By the year 2020, the nanotechnology market is expected to be three trillion dollars. With a quasi-exponential increase in consumer products, which contain nanomaterials, there is likely to be an equal increase in nanoparticles entering the environment. As a result, it is imperative to fully understand the relationship between nanomaterials and the food chain, including plants. In this study, the relationship between gold nanomaterials and the edible food crop, Helianthus annuus was investigated. First, an attempt to inhibit the uptake of nanoparticles into the roots of H. annuus was investigated by decreasing temperature. Second, the interactions between citrate-stabilized 20 nm diameter Au nanoparticles and sunflower seedlings were explored by exposing sunflower to a range of concentrations (3.0-40.0 mg/L). Nanoparticle sorption to roots was estimated using a linear isotherm with a distribution coefficient, Kd. Finally, sunflowers were exposed to 20 nm Au nanoparticles and 25x69 nm CTAB-stabilized Au nanorods. Results showed there was no change in biomass growth and transpiration between sunflowers that were exposed to nanoparticles and the unexposed controls. Thus Au gold nanoparticles (20 nm) were shown to have no phytostimulatory or phytotoxic effect on sunflower seedlings during eight to ten day exposure experiments. However, 25x69 nm gold nanorods were phytotoxic to sunflowers at 6.0 mg/L, indicating a potential charge or chemical effect of the surface coating of the nanorods compared to the spherical gold nanoparticles.

Excitonic photovoltaic devices, including organic, hybrid organic/inorganic, and dye-sensitized solar cells, are attractive alternatives to conventional inorganic solar cells due to their potential for low cost and low temperature solution-based processing on flexible substrates in large scale. Though encouraging, they are currently limited by the efficiency from not yet optimized structural and material parameters and poor overall knowledge regarding the fundamental details. This dissertation aims to achieve improved performance of hybrid solar cells by enhancing material property and designing new device architecture. The study begins with the addition of XD-grade single-walled carbon nanotube (XDSWNT) into poly(3-hexylthiophene) (P3HT) to improve the current density. By having a weight ratio of XDSWNT and P3HT equaled to 0.1:1, short-circuit current was quadrupled from 0.12 mA cm-2 to 0.48 mA cm-2 and solar cell efficiency was tripled from 0.023% to 0.07%, compared to devices with pure P3HT as a hole transport material. Secondly, a significant improvement in device efficiency with 250 nm long ZnO nanorod arrays as photoanodes has been achieved by filling the interstitial voids of the nanorod arrays with ZnO nanoparticles. The overall power conversion efficiency increased from 0.13% for a nanorod-only device to 0.34% for a device with combined nanoparticles and nanorod arrays. The higher device efficiency in solid-state DSSCs with hybrid nanorod/nanoparticle photoanodes is originated from both large surface area provided by nanoparticles for dye adsorption and efficient charge transport provided by the nanorod arrays to reduce the recombinations of photogenerated carriers. Followed by the novel layer-by-layer self-assembly deposition process, the hybrid photoanode study was extended to the longer ZnO nanorod arrays. The best performance, 0.64%, was achieved when the thickness of the photoanodes equaled to 1.2 ?m. Finally, the photovoltaic devices were modified by adding ZnO nanoarpticles into P3HT to increase interfacial area between ZnO and P3HT. The efficiency was enhanced from 0.18% to 0.45% when the ZnO nanorod arrays were 625 nm in length. Our successful design of the device morphology significantly contributes to the performance of solid-state hybrid solar cells.

