A cost-effective, scalable and versatile method of preparing nano-ink without hazardous chemical precursors is a prerequisite for widespread adoption of printed electronics. Precursor-free synthesis by spark discharge is promising for this purpose. The synthesis of platinum nanoparticles (PtNPs) using a spark discharge under Ar, N2, and air has been investigated to prepare highly conductive nano-ink. The size, chemical composition, and mass production rate of PtNPs significantly depended on the carrier gas. Pure metallic PtNPs with sizes of 5.5 ± 1.8 and 7.1 ± 2.4 nm were formed under Ar and N2, respectively. PtNPs with sizes of 18.2 ± 9.0 nm produced using air consisted of amorphous oxide PtO and metallic Pt. The mass production rates of PtNPs were 53 ± 6, 366 ± 59, and 490 ± 36 mg/h using a spark discharge under Ar, N2, and air, respectively. It was found that the energy dissipated in the spark gap is not a significant parameter that determines the mass production rate. Stable Pt nano-ink (25 wt.%) was prepared only on the basis of PtNPs synthesized under air. Narrow (about 30 μm) and conductive Pt lines were formed by the aerosol jet printing with prepared nano-ink. The resistivity of the Pt lines sintered at 750 °C was (1.2 ± 0.1)·10−7 Ω·m, which is about 1.1 times higher than that of bulk Pt.
In this work, we studied the formation of conductive silver lines with high aspect ratios (AR = thickness/width) > 0.1 using the modernized method of aerosol jet printing on a heated silicon substrate. The geometric (AR) and electrical (resistivity) parameters of the formed lines were investigated depending on the number of printing layers (1–10 layers) and the temperature of the substrate (25–300 °C). The AR of the lines increased as the number of printing layers and the temperature of the substrate increased. An increase in the AR of the lines with increasing substrate temperature was associated with a decrease in the ink spreading as a result of an increase in the rate of evaporation of nano-ink. Moreover, with an increase in the substrate temperature of more than 200 °C, a significant increase in the porosity of the formed lines was observed, and as a result, the electrical resistivity of the lines increased significantly. Taking into account the revealed regularities, it was demonstrated that the formation of silver lines with a high AR > 0.1 and a low electrical resistivity of 2–3 μΩ∙cm is advisable to be carried out at a substrate temperature of about 100 °C. The adhesion strength of silver films formed on a heated silicon substrate is 2.8 ± 0.9 N/mm2, which further confirms the suitability of the investigated method of aerosol jet printing for electronic applications.
The demand for the development of local laser sintering of nanoparticle arrays is explained by the expanding needs for printed electronics for functional microstructure formation, on heat-sensitive substrates in particular. This work is based on the research into the sintering of arrays of silver nanoparticles synthesized in a spark discharge and deposited on a substrate by focused aerosol flow. The sintering was done by continuous and pulsed lasers with wavelengths 527, 980 and 1054 nm. Sintered samples were studied by measuring the resistivity, cross-section profile area and microstructure features. The highest average conductivity, equal to the half of the bulk silver conductivity, was achieved when sintering by continuous radiation with a wavelength 980 nm. The results showed that when using pulsed radiation the direct heating of nanoparticles in the sample surface layer dominates with the formation of a pore-free conductive layer of around 0.5 μm thick and crystallite of 70–80 nm size. It was found that laser sintering by radiation with a wavelength 527 nm required an order of magnitude lower specific energy costs as compared to the longwave laser radiation. The high energy efficiency of laser sintering is explained by special conditions for radiation absorption at plasmon resonance.
We proposed a novel method of nanostructure preparation for observation of surface-enhanced Raman spectroscopy (SERS) and metal-enhanced fluorescence (MEF) based on the deposition of gold nanoparticles (GNPs) above the thin dye film by dry aerosol printing. We detected various enhanced SERS and MEF signals of films of malachite green (MG) and rhodamine B (RhB) mixtures, depending on the surface packing density of Au NPs on the strip, and found the optimum one to achieve the 3.5 × 105 SERS enhancement. It was shown that statistical methods of chemometrics such as projection on latent structures provided the opportunity to distinguish SERS of MG from 100 ppm RhB in a mixture, whereas separation of MEF signals are feasible even for a mixture of MG and 1 ppm RhB due to two-photon excitation.
In this work, we have, for the first time, experimentally verified the hypothesis of reducing the agglomeration rate of aerosol nanoparticles produced by spark discharge upon decreasing the carrier gas temperature in the range of 24 °C to –183 °C. The synthesis of nanoparticles was implemented as a result of spark ablation of electrodes manufactured from Au with a purity of 99.998% installed in a specially designed gas chamber dipped into liquid nitrogen (−196 °C) to cool down the carrier gas supplied through one of hollow electrodes. It follows from the analysis of transmission electron microscopy images that both the average size of primary nanoparticles and the degree of their sintering become lower if the gas is cooled. For example, in the case of using nitrogen as a carrier gas, the average size of primary nanoparticles decreases from 9.4 nm to 6.6 nm as the gas temperature decreases from 24 °C to –183 °C. This also causes the aggregates to become more branched, manifested by the reduction in their solidity from 92% to 76%. The agglomeration model of Feng based on Smoluchowski theory was employed to calculate particle size distributions that were found to be consistent with the experimental data. The gold nanoparticles synthesized at room and cryogenic temperatures of the carrier gas (N₂, Ar + H₂, He) were used to pattern plasmonic nanostructures on ceramic alumina substrates by using aerosol jet printing technology for the purpose of demonstrating the possibility of their application in surface-enhanced Raman spectroscopy (SERS). The SERS enhancement factor was estimated at 2 × 106 from the analysis of SERS and normal Raman spectra of 1,2-bis(4-pyridyl)ethylene used as an analyte.
Solvent-free aerosol jet printing has been investigated for fabricating metallic and semiconductor (gas-sensitive) microstructures based on copper nanoparticles on alumina, borosilicate glass, and silicon substrates. The synthesis of nanoparticles was carried out using a spark discharge directly in the printing process without the stage of preparing nano-ink. Printed lines with a width of 100–150 µm and a height of 5–7 µm were formed from submicron agglomerates consisting of primary nanoparticles 10.8 ± 4.9 nm in size with an amorphous oxide shell. The electrical resistivity, surface morphology, and shrinkage of printed lines were investigated depending on the reduction sintering temperature. Sintering of copper oxides of nanoparticles began at a temperature of 450 °C in a hydrogen atmosphere with shrinkage at the level of 45–60%. Moreover, aerosol heat treatment was used to obtain highly conductive lines by increasing the packing density of deposited nanoparticles, providing in-situ transformation of submicron agglomerates into spherical nanoparticles with a size of 20–50 nm. Copper lines of spherical nanoparticles demonstrated excellent resistivity at 5 μΩ·cm, about three times higher than that of bulk copper. In turn, semiconductor microstructures based on unsintered agglomerates of oxidized copper have a fairly high sensitivity to NH3 and CO. Values of response of the sensor based on non-sintered oxidized copper nanoparticles to ammonia and carbon monoxide concentration of 40 ppm were about 20% and 80%, respectively.