Browsing by Subject "Self-assembly"
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Item Applications of self-assembly : liquid crystalline semiconductors and DNA-conjugated microparticles(2012-12) Tang, Hao, 1985-; Willson, C. Grant, 1939-Self-assembly provides an efficient way to build complex structures with great flexibility in terms of components and properties. This dissertation presents two different forms of self-assembly for technical applications. The first example is the molecular assembly of liquid crystals (LCs). Attaching appropriate side chains on anthracene, oligothiophene, and oligoarenethiophene successfully constructed liquid crystalline organic semiconductors. The phase transitions of the LC semiconductors were analyzed by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The effect of the LC phase change on charge transport was probed by the space-charge limited current (SCLC) method and the field-effect transistor (FET) method. Mobility in the LC phase rose in anthracenyl esters but decreased in oligothiophenes and oligoarenethiophenes. The different electronic behavior of LC semiconductors may be caused by the difference in domain size and/or the difference in response to electric field. The second example of self-assembly in this dissertation is DNA-guided self-assembly of micrometer-sized particles. Patternable bioconjugation polymers were synthesized to allow for lithographic patterning and DNA conjugation. The base pairing of DNA was then used to drive the self-assembly of DNA-conjugated particles. The DNA conjugation chemistry was studied in detail using a fluorescence-based reaction test platform. The conjugated DNA on the polymer surface retained its ability to hybridize with its complement and was efficient in binding microspheres with complementary strands. Highly specific bead-to-bead assembly was analyzed using imaging flow cytometry, and the fractions of self-assembly products were explained on the basis of chemical equilibrium. The process of particle fabrication using photolithography was successfully developed, and the self-assembly of lithographically-patterned particles was demonstrated. We envision that the technologies described in this dissertation will be useful in a variety of fields ranging from microelectronics to biotechnology.Item Assembly of colloidal nanocrystals into phospholipid structures and photothermal materials(2012-08) Rasch, Michael; Korgel, Brian Allan, 1969-There has been growing interest in developing colloidal metal and semiconductor nanocrystals as biomedical imaging contrast agents and therapeutics, since light excitation can cause the nanocrystals to fluoresce or heat up. Recent advances in synthetic chemistry produced fluorescent 2-4 nm diameter silicon and 1-2 nm diaemeter CuInSSe nanocrystals, as well as 16 nm diameter copper selenide (Cu₂₋[subscript x]Se) nanocrystals exhibiting strong absorbance of near infrared light suitable for biomedical applications. However, the syntheses yield nanocrystals that are stabilized by an adsorbed layer of hydrocarbons, making the nanocrystals hydrophobic and non-dispersible in aqueous solution. Encapsulating these nanocrystals in amphiphilic polymer micelles enables the nanocrystals to disperse in water. Subsequently, the Si nanocrystals were injected into tissue to demonstrate fluorescence imaging, the photothermal transduction efficiency of copper selenide nanocrystals was characterized in water, and the copper selenide nanocrystals were used enhance the photothermal destruction of cancer cells in vitro. The polymer-encapsulated copper selenide nanocrystals were found to have higher photothermal transduction efficiency than 140 nm diameter Au nanoshells, which have been widely investigated for photothermal therapy. Combining the optical properties of metal and semiconductor nanocrystals with the drug-carrying capability of lipid vesicles has received attention lately since it may create a nanomaterial capable of performing simultaneous drug delivery, optical contrast enhancement, and photo-induced therapy. Hydrophobic, dodecanethiol-coated Au nanocrystals were dispersed in water with phosphatidylcholine lipids and characterized using cryo transmission electron microscopy. 1.8 nm diameter Au nanocrystals completely load the bilayer of unsaturated lipid vesicles when the vesicles contain residual chloroform, and without chloroform the nanocrystals do not incorporate into the vesicle bilayer. 