Title:
Controlling electronic properties and morphology of isoindigo-based polymers for photovoltaic applications
Controlling electronic properties and morphology of isoindigo-based polymers for photovoltaic applications
Author(s)
Grand, Caroline
Advisor(s)
Reynolds, John R.
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Abstract
Novel organic conjugated materials have led to new technologies in the field of flexible electronics, with applications in the area of sensors, field effect transistors, or photovoltaic devices. Several material parameters and properties come into play in these devices, including energy of the frontier molecular orbitals, thin film morphology, and charge transport. These properties can be controlled by the chemistry of organic materials, and through processing conditions. In particular, this dissertation focuses on the isoindigo unit as an electron deficient unit to tune polymer light absorption, charge separation, charge transport in the first part of this dissertation, and morphology control in organic photovoltaic (OPV) devices in a subsequent section. The first part of this dissertation introduces the synthesis and properties of isoindigo-containing polymers as n-type, p-type, or ambipolar semiconductors, and their application in all-polymer or polymer:fullerene blends OPV active layers. It is found that polymers with phenyl linkages along the backbone tend to have broader light absorption than polymers with alternating phenyl-thiophene rings; however, steric hindrance in the former leads to low charge mobilities, and poor device performance. In addition, this section highlights the importance of controlling phase separation in OPV devices by focusing on all-polymer blends, which show large phase separation, and polymer:fullerene blends, where the morphology can be controlled through processing additives generating a two-fold increase in device efficiency. Looking at poly(oligothiophene-isoindigo) polymers as model systems, emphasis is placed on photovoltage losses in these devices due to a decrease in effective energy gap between the polymers and fullerene as the oligothiophene donating strength is increased, as well as explanation of the device parameters through description of morphology as solubility is varied.
The second portion of this dissertation focuses on solution properties of polymers and their correlation to thin film morphology. A first study investigates the influence of alkyl side chains on solubility, molecular packing, and phase separation in blends of poly(terthiophene-alt-isoindigo) with fullerenes. Specifically, as side chains are lengthened, solubility is increased, but with limited impact on the blends morphology. On the other hand increased backbone torsion leads to variations in energy levels, polymer packing and large phase separation in blends with fullerenes. These thermodynamic parameters are to put in perspective with the kinetic control of film formation during the coating process. This is discussed in a second study, which looks at the mechanism of thin film formation when processing additives are used. In particular, this study highlights the interactions that provide a driving force for polymer crystallite formation, depending on the mechanism followed when aliphatic and aromatic additives are used. These observations are then used to predict the morphology in spin-coated thin films.
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Date Issued
2015-01-08
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Text
Resource Subtype
Dissertation