Physical Properties of Organic and Biomaterials: Fundamentals and Applications
Steven, Eden (author)
Brooks, James S. (professor directing dissertation)
Fadool, Debra A. (university representative)
Chiorescu, Irinel (committee member)
Vafek, Oskar (committee member)
Wahl, Horst D. (committee member)
Department of Physics (degree granting department)
Florida State University (degree granting institution)
Silk materials are natural protein-based materials with an exceptional toughness. In addition to their toughness, silk materials also possess complex physical properties and functions resulting from a particular set of amino-acid arrangement that produces structures with crystalline β-sheets connected by amorphous chains. Extensive studies have been performed to study their structure-function relationship leading to recent advancements in bio-integrated devices. Applications to fields other than textiles and biomedicine, however, have been scarce. In this dissertation, an investigation of the electronic properties, functionalization, and role of silk materials (spider silk and Bombyx mori cocoon silk) in the field of organic materials research is presented. The investigation is conducted from an experimental physics point of view where correlations with charge transport mechanisms in disordered, semiconducting, and insulating materials are made when appropriate. First, I present the electronic properties of spider silk fibers under ambient, humidified, iodized, polar solvent exposure, and pyrolized conditions. The conductivity is exponentially dependent on relative humidity changes and the solvent polarity. Iodine doping increases the conductivity only slightly but has pronounced effects on the pyrolization process, increasing the yield and flexibility of the pyrolized silk fibers. The iodized samples were further studied using magic angle spinning nuclear magnetic resonance (MAS-NMR) and Fourier transform infrared spectroscopy (FTIR) revealing non-homogenous iodine doping and I2 induced hydrogenation that are responsible for the minimal conductivity improvement and the pyrolization effects, respectively. Next, I present the investigation of silk fiber functionalization with gold and its role in electrical measurements. The gold functionalized silk fiber (Au-SS) is metallic down to cryogenic temperatures, has a certain amount of flexibility, and possesses magnetic field independent conductivity at low temperatures. This allows their use as micro-wires and flexible electrodes for transport measurements of small organic samples. I also found that neat spider silk fiber can be used as the mask for lithographic processes, providing a simple route of fabricating adhesive stamp electrodes for measuring transport properties of supra-micron samples in the lateral range of 15 μm - 100 μm and thickness > 1 μm at low temperatures and high magnetic fields. The current-voltage characteristic of the insulating channel in tape adhesive electrodes revealed Fowler-Nordheim tunneling mechanism. For electronic sensing and actuating device applications, I have developed a simple method for silk functionalization with carbon nanotubes (CNT) facilitated by polar attraction and supercontraction, a phenomenon where silk is softened when exposed to water. Uniform CNT coating and CNT penetration into the silk fiber surface are evident from the SEM and cross-sectional TEM studies. The conductivity of the carbon nanotube functionalized silk fiber (CNT-SS) follows variable range hopping behavior with activation energy similar to that observed in buckpaper. In addition to being electrically conducting, the CNT-SS is custom-shapeable, flexible, and sensitive to humidity, allowing its use as a heart-pulse and humidity resistive sensors, as well as for current-driven actuators. Finally, I present the investigation of the processed Bombyx mori silk thin film. The silk thin film exhibits actuating and self-healing properties similar to those of a biological muscle. Proof-of-concept silk-based bio-mimetic muscle and water-based memory device are demonstrated. The silk thin film is also used as the dielectric layer of a diF-TESADT organic field effect transistor (FET) where I observed a lower operating voltage and an enhancement in the mobility of the device compared with the FET using SiO2 dielectric layer, accompanied with an anomalous source-drain current-voltage characteristics. This dissertation aims to demonstrate the different aspects of exercising experimental physics to an inter-disciplinary research subject. The fundamental characterization and instrumentation developed in this work are intended to stimulate future discoveries by providing new experimental tools to study electronic transport properties of new materials. In addition, the device fabrication principles will be valuable for development of more environmental-friendly electronics. The treatment presented in this dissertation should serve as a roadmap for future studies of natural materials from an experimental physics point of view.
Actuator, Carbon nanotube, Electronic transport, Organic Field Effect Transistor, Sensor, Spider silk
November 5, 2012.
A Dissertation submitted to the Department of Physics in partial fulfillment of the requirements for the degree of Doctor of Philosophy.
Includes bibliographical references.
James S. Brooks, Professor Directing Dissertation; Debra A. Fadool, University Representative; Irinel Chiorescu, Committee Member; Oskar Vafek, Committee Member; Horst D. Wahl, Committee Member.
Florida State University
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