京都大学 / 新制・課程博士 / 博士(工学) / 甲第24642号 / 工博第5148号 / 新制||工||1983(附属図書館) / 京都大学大学院工学研究科化学工学専攻 / (主査)教授 大嶋 正裕, 教授 竹中 幹人, 教授 佐野 紀彰 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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Phosphorus (P) is poorly soluble in most soils and, thus, has poor plant uptake efficiency. AVAIL® and Carbond P (CBP) are new fertilizer products shown to increase P use efficiency (PUE) and increase crop yields when grown in P limiting soils. Carbond P has specifically been seen to increases P uptake and crop yields in soils low in P, although effectiveness in regards to soil organic matter is unknown. The objectives of these studies were to determine if the mode of action for these products is related to physiological response, to determine if Carbond P is toxic to plant roots when in direct contact at high rates, and determine the limitations of Carbond P in regards to biomass (yield), P uptake and concentration. We used a hydroponic study to compare CBP to AVAIL in evaluating plant toxicity and plant philological response. AVAIL and CBP were also compared to ammonium polyphosphate (APP) at pH 6 or 8 for hydroponically grown maize (Zea mays L.). Additionally, a glasshouse study evaluated the PUE of CBP with soil in which maize was grown. Soils were moderate or high in organic matter, with 0, 5, 15, 45, or 135 kg P2O5 ha-1 applied as either APP or CBP. Both studies showed that CBP is a suitable PUE enhancing fertilizer. In the greenhouse study, the high organic matter soil revealed that both CBP and APP fertilization resulted in similar increases in biomass yield and P concentration and uptake. However, in the moderate organic matter soil, biomass and total P uptake was significantly greater for CBP than APP at the two lowest P rates of fertilization and significantly higher for APP than CBP at the highest P application rate. In the hydroponic study, neither AVAIL nor CBP had any positive or adverse effects on the plants as compared to APP. These results, coupled with this and previous soil-based greenhouse and field studies with AVAIL and CBP, show that the increase in PUE is not a physiological growth stimulant response, but rather likely the result of impacts on P solubility in the soil. However, the presence of high organic matter in the soil seemed to negate the effects of the organic acid bonded P used in Carbond P. We conclude that CBP, and possibly other organic acid based fertilizers, can assist in furthering agricultural goals, as well as environmental responsibility with these known limits.

Bottom-up self-assembly can be used to create structures with sub-20 nm feature sizes or materials with advanced electrical properties. Here I demonstrate processes to enable such self-assembling systems including block copolymers and DNA origami, to be integrated into nanoelectronic devices. Additionally, I present a method which utilizes the high stability and electrical conductivity of graphene, which is a material formed using a bottom-up growth process, to create archival data storage devices. Specifically, I show a technique using block copolymer micelle lithography to fabricate arrays of 5 nm gold nanoparticles, which are chemically modified with a single-stranded DNA molecule and used to chemically attach DNA origami to a surface. Next, I demonstrate a method using electron beam lithography to control location of nanoparticles templated by block copolymer micelles, which can be used to enable precise position of DNA origami on a surface. To allow fabrication of conductive structures from a DNA origami template, I show a method using site-specific attachment of gold nanoparticles to and a subsequent metallization step to form continuous nanowires. Next, I demonstrate a long-term data storage method using nanoscale graphene fuses. Top-down electron beam lithography was used to pattern atomically thin sheets of graphene into nanofuses. To program the fuses, graphene is oxidized as the temperature of the fuse is raised via joule heating under a sufficiently high applied voltage. Finally, I investigate the effect of the fuse geometry and the electrical and thermal properties of the fuse material on the programming requirements of nanoscale fuses. Programming voltages and expected fuse temperatures obtained from finite element analysis simulations and a simple analytical model were compared with fuses fabricated from tellurium, a tellurium alloy, and tungsten.

Bottom-up self-assembly has the potential to fabricate nanostructures with advanced electrical features. DNA templates have been used to enable such self-assembling methods due to their versatility and compatibility with various nanomaterials. This dissertation describes research to advance several different steps of biotemplated nanofabrication, from DNA assembly to characterization. I assembled different nanomaterials including surfactant-coated Au nanorods, DNA-linked Au nanorods and Pd nanoparticles on DNA nanotubes ~10 micrometer long, and on ~400 nm long bar-shaped DNA origami templates. I optimized seeding by changing the surfactant and magnesium ion concentrations in the seeding solution. After successful seeding, I performed electroless plating on those nanostructures to fabricate continuous nanowires. Using the four-point probe technique, I performed resistivity measurements for Au nanowires on DNA nanotubes and obtained values between 9.3 x 10-6 and 1.2 x 10-3 ohm meter. Finally, I demonstrated the directed placement of DNA origami using block copolymer self-assembly. I created a gold nanodot array using block copolymer patterning and metal evaporation followed by lift-off. Then, I used different ligand groups and DNA hybridization to attach DNA origami to the nanodots. The DNA hybridization approach showed greater DNA attachment to Au nanodots than localization by electrostatic interaction. These results represent vital progress in understanding DNA-templated components, nanomaterials, and block copolymer nanolithography. The work in this dissertation shows potential for creating DNA-templated nanodevices and their placement in an ordered array in future nanoelectronics. Each of the described materials and techniques further has potential for addressing the need for increased complexity and integration for future applications.

