Artificial photosynthesis relies on the availability of semiconductors that are chemically stable and can efficiently capture solar energy. Although metal oxide semiconductors have been investigated for their promise to resist oxidative attack, materials in this class can suffer from chemical and photochemical instability. Here we present a methodology for evaluating corrosion mechanisms and apply it to bismuth vanadate, a state-of-the-art photoanode. Analysis of changing morphology and composition under solar water splitting conditions reveals chemical instabilities that are not predicted from thermodynamic considerations of stable solid oxide phases, as represented by the Pourbaix diagram for the system. Computational modelling indicates that photoexcited charge carriers accumulated at the surface destabilize the lattice, and that self-passivation by formation of a chemically stable surface phase is kinetically hindered. Although chemical stability of metal oxides cannot be assumed, insight into corrosion mechanisms aids development of protection strategies and discovery of semiconductors with improved stability.

Reactor and particle design considerations of particle suspension reactors for solar photoelectrochemical water splitting.

Several application fields can benefit from solar-hydrogen technologies via specific short-term and long-term pathways.

Acid diffusion during postexposure baking is viewed to be a limiting factor in the extension of lithography using chemically amplified resists to formation of nanoscale features. Quantification of thermally activated reaction-diffusion kinetics in these materials is therefore an important step in understanding the extendability of this class of resist systems. Previous investigations have addressed this issue, however there is poor agreement among them, and too few data exist in the literature to allow the systematics of the effect of polymer, photoacid generator, added base or other resist components on the diffusion process to be understood. We describe in this article a combined experimental and modeling protocol that is designed to elucidate the chemistry and physics of the reaction-diffusion process. Because it is physically based, not phenomenological, it provides a means of developing a set of predictive, mutually comparable data that will allow new insights to be developed into the nanoscale behavior of chemically amplified resist materials. We apply the protocol to a p-t-butyloxycarbonyloxystyrene/bis͑t-butylphenyl͒iodonium perfluorobutanesulfonate positive-tone photoresist system. The resulting kinetics measurements show that diffusion is environment sensistive and describable with two limiting diffusion coefficients. The Arrhenius parameters for the coefficients in p-t-butyloxycarbonyloxystyrene are D 0 ϭ1.9ϫ10 8 cm 2 /s and E a ϭ36.5 kcal/mol; those for diffusion in the deprotected polymer product p-hydroxystyrene are D 0 ϭ9ϫ10 Ϫ3 cm 2 /s and E a ϭ22.1 kcal/mol. The coefficients are much smaller than previously reported, resulting in a very slow diffusion rate. The model indicates that the considerable image spreading observed during the postexposure bake process is attributable primarily to the efficiency of the catalytic chemistry. Our results suggest that numerical models currently used for prediction of imaging in chemically amplified resists may require refinement in order to be useful for feature sizes below 100 nm and for new classes of resist systems.

No abstract

This article reports the first prospective life-cycle net energy assessment of a gigawatt-scale photoelectrochemical (PEC) hydrogen production facility.

An accurate description of the evolution of organic aerosol in the Earth's atmosphere is essential for climate models. However, the complexity of multiphase chemical and physical transformations has been challenging to describe at the level required to predict aerosol lifetimes and changes in chemical composition. In this work a model is presented that reproduces experimental data for the early stages of oxidative aging of squalane aerosol by hydroxyl radical (OH), a process governed by reactive uptake of gas phase species onto the particle surface. Simulations coupling free radical reactions and Fickian diffusion are used to elucidate how the measured uptake coefficient reflects the elementary steps of sticking of OH to the aerosol as a result of a gas-surface collision, followed by very rapid abstraction of hydrogen and subsequent free radical reactions. It is found that the uptake coefficient is not equivalent to a sticking coefficient or an accommodation coefficient: it is an intrinsically emergent process that depends upon particle size, viscosity, and OH concentration. An expression is derived to examine how these factors control reactive uptake over a broad range of atmospheric and laboratory conditions, and is shown to be consistent with simulation results. Well-mixed, liquid behavior is found to depend on the reaction conditions in addition to the nature of the organic species in the aerosol particle.

Criegee intermediates (CI), formed in alkene ozonolysis, are central for controlling the multiphase chemistry of organic molecules in both indoor and outdoor environments. Here, we examine the heterogeneous ozonolysis of squalene, a key species in indoor air chemistry. Aerosol mass spectrometry is used to investigate how the ozone (O) concentration, relative humidity (RH), and particle size control reaction rates and mechanisms. Although the reaction rate is found to be independent of RH, the reaction products and particle size depend upon HO. Under dry conditions (RH = 3%) the reaction produces high-molecular-weight secondary ozonides (SOZ), which are known skin irritants, and a modest change in particle size. Increasing the RH reduces the aerosol size by 30%, while producing mainly volatile aldehyde products, increases potential respiratory exposure. Chemical kinetics simulations link the elementary reactions steps of CI to the observed kinetics, product distributions, and changes in particle size. The simulations reveal that ozonolysis occurs near the surface and is O-transport limited. The observed secondary ozonides are consistent with the formation of mainly secondary CI, in contrast to gas-phase ozonolysis mechanisms.