L. Tapfer

Silver nanocrystals in silica by sol-gel processing

Abstract Silver nanocrystal doped silica films were prepared by the sol-gel process. The sol was prepared from 1:0.12:12:0.2:6:7 molar ratios of Si(OC2H5)4:AgNO3:H2O:HNO3:C3nH7OH:C4iH9OH. The glassy, highly transparent film with high dopant concentration (silver/silicon atomic ratio = 0.12) was successfully prepared by the dip-coating method. After drying in air at 60°C for 30 min, samples were heat-treated, in air, at 300, 350, 400, 450, 500 and 550°C using 30–100 min soaking periods for each step in a cumulative heating procedure. Measurements on the films were made by ultraviolet-visible and infrared spectroscopy, X-ray photoelectron spectroscopy, Rutherford backscattering spectrometry and transmission electron microscopy. Mechanisms of silver colloid formation in the densified silica matrix with respect to the thermal treatment are discussed. To understand the formation of silver nanocrystals from the silver silicate network, the corresponding doped bulk gel samples were analyzed by X-ray diffraction and differential scanning calorimetry.

Formation of copper and silver nanometer dimension clusters in silica by the sol‐gel process

Ag and Cu (pure and/or mixture) nanoclusters doped silica films were prepared by the sol‐gel process. In the case of Ag and Cu codoped silica films, Cu/Ag molar ratio was 1, 2, and 3 at constant (Ag+Cu)/SiO2 molar ratio of 0.175. Separated Ag and Cu nanoclusters are formed in the silica matrix. The size of the clusters and their distribution are dependent on the film composition. Optical absorption was measured from 185 to 800 nm. Intensity‐dependent nonlinear refractive index was measured for pure Cu and Ag–Cu (1:1 molar ratio) samples using z‐scan technique in the wavelength range from 570 to 596 nm. The measured nonlinear refractive index is of the order of 10−13 m2/W at a pulse repetition rate of 15.2 MHz.

Annealing behavior of silver, copper, and silver–copper nanoclusters in a silica matrix synthesized by the sol‐gel technique

Silver, copper, and mixed silver–copper nanocluster‐doped silica thin layers were prepared by the sol‐gel process. Samples were heat treated in different annealing atmospheres (air, argon, or 5%H2–95%N2) in the temperature range 500–1100 °C. Specimens were characterized by optical absorption spectroscopy, Rutherford backscattering spectrometry, x‐ray diffraction, and transmission electron microscopy. Cluster growth and dissolution, as well as migration of metal atoms towards the sample surface, with a subsequent evaporation, were observed to occur at temperatures that depend on the annealing atmosphere. In the mixed silver–copper system, the formation of Ag–Cu phase‐separated clusters was observed.

Synthesis and characterization of sol-gel silica films doped with size-selected gold nanoparticles.

Homogeneous nanocomposite silica films uniformly doped with size-selected gold nanoparticles (AuNPs) have been prepared by a combined use of colloidal chemistry and the sol-gel process. For this purpose, stable thiol-functionalized AuNPs (DDT-AuNPs) were first synthesized by a two-phase aqueous/organic system and, subsequently, dispersed in an acid-catalysed sol-gel silica solution. The microstructural morphology of the samples was investigated by x-ray diffraction and field emission scanning electron microscopy. X-ray photoelectron spectroscopy (XPS) and UV-vis optical spectrophotometry were instead employed to investigate the elemental chemical behaviour and the evolution of the surface plasmon resonance (SPR) band of the AuNPs from their synthesis up to the formation of the Au-doped silica films. The results show that the size, shape and crystalline domains of the AuNPs remain unchanged during the entire preparation process, indicating that their aggregation or decomposition was prevented. XPS results show that the DDT-AuNPs lose the capping shells and oxidize themselves when dispersed in acid-catalysed sol-gel solutions, and that bare AuNPs are embedded in the SiO(2) films. A large broadening of the SPR band, observed for systems with DDT-AuNPs, suggests the presence of interface effects which cause a surface electron density lowering. Thiol chain detachment from the AuNPs determines an increase of the SPR peak intensity while the oxidation of the Au surfaces causes a red shift of its position. The latter is no longer observed in doped films, suggesting that no interfacial effects between bare AuNPs and the host medium are present.

