This dissertation evaluates how gold nanoparticle structure and local environment influence resulting sensor function when using these nanomaterials for complex sample analysis. Molecular imprinted polymers (MIPs), a class of plastic antibodies, are engineered and incorporated into these nanosensors thereby facilitating the quantitative detection of a variety of small molecules when Raman spectroscopy and surface enhanced Raman scattering (SERS) are used for detection. First, homogeneous seeded growth gold nanosphere synthesis is evaluated as a function of ionic double layer composition and thickness. Systematically increasing the citrate concentration during synthesis improves nanomaterial shape homogeneity; however, further elevations of citrate concentration increase the number of internal and/or external atomic defects in the nanomaterials which leads to decreasing solution-phase stability. Next, spherical gold nanoparticles are modified with self-assembled monolayer (SAM), modeled using interfacial energy calculations, and experimental characterized using transmission electron microscopy, NMR, extinction spectroscopy, zeta potential, X-ray photoelectron spectroscopy, and flocculation studies to assess the morphology, surface chemistry, optical properties, surface charge, SAM packing density, and nanoparticle stability, respectively. The number of molecules on the nanostructures increases with increasing ionic strength (by decreasing the electrostatic interfacial energy between assembled molecules) which subsequently promotes nanoparticle stability. Third, plastic antibodies that recognize three drugs commonly used to treat migraines are engineered. These methacrylate-based MIPs are synthesized, extracted, characterized, and used to quantitatively and directly detect over-the-counter drugs in complex samples using Raman microscopy. These results along with numerical approximation methods to estimate drug binding site densities and dissociation constants with the MIPs serve as a foundation for understanding how modest recognition selectivity of MIPs coupled with shifts in the vibrational energy modes from the drugs upon hydrogen binding to the polymer backbone promote sensitive and selective drug detection in complex samples. Finally, nanomaterial incorporation into MIPs for applications in SERS-based biosensors is evaluated. Importantly, gold nanorod concentration increases the detectability of the same drugs using MIPs as pre-concentration and recognition elements. This combination of materials, theory, and applications forms a solid foundation which should aid in the design and development of MIP nanobiosensors for specific and sensitive detection of small molecules in complex matrices.

Organic photovoltaics (OPVs) have received tremendous attention in recent years due to their numerous attractive attributes such as, the potential for high power conversion efficiency (PCE), mechanical flexibility, and the potential for large-scale manufacturing via low-cost techniques. To date, the record PCE values for bulk-heterojunction (BHJ) OPVs exceed 18% for single-junction cells thanks to the rapid development of donors and acceptors materials for active layer. However, the progress of hole-transporting layer (HTL) systems, which is a key device component to reduce the additional performance losses of OPVs, has been limited with only a handful of materials available like PEDOT:PSS and MoOX. In this thesis, I introduce serval materials to unitize as hole-selective contact in high-performance OPVs. Firstly, the application of liquid-exfoliated two-dimensional transition metal disulfides (TMDs) is demonstrated as the HTLs in OPVs. The solution processing of few-layer WS2 suspensions was directly spun onto transparent indium-tin-oxide (ITO) electrodes yield solar cells with superior power conversion efficiency (PCE), improved fill-factor (FF), enhanced short-circuit current (JSC), and lower series resistance than devices based on PEDOT:PSS. Based on PM6:Y6:PC71BM BHJ layer, the cells with WS2 HTL exhibit the highest PCE of 17% thanks to the favorable photonic structure and reduced bimolecular recombination losses in WS2-based cells. Next, the self-assembled monolayer (SAM) namely 2PACz is utilized as hole-selective contact directly onto the ITO anode. The 2PACz modifies the work function of ITO while simultaneously affecting the BHJ layer’s morphology deposited atop. This ITO-2PACz anode is utilized in OPV with PM6:BTP-eC9:PC71BM, showing a remarkable PCE of 18.0%. The enhanced performance is attributed to reduced contact-resistance, lower bimolecular recombination losses, and improved charge transport within the BHJ layer. Lastly, the previously 2PACz SAM was functionalized with bromide functional groups, namely Br-2PACz, which is investigated as hole-extracting interlayers in OPVs. The highest occupied molecular orbital (HOMO) energy of Br-2PACz was measured at -6.01 eV, and significant changes the work function of ITO electrodes upon chemical functionalization. OPV cells based on PM6:BTP-eC9:PC71BM using ITO/Br-2PACz anodes exhibit a maximum PCE of 18.4%, outperforming devices with ITO/PEDOT:PSS (17.5%), resulting from lower interface resistance, improved hole transport, and longer carrier lifetimes.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20702号 / 工博第4399号 / 新制||工||1683(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 杉村 博之, 教授 河合 潤, 教授 邑瀬 邦明 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Solar photovoltaics (PV) is expected to be a critical contributor to mitigating the effects of climate change by helping to satisfy net zero emissions. Since crystalline silicon-based solar cells are close to their practical efficiency limit, further reducing the balance of system (BoS) costs is only possible by increasing the cell efficiencies. The most promising candidate is perovskite/silicon (Si) tandem solar cell technology, which allows efficient solar spectrum harvesting. This relatively new technology attracts attention due to its potential to dominate the PV market; however, it also brings challenges that must be overcome, like stability and scalability concerns. This thesis project focuses on optimizing and characterizing recombination junctions (RJs) for monolithic perovskite/Si tandem solar cells aimed at improved performance and stability. Tandem solar cell PV parameter measurements, encapsulated stability measurements, and thin film characterizations are performed for RJ developments. The optimizations are performed for tandem solar cells with solution-processing and hybrid methods. Self-assembled monolayer (SAM) molecules and transparent conductive oxide (TCO) recombination layer (RL) combinations are optimized to obtain tandems with hybrid technique. In addition, the influence of the thickness of TCO RL on the tandem devices’ performance is also investigated, particularly solution-processed tandems. The improvements are observed by thinning down the thickness of TCOs regardless of the material type. 3 Characterizations revealed that ultra-thin ( 5 nm) amorphous indium zinc oxide (IZO) RL allows more workfunction shift, homogeneous surface potential distribution with SAM deposition, and better carrier recombination suppression at the perovskite/hole transport layer (HTL) interface. Ultra-thin RL idea is combined with some optical improvements in the device architecture, and stable high-efficient perovskite/Si tandem solar cells with 32.5% power conversion efficiency (PCE) and 80% fill factor (FF) values are realized. In addition, the preliminary examples of tandem devices with a larger active area (4 cm2 ) are presented. Finally, the remaining challenges and alternative concepts are also discussed.

