Sharp exponential band tails in highly disordered lead sulfide quantum dot arrays
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Erslev, Peter T.↗
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Lead Sulfide Nanocrystal Quantum Dot Solar Cells with Trenched ZnO Fabricated via Nanoimprinting
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bio-inspired↗
Extraction of lead from waste CRT funnel glass by generating lead sulfide – An approach for electronic waste management
Highlights: • Sodium carbonate and free silica in the glass react to generate sodium silicate and carbon dioxide. • Sodium sulfide and lead silicate group of glass began to react to lead sulfide and sodium silicate. • Lead sulfide got together in the bottom of the crucible under the action of gravity. • The generated lead sulfide was separated and collected in the bottom of the crucible. - Abstract: Waste cathode ray tube (CRT) funnel glass is the key and difficult points in waste electrical and electronic equipment (WEEE) disposal. In this paper, a novel and effective process for the detoxification and reutilization of waste CRT funnel glass was developed by generating lead sulfide precipitate via a high-temperature melting process. The central function in this process was the generation of lead sulfide, which gathered at the bottom of the crucible and was then separated from the slag. Sodium carbonate was used as a flux and reaction agent, and sodium sulfide was used as a precipitating agent. The experimental results revealed that the lead sulfide recovery rate initially increased with an increase in the amount of added sodium carbonate, the amount of sodium sulfide, the temperature, and the holding time and then reached an equilibrium value. The maximum lead sulfide recovery rate was approximately 93%, at the optimum sodium carbonate level, sodium sulfide level, temperature, and holding time of 25%, 8%, 1200 °C, and 2 h, respectively. The glass slag can be made into sodium and potassium silicate by hydrolysis in an environmental and economical process.
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
Variable Surface Termination and Ligand Passivation of Lead Sulfide Nanocrystals Synthesized with Excess Lead Chloride
The surface termination and ligand passivation of semiconducting nanocrystals (NCs) impact the stability, optical properties, and self-assembly of NCs. In this work, we definitively characterize the surface of lead sulfide (PbS) NCs synthesized from excess PbCl 2 . With a combination of small-angle neutron scattering (SANS), photoluminescence, and 1D and 2D NMR experiments, we show that the surface termination of PbS NCs depends on the presence of PbCl 2 during ligand exchange. When excess PbCl 2 is removed prior to ligand exchange, PbS[RNH 3 + Cl – ] NCs are obtained, which are terminated by a monolayer of PbCl x on the {100} PbS facet and passivated by oleylammonium chloride ligands. On the other hand, when excess PbCl 2 remains in solution during ligand exchange, lead oleate forms and attaches to the {111} PbS facets of PbS[RNH 3 + Cl – ] NCs, creating PbS@PbCl x NCs. PbS@PbCl x NCs are coated in an epitaxial layer of PbCl x on both the {100} PbS and {111} PbS facets, making them 0.3–0.4 nm larger on average than PbS[RNH 3 + Cl – ] NCs with identical absorption wavelengths. Additionally, PbS@PbCl x NCs have a consistently higher photoluminescence quantum yield and longer photoluminescence lifetimes than PbS[RNH 3 + Cl – ] NCs. This study clarifies the surface structure of PbS NCs synthesized from excess PbCl 2 , highlighting ligand exchange strategies and reconciling observations from across the literature.
Anions↗
Peculiarities of Electron Transport and Photoconductivity in a Layer of Lead Sulfide Nanoparticles
The main laws of electron transport in layers of lead sulfide (PbS) nanoparticles deposited from aqueous ethanol suspensions were determined by analysis of their current–voltage characteristics. Optical spectra measured at wavelengths in the region of 3500 nm showed that these layers contain almost no any organic components. The photocurrent in deposited PbS nanopowders exhibits variation under the exposure to broadband radiation corresponding to “transparency window” of the atmosphere (8000–14 000 nm), in which the absorption on free charge carriers can take place.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Optical properties of nanostructured lead sulfide films with a D0{sub 3} cubic structure
The optical transmittance of nanostructured cubic PbS (lead sulfide) films with a D0{sub 3} structure is measured in the wavelength range 300 to 3200 nm. The film thicknesses are in the range {approx}120 to {approx}400 nm. Electron microscopy of the microstructure shows that about half of the films' particles are 60 nm or smaller in size. As the average particle size is decreased, the band gap E{sub g} increases from 0.85 to 1.5 eV, being noticeably larger than the band gap of coarse-grained PbS, 0.41 eV. This is indicative of a blue shift of the optical absorption band in nanostructured PbS films.
