Nanoscale Vertical Resolution in Optical Printing of Inorganic Nanoparticles.

Direct optical printing of functional inorganics shows tremendous potential as it enables the creation of intricate two-dimensional (2D) patterns and affordable design and production of various devices. Although there have been recent advancements in printing processes using short-wavelength light or pulsed lasers, the precise control of the vertical thickness in printed 3D structures has received little attention. This control is vital to the diverse functionalities of inorganic thin films and their devices, as they rely heavily on their thicknesses. This lack of research is attributed to the technical intricacy and complexity involved in the lithographic processes. Herein, we present a generalized optical 3D printing process for inorganic nanoparticles using maskless digital light processing. We develop a range of photocurable inorganic nanoparticle inks encompassing metals, semiconductors, and oxides, combined with photolinkable ligands and photoacid generators, enabling the direct solidification of nanoparticles in the ink medium. Our process creates complex and large-area patterns with a vertical resolution of ∼50 nm, producing 50-nm-thick 2D films and several micrometer-thick 3D architectures with no layer height difference via layer-by-layer deposition. Through fabrication and operation of multilayered switching devices with Au electrodes and Ag-organic resistive layers, the feasibility of our process for cost-effective manufacturing of multilayered devices is demonstrated.

3D microprinting of inorganic porous materials by chemical linking-induced solidification of nanocrystals.

Three-dimensional (3D) microprinting is considered a next-generation manufacturing process for the production of microscale components; however, the narrow range of suitable materials, which include mainly polymers, is a critical issue that limits the application of this process to functional inorganic materials. Herein, we develop a generalised microscale 3D printing method for the production of purely inorganic nanocrystal-based porous materials. Our process is designed to solidify all-inorganic nanocrystals via immediate dispersibility control and surface linking-induced interconnection in the nonsolvent linker bath and thereby creates multibranched gel networks. The process works with various inorganic materials, including metals, semiconductors, magnets, oxides, and multi-materials, not requiring organic binders or stereolithographic equipment. Filaments with a diameter of sub-10 µm are printed into designed complex 3D microarchitectures, which exhibit full nanocrystal functionality and high specific surface areas as well as hierarchical porous structures. This approach provides the platform technology for designing functional inorganics-based porous materials.