This dissertation contains six chapters detailing recent advances that have been made in the synthesis and characterization of metal-semiconductor hybrid nanocrystals (HNCs), and the applications of these materials. Primarily focused on the synthesis of well-defined II-VI semiconductor nanorod (NR) and tetrapod (TP) based constructs of interest for photocatalytic and solar energy applications, the research described herein discusses progress towards the realization of key design rules for the synthesis of functional semiconductor nanocrystals (NCs). As such, a blend of novel synthesis, advanced characterization, and direct application of heterostructured nanoparticles are presented. Additionally, for chapters two through six, a corresponding appendix is included containing supporting data pertinent to the experiments described in the chapter. The first chapter is a review summarizing the design, synthesis, properties, and applications of multicomponent nanomaterials composed of disparate semiconductor and metal domains. By coupling two compositionally distinct materials onto a single nanocrystal, synergistic properties can arise that are not present in the isolated components, ranging from self-assembly to photocatalysis. While much progress was made in the late 1990s and early 2000s on the preparation of a variety of semiconductor/metal hybrids towards goals of photocatalysis, comprehensive understanding of nanoscale reactivity and energetics required the development of synthetic methods to prepare well-defined multidimensional constructs. For semiconductor nanomaterials, this was first realized in the ability to tune nanomaterial dimensions from 0-D quantum dot (QD) structures to cylindrical (NR) and branched (TP) structures by exploitation of advanced colloidal synthesis techniques and understandings of NC facet reactivities. Another key advance in this field was the preparation of "seeded" NR and TP constructs, for which an initial semiconductor QD (often CdSe) is used to "seed" the growth of a second semiconductor material (for example, CdS). These advances led to exquisite levels of control of semiconductor nanomaterial composition, shape, and size. Concurrently, many developments were made in the functionalization of these NCs with metallic nanoparticles, allowing for precise tuning of metal nanoparticle deposition position on the surface of preformed semiconductor NCs. To date, photoinduced and thermally induced methods are most widely used for this, providing access to metal-semiconductor hybrid structures functionalized with Au, Pt, Ag2S, Pd, Au/Pt, Ni, and Co nanoparticles (to name a few). With colloidal nanomaterial preparation becoming analogous to traditional molecular systems in terms of selectivity, property modulation, and compositional control, the field of nanomaterial total synthesis has thus emerged in the past decade. With a large toolbox of reactions which afford selectivity at the nanoscale developed, to date it is possible to design a wider array of materials than ever before. Only recently (the past ~ 5 years), however, has the transition from design of model systems for fundamental characterization to realization of functional materials with optimized properties begun to be demonstrated. The emphasis of chapter 1 is thus on the key advances in the preparation of metal-semiconductor hybrid nanoparticles made to date, with seminal synthetic, characterization, and application milestones being highlighted. The second chapter is focused on the synthesis and characterization of well-defined CdSe-seeded-CdS (CdSe@CdS) NR systems synthesized by overcoating of wurtzite (W) CdSe quantum dots with W-CdS shells. 1-dimensional NRs have been interesting constructs for applications such as solar concentrators, optical gains, and photocatalysis. In each of these cases, a critical step is the localization of photoexcited excitons from the light-harvesting CdS NR "antenna" into the CdSe QD seed, from which emission is primarily observed. However, effects of seed size and NR length on this process remained unexplored prior to this work. Previous work had demonstrated that, for core@shell CdSe@CdS systems, small CdSe seed sizes (< 2.8 nm in diameter) resulted in quasi-type II alignment between semiconductor components (with photoexcited electrons delocalized across the structure and holes localized in the CdSe seed), and large seed sizes (> 2.8 nm) resulted in type I alignment (with photoexcited electrons and holes localized in the CdSe seed). Through synthetic control over CdSe@CdS NR systems, materials with small and large CdSe seeds were prepared, and for each seed size, multiple NR lengths were prepared. Through transient absorption studies, it was found that band alignment did not affect the efficiency of charge localization in the CdSe core, whereas NR length had a profound effect. This work indicated that longer NRs resulted in poor exciton localization efficiencies owing to ultrafast trapping of photoexcited excitons generated in the CdS NR. Thus, with increasing rod length, poorer efficiencies were observed. This work served to highlight the ideal size range for CdSe@CdS NR constructs targeted towards photocatalysis, with ~ 40 nm NRs exhibiting the best rod-to-seed localization efficiencies. Additionally, it served to expand the understanding of exciton trapping in colloidal NC systems, allowing development of a predictive model to help guide the preparation of other nanorod based