Additive Nanomanufacturing of Multimaterial 3D Core-Shell Functional Microarchitectures

The development of micro/nanoscale functional systems has created a growing demand for compact electrochemical components. Three dimensional core-shell electrochemical microarchitectures are especially promising because they combine efficient footprint utilization, rapid electron transport, and large active surface areas. Their realization, however, requires high spatial precision, programmable 3D geometries, and site-selective integration of multiple functional materials. Two-photon polymerization (TPP) offers the required resolution and geometric freedom, but converting TPP-defined polymer architectures into high-fidelity, high-conductivity 3D structures and achieving heterogeneous multimaterial integration remain challenging. Here, we present an additive nanomanufacturing with conformal electrodeposition (ANCE) strategy for the high-fidelity site-selective heterogeneous integration of multiple functional materials into complex 3D core-shell microarchitectures. TPP-printed polymer structures are first converted into high-fidelity 3D Au frameworks, which subsequently serve as conductive scaffolds for the site-selective electrodeposition of diverse functional materials, including metals, alloys, and metal oxides, circumventing repeated resin exchange or nanoscale realignment issues. As a proof of concept, MnOx and Zn are sequentially electrodeposited onto the spatially separated 3D Au frameworks, forming an on-chip 3D zinc-ion microbattery prototype. The assembled device exhibits reversible electrochemical operation and powers a microscale UV photosensor fabricated via femtosecond laser direct writing. This strategy provides a promising route from TPP-defined geometries to miniaturized core-shell multimaterial electrochemical devices.