This dissertation contains four chapters with advances relevant to the fields of nanoparticle synthesis and nanoparticle self-assembly: a review of nanoparticle self-assembly, or “colloidal polymers”; dumbbell heterostructured nanorod synthesis; dipolar matchstick heterostructured nanorod synthesis; and self-assembly of dipolar matchsticks to form colloidal polymers. These chapters are followed by appendices containing supporting data for chapters two through four. The first chapter is a review summarizing current research involving the 1-D assembly of nanocrystals to form “colloidal polymers.” One of the major goals of materials chemistry is to synthesize hierarchical materials with precise controlled particle ordering covering all length scales of interest (termed, the “bottom up” approach). Recent advances in the synthesis of inorganic colloids have enabled the construction of complex morphologies for particles in the range of 1 – 100 nm. The next level of structural order is to control the structure of assemblies formed from these materials. Linear nanoparticle assemblies are particularly challenging to achieve due to the need to impart functionality to colloids such that (typically) only two sites are active per particle. An emerging idea in the literature which addresses this challenge is to consider linear assemblies of inorganic nanoparticles as colloidal analogs to traditional polymers. This conceptual framework has enabled the formation of linear assemblies having controlled composition (to form segmented and statistical copolymers), architecture (linear, branched, cyclic), and degree of polymerization (chain length). However, this emerging field of synthesizing colloidal polymers has not yet been reviewed in terms of methods to control fundamental polymer parameters. Therefore, linear nanoparticle assembly is reviewed in chapter 1 by applying concepts from traditional polymer science to nanoparticle assembly. The emphasis of chapter 1 is on controlling degree of polymerization, architecture, and composition for colloidal polymers, and seminal examples are highlighted which control these parameters. The second chapter is centered on a novel methodology to install ferromagnetic cobalt domains onto core@shell, “CdSe@CdS” nanorods. While the structures synthesized in this work were novel, the key advance from this work was the development of a methodology to separate nanorod activation from deposition of ferromagnetic cobalt domains onto semiconductor nanorods. As synthesized CdSe@CdS nanorods are passivated with strongly binding phosphonic acid ligands, and these ligands prevent direct deposition of many materials (such as cobalt). Synthetic methods must therefore modify nanorod surfaces prior to deposition of additional nanoparticle domains (tips). Previous synthetic methods for the deposition of magnetic domains onto nanorod termini typically combined activation of nanorod termini and metal deposition into a single synthetic step. While these previous reports were successful in achieving tipped nanorods, the coupling of these two reactions required matching the kinetics of nanorod activation and decomposition/reduction of metal precursors in order to achieve the desired heterostructure morphology. However, the presence of ligands used for nanorod activation can also affect the rate of metal precursor decomposition/reduction and the propensity of the metal to form free nanoparticles through homogeneous nucleation. Thus, simultaneous nanorod activation and metal deposition hinders modification of these syntheses to obtain differing heterostructured morphologies. In the work presented in chapter 2, we chemically activate nanorod termini towards cobalt deposition in a separate chemical step from deposition of metallic cobalt nanoparticle domains. First, reductive platinum deposition conditions were utilized to activate nanorod termini towards the deposition of cobalt domains, which were deposited in a subsequent reaction step. Then, the kinetics of nanorod activation during platinum deposition were tracked, and the platinum-tipped nanorod morphologies were correlated with the results of subsequent cobalt deposition reactions. Ultimately, controlled placement of cobalt domains onto one or both nanorod termini was demonstrated based on the degree of activation during platinum deposition. Cobalt nanoparticle tips were then selectively oxidized to form CoₓOy-tipped nanorods, which were a novel class of p-n type nanomaterials achieved over a total of five synthetic steps. Relevant supporting details for the synthesis of these dumbbell tipped nanorods are provided in Appendix A. The third chapter describes the synthesis of CoNP-tipped nanorods with a single, strongly dipolar, ferromagnetic CoNP-tip per nanorod. The key synthetic advance was the ability to activate a single terminus per nanorod without activation of lateral nanorod facets, which was vital in achieving these larger, dipolar, cobalt tips (rather than lateral decoration of cobalt onto nanorod lateral facets). These dipolar “matchstick” CoNP-tipped nanorods then spontaneously formed linear assemblies carrying nanorod side chains as pendant functionality. Activation of CdSe@CdS nanorods was found to occur through the deposition of small (< 2 nm) PtNP-tips which were not readily observable by standard characterization techniques. The finding that small (< 2 nm) PtNP-tips altered nanorod reactivity towards cobalt deposition emphasized the effect of subtle changes to nanorod surface chemistry. Relevant supporting details for the synthesis of these dipolar matchstick tipped nanorods are provided in appendix B. The fourth chapter is centered on the self-assembly of dipolar matchstick cobalt-tipped nanorods to form colloidal (co)polymers reminiscent of traditional bottlebrush polymers, with controlled composition and phase behavior on carbon surfaces. Similar to earlier findings in traditional polymer science, nanorod side chain length was found to significantly impact surface assembly of these colloidal analogs of bottlebrush copolymers, which provided a useful parameter for affecting surface wetting and phase behavior of nanoparticle thin films. This work was also the first demonstration of colloidal copolymers from the dipolar assembly of magnetic nanoparticles, where both segmented and statistical copolymer compositions were achieved. We then demonstrated, for the first time, that a colloidal copolymer with segmented composition can form a mesoscopic phase separated morphology which is similar to that observed for traditional block copolymers. This key advance opens the possibility of controlling structural ordering over still longer length scales by the development of methods to control phase separated morphologies in a manner similar to traditional block copolymers. Relevant supporting details for the synthesis and assembly of these colloidal bottlebrush polymers are provided in appendix C.

