Conjugated polymers, Fullerenes, Nanoparticles, Poly(3-hexylthiophene), Solar cells, Spectrum analysis


Conjugated polymer architecture and morphology are two of the key factors that determine corresponding opto-electronic device performance. It is well-known that conjugated polymers display a variety of conformations and exhibit aggregation in their materials and even for individual polymer chains. The intrinsic structural heterogeneity of conjugated polymers strongly complicates the active layer morphology and phase separation, which are crucial for photoinduced charge generation and transport in polymer based bulk heterojunction-organic photovoltaics device (BHJ-OPVs). Aiming to probe the molecular level correlations between conjugated polymer architecture, morphology and optoelectronic properties, single molecule spectroscopy (SMS) and single particle spectroscopy (SPS) were employed. The molecular level folding properties of conjugated polymers were studied and correlated to the chemical architecture and rigidness of the polymer backbones by means of SMS and single molecule polarization anisotropy imaging. First, a block copolymer consisting of poly(3-hexylthiophene) (P3HT) and (60)fullerene (C₆₀) was investigated due to its potential for forming active layers in OPV devices that exhibit long-term phase stability and efficient exciton dissociation into free charge carriers. It was demonstrated that the grafting of the C₆₀-containing block does not significantly affect the conformation of the backbone of the P3HT block. Next, a series of thiophene based polymers showing different macroscale crystallization behavior were investigated. The rigidness of the conjugated polymer backbones was found to be correlated with the chemical architecture of the molecules. However, even the polymers that show no folding in their respective crystals and are thus expected to be the most rigid, still exhibit folding at the single molecule level. From this work it is clear that besides chemical architecture, intermolecular interactions in the crystal structure also need to be considered. For conjugated polymer materials, in this dissertation specifically the blends of conjugated polymers with fullerenes as found in the active layer of OPVs, the investigation of the molecular level correlations between conjugated polymer architecture, morphology and optoelectronic properties can be prohibitively complex due to the presence of a large number of molecules. Furthermore, in the research presented herein, as well as in the literature, it has been clearly shown that the polymer molecules themselves exhibit severe heterogeneity in their properties (chain morphology, aggregation, optical and electronic properties). Therefore, in order to simplify the structure-property investigations concerning nanodomains in BHJ-OPVs, we developed P3HT/PC₆₀BM (PC₆₀BM: (6,6)-phenyl-C₆₁-butyric acid methyl ester) composite nanoparticles (NPs). The size of the nanoparticles corresponds with a few polymer and fullerene domains when considering a similarly sized volume in the active layer of OPVs. Single particle spectroscopy combined with this unique nanoparticle material system reveals variations in molecular conformation and aggregation of the conjugated polymer chains upon doping with different weight percentages of fullerene. These newly developed NPs were embedded in a hole-injection device to study the exciton-hole polaron interactions and the charge transfer processes at the interface between a hole-transporting layer and the NPs. Pronounced charge trapping was observed for donor-acceptor blend NPs due to the large amount of photogenerated free charge carriers. Besides fundamental studies on morphology-property relations for thiophene based conjugated polymers, fabrication of BHJ-OPVs based on P3HT and PC₆₀BM was also completed. Low band gap polymer PTB-7 (poly((4,8-bis((2-ethylhexyl)oxy)benzo (1,2-b:4,5-b')dithiophene-2,6-diyl)(3-fluoro-2-((2-ethylhexyl)carbonyl)thieno(3,4-b) thiophenediyl))) and a near-infrared (NIR) small dye molecule were incorporated into active layers of these P3HT/PC₆₀BM BHJ-OPVs to expand the photoresponse of the devices. The effects of doping the P3HT/PC₆₀BM BHJ-OPVs with PTB-7 and NIR dye on the device performance and film morphology were investigated. The doping of PTB-7 can efficiently extend the photoresponse of the resultant devices into the NIR regime and improve the device performance with respect to the reference (undoped) devices, demonstrating an elegant and pragmatic approach in improving light-harvesting efficiency in BHJ-OPVs.


If this is your thesis or dissertation, and want to learn how to access it or for more information about readership statistics, contact us at

Graduation Date





Gesquiere, Andre J.


Doctor of Philosophy (Ph.D.)


College of Sciences










Release Date

August 2011

Length of Campus-only Access


Access Status

Doctoral Dissertation (Open Access)

Included in

Chemistry Commons