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At least 37 records · Page 2

Synthesis of luminescent core/shell α-Zn 3 P 2 /ZnS quantum dots

Metal chalcogenide nanoparticles offer vast control over their optoelectronic properties via size, shape, composition, and morphology which has led to their use across fields including optoelectronics, energy storage, and catalysis. While cadmium and lead-based nanocrystals are prevalent in applications, concerns over their toxicity have motivated researchers to explore alternate classes of nanomaterials based on environmentally benign metals such as zinc and tin. The goal of this research is to identify material systems that offer comparable performance to existing metal chalcogenide systems from abundant, recyclable, and environmentally benign materials. With band gaps that span the visible through the infrared, II–V direct band gap semiconductors such as tetragonal zinc phosphide (α-Zn 3 P 2 ) are promising candidates for optoelectronics. To date, syntheses of α-Zn 3 P 2 nanoparticles have been hindered because of the toxicity of zinc and phosphorus precursors, surface oxidation, and defect states leading to carrier trapping and low photoluminescence quantum yield. Here, we report a colloidal synthesis of quantum confined α-Zn 3 P 2 nanoparticles from common phosphorus precursor tris(trimethylsilyl)phosphine and environmentally benign zinc carboxylates. Shelling of the nanoparticles with zinc sulfide is shown as a method of preventing oxidation and improving the optical properties of the nanoparticles. These results show a route to stabilizing α-Zn 3 P 2 nanoparticles for optoelectronic device applications.

25 ENERGY STORAGE↗

Location and characterization of heterogeneous phases within Mary Rose wood

Preserving the Mary Rose oak hull for future generations is a major challenge due to the highly heterogeneous nature of waterlogged wooden artifacts, which contain polycrystalline, amorphous, and nanostructured materials that test traditional characterization methods. Effective conservation requires detailed knowledge of the distribution and chemical nature of these species to develop strategies for preventing multiple chemo-mechanical degradation pathways. Here, we apply synchrotron-based computed tomography total scattering methods to the Mary Rose keelson wood that provides valuable position-resolved structural information on multiple embedded species of different length and concentration scales. We identify 5 nm zinc sulfide nanoparticles in the wood, presumably deposits from bacteria operating on the sulfur energy cycle under the anaerobic conditions on the seabed. These are identified as precursors to acid attack on the wood upon removal to an aerobic environment. These insights inform not only next-generation conservation strategies, but also the efficacy and unforeseen issues of previous treatments.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Surface Effects on Pyrene Luminescence Excitation

Pyrene is a polycyclic aromatic hydrocarbon with fluorescence in the 370-400 nm range. The optical properties of pyrene deposited on different substrates were investigated from experimental and theoretical points of view. In contrast to prior studies of surface-enhanced fluorescence, in this work all substrates were semiconductors or insulators. Experimentally, the intensity of photoluminescence (PL) and PL excitation (PLE) spectra were investigated. PLE spectra of pyrene’s monomer emission show that the intensities of the two main absorption peaks vary according to the chosen substrate. Here, calculations for pyrene on zinc sulfide (ZnS) and surface-oxidized diamond suggest that this connection arises from the alignment of the pyrene electronic levels relative to the band edges of the substrate. The absorption peak at 272 nm (4.56 eV) is shown to depend on the HOMO-1→LUMO orbital contribution while the 335 nm (3.70 eV) peak depends upon the HOMO→LUMO transition. When the HOMO-1 level falls inside the substrate valence band, as in the case of ZnS, there is significant hybridization of the molecular state with surface states that causes an enhancement of the 272 nm peak. For pyrene on diamond, however, the HOMO-1 level falls in the substrate bandgap, leading to negligible hybridization and thus no enhancement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rugged nanoparticle tracers for mass tracking in explosive events

