Subtractive Patterning of Nanoscale Thin Films Using Acid-Based Electrohydrodynamic-Jet Printing.

As an alternative to traditional photolithography, printing processes are widely explored for the patterning of customizable devices. However, to date, the majority of high-resolution printing processes for functional nanomaterials are additive in nature. To complement additive printing, there is a need for subtractive processes, where the printed ink results in material removal, rather than addition. In this study, a new subtractive patterning approach that uses electrohydrodynamic-jet (e-jet) printing of acid-based inks to etch nanoscale zinc oxide (ZnO) thin films deposited using atomic layer deposition (ALD) is introduced. By tuning the printing parameters, the depth and linewidth of the subtracted features can be tuned, with a minimum linewidth of 11 µm and a tunable channel depth with ≈5 nm resolution. Furthermore, by tuning the ink composition, the volatility and viscosity of the ink can be adjusted, resulting in variable spreading and dissolution dynamics at the solution/film interface. In the future, acid-based subtractive patterning using e-jet printing can be used for rapid prototyping or customizable manufacturing of functional devices on a range of substrates with nanoscale precision.

Integrating Structural Colors with Additive Manufacturing Using Atomic Layer Deposition.

We demonstrate tunable structural color patterns that span the visible spectrum using atomic layer deposition (ALD). Asymmetric metal-dielectric-metal structures were sequentially deposited with nickel, zinc oxide, and a thin copper layer to form an optical cavity. The color response was precisely adjusted by tuning the zinc oxide (ZnO) thickness using ALD, which was consistent with model predictions. Owing to the conformal nature of ALD, this allows for uniform and tunable coloration of non-planar three-dimensional (3D) objects, as exemplified by adding color to 3D-printed parts produced by metal additive manufacturing. Proper choice of inorganic layered structures and materials allows the structural color to be stable at elevated temperatures, in contrast to traditional paints. To print multiple colors on a single sample, polymer inhibitors were patterned in a desired geometry using electrohydrodynamic jet (e-jet) printing, followed by area-selective ALD in the unpassivated regions. The ability to achieve 3D color printing, both at the micro- and macroscales, provides a new pathway to tune the optical and aesthetic properties during additive manufacturing.

Area-Selective Atomic Layer Deposition Patterned by Electrohydrodynamic Jet Printing for Additive Manufacturing of Functional Materials and Devices.

There is an increasing interest in additive nanomanufacturing processes, which enable customizable patterning of functional materials and devices on a wide range of substrates. However, there are relatively few techniques with the ability to directly 3D print patterns of functional materials with sub-micron resolution. In this study, we demonstrate the use of additive electrohydrodynamic jet (e-jet) printing with an average line width of 312 nm, which acts as an inhibitor for area-selective atomic layer deposition (AS-ALD) of a range of metal oxides. We also demonstrate subtractive e-jet printing with solvent inks that dissolve polymer inhibitor layers in specific regions, which enables localized AS-ALD within those regions. The chemical selectivity and morphology of e-jet patterned polymers towards binary and ternary oxides of ZnO, Al2O3, and SnO2 were quantified using X-ray photoelectron spectroscopy, atomic force microscopy, and Auger electron spectroscopy. This approach enables patterning of functional oxide semiconductors, insulators, and transparent conducting oxides with tunable composition, Å-scale control of thickness, and sub-µm resolution in the x-y plane. Using a combination of additive and subtractive e-jet printing with AS-ALD, a thin-film transistor was fabricated using zinc-tin-oxide for the semiconductor channel and aluminum-doped zinc oxide as the source and drain electrical contacts. In the future, this technique can be used to print integrated electronics with sub-micron resolution on a variety of substrates.