<p>Dye-sensitized Solar Cells (DSSCs) with liquid electrolyte lack long term stability because of volatility of the electrolyte and assembly problems. Replacement of the volatile liquid-state electrolyte with solid-state hole conductor thus becomes necessary. A small molecule based hole conductor, Copper Phthalocyanine (CuPc), is proposed here to replace the liquid electrolyte, for its intrinsic thermal and chemical stabilities. However, a lower short circuit current was found in the CuPc solid state device from I-V curve, which is closely related to the inefficient hole transport in the CuPc thin film. Therefore, Two-Dimensional Grazing Incidence X-ray Diffraction (2D GIXRD) is utilized to study the phase and texture of CuPc thin film. It is found that the CuPc thin film has a cystallinity of greater than 80%, which is good for hole conducting. However, the <em>β</em>-phase formation lowers the overall hole conductivity. The hole conductivity of <em>β</em>-phase CuPc is two orders of magnitude smaller than that of <em>α</em>-phase CuPc, due to a less overlap in the <em>π-π</em> stacking. As a result, the low hole conductivity of <em>β</em>-phase CuPc is the reason that leads to an inefficient hole transport and reduces the short-circuit current of the solid-state DSSC. Therefore, future work will be necessary to isolate <em>α</em>-phase CuPc, in order to be successfully applied into the solid-state DSSCs.</p> / Master of Science (MSc)

<p>Effects of a nanometer-size, reactive polyhedral oligomeric silsesquioxane (POSS) on a thermoset’s polymerization kinetics and dielectric relaxation have been investigated by using differential scanning calorimetry (DSC) and dielectric spectroscopy. Four amines, hexylamine (HA), ethylene diamine (EDA), isophorone diamine (IPDA), and diethylene triamine (DETA) were used to crosslink epoxy resin DGEBA and a multi functionalized -glycidyl POSS. The polymers formed ranged from POSS-free to POSS-only network structure, while maintaining an equal ratio of reactive groups.</p> <p>Calorimetric studies of stoichiometric DETA and IPDA samples performed by ramp-heating showed that the polymerization kinetics increased with low POSS content, but progressively decreased upon further addition, and the POSS-only mixtures reacted the slowest. The same pattern of changes in the rate of polymerization was observed by isothermal polymerization of the DETA mixtures. The results have been interpreted based on changes in viscosity and diffusion coefficients according to the Stokes-Einstein and Smoluchowski equations. Furthermore, isothermal polymerization of stoichiometric DETA and EDA samples showed that the extent of reaction increased with POSS, indicating that it might be easier to form a higher crosslinked thermoset with higher amounts of POSS.</p> <p>Non-isothermal polymerization of POSS-IPDA mixtures was also investigated under off-stoichiometric conditions. Unlike the reaction mechanisms of non-stoichiometric DGEBA-IPDA mixtures, a significant difference in reactivity of primary and secondary amines in the POSS-IPDA reaction was not observed.</p> <p>Dielectric relaxation studies were performed in real time during polymerization. The distribution of relaxation rates increased with an increase in POSS, and the duration of polymerization required to reach a specific relaxation time increased. Furthermore, the time at which the dielectric loss minimum and peak occurred increased with POSS, however, when only POSS was reacted with the amine, an <em>a</em>-relaxation peak was not observed. A frequency-dependent increase in permittivity during polymerization was observed with the POSS-only EDA, DETA, and HA samples, and a corresponding change in the loss was not detected. It was attributed to a structure-dependent increase in interfacial polarization.</p> <p>Although not related to the polymerization study, work done on the residual entropy of glasses is included here. To help resolve the controversy of the residual entropy of glassy materials, specific heat data taken from the literature were analyzed. The changes in entropy of a glass on cooling and heating paths were determined, and it was found that the upper and lower limits of entropy differed by no more than 2 %. This showed that although the thermodynamic path through the glass transition is irreversible, this irreversibility has a negligibly small effect on determining the entropy.</p> / Master of Applied Science (MASc)

