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Item type:Publication, Access status: with files , Wafer-scale fabrication of mesoporous silicon functionalized with electrically conductive polymers(Elsevier, 2024-08-01); ; ; The fabrication of hybrid materials consisting of nanoporous hosts with conductive polymers is a challenging task, since the extreme spatial confinement often conflicts with the stringent physico-chemical requirements for polymerization of organic constituents. Here, several low-threshold and scalable synthesis routes for such hybrids are presented. First, the electrochemical synthesis of composites based on mesoporous silicon (pSi) and the polymers PANI, PPy and PEDOT is discussed and validated by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDX). Polymer filling degrees of ≥74 % are achieved. Second, the production of PEDOT/pSi hybrids, based on the solid-state polymerization (SSP) of DBEDOT to PEDOT is shown. The resulting amorphous structure of the nanopore-embedded PEDOT is investigated via in-situ synchrotron-based X-ray scattering. In addition, a twofold increase in the electrical conductivity of the hybrid compared to the porous silicon host is shown, making this system particularly promising for thermoelectric applications.Publicationtype: Journal Article16 55 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: with files , How nanoporous silicon-polypyrrole hybrids flex their muscles in aqueous electrolytes: in operando high-resolution x-ray diffraction and electron tomography-based micromechanical computer simulations(American Physical Society (APS), 2022-11-28); ; ; ; Macroscopic strain experiments have revealed that silicon crystals traversed by parallel, channel-like nanopores functionalized with the artificial muscle polymer polypyrrole (PPy) exhibit large and reversible electrochemomechanical actuation in aqueous electrolytes. On a macroscopic scale these actuation properties are well understood. However, on the microscopical level this system still bears open questions, as to how the electrochemical expansion and contraction of PPy acts on to np-Si pore walls and how the collective motorics of the pore array emerges from the single-nanopore behavior. Here we present synchrotron-based, in operando x-ray diffraction on the evolving electrostrains in epilayers of this material grown on bulk silicon. An analysis of these experiments with micromechanical finite-element simulations, that are based on a full three-dimensional reconstruction of the nanoporous medium by transmission electron microscopy (TEM) tomography, shows that the in-plane mechanical response is dominantly isotropic despite the anisotropic elasticity of the single-crystalline host matrix. However, the structural anisotropy originating from the parallel alignment of the nanopores led to significant differences between the in- and out-of-plane electromechanical response. This response is not describable by a simple two-dimensional arrangement of parallel cylindrical channels. Rather, the simulations highlight that the dendritic shape of the silicon pore walls, including pore connections between the main channels, causes complex, highly inhomogeneous stress-strain fields in the crystalline host. Time-dependent x-ray scattering experiments on the dynamics of the actuator properties hint towards the importance of diffusion limitations, plastic deformation, and creep in the nanoconfined polymer upon (counter)ion adsorption and desorption, the very pore-scale processes causing the macroscopic electroactuation. From a more general perspective, our study demonstrates that the combination of TEM tomography-based micromechanical modeling with high-resolution x-ray scattering experiments provides a powerful approach for in operando analysis of nanoporous composites from the single nanopore up to the porous-medium scale.Publicationtype: Journal ArticleScopus© Citations 5 54 55 - Some of the metrics are blocked by yourconsent settings
Item type:Publication, Access status: with files , Synthesis of organic–inorganic hybrids based on the conjugated polymer P3HT and mesoporous silicon(Elsevier, 2022-08-13); ; ; ; Organic–inorganic hybrids are a class of functional materials that combine favorable properties of their constituents to achieve an overall improved performance for a wide range of applications. This article presents the synthesis route for P3HT-porous silicon hybrids for thermoelectric applications. The conjugated polymer P3HT is incorporated into the porous silicon matrix by means of melt infiltration. Gravimetry, sorption isotherms and energy dispersive X-ray spectroscopy (EDX) mapping indicate that the organic molecules occupy more than 50% of the void space in the inorganic host. We demonstrate that subsequent diffusion-based doping of the confined polymer in a FeCl3 solution increases the electrical conductivity of the hybrid by five orders of magnitude compared to the empty porous silicon host.Publicationtype: Journal ArticleScopus© Citations 6 48 71