Photoinduced hole-transfer in semiconducting polymer/low-bandgap cyanine dye blends: evidence for unit charge separation quantum yield

Power-conversion efficiencies of organic heterojunction solar cells can be increased by using semiconducting donor-acceptor materials with complementary absorption spectra extending to the near-infrared region. Here, we used continuous wave fluorescence and absorption, as well as nanosecond transient absorption spectroscopy to study the initial charge transfer step for blends of a donor poly(p-phenylenevinylene) derivative and low-band gap cyanine dyes serving as electron acceptors. Electron transfer is the dominant relaxation process after photoexcitation of the donor. Hole transfer after cyanine photoexcitation occurs with an efficiency close to unity up to dye concentrations of similar to 30 wt%. Cyanines present an efficient self-quenching mechanism of their fluorescence, and for higher dye loadings in the blend, or pure cyanine films, this process effectively reduces the hole transfer. Comparison between dye emission in an inert polystyrene matrix and the donor matrix allowed us to separate the influence of self-quenching and charge transfer mechanisms. Favorable photovoltaic bilayer performance, including high open-circuit voltages of similar to 1 V confirmed the results from optical experiments. The characteristics of solar cells using different dyes also highlighted the need for balanced adjustment of the energy levels and their offsets at the heterojunction when using low-bandgap materials, and accentuated important effects of interface interactions and solid-state packing on charge generation and transport.

Escape and transport for an open bouncer: Stretched exponential decays

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Unconventional Hall effect near charge neutrality point in a two-dimensional electron-hole system

The transport properties of the two-dimensional system in HgTe-based quantum wells containing simultaneously electrons and holes of low densities are examined. The Hall resistance, as a function of perpendicular magnetic field, reveals an unconventional behavior, different from the classical N-shaped dependence typical for bipolar systems with electron-hole asymmetry. The quantum features of magnetotransport are explained by means of numerical calculation of the Landau level spectrum based on the Kane Hamiltonian. The origin of the quantum Hall plateau sigma(xy) = 0 near the charge neutrality point is attributed to special features of Landau quantization in our system.

Charge transport properties of organic conjugated polymers for photovoltaic applications

Charge transport in conjugated polymers as well as in bulk-heterojunction (BHJ) solar cells made of blends between conjugated polymers, as electron-donors (D), and fullerenes, as electron-acceptors (A), has been investigated. It is shown how charge carrier mobility of a series of anthracene-containing poly(p-phenylene-ethynylene)-alt-poly(p-phenylene-vinylene)s (AnE-PVs) is highly dependent on the lateral chain of the polymers, on a moderate variation of the macromolecular parameters (molecular weight and polydispersity), and on the processing conditions of the films. For the first time, the good ambipolar transport properties of this relevant class of conjugated polymers have been demonstrated, consistent with the high delocalization of both the frontier molecular orbitals. Charge transport is one of the key parameters in the operation of BHJ solar cells and depends both on charge carrier mobility in pristine materials and on the nanoscale morphology of the D/A blend, as proved by the results here reported. A straight correlation between hole mobility in pristine AnE-PVs and the fill factor of the related solar cells has been found. The great impact of charge transport for the performance of BHJ solar cells is clearly demonstrated by the results obtained on BHJ solar cells made of neat-C70, instead of the common soluble fullerene derivatives (PCBM or PC70BM). The investigation of neat-C70 solar cells was motivated by the extremely low cost of non-functionalized fullerenes, compared with that of their soluble derivatives (about one-tenth). For these cells, an improper morphology of the blend leads to a deterioration of charge carrier mobility, which, in turn, increases charge carrier recombination. Thanks to the appropriate choice of the donor component, solar cells made of neat-C70 exhibiting an efficiency of 4.22% have been realized, with an efficiency loss of just 12% with respect to the counterpart made with costly PC70BM.