photocatalytic systems. The third chapter describes the synthesis of Au-tipped CdSe NRs and studies of the effects of selective metal nanoparticle deposition on the band edge energetics of these model photocatalytic systems. Previous studies had demonstrated ultrafast localization of photoexcited electrons in Au nanoparticles (AuNP) (and PtNP) deposited at the termini of CdSe and CdSe@CdS NR constructs. Also, for similar systems, the hydrogen evolution reaction (HER) had been studied, for which it was found that noble metal nanoparticle tips were necessary to extract photoexcited electrons from the NR constructs and drive catalytic reactions. However, in these studies, energetic trap states, generally ascribed to surface defects on the NC surface, are often cited as contributing to loss of catalytic efficiency. In this study, we found that the literature trend of assuming the band-edge energetics of the parent semiconductor NC applies to the final metal-functionalized catalyst did not present a complete picture of these systems. Through a combination of ultraviolet photoelectron spectroscopy and waveguide based spectroelectrochemistry on films of 40 nm long CdSe NRs before and after AuNP functionalization, we found that metal deposition resulted in the formation of mid-gap energy states, which were assigned as metal-semiconductor interface states. Previously these states had only been seen in single particle STS studies, and their identification in this study from complementary characterization techniques highlighted a need to further understand the nature of the interface between metal/semiconductor components for the design of photoelectrochemical systems with appropriate band alignments for efficient photocatalysis. The fourth chapter transitions from NR constructs to highly absorbing CdSe@CdS TP materials, for which a single zincblende (ZB) CdSe NC is used to seed the growth of four identical CdS arms. These arms act as highly efficient light absorbers, resulting in absorption cross sections an order of magnitude greater than for comparable NR systems. In the past, many studies have been published on the striking properties of TP nanocrystals, such as dual wavelength fluorescence, multiple exciton generation, and inherent self-assembly owing to their unique geometry. Nonetheless, these materials have not been exploited for photocatalysis, primarily owing to challenges in preparing TP from ultrasmall ZB-CdSe seed size (owing to phase instability of the zincblende crystal structure), thus preventing access to quasi-type II structures necessary for efficient photocatalysis. In this study, we successfully break through the type I/quasi-type II barrier for TP NCs, reclaiming lost ground in this field and demonstrating for the first time quasi-type II behavior in CdSe@CdS TPs through transient absorption measurements. This was enabled by new synthetic protocols for the synthesis and stabilization of ultrasmall (1.8 – 2.8 nm) ZB-CdSe seeds, as well as for the synthesis of CdSe@CdS TPs with arm lengths of 40 nm. Easily scalable, TPs were prepared on gram scales, and the quasi-type II systems showed dramatically enhanced rates of selective photodeposition of AuNP tips under ultraviolet and solar irradiation. These are promising materials for photocatalytic and solar energy applications. The fifth chapter continues with the study of CdSe@CdS TPs, and elaborates on a new method for the selective functionalization of the highly symmetrical TP construct. Previous studies had demonstrated that access to single noble metal NP tips was vital for efficient photocatalytic HER from NR constructs. However, TP materials have been notoriously difficult to selectively functionalize, owing to their symmetric nature. Using a novel photoinduced electrochemical Ostwald ripening process, we found that initially randomly deposited AuNPs could be ripened to a single, large (~ 7 nm) AuNP tip at the end of one arm of a type I CdSe@CdS TP with 40 nm arms. To demonstrate the selectivity of this tipping process, dipolar cobalt was selectively overcoated onto the AuNP tips of these TPs, resulting in dipolar Au@Co-CdSe@CdS TP nanocrystals. These particles were observed to spontaneous self-assemble into 1-D mesoscopic chains, owing to pairing of N-S dipoles of the ferromagnetic CoNPs, resulting in the first example of “colloidal polymers” (CPs) bearing bulky, tetrapod ("giant t-butyl") pendant groups. The sixth chapter elaborates further on the preparation of colloidal polymers, further extending the analogy between molecular and colloidal levels of synthetic control. One challenge in the field of colloidal science is the realization of new modes of self-assemble for compositionally distinct nanoparticles. In this work, it was found that Au@Co nanoparticle dipole strength could be systematically varied by tuning of AuNP size on CdSe@CdS nanorods/tetrapods. In the first example of a colloidal analogue to reactivity ratios observed for traditional chain growth polymerization systems, highly disparate AuNP tip sizes (and thus final Au@Co NP dipole strength) were found to result in segmented colloidal copolymers upon dipolar self-assembly, whereas similar AuNP tip sizes ultimately led to random dipolar assemblies. Clearly visualized through incorporation of NR and TP sidechains into these colloidal polymers, this study presented a compelling case for continued exploration of colloidal analogues to traditional molecular levels of synthetic control.

