Effects of unique ion chemistry on thin-film growth by plasma–surface interactions

Plasma processing is a standard industrial method for the modification of material surfaces and the deposition of thin films. Polyatomic ions and neutrals larger than a triatomic play a critical role in plasma-induced surface chemistry, especially in the deposition of polymeric films from fluorocarbon plasmas. In this paper, low energy CF3+ and C3F5+ ions are used to modify a polystyrene surface. Experimental and computational studies are combined to quantify the effect of the unique chemistry and structure of the incident ions on the result of ion-polymer collisions. C3F5+ ions are more effective at growing films than CF3+, both at similar energy/atom of ≈6 eV/atom and similar total kinetic energies of 25 and 50 eV. The composition of the films grown experimentally also varies with both the structure and kinetic energy of the incident ion. Both C3F5+ and CF3+ should be thought of as covalently bound polyatomic precursors or fragments that can react and become incorporated within the polystyrene surface, rather than merely donating F atoms. The size and structure of the ions affect polymer film formation via differing chemical structure, reactivity, sticking probabilities, and energy transfer to the surface. The different reactivity of these two ions with the polymer surface supports the argument that larger species contribute to the deposition of polymeric films from fluorocarbon plasmas. These results indicate that complete understanding and accurate computer modeling of plasma–surface modification requires accurate measurement of the identities, number densities, and kinetic energies of higher mass ions and energetic neutrals.

The importance of being discrete: Life always wins on the surface

Many systems in chemistry, biology, finance, and social sciences present emerging features that are not easy to guess from the elementary interactions of their microscopic individual components. In the past, the macroscopic behavior of such systems was modeled by assuming that the collective dynamics of microscopic components can be effectively described collectively by equations acting on spatially continuous density distributions. It turns out that, to the contrary, taking into account the actual individual/discrete character of the microscopic components of these systems is crucial for explaining their macroscopic behavior. In fact, we find that in conditions in which the continuum approach would predict the extinction of all of the population (respectively the vanishing of the invested capital or the concentration of a chemical substance, etc.), the microscopic granularity insures the emergence of macroscopic localized subpopulations with collective adaptive properties that allow their survival and development. In particular it is found that in two dimensions “life” (the localized proliferating phase) always prevails.

Geochemistry of corals: Proxies of past ocean chemistry, ocean circulation, and climate

This paper presents a discussion of the status of the field of coral geochemistry as it relates to the recovery of past records of ocean chemistry, ocean circulation, and climate. The first part is a brief review of coral biology, density banding, and other important factors involved in understanding corals as proxies of environmental variables. The second part is a synthesis of the information available to date on extracting records of the carbon cycle and climate change. It is clear from these proxy records that decade time-scale variability of mixing processes in the oceans is a dominant signal. That Western and Eastern tropical Pacific El Niño-Southern Oscillation (ENSO) records differ is an important piece of the puzzle for understanding regional and global climate change. Input of anthropogenic CO2 to the oceans as observed by 13C and 14C isotopes in corals is partially obscured by natural variability. Nonetheless, the general trend over time toward lower δ18O values at numerous sites in the world’s tropical oceans suggests a gradual warming and/or freshening of the surface ocean over the past century.