Microprocessors, long-lasting batteries, and sensors are a number of examples of nanotechnology revolutionising our daily lives. Nanotechnology is the study, development, and manufacturing of structures and devices which derive unique and novel properties from nanoscale phenomena. To realise such structures and devices, a set of processes summarised under the term ’nanomanufacturing’ (NM) is required to fabricate at the nanoscale. NM includes a wide range of strategies and methods where nanoparticles (NPs) serve as one of the building blocks. Therefore, NP manipulation is essential to addressing the desired applications. Because of their flexibility and efficiency, direct writing (DW) methods have received considerable attention in many studies. With nanoparticle direct writing, patterns and features can be created locally on a surface without the need for lithography processes. Inkjet printing (IJP) and aerosol jet printing (AJP) are widely used DW NP deposition methods for creating patterns with a resolution of less than 100 μm. Both these methods deposit NP from the liquid phase and employ a variety of chemical agents, which can lead to contamination, affecting the properties of the film. Additionally, due to liquid-substrate interaction, high-resolution NP deposition using wet techniques necessitates proper surface modification. Compared to NP liquid-phase-based approaches, dry methods do not involve any chemical agent, thus reducing the possibility of contamination. To use dry-synthesised NPs in a direct-writing method, particles in a gas flow should be focused and deposited on a substrate. The main challenge in fabricating high-resolution patterns employing dry-synthesised NPs is the deposition of fine NPs (<100 nm) from the gas flow onto a defined location or region on the substrate due to their extremely small size and lower relaxation time (time required for a particle to adjust its velocity to a new condition). This dissertation presents a novel, simple, and solvent-free method for selective NP deposition on various substrates, enabling the DW of NPs...@en

One of the essential requirements to create nanoparticle (NP)-based applications and functions is the ability to control their deposition in specific locations. Many methods have been proposed, with wet direct writing (DW) techniques such as inkjet printing being the most employed. These methods generally depend on off-line and solvent-based NP synthesis leading to contamination and impurity in the final NP film as well as inhomogeneity in the deposition caused by solution-substrate interactions. This paper introduces a dry aerosol direct writing (dADW) method, which combines spark ablation-based and solvent-free NP synthesis with spatially selective deposition using aerodynamic focusing in a vacuum chamber. The challenge is to print high-resolution lines and spots of nanoparticles with a diameter < 100 nm. We study two aerodynamic nozzle concepts, a converging nozzle (CN) and a sheath gas nozzle (SGN), and investigate numerically how their design, as well as operating parameters, relate to the deposition process performance. This is quantified by three criteria: contraction factor, focusing ratio, and collection efficiency. We also compared our numerical results to experimental assays by manufacturing two SGNs and three CNs and evaluating the performance of each nozzle in terms of resolution, sharpness and thickness of the line. Using one of the SGN designs with an outlet diameter of 248 µm and an aerosol to total flow rate ratio of 0.17, we achieved a high-resolution line with a width of 67 µm, i.e., equal to 27% of the nozzle diameter, when printing < 100 nm Au NPs. The presented additive manufacturing method enables, therefore, the creation of high-resolution and sharp patterns of metallic nanoparticles, which can be employed in a wide range of applications, ranging from interconnects to optical and gas sensors.

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The ability to tune the localised surface plasmon resonance (LSPR) behaviour of metal nanostructures has great importance for many optical sensor applications such as metal (plasmon) enhanced fluorescence spectroscopy and surface-enhanced Raman scattering (SERS). In this paper, we used Aerosol Direct Writing (ADW) to selectively deposit fine gold nanoparticles (AuNPs) patterns. A low-temperature thermal post-treatment (below 200 °C) provides enough energy to merge and transform AuNPs into larger features significantly different from non-thermally treated samples. The optical behaviour of non-treated and thermally treated AuNP films was investigated by photoluminescence (PL) spectroscopy. The PL measurements showed a red-shift, compared to bulk gold, using 488 nm and 514 nm laser excitation, and a blue-shift using 633 nm laser excitation. The thermal post-treatment leads to a further blue-shift compared to non-treated samples in the presence of both 514 and 633 nm laser. Finally, the AuNPs patterns were employed as a SERS-active substrate to detect low-concentrated (10⁻⁸M) rhodamine B. This method's ability to selectively deposit 3D gold nanostructures and tune their optical behaviour through a low-temperature thermal treatment allows optimisation of the optical response and enhancement of the Raman signal for specific bio-analytes.

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Surface-enhanced Raman scattering (SERS) substrates are of great interest for detecting low-concentrated analytes. However, issues such as multistep processing, cost, and possible presence of hazardous substances in the fabrication still represent a significant drawback. In this paper, an innovative direct writing method is introduced for solvent-free and spatially selective deposition of fine metal copper nanoparticles (CuNPs), with size distribution below 20 nm, generated in-line through a spark ablation method (SAM). The deposited CuNPs' morphology and composition were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), and energy-dispersive X-ray spectroscopy (EDS). The resulting CuNP patterns feature porous 3D microdomains with nanometric structures serving as hot spots for Raman signal enhancement. Low-temperature post-treatment (below 200 °C) of the deposited CuNPs significantly evolves its morphology and leads to sintering of NPs into a semicrystalline structure with sharp geometric features, which resulted in a more than 10-fold increase of the enhancement factor (up to 2.1 × 105) compared to non-heat-treated samples. The proposed method allows creating SERS substrates constituted by sharp 3D metallic nanopatterns selectively deposited onto specific regions, which paves the way for new printed, highly sensitive SERS-based sensors.

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