Direct visualization of nanoparticle morphology in thermally sintered nanoparticle ink traces and the relationship among nanoparticle morphology, incomplete polymer removal, and trace conductivity.

A key challenge encountered by printed electronics is that the conductivity of sintered metal nanoparticle (NP) traces is always several times smaller than the bulk metal conductivity. Identifying the relative roles of the voids and the residual polymers on NP surfaces in sintered NP traces, in determining such reduced conductivity, is essential. In this paper, we employ a combination of electron microscopy imaging and detailed simulations to quantify the relative roles of such voids and residual polymers in the conductivity of sintered traces of a commercial (Novacentrix) silver nanoparticle-based ink. High resolution transmission electron microscopy imaging revealed details of the morphology of the inks before and after being sintered at 150 °C. Prior to sintering, NPs were randomly close packed into aggregates with nanometer thick polymer layers in the interstices. The 2D porosity in the aggregates prior to sintering was near 20%. After heating at 150 °C, NPs sintered together into dense aggregates (nanoaggregates or NAgs) with sizes ranging from 100 to 500 nm and the 2D porosity decreased to near 10%. Within the NAgs, the NPs were mostly connected via sintered metal bridges, while the outer surfaces of the NAgs were coated with a nanometer thick layer of polymer. Motivated by these experimental results, we developed a computational model for calculating the effective conductivity of the ink deposit represented by a prototypical NAg consisting of NPs connected by metallic bonds and having a polymer layer on its outer surface placed in a surrounding medium. The calculations reveal that a NAg that is 35%-40% covered by a nanometer thick polymeric layer has a similar conductivity compared to prior experimental measurements. The findings also demonstrate that the conductivity is less influenced by the polymer layer thickness or the absolute value of the NAg dimensions. Most importantly, we are able to infer that the reduced value of the conductivity of the sintered traces is less dependent on the void fraction and is primarily attributed to the incomplete removal of the polymeric material even after sintering.

Numerical Study of the Coalescence and Mixing of Drops of Different Polymeric Materials.

In this study, we employ direct numerical simulation (DNS) to investigate the solutal hydrodynamics dictating the three-dimensional coalescence of microscopic, identical-sized sessile drops of different but miscible shear-thinning polymeric liquids (namely, PVAc or polyvinyl acetate and PMMA or polymethylmethacrylate), with the drops being in partially wetted configuration. Despite the ubiquitousness of the interaction of different dissimilar droplets in a variety of engineering problems ranging from additive manufacturing to understanding the behavior of photonic crystals, coalescence of drops composed of different polymeric and non-Newtonian materials has not been significantly explored. Interaction of such dissimilar droplets often involves simultaneous drop spreading, coalescence, and mixing. The mixing dynamics of the dissimilar drops are governed by interphase diffusion, the residual kinetic energy of the drops stemming from the fact that coalescence starts before the spreading of the drops have been completed, and the solutal Marangoni convection. We provide the three-dimensional velocity fields and velocity vectors inside the completely miscible, dissimilar coalescing droplets. Our simulations explicate the relative influence of these different effects in determining the flow field at different locations and at different time instances and the consequent mixing behavior inside the interacting drops. We also show the non-monotonic (in terms of the direction of migration) propagation of the mixing front of the miscible coalescing drops over time. We also establish that the overall mixing (on either side of the mixing front) speeds up as the Marangoni effects dictate the mixing. We anticipate that our study will provide an important foundation for studying miscible multi-material liquid systems, which will be crucial for applications such as inkjet or aerosol jet printing, lab-on-a-chip, polymer processing, etc.

Coalescence of Microscopic Polymeric Drops: Effect of Drop Impact Velocities.

In this paper, we employ the direct numerical simulation (DNS) method for probing three-dimensional, axisymmetric coalescence of microscale, power-law-obeying, and shear-thinning polymeric liquid drops of identical sizes impacting a solid, solvophilic substrate with a finite velocity. Unlike the cases of drop coalescence of Newtonian liquid drops, coalescence of non-Newtonian polymeric drops has received very little attention. Our study bridges this gap by providing (1) the time-dependent, three-dimensional (3D) velocity field and 3D velocity vectors inside two coalescing polymeric drops in the presence of a solid substrate and (2) the effect of the drop impact velocity (on the solid substrate), quantified by the Weber number (We), on the coalescence dynamics. Our simulations reveal that the drop coalescence is qualitatively similar for different We values, although the velocity magnitudes involved, the time required to attain different stages of coalescence, and the time needed to attain equilibrium vary drastically for finitely large We values. Finally, we provide detailed simulation-based, as well as physics-based, scaling laws describing the growth of the height and the width of the bridge (formed due to coalescence) dictating the 3D coalescence event. Our analyses reveal distinct scaling laws for the growth of bridge height and width for early and late stages of coalescence as a function of We. We also provide simulation-based coalescence results for the case of two unequal sized drops impacting on a substrate (nonaxisymmetric coalescence) as well as results for axisymmetric coalescence for drops of different rheology. We anticipate that our findings will be critical in better understanding events such as inkjet or aerosol jet polymer printing, dynamics of polymer blends, and many more.

High-quality uniform dry transfer of graphene to polymers.

In this paper we demonstrate high-quality, uniform dry transfer of graphene grown by chemical vapor deposition on copper foil to polystyrene. The dry transfer exploits an azide linker molecule to establish a covalent bond to graphene and to generate greater graphene-polymer adhesion compared to that of the graphene-metal foil. Thus, this transfer approach provides a novel alternative route for graphene transfer, which allows for the metal foils to be reused.

Formation of silicon-based molecular electronic structures using flip-chip lamination.

We report the fabrication of molecular electronic test structures consisting of Au-molecule-Si junctions by first forming omega-functionalized self-assembled monolayers on ultrasmooth Au on a flexible substrate and subsequently bonding to Si(111) with flip-chip lamination by using nanotransfer printing (nTP). Infrared spectroscopy (IRS), spectroscopic ellipsometry (SE), water contact angle (CA), and X-ray photoelectron spectroscopy (XPS) verified the monolayers self-assembled on ultrasmooth Au were dense, relatively defect-free, and the -COOH was exposed to the surface. The acid terminated monolayers were then reacted with a H-terminated Si(111) surface using moderate applied pressures to facilitate the interfacial reaction. After molecular junction formation, the monolayers were characterized with p-polarized backside reflection absorption infrared spectroscopy (pb-RAIRS) and electrical current-voltage measurements. The monolayer quality remains largely unchanged after lamination to the Si(111) surface, with the exception of changes in the COOH and Si-O vibrations indicating chemical bonding. Both vibrational and electrical data indicate that electrical contact to the monolayer is formed while preserving the integrity of the molecules without metal filaments. This approach provides a facile means to fabricate high-quality molecular junctions consisting of dense monolayers chemically bonded to metal and silicon electrodes.