investigated for improving the thermoelectric figure of merit defined as ZT=S²[sigma]T/K, where S is the Seebeck coefficient, [sigma] is the electrical conductivity, K is the thermal conductivity, and T is the absolute temperature. The objective of the work presented in this dissertation is to address the challenges in the measurements of all the three intrinsic thermoelectric properties on the same individual nanowire sample or along the in plane direction of a thin film, and in correlating the measured properties with the crystal structure of the same nanowire or thin film sample. This objective is accomplished by the development of a four-probe thermoelectric measurement procedure based on a micro-device to measure the intrinsic K, [sigma], and S of the same nanowire or thin film and eliminate the contact thermal and electrical resistances from the measured properties. Additionally the device has an etched through hole that facilitates the structural characterization of the sample using transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS). This measurement method is employed to characterize individual electrodeposited Bi[subscript 1-x]Te[subscript x] nanowires. A method based on annealing the nanowire sample in a forming gas is demonstrated for making electrical contact between the nanowire and the underlying electrodes. The measurement results show that the thermoelectric propertied of the nanowires are sensitive to the crystal quality and impurity doping concentration. The highest ZT found in three nanowires is about 0.3, which is still lower than that of bulk single crystals at the optimum carrier concentration. The lower ZT found in the nanowires is attributed to the high impurity or carrier concentration and defects in the nanowires. The micro-device is further modified to extend its use to characterization of the in-plane thermoelectric properties of thin films. Existing practice for thermoelectric characterization of thin films is obtaining K in the cross plane direction using techniques such as the 3[omega] method or time domain laser thermal reflectance technique whereas the [sigma] and S are usually obtained in the in-plane direction. However, transport properties of nanostructured thin films can be highly anisotropic, making this combination of measurements along different directions unsuitable for obtaining the actual ZT value. Here, the micro-device is used to measure all three thermoelectric properties in the in-plane direction, thus obtaining the in-plane ZT. A procedure based on a nano-manipulator is developed to assemble etched thin film segments on the micro-device. Measurement results of two different types of thin films are presented in this dissertation. The first type is mis-oriented, layered thin films grown by the Modulated Elemental Reactant Technique (MERT). Three different structures of such thin films are characterized, namely WSe₂, W[subscript x](WSe₂)[subscript y] and (PbSe₀.₉₉)[subscript x](WSe₂)[subscript x] superlattice films. All three structures exhibit in-plane K values much higher than their cross-plane K values, with an increased anisotropy compared to bulk single crystals for the case of the WSe₂ film. The increased anisotropy is attributed to the in-plane ordered, cross-plane disordered nature of the mis-oriented, layered structure. While the WSe₂ film is semi-insulating and the W[subscript x](WSe₂)[subscript y] films are metallic, the (PbSe₀.₉₉)[subscript x](WSe₂)[subscript x] films are semiconducting with its power factor (S²[sigma]) greatly improved upon annealing in a Se vapor environment. The second type of thin films is semiconducting InGaAlAs films with and without embedded metallic ErAs nanoparticles. These nanoparticles are used to filter out low energy electrons with the introduction of Schottky barriers so as to increase the power factor and scatter long to mid range phonons and thus suppress K. The in-plane measurements show that both the S and [sigma] increase with increasing temperature because of the electron filtering effect. The films with the nanoparticles exhibited an increase in [sigma] by three orders of magnitude and a decrease in S by only fifty percent compared to the films without, suggesting that the nanoparticles act as dopants within the film. On the other hand, the measured in-plane K shows little difference between the films with and without nanoparticles. This finding is different from those based on published cross-plane thermal conductivity results. / text

Polymer thin films are ubiquitous in a variety of everyday applications from cookware to packaging. Light can be used to both probe and manipulate the mobility of polymers in thin films. The first project involves the self-diffusion of poly(isobutyl methacrylate) (PiBMA) in thin films using fluorescence recovery after patterned photobleaching (FRAPP). PiBMA is an ideal polymer for this study because it exhibits a film thickness-independent glass transition temperature (Tg) on silicon oxide substrates in film thicknesses down to 14 nm. Since the diffusion coefficient of a polymer depends on the proximity of the experimental temperature to its Tg, nanoconfined diffusion can be measured without superimposed influence from Tg nanoconfinement effects. In this study, self-diffusion of PiBMA parallel to the confining interfaces was found to be film thickness independent to ~30 nm. The reason for the film thickness independence of the Tg of PiBMA is the balance between enhanced mobility at the free interface and hydrogen bonding with the substrate. However, when hydroxyls on the substrate are masked, the Tg of PiBMA decreases with decreasing film thickness. In this case, the diffusion coefficient increases with decreasing film thickness in a way consistent with additional distance from Tg. The second project involves a new approach for creating topographic patterns in thin films via the Marangoni effect, which describes how small variations in surface energy can promote dramatic movement of fluids. Topographic patterns created using this method are potentially useful in a variety of applications, such as the creation of soft lithography stamps. Using a photomask, surface energy gradients can be patterned into solid polymer films. Upon heating the polymer film to a liquid state the Marangoni effect causes the polymer to flow creating three-dimensional topography. This technique was first demonstrated in polystyrene, which undergoes a partial dehydrogenation of the polymer backbone upon photoexposure. However, as exposed and unexposed regions inter-diffuse the topographic features decay. A solution to this problem is to use two orthogonally acting photosensitizers in the polymer film, one for topography creation, and the other for cross-linking which stabilizes the topography at high temperature. / text

This text describes the synthesis of surface-oriented multilayers based on novel monomeric species. The impetus of this study is to incorporate atypical species and techniques in order to prepare well-ordered assemblies on gold surfaces. These thin films were characterized by one or more of following techniques: grazing angle FT-IR; optical ellipsometry and x-ray photoelectron spectroscopy. First, chemical vapor deposition polymerization was used to prepare surface-oriented monolayers on amine functionalized gold from 4-aminobenzaldehyde and 5-phenyl-1, 3-dioxolane-2, 4-dione. The 4-aminobenzaldehyde showed regular increases in the intensity of characteristic IR absorptions with number of deposition cycles while the dioxolane showed no regularity in this respect. We infer from our data that this technique is a practical way to synthesize highly conjugated polymers. Secondly, we investigated the preparation of surface oriented materials based on host-guest assemblies. Cyclodextrin functionalized gold surfaces could serve as orientational templates for multilayered well-ordered host-guest materials. However, in our study, thiol modified cyclodextrin showed no ability to organize surface multilayers via surface crystallization in the presence of the appropriate host; nor did it show an ability to pre-organize in solution via polyethylene glycol rotaxane formation followed by surface attachment. Finally, surface-oriented organometallic monolayers and multilayers were prepared from alkyne functionalized gold surfaces. Using bis-orthodimethylaminomethyl (NCN) ligands we synthesized two unique surface-oriented organometallic assemblies. Palladium NCN hydrosulfides formed monolayers on gold. Characterization by FT-IR, XPS and ellipsometry show that these species similar to their thiol counterparts. In addition, organometallic polymers were grown from alkyne functionalized surfaces. The thickness of these films, which reached 40 Å by ellipsometry was dependent upon the nature of the alkyne initiator. / text

Not available / text