(Invited) Electrochemically Induced Deposition of Thin-Film Oxides and Electronic Insulators
Authors: Vereecken Philippe M. , Vanheusden Genis 
Published: July 2022

Electrodeposition is typically associated with the electroreduction of metal ions for the deposition of metals, alloys or semiconductors. Compounds can be electrodeposited when the metal ions form an insoluble compound upon change of its valence state at the electrode surface. A well-known example is the anodic deposition of MnO2, where aqueous solvated Mn2+ ions are oxidized to the insoluble Mn(IV) in acid sulfate solutions. Alternatively, the precipitation of a compound or oxide can be triggered by changing the local pH at the electrode by a suitable electrochemical reaction. The use of electrochemical formed base from so-called probase molecules has found applications in formation of oxides, phosphates but also organic materials such metal organic frameworks (MOFs). Nitrate was one of the first pro-bases suggested for the electrochemical precipitation of ZnO. An alternate electrochemical approach for depositing compounds and oxides is the electrochemical initiation of a sol-gel reaction first developed for the silica sol-gel process by Shacham et al. [1] During deposition, an electrode is submerged into a precursor solution followed by the application of a cathodic current. The chemical reaction is triggered by electro-generating the OH- catalyst that is required for the polycondensation of the silica precursor. Since this occurs near the surface, the method results in silica thin films deposited only on the electrode surface. Finally, also electro-polymerization can lead to thin insulating films. In this paper, several of these reaction paths will be explored. The initial stages of MnO2 electrodeposition are strongly dependent on the starting surface and determines the adhesion and attainable film thickness [2]. The relationship between (intentionally) introduced meso-porosity, growth rate and film thickness will be discussed. The poor electronic conductivity of oxides makes that the reaction is maintained by ionic conduction through the films, similar as for oxide formation by anodization. For the formation of micron thick oxide films, also good control of hydrodynamic conditions is essential. [3] The resistive nature of the layers typically allows also for good conformality over high aspect ratio substrates. Conformal deposition of oxide thin-film coatings on high aspect ratio structures is typically claimed by Atomic Layer Deposition. Inorganic-organic hybrid films such as metal cones can be similarly deposited by Molecular Layer Deposition (MLD). [4] The nature of the surface limited reactions of these vapor-phase methods allows for the formation of continuous sub-nanometer to a few tens of nanometer thin films with uniform thickness over the most complex architectures. The accuracy of the technique goes at the cost of long deposition cycles especially when very large surface areas with extreme aspect ratios (>100) are involved. The intrinsic resistive nature of the electrodeposited oxide and insulator films allows for excellent conformal coatings with growth rates much more suited for thicker films without loss in conformality or uniformity. In this paper, we will show examples where electrochemical induced deposition process are used also to coat nano-architectures such as our nanomesh with very large surface area (100 cm2 per planar cm2) and aspect ratio (100x).

[1] Shacham, B. R., Avnir, D. & Mandler, D. Electrodeposition of Methylated Sol-Gel Films on Conducting Surfaces. Adv. Mater. 384–388 (1999).

[2] "Electrodeposition of Adherent Submicron to Micron Thick Manganese Dioxide Films with Optimized Current Collector Interface for 3D Li-Ion Electrodes" Marina Timmermans, Nouha Labyedh, Felix Mattelaer, Stanislaw Zankowski, Stella Deheryan, Christophe Detavernier, and Philippe M. Vereecken, J. Electrochem. Soc. 164, 14, D954-D963 (2017).

[3] Aggregate-Free Micrometer-Thick Mesoporous Silica Thin Films on Planar and Three-Dimensional Structured Electrodes by Hydrodynamic Diffusion Layer Control during Electrochemically Assisted Self-Assembly”, G Vanheusden, H Philipsen, SJF Herregods, PM Vereecken, Chemistry of Materials (2021).

[4] “Molecular Layer Deposition of "Magnesicone", a Magnesium-based Hybrid Material" Jeroen Kint, Felix Mattelaer, Sofie S. T. Vandenbroucke, Arbresha Muriqi, Matthias M. Minjauw, Mikko Nisula, Philippe M. Vereecken, Michael Nolan, Jolien Dendooven, and Christophe Detavernier, Chem. Mater. 32, 11, 4451–4466, (2020).