Here, we report a thorough study on the ability of fluorene-based semiconducting polymers to disperse large-diameter (average diameter ⟨d⟩ ≈ 1.3 nm) laser vaporization (LV) single-walled carbon nanotubes (SWCNTs). We demonstrate the ability to select purely semiconducting species using poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(6,6'-{2,2'-bipyridine})] (PFO-BPy) and poly[(9,9-dihexylfluorenyl-2,7-diyl)-co-(9,10-anthracene)] (PFH-A), producing samples with narrow and bright excitonic emission relative to comparable aqueous dispersions. Rapid processing and high yields offer the ability to easily incorporate these semiconducting SWCNTs into commercially scalable applications, as demonstrated by large-area thin films prepared by ultrasonic spraying. By modifying the growth temperature of the LV synthesis, we demonstrate the ability to tune the range of diameters and chiralities within dispersions by exerting synthetic control over the composition of the starting material. This synthetic control allows us to show that PFH-A preferentially disperses near-armchair semiconducting SWCNTs over a large range of diameters (0.8 nm < d < 1.4 nm) and induces unique solvatochromic shifts for the excitonic transitions of nanotubes with particular chiral indices.

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The time scales for interfacial charge separation and recombination play crucial roles in determining efficiencies of excitonic photovoltaics. Near-infrared photons are harvested efficiently by semiconducting single-walled carbon nanotubes (SWCNTs) paired with appropriate electron acceptors, such as fullerenes (e.g., C60). However, little is known about crucial photochemical events that occur on femtosecond to nanosecond time scales at such heterojunctions. Here, we present transient absorbance measurements that utilize a distinct spectroscopic signature of charges within SWCNTs, the absorbance of a trion quasiparticle, to measure both the ultrafast photoinduced electron transfer time (τpet) and yield (ϕpet) in photoexcited SWCNT–C60 bilayer films. The rise time of the trion-induced absorbance enables the determination of the photoinduced electron transfer (PET) time of τpet ≤ 120 fs, while an experimentally determined trion absorbance cross section reveals the yield of charge transfer (ϕpet ≈ 38 ± 3%). The extremely fast electron transfer times observed here are on par with some of the best donor:acceptor pairs in excitonic photovoltaics and underscore the potential for efficient energy harvesting in SWCNT-based devices.

In this report, we investigate the electrical and optical properties of thin conducting films of SWNTs after treatment with small molecule and polymeric amines. Among those tested, we find hydrazine to be the most effective n-type dopant. We use absorbance, Raman, X-ray photoelectron, and nuclear magnetic resonance spectroscopies on thin conducting films and opaque buckypapers treated with hydrazine to study fundamental properties and spectroscopic signatures of n-type SWNTs and compare them to SWNTs treated with nitric acid, a well-characterized p-type dopant. We find that hydrazine physisorbs to the surface of semiconducting and metallic SWNTs and injects large electron concentrations, raising the Fermi level as much as 0.7 eV above that of intrinsic SWNTs. Hydrazine-treated transparent SWNT films display sheet resistances nearly as low as p-type nitric-acid-treated films at similar optical transmittances, demonstrating their potential for use in photovoltaic devices as low work function transparent electron-collecting electrodes.