Tracing the flow of solid matter during an explosion requires a rugged tag that can be measured by a unique identifiable signature. Silica-covered semiconductor quantum dots (QDs) provide a unique and tunable photoluminescent signature that emits from within a sacrificial outer layer. Five types of silica-covered zinc sulfide QDs were synthesized and covalently bound to commercial luminescent powders. The combination of five dots and five powders enables a matrix of 25 unique tags. The tracers are shown to be tolerant of environments associated with chemical explosives and provides a unique tag to evaluate debris fields.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF↗

Transformation pressure of ZnS by a new primary pressure technique

An experiment designed to measure the transformation pressure of zinc sulfide by a primary pressure method using an indentor-anvil system made of single-crystal diamond is discussed. A nonsorting electrode-grid which can be applied directly to the anvil using optical lithography is described, together with the procedures used for positioning.

Ruoff, A. L.↗

Use of gamma ray radiation to parallel the plates of a Fabry-Perot interferometer

The use of gamma radiation to parallel the plates of a Fabry-Perot etalon is examined. The method for determining the etalon parallelism, and the procedure for irradiating the posts are described. Changes in effective gap for the etalon over the surface are utilized to measure the parallelism of the Fabry-Perot etalon. An example in which this technique is applied to an etalon of fused silica plates, which are 132 mm in diameter and coded with zinc sulfide and cryolite, with Zerodur spaces 2 cm in length. The effect of the irradiation of the posts on the thermal performance of the etalon is investigated.

Skinner, Wilbert R.↗

Diamondlike carbon protective coatings for optical windows

Diamondlike carbon (DLC) films were deposited on infrared transmitting optical windows and were evaluated as protective coatings for these windows exposed to particle and rain erosion. The DLC films were deposited on zinc selenide (ZnSe) and zinc sulfide (ZnS) by three different ion beam methods: (1) sputter deposition from a carbon target using an 8-cm argon ion source; (2) direct deposition by a 30-cm hollow cathode ion source with hydrocarbon gas in argon; and (3) dual beam direct deposition by the 30-cm hollow cathode ion source and an 8-cm argon ion source. In an attempt to improve the adherence of the DLC films on ZnSc and ZnS, ion beam cleaning, ion implantation with helium and neon ions, or sputter deposition of a thin, ion beam intermediate coating was employed prior to deposition of the DLC film. The protection that the DLC films afforded the windows from particle and rain erosion was evaluated, along with the hydrogen content, adherence, intrinsic stress, and infrared transmittance of the films. Because of the elevated stress levels in the ion beam sputtered DLC films and in those ion beam deposited with butane, films thicker than 0.1 micron and with good adherence on ZnS and ZnSe could not be generated. An intermediate coating of germanium successfully allowed the DLC films to remain adherent to the optical windows and caused only negligible reduction in the specular transmittance of the ZnS and ZnSe at 10 microns.

Swec, Diane M.↗

Diamondlike carbon protective coatings for optical windows

Diamondlike carbon (DLC) films were deposited on infrared transmitting optical windows and were evaluated as protective coatings for these windows exposed to particle and rain erosion. The DLC films were deposited on zinc selenide (ZnSe) and zinc sulfide (ZnS) by three different ion beam methods: (1) sputter deposition from a carbon target using an 8-cm argon ion source; (2) direct deposition by a 30-cm hollow cathode ion source with hydrocarbon gas in argon; and (3) dual beam direct deposition by the 30-cm hollow cathode ion source and an 8-cm argon ion source. In an attempt to improve the adherence of the DLC films on ZnSc and ZnS, ion beam cleaning, ion implantation with helium and neon ions, or sputter deposition of a thin, ion beam intermediate coating was employed prior to deposition of the DLC film. The protection that the DLC films afforded the windows from particle and rain erosion was evaluated, along with the hydrogen content, adherence, intrinsic stress, and infrared transmittance of the films. Because of the elevated stress levels in the ion beam sputtered DLC films and in those ion beam deposited with butane, films thicker than 0.1 micron and with good adherence on ZnS and ZnSe could not be generated. An intermediate coating of germanium successfully allowed the DLC films to remain adherent to the optical windows and caused only negligible reduction in the specular transmittance of the ZnS and ZnSe at 10 microns.