Light-emitting nanocomposite CdS–polymer electrospun fibres via in situ nanoparticle generation

We report on the simple, in situ generation of CdS nanocrystals inside electrospun polymer fibres by thermal decomposition of a cadmium thiolate precursor, leading to nanocomposite light-emitting fibres. The modifications induced in the precursor by the thermal decomposition are investigated by a morphological, structural and spectroscopic analysis of the resulting nanocomposite fibres. This approach allows us to overcome nanofabrication difficulties related to disfavoured micro- or nanofluidic molecular flow as given by the direct incorporation of particles in the electrospinning solution. This method therefore enables the synthesis of luminescent, CdS-based composite fibres with emission peaked in the visible range, suitable as building blocks for nanophotonic devices based on light-emitting nanomaterials.

CdS-polymer nanocomposites and light-emitting fibers by in situ electron-beam synthesis and lithography.

A straightforward, electron-beam induced synthesis and patterning approach to the in situ generation of CdS nanocrystals in nanocomposite films and light-emitting electrospun nanofibers is used. Smartly combining room-temperature nanoimprinting, electrospinning, and electron-beam decomposition of nanocrystal precursors and subsequent nucleation of nanoparticles in a polymer matrix allows exploitation of the most favorable flow conditions of organics to produce various nanocomposite nanostructures.

Optical and structural properties of ternary alloy AlxGa1−xAs/AlAs multiple‐quantum‐well structures

The linear and nonlinear optical properties of a series of ternary alloy AlxGa1−xAs/AlAs multiple‐quantum‐well structures have been investigated and related to the multilayer configuration. The direct energy gap was found to scale with the AlAs mole fraction as predicted by Lee and Yuravel [Phys. Rev. B 21, 659 (1980)] and the band offset ratio to depend on the alloy composition. Exciton absorption bleaching was observed at room temperature and the nonlinear absorption cross sections were estimated for the first two confined excitonic states. Finally, the possibility of achieving optical gain for the type‐II band alignment along the growth direction as well as in the layer plane is demonstrated.

Mono- and bi-functional arenethiols as surfactants for gold nanoparticles: synthesis and characterization.

Stable gold nanoparticles stabilized by different mono and bi-functional arenethiols, namely, benzylthiol and 1,4-benzenedimethanethiol, have been prepared by using a modified Brusts two-phase synthesis. The size, shape, and crystalline structure of the gold nanoparticles have been determined by high-resolution electron microscopy and full-pattern X-ray powder diffraction analyses. Nanocrystals diameters have been tuned in the range 2 ÷ 9 nm by a proper variation of Au/S molar ratio. The chemical composition of gold nanoparticles and their interaction with thiols have been investigated by X-ray photoelectron spectroscopy. In particular, the formation of networks has been observed with interconnected gold nanoparticles containing 1,4-benzenedimethanethiol as ligand.

Synthesis and Microstructural Investigations of Organometallic Pd(II) Thiol-Gold Nanoparticles Hybrids

In this work the synthesis and characterization of gold nanoparticles functionalized by a novel thiol-organometallic complex containing Pd(II) centers is presented. Pd(II) thiol,trans, trans-[dithiolate-dibis(tributylphosphine)dipalladium(II)-4,4′-diethynylbiphenyl] was synthesized and linked to Au nanoparticles by the chemical reduction of a metal salt precursor. The new hybrid made of organometallic Pd(II) thiol-gold nanoparticles, shows through a single S bridge a direct link between Pd(II) and Au nanoparticles. The size-control of the Au nanoparticles (diameter range 2–10 nm) was achieved by choosing the suitable AuCl4−/thiol molar ratio. The size, strain, shape, and crystalline structure of these functionalized nanoparticles were determined by a full-pattern X-ray powder diffraction analysis, high-resolution TEM, and X-ray photoelectron spectroscopy. Photoluminescence spectroscopy measurements of the hybrid system show emission peaks at 418 and 440 nm. The hybrid was exposed to gaseous NOxwith the aim to evaluate the suitability for applications in sensor devices; XPS measurements permitted to ascertain and investigate the hybrid –gas interaction.

Heavy carbon doping of GaAs grown by solid‐source molecular‐beam epitaxy

We study the incorporation of carbon in GaAs at doping levels beyond 1019 cm−3 grown by conventional solid‐source molecular‐beam epitaxy. The correlation of Hall effect measurements at 77 and 300 K and of double crystal x‐ray diffractometry allows us to determine the fraction of carbon incorporated on As sites acting as acceptors. These experiments reveal the onset of compensation at the highest doping levels of 5×1019 cm−3.