<p>The development of all-electric or plug-in hybrid vehicles requires the use of advanced energy storage devices with high power. Dedicated for energy storage, electrochemical supercapacitors (ES) offer the advantage of high power density. High power ES can provide load-leveling for batteries and fuel cells during starting, acceleration, hill climbing and braking. ES are important for reducing cycling of batteries, thus extending their lifetime by energy storage and delivery during fast transient operations such as in braking (storage) or start up and acceleration (supply).</p> <p>The interest in polypyrrole (PPY) for the application in ES is attributed to the high specific capacitance (SC) of this material. The possibility of PPY deposition on stainless steel substrates is important for the practical applications of PPY films in ES, using low cost stainless steel current collectors. The important task is to avoid anodic dissolution of the substrates during PPY electropolymerization. Polypyrrole (PPY) films were electrochemically deposited on stainless steel substrates or Ni plaque from aqueous pyrrole solutions containing anionic additives. The method resulted in the formation of adherent and uniform films. The deposition yield was investigated at galvanostatic conditions. It was found that anionic additives can be used for the dispersion of multiwall carbon nanotubes (MWCNTs) and fabrication of composite PPY–MWCNT films. The deposition yield was studied under galvanostatic conditions. The mechanism of PPY–MWCNTs deposition was discussed. The incorporation of MWCNTs into the PPY during electropolymerization resulted in the formation of porous films. The films were investigated for the application in electrodes of electrochemical supercapacitors. Electrochemical testing in the 0.5M Na₂SO₄ electrolyte solutions showed a capacitive behaviour in a voltage window of -0.5 to +0.4 V versus a saturated calomel electrode. The results indicated that the PPY–MWCNT films deposited on the stainless steel and nickel plaque substrates are promising electrode materials for ES.</p> / Master of Applied Science (MASc)

<p>Electrochemical methods show great promise in the deposition of biocompatible coatings for biomedical applications with advanced functionality. Consequently, methods of creating coatings of bioactive materials, such as halloysite nanotubes (HNT), hydroxyapatite (HA), chitosan, hyaluronic acid (HYH), poly-L-ornithine (PLO) and poly-L-lysine (PLL) and polyacrylic acid (PAA) have been developed through the use of electrophoretic deposition (EPD). The co-deposition of these materials are achieved at voltages ranging from 5 to 20 V on a 304 stainless steel substrate using suspensions of 0.5 and 1.0 gL^-1 biopolymer (chitosan, PAA, PLO, PLL) containing 0.3, 0.5 0.6, 1.0 and 2.0 gL^-1 bioceramic (HNT, HA). The resulting films were then investigated to further understand the kinetics and mechanics of deposition, determine their properties, and evaluate their suitability for physiological applications. The films were studied using X-Ray Diffraction (XRD), Differential Thermal Analysis and Thermogravimetric Analysis (DTA/TGA), Scanning Electron Microscopy (SEM), Quartz Crystal Microbalance (QCM) and Linear Polarisation. The results indicate that film thickness, composition and morphology can be controlled and modified at will, and that the deposition of composite films, multilayer laminates and functionally graded films are possible.</p> / Master of Applied Science (MASc)

<p>As a promising new technology, organic photovoltaics (OPVs) have been widely studied recently. To improve the device efficiency for commercial use of 10%, a number of attempts have been made in my research. The ultra-low frequency AC field was first employed, to align p/n polymers during fabrication. The resulting devices showed 15% increase in device efficiency, attributed to the optimized morphology and enlarged p/n interface. During the improvement process, dual nanostructures of the polymers were found, the highly oriented layer and the randomly distributed part, which provided a better understanding of the OPVs under the AC field alignment.</p> <p>The OPV stability was then studied by impedance measurements, to track multi-interface degradation without breaking the device. It was found the degradation of p/n junction was attributed to the deteriorated morphology and oxidized polymers, whereas the semiconductor/metal interface changed by producing metal oxides as degradation products.</p> <p>The dramatic contrast between the bilayer and bulk heterojunctions (BHJ) was at last investigated by capacitance measurements in vacuum. The existing models of the BHJs had difficulty explaining the higher overall capacitance, compared with that from the bilayer devices. The resulting puzzling charge density was clarified by separating the measured capacitance into two parallel components, one from the space charge of the proposed Schottky junction, and the other from the dark dipoles presumably formed spontaneously across the donor/acceptor interface.</p> / Doctor of Philosophy (PhD)

The central objective of the study was to fractionate sedimenting organic materials according to their source (allochthonous or autochthonous) and ultimately to determine the degree of biodegradability of contributions from either source with particular reference to activities at the mud-water interface.