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The emergence of novel electronic, optical and magnetic properties in ordered two-dimensional (2D) nanoparticle ensembles, due to collective dipolar interactions of surface plasmons or excitons or magnetic moments have motivated intense research efforts into fabricating functional nanostructure assemblies. Such functional assemblies (i.e., highly-integrated and addressable) have great potential in terms of device performance and cost benefits. Presently, there is a paradigm shift from lithography based top-down approaches to bottom-up approaches that use self-assembly to engineer addressable architectures from nanoscale building blocks. The objective of this dissertation was to develop appropriate processing tools that can overcome the common challenges faced in fabricating floating gate memory devices using self-assembled 2D metal nanoparticle arrays as charge storage nodes. The salient challenges being to synthesize monodisperse nanoparticles, develop large scale guided self-assembly processes and to integrate with Complementary Metal Oxide Semiconductor (CMOS) memory device fabrication processes, thereby, meeting the targets of International Technology Roadmap for Semiconductors (ITRS) – 2017, for non-volatile memory devices. In the first part of the thesis, a simple and robust process for the formation of wafer-scale, ordered arrays using dodecanethiol capped gold nanoparticles is reported. Next, the results of ellipsometric measurements to analyze the effect of excess ligand on the self-assembly of dodecanethiol coated gold nanoparticles at the air-water interface are discussed. In a similar vein, the technique of drop-casting colloidal solution is extended for tuning the interparticle spacing in the sub-20 nm regime, by altering the ligand length, through thiol-functionalized polystyrene molecules of different molecular weights. The results of characterization, using the complementary techniques of Atomic Force Microscopy (AFM) and Field-Emission Scanning Electron Microscopy (FESEM), of nanoparticle arrays formed by polystyrene thiol (average molecular weight 20,000 g/mol) grafted gold nanoparticles (7 nm diameter) on three different substrates and also using different solvents is then reported. The substrate interactions were found to affect the interparticle spacing in arrays, changing from 20 nm on silicon to 10 nm on a water surface; whereas, the height of the resultant thin film was found to be independent of substrate used and to correlate only with the hydrodynamic diameter of the polymer grafted nanoparticle in solution. Also, the mechanical properties of the nanoparticle thin films were found to be significantly altered by such compression of the polymer ligands. Based on the experimental data, the interparticle spacing and packing structure in these 2D arrays, were found to be controlled by the substrate, through modulation of the disjoining pressure in the evaporating thin film (van der Waals interaction); and by the solvent used for drop casting, through modulation of the hydrodynamic diameter. This is the first report on the ability to vary interparticle spacing of metal nanoparticle arrays by tuning substrate interactions alone, while maintaining the same ligand structure. A process to fabricate arrays with square packing based on convective shearing at a liquid surface induced by miscibility of colloidal solution with the substrate is proposed. This obviates the need for complex ligands with spatially directed molecular binding properties. Fabrication of 3D aggregates of polymer-nanoparticle composite by manipulating solvent-ligand interactions is also presented. In flash memory devices, charges are stored in a floating gate separated by a tunneling oxide layer from the channel, and the tunneling oxide thickness is scaled down to minimize power consumption. However, reduction in tunneling oxide thickness has reached a stage where data loss can occur due to random defects in the oxide. Using metal nanoparticles as charge-trapping nodes will minimize the data loss and enhance reliability by compartmentalizing the charge storage. In the second part of the thesis, a scalable and CMOS compatible process for fabricating next-generation, non-volatile, flash memory devices using the self-assembled 2D arrays of gold nanoparticles as charge storage nodes were developed. The salient features of the fabricated devices include: (a) reproducible threshold voltage shifts measured from devices spread over cm2 area, (b) excellent retention (>10 years) and endurance characteristics (>10000 Program/Erase cycles). The removal of ligands coating the metal nanoparticles using mild RF plasma etching was found, based on FESEM characterization as well as electrical measurements, to be critical in maintaining both the ordering of the nanoparticles and charge storage capacity. Results of Electrostatic Force Microscope (EFM) measurements are presented, corroborating the need for ligand removal in obtaining reproducible memory characteristics and reducing vertical charge leakage. The effect of interparticle spacing on the memory characteristics of the devices was also studied. Interestingly, the arrays with interparticle spacing of the order of nanoparticle diameter (7 nm) gave rise to the largest memory window, in comparison with arrays with smaller (2 nm) or larger interparticle spacing (20 nm). The effect of interparticle spacing and ligand removal on memory characteristics was found to be independent of different top-oxide deposition processes employed in device fabrication, namely, Radio-frequency magnetron sputtering (RF sputtering), Atomic Layer Deposition (ALD) and electron-beam evaporation. In the final part of the thesis, a facile method for transforming polydisperse citrate capped gold nanoparticles into monodisperse gold nanoparticles through the addition of excess polyethylene glycol (PEG) molecules is presented. A systematic study was conducted in order to understand the role of excess ligand (PEG) in enabling size focusing. The size focusing behavior due to PEG coating of nanoparticles was found to be different for different metals. Unlike the digestive ripening process, the presence of PEG was found to be critical, while the thiol functionalization was not needed. Remarkably, the amount of adsorbed carboxylate-PEG mixture was found to play a key role in this process. The stability of the ordered nanoparticle films under vacuum was also reported. The experimental results of particle ripening draw an analogy with the well-established Pechini process for synthesizing metal oxide nanostructures. The ability to directly self-assemble nanoparticles from the aqueous phase in conjunction with the ability to transfer these arrays to any desired substrate using microcontact printing can foster the development of applications ranging from flexible electronics to sensors. Also, this approach in conjunction with roll-to-roll processing approaches such as doctor-blade casting or convective assembly can aid in realizing the goal of large scale nanostructure fabrication without the utilization of organic solvents.