Copper formate complexes with various primary amines, secondary amines and pyridines were prepared, and their decomposition into conductive films was characterized. A comparison of the various complexes reveals that the temperature of thermolysis depends on the number of hydrogen bonds that can be formed between the amine and formate ligands. The particle size resulting from sintering of the copper complexes is shown to depend on the fraction of amine ligand released during the thermolysis reaction. The particle size in turn is shown to govern the electrical properties of the copper films. Correlations between the properties of the amines, such as boiling point and coordination strength, with the morphology and electrical performance of the copper films were established and provide a basis for the molecular design of copper formate molecular inks.

Abstract3D printing has enabled materials, geometries and functional properties to be combined in unique ways otherwise unattainable via traditional manufacturing techniques, yet its adoption as a mainstream manufacturing platform for functional objects is hindered by the physical challenges in printing multiple materials. Vat polymerization offers a polymer chemistry-based approach to generating smart objects, in which phase separation is used to control the spatial positioning of materials and thus at once, achieve desirable morphological and functional properties of final 3D printed objects. This study demonstrates how the spatial distribution of different material phases can be modulated by controlling the kinetics of gelation, cross-linking density and material diffusivity through the judicious selection of photoresin components. A continuum of morphologies, ranging from functional coatings, gradients and composites are generated, enabling the fabrication of 3D piezoresistive sensors, 5G antennas and antimicrobial objects and thus illustrating a promising way forward in the integration of dissimilar materials in 3D printing of smart or functional parts.

Pyridine derivatives coordinated to copper(ii) formates are shown to have lower decomposition temperatures than the alkylamine analogues. Using heating profiles compatible with low temperature substrates, deposited inks made from these compounds are transformed into copper traces with a resistivity value of 14 μΩ cm when sintered at 135 °C in <5 minutes.

Screen printing is the most common method used for the production of printed electronics. Formulating copper (Cu) inks that yield conductive fine features with oxidation and mechanical robustness on low-temperature substrates will open up opportunities to fabricate cost-effective devices. We have formulated a screen-printable Cu metal-organic decomposition (MOD) ink comprising Cu formate coordinated to 3-(diethylamino)-1,2-propanediol, a fractional amount of Cu nanoparticles (CuNPs), and a binder. This simple formulation enables ∼70–550 μm trace widths with excellent electrical [∼8–15 mΩ/□/mil or 20–38 μΩ·cm] and mechanical properties with submicron-thick traces obtained by intense pulse light (IPL) sintering on Kapton and poly­(ethylene terephthalate) (PET) substrates. These traces are mechanically robust to flexing and creasing where less than 10% change in resistance is observed on Kapton and ∼20% change is observed on PET. Solderable Cu traces were obtained only with the combination of the Cu MOD precursor, CuNP, and polymer binder. Both thermally and IPL sintered traces showed shelf stability (<10% change in resistance) of over a month in ambient conditions and 10–70% relative humidity, suitable for day-to-day fabrication. To demonstrate utility, light-emitting diodes (LEDs) were directly soldered to IPL sintered Cu traces in a reflow oven without the need for a precious metal interlayer. The LEDs were functional not only during bending and creasing of the Cu traces but even after 180 min at 140 °C in ambient air without losing illumination intensity. High definition television antennas printed on Kapton and PET were found to perform well in the ultrahigh frequency region. Lastly, single-walled carbon nanotube-based thin-film transistors on a silicon wafer were fabricated with a screen-printed Cu source and drain electrodes, which performed comparably to silver electrodes with mobility values of 12–15 cm2 V−1 s−1 and current on/off ratios of ∼105 and as effective ammonia sensors providing parts per billion-level detection.

A new broadband UV light‐based processing method for a screen printable silver oxalate molecular ink is developed that enables structural electronics to be produced on complex thermoformed 3D objects. The production of these 3D devices is driven by the light‐induced reduction of silver oxalate to form an interfacial silver nanoparticle layer that allows the ink to transition to a viscous liquid intermediate and elongate up to 50% without cracking during thermoforming. Ultimately, this enables the development of 3D electronics devices with significantly less limitations on geometry, shape, size, and depth in comparison to commercially available inks. UV processing is also effective for 2D traces on low temperature PET substrate, where in situ produced silver nanoparticles can subsequently absorb light and further facilitate the rapid conversion of the silver oxalate to metallic silver through a self‐limiting thermal decomposition. The resulting traces have superior electrical properties and are produced in significantly less time in comparison to thermal sintering. Together, UV processing and the silver oxalate molecular ink serve as a platform for both the rapid production of conductive silver traces on low temperature substrates and the development of novel thermoformed 3D human‐machine interface devices, areas of interest for both academia and industry.