Dynamics of Radical Ions of Hydroxyhexafluoroisopropyl-Substituted Benzenes.

Fluorination of resist materials is an effective method used to enhance the energy deposition of extreme ultraviolet (EUV) light in the fabrication of next-generation semiconductor devices. The dynamics of radical ions are important to understand when considering the radiation-chemistry of the resist materials using EUV and electron beam lithography. Here, the dynamics of the radical anions and cations of benzenes with one or two 2-hydroxyhexafluoroisopropyl groups (HFABs) were studied using radiolysis techniques. The formation of dimer radical cations was observed only in the monosubstituted benzene solutions of 1,2-dichloroethane. If the compound contained more than two substituents, it was found to hinder the necessary π-π overlapping. Pulse radiolysis of HFABs in tetrahydrofuran showed a characteristic spectral shift of the radical anion within the region of several hundred nanoseconds. From the results of low-temperature spectroscopy and density functional calculations, it is suggested that excess electrons of the 2-hydroxyhexafluoroisopropyl group of the radical anions cause dissociation into neutral radicals.

Tracing the sources of gaseous components (222Rn, CO2 and its carbon isotopes) in soil air under a cool-deciduous stand in Sapporo, Japan.

Radon ((222)Rn) and carbon dioxide were monitored simultaneously in soil air under a cool-temperate deciduous stand on the campus of Hokkaido University, Sapporo, Japan. Both (222)Rn and CO(2) concentrations in soil air varied with atmospheric (soil) temperature in three seasons, except for winter when the temperature in soil air remained constant at 2-3 degrees C at depth of 80 cm. In winter, the gaseous components were influenced by low-pressure region passing through the observation site when the ground surface was covered with snow of ~1 m thickness. Carbon isotopic analyses of CO(2) suggested that CO(2) in soil air may result from mixing of atmospheric air and soil components of different origins, i.e. CO(2) from contemporary soil organic matter and old carbon from deeper source, to varying degrees, depending on seasonal meteorological and thus biological conditions.

Meteorological parameters contributing to variability in 222Rn activity concentrations in soil gas at a site in Sapporo, Japan.

Continuous (222)Rn monitoring in soil gas since November 22, 2004 has revealed variability in activity concentration with time in the semi-natural woods on the campus of Hokkaido University in Sapporo, Japan. Among various factors affecting soil radon levels and variability, temperature was found to be dominant during three seasons when activity concentrations of (222)Rn showed a diurnal high and nocturnal low with a boundary around 10 o'clock in the morning. This pattern was disturbed by low pressure fronts with occasional rain. The activity gradually decreased as soil temperatures decreased from late November to mid-December. After the ground surface was completely covered with snow, soil radon levels became low with a small fluctuation. There were several peaks of (222)Rn on the time-series chart in winter. Those peaks appearing in early winter and early spring may be interpreted by considering meteorological parameters. In a few cases, the radon activity suddenly increased with increasing pressure in the soil at a depth of 10 cm, which may be associated with subsurface events such as seismic activity in the area.

Variation of (222)Rn activity concentration in soil gas at a site in Sapporo, Japan.

Several factors controlling the soil radon level in the present site were found to be changing air-filled porosity caused by fluctuations in moisture content, differences between the atmospheric and soil temperatures as well as volumetric (226)Ra content of the soil. The radon activity increased significantly in early October, especially at point 1, possibly as a result of a magnitude 8.0 earthquake which occurred on September 26, 2003, with epicenter located offshore near Tokachi, Hokkaido.

Mesoscale variability of vertical profiles of environmental radionuclides (40K, 226Ra, 210Pb and 137Cs) in temperate forest soils in Germany.

Vertical profiles of environmental radionuclides (40K, 226Ra, 210Pb and 137Cs) were investigated in several temperate forest soils in Germany to estimate heterogeneity of the soil horizon of interest. Absolute values of the activity concentrations of these nuclides varied to a large extent depending on the properties of individual forests as well as local geology. Several trends were generally observed independent of the location: (1) Activity concentrations of 40K increased with increasing soil density reflecting that most potassium is contained in mineral components of the soil. The variations in the 40K activity with depth may relate to biological activities in subsoil, such as root uptake of the nutrients. (2) Profiles of 226Ra with depth could be an indicator for evaluating soil heterogeneity within a horizon of interest. They are also useful to estimate anthropogenic 210Pb (210Pbexc) derived from the atmosphere via dry fallout or wet deposition. In several forests, there appeared surface enrichment of 210Pb down to a depth of approximately 10 cm, in which the 210Pb would have come from the atmosphere by combustion of fossil fuels. (3) Depth profiles of 137Cs were roughly divided into three types in which (a) the activity concentration decreased exponentially with soil depth, (b) small amounts of 137Cs existed only in the upper-most layer of the soil (0-5 cm) and (c) 137Cs disappeared at certain depths and appeared again at deeper portions of the soil. Consequences of bioturbation could be deduced from variability in vertical profiles of the environmental radionuclides. It is probable that a site showing an exponential decrease of the 137Cs activity with depth and also having a surface enrichment of 210Pb is not significantly influenced by bioturbation.

Investigation of the soil radon variation during the winter months in Sapporo, Japan.

Soil radon was measured from late October 2000 to January 2001 at three test sites on the campus of Hokkaido University in Sapporo, Japan. Factors affecting radon concentrations were investigated with relation to meteorological data, as well as soil 226Ra content, mineral composition, water content, and pH, Eh and conductivity. Soil radon varied with time and with sampling site appreciably, in a manner unaltered by the surface geology. However, the ratio of radon isotopes (220Rn/222Rn) in the soil was constant within each sampling site, regardless of varying concentration of these nuclides during the monitoring period. Snow covering on the soil surfaces may affect the 222Rn concentration.