Precise Electrodeposition of Mo 6 ‐Cluster Thin Films: Mechanistic Pathways to Ambipolar Photoelectrodes With Tailored Microstructure
Abstract
Photoelectrodes based on transition metal clusters (MCs) are critical for advancing solar energy conversion, where precise control over film morphology and electronic properties is essential. While electrophoretic deposition (EPD) has been widely used for the design of MCs-based photoelectrodes, its intrinsic limitations—such as poor film homogeneity, crack formation, and limited microstructural control—compromise device performance. In this study, we demonstrate that electrodeposition (ED) of [{Mo6Ii8}Ia6]2− clusters produces homogeneous, crack-free films with the composition [{Mo6Ii8}Ia4(H2O)a2}]·xH2O. The ED process, driven by a two-step oxidation mechanism (1.1 and 1.6 V vs. Ag/AgCl), enables unprecedented control over film thickness (60–600 nm) and microstructure, resulting in increased photoconductivity (photocurrent 2–3 times higher and lower charge transfer resistance, Rtc ∼ 500 Ω). The films exhibit ambipolar conductivity and a quasi-pinned mid-gap Fermi level, confirming their potential for high-performance solar energy applications. Compared to EPD-derived films, ED films show enhanced charge extraction efficiency and minimized recombination losses, which are attributed to their defect-free microstructure and stable electronic properties. This work establishes ED as a superior method for fabricating high-quality MC-based photoelectrodes, addressing key limitations of traditional deposition techniques.
Related
- Hard carbon anodes for sodium-ion batteries: from mechanistic reconciliation, precursor-tailored microstructure regulation to industrial scale-up
- Phytogenic zinc oxide nanoparticles in breast cancer therapy: an ethnopharmacological perspective on multi-targeted mechanistic pathways and translational constraints
- Stable Cu2O/TiO2 nanorod photoelectrodes for enhanced photoelectrochemical water splitting in ethanol-assisted systems
- Molybdenum cluster iodides for improved CsPbBr 3 perovskite photoelectrodes: a superatomic approach to stability, passivation, and optoelectronic performance
- Copper electrodeposition localized in picoliter droplets using microcantilever arrays
BibTeX
@article{gendre2026precise,
title = {{Precise Electrodeposition of Mo 6 ‐Cluster Thin Films: Mechanistic Pathways to Ambipolar Photoelectrodes With Tailored Microstructure}},
author = {Antoine Le Gendre and Kurt Kpoton and Noee Dumait and Maria Amela-Cortes and Stéphane Cordier and Adèle Renaud},
journal = {ChemPhotoChem},
year = {2026},
month = jul,
doi = {10.1002/cptc.70217},
url = {https://hal.science/hal-05742443v1},
note = {CC BY-NC 4.0},
}
RIS
TY - JOUR
TI - Precise Electrodeposition of Mo 6 ‐Cluster Thin Films: Mechanistic Pathways to Ambipolar Photoelectrodes With Tailored Microstructure
AU - Antoine Le Gendre
AU - Kurt Kpoton
AU - Noee Dumait
AU - Maria Amela-Cortes
AU - Stéphane Cordier
AU - Adèle Renaud
PY - 2026
DA - 2026/07/10
JO - ChemPhotoChem
DO - 10.1002/cptc.70217
UR - https://hal.science/hal-05742443v1
AB - Photoelectrodes based on transition metal clusters (MCs) are critical for advancing solar energy conversion, where precise control over film morphology and electronic properties is essential. While electrophoretic deposition (EPD) has been widely used for the design of MCs-based photoelectrodes, its intrinsic limitations—such as poor film homogeneity, crack formation, and limited microstructural control—compromise device performance. In this study, we demonstrate that electrodeposition (ED) of [{Mo6Ii8}Ia6]2− clusters produces homogeneous, crack-free films with the composition [{Mo6Ii8}Ia4(H2O)a2}]·xH2O. The ED process, driven by a two-step oxidation mechanism (1.1 and 1.6 V vs. Ag/AgCl), enables unprecedented control over film thickness (60–600 nm) and microstructure, resulting in increased photoconductivity (photocurrent 2–3 times higher and lower charge transfer resistance, Rtc ∼ 500 Ω). The films exhibit ambipolar conductivity and a quasi-pinned mid-gap Fermi level, confirming their potential for high-performance solar energy applications. Compared to EPD-derived films, ED films show enhanced charge extraction efficiency and minimized recombination losses, which are attributed to their defect-free microstructure and stable electronic properties. This work establishes ED as a superior method for fabricating high-quality MC-based photoelectrodes, addressing key limitations of traditional deposition techniques.
SN - 2367-0932
ER -