1.8 nm Au nanocrystals dispersed in water with saturated lipids to form lipid-coated nanocrystal agglomerates, which sometimes adhered to vesicles, and the shape of the agglomerates varied from linear nanocrystal chains, to flat sheets, to spherical clusters as the lipid fatty acid length was increased from 12 to 18 carbons. Including squalene formed lipid-stabilized emulsion droplets which were fully loaded with the Au nanocrystals. Results with 4.1 nm Au and 2-3 nm diameter Si nanocrystals were similar, but these nanocrystals could not completely load the bilayers of unsaturated lipids.Item Block copolymers for vesicles: self-assembled behavior for use in biomimicry(2009-05-15) Gaspard, Jeffery SimonThe objective of this research is to investigate synthetic and polypeptide block copolymers, the structures they form, their response to various stimuli in solution and their capabilities for use in biomimicry. The self-assembled structures of both polymers will be used as a basis for the templating of hydrogels materials, both in the interior and on the surface of the vesicles. The resulting particles will be designed to show the structural and mechanical properties of living cells. The synthetic block copolymers are a polyethylene glycol and polybutadiene (PEO-b-PBd) copolymer and the polypeptide block copolymers are Lysine and Glysine (K-b-G) copolymers. Investigation of the structures synthetic block copolymers will focus on whether the polymer can form vesicles, how small of a vesicle structure can be made, and the formation of internal polymer networks. Subsequent investigations will look at the needed steps for biomimicry, using the synthetic block copolymers as a starting point and transitioning to a polypeptide block copolymer. The Lysine-Glysine copolymers are a new system of materials that form fluid vesicle structures. Therefore, we must characterize its assembly behavior and investigate how it responds to solution conditions, before we investigate how to make a cellular mimic from it. The size and mechanical behavior of the K-G vesicles will be measured to compare and contrast with the synthetic systems. The goals for creating a biomimic include a hollow sphere structure with a fluid bilayer, a vesicle that has controllable mechanical properties, and a vesicle with controllable surface chemistry. Overall, these experiments were a success; we showed that we can effectively control the size of vesicles created, the material properties of the vesicles, as well as the surface chemistry of the vesicles. Investigations into a novel polypeptide block copolymer were conducted and the block copolymer showed the ability to create vesicles that are responsive to changing salt and pH concentrations.Item Controlled self-assembly of charged particles(2010-05) Shestopalov, Nikolay Vladimirovic; Rodin, G. J. (Gregory J.); Henkelman, GraemeSelf-assembly is a process of non-intrusive transformation of a system from a disordered to an ordered state. For engineering purposes, self-assembly of microscopic objects can benefit significantly from macroscopic guidance and control. This dissertation is concerned with controlling self-assembly in binary monolayers of electrically charged particles that follow basic laws of statistical mechanics. First, a simple macroscopic model is used to determine an optimal thermal control for self-assembly. The model assumes that a single rate-controlling mechanism is responsible for the formation of spatially ordered structures and that its rate follows an Arrhenius form. The model parameters are obtained using molecular dynamics simulations. The optimal control is derived in an analytical form using classical optimization methods. Two major lessons were learned from that work: (i) isothermal control was almost as effective as optimal time-dependent thermal control, and (ii) neither electrostatic interactions nor thermal control were particularly effective in eliminating voids formed during self-assembly. Accordingly, at the next stage, the focus is on temperature-pressure control under isothermal-isobaric conditions. In identifying optimal temperature and pressure conditions, several assumptions, that allow one to relate the optimal conditions to the phase diagram, are proposed. Instead of verifying the individual assumptions, the entire approach is verified using molecular dynamics simulations. It is estimated that under optimal isothermal-isobaric conditions the rate of self-assembly is about five time faster than that under optimal temperature control conditions. It is argued that the proposed approach of relating optimal conditions to the phase diagram is applicable to other systems. Further, the work reveals numerous and useful parallels between self-assembly and crystal physics, which are important to exploit for developing robust engineering self-assembly processes.Item Design, synthesis, and engineering of advanced materials for block copolymer lithography(2015-05) Durand, William John; Willson, C. Grant, 1939-; Ellison, Christopher J.; Bonnecaze, Roger T; Truskett, Thomas M; Akinwande, DejiBlock copolymers (BCPs) are an attractive alternative for patterning applications used to produce next-generation microelectronic devices. Advancements require the development of high interaction parameter χ BCPs that enable patterning at the sub-10 nm length scale. Several organosilicon BCPs were designed to both enhance χ and impart an inherent etch selectivity that facilitates pattern transfer processes. Increasing the BCP silicon content both increases χ and bolsters the etch resistance, providing a pathway to designing new high-χ materials. Unfortunately, the BCPs investigated are not amenable to thermal annealing because the organosilicon block preferentially segregates to an air/vacuum interface and drives orientation parallel to the surface. A series of spin-coatable, polarity-switching top coats (as well as other strategies) were developed to provide a “neutral” top interface and promote the perpendicular orientation of BCP domains. In addition, a methodology for evaluating the neutral condition, relying on thickness quantization and the corresponding wetting behavior (i.e. island/hole topography) of lamellae. The top coat strategy was demonstrated for several BCP systems, and perpendicular structures can successfully be etched on commercial tools and be transferred into underlying substrates. The interaction parameter χ was evaluated using two methods to compare the performance of several BCPs: the order-disorder transition (ODT) of symmetric diblock copolymers, and the absolute scattering profile of a disordered BCP melt. Both methods, while severely limited for quantitative comparison, indicate trends towards higher χ with additional appended polar and organosilicon functional groups. Furthermore, the pattern fidelity is shown to be a function of the overall BCP segregation strength. The free energy of confined lamella was modeled algebraically to produce response surface plots capable of identifying process conditions favorable for perpendicular orientation. Thickness independent perpendicular orientation is only favorable using two neutral interfaces. Incommensurate film thicknesses are the most favorable, with commensurability conditions dependent on the wetting behavior at each interface. The modeling was supplemented with an extensive body of thin film experimental work that qualitatively agrees well with the above conclusions.Item Determining arrangements of optically bound nanoparticle clusters in three dimensions in a Gaussian beam standing wave optical trap(2015-08) Grimm, Philipp Martin; Florin, Ernst-Ludwig; Fink, ManfredThe invention of optical tweezers in 1986 has enabled controlled trapping and manipulating of dielectric particles in the microscopic and nanoscopic regime. More recently, using a specialized optical trap, a novel ultra-strong particle-particle interaction, based on scattered fields and induced dipoles was discovered, namely lateral optical binding. It can be used to achieve self-assembly of nanoparticles into contactless clusters with stable configurations. Experiments have shown that coupling of these clusters to the external electromagnetic field depends on the cluster geometry. The observation was attributed to asymmetries in cluster constituents, such as different particle radii, but a simultaneous experimental observation of cluster geometry and particle radii remained challenging. In this thesis a new method is introduced which measures simultaneously the configuration of a pair of optically bound nanoparticles in three dimensions as well as the ratio of particle radii. This ratio is approximated in two different ways, by analyzing the particle widths in darkfield microscopy images and by analyzing the power of the light scattered from the nanospheres. After validating the procedure and data evaluation for a single immobilized bead it was applied to optically bound particle pairs in a Gaussian beam standing wave optical trap. Both particle size estimations provide similar results. It can be concluded that the difference in brightness observed for distinct nanoparticles originates from a difference in their radii and not from their relative displacements along the optical axis. Nevertheless, two particles with significant difference in radius tend to assemble at slightly different axial positions. This deviation from ideal lateral optical binding may cause additional geometry dependency on the coupling of the cluster to the external optical field and should be included into simulations on optical binding dynamics. Finally, an astonishing symmetry break even for particle pairs with similar radii was observed. The center of mass of these clusters shows a shift a few times as large as the exciting wavelength and particle separation distance away from the trap center to a new, well-defined