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Heteroatom substitution is one promising way to favorably alter electronic transport in conductive polymers to improve their performance in thermoelectric devices. This study reports the spectroscopic, structural, and thermoelectric properties of poly (3-(3',7'-dimethyloctyl) chalcogenophenes) (P3RX) doped with 2, 3,5,7,8,, where the doping methodology, the heteroatom (X = Thiophene (T), Selenophene (Se), Tellurophene (Te)) and the extent of doping are systematically varied. Spectroscopic measurements reveal that while all P3RX polymers are appreciably doped, the doping mechanism is inherently different between the polymers. Poly(3-hexylthiophene) (P3HT, used in this study as a control) and P3RTe doped primarily via integer charge transfer (ICT), whereas P3RSe and P3RT appear to be doped via charge-transfer complex (CTC) mechanisms. Despite these differences, all polymers saturate with roughly the same number of F4TCNQ counterions (1 dopant per 4 to 6 heterocycles), reinforcing the idea that the extent of charge transfer from polymer to dopant varies significantly on the preferred doping mechanism. Grazing incidence wide-angle X-ray scattering measurements provide insight into the structural driving forces behind these different doping mechanisms -P3RT and P3RSe have similar microstructures in which F4TCNQ intercalates between the π-stacked backbones resulting in CTC doping (localized charge carriers), while P3HT and P3RTe have microstructures in which F4TCNQ intercalates in the alkyl-side chain region, giving rise to ICT doping (delocalized charge carriers). These structural and spectroscopic observations shed light on why P3HT and P3RTe

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Cellulosic materials are widely used in daily life for paper products and clothing as well as for emerging applications in sustainable packaging and inexpensive medical diagnostics. Cellulose has a high density of hydroxyl groups that create strong intra-and interfiber hydrogen bonding. These abundant hydroxyl groups also make cellulose superhydrophilic. Schemes for hydrophobization and spatially selective hydrophobization of cellulosic materials can expand the application space for cellulose. Cellulose is often hydrophobized through wet chemistry surface modification methods. This work reports a new modification method using a combination of atomic layer deposition (ALD) and atmospheric heating to alter the wettability of purely cellulosic chromatography paper. We find that once the cellulosic paper is coated with a single ALD cycle (1cy-ALD) of Al 2 O 3 , it can be made sticky superhydrophobic after a 150 °C ambient post-ALD heating step. An X-ray photoelectron spectroscopy investigation reveals that the ALD-modified cellulosic surface becomes more susceptible to adsorption of adventitious carbon upon heating than an untreated cellulosic surface. This conclusion is further supported by the ability to use alternating air plasma and heat treatments to reversibly transition between the hydrophilic and hydrophobic states. We attribute the apparent abruptness of this wetting transition to a Cassie−Wenzel-like phenomenon, which is also consistent with the sticky hydrophobic wetting behavior. Using scanning probe methods, we show that the surfaces have roughness at multiple length scales. Using a Cassie−Wenzel model, we show how a small change in the surface's Young's contact angleupon adsorption of adventitious carboncan lead to an abrupt increase in hydrophobicity for surfaces with such roughnesses. Finally, we demonstrate the ability to spatially pattern the wettability on these 1cy-ALD-treated cellulosic papers via selective heating. This ALD-treated hydrophobic paper also shows promise for microliter droplet manipulation and patterned lab-on-paper devices.

Nanocellulosic films (nanopapers) are of interest for packaging, printing, chemical diagnostics, flexible electronics and separation membranes. These nanopaper products often require chemical modification to enhance functionality. Most chemical modification is achieved via wet chemistry methods that can be tedious and energy intensive due to post-processing drying. Here, we discuss the use of atomic layer deposition (ALD), a vapor phase modification technique, to quickly and simply make nanopaper hydrophobic and enhance its wet strength and durability. Specifically, we find that just "a few" ALD cycles (#10) of either aluminum oxide or titanium oxide is sufficient to significantly increase the durability of cellulose nanofibril (CNF) paper in aqueous media, even under aggressive sonication conditions. Keeping the number of ALD cycles low makes the process more scalable for commodity manufacturing. We investigate whether this increase in wet strength is due to enhanced hydrophobic attractions or stronger hydrogen bonding between CNF fibers. The current evidence suggests that the latter mechanism is likely dominant, with ab initio calculations suggesting that newly created M-OH terminations on the cellulose nanofibrils increase hydrogen bond strength between fibers and impede CNF hydration and dispersion. ALD treated nanopapers are also found to preferentially transport hexane over water, suggesting their potential use in oil/water demulsification devices.