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Microwave reflection photoconductive decay carrier lifetimes of Ge0.94Sn0.06 materials on oriented GaAs substrates at 300 K. 

Germanium alloyed with α-tin (GeSn) transitions to a direct bandgap semiconductor of significance for optoelectronics. It is essential to localize the carriers within the active region for improving the quantum efficiency in a GeSn based laser. In this work, epitaxial GeSn heterostructure material systems were analyzed to determine the band offsets for carrier confinement: (i) a 0.53% compressively strained Ge 0.97 Sn 0.03 /AlAs; (ii) a 0.81% compressively strained Ge 0.94 Sn 0.06 /Ge; and (iii) a lattice matched Ge 0.94 Sn 0.06 /In 0.12 Al 0.88 As. The phonon modes in GeSn alloys were studied using Raman spectroscopy as a function of Sn composition, that showed Sn induced red shifts in wavenumbers of the Ge–Ge longitudinal optical phonon mode peaks. The material parameter b representing strain contribution to Raman shifts of a Ge 0.94 Sn 0.06 alloy was determined as b = 314.81 ± 14 cm −1 . Low temperature photoluminescence measurements were performed at 79 K to determine direct and indirect energy bandgaps of E g,Γ = 0.72 eV and E g,L = 0.66 eV for 0.81% compressively strained Ge 0.94 Sn 0.06 , and E g,Γ = 0.73 eV and E g,L = 0.68 eV for lattice matched Ge 0.94 Sn 0.06 epilayers. Chemical effects of Sn atomic species were analyzed using X-ray photoelectron spectroscopy (XPS), revealing a shift in Ge 3d core level (CL) spectra towards the lower binding energy affecting the bonding environment. Large valence band offset of Δ E V = 0.91 ± 0.1 eV and conduction band offset of Δ E C,Γ–X = 0.64 ± 0.1 eV were determined from the Ge 0.94 Sn 0.06 /In 0.12 Al 0.88 As heterostructure using CL spectra by XPS measurements. The evaluated band offset was found to be of type-I configuration, needed for carrier confinement in a laser. In addition, these band offset values were compared with the first-principles-based calculated Ge/InAlAs band alignment, and it was found to have arsenic up-diffusion limited to 1 monolayer of epitaxial GeSn overlayer, ruling out the possibility of defects induced modification of band alignment. Furthermore, this lattice matched GeSn/InAlAs heterostructure band offset values were significantly higher than GeSn grown on group IV buffer/substrates. Therefore, a lattice matched GeSn/InAlAs material system has large band offsets offering superior carrier confinement to realize a highly efficient GeSn based photonic device. 

Abstract. Mount Somma–Vesuvius is a stratovolcano that represents a geological hazard to the population of the city of Naples and surrounding towns in southern Italy. Historically, volcanic eruptions at Mt. Somma–Vesuvius (SV) include high-magnitude Plinian eruptions, such as the infamous 79 CE eruption that occurred after 295 years of quiescence and killed thousands of people in Pompeii and surrounding towns and villages. The last eruption at SV was in 1944 and showed a Volcanic Explosivity Index (VEI) of 3 (0.01 km3 of volcanic material erupted). Following the 1944 eruption, SV has been dormant for the past nearly 79 years, with only minor fumarolic and seismic activity. During its long history, centuries of dormancy at SV have ended with Plinian eruptions (VEI 6) that signal the beginning of a new cycle of eruptive activity. Thus, the current dormancy stage demands a need to better understand the mechanism involved in high-magnitude eruptions in order to better predict future eruption magnitude and style. Despite centuries of research on the SV volcanic system, many questions remain, including the evolution of magmatic volatiles from deep primitive magmas to shallower more evolved magmas. Developing a better understanding of the physical and chemical processes associated with volatile evolution at SV can provide insights into magma dynamics and the mechanisms that trigger highly explosive eruptions at SV. In this study, we present new data for the pre-eruptive volatile contents of magmas associated with four Plinian and two inter-Plinian eruptions at SV based on analyses of reheated melt inclusions (MIs) hosted in olivine. We correct the volatile contents of bubble-bearing MIs by taking into account the volatile contents of bubbles in the MIs. We recognize two groups of MIs: one group hosted in high-Fo olivine (Fo85–90) and relatively rich in volatiles and the other group hosted in low-Fo olivine (Fo70–69) and relatively depleted in volatiles. The correlation between volatile contents and compositions of host olivines suggests that magma fractionation took place under volatile-saturated conditions and that more differentiated magmas reside at shallower levels relative to less evolved/quasi-primitive magmas. Using the CO2 contents of corrected MIs hosted in Fo90 olivine from SV, we estimate that 347 to 686 t d−1 of magmatic CO2 exsolved from SV magmas during the last 3 centuries (38–75 Mt in total) of volcanic activity. Although this study is limited to only few SV magmas, we suggest that further study applying similar methods could shed light on the apparent lack of correlation between the volatile contents of MIs and the style and age of eruptions. Further, such studies could provide additional constraints on the origin of CO2 and the interaction between the carbonate platform and ascending magmas below SV. 

