During the past decade, significant progress has been made in the field of resonant optics ranging from fundamental aspects to concrete applications. While several techniques have been introduced for the fabrication of highly defined metallic nanostructures, the synthesis of complex, free-standing three-dimensional (3D) structures is still an intriguing, but so far intractable, challenge. In this study, we demonstrate a 3D direct-write synthesis approach that addresses this challenge. Specifically, we succeeded in the direct-write fabrication of 3D nanoarchitectures via electron-stimulated reactions, which are applicable on virtually any material and surface morphology. By that, complex 3D nanostructures composed of highly compact, pure gold can be fabricated, which reveal strong plasmonic activity and pave the way for a new generation of 3D nanoplasmonic architectures that can be printed on-demand.

Focused electron beam induced deposition (FEBID) is one of the few techniques that enables direct-write synthesis of free-standing 3D nanostructures. While the fabrication of simple architectures such as vertical or curving nanowires has been achieved by simple trial and error, processing complex 3D structures is not tractable with this approach. In part, this is due to the dynamic interplay between electron-solid interactions and the transient spatial distribution of absorbed precursor molecules on the solid surface. Here, we demonstrate the ability to controllably deposit 3D lattice structures at the micro/nanoscale, which have received recent interest owing to superior mechanical and optical properties. A hybrid Monte Carlo-continuum simulation is briefly overviewed, and subsequently FEBID experiments and simulations are directly compared. Finally, a 3D computer-aided design (CAD) program is introduced, which generates the beam parameters necessary for FEBID by both simulation and experiment. Using this approach, we demonstrate the fabrication of various 3D lattice structures using Pt-, Au-, and W-based precursors.

While 3D-printing is currently experiencing significant growth and having a significant impact on science and technology, the expansion into the nanoworld is still a highly challenging task. Among the increasing number of approaches, focused electron-beam-induced deposition (FEBID) was recently demonstrated to be a viable candidate toward a generic direct-write fabrication technology with spatial nanometer accuracy for complex shaped 3D-nanoarchitectures. In this comprehensive study, we explore the parameter space for 3D-FEBID and investigate the implications of individual and interdependent parameters on freestanding nanosegments, which act as a fundamental building block for complex 3D-structures. In particular, the study provides new basic insights such as precursor transport limitations and angle dependent growth rates, both essential for high-fidelity fabrication. Complemented by practical aspects, we provide both basic insights in 3D-growth dynamics and technical guidance for specific process adaption to enable predictable and reliable direct-write synthesis of freestanding 3D-nanoarchitectures.