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The number of renewable sources, namely photovoltaics (PV), continues to grow within distribution systems. How placements impact a system's performance remains a concern within both the research and the utility communities. Beyond system node voltages and real power losses, this work looks to industry standard imbalance metrics and the changes experienced on these values with varied levels of PV. Specifically, four imbalance metrics are presented and studied for an actual 906-bus distribution system. Multiple loading conditions and photovoltaic placement schemes are explored to compare the changes seen on these metrics across a variety of scenarios experienced by the network.

Silver gallium sulfide nanocrystals were synthesized and characterized by fluorescence, TEM, EDS, and XRD to better understand the material system with an ideal band gap of 2.7 eV. The crystals were found to nucleate in the monoclinic structure, and develop two fluorescence peaks (650, 460 nm) influenced by stoichiometry.

Silver gallium sulfide nanocrystals were synthesized and characterized by fluorescence, TEM, EDS, and XRD to better understand the material system with an ideal band gap of 2.7 eV. The crystals were found to nucleate in the monoclinic structure, and develop two fluorescence peaks (650, 460 nm) influenced by stoichiometry.

The partial transformation of ionic nanocrystals through cation exchange has been used to synthesize nanocrystal heterostructures. We demonstrate that the selectivity for cation exchange to take place at different facets of the nanocrystal plays an important role in determining the resulting morphology of the binary heterostructure. In the case of copper(I) (Cu(+)) cation exchange in cadmium sulfide (CdS) nanorods, the reaction starts preferentially at the ends of the nanorods such that copper sulfide (Cu(2)S) grows inward from either end. The resulting morphology is very different from the striped pattern obtained in our previous studies of silver(I) (Ag(+)) exchange in CdS nanorods where nonselective nucleation of silver sulfide (Ag(2)S) occurs (Robinson, R. D.; Sadtler, B.; Demchenko, D. O.; Erdonmez, C. K.; Wang, L.-W.; Alivisatos, A. P. Science 2007, 317, 355-358). From interface formation energies calculated for several models of epitaxial connections between CdS and Cu(2)S or Ag(2)S, we infer the relative stability of each interface during the nucleation and growth of Cu(2)S or Ag(2)S within the CdS nanorods. The epitaxial attachments of Cu(2)S to the end facets of CdS nanorods minimize the formation energy, making these interfaces stable throughout the exchange reaction. Additionally, as the two end facets of wurtzite CdS nanorods are crystallographically nonequivalent, asymmetric heterostructures can be produced.

Photodeposition of Pt on Colloidal CdS and CdSe/CdS Semiconductor Nanostructures Gordana Dukovic, Maxwell G. Merkle, James H. Nelson, Steven M. Hughes, and A. Paul Alivisatos* Department of Chemistry, University of California, Berkeley and Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA Semiconductor photocatalysis has been identified as a promising avenue for the conversion of solar energy into environmentally friendly fuels, most notably by the production of hydrogen from water.[1–5] Nanometer-scale materials in particular have attracted considerable scientific attention as the building blocks for light-harvesting applications.[6,7] Their desirable attributes include tunability of the optical properties with size, amenability to relatively inexpensive low-temperature processing, and a high degree of synthetic sophistication leading to increasingly complex and multi-functional architectures. For photocatalysis in particular, the high surface- to- volume ratios in nanoscale materials should lead to an increased availability of carriers for redox reactions on the nanoparticle surface. Recombination of photoexcited carriers directly competes with photocatalytic activity.[3] Charge separation is often achieved with multi-component heterostructures. An early example is the case of TiO2 powders functionalized with Pt and RuO2 particles, where photoexcited electrons are transferred to Pt (the reduction site) and holes to RuO2 (the oxidation site).[8] More recently, many colloidally synthesized nanometer-scale metal–semiconductor heterostructures have been reported.[7,9,10] A majority of these structures are made by thermal methods.[7,10] We have chosen to study photochemical formation of metal–semiconductor heterostructures. The detailed understanding of the mechanisms involved in photodeposition of metals on nanometer-scale semiconductors is necessary to enable a high degree of synthetic control. At the same time, because the results of metal deposition can be directly observed by electron microscopy, it can be used to understand how factors such as nanocrystal composition, shape, carrier dynamics, and surface chemistry influence the photochemical properties of semiconductor nanocrystals. In this communication, we report on the photodeposition of Pt on colloidal CdS and CdSe/CdS core/shell nanocrystals. Among the II–VI semiconductors, CdS is of particular interest because it has the correct band alignment for water photolysis[2] and has been demonstrated to be photocatalytically active.[11–16] We have found that the photoexcitation of CdS and CdSe/CdS in the presence of an organometallic Pt precursor leads to deposition of Pt nanoparticles on the semiconductor surface. Stark differences are observed in the Pt nanoparticle location on the two substrates, and the photodeposition can be completely inhibited by the modification of the semiconductor surface. Our results suggest that tuning of the semiconductor band structure, spatial organization and surface chemistry should be crucial in the design of photocatalytic nanostructures.

