Resolving the Heat Generated from ZrO2 Atomic Layer Deposition Surface Reactions.

In situ pyroelectric calorimetry and spectroscopic ellipsometry were used to investigate surface reactions in atomic layer deposition (ALD) of zirconium oxide (ZrO2 ). Calibrated and time-resolved in situ ALD calorimetry provides new insights into the thermodynamics and kinetics of saturating surface reactions for tetrakis(dimethylamino)zirconium(IV) (TDMAZr) and water. The net ALD reaction heat ranged from 0.197 mJ cm-2 at 76 °C to 0.155 mJ cm-2 at 158 °C, corresponding to an average of 4.0 eV/Zr at all temperatures. A temperature dependence for reaction kinetics was not resolved over the range investigated. The temperature dependence of net reaction heat and distribution among metalorganic and oxygen source exposure is attributed to factors including growth rate, equilibrium surface hydroxylation, and the extent of the reaction. ZrO2 -forming surface reactions were investigated computationally using DFT methods to better understand the influence of surface hydration on reaction thermodynamics.

Resolving the Heat of Trimethylaluminum and Water Atomic Layer Deposition Half-Reactions.

Atomic layer deposition (ALD) is a surface synthesis technique that is characterized by self-limiting reactions between gas-phase precursors and a solid substrate. Although ALD processes have been demonstrated that span the periodic table, a greater understanding of the surface chemistry that affords ALD is necessary to enable greater precision, including area- and site-selective growth. We offer new insight into the thermodynamics and kinetics of the trimethylaluminum (TMA) and H2O ALD half-reactions with calibrated and time-resolved in situ pyroelectric calorimetry. The half-reactions produce 3.46 and 2.76 eV/Al heat, respectively, which is greater than the heat predicted by computational models based on crystalline Al2O3 substrates and closely aligned with the heat predicted by standard heats of formation. The pyroelectric thin-film calorimeter offers submillisecond temporal resolution that uniquely and clearly resolves precursor delivery and reaction kinetics. Both half-reactions are observed to exhibit multiple kinetic rates, with average TMA half-reaction rates at least 2 orders of magnitude faster than the H2O half-reaction kinetics. Comparing the experimental heat with published computational literature and additional first-principles modeling highlights the need to refine our models and mechanistic understanding of even the most ubiquitous ALD reactions.

Geometric Optimization of Bismuth Vanadate Core-Shell Nanowire Photoanodes using Atomic Layer Deposition.

In this study, systematic geometric tuning of core-shell nanowire (NW) architectures is used to decouple the contributions from light absorption, charge separation, and charge transfer kinetics in photoelectrochemical water oxidation. Core-shell-shell NW arrays were fabricated using a combination of hydrothermal synthesis of ZnO and atomic layer deposition (ALD) of SnO2 and BiVO4. The length and spacing of the NW scaffold, as well as the BiVO4 film thickness, were systematically tuned to optimize the photoelectrochemical performance. A photocurrent of 4.4 mA/cm2 was measured at 1.23 V vs RHE for sulfite oxidation and 4.0 mA/cm2 at 1.80 V vs RHE for water oxidation without a cocatalyst, which are the highest values reported to date for an ALD-deposited photoanode. Electromagnetic simulations demonstrate that spatial heterogeneity in light absorption along the core-shell NW length has a critical role in determining internal quantum efficiency. The mechanistic understandings in this study highlight the benefits of systematically optimizing electrode geometry at the nanoscale when designing photoelectrodes.

Rational Design of Hyperbranched Nanowire Systems for Tunable Superomniphobic Surfaces Enabled by Atomic Layer Deposition.

Superomniphobic surfaces display contact angles of θ* > 150° and low contact angle hysteresis with virtually all high and low surface tension liquids. The introduction of hierarchical scales of texture can increase the contact angles and decrease the contact angle hysteresis of superomniphobic surfaces by reducing the solid-liquid contact area. Thus far, it has not been possible to fabricate superomniphobic surfaces with three or more hierarchical scales of texture where the size, spacing, and angular orientation of features within each scale of texture can be independently varied and controlled. Here, we report a method for tunable control of geometry in hyperbranched ZnO nanowire (NW) structures, which in turn enables the rational design and fabrication of superomniphobic surfaces. Branched NWs with tunable density and orientation were grown via a sequential hydrothermal process, in which atomic layer deposition was used for NW seeding, disruption of epitaxy, and selective blocking of NW nucleation. This approach allows for the rational design and optimization of three-level hierarchical structures, in which the geometric parameters of each level of hierarchy can be individually controlled. We demonstrate the coupled relationships between geometry and contact angles for a variety of liquids, which is supported by mathematical models. The highest performing superomniphobic surface was designed with three levels of hierarchy and achieved the following advancing/receding contact angles with water 172°/170°, hexadecane 166°/156°, octane 162°/145°, and heptane 160°/130°.

Macroporous p-GaP Photocathodes Prepared by Anodic Etching and Atomic Layer Deposition Doping.

P-type macroporous gallium phosphide (GaP) photoelectrodes have been prepared by anodic etching of an undoped, intrinsically n-type GaP(100) wafer and followed by drive-in doping with Zn from conformal ZnO films prepared by atomic layer deposition (ALD). Specifically, 30 nm ALD ZnO films were coated on GaP macroporous films and then annealed at T = 650 °C for various times to diffuse Zn in GaP. Under 100 mW cm(-2) white light illumination, the resulting Zn-doped macroporous GaP consistently exhibit strong cathodic photocurrent when measured in aqueous electrolyte containing methyl viologen. Wavelength-dependent photoresponse measurements of the Zn-doped macroporous GaP revealed enhanced collection efficiency at wavelengths longer than 460 nm, indicating that the ALD doping step rendered the entire material p-type and imparted the ability to sustain a strong internal electric field that preferentially drove photogenerated electrons to the GaP/electrolyte interface. Collectively, this work presents a doping strategy with a potentially high degree of controllability for high-aspect ratio III-V materials, where the ZnO ALD film is a practical dopant source for Zn.