Thesis advisor: Lawrence T. Scott / Thesis advisor: James P. Morken / Expeditious establishment of molecular complexity in a stereoselective manner is a prominent goal in organic synthesis. In this regard, multicomponent coupling reactions have received substantial attention due to their ability to access complex molecules from simple starting materials in a single step. Chapter 1 is a comprehensive review on catalytic bismetallative multicomponent reactions. The scope of this process in terms of both bismetallic reagents and the pi components are broad enough to be generally applied to more elaborate synthetic sequences. Particularly, contemporary applications of the bismetallative multicomponent coupling reactions, in which high enantio- and/or diastereoselectivities are displayed, have enabled the study of this area to make a significant step forward. Chapter 2 presents nickel-catalyzed coupling reactions of aldehyde, diene, and a diboron reagent in the presence of a trialkyl phosphine ligand. Compared to borylation reactions with one pi-component, these borylative multicomponent reactions (involving two pi components) lead to formation of a new C-C bond between the pi components as well as generation of highly functionalized, stereodefined products. Chapter 3 describes a remarkable turnover in regioselectivity of the borylative multicomponent coupling when PCy3 is replaced with P(SiMe3)3. In particular, the products from the reactions with P(SiMe3)3 feature three contiguous stereocenters and an alpha-chiral allylboronate. The effect of P(SiMe3)3 ligand on the product selectivity is intriguing. According to the experimental and computational results, it has an ability to act as an electron acceptor, which will facilitate reductive elimination from the intermediate nickel complex during the course of the reaction. In Chapter 4, we show that borylative ketone-diene coupling reactions can be accomplished in high yields and with excellent levels of diastereocontrol. This reaction occurs in a predictable fashion, yet with regioselection that is distinct from related aldehyde-diene coupling reactions. The reaction products from these coupling processes, which possess tertiary alcohol functionality and an allylic alcohol moiety, are particularly well suited for the preparation of polyketide natural products. Chapter 5 presents investigations on bowl-shaped geodesic polyarenes, which are the missing links between the "classic" planar polycyclic aromatic hydrocarbons (PAHs) and the spheroidal fullerenes. The present study has shown that open geodesic polyarenes can feature chemistry inherent to both classes of aromatics. The curved pi system induces unequal environments on the two faces of circumtrindene, significant strain energy to the molecule, and non-identical bond lengths. Along with the electronic effects, the stereoelectronic effect enabled the site-selective functionalization with fullerene-type chemistry. On the other hand, the edge carbons, which are not present in fullerenes, still possess reactivity of common planar PAHs. Chapter 6 describes the intermolecular oxidative cyclotrimerization reactions of alkenes and aromatic compounds with DDQ and trifluoromethanesulfonic acid. The Scholl-type oxidation reactions involving alkenes have never been demonstrated. Moreover, the DDQ/acid system has never been used for the intermolecular oxidative cyclization reactions. This convenient non-metallic reagent system (DDQ/TfOH) is advantageous over the metal-based Scholl-type oxidants because it eliminates the possibility of halogenation of aromatic compounds and the reduced oxidant can be reoxidized. In Chapter 7, the regioselective formation of cyclic trimers from substituted benzenes and heteroaromatic compounds is demonstrated. This DDQ/TfOH method provides a simple and convenient synthetic route toward star-shaped oligomers containing triphenylene or isotruxene cores. Furthermore, the experimental outcome suggests that this oxidative process proceeds by an electron transfer mechanism. This is the first experimental evidence for mechanistic details on the Scholl-type oxidation. / Thesis (PhD) — Boston College, 2013. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