Swec, Diane M.↗

Space environmental effects on coated optics

Several high reflectance mirrors and an output window were selected for the Long Duration Exposure Facility (LDEF) by pre-flight screening using laboratory simulation of natural space radiation. One mirror, a silicon/aluminum oxide design, showed expected excellent stability in orbit and a long shelf life. An aluminum oxide coated calcium fluoride window also showed good stability. Less stable but more interesting behavior was observed in the zinc sulfide based mirrors that showed contamination effects and related dendrite formation. These samples, which were located on both leading and trailing edges, also had interesting impact sites.

T M Donovan↗

Quantum Dots Microstructured Optical Fiber for X-Ray Detection

Microstructured optical fibers containing quantum dots scintillation material comprised of zinc sulfide nanocrystals doped with magnesium sulfide are presented. These quantum dots are applied inside the microstructured optical fibers using capillary action. The x-ray photon counts of these fibers are compared to the output of a collimated CdTe solid state detector over an energy range from 10 to 40 keV. The results of the fiber light output and associated effects of an acrylate coating and the quantum dot application technique are discussed.

DeHaven, Stan↗

Quantum Dots Microstructured Optical Fiber for X-Ray Detection

A novel concept for the detection of x-rays with microstructured optical fibers containing quantum dots scintillation material comprised of zinc sulfide nanocrystals doped with magnesium sulfide is presented. These quantum dots are applied inside the microstructured optical fibers using capillary action. The x-ray photon counts of these fibers are compared to the output of a collimated CdTe solid state detector over an energy range from 10 to 40 keV. The results of the fiber light output and associated effects of an acrylate coating and the quantum dots application technique are discussed.

DeHaven, S. L.↗

A photochargeable semiconductor for highly efficient dehydrogenative coupling of amines

The development of materials with high photocatalytic efficiency is essential for sustainable chemical transformations. Here, in this work, we introduce photochargeable zinc indium sulfide nanocrystals with notable charge storage capacity, enabling highly efficient photocatalytic dehydrogenative coupling of amines. Combined with a nickel cocatalyst, the nanocrystals deliver diamines and hydrogen at rates exceeding 120 mmol per gram of photocatalyst per hour, with > 95% selectivity and an apparent quantum efficiency of up to 39.4% under ambient conditions. The system exhibits excellent scalability, demonstrated by a reaction on a 20-g scale, and broad versatility in promoting amino acid ester coupling and polymerization reactions with concurrent hydrogen evolution. Mechanistic studies attribute the photocharging capability of zinc indium sulfide nanocrystals to in situ-generated trap states such as sulfur vacancies, which extend hydrogen production into the dark catalytic cycle and enhance the overall charge utilization efficiency. These findings position photochargeable semiconductors as promising platforms for a wide range of photocatalytic applications.

nanoscale devices↗

Next Generation Thin-Film Solar Absorbers Based on Chalcogenides

Harvesting solar energy has never been more important than today as the world is combating the implications of global climate change. Grid decarbonization is a central component of efforts to keep the global temperature increase below 2 °C following the 2015 Paris Agreement. The Sun is the cleanest and most abundant renewable energy source with the Earth’s surface receiving enough energy in an hour to meet the world’s annual energy demands. Therefore, we need to take advantage of the essentially limitless clean solar energy for powering our society; this can be achieved using photovoltaics (PV), direct conversion of sunlight into electricity using semiconductor materials. To gain full advantage of this technology, however, the cost of PV must be competitive with the more traditional carbon-based sources (coal, oil, and natural gas). Most recent developments on this front, including the current state-of-the-art solar cell technologies and ongoing work on a new generation of light absorbing chalcogenide materials, are discussed by Lydia Wong and colleagues in a comprehensive new review article (10.1021/acs.chemrev.1c00301). The Review covers a broad class of materials and provides a comparison between different materials on the basis of diode parameters and DFT calculations. Furthermore, this Highlight will focus specifically on copper zinc tin sulfide (CZTS).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrostatic Asymmetry of Wurtzite Nanocrystals and Resulting Photocatalytic Properties

