Reactive multilayer systems represent an innovative approach for potential usage in chip joining applications. As there are several factors governing the energy release rate and the stored chemical energy, the impact of the morphology and the microstructure on the reaction behavior is of great interest. In the current work, 3D reactive microstructures with nanoscale Al/Ni multilayers were produced by alternating deposition of pure Ni and Al films onto nanostructured Si substrates by magnetron sputtering. In order to elucidate the influence of this 3D morphology on the phase transformation process, the microstructure and the morphology of this system were characterized and compared with a flat reactive multilayer system on a flat Si wafer. The characterization of both systems was carried out before and after a rapid thermal annealing treatment by using scanning and transmission electron microscopy of the cross sections, selected area diffraction analysis, and differential scanning calorimetry. The bent shape of multilayers caused by the complex topography of silicon needles of the nanostructured substrate was found to favor the atomic diffusion at the early stage of phase transformation and the formation of two intermetallic phases Al_0.42Ni_0.58 and AlNi₃, unlike the flat multilayers that formed a single phase AlNi after reaction.

Fast energy release, which is a fundamental property of reactive multilayer systems, can be used in a wide field of applications. For most applications, a self-propagating reaction and adhesion between the multilayers and substrate are necessary. In this work, a distinct approach for achieving self-propagating reactions and adhesion between deposited Ni/Al reactive multilayers and silicon substrate is demonstrated. The silicon surface consists of random structures, referred to as silicon grass, which were created by deep reactive ion etching. Using the etching process, structure units of heights between 8 and 13 µm and density between 0.5 and 3.5 structures per µm² were formed. Ni and Al layers were alternatingly deposited in the stoichiometric ratio of 1:1 using sputtering, to achieve a total thickness of 5 µm. The analysis of the reaction and phase transformation was done with high-speed camera, high-speed pyrometer, and X-ray diffractometer. Cross-sectional analysis showed that the multilayers grew only on top of the silicon grass in the form of inversed cones, which enabled adhesion between the silicon grass and the reacted multilayers. A self-propagating reaction on silicon grass was achieved, due to the thermally isolating air pockets present around these multilayer cones. The velocity and temperature of the reaction varied according to the structure morphology. The reaction parameters decreased with increasing height and decreasing density of the structures. To analyze the exact influence of the morphology, further investigations are needed.

Surface structuring methods are crucial in semiconductor manufacturing, as they enable the creation of intricate structures on the semiconductor surface, influencing the material's electrical, mechanical, and chemical properties. Herein, one such structuring method known as reactive ion etching to create black Si structures on silicon substrates is employed. After thermal oxidation, their influence on the reaction of Al/Ni nanoscale multilayers is studied. It reveals distinct reactive behaviors without corresponding differences in energy release during differential scanning calorimetry measurements. Higher oxidized black Si structure densities result in elevated temperatures and faster reaction propagation, showing fewer defects and reduced layer connections in cross‐sectional analyses. The properties of the reactive multilayers (RML) on high structure density show the same performance as a reaction on flat thermal SiO₂, causing delamination when exceeding 23 structures per μm². Conversely, lower structure density ensures attachment of RML to the substrate due to an increased number of defects, acting as predetermined breaking points for the AlNi alloy. By establishing the adhesion between the reacted multilayer and the substrate, surface structuring could lead to a potential increase in bond strength when using RML for bonding.

The influence of intentionally externally induced cracks in reactive Al/Ni multilayer systems is investigated. These cracks affect the reaction dynamics and enable tailoring of the reaction path and the overall velocity of the reaction front. The influence of layer variations onto mechanical crack formation and resulting reaction behavior are investigated. High‐speed camera imaging shows the meandering propagation of the reaction front along the crack paths. Therefore, the mechanical cracking process significantly changes the total velocity of the reaction front and thus offers a possibility to control the self‐propagating high‐temperature synthesis process. It is shown that the phase formation remains unaffected despite the applied strains and cracks. This favorable stability in phase formation ensures predictability and provides insight into the adaptation of RMS for precision applications in joints. The results expand the understanding of mechanical cracking as a tool to influence high‐temperature synthesis in reactive multilayer coatings and provide an opportunity to expand the range of applications.

Free‐standing Ni/Al multilayer films with a planar morphology, a bilayer thickness of 20 nm, and an average composition of Ni₅₀Al₅₀ (at%) deposited by direct current magnetron sputtering are investigated by nanocalorimetry and conventional calorimetry. Both the novel fast differential scanning calorimeter (FDSC) Flash DSC 2+ from Mettler–Toledo (MT) and conventional calorimeter MT DSC 3 are used to cover a range of heating rates from 0.1 to 10⁴ K s⁻¹. A quantitative kinetic study of the interdiffusion and phase reaction sequence is performed via a Kissinger analysis covering five orders of magnitude of heating rates. Using the calorimetric data, the derived apparent activation energies suggest monotonic reaction kinetics over the entire range of heating rates applied. To correct the thermal lag at the highest heating rates with the FDSC for nonadhered free‐standing films, a new methodology for its correction is used. Overall, this work extends the application of commercial FDSC to nonadhered films.