xx, 361 p. A print copy of this thesis is available through the UO Libraries. Search the library catalog for the location and call number. / Highly conjugated carbon-rich molecules have attracted interest in recent years due to unique electronic, optical and materials properties. Carbon networks based upon the phenylacetylene subunit are increasingly recognized as building blocks for a host of sensing and electronics components due to the rigidity and linearity of carbon-carbon triple bonds. Further extending this motif into a macrocycle, generating a dehydrobenzoannulene (DBA), also confers planarity, increasing the à -conjugation and giving rise to enhanced materials behavior. Functionalization of arylacetylenes and DBAs with electron donating and accepting groups manipulates the energetics such that finely-tuned optoetectronic properties can be devised for customized applications, including fluorescent sensor arrays, organic light-emitting diodes, and nonlinear optical materials. Fundamental structure-property relationship studies into certain physical modifications of molecular architecture effects on the photophysics, intramolecular charge transfer (ICT), or complexation properties are of importance in the rational design of the next generation of organic electronics. Chapter I provides a review of recent advances in the field of annulene chemistry. It is organized by cycle type, size, and application within each category. Chapter II describes syntheses and ion responses of an array of donor/acceptor-functionalized arylacetylenes. The independent manipulation of frontier molecular orbital (FMO) energy levels is discussed in relation to a fluorescent switching phenomenon. Chapter III expands this effect to include [15]DBAs. The consequences of incorporating protonatable donor/acceptor groups into a macrocycle, as well as placement of the acceptor nitrogen are examined, and comparison of calculations to experimental results imply generation of transient ICT species with induced FMO localizations. Chapter IV describes the syntheses of acyclic tetrakis(phenylethynyl)benzene (TPEB) and [14]- and [15]DBA systems utilizing fluorinated acceptor groups. Comparisons between these inductive acceptors and earlier resonance acceptors are made, and imply greater stability and processing potential for optoelectronic applications. Chapter V describes a series of bis[18]DBAs functionalized with dibutylamino groups as donors and nitro groups as acceptors. The effects of 2-donor/2-acceptor versus 4-donor/4-acceptor motifs are explored, and trends are identified in the systematic adjustment of the optical band gap that will have important implications for the design of two-photon absorbing materials. This dissertation includes my previously published and co-authored material. / Adviser: Michael M. Haley

Conjugated macrocycles have emerged as novel structural motifs that modulate the electronic properties of organic molecules because of their strained and contorted structures. Cycloparaphenylenes, known as nanohoops, are a particularly attractive scaffold for the design of new types of carbon nanomaterials because of their size-selective synthesis, radially oriented π-systems and tunable electronic properties. The development of modular syntheses of nanohoops over the past decade should enable the preparation of substituted derivatives that can be tuned for applications in biology and materials science. Chapter I provides a brief overview of conjugated macrocycles recently reported in the literature with a discussion of the structural effects that are responsible for the remarkable properties of this class of molecules. Chapter II highlights a scalable and mild synthetic approach developed in our lab to prepare nanohoop conjugated macrocycles and expands the generality of this methodology with the formal synthesis of natural product Acerogenin E. Chapter III describes the synthesis of cycloparaphenylenes with versatile functional handles and uncovers the reactivity of the strain nanohoop backbone under reaction conditions that promote the formation of radical cations. Chapter IV takes advantage of the functional groups described in chapter III to develop the first example of nanohoops as a new class of biocompatible fluorophores. Chapter V details a novel synthetic approach that enables the incorporation of the linear acene pentacene into the nanohoop backbone and reports our findings on the impact that the macrocyclic structure has on the properties of this organic semiconductor. In summary, the findings discussed in this dissertation provide synthetic strategies for the selective functionalization of nanohoops and highlight this class of molecules as a novel scaffold for the design of new types of carbon nanomaterials. This dissertation includes previously published and unpublished co-authored material.

<p> </p><p>Organic semiconductors are prime candidates for thermoelectric applications, because one can maximize the dimensionless figure of merit ZT (by maximizing the Seebeck coefficient and electrical conductivity) while simultaneously minimizing the thermal conductivity. In this work, we explore a few materials and try to find their thermoelectric characteristics. For the n-leg of the thermogenerator, we studied a modified fullerene (PCBM) which is doped with TDAE vapor. For the p-leg, we studied PEDOT and found the TDAE dedoping level at which the figure of merit is maximized.</p>