Pulsed heating atomic layer deposition (PH-ALD) for epitaxial growth of zinc oxide thin films on c-plane sapphire.

An in situ pulsed heating atomic layer deposition (PH-ALD) technique is used to grow heteroepitaxial ZnO thin films on c-plane sapphire with temperature-sensitive metalorganic precursors. During metalorganic precursor delivery, the substrate is maintained at a base temperature of 110 °C to prevent thermal decomposition of the precursors. After the substrate is sequentially exposed to the metalorganic precursor and water co-reactant at this low temperature, a high-power resistive heater is used to rapidly heat the substrate to between 400 and 900 °C to drive film crystallization. These in situ heat pulses enable epitaxial growth of (0001) ZnO films on c-plane sapphire. Rocking curves with FWHM of values as low as 0.53° are achieved. In contrast, films deposited entirely at 110 °C appear random polycrystalline and post-deposition annealing to 900 °C achieves only partial "epitaxial character" with a notably different in-plane orientation. Variations in heat pulse temperature and the number of deposition cycles between heat pulses are explored. Epitaxial growth persists up to 5 deposition cycles per heat pulse, with the 2θ-ω FWHM increasing to 1-2°. To further reduce process times, a templating approach is also explored in which a limited number of "template" layers are initially deposited with PH-ALD followed by low-temperature ALD at 110 °C. Epitaxial growth is encouraged with as few as 5 cycles of PH-ALD followed by 495 cycles of low-temperature ALD. Crystal quality further improves by using up to 50 template cycles, with a 2θ-ω FWHM of 1.3°. Epilayers also show enhanced photoluminescence (PL) at room temperature. These results demonstrate how in situ pulse-heating can be used to promote epitaxial film growth in ALD processes using temperature-sensitive metalorganic precursors.

Quantifying charge carrier localization in chemically doped semiconducting polymers.

Charge transport in semiconducting polymers ranges from localized (hopping-like) to delocalized (metal-like), yet no quantitative model exists to fully capture this transport spectrum and its dependency on charge carrier density. In this study, using an archetypal polymer-dopant system, we measure the temperature-dependent electrical conductivity, Seebeck coefficient and extent of oxidation. We then use these measurements to develop a semi-localized transport (SLoT) model, which captures both localized and delocalized transport contributions. By applying the SLoT model to published data, we demonstrate its broad utility. We are able to determine system-dependent parameters such as the maximum localization energy of the system, how this localization energy changes with doping, the amount of dopant required to achieve metal-like conductivity and the conductivity a system could have in the absence of localization effects. This proposed SLoT model improves our ability to predict and tailor electronic properties of doped semiconducting polymers.

Thermally Stimulated Wettability Transformations on One-Cycle Atomic Layer Deposition-Coated Cellulosic Paper: Applications for Droplet Manipulation and Heat Patterned Paper Fluidics.

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 Al2O3, 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.

Controlling wettability, wet strength, and fluid transport selectivity of nanopaper with atomic layer deposited (ALD) sub-nanometer metal oxide coatings.

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.