Seismic stratigraphy of the Blue Hole (Lighthouse Reef, Belize), a late Holocene climate and storm archive

Five seismic units may be identified in the similar to 8 m thick Holocene sediment package at the bottom of the Blue Hole, a 120 m deep sinkhole located in the atoll lagoon of Lighthouse Reef, Belize. These units may be correlated with the succession of an existing 5.85-m-long sediment core that reaches back to 1385 kyrs BP. The identification of seismic units is based on the fact that uniform, fine-grained background sediments show weak reflections while alternating background and coarser-grained event (storm) beds exhibit strong reflections in the seismic profiles. The main source of sediments is the marginal atoll reef and adjacent lagoon area to the east and north. Northeasterly winds and storms transport sediment into the Blue Hole, as seen in the eastward increase in sediment thickness, i.e., the eastward shallowing of the Blue Hole. Previous assumptions of much thicker Holocene sediment packages in the Blue Hole could not be confirmed. So far, close to 6-m-long cores were retrieved from the Blue Hole but the base of the sedimentary succession remains to be recovered. The nature of the basal sediments is unknown but mid-Holocene and possibly older, Pleistocene sinkhole deposits can be expected. The number of event beds identified in the Blue Hole (n = 37) during a 1.385 kyr-long period and the number of cyclones listed in historical databases suggest that only strong hurricanes (categories 4 and 5) left event beds in the Blue Hole sedimentary succession. Storm beds are numerous during 13-0.9 kyrs BP and 0.8-0.5 kyrs BP.

New geometries for black hole horizons

We construct several classes of worldvolume effective actions for black holes by integrating out spatial sections of the worldvolume geometry of asymptotically flat black branes. This provides a generalisation of the blackfold approach for higher-dimensional black holes and yields a map between different effective theories, which we exploit by obtaining new hydrodynamic and elastic transport coefficients via simple integrations. Using Euclidean minimal surfaces in order to decouple the fluid dynamics on different sections of the worldvolume, we obtain local effective theories for ultraspinning Myers-Perry branes and helicoidal black branes, described in terms of a stress-energy tensor, particle currents and non-trivial boost vectors. We then study in detail and present novel compact and non-compact geometries for black hole horizons in higher-dimensional asymptotically flat space-time. These include doubly-spinning black rings, black helicoids and helicoidal p-branes as well as helicoidal black rings and helicoidal black tori in D ≥ 6.

Stable isotope analysis and temperature reconstruction data from DSDP Hole 94-609B and ODP Hole 162-984B

The Greenland ice sheet is accepted as a key factor controlling the Quaternary glacial scenario. However, the origin and mechanisms of major Arctic glaciation starting at 3.15 Ma and culminating at 2.74 Ma are still controversial. For this phase of intense cooling Ravelo et al. proposed a complex gradual forcing mechanism. In contrast, our new submillennial-scale paleoceanographic records from the Pliocene North Atlantic suggest a far more precise timing and forcing for the initiation of northern hemisphere glaciation (NHG), since it was linked to a 2-3 °C surface water warming during warm stages from 2.95 to 2.82 Ma. These records support previous models, claiming that the final closure of the Panama Isthmus (3.0- ~2.5 Ma induced an increased poleward salt and heat transport. Associated strengthening of North Atlantic Thermohaline Circulation and in turn, an intensified moisture supply to northern high latitudes resulted in the build-up of NHG, finally culminating in the great, irreversible climate crash at marine isotope stage G6 (2.74 Ma). In summary, there was a two-step threshold mechanism that marked the onset of NHG with glacial-to-interglacial cycles quasi-persistent until today.

Age model and Nd isotope ratios of DSDO Hole 43-386 and ODP Hole 210-1276A

Modern thermohaline circulation plays a role in latitudinal heat transport and in deep-ocean ventilation, yet ocean circulation may have functioned differently during past periods of extreme warmth, such as the Cretaceous. The Late Cretaceous (100-65 Ma) was an important period in the evolution of the North Atlantic Ocean, characterized by opening ocean gateways, long-term climatic cooling and the cessation of intermittent periods of anoxia (oceanic anoxic events, OAEs). However, how these phenomena relate to deep-water circulation is unclear. We use a proxy for deep-water mass composition (neodymium isotopes; e-Nd) to show that, at North Atlantic ODP Site 1276, deep waters shifted in the early Campanian (~78-83 Ma) from e-Nd values of ~-7 to values of ~-9, consistent with a change in the style of deep-ocean circulation but >10 Myr after a change in bottom water oxygenation conditions. A similar, but more poorly dated, trend exists in e-Nd data from DSDP Site 386. The Campanian e-Nd transition observed in the North Atlantic records is also seen in the South Atlantic and proto-Indian Ocean, implying a widespread and synchronous change in deep-ocean circulation. Although a unique explanation does not exist for the change at present, we favor an interpretation that invokes Late Cretaceous climatic cooling as a driver for the formation of Southern Component Water, which flowed northward from the Southern Ocean and into the North Atlantic and proto-Indian Oceans.

