Photoluminescence activity of Yang and Secco etched multicrystalline silicon material

Ultraviolet and blue-green photoluminescence (PL) was investigated on multicrystalline silicon (mc-Si) samples chemically etched by Secco and Yang solutions. The samples were characterized by dislocation density (10⁵-10⁶ cm⁻²). The form of etched pits is triangular with Yang etch and like a honeycomb with Secco etch as observed with a scanning electron microscope (SEM). These textures of mc-Si wafers give a PL activity similar to that obtained with nanostructures of porous silicon (PS) as reported in the literature. The ultraviolet PL spectra observed with Yang etch shift to the blue-green spectrum range when applying Secco etch. In our experiments we have observed 3-5 μm diameter macro pores separated by a high density of nanowalls. These observations suggest that the origin of the PL activity are quantum dots resulting from the silicon nanocrystallites obtained after few minutes of chemical etching.     

Enhancement of the emission yield of silicon nanocrystals in silica due to surface passivation

The ability of surface passivation to enhance the photoluminescence (PL) emission of Si nanocrystals in SiO₂ has been investigated. Silicon precipitation in implanted samples takes place in a time scale of few minutes at 1100°C. For longer annealing at the same temperature, the PL intensity of the Si nanocrystals increases and eventually reaches saturation, while it correlates inversely with the amount of Si dangling bonds at the Si–SiO₂ interface (P_b centers), as measured by electron spin resonance. This combined behavior is independent on the silica matrix properties, implantation profiles and annealing atmosphere and duration. The observation that the light emission enhancement is directly related to the annealing of P_b centers is confirmed by treatment in forming gas. This mild hydrogenation at much lower temperature (450°C) leads to a complete passivation of the P_b defects, increasing at the same time the PL yield and the lifetime.     

Hydroxyapatite gels and nanocrystals prepared through a sol-gel process

We have investigated the effect of the Ca/P molar ratio on the structural and morphological properties of hydroxyapatite (HA) gels and nanocrystals. The sol-gel process was carried out in aqueous, and alternatively in alcoholic medium (50% water-50% ethanol), at 37°C. Gel samples were obtained by drying the sols at 37°C or at 80°C, whereas powder samples were obtained by filtering the sols. Heat treatment at temperatures as low as 300°C is enough to obtain pure HA from the gels with a Ca/P molar ratio of 1.00 and 1.67. At variance, heat treatment of the gels with a Ca/P of 2.55 always produces secondary phases. The degree of crystallinity of HA increases with the Ca/P molar ratio of the sols, and it is slightly affected by the presence of ethanol in the precipitation medium. Filtering of the sols provides powders constituted of nanocrystalline HA that exhibit degree of crystallinity, crystal morphology and thermal stability closely related to the sols composition.     

AFM of adsorbed polyelectrolytes on cellulose I surfaces spin-coated on silicon wafers

Thin layers of cellulose I nanocrystals were spin-coated onto silicon wafers to give a flat model cellulose surface. A mild heat treatment was required to stabilize the cellulose layer. Interactions of this surface with polyelectrolyte layers and multilayers were probed by atomic force microscopy in water and dilute salt solutions. Deflection–distance curves for standard silicon nitride tips were measured for silicon, cellulose-coated silicon, and for polyelectrolytes adsorbed on the cellulose surface. Transfer of polymer to the tip was checked by running deflection–distance curves against clean silicon. Deflection–distance curves were relatively insensitive to adsorbed polyelectrolyte, but salt addition caused transfer of cationic polyelectrolyte to the tip, and swelling of the polyelectrolyte multilayers.     

Visible and near-IR luminescence via energy transfer in rare earth doped mesoporous titania thin films with nanocrystalline walls

Selected photoluminescence in the wavelength range of 600-1540 nm is generated by energy transfer from a light-gathering mesostructured host lattice to an appropriate rare earth ion. The mesoporous titania thin films, which have a well-ordered pore structure and two-phase walls made of amorphous titania and TiO₂ nanocrystallites, were doped with up to 8 mol% lanthanide ions, and the ordered structure of the material was preserved. Exciting the titania in its band gap results in energy transfer and it is possible to observe photoluminescence from the crystal field states of the rare earth ions. This process is successful for certain rare earth ions (Sm³⁺, Eu³⁺, Yb³⁺, Nd³⁺, Er³⁺) and not for others (Tb³⁺, Tm³⁺). A mechanism has been proposed to explain this phenomenon, which involves energy transfer through surface states on titania nanocrystals to matching electronic states on the rare earth ions.     

