Studying and controlling order within nanoparticle monolayers fabricated through electrophoretic deposition.

摘要

Just as ensembles of ordered atoms (a crystal) exhibit collective properties which give rise to phenomena that do not exist for a single atom, the same is true of NP ensembles; ordered arrays of NPs (supercrystals) exhibit properties that are not observed in individual NPs. These collective properties open the door for even more applications for nanomaterials. A few examples that demonstrate this fact will be discussed.;In the first example, photoluminescent (PL) optical properties of three CdSe NP systems were studied: one ordered array of NPs, one unordered array, and one system of isolated NPs. In these three systems, the ordered array showed a significantly sharper PL peak compared to the unordered array and the individual NPs. In a second example, the electrical properties for three systems of Ag NPs were studied: one hexagonally packed 2D array of Ag NPs, one cubically packed 2D array, and one individual NP. I-V curves of each system were measured and produced dramatically different behaviors simply due to the change in arrangement of NPs. In a final example, arrays of Ag NPs were created and then sintered. By sintering ordered arrays, it was possible to create large monocrystals of silver; monocrystals could not be created using unordered arrays. These are just three examples that elucidate the control over a wide range of properties that can be achieved by tuning the order within NP ensembles.;Given the potential of films composed of ordered NP arrays, many researchers have been investigating how to create and control such arrays using a variety of techniques. For example, ligand-mediated assembly is being studied using a variety of ligands. DNA ligands, in particular, offer a powerful way to control NP assemblies. Evaporative self-assembly has been used to create large supercrystals of one, two, and even more types/sizes of NPs. Assisted assembly incorporating electric and/or magnetic fields has shown promise in creating ordered NP arrays. Spin-casting and Langmuir Blodgett films can be used to create very thin NP films. Templated substrates in combination with spin coating have been used to order blockcopolymers; this could be adapted for NP arrays as well.;Some of these techniques can be applied for forming ordered arrays of NPs in two-dimensions, creating nanoparticle monolayers (NPMs), the focus of this work. NPMs are attractive for many applications in devices such as magnetic storage, solar cells, and biosensors. One particularly attractive feature of NPMs is the high surface area to volume ratio of the films. For example, through collaboration, we are investigating PL properties of two monolayers, composed of two different types of NPs, stacked on top of one another.;Although challenging, there now are a variety of techniques for the fabrication of NPMs. This dissertation introduces a new process by which one can fabricate monolayers, electrophoretic deposition (EPD). Literature exists on using EPD to fabricate NPMs, but this literature is very limited. One such study deposited films of Au NPs on carbon films and another Pt NPs on carbon films. To the best of our knowledge, only NPMs of metallic NPs on carbon have been fabricated. Of the EPD studies in which NPMs have been fabricated, the technique has not been investigated in depth or has not been generalized for deposition of many types of materials.;If NPM formation via EPD could be generalized, the NPMs could be industrially attractive as EPD has many industrially advantageous properties. For instance, EPD is highly versatile in multiple ways: many types of particles can be deposited, the size of the electrodes can be varied over many orders of magnitude, and a large variety of solvents can be used to suspend NPs. For example, our group has deposited materials of different shapes including tubes, sheets, and spheres; different materials such as polymers, metals, semiconductors, and magnetic materials; and on a variety of substrates including steel, silicon, silicon dioxide, indium tin oxide, and gold. In addition, EPD is very simple to perform, forms smooth films, and forms films quite rapidly. By fabricating NPMs of many types of NPs, the technique used herein has proven to be generalizable and thus could be industrially attractive. (Abstract shortened by UMI.).