Bottom-up nanostructure assembly has been a central theme of materials synthesis over the past few decades. Semiconductor quantum dots and nanowires provide additional degrees of freedom for charge confinement, strain engineering, and surface sensitivity-properties that are useful to a wide range of solid state optical and electronic technologies. A central challenge is to understand and manipulate nanostructure assembly to reproducibly generate emergent structures with the desired properties. However, progress is hampered due to the interdependence of nucleation and growth phenomena. Here we show that by dynamically adjusting the growth kinetics, it is possible to separate the nucleation and growth processes in spontaneously formed GaN nanowires using a two-step molecular beam epitaxy technique. First, a growth phase diagram for these nanowires is systematically developed, which allows for control of nanowire density over three orders of magnitude. Next, we show that by first nucleating nanowires at a low temperature and then growing them at a higher temperature, height and density can be independently selected while maintaining the target density over long growth times. GaN nanowires prepared using this two-step procedure are overgrown with three-dimensionally layered and topologically complex heterostructures of (GaN/AlN). By adjusting the growth temperature in the second growth step either vertical or coaxial nanowire superlattices can be formed. These results indicate that a two-step method allows access to a variety of kinetics at which nanowire nucleation and adatom mobility are adjustable.
Solid organic matter (OM) plays an essential role in the generation, migration, storage, and production of hydrocarbons from economically important shale rock formations. Electron microscopy images have documented spatial heterogeneity in the porosity of OM at nanoscale, and bulk spectroscopy measurements have documented large variation in the chemical composition of OM during petroleum generation. However, information regarding the heterogeneity of OM chemical composition at the nanoscale has been lacking. Here we demonstrate the first application of atomic force microscopy-based infrared spectroscopy (AFM-IR) to measure the chemical and mechanical heterogeneity of OM in shale at the nanoscale, orders of magnitude finer than achievable by traditional chemical imaging tools such as infrared microscopy. We present a combination of optical microscopy and AFM-IR imaging to characterize OM heterogeneity in an artificially matured series of New Albany Shales. The results document the evolution of individual organic macerals with maturation, providing a microscopic picture of the heterogeneous process of petroleum generation.
High‐quality single‐crystals of (Al,Fe)‐bearing bridgmanite, Mg0.88 Fe3+0.065Fe2+0.035Al0.14Si0.90O3, of hundreds of micrometer size were synthesized at 24 GPa and 1800 °C in a Kawai‐type apparatus from the starting hydrous melt containing ~6.7 wt% water. Analyses of synthesized bridgmanite using petrographic microscopy, scanning electron microscopy, and transmission electron microscopy show that the crystals are chemically homogeneous and inclusion free in micrometer‐ to nanometer‐spatial resolutions. Nanosecondary ion mass spectrometry (NanoSIMS) analyses on selected platelets show ~1,020(±70) ppm wt water (hydrogen). The high water concentration in the structure of bridgmanite was further confirmed using polarized and unpolarized Fourier‐transform infrared spectroscopy (FTIR) analyses with two pronounced OH‐stretching bands at ~3,230 and ~3,460 cm−1. Our results indicate that lower‐mantle bridgmanite can accommodate relatively high amount of water. Therefore, dehydration melting at the topmost lower mantle by downward flow of transition zone materials would require water content exceeding ~0.1 wt%.
Available online xxxx Editor: J. BrodholtKeywords: elasticity of single crystal San Carlos olivine high pressure and temperature metastable olivine wedge mantle seismic anisotropy Elasticity of single-crystal San Carlos olivine has been derived from sound velocity and density measurements at simultaneous high pressure-temperature conditions up to 20 GPa and 900 K using in situ Brillouin spectroscopy and single-crystal X-ray diffraction in externally-heated diamond anvil cells. These experimental results are used to evaluate the combined effect of pressure and temperature on full elastic constants of single-crystal olivine to better understand its velocity profiles and anisotropies in the deep mantle. Analysis of the results shows that the shear moduli display strong concave behaviors as a function of pressure at a given high temperature, while the longitudinal modulus, C 11 , and the off-diagonal moduli, C 12 and C 13 , exhibit greater temperature dependence at higher pressures than at relatively lower pressures. Using a finite-strain theory and thermal equation of state modeling for a pyrolitic mantle composition along an expected mantle geotherm, our results show that the magnitude of the V P and V S jumps at the 410-km depth are 6% and 6.4%, respectively, which are greater than that found in seismic observations, suggesting a mantle olivine content of 40-50 vol%, which is less than what is expected for the pyrolite model. Our modeled velocity profiles for a metastable olivine wedge in the subduction slabs along a representative cold slab geotherm are 6% and 10% lower than those of wadsleyite and ringwoodite, respectively, at corresponding depths of the normal mantle. Our modeled results also show that metastable olivine in the cold slabs could have strong V P and V S anisotropies. The maximum V P anisotropy is estimated to be 19-22% at transition zone depth, whereas the maximum V S splitting is 13-23% and increases with depth. As a result, the presence of a metastable olivine wedge at the transition zone depth would exhibit a seismic signature of low velocity and strong seismic anisotropy which are consistent with recent seismic observations for various locations of the slabs and can be used as mineral physics constraints for future seismic detections of the metastable olivine wedges in the deep mantle.
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