Synthesis and Characterization of Lead Sulfide Nanoparticles in Zirconia-Silica-Urethane Thin Films Prepared by the Sol-Gel Process

PbS nanocrystals (NCs) ranging between 4–8 nm were incorporated into Zirconium-Silica-Urethane (ZSUR) matrix obtained by the sol-gel method. The sizes of the particles were controlled by temperature treatment and by concentration of PbS in ZSUR matrix. The sizes of PbS NCs were determined by TEM measurements. The quantum size effect could also be extracted from optical absorption and photoluminescence spectra. The new matrix allows incorporation of up to 40% PbS forming a characteristic structure of dendrite by reacting lead acetate with ammonium thiocyanate in sol-gel matrix. The sol precursors of the matrix for Zirconium-Silica-Urethane contained zirconium oxide (ZrO₂) matrix solution, tetramethoxysilane (TMOS), 3-glycid oxypropyl trimethoxysilane (GLYMO) and polyethylene urethane silane (PEUS) synthesized separately. The ZrO₂ matrix solution was obtained from zirconium n-tetrapropoxide in propanol and acetic acid was used as a chelating agent to stabilize the zirconium oxide precursor.     

Synthesis,structural and electrical characterization of PbS NCs in titania sol–gel films

Nanocrystals of lead sulfide were grown in TiO₂ (titania) thin films prepared by a sol-gel process. The synthetic procedure as well as the structural, optical, and electrical properties of the films are demonstrated. The structures and morphology of PbS nanocrystals were analyzed using HRTEM, SAED, AFM, HRSEM, XRD and EDAX elemental analysis technique. When the concentration of PbS in the titania matrix is 20 mol%, PbS NCs with a diameter of 2.0 nm are created. At a higher PbS concentration (> 40 mole%) in the titania matrix, PbS NCs and PbS clusters are created not only within the TiO₂ film but also on the external surface of the TiO₂ film. By increasing the PbS concentration up to 50 mol%, PbS nanocrystals of 6–8 nm in diameter are formed within the titania film and PbS clusters with a base size of about 100 nm² and a height up to about 20 nm were self assembled on the external surface of TiO₂ film. Quantum size effect and band gap energies were obtained from shifts of the absorption edge. For electrical measurements, PbS–TiO₂ films were deposited on an ITO/glass substrate, and then covered with gold contact. The electrical properties of ITO/PbS NCs–TiO₂/Au and ITO/PbS NCs–TiO₂/PbS cluster/Au structures were studied. I–V characteristics of the one layer structure are nearly linear and symmetric, while those of the two-layer structure exhibit rectifying behavior.     

Optical and Conductivity Properties of PbS Nanocrystals in Amorphous Zirconia Sol-Gel Films

Lead sulfide (PbS) nanocrystals (NCs), embedded in amorphous zirconia sol-gel film with different PbS mole concentration (5–30%), were grown at temperature, ranging from 200°C to 350°C. The size of PbS NCs was determined by TEM and by blue shift of the absorption edge. The size increased with an increase of the synthesis temperature and PbS mole concentration. The optical and electrical properties of various sizes of PbS NCs in zirconia film are investigated utilizing absorption, photoluminescence (PL) and current-voltage measurement. The PL spectra were Stokes shifted from the corresponding absorption edge by about 0.5 eV. The latter can be associated with recombination process from surface state. The electrical properties were investigated by the deposition of the PbS NCs-zirconia films on ITO/glass substrate, followed by their coverage with gold contact. The current-voltage characteristics depend on the PbS NCs size and exhibits nonlinear nearly symmetric curve, associated with the space-charge limited current or the tunneling of carriers through the nanocrystalline film.     

Synthesis and characterization of PbSe and PbSe/PbS core–shell colloidal nanocrystals

A new colloidal procedure, for the synthesis of PbSe and PbSe/PbS core–shell semiconductor nanocrystals (NCs), is reported. The synthesis includes the reaction between tributyl-phosphine selenium and lead 2-ethyl-hexanoate, under inert gas at room temperature. High-resolution transmission electron microscopy (HRTEM), X-ray energy dispersive spectroscopy (EDS), absorption and photoluminescence (PL) spectroscopy were used to characterize the samples. The EDS and HRTEM confirmed the existence of rock-salt cubic structures of the PbSe. Furthermore, the HRTEM showed the formation of PbSe/PbS core–shell structures, with epitaxial shell layer with thickness varying between 1 and 4 ML. The absorption spectra of these materials exhibited distinct transitions, related to the e1–h1, e2–h2 and e2–h3 and e2–h1 transitions. These bands are blue shifted with decrease in the NCs diameter. However, the e1–h1 is slightly red shifted with increase in the PbS shell thickness. The last effect can be due to an electronic mixing of the PbSe and PbS conduction states. The PL measurements showed a substantial increase of the exciton emission in the core–shell structures, arising by an efficient chemical passivation of the PbSe core.     

Synthesis and characterization of PbS nanorods and nanowires

 A surfactant assisted solvotermal approach for the controllable synthesis of PbS nanowires and nanorods is applied. The synthesis is based on decomposition of lead thiocyanate in boiling benzyl alcohol with Cetyl trimethyl ammonium bromide used as a surfactant. Nanowires of PbS (about 2–3 μm with an average diameter of 30–50 nm) and nanorods (200–300 nm in length with an axial ratio of 4–5) were synthesised. The nanostructures were characterized by high resolution transmission electron microscopy (HR-TEM), scanning electron microscopy (SEM), selected area electron diffraction (SAED) and X-ray diffraction analysis. The experimental results indicate that the reaction duration and concentration of surfactant play key roles in determining the final morphologies of PbS blocks building and also in their crystallinity. A possible mechanism for creation of PbS nanowires and nanorods is discussed.     

Air-stable PbSe/PbS and PbSe/PbSexS1-x core-shell nanocrystal quantum dots and their applications

The optical properties and functionality of air-stable PbSe/PbS core-shell and PbSe/PbSexS1-x core-alloyed shell nanocrystal quantum dots (NQDs) are presented. These NQDs showed chemical robustness over months and years and band-gap tunability in the near infrared spectral regime, with a reliance on the NQD size and composition. Furthermore, these NQDs exhibit high emission quantum efficiencies of up to 65% and an exciton emission band that is narrower than that of the corresponding PbSe NQDs. In addition, the emission bands showed a peculiar energy shift with respect to the relevant absorption band, changing from a Stokes shift to an anti-Stokes shift, with an increase of the NQD diameter. The described core-shell structures and the corresponding PbSe core NQDs were used as passive Q-switches in eye-safe lasers of Er:glass, where they act as saturable absorbers. The absorber saturation investigations revealed a relatively large ground-state cross-section of absorption (sigma gs = 10(-16) - 10(-15) cm2) and a behavior of a "fast" absorber with an effective lifetime of tau eff approximately 4.0 ps is proposed. This lifetime is associated with the formation of multiple excitons at the measured pumping power. The product of sigma gs and tau eff enables sufficient Q-switching performance and tunability in the near infrared spectral regime. The amplified spontaneous emission properties of PbSe NQDs were examined under continuous illumination by a diode laser at room temperature, suitable for standard device conditions. The results revealed a relatively large gain parameter (g = 2.63 - 6.67 cm-1). The conductivity properties of PbSe NQD self-assembled solids, annealed at 200 degrees C, showed an Ohmic behavior at the measured voltages (up to 30 V), which is governed by a variable-range-hopping charge transport mechanism.