Electrochemical Activation of Atomic-Layer-Deposited Nickel Oxide for Water Oxidation.

NiO-based electrocatalysts, known for their high activity, stability, and low cost in alkaline media, are recognized as promising candidates for the oxygen evolution reaction (OER). In parallel, atomic layer deposition (ALD) is actively researched for its ability to provide precise control over the synthesis of ultrathin electrocatalytic films, including film thickness, conformality, and chemical composition. This study examines how NiO bulk and surface properties affect the electrocatalytic performance for the OER while focusing on the prolonged electrochemical activation process. Two ALD methods, namely, plasma-assisted and thermal ALD, are employed as tools to deposit NiO films. Cyclic voltammetry analysis of ∼10 nm films in 1.0 M KOH solution reveals a multistep electrochemical activation process accompanied by phase transformation and delamination of activated nanostructures. The plasma-assisted ALD NiO film exhibits three times higher current density at 1.8 V vs RHE than its thermal ALD counterpart due to enhanced ß-NiOOH formation during activation, thereby improving the OER activity. Additionally, the rougher surface formed during activation enhanced the overall catalytic activity of the films. The goal is to unravel the relationship between material properties and the performance of the resulting OER, specifically focusing on how the design of the material by ALD can lead to the enhancement of its electrocatalytic performance.

Tuning Material Properties of Oxides and Nitrides by Substrate Biasing during Plasma-Enhanced Atomic Layer Deposition on Planar and 3D Substrate Topographies.

Oxide and nitride thin-films of Ti, Hf, and Si serve numerous applications owing to the diverse range of their material properties. It is therefore imperative to have proper control over these properties during materials processing. Ion-surface interactions during plasma processing techniques can influence the properties of a growing film. In this work, we investigated the effects of controlling ion characteristics (energy, dose) on the properties of the aforementioned materials during plasma-enhanced atomic layer deposition (PEALD) on planar and 3D substrate topographies. We used a 200 mm remote PEALD system equipped with substrate biasing to control the energy and dose of ions by varying the magnitude and duration of the applied bias, respectively, during plasma exposure. Implementing substrate biasing in these forms enhanced PEALD process capability by providing two additional parameters for tuning a wide range of material properties. Below the regimes of ion-induced degradation, enhancing ion energies with substrate biasing during PEALD increased the refractive index and mass density of TiO x and HfO x and enabled control over their crystalline properties. PEALD of these oxides with substrate biasing at 150 °C led to the formation of crystalline material at the low temperature, which would otherwise yield amorphous films for deposition without biasing. Enhanced ion energies drastically reduced the resistivity of conductive TiN x and HfN x films. Furthermore, biasing during PEALD enabled the residual stress of these materials to be altered from tensile to compressive. The properties of SiO x were slightly improved whereas those of SiN x were degraded as a function of substrate biasing. PEALD on 3D trench nanostructures with biasing induced differing film properties at different regions of the 3D substrate. On the basis of the results presented herein, prospects afforded by the implementation of this technique during PEALD, such as enabling new routes for topographically selective deposition on 3D substrates, are discussed.