Hydrogen evolution via proton reduction occurs at a high rate at the surface of Pt than at Au electrodes. Using cyclic voltammetry, chemically modified nanometer-sized Au electrodes, prepared by the Laser-Assisted Puller Method, were employed to examine current amplification by electrocalysis at Pt nanoparticles adsorbed on the modified Au electrode surfaces. The electrodes were modified with Self-Assembled Monolayers (SAMs) of cysteamine and soaked in Pt colloid solutions overnight. Monitoring the decrements of the characteristic steady-state catalytic current for proton reduction indicated that aggregates of Pt nanoparticles are adsorbed on the cysteamine monolayers and desorb from them particle by particle. The results also indicate that some particles are strongly attached to the modified electrode surface and do not deplete even after thorough rinsing.

No description available.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第24074号 / 理博第4841号 / 新制||理||1692(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 寺西 利治, 教授 島川 祐一, 教授 倉田 博基 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Steel producers use various organic and inorganic coatings to protect cold-rolled steel (CRS) sheets from corrosion during shipment and storage. It is well known that CRS sheets can be protected from corrosion by galvanizing, phosphating, chromating, topcoating with organic, or their combinations. The chromate rinsing is particularly effective for preventing white rusting of galvanized steel. But there is an increasing interest in a replacement for the chromating process because of environmental and health concerns. The objective of the present work is to develop a chrome-free conversion coating for steel sheets. Various carboxylic acids and their salts have been studied for coating phosphated electrogalvanized (EG) steel sheets, including 10-undecenoic acid (UA), oleic acid (OA), and other fatty acids such as stearic acid (SA) and palmitic acid (PA). When they were used alone, or subsequently coated with resin, they could produce a highly hydrophobic surface and improve the corrosion resistance. Thiols such as 1-octadecanethiol (ODT) can form a self-assembled monolayer on metal substrates. This close-packed monolayer could provide an excellent corrosion resistance for EG steel sheets. It was capable of withstanding 50~60 hours of salt spray test (SST) although its thickness was only a few nanometers. The EG steel itself usually started rusting only after 2~4 hours of salt spray. In another coating system, thiols were mixed with a conventional resin to improve the corrosion resistance of EG steel. This new technique gave 100~120 hours of corrosion resistance. When the resin was applied directly on EG steel surface, its corrosion resistance was less than 72 hours. It was shown that further optimization of this technique increased the corrosion resistance to 200 hours and more in the standard SST. / Ph. D.