Efficient light absorption and high energy of charge carriers of zinc cadmium sulfide (ZCS) make this semiconductor attractive for many photocatalytic reactions. Despite marked successes in shape-controlled synthesis of ZCS central to their photocatalytic performance, recombination of charge carriers as they migrate through the nanoscale particles results in losses of excitation energy, markedly reducing the photocatalytic activity of ZCS and other heterogeneous photocatalysts. Here, in this study, we show that the electrostatic asymmetry of nanostructures, previously discovered for nearly spherical nanoparticles, also manifests in wurtzite ZCS with planar geometry. The electrostatic asymmetry assists charge separation and substantially increases the yield of photocatalytic reactions in monocrystalline ZCS. The synthesized ZCS nanorods and nanoplates with identical chemical composition were found to have markedly different photocatalytic activity for evolution of hydrogen in water. Despite much smaller specific surface areas, the ~500 nm wide nanoplates displayed a hydrogen evolution rate 12 times higher than the ~35 nm long nanorods, also outperforming other ZCS photocatalysts. Experimental and computational data indicate that the homo- and heterojunction-free ZCS nanoplates with continuous wurtzite lattice behave essentially as nanoscale dipoles with intrinsic dipole moment as high as 48.39 D per unit cell. Electric-field-directed migration of charge carriers stimulates their localization on opposite parts of the nanoplates. Direct imaging of the intraparticle electrical field using off-axis electron holography confirmed their electrostatic asymmetry. Polarization-enhanced charge separation provides a new pathway to efficient and stable photocatalysts for sustainable energy technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sputtered p-Type Cu x Zn 1– x S Back Contact to CdTe Solar Cells

As thin-film cadmium telluride (CdTe) solar cells gain prominence, one particular challenge is optimizing contacts and their interfaces to transfer charge without losses in efficiency. Back contact recombination is still significant and will prevent CdTe solar technology from reaching its full potential in device efficiency, and transparent back contacts have not been developed for bifacial solar technology or multijunction solar cells. To address these challenges, here we investigate sputtered Cu x Zn 1– x S as a p-type semi-transparent back contact material to thin-film polycrystalline CdTe solar cells at Cu concentrations x = 0.30, 0.45, and 0.60. This material is selected for its high hole conductivity (160–2120 S cm –1 ), wide optical band gap (2.25–2.75 eV), and variable ionization potential (approximately 6–7 eV) that can be aligned to that of CdTe. We report that without device optimization, CdTe solar cells with these Cu x Zn 1– x S back contacts perform as well as control cells with standard ZnTe:Cu back contacts. We observe no reduction in external quantum efficiency, low contact barrier heights of approximately 0.3 eV, and carrier lifetimes on par with those of baseline CdTe. These cells are relatively stable over one year in air, with V OC and efficiency of the x = 0.30 cell decreasing by only 1 and 3%, respectively. Using scanning electron microscopy and scanning transmission electron microscopy to investigate the Cu x Zn 1– x S/CdTe interface, we demonstrate that the Cu x Zn 1– x S layer segregates into a bilayer of Cu-Te-S and Zn-Cd-S, and thermodynamic reaction calculations support these findings. Despite its bilayer formation, the back contact still functions well. This investigation explains some of the physical mechanisms governing the device stack, inspires future work to understand interfacial chemistry and charge transfer, and elicits optimization to achieve higher-efficiency CdTe cells.

14 SOLAR ENERGY↗