Quartz content, accumulation and sedimentation rates at DSDP Hole 91-595A

The quartz contents of sediments from Hole 595A, determined by X-ray diffractometry, serve as an indicator of eolian transport of terrigenous material to the central southern Pacific. The quartz contents are very small and, within limits of analytical resolution, vary only slightly from the Cretaceous to the present. However, the accumulation rate of the eolian quartz does change significantly. The quartz accumulation reflects the changing position of the site with respect to the terrigenous source areas and the variations in wind systems through time.

Mineralogical and grain size analysis of ODP Hole 119-745B from the Southern Ocean

The upper Miocene to Pleistocene sediments recovered at ODP Sites 745 and 746 in the Australian-Antarctic Basin are characterized by cyclic facies changes. Sedimentological investigations of a detailed Quaternary section reveal that facies A is dominated by a high content of siliceous microfossils, a relatively low terrigenous sediment content, an ice-rafted component, low concentrations of fine sediment particles, and a relatively high smectite content. This facies corresponds to interglacial sedimentary conditions. Facies B, in contrast, is characteristic of glacial conditions and is dominated by a large amount of terrigenous material and a smaller opaline component. There is also a prominent ice-rafted component. The microfossils commonly are reworked and broken. The clay mineral assemblages show higher proportions of glacially derived illite and chlorite. A combination of four different processes, attributed to glacial-interglacial cycles, was responsible for the cyclic facies changes during Quaternary time: transport by gravity, ice, and current and changes in primary productivity. Of great importance was the movement of the grounding line of the ice shelves, which directly influenced the intensity of ice rafting and of gravitational sediment transport to the deep sea. The extension of the ice shelves was also responsible for the generation of cold and erosive Antarctic Bottom Water, which controlled the grain-size distribution, particularly of the fine fraction, in the investigated area.

Calcareous dinoflagellates in Cretaceous to Recent sediments of DSDP Hole 39-356

Calcareous dinoflagellates often dominate the dinoflagellate cyst assemblage in Cretaceous to Recent oceanic sediments. However, their distribution in Paleogene sediments has scarcely been studied. The investigation of samples from DSDP Site 356 for their calcareous dinoflagellate content revealed 35 mainly long-ranging taxa. The associations and characteristic wall types (pithonelloid, oblique, radial, tangential) fluctuate quantitatively and qualitatively in distinct stratigraphic patterns. Significant shifts, primarily at the K/T boundary and the Paleocene/Eocene boundary, reflect changes in environmental conditions. Certain dinoflagellates forming calcareous cysts, such as Operculodinella operculata, were well adapted to the relatively rapid change of environmental conditions at the K/T boundary, thus blooming to dominate the carbonate flux to the ocean floor. In contrast to the stable Paleocene associations, Eocene calcareous dinoflagellates show fluctuations in relative abundances. These fluctuations can possibly be attributed to redeposition related to increased seaward transport of specimens, due to strengthened western boundary currents. The flora includes two new genera, one new species, and two new forms: Retesphaera diadema Hildebrand-Habel, Willems et Versteegh, gen. et. sp. nov., Cervisiella saxea (Stradner, 1961) Hildebrand-Habel, Willems et Versteegh, gen. et comb. nov., Sphaerodinella? tuberosa forma elongata Hildebrand-Habel, Willems et Versteegh, comb. et forma nov., Sphaerodinella? tuberosa forma variospinosa Hildebrand-Habel, Willems et Versteegh, comb. et forma nov. Three new combinations are proposed: Cervisiella saxea (Stradner, 1961) Hildebrand-Habel, Willems et Versteegh, gen. et comb. nov., Operculodinella operculata (Bramlette et Martini, 1964) Hildebrand-Habel, Willems et Versteegh, comb. nov., and Sphaerodinella? tuberosa (Kamptner, 1963) Hildebrand-Habel, Willems et Versteegh, comb. nov. The genus Operculodinella Kienel, 1994 is emended.

