Highly ordered, mesoporous silica thin films with high mass-transport capabilities can be deposited on conductive substrates using the electrochemically assisted self-assembly method. State-of-the-art is, however, limited to films of 50−150 nm thickness, while for thicker layers, the undesired formation of aggregated particles becomes prevalent. In this work, we demonstrate that diffusion layer control using a rotating disk electrode is pivotal to yield aggregate-free films in a wide thickness range (11−2500 nm). The influence of the electrode rotation rate, deposition time/charge, and current as well as temperature on the deposition rate was studied. We show that the film thickness can be inferred from potential transients as the resistivity of the film becomes constant from about 500 nm. Fourier transform infrared spectroscopy, scanning electron microscopy, and transmission electron microscopy were used to determine the morphology and composition of the deposits while a redox probe demonstrated permeability through layers up to 1800 nm thickness. Finally, the coating of micropillars (2 μm diameter, 2 μm spacing, and 50 μm high) and filling of nanotrenches (50 nm wide, 50 nm spacing, and 125 nm deep) with mesoporous silica are shown. The reported results show the first aggregate-f ree thick layers and coating of threedimensional structured electrodes in a single deposition.

No abstract

The synthesis of ordered nanocomposite or nanoporous silica thin films by template-assisted sol-gel processes offers interesting applications in various fields including catalysis, sensors, membranes and energy. The electrochemically assisted self-assembly method allows the growth of highly ordered vertically aligned nanoporous silica thin films on conductive substrates. This orientation, optimized for high mass-transport capabilities, is difficult to obtain by classical approaches. The method involves submerging the conductive substrate in a pre-hydrolyzed precursor liquid followed by the application of a cathodic potential, thereby causing the electrogeneration of hydroxide ions. The pH increase in the diffusion layer near the electrode surface catalyzes the sol-gel formation and the result is a silica thin film that grows on the conductive substrate. The addition of cetyltrimethylammonium bromide (CTAB) micelle templates leads to the formation of a highly ordered nanostructure. A fundamental limitation of the method as reported in the literature is that the maximum layer thickness which can be obtained is rather limited due to the formation of aggregate by-products. In our contribution we show that diffusion layer thickness control is essential to obtain aggregate-free layers. Silica formation is catalyzed by OH- formed in the electrode’s diffusion layer, which quickly grows up to hundreds of microns under stationary conditions, thereby leading to composite thin films as well as precipitation of aggregates. By using a rotating disc electrode, the hydrodynamic layer is controlled, enabling aggregate-free film growth over a wide thickness range. Additionally, thin film coatings on high aspect ratio micropillar structures were demonstrated. Parameters such as precursor age, deposition temperature and deposition current were systematically investigated and the deposits were characterized using SEM, ellipsometry, TEM, FT-IR and an electrochemical redox probe. Using these techniques, we demonstrated the controlled growth of aggregate-free, uniform and nanostructured thin films with high mass-transport capabilities and thicknesses of 20 nm up to 15 µm, thereby significantly expanding the range of 50-150 nm as reported in literature. These results are explained using a single hydrodynamic layer model. Figure 1

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).