equilibrium position. This observation challenges the current theoretical explanation of the lateral shifts which requires an asymmetry in the cluster constituents.Item The development of depsipeptides as tissue engineering scaffolds : synthesis, characterization, and self-assembly into hydrogels(2013-05) Nguyen, Mary Minh Chau; Suggs, Laura J.The development of novel, peptide based structures for tissue engineering materials has been widely researched, and its popularity can be attributed to advancements in technological analysis methods. Using principles based on protein structure and organization, this work describes the novel self-assembly of depsipeptides, which incorporate alternating esters within a native peptide backbone. Chapter 1 introduces and reviews peptide mimics for their utility for tissue engineering applications. Chapter 2 describes the methodology in synthesizing and characterization a depsipeptide library using both solution and solid phase methods. Chapter 3 discusses the effects of depsipeptide length, concentration, and sequence within a range of ionic concentrations and pH ranges on the self-assembly of depsipeptides into spherical nanostructures, fibers, or hydrogels. Chapter 4 describes proposed methods to increase the rate of gelation, followed by discussions of biocompatibility studies from other self-assembling peptide and modified-peptide systems in vitro and in vivo. The work described in this dissertation demonstrates that the synthesis and self-assembly of a depsipeptide family which alternates esters into a native peptide backbone does not disrupt the formation of higher order structures. This study illustrates the potential to synthesize a wide range of depsipeptides with variable side chains and hydrophobic character, as understanding these effects on self-assembly is imperative to the development of biomimetic materials for tissue engineering applications.Item Discotic Liquid Crystals and Polymersomes: Molecule Goniometers(2012-10-19) Chang, Ya-WenControlling the assembly of amphiphilic molecules and micron-sized, disk-shaped particles at different length scales into ordered structures enables bottom-up organization which is of great interest to emerging technologies based on structured materials. The primary object of this work is the investigation of structure forming components - Zirconium phosphate (ZrP) discotic particles and polymersomes/ amphiphiles on their self-assembly and interactions. The effect of bilayer architecture of polymersomes on surface reactivity was investigated via fluorescent probing method. Established through complementary experiments, correlation between reactivity and molecule diffusivity in polymer-rich environment revealed the mechanism of reduced reactivity when tethered reactive groups are located deeper within the hydrophilic polymer layer. The phase diagram of charged nanoplatelets was constructed as a function of particle concentration, surface cation moiety, and ionic strength. Influence of surface cation on the isotropic-nematic transition was done by measuring the transition boundaries of discotic suspensions prepared by acid-base exfoliation reaction with a series of exfoliating agents. Furthermore, a novel phase transition was found, where platelet-platelet interaction was influenced synergistically by ionic strength and ion exchange. At low pH, directional inter-platelet attractions lead to the formation of low volume fraction colloidal gels. Alternative surface modification approaches, including biomolecule deposition and alkyl chain grafting were explored. Finally, self-assembly of platelets in emulsions and oil-water interface was examined. Surface modification was applied to link surface properties to stable emulsion-forming ability in mixed surfactant-particle system. Emulsion uniformity was achieved by microfluidic flow focusing method. Surface engineering and interaction control was demonstrated throughout this work to be viable approaches to the fundamental understanding of collective behaviors of individual building blocks.Item Electronic materials based on conducting metallopolymers and self-assembly(2014-12) Nguyen, Minh Tu, Ph. D.; Holliday, Bradley J.; Korgel, Brian A.; Rose, Michael J.; Humphrey, Simon M.; Vanden Bout, David A.Conducting metallopolymers (CMPs) have been extensively studied due to their potential for various applications in sensing, catalysis, light-emitting diodes, and energy harvesting and storage. The incorporation of metal centers into conjugated organic polymer backbones not only makes these materials multi-functional, but also changes the properties, such as electroactivity and conductivity. In this work, we aim to take advantage of the direct electronic interaction between metal centers and polymer backbones