Semiconducting single-walled carbon nanotubes (s-SWCNTs) have recently attracted attention for their promise as active components in a variety of optical and electronic applications, including thermoelectricity generation. Here we demonstrate that removing the wrapping polymer from the highly enriched s-SWCNT network leads to substantial improvements in charge carrier transport and thermoelectric power factor. These improvements arise primarily from an increase in charge carrier mobility within the s-SWCNT networks because of removal of the insulating polymer and control of the level of nanotube bundling in the network, which enables higher thin-film conductivity for a given carrier density. Ultimately, these studies demonstrate that highly enriched s-SWCNT thin films, in the complete absence of any accompanying semiconducting polymer, can attain thermoelectric power factors in the range of ∼400 μW m −1 K −2 , which is on par with that of some of the best single-component organic thermoelectrics demonstrated to date.
Conjugated alternating copolymers were designed with
low optical
band gaps for organic photovoltaic (OPV) applications by considering
quinoid resonance stabilization. Copolymers of thienoisoindoledione
(TID) and benzodithiophene (BDT) had appreciably lower band gaps (by
∼0.4 eV) than copolymers of thienopyrroledione (TPD) and BDT.
In addition to intramolecular charge transfer stabilization (i.e.,
the “push-pull” effect), the former copolymer’s
quinoid resonance structure is stabilized by a gain in aromatic resonance
energy in the isoindole unit. Additionally, the HOMO levels of the
copolymers could be tuned with chemical modifications to the BDT monomer,
resulting in open circuit voltages of greater than 1 V in photovoltaic
devices. Despite the optimized band gap, TID containing polymers displayed
lower photoconductance, as determined by time-resolved microwave conductivity,
and decreased device efficiency (2.1% vs 4.8%) as compared with TPD
analogues. These results were partially attributed to morphology,
as computational modeling suggests TID copolymers have a twisted backbone,
and X-ray diffraction data indicate the polymer films do not form
ordered domains, whereas TPD copolymers are considerably more planar
and are shown to form partially ordered domains.
Controlling steric interactions between
neighboring repeat units in donor–acceptor (D–A) alternating
copolymers can positively impact morphologies and intermolecular electronic
interactions necessary to obtain high performances in organic photovoltaic
(OPV) devices. Herein, we design and synthesize 12 new conjugated
D–A copolymers, employing ethynylene linkages for this control.
We explore D–A combinations of fluorene, benzodithiophene,
and diketopyrrolopyrrole with analogues of pyromellitic diimide, thienoisoindoledione,
isothianaphthene, thienopyrazine, and thienopyrroledione. Computational
modeling suggests the ethynylene-containing polymers can adopt virtually
planar conformations, while many of the analogous polyarylenes lacking
the ethynylene linkage are predicted to have quite twisted backbones
(>35°). The introduction of ethynylene linkages into these
D–A systems universally results in a significant blue-shift
in the absorbance spectra (by as much as 100 nm) and a deeper HOMO
value (∼0.1 eV) as compared to the polyarylene analogues. The
contactless time-resolved microwave conductivity technique is used
to measure the photoconductance of polymer/fullerene blends and is
further discussed as a tool for screening potential active layer materials
for OPV devices. Finally, we demonstrate that an ethynylene-linked
alternating copolymer of diketopyrrolopyrrole and thienopyrroledione,
with a rather deep LUMO estimated at −4.2 eV, shows increased
photoconductance when blended with a perfluoroalkyl fullerene C60(CF3)2 as compared to the standard
PC61BM. We attribute the change in increased free carrier
generation to the higher electron affinity of C60(CF3)2 that is more appropriately matched with the
deeper LUMO of the polymer.
Anion exchange membranes (AEMs) are of high interest for a number of electrochemical device applications including fuel cells, electrolyzers, and flow batteries. Perfluorinated sulfonic acid polymers have been the standard polymer used in the much more established area of proton exchange membrane based devices due to specific advantageous attributes including chemical stability, high conductivity, high water mobility, and the ability to create high performance electrodes. These attributes would make for desirable AEMs, but synthesizing perfluorinated AEMs has been limited and has significant challenges. Here, we report our efforts to develop novel synthesis routes to sulfonamide-linked alkyl ammonium perfluorinated AEMs. We have demonstrated the ability to achieve both high levels of ion exchange and membrane conductivity. We have achieved improved durability by extending the length of the alkyl tether from 3 to 6 carbons, and we have demonstrated the ability to process these polymers into membranes, ionomer solutions/dispersions, and fuel cells with reasonable performance.
A series of new donor−acceptor π-conjugated copolymers incorporating 5,10-dihydroindolo [3,2-b]indole (DINI) as an electron donating unit have been designed, synthesized, and explored in bulk heterojunction solar cells with diketopyrrolopyrrole and thienopyrroledione as the electron accepting units. A significant effect of the size and shape of the pendant alkyl substituents attached to the DINI unit on the optical and electronic properties of the copolymers is described. Our study reveals a good correlation between the theoretical calculations performed on the selected materials and the experimental HOMO, LUMO, absorption spectra, and band gap energies of the corresponding copolymers. The band gaps of the conjugated copolymers can be tailored over 0.4 eV by the electron-withdrawing nature of the different acceptor units to provide better overlap with the solar spectrum, and the energy levels can be tuned ∼0.2 eV depending on the alkyl substituents employed. For the polymers in this study, a nonoptimized power conversion efficiency as high as 3% was observed.
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