Polyimides are frequently used as insulating layers in the microelectronics industry. These polymers are tough, have high thermal stability, and have favorable dielectric properties; consequently, polyimides are excellent materials for insulating layers in microelectronic devices. In this research, self-assembled monolayers are investigated for use as an adhesion promoter for metal substrates, and for corrosion protectors of the metal surface. Gold substrates modified by adsorption of 3- and 4-aminothiophenol monolayers, 3- and (4-mercaptophenyl) phthalimide (MPP) monolayers, and by reaction of the 3- and 4-aminothiophenol monolayers with the phthalic anhydride were studied using reflection absorption infrared spectroscopy, contact angle measurement, ellipsometry, and electrochemical measurements. Reactions on the monolayers are used to model the attachment of an insulating polyimide to the substrate. The covalent attachment of the anhydride is confirmed, and the efficiency of the reaction of the aminothiolphenol monolayers is investigated. The reactivity of the aminothiolphenol monolayers is found to depend on the position of the amino-group around the phenyl ring. Impedance spectroscopy is used to investigate the ionic insulating properties of these systems. The 4-mercaptophthalimide monolayer is found to have the highest monolayer resistance to ion transport. This result suggests that it forms the most densely packed monolayer. The monolayer resistance of the surfaces prepared by adsorption of the aminothiolphenol isomers followed by reaction with phthalic anhydride is much lower than the corresponding deposited mercaptophthalimide monolayers. These results suggest that the reaction efficiency is low. Impedance spectroscopy and polarization measurements suggests a higher protection efficiency for 3-mercaptophenylphthalimide. These results will be discussed in the context of the ability of the isomeric mercaptophthalimide monolayers to serve as protectors against substrate corrosion. / Ph. D.

Throughout the study of polymer adsorption at the air/water and solid/water interfaces, surface tension measurements and surface plasmon resonance (SPR) spectroscopy have been identified as key methods for the acquisition of structural and thermodynamic information. These techniques were used to determine air/water and cellulose/water interfacial properties of pullulan (P) and pullulan cinnamates (PCs), 2-hydroxypropyltrimethylammonium xylans (HPMAXs), and hydroxypropyl xylans (HPXs). Hydrophobic modification of pullulan with cinnamate groups promoted adsorption onto model surfaces of regenerated cellulose. In order to understand the relative contributions of hydrophilic and hydrophobic interactions towards PC adsorption, PC adsorption onto self-assembled monolayers (SAMs) with different functional groups was also studied. As the degree of cinnamate substitution increased, greater adsorption onto cellulose, methyl-terminated SAMs (SAM-CH3), and hydroxyl-terminated SAMs (SAM-OH) was observed. This study showed that hydrogen bonding alone could not provide a complete explanation for PC adsorption onto cellulose. The adsorption of cationic 2-hydroxypropyltrimethylammonium (HPMA) xylans with different degrees of substitution (DS) onto SAMs and regenerated cellulose was studied by SPR. Surface concentration (Р) exhibited a maximum (Рmax) for HPMAX adsorption onto carboxylic acid-terminated SAMs (SAM-COOH) at an intermediate HPMA DS of 0.10. This observation was indicative of a relatively flat conformation for adsorbed HPMAXs with higher HPMA DS because of higher linear charge densities along the polymer backbone. Рobserved for HPMAX adsorption onto regenerated cellulose and SAM-OH surfaces was relatively low compared to HPMAX adsorption onto SAM-COOH surfaces. Surface tension measurements for aqueous solutions of HPX by the Wilhelmy plate technique showed that surface tension changes ("γ = γwater " γHPX(aq)) increased and critical aggregation concentrations generally decreased with increasing hydroxypropyl (HP) DS. Hence, even though HP substitution was necessary to induce aqueous solubility, excessive hydroxypropylation promoted aggregation in water. SPR studies indicated that HPXs did not adsorb significantly onto regenerated cellulose or SAM-OH surfaces (submonolayer coverage). In contrast, HPX did adsorb (~monolayer coverage) onto SAM-CH3 surfaces. Collectively, these studies showed natural polymers could be chemically modified to produce surface modifying agents with sufficient chemical control, whereby the surface properties of the resulting systems could be explained in terms of chemical structure and intermolecular interactions. / Ph. D.