in these metallopolymers to make novel materials that could be used for photovoltaic and spintronic applications. Furthermore, a fundamental study on the interactive role of transition metals in conducting metallopolymers has been conducted, which could help to provide insights for the rational design of metallopolymers for certain applications. Charge transfer in hybrid photovoltaics is often inhibited by the capping ligands on inorganic semiconductors. To bypass the ligand effect, my study was focused on preparing a conducting metallopolymer, in which metal ions are directly bound to the conjugated organic backbone. These metal ions will serve as nucleation or seed points upon which the inorganic semiconductor can grow directly within the polymer matrix. This fabrication method provides materials with direct bonds between the inorganic semiconductor and the conducting polymer backbone and therefore results in direct electronic communication between the donor and acceptor. With this material, the charge transfer limited by capping ligands could be overcome and can result in highly efficient devices when utilized in solar cells. Besides the efforts to harvest energy form renewable resources, changing the way that we use energy (e.g., in lighting and information storage) could also help to reduce our energy demand. The bistability offered by spin-crossover (SCO) complexes has resulted in sustained research interest due to potential applications in molecular electronics such as memory storage. Interested in making memory devices with a bottom up approach, we have designed and prepared CMPs that are not only conductive but also possess spin-crossover behavior. The novelty of this study lies in the fact that spin-switching could be possibly obtained by changing the oxidation states of metal centers, which could be done at room temperature, offering a new method for spin switching compared to conventional methods for SCO such as in thermal-induced spin transition. To study the charge delocalization and charge transport in CMPs, a series of conducting polymers of Schiff-base ligands and metal complexes have been prepared and characterized. Our successful syntheses of ligand polymers allows for full characterization and direct comparison of these polymers to the corresponding metal-containing polymers, from which the role of the metal centers is elucidated. The effects of conjugation length on electrochemical and spectroscopic properties are also investigated and discussed.Item Graphoepitaxy for directed self-assembly of particle monolayers(2016-05) Ferraro, Mark Edward; Bonnecaze, R. T. (Roger T.); Truskett, Thomas Michael, 1973-; Ganesan, Venkat; Henkelman, Graeme; Willson, Carlton GMany promising nanotechnologies, such as bit-patterned magnetic media, require highly ordered, defect-free monolayers of particles. Thus, there is a need for cost-efficient and robust manufacturing techniques to reliably fabricate such structures. Self-assembly of particles from suspensions has emerged as a promising nanomanufacturing method, and the tunability of nanoparticle interactions can lead to a diverse array of thermodynamically accessible structures. Nonetheless, particles deposited on surfaces in the absence of external bias often form highly defective structures. Recently, template-directed self-assembly techniques such as graphoepitaxy have been successfully applied to produce low-defectivity block copolymer morphologies with desired nanoscale features. The role of a template in directing the assembly of particulate systems, however, is still poorly understood. The use of larger scale patterned substrates to drive smaller scale assembly of particle monolayers can potentially expand the set of achievable lattices, and could be used in nanopatterning processes or in the manufacture of functional materials. In this dissertation, classical density functional theory (DFT), grand canonical Monte Carlo (GCMC) simulations, and cell theory are used to assess the suitability of graphoepitaxial assembly for particle monolayers and to predict the limits of pattern multiplication in three separate systems. The first two involve the assembly of hard sphere and hard rectangle particle monolayers on surfaces with closed square and closed rectangle template geometries, respectively. The third involves the assembly of spherical and rectangular particles on surfaces patterned with posts. Pattern multiplication limits for these systems (~10x) can be understood in terms of the balance between favorable enthaplically-driven structuring near the boundaries and unfavorable loss of configurational entropy upon forming the targeted structure.Item Heterogeneous or Competitive Self-Assembly at Liquid-Liquid Interfaces(Texas Tech University, 