Conformal Electrodeposition of Mesoporous Silica over High Aspect Ratio (AR>100) Nanomesh Electrodes
Authors: Rishikesan Venkataramana , Vanheusden Genis , Chanut Nicolas , Ameloot Rob , Vereecken Philippe M. 
Published: February 2024

The high surface area provided by the nanopores of ordered mesoporous silica thin films enables a wide range of electrochemical applications such as sensors, catalysis, energy storage and ion-selective membranes. Further improvements are possible by coating such thin films on large surface area electrodes with high aspect ratios (> 100) to increase the active surface area. Atomic layer deposition (ALD) is often preferred to deposit conformal thin film oxides on high aspect ratio structures. Such vapor-phase depositions are limited by the available surface reactive sites to deposit thin films of thickness ranging from sub-nanometer to few tens of nanometer. However, there is a tradeoff in terms of deposition time/cycles to achieve quality films especially when high aspect ratios (>100) substrates are introduced. Electrochemistry offers an alternative, versatile method to conformally coat layers on 3D electrode surfaces. The electrochemically assisted self-assembly (EASA) of mesoporous silica, utilizes electrochemical reactions to locally increase the pH near the electrode surface, which in turn catalyzes the silica gelation and surfactant self-assembly, thus causing the controlled growth of mesoporous silica thin films [1]. Recently, our group has shown that good quality mesoporous silica films with thickness between 20-2000 nm could be achieved by controlling the hydrodynamic layer in a rotating disc electrode setup [2]. Moreover, EASA of mesoporous silica offers meso-channels that are aligned perpendicular to the underlaying conductive substrate which is optimal for mass-transport.
In this follow-up work, we demonstrate a reliable, electrochemically controlled, conformal deposition of mesoporous silica onto large surface area nanomesh electrodes with an aspect ratio close to 100. Nanomesh electrodes developed in our group at imec, is built up of a regularly spaced (50 nm), inter-connected network of vertical and horizontal nanowires of diameter ~40 nm. These electrodes offer an 80x area enhancement (80 cm2 per geometric cm2) while maintaining a porosity close to 75%. We show that, the extent of silica deposition over these nanomesh electrodes can be electrochemically controlled from conformal coatings (~10 nm thick) uniformly coating the whole nanomesh architecture to complete fill and overfill of the nanomesh electrodes (~4 µm thick). Furthermore, excellent mass-transport properties of various silica coated nanomesh electrodes has been demonstrated using a ruthenium hexaammine redox probe. Finally, the area enhancement offered by the silica coated Ni nanomesh is demonstrated using the characteristic accumulation of a positively charged [Ru(NH3)6]3+ probe within the negatively charged silica nanochannels, which shows 55x increase for the amount of charge from the probe stored in the coated nanomesh, compared to a planar silica layer, consistent with the expected surface area enhancement of the 4 µm thick nanomesh electrodes.

References

[1] Walcarius Alain, et al. Nature materials 6.8 (2007): 602-608.
[2] Vanheusden Genis, et al. Chemistry of Materials 33.17 (2021): 7075-7088.

Figure 1