Planktonic foraminifera oxygen isotope and trace metal data ODP Hole 172-1056A, 46-54 ka BP

Salinity increase in the subtropical gyre system may have pre-conditioned the North Atlantic Ocean for a rapid return to stronger overturning circulation and high-latitude warming following meltwater events during the Last Glacial period. Here we investigate the Gulf Stream - subtropical gyre system properties over Dansgaard-Oeschger (DO) cycles 14 to 12, including Heinrich ice-rafting event 5. During the Holocene and Last Glacial Maximum a positive gradient in surface dwelling planktonic foraminifera d18O (Globigerinoides ruber) can be observed between the Gulf Stream and subtropical gyre, due to decreasing temperature, increasing salinity, and a change from summer to year-round occurrence of G. ruber. We assess whether this gradient was a common feature during stadial-interstadial climate oscillations of Marine Isotope Stage 3, by comparing existing G. ruber d18O from ODP Site 1060 (subtropical gyre location) and new data from ODP Site 1056 (Gulf Stream location) between 54 and 46 ka. Our results suggest that this gradient was largely absent during the period studied. During the major warm DO interstadials 14 and 12 we infer a more zonal and wider Gulf Stream, influencing both ODP Sites 1056 and 1060. A Gulf Stream presence during these major interstadials is also suggested by the large vertical d18O gradient between shallow dwelling planktonic foraminifera species, especially G. ruber, and the deep dwelling species Globorotalia inflata at site 1056, which we associate with strong summer stratification and Gulf Stream presence. A major reduction in this vertical d18O gradient from 51 ka until the end of Heinrich event 5 at 48.5 ka suggests site 1056 was situated within the subtropical gyre in this mainly cold period, from which we infer a migration of the Gulf Stream to a position nearer to the continental shelf, indicative of a narrower Gulf Stream with possibly reduced transport.

Planktic foraminifera from ODP Hole 117-723B

Upwelling occurs during the summer off the coast of Oman when the Asian monsoon produces strong southwest winds in the northern Arabian Sea. Ekman transport driven by the southwest monsoon winds upwells cool nutrient-rich waters along the coast which contrast with the warmer, less productive waters offshore. The spatial pattern of foraminifers in the sediments corresponds with the coastal environmental gradient. The upwelling species Globigerina bulloides dominates the sediment assemblage on the continental margin, while Globigerinita glutinata is more abundant offshore, creating a coastal gradient in fauna. We reconstructed the upwelling faunal gradient using high resolution oxygen isotope stratigraphy to correlate between Hole 723B on the Oman Margin, and a core from the Owen Ridge (RC2761), adjacent Site 722. A gradient similar in magnitude to the present, implying upwelling conditions similar to today existed during each interglacial time during the late Pleistocene interval from 0 to 300 k.y. The gradient was reduced or absent during glacial times implying diminshed southwest winds along the coast of Oman, not strong enough to produce an environmental gradient between the coast and offshore sites.

Grain size composition and age of ODP Hole 167-1017E sediments

Siliciclastic sedimentation at Ocean Drilling Program Site 1017 on the southern slope of the Santa Lucia Bank, central California margin, responded closely to oceanographic and climatic change over the past ~130 ka. Variation in mean grain-size and sediment sorting within the ~25-m-thick succession from Hole 1017E show Milankovitch-band to submillenial-scale variation. Mean grain size of the "sortable silt" fraction (10-63 µm) ranges from 17.6 to 33.9 µm (average 24.8 µm) and is inversely correlated with the degree of sorting. Much of the sediment has a bimodal or trimodal grain-size distribution that is composed of distinct fine silt, coarse silt to fine sand, and clay-size components. The position of the mode and the sorting of each component changes through the succession, but the primary variation is in the presence or abundance of the coarse silt fraction that controls the overall mean grain size and sorting of the sample. The occurrence of the best-sorted, finest grained sediment at high stands of sea level (Holocene, marine isotope Substages 5c and 5e) reflect the linkage between global climate and the sedimentary record at Site 1017 and suggest that the efficiency of off-shelf transport is a key control of sedimentation on the Santa Lucia Slope. It is not clear what proportion of the variation in grain size and sorting may also be caused by variations in bottom current strength and in situ hydrodynamic sorting.