36 MATERIALS SCIENCE↗
3-D Atomic-Scale Mapping of Manganese Dopants in Lead Sulfide Nanowires
Dopants in nanowires, whether intentional or unintentional, can ultimately control the material's properties and therefore need to be understood on the atomic scale. We study vapor-liquid-solid grown manganese-doped lead sulfide nanowires by atom-probe tomography for the first time for lead salt materials. The three-dimensional chemical concentration maps at the atomic scale demonstrate a radial distribution profile of Mn ions, with a concentration of only 0.18 at.% and 0.01 at.% for MnCl2 and Mn-acetate precursors, respectively. The ability to characterize these small concentrations of dopant atoms in Pb1-xMnxS nanowires (x = 0.0036 and 0.0002), important for spintronic and thermoelectric devices, sets a platform for similar analyses for all nanostructures. First-principles calculations confirm that Mn atoms substitute for Pb in the PbS structure.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Structural and optical studied of nano structured lead sulfide thin films prepared by the chemical bath deposition technique
Lead (II) Sulfide PbS thin films were deposited on glass substrates at 25°C by chemical bath deposition (CBD) method. The structural properties of the films were studied as a function of the concentration of Thiourea (CS (NH{sub 2}){sub 2}) as Source of Sulfide and deposition time. The surface morphology of the films was characterized by X-ray diffraction and SEM. The obtained results showed that the as-deposited films Polycrystalline had cubic crystalline phase that belong to S.G: Fm3m. We found that they have preferred orientation [200]. Also the thickness of thin films decrease with deposition time after certain value and, it observed free sulfide had orthorhombic phase. Optical properties showed that the thin films have high transmission at visible range and low transmission at UV, IR range. The films of PbS have direct band gap (I.68 - 2.32 ev) at 300 K the values of band energy decreases with increases thickness of the Lead (II) Sulfide films.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Performance optimization of solar cells based on colloidal lead sulfide nanocrystals
Colloidal semiconducting quantum dot nanocrystals (NCs) have attracted extensive interest as active building-block for low-cost solution-processed photovoltaic due to their size tunable absorption from the visible to near IR. Among various nanocrystal composition, lead sulfide (PbS), having a bulk bandgap of 0.41 eV, are particularly attractive for photovoltaic applications due to their excellent photosensitivity in the near IR. Starting from colloidal synthesis, in this project functional solar cells are fabricated and characterized based on the nearly monodispersed colloidal PbS nanocrystals that we synthesized. These NC-solar cells are fabricated under a “depleted heterojunction” device architecture containing a planar “tipe II” heretojunction formed by a layer of electron-transporting TiO{sub 2} and a layer of PbS NCs. Relevant structural, optical, and electrical characterizations are performed on NCs and their devices. To understand the operational mechanism of these NC-based solar cells, various material and device aspects are investigated in this work aiming for optimized photovoltaic performance. These aspects include the effect of: (1) NC dimensions (and thus their band gaps); (2) passivation of surface traps through post-synthesis treatments; (3) NC surface ligand-exchange; and (4) interfacial modifications at the heterojunction. The most optimized photovoltaic performance is found after combining the surface trap passivation strategy by halides, ligand-exchange by 3-mercaptopropionic acids, and interfacial TiCl4 treatment, leading to a peak open-circuit voltage of 0.53 V, a short-circuit current density of 14.03 mAcm{sup −2}, and a power conversion efficiency of 3.25%.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
A simple route for making surfactant free lead sulfide (PbS) quantum dots
