Characterizing the Mechanical Properties and Phase Behavior of Conjugated Polymers
Restricted (Penn State Only)
- Author:
- Fenton, Abigail
- Graduate Program:
- Chemical Engineering
- Degree:
- Doctor of Philosophy
- Document Type:
- Dissertation
- Date of Defense:
- June 01, 2022
- Committee Members:
- Robert Hickey, Outside Field Member
Scott Milner, Major Field Member
Ralph Colby, Co-Chair & Dissertation Advisor
Harry Allcock, Outside Unit Member
Seong H. Kim, Professor in Charge/Director of Graduate Studies
Enrique Gomez, Co-Chair, Major Member & Dissertation Advisor - Keywords:
- Conjugated Polymers
Rheology
Plateau Modulus
Liquid Crystallinity
Mechanical Properties
Phase Behavior
Organic Electronics
Neutron Scattering
Entanglements
Polymer Physics - Abstract:
- Advances in technology and consumer electronics has brought us quickly from large stationary desktop computers to portable and wearable technology like smart watches. These developments and advances to bring technology closer to the consumer have sparked interest in developing flexible electronics that would allow even closer integration with the user. Since the most common inorganic semiconductor used in electronics, silicon, is very rigid and brittle, it is not a likely candidate for use in stretchable electronics. One of the main advantages organic semiconductors, such as conjugated polymers, have over traditionally used inorganic semiconductors is that they are flexible and can be stretched. Flexibility and ductility are especially important in the field of bioelectronics where implantable or wearable devices need to move with the body without disrupting soft tissues. Conjugated polymers have a wide range of mechanical modulus and are much closer in stiffness to biological tissues than that of inorganic materials such as silicon. This makes conjugated polymers an ideal class of material for creating truly stretchable electronics. However, fundamental characteristics of these materials that have an impact on both mechanical and electronic performance, such as their glass transition temperature, Tg, entanglement molecular weight, Me, Kuhn length, lk, and phase behavior are not well understood. This prevents the formation of rational design systems that could accelerate progress in producing conjugated polymers with electronic and mechanical properties that are application specific. This dissertation focuses on using several characterization techniques, including oscillatory shear rheology, along with theoretical models and computational tools to further understand these fundamental parameters and provide tools that can aid in the development of new conjugated polymers for advancing the stretchable electronics industry. We begin by establishing discussing the characterization techniques and computational tools commonly used to investigate Tg, Me, lk, and phase behavior in polymers and provide information on how to apply these techniques specifically to conjugated polymers including several tips for overcoming challenges and detailed operating procedures. We then present a method for the prediction of the plateau modulus G0N, and therefore Me, of conjugated polymers using the relationship between Kuhn length lk, Kuhn monomer volume v0, and plateau modulus G0 N, initially proposed by Graessley and Edwards for flexible polymers, and extended by Everaers. We discuss the large gap in experimental data between the flexible and stiff regimes which currently prevents the prediction of mechanical properties from chain structure for any polymer in this region. We show that, given the chain architecture, including a semiflexible backbone and side chains, conjugated polymers are an ideal class of material to study this cross-over region. Using small angle neutron scattering, oscillatory shear rheology, and the freely rotating chain model, we reveal that twelve polymers with aromatic backbones populate a large part of this gap. We also have shown that a few of these polymers exhibit nematic ordering, which lowers G0N. When fully isotropic, these polymers follow a relationship between lk, v0, and G0N, with a simple crossover proposed in terms of the number of Kuhn segments in an entanglement strand Ne. Next, we focus on characterizing phase behavior in these conjugated polymers. Liquid crystalline phases have been shown to lower the modulus of polymers and affect their charge transport properties, thus understanding and mapping their phase behavior is important for obtaining the best mechanical and electrical performance. We first investigate the phase behavior and glass transition of high-performance, yet seemingly amorphous polymer C16IDT-BT as a function of molecular weight. Using rheology, in-situ wide angle X-ray scattering (WAXS), and in-situ polarized optical microscopy (POM), we reveal that C16IDT-BT has three unique phases and we present our hypothesis on classifying the phases. We also look at the effects of side chain placement on the phase behavior in another high-performance polymer, PBTTT-C14. PBTTT-C14’s phase behavior has been previously classified as a semicrystalline polymer with a smectic like phase, thus it is an ideal material to investigate how changes to the chemical structure affect higher order liquid crystalline phases. Using differential scanning calorimetry (DSC) and rheology, we show that increasing the steric hindrance by changing the C14 side chain placement can suppress crystallinity but have no impact on the liquid crystalline phase. Further increasing the steric hindrance shows suppression of both the crystalline and liquid crystalline phases. Finally, some future directions are included to better understand key relationships between structure and performance in conjugated polymers and to improve upon current tools and create new tools to aid in the rational design of new conjugated polymers for use in soft electronics applications.