Formation of cobalt sulfide hollow nanocrystals through amechanism similar to the Kirkendall Effect has been investigated indetail. It was found that performing the reaction at>120oC leads tofast formation of a single void ins ide each shell, whereas at roomtemperature multiple voids are formed within each shell, which can beattributed to strongly temperature-dependent diffusivities for vacancies.The void formation process is dominated by outward diffusion of cobaltcations; still, significant inward transport of sulfur anions can beinferred to occur as the final voids are smaller in diameter than theoriginal cobalt nanocrystals. Comparison of volume distributions forinitial and final nanostructures indicates excess apparent volume inshells implying significant porosity and/or a defective structure.Indirect evidence for shells to fracture during growth at lowertemperatures was observed in shell size statisticsand TEM of as-grownshells. An idealized model of the diffusional process imposes two minimalrequirements on material parameters for shell growth to be obtainablewithin a specific synthetic system.

Branched nanocrystal heterostructures synthesized from CdSe and CdTe exhibit a type II band structure alignment that induces separation of charge upon photoexcitation and localizes carriers to different regions of the tetrahedral geometry. The dynamics of carrier relaxation examined with femtosecond pump-probe spectroscopy showed heterostructures having rise times and biexponential decays longer than those of nanorods with similar dimensions. This is attributed to weaker interactions with surface states and nonradiative relaxation channels afforded by the type II alignment.

We report on high-resolution transmission electron microscope structural studies of InAs colloidal semiconductor nanocrystal quantum dots (NCQDs) on ultrathin GaAs (001) semiconductor single-crystal substrates. We employ a benign method for preparing electron transparent specimens that is suitable for the study of such fragile samples. The image contrast comprises contributions from electron scattering from both the NCs and the GaAs substrate. Long-term electron exposure studies reveal different damage mechanisms operative in the nanocrystals and the substrate.

Integration of semiconductor epitaxical nanostructures and nanocrystals into two classes of quantum structures, uncovered adsorbed nanocrystals or buried via epitaxical overgrowth, is successfully demonstrated through structural and optical studies. The combination InGaAs/GaAs epitaxical structures and InAs nanocrystals is employed as a vehicle with the functional aim of exploiting the well developed optoelectronic communication technology based on the former with the biochemical and biomedical applications for which the latter are well suited.

High quality manganese oxide thin films with smooth surfaces and even thicknesses have been prepared with a nonaqueous sol–gel process involving reduction of tetraethylammonium permanganate in methanol. Spin-coated films have been cast onto soft glass, quartz, and Ni foil substrates, with two coats being applied for optimum crystallization. The addition of alkali metal cations as dopants results in exclusive formation of the layered birnessite phase. By contrast, analogous reactions in bulk sol–gel reactions yield birnessite, tunneled, and spinel phases depending on the dopant cation. XRD patterns confirm the formation of well-crystallized birnessite. SEM images of Li-, Na-, and K–birnessite reveal extremely smooth films having uniform thickness of less than 0.5 μm. Thin films of Rb– and Cs–birnessite have more fractured and uneven surfaces as a result of some precipitation during the sol–gel transformation. All films consist of densely packed particles of about 0.1 μm. When tetrabutylammonium permanganate is used instead of tetraethylammonium permanganate, the sol–gel reaction yields amorphous manganese oxide as the result of diluted Mn sites in the xerogel film. Bilayer films have been prepared by casting an overcoat of K–birnessite onto an Na–birnessite film. However, Auger depth profiling indicates considerable mixing between the adjacent layers.

The development of colloidal quantum dots has led to practical applications of quantum confinement, such as in solution-processed solar cells1, lasers2 and as biological labels3. Further scientific and technological advances should be achievable if these colloidal quantum systems could be electronically coupled in a general way. For example, this was the case when it became possible to couple solid-state embedded quantum dots into quantum dot molecules4,5. Similarly, the preparation of nanowires with linear alternating compositions—another form of coupled quantum dots—has led to the rapid development of single-nanowire light-emitting diodes6 and single-electron transistors7. Current strategies to connect colloidal quantum dots use organic coupling agents8,9, which suffer from limited control over coupling parameters and over the geometry and complexity of assemblies. Here we demonstrate a general approach for fabricating inorganically coupled colloidal quantum dots and rods, connected epitaxially at branched and linear junctions within single nanocrystals. We achieve control over branching and composition throughout the growth of nanocrystal heterostructures to independently tune the properties of each component and the nature of their interactions. Distinct dots and rods are coupled through potential barriers of tuneable height and width, and arranged in three-dimensional space at well-defined angles and distances. Such control allows investigation of potential applications ranging from quantum information processing to artificial photosynthesis.