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第18382号 / エネ博第294号 / 新制||エネ||61(附属図書館) / 31240 / 京都大学大学院エネルギー科学研究科エネルギー基礎科学専攻 / (主査)教授 佐川 尚, 教授 八尾 健, 教授 萩原 理加 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DGAM

This thesis is focused on understanding the interactions between molecules and surface-enhanced Raman scattering (SERS) substrates that are typically unresolved due to the diffraction limit of light. Towards this end, we have developed and tested several different sub-diffraction-limited imaging techniques in order to observe these interactions. First, we utilize an isotope-edited bianalyte approach combined with super-resolution imaging via Gaussian point-spread function fitting to elucidate the role of Raman reporter molecules on the location of the SERS emission centroids. By using low concentrations of two different analyte molecules, we find that the location of the SERS emission centroid depends on the number and positions of the molecules present on the SERS substrate. It is also known that SERS enhancement partially results from the molecule coupling its emission into the far-field through the plasmonic nanostructure. This results in a particle-dictated, dipole-like emission pattern, which cannot be accurately modeled as a Gaussian, so we tested the applicability of super-resolution imaging using a dipole-emission fitting model to this data. To test this model, we first fit gold nanorod (AuNR) luminescence images, as AuNR luminescence is primarily coupled out through the longitudinal dipole plasmon mode. This study showed that a three-dimensional dipole model is necessary to fit the AuNR emission, with the model providing accurate orientation and emission wavelength parameters for the nanostructure, as confirmed using correlated AFM and spectroscopy. The dipole fitting technique was next applied to single- and multiple-molecule SERS emission from silver nanoparticle dimers. We again found that a three-dimensional dipole PSF was necessary to accurately model the emission and orientation parameters of the dimer, but that at the single molecule level, the movement of the molecule causes increased uncertainty in the orientation parameters determined by the fit. Finally, we describe progress towards using a combined atomic force/optical microscope system in order to position a carbon nanotube analyte at known locations on the nanoparticle substrate. This would allow for the simultaneous mapping of nanoparticle topography and exact locations of plasmonic enhancement around the nanostructure, but consistently low signal-to-noise kept this technique from being viable. / text

This work will describe research directed towards the synthesis of anisotropic gold nanoparticles as well as their functionalization and biological applications. The thesis will begin by describing a new technique for the high-yield synthesis of gold nanorods using hydroquinone as a reducing agent. This addresses important limitations of the traditional nanorod synthesis including low yield of gold ions conversion to metallic form and inability to produce rods with longitudinal surface plasmon peak above 850 nm. The use of hydroquinone was also found to improve the synthesis of gold nanowires via the nanorod-seed mediated procedure developed in our lab. The thesis will next present the synthesis of novel starfruit-shaped nanorods, mesorods, and nanowires using a modified nanorod-seed mediated procedure. The starfruit particles displayed increased activity as surface-enhanced Raman spectroscopy (SERS) substrates as compared to smooth structures. Next, a method for the functionalization of gold nanorods using a cationic thiol, 16-mercaptohexadecyltrimethylammonium bromide (MTAB), will be described. By using this thiol, we were able to demonstrate the complete removal of toxic surfactant from the nanorods and were also able to precisely quantify the grafting density of thiol molecules on the nanorod surface through a combination of several analytical techniques. Finally, this thesis will show that MTAB-functionalized nanorods are nontoxic and can be taken up in extremely high numbers into cancer cells. The thesis will conclude by describing the surprising uptake of larger mesorods and nanowires functionalized with MTAB into cells in high quantities.