2009-08) Luo, Mingxiang; Dai, Lenore L.; Simon, Sindee L.; Hase, William L.; Vaughn, Mark W.; Khare, RajeshSelf-assembly of nano-sized objects at liquid-liquid interfaces is of tremendous interest for various natural and industrial applications. For example, surfactant interfacial self-assembly is critical in numerous processes such as lubrication, detergency, biological transferring, and polymer processing. On the other hand, self-assembled nanoparticles at liquid-liquid interfaces serve as building blocks for bottom-up assembly of new functional materials with unique physical properties. However, many industrial processes are performed in the presence of both surfactants and nanoparticles. In spite of the importance, interfacial adsorption when a system contains both surfactants and colloidal particles has not been extensively studied. In particular, there is a limited understanding when nanoparticles are involved. In this dissertation, I have performed molecular dynamics simulations and some experimental work to study the heterogeneous or competitive self-assembly of surfactants and nanoparticles at water-trichloroethylene (TCE) interfaces. Interfacial structures, morphology, dynamics properties, and the influences of surfactant and nanoparticle assembly on interfacial properties were studied. I also included some preliminary study on hybrid organic-inorganic solar cells, in which the self-assembly of polymers and nanoparticles in the bulk solution and at liquid-solid interfaces is considered to be critical in film morphology. Polymer-fullerene bulk heterojunctions (BHJs) are currently the most efficient combination for organic solar cells; however, the efficiency is not good. One of the promising approaches to improve device efficiency is to use semiconductor nanocrystals as electron acceptor or alkyl thiols as co-solvent. Hybrid polymer-inorganic nanocrystal composites offer an attractive means to combine the merits of polymer and inorganic nanocrystals to achieve higher power conversion efficiency. This study focuses on integrating ZnO and CdSe nanocrystals or 1-octadecanethiol (ODT) into P3HT: PCBM BHJs to improve photovoltaic performance under ambient conditions. The preliminary results reveal that both CdSe and ODT under optimum conditions provided significant enhancement on power conversion efficiency compared with pure organic composites; however, ZnO failed to improve the device performance.Item Inverse design methods for targeted self-assembly(2014-12) Jain, Avni; Truskett, Thomas Michael, 1973-In this thesis, we study the problem of what microscopic thermodynamic driving forces can stabilize target macroscopic structures. First, we demonstrate that inverse statistical mechanical optimization can be used to rationally design inter-particle interactions that display target open structures as ground states over a wide range of thermodynamic conditions. We focus on designing simple interactions (e.g., isotropic, convex-repulsive) that drive the spontaneous assembly of material constituents to low-coordinated ground states of diamond and simple cubic lattices. This is significant because these types of phases are typically accessible given more complex systems (e.g., particles with orientation-dependent attractive interactions) and for a narrow range of conditions. We subject the optimal interactions to stringent stability tests and also observe assembly of the target structures from disordered fluid states. We then use extensive free energy based Monte Carlo simulation techniques to construct the equilibrium phase diagrams for the model materials with interactions designed to feature diamond and simple cubic ground states, i.e., at zero temperatures. We find that both model materials, despite the largely featureless interaction form, display rich polymorphic phase behavior featuring not only thermally stable target ground state structures, but also a variety of other crystalline (e.g., hexagonal and body-centered cubic) phases. Next, we investigate whether isotropic interactions designed to stabilize given two-dimensional (2D) lattices (e.g., honeycomb or square) will favor their analogous three-dimensional (3D) structures (e.g., diamond or simple cubic), and vice versa. We find a remarkable transferability of isotropic potentials designed to stabilize analogous morphologies in 2D and 3D, irrespective of the exact interaction form, and we discuss the basis of this cross-dimensional behavior. Our results suggest that computationally inexpensive 2D material optimizations can assist in isolating rare isotropic interactions that drive the assembly of materials into 3D open lattice structures.Item Nanofabrication via directed assembly: a computational study of dynamics, design & limits(2016-08) Arshad, Talha Ali; Bonnecaze, R. T. (Roger