In organic optoelectronics, order of conjugated molecules is required for good charge transport, but strong aggregation behavior may generate grain boundaries and trapping, opposing those benefits. Side chains on a polymer's backbone are major reason for and also tool to modify its morphological characteristics. In this report, we show on the example poly(9,9-dioctylfluorenylco-bithiophene) (F8T2) that by a combination of two types of side-chains on the backbone of equal number of carbons, one promoting crystallization, another hindering it, organization of the main chains can be controlled, without changing its major properties. We compare the traditional F8T2 derivative with octyl substituent with two modified species, one containing solely 2ethylhexyl side-chains and another with both types randomly distributed. Thermal characteristics, photophysics and morphology are compared and effects on film formation and 2 charge transport in bulk-heterojunction blends demonstrated on photovoltaic devices utilizing F8T2s as donor and the fullerene derivative ICBA as acceptor material.
The effects of interface roughness between donor and acceptor in a bilayer heterojunction solar cell were investigated on a polymer–polymer system based on poly(3-hexylthiophene) (P3HT) and poly(dioctylfluorene-alt-benzothiadiazole) (F8BT). Both polymers are known to reorganize into semicrystalline structures when heated above their glass-transition temperature. Here, the bilayers were thermally annealed below glass transition of the bulk polymers (≈140 °C) at temperatures of 90, 100, and 110 °C for time periods from 2 min up to 250 min. No change of crystallinity could be observed at those temperatures. However, X-ray reflectivity and device characteristics reveal a coherent trend upon heat treatment. In X-ray reflectivity investigations, an increasing interface roughness between the two polymers is observed as a function of temperature and annealing time, up to a value of 1 nm. Simultaneously, according bilayer devices show an up to 80% increase of power conversion efficiency (PCE) for short annealing periods at any of the mentioned temperatures. Together, this is in agreement with the expectations for enlargement of the interfacial area. However, for longer annealing times, a decrease of PCE is observed, despite the ongoing increase of interface roughness. The onset of decreasing PCE shifts to shorter durations the higher the annealing temperature. Both, X-ray reflectivity and device characteristics display a significant change at temperatures below the glass transition temperatures of P3HT and F8BT.
Silicon carbide (SiC), is an artificial semiconductor used for high-power transistors and blue LEDs, for its extraordinary properties. SiC will be attractive for more applications, but large-scale or large-surface area fabrication, with control over defects and surface is challenging. Sol-gel based techniques are an affordable alternative toward such requirements. This report describes two types of microcrystalline SiC derived after carbothermal reduction from sol-gel-based precursors, one with nitrogen added, the other aluminum. Characterization of their bulk, structure, and surface shows that incorporation of dopants affects the formation of polytypes and surface chemistry. Nitrogen leads exclusively to cubic SiC, exhibiting a native oxide surface. Presence of aluminum instead promotes growth of hexagonal polytypes and induces self-passivation of the crystallites' surface during growth. This is established by hydrogenation of silicon bonds and formation of a protecting aluminum carbonate species. XPS provides support for the suggested mechanism. This passivation is achieved in only one step, solely by aluminum in the precursor. Hence, it is shown that growth, doping and passivation of SiC can be performed as "one-pot synthesis". Material without insulating oxide and a limited number of defects is highly valuable for applications involving surface-sensitive charge-transfer reactions, therefore the potential of this method is significant.
In hybrid solar cells, a nanoscale donor/acceptor junction between an organic and an inorganic semiconductor material is mostly established by mixing the organic semiconductor with inorganic nanocrystals or by infiltration into an inorganic nanostructure scaffold. In this report, we describe the characteristics of submicron-sized cubic silicon carbide and its potential as acceptor material in hybrid photovoltaics. The SiC nanocrystals are derived from a sol-gel based precursor after carbothermal reduction. The process allows reasonable control of nanostructure size and optoelectronic properties can be altered by SiC doping via sol-gel processing additives. SiC has widely been neglected from this application in the past, because of its indirect band gap and high fabrication costs. Still, its band energies are suitable to match the HOMO/LUMO of common organic donors, providing a promising outlook for its acceptor functionality in hybrid photovoltaics. This is shown by fast-laser spectroscopy on according P3HT:SiC hybrid layers, which shows indication for potential long-lived P3HT polaron emission.Peer reviewe
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