Chemical deposition of semiconducting cadmium selenide quantum dots in thin film form and investigation of their optical and electrical properties

Cadmium selenide quantum dots with cubic crystal structure are chemically deposited in thin film form using selenosulfate as a precursor for selenide ions and ammonia buffer with double role: as a ligand and as a pH value controller. The optical band gap energies of as-deposited and thermally treated cadmium selenide thin films, calculated within the framework of parabolic approximation for the dispersion relation, on the basis of equations which arise from the Fermi's golden rule for electronic transitions from valence to conduction band, are 2.08 and 1.77 eV, correspondingly. The blue shift of band gap energy of 0.34 eV for as-deposited thin films with respect to the bulk value is due to the quantum size effects (i.e., nanocrystals behave as quantum dots) and this finding is in agreement with the theoretical predictions. During the thermal treatment the nanocrystals are sintered, the increase of crystal size being in correlation with the decrease of band gap energy. The annealed thin films are practically non-quantized. From the resistance-temperature measurements, on the basis of the dependence of ln(R/Ω) vs 1/T in the region of intrinsic conduction, the thermal band gap energy (at 0 K) of 1.85 eV was calculated.     

Self‐Assembly Film of Zeolite Y Nanocrystals Loading Palladium on an Au Electrode for Electrochemical Applications

Nano‐scale zeolite Y crystals were synthesized, and palladium nanoparticles were prepared in the supercage of the zeolite by “ship‐in‐a‐bottle” approach. A novel method to fabricate zeolite‐modified electrode (ZME) loading Pd nanoparticles was developed, in which the zeolite Y loading Pd²⁺ ions was self‐assembled on (3‐mercaptopropyl) trimethoxysilane‐attached Au surface to form the stable and density packed multilayers (SAM‐ZME). The structures of zeolite Y and the SAM‐ZME were investigated by using TEM, XRD and SEM techniques. Pd²⁺ ions in the SAM‐ZME were converted into Pd nanoparticles (Pd_n⁰) by two steps consisting of the electrochemical reduction as well as the succeeding admission and release of CO. The redox couple [Fe(CN)₆]^3?/4? was used to probe the electron‐transfer barrier properties during self‐assembling process. Moreover, the special properties of the SAM‐ZME loading Pd_n⁰ were studied by using cyclic voltammetry and CO‐probe in situ FTIR spectroscopy. The results illustrated that Pd_n⁰ in the SAM‐ZME exhibits higher electrocatalytic activity for oxidation of adsorbed CO than that of ZME prepared in our previous study by zeolite coating method. The present study is of importance in design and preparation of SAM‐ZME, which poccesseses excellent properties for the immobilization of electrocatalysts or biomolecules.     

H and H NMR studies of cyclohexane nanocrystals in controlled pore glasses

The formation and behaviour of cyclohexane and cyclohexane-d₁₂ nanocrystals in mesoporous solids of well-defined dimensional constraints are studied by ¹H and ²H NMR. The NMR line widths, spin–spin relaxation times (T₂), spin–lattice relaxation times (T₁) and diffusivities (D) were measured as a function of temperature, and the results are discussed with reference to the values obtained for the bulk materials. The confined solids exhibit substantial changes in the phase behaviour and molecular dynamics. Thus, the line-shape measurements reveal a two-phase system consisting of a highly mobile component at the surface of the pore and a plastically crystalline phase in the centre of the pore. The liquid-like surface layer in the mesopores is observable well below the reduced transition temperature of the confined cyclohexane. However, the T₂ and diffusion measurements show that the mobile phase also embraces a minor component attributed to non-frozen liquid in pockets or offshoots.     

Defect-effects on the photoluminescence of ZrO2 bulk,film and nanocrystals

The photoluminescence (PL) properties of ZrO₂ have been measured at different temperatures between 7 and 300 K, using various kinds of ZrO₂ specimens: bulk crystal melt-grown by a large solar furnace, thermally oxidized zirconium plate (ZrO₂ film crystal on Zr ) and nanocrystals (surface area: 35–45m²/g, diameter: 20–30 nm). The results clarify the deep and shallow energy level structures in the energy gap. Reversible UV-laser-light-induced spectral changes are observed for all of the specimens in different specimen-atmospheres (vacuum and O₂ gas). The results elucidate the defect-effects of the PL properties and the PL enhancement mechanism in ZrO₂ nanocrystals.     

Two- and three-dimensional restricted geometry case of luminescence quenching

We present general analytical expression for two and three-dimensional cases of static energy transfer kinetics in doped nanoparticles (of round, spherical and cylindrical shape). A series of numerical experiments has been performed using Monte-Carlo simulation. The analytical expressions have shown very good coincidence with the computer simulation.