T.); Ellison, Christopher J.; Ganesan, Venkat; Sreenivasan, S. V.; Willson, Carlton G.Three early-stage techniques, for the fabrication of metallic nanostructures, creation of controlled topography in polymer films and precise deposition of nanowires are studied. Mathematical models and computational simulations clarify how interplay of multiple physical processes drives dynamics, provide a rational approach to selecting process parameters targeting specific structures efficiently and identify limits of throughput and resolution for each technique. A topographically patterned membrane resting on a film of nanoparticles suspended in a solvent promotes non-uniform evaporation, driving convection which accumulates particles in regions where the template is thin. Left behind is a deposit of particles the dimensions of which can be controlled through template thickness and topography as well as film thickness and concentration. Particle distribution is shown to be a competition between convection and diffusion represented by the Peclet number. Analytical models yield predictive expressions for bounds within which deposit dimensions and drying time lie. Ambient evaporation is shown to drive convection strong enough to accumulate particles 10 nm in diameter. Features up to 1 µm high with 10 nm residual layers can be deposited in < 3 minutes, making this a promising approach for continuous, single-step deposition of metallic nanostructures on flexible substrates. Selective exposure of a polystyrene film to UV radiation has been shown to result in non-uniform surface energy which drives convection on thermal annealing, forming topography. Film dynamics are shown to be a product of interplay between Marangoni convection, capillary dissipation and diffusion. At short times, secondary peaks form at double the pattern density of the mask, while at long times pattern periodicity follows the mask. Increased temperature, larger surface tension differentials and thick films result in faster dynamics and larger features. Electric fields in conjunction with fluid flow can be used to position semi-conducting nanowires or nanotubes at precise locations on a substrate. Nanowires are captured successfully if they arrive within a region next to the substrate where dielectrophoresis dominates hydrodynamics. Successful assembly is predicated upon a favorable balance of hydrodynamics, dielectrophoresis and diffusion, represented by two dimensionless groups. Nanowires down to 20 nm in length can be assembled successfully.Item Self-Assembly of Organic Nanostructures(2012-10-19) Wan, AlbertThis dissertation focuses on investigating the morphologies, optical and photoluminescence properties of porphyrin nanostructures prepared by the self-assembly method. The study is divided into three main parts. In the first part, a large variety of porphyrin nanostructures, including nanoplates, nanofibers, nanoparticles and nanowires, were obtained through direct acidification of tetra(p-carboxyphenyl)porphyrin (TCPP) in aqueous solution. Protonation of the carboxylate groups of TCPP resulted in the formation of nanoplates through the J-aggregation of the porphyrin. Further protonating the core nitrogens of TCPP formed the porphyrin diacids which organized into well-defined structures through their interactions with counter-anions in the solution. The structures of the resulting assemblies were found to be counterion dependent. In the second part of this work, we explored the optical memory effect of the porphyrin thin film. We found that the morphology and the emission of the porpyrin thin film on Si can be changed by varying the pH of its surrounding solution. The changing in morphology and light emission of the thin film resulted from the protonation or deprotonation of TCPP'S core nitrogens. By selectively deprotonating the TCPP dications in a confined region utilizing the water meniscus between an AFM tip and the surface, Fluorescence patterns can be generated on the thin film. The fluorescence patterns can be easily erased by re-protonating the porphyrin. In the third part of this study, porphynoid nanoparticles were deposited on a surface energy gradient, and then characterized by AFM in order to investigate how the surface energy influences thier morphologies. The surface energy gradient was prepared by selectively oxidizing a self-assembly monolayer of octadecyltrichlorosilane (OTS) by UV-ozone. The nanoparticles disassemble into smaller nanoparticles with narrower size distribution on the surface with higher surface energy. Lastly, we engaged in characterizing the morphologies of polymer nanocomposites prepared by layer-by-layer assembly for wettability control. The surface roughness of the nanocopmosite in air and in salt solutions was also