Thin-wall Single-crystal Gold Nanoelectrodes towards Advanced Chemical Probing and Imaging

Milad Sabzehparvar; Fatemeh Kiani; Germán García Martínez; Omer Can Karaman; Victor Boureau; Lucie Navratilova; Giulia Tagliabue

arXiv · 2504.19892

Thin-wall Single-crystal Gold Nanoelectrodes towards Advanced Chemical Probing and Imaging

Milad Sabzehparvar·Fatemeh Kiani·Germán García Martínez·Omer Can Karaman·Victor Boureau·Lucie Navratilova·Giulia Tagliabue

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Abstract

Thin-wall metal ultramicro- and nanoelectrodes (UMEs/NEs), especially gold NEs, are indispensable for high-resolution electrochemical microscopy, biosensing, and fundamental research. However, their damage susceptibility and the lack of scalable fabrication methods hinder broader adoption. We present a versatile wet-chemical approach for high-throughput fabrication of thin-wall Au NEs/UMEs and multifunctional NEs with ~80% reproducibility. This method is based on a unique template-assisted 1D growth of single-crystalline Au in borosilicate nanopipettes followed by electrochemical contacting with tungsten microwires, and focused ion beam milling, ensuring precise control over NEs dimensions. Adaptable to various metals and integrable in multifunctional probes, the method facilitates batch production of high-quality NEs with standardized electrical connections. Structural and electrochemical characterization reveals a twinned single-crystalline Au core, a seamless Au/glass interface, and highly stable electrochemical performance. Notably, smaller electrodes exhibit higher current densities, enhancing chemical detection sensitivity. Specifically, we demonstrate outstanding spatial (< 200 nm) and current (< 1 pA) resolutions, low limit of detection (~11.0 μM) and high stability (7 h) in scanning photoelectrochemical microscopy (photo-SECM), by detecting photo-oxidation reaction on atomically smooth Au micro-flakes. We also demonstrate growth in double-barrel pipettes for SECM/SICM probes as well as Pt NEs. Overall, this scalable method addresses longstanding challenges in NEs, paving the way for advanced electrochemical and spectro-electrochemical microscopy, including SERS/TERS integration. With single-crystalline surfaces, these electrodes open new frontiers in catalysis, interfacial electrochemistry, biosensing, and molecular-scale investigations.

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Milad Sabzehparvar, Fatemeh Kiani, Germán García Martínez, Omer Can Karaman, Victor Boureau, Lucie Navratilova, Giulia Tagliabue. 2025-04-28. Thin-wall Single-crystal Gold Nanoelectrodes towards Advanced Chemical Probing and Imaging. https://arxiv.org/abs/2504.19892

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