Kinetics and coverage dependent reaction mechanisms of the copper atomic layer deposition from copper dimethylamino-2-propoxide and diethylzinc

Atomic layer deposition (ALD) has been recognized as a promising method to deposit conformal and uniform thin film of copper for future electronic devices. However, many aspects of the reaction mechanism and the surface chemistry of copper ALD remain unclear. In this paper, we employ plane wave density functional theory (DFT) to study the transmetalation ALD reaction of copper dimethylamino-2-propoxide [Cu(dmap)2] and diethylzinc [Et2Zn] that was realized experimentally by Lee et al. [ Angew. Chem., Int. Ed. 2009, 48, 4536−4539]. We find that the Cu(dmap)2 molecule adsorbs and dissociates through the scission of one or two Cu–O bonds into surface-bound dmap and Cu(dmap) fragments during the copper pulse. As Et2Zn adsorbs on the surface covered with Cu(dmap) and dmap fragments, butane formation and desorption was found to be facilitated by the surrounding ligands, which leads to one reaction mechanism, while the migration of ethyl groups to the surface leads to another reaction mechanism. During both reaction mechanisms, ligand diffusion and reordering are generally endothermic processes, which may result in residual ligands blocking the surface sites at the end of the Et2Zn pulse, and in residual Zn being reduced and incorporated as an impurity. We also find that the nearby ligands play a cooperative role in lowering the activation energy for formation and desorption of byproducts, which explains the advantage of using organometallic precursors and reducing agents in Cu ALD. The ALD growth rate estimated for the mechanism is consistent with the experimental value of 0.2 Å/cycle. The proposed reaction mechanisms provide insight into ALD processes for copper and other transition metals.

Interpreting independence in Latin American cinema today: the digital option

Globalisation has transformed “independence” into, at best, “inter-dependence”. In Latin American film, this process has been experienced as a decline in the national productions, now usually co-productions, and a tendency towards the self-exoticising as films cater for a festival-circuit global audience; similarly, theatrical exhibition takes place in one of a handful of the global multiplex complexes. Moreover, narrative film itself has long been regarded as inherently “dependent”, on the conservative sectors that have provided its finance, with the word “independent” referring to authorial features only. However, the very same processes that have allowed for such an unprecedented corporate control of these film industries have also spawned a parallel network of local, regional and national filmmaking, distribution and exhibition through digital media. From the “Mi Cine” project in Mexico to the “Cine Piquetero” in Argentina, digital filmmaking is empowering viewers and restoring agency to local filmmakers. In this paper I argue for this understanding of “independence” in the contemporary cinematic spheres of Latin America: the re-appropriation, amidst the transnationalism of the day, of the democratising potential of cinema that Walter Benjamin once thought was inherent to the medium.