Thin film networks of highly purified semiconducting carbon nanotubes (CNTs) are being explored for energy harvesting and optoelectronic devices because of their exceptional transport and optical properties. The nanotubes in these films are in close contact, which permits energy to flow through the films, although the pathways and mechanisms for energy transfer are largely unknown. Here we use a broadband continuum to collect femtosecond two-dimensional white-light spectra. The continuum spans 500 to 1,300 nm, resolving energy transfer between all combinations of bandgap (S 1 ) and higher (S 2 ) transitions. We observe ultrafast energy redistribution on the S 2 states, non-Förster energy transfer on the S 1 states and anti-correlated energy levels. The two-dimensional spectra reveal competing pathways for energy transfer, with S 2 excitons taking routes depending on the bandgap separation, whereas S 1 excitons relax independent of the bandgap. These observations provide a basis for understanding and ultimately controlling the photophysics of energy flow in CNT-based devices.

Ecological theory predicts that individual survival should vary between sex and age categories due to differences in allocation of nutritional resources for growth and reproductive activities. During periods of environmental stress, such relationships may be exacerbated, and affect sex and age classes differently. We evaluated support for hypotheses about the relative roles of sex, age, and winter and summer climate on the probability of mountain goat (Oreamnos americanus) survival in coastal Alaska. Specifically, we used known‐fates analyses (Program MARK) to model the effects of age, sex, and climatic variation on survival using data collected from 279 radio‐marked mountain goats (118 M, 161 F) in 9 separate study areas during 1977–2008. Models including age, sex, winter snowfall, and average daily summer temperature (during Jul–Aug) best explained variation in survival probability of mountain goats. Specifically, our findings revealed that old animals (9+ yr) have lower survival than younger animals. In addition, males tended to have lower survival than females, though differences only existed among prime‐aged adult (5–8 yr) and old (9+ yr) age classes. Winter climate exerted the strongest effects on mountain goat survival; summer climate, however, was significant and principally influenced survival during the following winter via indirect effects. Furthermore, old animals were more sensitive to the effects of winter conditions than young or prime‐aged animals. These findings detail how climate interacts with sex and age characteristics to affect mountain goat survival. Critically, we provide baseline survival rate statistics across various age, sex, and climate scenarios. These data will assist conservation and management of mountain goats by enabling detailed, model‐based demographic forecasting of human and/or climate‐based population impacts. © 2011 The Wildlife Society.

We utilize femtosecond transient absorption spectroscopy to study dynamics of photoexcitation migration in films of semiconducting single-wall carbon nanotubes. Films of nanotubes in close contact enable energy migration such as needed in photovoltaic and electroluminescent devices. Two types of films composed of nanotube fibers are utilized in this study: densely packed and very porous. By comparing exciton kinetics in these films, we characterize excitation transfer between carbon nanotubes inside fibers versus between fibers. We find that intrafiber transfer takes place in both types of films, whereas interfiber transfer is greatly suppressed in the porous one. Using films with different nanotube composition, we are able to test several models of exciton transfer. The data are inconsistent with models that rely on through-space interfiber energy transfer. A model that fits the experimental results postulates that interfiber transfer occurs only at intersections between fibers, and the excitons reach the intersections by diffusing along the long-axis of the tubes. We find that time constants for the inter- and intrafiber transfers are 0.2-0.4 and 7 ps, respectively. In total, hopping between fibers accounts for about 60% of all exciton downhill transfer prior to 4 ps in the dense film. The results are discussed with regards to transmission electron micrographs of the films. This study provides a rigorous analysis of the photophysics in this new class of promising materials for photovoltaics and other technologies.

We observe ultrafast energy transfer between bare carbon nanotubes in a thin film using two-dimensional (2D) white-light spectroscopy. Using aqueous two-phase separation, semiconducting carbon nanotubes are purified from their metallic counterparts and condensed into a 10 nm thin film with no residual surfactant. Cross peak intensities put the time scale for energy transfer at <60 fs, and 2D anisotropy measurements determine that energy transfer is most efficient between parallel nanotubes, thus favoring directional energy flow. Lifetimes are about 300 fs. Thus, these results are in sharp contrast to thin films prepared from nanotubes that are wrapped by polymers, which exhibit picosecond energy transfer and randomize the direction of energy flow. Ultrafast energy flow and directionality are exciting properties for next-generation photovoltaics, photodetectors, and other devices.

Semiconducting single-walled carbon nanotubes (s-SWCNTs) have attracted significant attention as a photoactive component in thin film photovoltaic solar cells and photodetectors due to their strong optical absorptivity and high charge transport mobility. However, the external quantum efficiency (QE) of s-SWCNT/acceptor heterojunction solar cells has been limited by poor exciton harvesting efficiency. Exciton trapping and quenching at defects are a suspected source of loss. Here, we study the influence of defects on bilayer s-SWCNT/C 60 planar heterojunction photovoltaic devices via both experiment and modeling. First, diazonium chemistry is used to introduce covalent sp 3 sidewall defects to s-SWCNTs at various densities that are estimated using Raman and transient absorption spectroscopy. s-SWCNT/C 60 heterojunction photovoltaic cells are then fabricated that show a significant decrease in peak external QE (e.g., from 40% to 8%) with increasing defect density. Second, a diffusion-limited contact quenching Monte Carlo model is developed to assess the contributions of exciton quenching defects on exciton migration in bilayer s-SWCNT/C 60 heterojunction devices. The model indicates that current state-of-the-art s-SWCNT-based devices are defect limited and suggests that significant gains in exciton harvesting efficiency can be realized if more pristine, longer s-SWCNTs are utilized.

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Variation in core body temperature of mammals is a result of endogenous regulation of heat from metabolism and the environment, which is affected by body size and life history. We studied moose (Alces alces) in Alaska to examine the effects of endogenous and exogenous factors on core body temperature at seasonal and daily time scales. We used a modified vaginal implant transmitter to record core body temperature in adult female moose at 5-min intervals for up to 1 year. Core body temperature in moose showed a seasonal fluctuation, with a greater daily mean core body temperature during the summer (38.2°C, 95% CI = 38.1–38.3°C) than during the winter (37.7°C, 95% CI = 37.6–37.8°C). Daily change in core body temperature was greater in summer (0.92°C, 95% CI = 0.87–0.97°C) than in winter (0.58°C, 95% CI = 0.53–0.63°C). During winter, core body temperature was lower and more variable as body fat decreased among female moose. Ambient temperature and vapor pressure accounted for a large amount of the residual variation (0.06–0.09°C) in core body temperature after accounting for variation attributed to season and individual. Ambient temperature and solar radiation had the greatest effect on the residual variation (0.17–0.20°C) of daily change in core body temperature. Our study suggests that body temperature of adult female moose is influenced by body reserves within seasons and by environmental conditions within days. When studying northern cervids, the influence of season and body condition on daily patterns of body temperature should be considered when evaluating thermal stress.

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