Microporous manganese oxides have been prepared by nonaqueous sol−gel reactions involving tetrabutylammonium (TBA) or tetraethylammonium (TEA) permanganate and methanol in the presence of alkali cation dopants. Layered birnessite-type materials were obtained for Na+ and K+ dopants in a 0.5:1 reactant ratio with manganese. Na−birnessite was isolated in hydrated and dehydrated forms (7 vs 5.6 A interlayer spacing) whereas only the hydrated K−birnessite was observed. Cryptomelane was generated with a K:Mn ratio of 0.25:1. Spinel manganese oxides were formed with Li+ dopants using 0.5:1 and 0.75:1 Li:Mn ratios. The materials were characterized by powder X-ray diffraction (XRD), elemental analyses, Mn oxidation state determination, thermogravimetric analysis, and scanning electron microscopy. Thin films of manganese oxides were prepared by spin coating TEAMnO4-derived sols onto glass slides. Unlike the bulk gel syntheses, only layered birnessite phases were obtained for thin films with Li+, Na+, and K+ dopants...

In the present work, we analyze the geometry and composition of the nanostructures obtained from the oxidation of iron nanoparticles. The initial oxidation of iron takes place by outward diffusion of cations through the growing oxide shell. This net material flow is balanced by an opposite flow of vacancies, which coalesce at the metal/oxide interface. Thus, the partial oxidation of colloidal iron nanoparticles leads to the formation of core−void−shell nanostructures. Furthermore, the complete oxidation of iron nanoparticles in the 3−8 nm size range leads to the formation of hollow iron oxide nanoparticles. We analyze the size and temperature range in which vacancy coalescence during oxidation of amine-stabilized iron nanoparticles takes place. Maghemite is the crystallographic structure obtained from the complete oxidation of iron nanoparticles under our synthetic conditions.

Nanocrystals of cadmium selenide exhibit a form of polytypism with stable forms in both the wurtzite and zinc blende crystal structures. As a result, wurtzite nanorods of cadmium selenide tend to form stacking faults of zinc blende along the c-axis. These faults were found to preferentially form during the growth of the (001) face, which accounts for 40% of the rod's total length. Since II-VI semiconductor nanorods lack inversion symmetry along the c-axis of the particle, the two ends of the nanorod may be identified by this anisotropic distribution of faults.

Hollow nanocrystals have been synthesized through a mechanism analogous to the Kirkendall Effect. When a cobalt nanocrystal reacts with sulfur in solution, the outward diffusion of cobalt atoms is faster than the inward diffusion of sulfur atoms through the sulfide shell. The dominating outward diffusion of cobalt cations produces vacancies that can condense into a single void in the center of the nanocrystal at high temperatures. This process provides a general route to the synthesis of hollow nanostructures of a large number of compounds and is described in the Full Paper by A. P. Alivisatos and co-workers on p. 1389. Formation of cobalt sulfide hollow nanocrystals through a mechanism similar to the Kirkendall Effect has been investigated in detail. It is found that performing the reaction at > 120 °C leads to fast formation of a single void inside each shell, whereas at room temperature multiple voids are formed within each shell, which can be attributed to strongly temperature-dependent diffusivities for vacancies. The void formation process is dominated by outward diffusion of cobalt cations; still, the occurrence of significant inward transport of sulfur anions can be inferred as the final voids are smaller in diameter than the original cobalt nanocrystals. Comparison of volume distributions for initial and final nanostructures indicates excess apparent volume in shells, implying significant porosity and/or a defective structure. Indirect evidence for fracture of shells during growth at lower temperatures was observed in shell-size statistics and transmission electron microscopy images of as-grown shells. An idealized model of the diffusional process imposes two minimal requirements on material parameters for shell growth to be obtainable within a specific synthetic system.

Integration of semiconductor epitaxical nanostructures and nanocrystals into two classes of quantum structures, uncovered adsorbed nanocrystals or buried via epitaxical overgrowth, is successfully demonstrated through structural and optical studies. The combination InGaAs/GaAs epitaxical structures and InAs nanocrystals is employed as a vehicle with the functional aim of exploiting the well developed optoelectronic communication technology based on the former with the biochemical and biomedical applications for which the latter are well suited.

Cation exchange has been investigated in a wide range of nanocrystals of varying composition, size, and shape. Complete and fully reversible exchange occurs, and the rates of the reactions are much faster than in bulk cation exchange processes. A critical size has been identified below which the shapes of complex nanocrystals evolve toward the equilibrium shape with lowest energy during the exchange reaction. Above the critical size, the anion sublattice remains intact and the basic shapes of the initial nanocrystals are retained throughout the cation exchange. The size-dependent shape change can also be used to infer features of the microscopic mechanism.

Integration of epitaxical and colloidal semiconductor nanostructures into hybrid structures can potentially open unprecedented functionalities and applications. We present here some results of a study of the structural and optical nature of adsorbed InAs nanocrystal quantum dots (NCQDs) on GaAs(001) substrates containing buried nanostructures, providing the first evidence of excitation transfer from NCQDs to the substrate. Results are also presented for the overgrowth of GaAs on the InAs NCQDs, addressing the all important issue of approach to removal of the chemical contamination left behind by the solvent during adsorption of the NCQDS. It is shown that high structural and optical quality buried integrated structures are feasible, thus opening a new field of investigation.