In this study, zinc oxide (ZnO) nanotip and nanorod were grown on glass substrate by aqueous solution deposition (ASD). Both characteristics of the two nanostructures were investigated. For fabrication of ZnO nanostructure UV photodetector, In-Zn inter-digitated metal electrode was evaporated on the top of the grown ZnO nanostructure to form the contact via. Compared with the common value (375 nm), both the peaks from the PL spectra of ZnO nanotip and nanorod are red-shifted (409 nm) due to the massive defects in nanotip and nanorod. In order to improve the photosensiblity, heterojunction of ZnO nanostructure/TiO2 film was prepared and were made into UV photodetector. Photoresponses of both nanotip and nanorod were improved after N2O annealing at 300oC. With the heterojunction of ZnO 1D nanostructure on TiO2 film, the photoresponses of both ZnO nanotip/TiO2 film can reach to 22.85, and the rise time and decay time are 40 and 82 seconds, respectively. On the other side, the photoresponses of both ZnO nanorod/TiO2 film can reach to 27.44, and the rise time and decay time are 22 and 133 seconds, respectively.

Abstract ¡@¡@Biosensor chip has a lot of advantages, such as label-free, ultra-sensitive, highly selective, fast and real-time detection. Fabricating biosensor chip has great benefits for gene-detection, protein-detection, medical diagnosis and development of new medicine. This research will integrate the biomedical, chemistry, and physics, and also combined with biochemical technology and semiconductor technology to produce biosensor chip. ¡@¡@We use microelectronic semiconductor process technology to fabricate silicon nanowire field effect transistors (SiNW-FET). The source-drain current versus the voltage curve (Isd-Vsd) shows that the contact pad and the silicon nanowire form ohmic contact. And then we use chemical surface modification technologies to modified biotin on SiNW-FET to detect streptavidin. ¡@¡@In addition, we also grow AlGaN/GaN film by MBE, and fabricate nitride¡Vbased high electron mobility transistor (HEMT) by microelectronic semiconductor process technology. In this study, we apply HEMT in biosensor for pancreatic cancer marker CA19-9 antigen. And we modify pancreatic cancer marker CA19-9 antibody on the biosensor chip surface to detect pancreatic cancer marker CA19-9 antigen molecule. ¡@¡@Most of biomolecules are with weak charges, which can form chemical gating effect and change the conductance of p-type SiNW. And according to the streptavidin microfluidic measurement of biotin-modified SiNW-FET, the detection limit of streptavidin was 10-9 M. And the detection limit of pancreatic cancer marker CA19-9 antigen for N-HEMT biosensor was 150 U/mL.

The persistence of high global mortality rates directly attributable to cardiovascular disease drives ongoing research into novel approaches for improved diagnosis and treatment of its primary underlying cause, atherosclerosis. Combined intravascular ultrasound and photoacoustic (IVUS/IVPA) imaging is one such modality, actively being developed as a tool for improved characterization of high-risk atherosclerotic plaques. The pathophysiology associated with progression and destabilization of atherosclerotic plaques leads to characteristic changes in arterial morphology and composition. IVUS/IVPA imaging seeks to expand upon the ability of clinically utilized intravascular ultrasound (IVUS) imaging to assess vessel anatomy by adding improved sensitivity to image the underlying cellular and molecular composition through intravascular photoacoustic (IVPA) imaging of either endogenous chromophores (e.g. lipid) or exogenously delivered contrast agents. This dissertation focuses on the expansion of IVUS/IVPA imaging using exogenous contrast agents to enable the detection and subsequent optically-triggered therapy of atherosclerotic plaques. The passive extravasation and aggregation of systemically injected plasmonic gold nanorods absorbing within the near infrared tissue optical window within plaques of atherosclerotic rabbit models is first demonstrated, along with the ability to localize the contrast agents using ex vivo IVUS/IVPA imaging. The motivation for nanoparticle labeling of atherosclerosis is then expanded from that of purely image contrast agents to vehicles for image-guided, dual-modality phototherapy. The integrated IVUS/IVPA imaging catheter is utilized for photothermal delivery with simultaneous IVPA temperature monitoring using the high optical absorption of gold nanorod contrast agents to enable localized heating. Subsequently, the potential role for IVUS/IVPA-guided phototherapy is further expanded through the characterization and in vitro assessment of novel multifunctional theranostic nanoparticles comprised of a gold nanorod core with a degradable, photosensitizer-doped silica shell. Together, the results presented within this dissertation provide a framework for ongoing research into the expansion of IVUS/IVPA imaging as a platform for complimentary diagnosis and local treatment of atherosclerotic plaques using multifunctional theranostic nanoparticle contrast agents. / text

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.