As-deposited thin films grown by vapor deposition often exhibit large intrinsic stresses that can lead to film failure. While this is an “old” materials problem, our understanding has only recently begun to evolve in a more sophisticated fashion. Sensitive real-time measurements of stress evolution during thin-film deposition reveal a generic compressive–tensile–compressive behavior that correlates with island nucleation and growth, island coalescence, and postcoalescence film growth. In this article, we review the fundamental mechanisms that can generate stresses during the growth of Volmer–Weber thin films. Compressive stresses in both discontinuous and continuous films are generated by surface-stress effects. Tensile stresses are created during island coalescence and grain growth. Compressive stresses can also result from the flux-driven incorporation of excess atoms within grain boundaries. While significant progress has been made in this field recently, further modeling and experimentation are needed to quantitatively sort out the importance of the different mechanisms to the overall behavior.
We introduce a simple and inexpensive procedure for epitaxial lift-off of wafer-size flexible and transparent foils of single-crystal gold using silicon as a template. Lateral electrochemical undergrowth of a sacrificial SiO layer was achieved by photoelectrochemically oxidizing silicon under light irradiation. A 28-nanometer-thick gold foil with a sheet resistance of 7 ohms per square showed only a 4% increase in resistance after 4000 bending cycles. A flexible organic light-emitting diode based on tris(bipyridyl)ruthenium(II) that was spin-coated on a foil exploited the transmittance and flexibility of the gold foil. Cuprous oxide as an inorganic semiconductor that was epitaxially electrodeposited onto the gold foils exhibited a diode quality factor of 1.6 (where = 1.0 for an ideal diode), compared with a value of 3.1 for a polycrystalline deposit. Zinc oxide nanowires electrodeposited epitaxially on a gold foil also showed flexibility, with the nanowires intact up to 500 bending cycles.
In the early stage of growth of a metal film on a substrate by the Volmer–Weber mechanism, a tensile stress in the film is observed to arise at about the point in the process when islands of deposited material begin to coalesce. The mechanism commonly proposed as the origin of this tensile stress is that the coalescing islands deform in order to form a relatively low energy grain boundary, at the expense of some surface energy by surface area reduction, and that this proceeds until a stress is generated that has magnitude sufficient to prevent further area reduction. Several models have been proposed for this process, but the inferred tensile stress estimates have been much larger than observed stress magnitudes in many cases. The purpose here is to introduce a model for the process based on the theory of contact of elastic solids with cohesion. A description of the process is developed on this premise for one-dimensional, two-dimensional, and three-dimensional states of deformation of coalescing islands. It is found that the latter case leads to an estimate of film stress generally consistent with observations. The features of the model for different dimensionalities are compared and contrasted with each other, as well as with other models which have been proposed for this process.
We have simultaneously measured the evolution of intermetallic volume, stress, and whisker density in Sn and Pb-Sn alloy layers on Cu to study the fundamental mechanisms controlling whisker formation. For pure Sn, the stress becomes increasingly compressive and then saturates, corresponding to a plastically deformed region spreading away from the growing intermetallic particles. Whisker nucleation begins after the stress saturates. Pb-Sn layers have similar intermetallic growth kinetics but the resulting stress and whisker density are much less. Measurements after sputtering demonstrate the important role of the surface oxide in inhibiting stress relaxation.
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