No abstract

Energetic barriers to charge separation are examined in photovoltaic polymer blends based on regioregular-poly(3-hexylthiophene) (P3HT) and two classes of electron acceptors: a perylene diimide (PDI) derivative and a fullerene (PCBM). Temperature-dependent measurements using ultrafast vibrational spectroscopy are used to directly measure the free energy barriers to charge separation. Charge separation in P3HT:PDI polymer blends occurs through activated pathways, whereas P3HT:PCBM blends exhibit activationless charge separation. X-ray scattering measurements reveal that neither the PDI derivative nor PCBM form highly crystalline domains in their polymer blends with P3HT. The present findings suggest that fullerenes are able to undergo barrierless charge separation even in the presence of structural disorder. In contrast, perylene diimides may require greater molecular order to achieve barrierless charge separation.

Recent evidence has demonstrated that amorphous mixed phases are ubiquitous within mesostructured polythiophene-fullerene mixtures. Nevertheless, the role of mixing within nanophases on charge transport of organic semiconductor mixtures is not fully understood. To this end, we have examined the electron mobility in amorphous blends of poly(3-hexylthiophene) and phenyl-C(61)-butyric acid methyl ester. Our studies reveal that the miscibility of the components strongly affects electron transport within blends. Immiscibility promotes efficient electron transport by promoting percolating pathways within organic semiconductor mixtures. As a consequence, partial miscibility may be important for efficient charge transport in polythiophene-fullerene mixtures and organic solar cell performance.

Charge carrier mobilities in conjugated semicrystalline polymers depend on morphological parameters such as crystallinity, crystal orientation, and connectivity between ordered regions. Despite recent progress in the development of conducting polymers, the complex interplay between the aforementioned parameters and their impact on charge transport is not fully understood. By varying the casting solvents and thermal annealing, we have systematically modulated the crystallization of poly(3-hexylthiophene-2,5-diyl) (P3HT) and poly[2,5-bis(3-hexadecylthiophen-2yl)thieno(3,2-b)thiophene] (PBTTT) thin films to examine the role of microstructure on charge mobilities. In particular, we achieve equal crystallinities through different processing routes to examine the role of structural parameters beyond the crystallinity on charge mobilities. As expected, a universal relationship does not exist between the crystallinity in either P3HT and PBTTT active layers and the charge mobility in devices. In P3HT films, higher boiling point solvents yield longer conjugation lengths, an indicator of stronger intracrystalline order, and therefore higher device mobilities. In contrast, the charge mobilities of PBTTT devices depend on the interconnectivity between crystallites and intercrystalline order in the active layer.

Through a combination of X-ray scattering and energy-filtered electron microscopy, we have quantitatively examined the relationship between the mesostructure of the photoactive layer and device performance in PBTTT/PC(71)BM solar cells. We can predict device performance from X-ray structural data through a simple morphological model which includes the exciton diffusion length.

We have examined the effects of crystallization kinetics of poly(3-hexylthiophene) and poly[2,5-bis(3-hexadecylthiophen-2-yl)thieno(3,2-b)thiophene] on microstructure and charge transport. Rapid crystallization increases the density of tie molecules in polythiophenes. As a consequence, ordered regions are better connected resulting in higher charge carrier mobilities. Our results suggest that controlling the crystallization kinetics might be an important factor for maximizing the charge mobility in semicrystalline polythiophene thin films.

No abstract

Barriers to charge transfer at electrode‐semiconductor contacts are ubiquitous and limit the applicability of organic semiconductors in electronic devices. Molecular or ionic doping near contacts can alleviate charge injection or extraction problems by enabling charge tunneling through contact barriers, but the soft nature of organic materials allows for small molecule dopants to diffuse and migrate, degrading the performance of the device and limiting effective interfacial doping. Here, it is demonstrated that contact doping in organic electronics is possible through ionic polymer dopants, which resist diffusion or migration due to their large size. Sub‐monolayer deposition of non‐conjugated strong polyelectrolytes, e.g., sulfonated poly(sulfone)s, at the anode‐semiconductor interface of organic photovoltaics enables efficient hole extraction at the anode. The performance of contact‐doped organic photo­voltaics nearly matches the performance of devices composed of traditional hole transport layers such as poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). The degree of sulfonation of the dopant polymer and the thickness of the ionic dopant layer is shown to be critical for optimizing doping and the efficiency of the device.