We report the first experimental characterization of isomerically pure and pristine C120 fullertubes, [5,5] C120-D5d(1) and [10,0] C120-D5h(10766). These new molecules represent the highest aspect ratio fullertubes isolated to date; for example, the prior largest empty cage fullertube was [5,5] C100-D5d(1). This increase of 20 carbon atoms represents a gigantic leap in comparison to three decades of C60–C90 fullerene research. Moreover, the [10,0] C120-D5d(10766) fullertube has an end-cap derived from C80-Ih and is a new fullertube whose C40 end-cap has not yet been isolated experimentally. Theoretical and experimental analyses of anisotropic polarizability and UV–vis assign C120 isomer I as a [5,5] C120-D5d(1) fullertube. C120 isomer II matches a [10,0] C120-D5h(10766) fullertube. These structural assignments are further supported by Raman data showing metallic character for [5,5] C120-D5d(1) and nonmetallic character for C120-D5h(10766). STM imaging reveals a tubular structure with an aspect ratio consistent with a [5,5] C120-D5d(1) fullertube. With microgram quantities not amenable to crystallography, we demonstrate that DFT anisotropic polarizability, augmented by long-accepted experimental analyses (HPLC retention time, UV–vis, Raman, and STM) can be synergistically used (with DFT) to down select, predict, and assign C120 fullertube candidate structures. From 10 774 mathematically possible IPR C120 structures, this anisotropic polarizability paradigm is quite favorable to distinguish tubular structures from carbon soot. Identification of isomers I and II was surprisingly facile, i.e., two purified isomers for two possible structures of widely distinguishing features. These metallic and nonmetallic C120 fullertube isomers open the door to both fundamental research and application development. 

Inclusions of basaltic melt trapped inside of olivine phenocrysts during igneous crystallization provide a rich, crystal-scale record of magmatic processes ranging from mantle melting to ascent, eruption, and quenching of magma during volcanic eruptions. Melt inclusions are particularly valuable for retaining information on volatiles such as H 2 O and CO 2 that are normally lost by vesiculation and degassing as magma ascends and erupts. However, the record preserved in melt inclusions can be variably obscured by postentrapment processes, and thus melt inclusion research requires careful evaluation of the effects of such processes. Here we review processes by which melt inclusions are trapped and modified after trapping, describe new opportunities for studying the rates of magmatic and volcanic processes over a range of timescales using the kinetics of post-trapping processes, and describe recent developments in the use of volatile contents of melt inclusions to improve our understanding of how volcanoes work. ▪  Inclusions of silicate melt (magma) trapped inside of crystals formed by magma crystallization provide a rich, detailed record of what happens beneath volcanoes. ▪  These inclusions record information ranging from how magma forms deep inside Earth to its final hours as it ascends to the surface and erupts. ▪  The melt inclusion record, however, is complex and hazy because of many processes that modify the inclusions after they become trapped in crystals. ▪  Melt inclusions provide a primary archive of dissolved gases in magma, which are the key ingredients that make volcanoes erupt explosively. 