This thesis discusses the full scope of a project exploring the physics of hierarchical clusters of interacting nanomagnets. These clusters may be relevant for novel applications such as multilevel data storage devices. The work can be grouped into three main activities: micromagnetic simulation, fabrication and characterization of proof-ofconcept prototype devices, and efforts to scale down the structures by creating the hierarchical structures with the aid of diblock copolymer self assembly. Theoretical micromagnetic studies and simulations based on Landau-Lifshitz- Gilbert (LLG) equation were conducted on nanoscale single domain magnetic entities. For the simulated nanomagnet clusters with perpendicular uniaxial anisotropy, the simulation showed the switching field distributions, the stability of the magnetostatic states with distinctive total cluster perpendicular moments, and the stepwise magnetic switching curves. For simulated nanomagnet clusters with in-plane shape anisotropy, the simulation showed the stepwise switching behaviors governed by thermal agitation and cluster configurations. Proof-of-concept cluster devices with three interacting Co nanomagnets were fabricated by e-beam lithography (EBL) and pulse-reverse electrochemical deposition (PRECD). EBL patterning on a suspended 100 nm SiN membrane showed improved lateral lithography resolution to 30 nm. The Co nanomagnets deposited using the PRECD method showed perpendicular anisotropy. The switching experiments with external applied fields were able to switch the Co nanomagnets through the four magnetostatic states with distinctive total perpendicular cluster magnetization, and proved the feasibility of multilevel data storage devices based on the cluster concept. Shrinking the structures size was experimented by the aid of diblock copolymer. Thick poly(styrene)-b-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer templates aligned with external electrical field were used to fabricate long Ni/Fe magnetic nanowire array, dominant shape anisotropy was observed and compared to the result from previously reported Co nanowire array with strong crystalline anisotropy. Guided diblock copolymer poly(styrene)-b-poly(4-vinyl pyridine) (PS-b-P4VP) self assembly was performed to generate clustered microdomains. Direct e-beam patterning on PS-b-P4VP thin film showed precise and arbitrary patterning on the lateral ordering of the self assembly. Graphoepitaxy of self-assembled PS-b-P4VP copolymers on isolated SiN triangular plateaus successfully resulted in the exact clusters of three microdomains. Theoretical consideration and system modeling based on the micellar configuration of the microdomains were done, and the distribution of the cluster’s size and number of elements were explained qualitatively.

Block copolymer (BCP) nanocomposites are an important class of hybrid materials in which the BCP guides the spatial location and the periodic assembly of the additives. High loadings of well-dispersed nanofillers are generally important for many applications including mechanical reinforcing of polymers. In particular the composites shown in this work might find use as etch masks in nanolithography, or for enabling various phase selective reactions for new materials development. This work explores the use of hydrogen bonding interactions between various additives (such as homopolymers and non-polymeric additives) and small, disordered BCPs to cause the formation of well-ordered morphologies with small domains. A detailed study of the organization of homopolymer chains and the evolution of structure during the process of ordering is performed. The results demonstrate that by tuning the selective interaction of the additive with the incorporating phase of the BCP, composites with significantly high loadings of additives can be formed while maintaining order in the BCP morphology. The possibility of high and selective loading of additives in one of the phases of the ordered BCP composite opens new avenues due to high degree of functionalization and the proximity of the additives within the incorporating phase. This aspect is utilized in one case for the formation of a network structure between adjoining additive cores to derive mesoporous inorganic materials with their structures templated by the BCP. The concept of additive-driven assembly is extended to formulate BCP-additive blends with an ability to undergo photo-induced ordering. Underlying this strategy is the ability to transition a weakly interacting additive to its strongly interacting form. This strategy provides an on-demand, non-intrusive route for formation of well-ordered nanostructures in arbitrarily defined regions of an otherwise disordered material. The second area explored in this dissertation deals with the incorporation of additives into photoresists for next generation extreme ultra violet (EUV) photolithography applications. The concept of hydrogen bonding between the additives and the polymeric photoresist was utilized to cause formation of a physical network that is expected to slow down the diffusion of photoacid leading to better photolithographic performance (25-30 nm resolution obtained).

Hybrid organic-inorganic materials represent a new class of materials having scientific and technological potential. In this thesis, Polyhedral Oligomeric Silsesquioxanes (POSS) are used as an inorganic building block which has been tethered to an organic polymer. POSS are silica precusors, having a well defined silsesquioxane cental core surrounded by an organic periphery which makes them compatible with monomers and possibly polymers. The objectives of this study are to (1) study the basic structures of POSS homopolymers, (2) to incorporate POSS building blocks by a bottomup approach into polymer chains and study the resulting morphologies, and (3) to study the thin film behavior of POSS block copolymers. PMA and styryl POSS homopolymers of different peripheries were synthesized by ATRP and mass spectrometry studies were carried out by MALDI-TOF and ESI. PMA POSS chains undergo a number of fragmentations while styrly POSS chains have a relatively robust backbone. Poly(ethylene-butylene-b-MAPOSS), AB type copolymers and poly(MAPOSS-b-styrene-b-MAPOSS), ABA type copolymers were synthesized by a combination of anionic and ATRP polymerization. Spheres, inverse cylinders, lamellar and crystalline lamellar morphologies were observed for the poly(ethylene-butylene-b- MAPOSS) copolymers. In the poly(MAPOSS-b-styrene-b-MAPOSS) copolymers, cylindrical, lamellar and perforated lamellar morphologies were obtained. Beyond the interaction parameter (χ), total degree of polymerization (N) and volume fraction (f), the conformational asymmetry (ε) also plays an important role in determining the morphology of these block copolymer. Crystallization of the POSS phase and better thermal properties were observed in the both block copolymers. Thin film studies of poly(MAPOSS-b-styrene-b-MAPOSS) copolymers showed that the microdomains can be oriented either parallel or perpendicular to the substrate depending upon the film thickness, morphology and relative volume fractions of the connecting blocks. By removal of the organic phase, ordered mesoporous low dielectric constant silica films were obtained. These hybrid block copolymers are a potential candidate for nanopatterning applications.