Scalable and simple methods for selective extraction of pure, semiconducting (s) single-walled carbon nanotubes (SWNTs) is of profound importance for electronic and photovoltaic applications. We report a new, one-step procedure to obtain respective large-diameter s- and metallic (m)-SWNT enrichment purity in excess of 99% and 78%, respectively, via interaction between the aromatic dispersing agent and SWNTs. The approach utilizes N-dodecyl isoalloxazine (FC12) as a surfactant in conjunction with sonication and benchtop centrifugation methods. After centrifugation, the supernatant is enriched in s-SWNTs with less carbonaceous impurities, whereas precipitate is enhanced in m-SWNTs. In addition, the use of an increased centrifugal force enhances both the purity and population of larger diameter s-SWNTs. Photoinduced energy transfer from FC12 to SWNTs is facilitated by respective electronic level alignment. Owing to its peculiar photoreduction capability, FC12 can be employed to precipitate SWNTs upon UV irradiation and observe absorption of higher optical transitions of SWNTs. A thin-film transistor prepared from a dispersion of enriched s-SWNTs was fabricated to verify electrical performance of the sorted sample and was observed to display p-type conductance with an average on/off ratio over 10(6) and an average mobility over 10 cm(2)/V·s.
Ternary organic photovoltaic (OPV) devices with multiple light-absorbing active materials have emerged as an efficient strategy for realizing further improvements in the power conversion efficiency (PCE) without building complex multijunction structures. However, the third component often acts as recombination centers and, hence, the optimization of ternary blend morphology poses a major challenge to improving the PCE of these devices. In this work, the performance of OPVs is enhanced through the morphological modification of nonfullerene acceptor (NFA)-containing binary active layers. This modification is achieved by incorporating fullerenes into the layers. The uniformly dispersed fullerenes are sufficiently continuous and successfully mediate the ordering of NFA without charge or energy transfer. Owing to the simultaneous improvement in the charge generation and extraction, the PCE (12.1%) of these parallel-linked ternary devices is considerably higher than those of the corresponding binary devices (9.95% and 7.78%). Moreover, the additional energy loss of the ternary device is minimized, compared with that of the NFA-based binary device, due to the judicious control of the effective donor:acceptor composition of the ternary blends.
Symmetry breaking of single-walled carbon nanotubes (SWNTs) has profound effects on their optoelectronic properties that are essential for fundamental study and applications. Here, we show that isomeric SWNTs that exhibit identical photoluminescence (PL) undergo symmetry breaking by flavin mononucleotide (FMN) and exhibit dual PLs and different binding affinities (K). Increasing the FMN concentration leads to systematic PL shifts of SWNTs according to structural modality and handedness due to symmetry breaking. Density gradient ultracentrifugation using a FMN-SWNT dispersion displays PL shifts and different densities according to SWNT handedness. Using the optical titration method to determine the PL-based K of SWNTs against an achiral surfactant as a titrant, left- and right-handed SWNTs display two-step PL inflection corresponding to respective K values with FMN, which leads to the determination of the enantiomeric excess (ee) of the SWNT ensemble that was confirmed by circular dichroism measurement. Decreasing the FMN concentration for the SWNT dispersion leads to enantiomeric selection of SWNTs. The titration-based ee determination of the widely used sodium cholate-based SWNT dispersion was also demonstrated by using FMN as a cosurfactant.
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