Highlights: • Surfactant free PbS NCs were successfully synthesised using CoSP technique. • The technique eliminates the requirements of washing to remove the ligands. • Grinding using mortar and pestle creates well separated PbS QDs. • Surfactant free PbS NCs are stable and do not show any degradation with time. - Abstract: An efficient, cost effective and less time consuming method suitable for mass production of surfactant free quantum dots (QDs) of lead sulfide (PbS) is reported. PbS nanocrystals (NCs) are first synthesised by continuous spray pyrolysis (CoSP) technique and de-agglomeration into PbS quantum dots (QDs) is achieved by vigorous mechanical grinding using mortar and pestle. Lead acetate and thiourea were used as the precursor materials for preparation of surfactant free PbS NCs. The broadening in XRD peaks of ground NCs as compared to as synthesized PbS NCs clearly indicated the reduction in particle size to be QDs of PbS. The TEM images also showed that ground PbS NCs were nearly spherical in shape having an average diameter in the range of 4–6 nm. The shift in optical gap from 0.41 eV to 1.47 eV supported the QD formation.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Design of Lead Telluride Based Thermoelectric Materials through Incorporation of Lead Sulfide Inclusions or Ligand Stripping of Nanosized Building Blocks
Design of thermoelectric materials focuses on the optimization of several unfavorably coupled factors: electrical conductivity, Seebeck coefficient, and thermal conductivity. Recent work in thermoelectrics has focused on decreasing lattice thermal conductivity by nanostructuring thermoelectric materials, while recent work in photovoltaics has demonstrated ligand stripping as a means to increased electron mobility in thin films of nanoparticles. In the present work, these two features are combined. A multigram scale synthesis of dispersible, lead telluride nanocrystals (25–50 nm) is developed using hot-injection methods in common organic solvents. These nanocrystals (NCs) are ligand stripped with sulfide (PbTe-S) or iodide (PbTe-I) sources to result in p-type or n-type materials with large Seebeck coefficients at room temperature of 520 or –540 μV·K –1 , respectively. Sequential stripping with sulfide and then iodide (PbTe-SI) resulted in a small Seebeck due to counter doping. PbTe-S and PbTe-SI are found to generate nanostructured composites by growth of lead sulfide nanocrystals (~50–60 nm) in situ upon annealing. However, the electrical conductivities are low (<1 S·cm –1 ) due to excess doping during the ligand stripping. Intentional formation of a nanocomposite (PbTe–PbS) is achieved by combining PbTe NCs with 4–6 nm diameter lead sulfide particles via mixing by incipient wetness with a target of 8 mol % lead sulfide. The resulting nanocomposite is n-type with a Seebeck coefficient of –160 μV·K –1 and an electrical conductivity of 42 S·cm –1 at room temperature. The lattice thermal conductivities of all materials at room temperature are substantially lower than those of bulk lead telluride (2.0 W m –1 ·K –1 ). However, thermoelectric figure of merit (ZT) values are low for all samples (maximum ZT = 0.03 for PbTe–PbS), attributed primarily to the low electrical conductivities. As a result, this work underscores the importance of developing new methods for augmenting electrical conductivity if nanoparticle assemblies are to be practically employed in thermoelectrics.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Study of the self-organization processes in lead sulfide quantum dots
A procedure is described for the synthesis of nanoparticles based on lead chalcogenides. The procedure combines the synthesis of colloidal quantum dots (QDs) in aqueous solutions with simultaneous organization of the QDs into ordered arrays. The processes of the self-organization of QDs are analyzed at the nano- and microscopic levels by the photoluminescence method, atomic-force microscopy, and optical microscopy.
36 MATERIALS SCIENCE↗
Properties of Lead-Sulfide Nanoparticles in a Multicrystalline Structure
The structural and electrical properties of PbS nanoparticles (40–70 nm), produced by a chemical reaction of sodium hydroxide with lead nitrate and electrophoretically deposited onto a conductive substrate, are investigated. The composition and structure of the nanoparticles are identified by X-ray analysis as pure PbS phase with a face-centered cubic lattice. Several minima, related to plasma-resonance absorption at 10–17 μm, are observed in the frustrated total internal reflection (FTIR) spectra. The layer morphology and the nanoparticle shape and sizes are determined by scanning electron and tunneling microscopy. The threedimensional topograms show that the surface fine structure is a set of faceted pyramidal spikes with a size of 5–10 nm and a density of ~400 μm{sup –2}. An analysis of the tunneling current–voltage characteristics of individual nanospikes shows the presence of low-field emission and makes it possible to determine the barrier heights (1.6–1.8 eV), which are explained within the quantum-dot (QD) model.