measured to study the correlation between the wettability of the polymer surface and its surface roughness.Item Surface functionalization and self-assembly of ligand-stabilized silicon nanocrystals(2015-05) Yu, Yixuan; Korgel, Brian Allan, 1969-; Ekerdt, John; Milliron, Delia; Mullins, Charles; Downer, MikeSilicon nanocrystals or quantum dots combine the abundance and nontoxicity of silicon with size-tunable energy band structure of quantum dots to form a new type of functional material that has applications in biomedical fluorescence imaging, photodynamic therapy, light-emitting devices, and solar cells. The surface is the major concern for using silicon nanocrystals in bio-related applications. Room temperature hydrosilylation is introduced to functionalize silicon nanocrystals in the dark to minimize temperature/photon-induced side reactions that can potentially damage the nanocrystal surface and capping ligands. As a proof of concept, silicon nanocrystals are passivated with styrene at room temperature, without showing styrene polymerization. Silicon nanocrystals are also conjugated to iron oxide nanocrystals through room temperature hydrosilylation to generate fluorescent/magnetic cell labeling probes. Thermally-induced thiolation is used to generate silicon nanocrystals passivated with silicon-sulfur bond that is metastable and can turn to silicon-carbon bond through a ligand exchange. The band gap and emission color of silicon nanocrystals depend on size. Monodisperse silicon nanocrystals and their self-assembly are of great importance for the applications in light-emitting devices and solar cells. Silicon nanocrystals are size-selected through a modified size-selective precipitation. Face-centered cubic superlattices are formed with monodisperse silicon nanocrystals, and characterized by using grazing incidence small angle X-ray scattering. The structure of silicon nanocrystal superlattice is stable at temperatures up to 375oC, due to the covalent Si-C bond on the nanocrystal surface. Silicon and gold nanocrystals are assembled to a simple hexagonal AlB2 binary superlattice that shows interesting thermal behavior. Finally, superlattices made with alkane thiol-capped sub-2 nm gold nanocrystals are used as model systems to study the superlattice phase transitions. Halide ions are found to be critical for order-to-order structural rearrangements in dodecanethiol-capped 1.9 nm gold nanocrystals superlattices at 190oC. Reversible amorphous-to-crystalline transition upon heating is discovered for octadecanethiol capped 1.66 nm gold nanocrystal superlattices, which is attributed to the ligand melting transition.Item Ultra-precise manipulation and assembly of nanoparticles using three fundamental optical forces(2012-12) Demergis, Vassili; Florin, Ernst-Ludwig; Shubeita, George T; Fink, Manfred; Makarov, Dmitrii E; Korgel, Brian AThe invention of the laser in 1960 opened the door for a myriad of studies on the interactions between light and matter. Eventually it was shown that highly focused laser beams could be used to con fine and manipulate matter in a controlled way, and these instruments were known as optical traps. However, challenges remain as there is a delicate balance between object size, precision of control, laser power, and temperature that must be satisfied. In Part I of this dissertation, I describe the development of two optical trapping instruments which substantially extend the allowed parameter ranges. Both instruments utilize a standing wave optical field to generate strong optical gradient forces while minimizing the optical scattering forces, thus dramatically improving trapping efficiency. One instrument uses a cylinder lens to extend the trapping region into a line focus, rather than a point focus, thereby confining objects to 1D motion. By translation of the cylinder lens, lateral scattering forces can be generated to transport objects along the 1D trapping volume, and these scattering forces can be controlled independently of the optical gradient forces. The second instrument uses a collimated beam to generate wide, planar trapping regions which can con fine nanoparticles to 2D motion. In Part II, I use these instruments to provide the first quantitative measurements of the optical binding interaction between nanoparticles. I show that the optical binding force can be over 20 times stronger than the optical gradient force generated in typical optical traps, and I map out the 2D optical binding energy landscape between a pair of gold nanoparticles. I show how this ultra-strong optical binding leads to the self-assembly of multiple nanoparticles into larger contactless clusters of well de ned geometry. I nally show that these clusters have a geometry dependent coupling to the external optical field.