Abstract We have examined the suitability of a quartz-inclusions-in-epidote (qtz-in-ep) mineral barometer to better constrain P-T histories of epidote-bearing lithologies. Theoretical calculations applying an isotropic elastic model suggest that the qtz-in-ep barometer exhibits minimal temperature dependence, and thus, offers the potential to constrain growth conditions of epidote in various geologic environments, including skarn deposits, epidote-bearing granitoids, and metamorphic rocks. To test if the applied equations of state and isotropic elastic model reasonably simulate the elastic evolution of two anisotropic minerals, we measured Raman shifts of the 464 cm–1 band of quartz inclusions relative to that of an unencapsulated quartz standard. We calculated a quartz inclusion pressure (Pincl464) at various temperatures and compared these values with temperature-dependent Pincl predicted by elastic modeling (Pinclmod) at elevated temperatures. Three epidote-bearing samples with reasonably well-constrained P-T histories were also examined: (1) sample HF14C from the Upper Schieferhuelle in the Western Tauern Window, Italy (Pincl464=0.01 GPa); (2) sample LdC-31C from Lago di Cignana, Italy (Pincl464≈0.16 GPa); and (3) sample FT1E from the Frosnitz Tal in the Western Tauern region, Austria (Pincl464=0.57 GPa). Entrapment pressures (Pent464) calculated from Pincl464 determined at various temperatures show nominal differences from Pent calculated from Pinclmod, suggesting that for qtz-in-ep pairs, the calculated Pent does not significantly vary with the temperature of measurement. Furthermore, our calculated Pent464 for a sample from the Upper Schieferhuelle is in agreement with petrographic context and previously established P conditions, and the Pent464 determined for the Frosnitz Tal sample closely approximate previously reported pressures. The Lago di Cignana sample is derived from an epidote vein that is encased in a high-P foliation, and the calculated Pent464 is consistent with early, low-P epidote vein formation that pre-dates high-P metamorphism, or alternatively, late vein formation during exhumation, and confirms that the epidote did not form at or near peak conditions (~2.0 GPa). The results of this study indicate that the qtz-in-ep barometer potentially provides another tool that geoscientists can employ to better constrain P-T conditions in some epidote-bearing environments, where conventional thermobarometric techniques cannot be applied. 

A 2 to 4 °C warming episode, known as the Latest Maastrichtian warming event (LMWE), preceded the Cretaceous–Paleogene boundary (KPB) mass extinction at 66.05 ± 0.08 Ma and has been linked with the onset of voluminous Deccan Traps volcanism. Here, we use direct measurements of melt-inclusion CO₂concentrations and trace-element proxies for CO₂to test the hypothesis that early Deccan magmatism triggered this warming interval. We report CO₂concentrations from NanoSIMS and Raman spectroscopic analyses of melt-inclusion glass and vapor bubbles hosted in magnesian olivines from pre-KPB Deccan primitive basalts. Reconstructed melt-inclusion CO₂concentrations range up to 0.23 to 1.2 wt% CO₂for lavas from the Saurashtra Peninsula and the Thakurvadi Formation in the Western Ghats region. Trace-element proxies for CO₂concentration (Ba and Nb) yield estimates of initial melt concentrations of 0.4 to 1.3 wt% CO₂prior to degassing. Our data imply carbon saturation and degassing of Deccan magmas initiated at high pressures near the Moho or in the lower crust. Furthermore, we find that the earliest Deccan magmas were more CO₂rich, which we hypothesize facilitated more efficient flushing and outgassing from intrusive magmas. Based on carbon cycle modeling and estimates of preserved lava volumes for pre-KPB lavas, we find that volcanic CO₂outgassing alone remains insufficient to account for the magnitude of the observed latest Maastrichtian warming. However, accounting for intrusive outgassing can reconcile early carbon-rich Deccan Traps outgassing with observed changes in climate and atmospheric pCO₂.