36 MATERIALS SCIENCE↗
Influence of interparticle electronic coupling on the temperature and size dependent optical properties of lead sulfide quantum dot thin films
We report on the quantum dot (QD) size, temperature, and inter-dot coupling dependence on the optical absorption and emission for PbS QD thin films. Inter-dot coupling is induced by ligand exchange from oleic acid to 1,2-ethanedithiol, and the expected band gap red-shift observed for coupled QD thin films is accompanied by a modification to the temperature-dependence of the band gap energy. The amplitude and temperature dependence of the photoluminescence (PL) Stokes shift support recombination via a mid-gap state and also indicate that the application of band gap-specific models to fit the temperature dependence PL peak energy is inadequate. Electronically coupled QD thin films show PL quenching with decreasing temperature, following a Boltzmann model which is consistent with thermally activated carrier transport. Enhancing the inter-dot coupling results in the dynamic PL decay signal changing from single- to bi-exponential behavior, reveals a size-dependent transport activation energy, and yields a negative temperature dependent band gap energy for the smallest QD diameters.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Pyroelectricity of Lead Sulfide (PbS) Quantum Dot Films Induced by Janus-Ligand Shells
Asymmetry is an essential property to control. To do that in nanocrystalline systems we have developed methods to produce Janus-ligand shells on otherwise symmetric PbS quantum dots (QDs). In this work, we demonstrate that control by constructing a system that exhibits pyroelectricity built from spherical PbS QDs. We observed a pyroelectric current in two different configurations. In one configuration, the QDs are self-assembled into close-packed arrays while in the second configuration, the QDs are dispersed into an electro-inactive polymer, polydimethylsiloxane. Both exhibit a pyroelectric response. In the first configuration we estimate a lower limit of the pyroelectric coefficient to be 1.97 × 10 -7 C/m 2 K, which is likely limited by the degree of QD alignment during film formation but is already on par with common pyroelectric systems. Compared with inorganic ceramic-like and polymeric pyroelectric materials, pyroelectric films self-assembled from polar QDs are easier to prepare, responsive to light with different energies based on QD exciton energy, and the polarization of each QD could be easily tuned by constructing different Janus-ligand shells.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
The dynamics of energy and charge transfer in lead sulfide quantum dot solids
We report on a systematic time-resolved photoluminescence study of the competing energy and charge transfer rates in PbS QDs of differing sizes in the same QD solid as a function of both temperature and ligand-controlled different inter-QD average separations. This complements previous studies that typically varied only one parameter and reveals new aspects while also confirming some known features. For the smallest PbS QDs, the dominant decay process is nonradiative resonant energy transfer (NRET) to adjacent larger dots for all separations but at a rate that increases with decreasing temperature. For the largest QDs, NRET being forbidden, the decay is found to be exponential in the inter-QD separation consistent with carrier tunneling but, for each fixed tunneling distance, exhibiting a thermally activated tunneling carrier population with the activation energy dependent upon the ligand length controlling the inter-QD separation. A consistent understanding of this expanded and rich decay rate behavior of both large and small QDs, we show, can be obtained by accounting for the ligand length dependent (a) dielectric environment of the QD solid modeled using an effective medium description, (b) the energy cost of dissociating the exciton into electron and hole in neighboring QDs, and (c) the potential participation of midgap states. Implications of the findings for NRET based photovoltaics are discussed.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Homolytic cleavage of both heme-bound hydrogen peroxide and hydrogen sulfide leads to the formation of sulfheme
Many heme-containing proteins with a histidine in the distal E7 (HisE7) position can form sulfheme in the presence of hydrogen sulfide (H 2 S) and a reactive oxygen species such as hydrogen peroxide. For reasons unknown, sulfheme derivatives are formed specifically on solvent-excluded heme pyrrole B. Sulfhemes severely decrease the oxygen-binding affinity in hemoglobin (Hb) and myoglobin (Mb). Here, use of hybrid quantum mechanical/molecular mechanical methods has permitted characterization of the entire process of sulfheme formation in the HisE7 mutant of hemoglobin I (HbI) from Lucina pectinata. This process includes a mechanism for H 2 S to enter the solvent-excluded active site through a hydrophobic channel to ultimately form a hydrogen bond with H 2 O 2 bound to Fe(III). Proton transfer from H 2 O 2 to His64 to form compound (Cpd) 0, followed by hydrogen transfer from H 2 S to the Fe(III) H 2 O 2 complex, results in homolytic cleavage of the O–O and S–H bonds to form a reactive thiyl radical (HS*), ferryl heme Cpd II, and a water molecule. Subsequently, the addition of HS to Cpd II, followed by three proton transfer reactions, results in the formation of a three-membered ring ferric sulfheme that avoids migration of the radical to the protein matrix, in contrast to that in other peroxidative reactions. The transformation of this three-membered episulfide ring structure to the five-membered thiochlorin ring structure occurs through a significant potential energy barrier, although both structures are nearly isoenergetic. Both three- and five-membered ring structures reveal longer N B –Fe(III) bonds compared with other pyrrole nitrogen–Fe(III) bonds, which would lead to decreased oxygen binding. Altogether, these results are in agreement with a wide range of experimental data and provide fertile ground for further investigations of sulfheme formation in other heme proteins and additional effects of H 2 S on cell signaling and reactivity.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Pickering Emulsions of Self-Assembled Lead Sulfide Quantum Dots with Janus-Ligand Shells as Nanoreactors for Photocatalytic Reactions
Not Available
77 NANOSCIENCE AND NANOTECHNOLOGY↗