Sol-gel synthesis of luminescent InP nanocrystals embedded in silica glasses

III-V semiconductor nanocrystals rarely exist as spherical inclusions inside glasses, due to difficulties during their preparation, such as high toxic reagents or fast oxidation under usual glass technology temperatures. In this letter a sol-gel method for synthesis of InP nanocrystals embedded in silica glasses was described. Gels were synthesized by hydrolysis of a complex solution of Si(OC2H5)4, InCl3.4H2O, and PO(OC2H5)3. Then, the gels were heated at 600 degrees C in the presence of H2 gas to form fine cubic InP crystallites. Raman spectrum showed an InP longitudinal-optic mode (342 cm(-1)) and a transverse-optic mode (303 cm(-1)). The size of InP nanocrystals was found to be from 2 to 8 nm in diameter by transmission electron microscopy. A strong photoluminescence with a peak at 856 nm was observed from InP nanocrystals embedded in silica glasses. The results suggest that it might be possible to synthesize other III-V semiconductor nanocrystals embedded in silica glasses through the sol-gel process.     

Controlled synthesis of semiconductor PbWO4 nanocrystals inside silica SBA-15 materials

A new flexible approach is developed to synthesize PbWO₄ nanoparticles inside the channels of mesoporous silica SBA-15. Mesoporous SBA-15 silica with 7 nm pores was produced by a hydrothermal process and used as a hard template. PbWO₄ nanoparticles were synthesized and incorporated into the mesoporous silicate support in a low-power ultrasonication condition. The as-synthesized samples were characterized by Raman spectroscopy, diffuse reflectance UV–vis spectroscopy (UV–vis), powder X-ray diffraction (XRD), small-angle X-ray diffraction (SAXRD), nitrogen adsorption and transmission electron microscopy (TEM). It was found that PbWO₄ nanoparticles appeared among the channels of SBA-15. Blue shift was observed in UV–vis absorption spectra due to the quantum size effect of PbWO₄ nanoparticles. This preparation method is also capable of synthesis of various semiconductor nanoparticles with controlled size and morphology inside the channels of mesoporous materials.     

Thermal evolution of cobalt nanocrystals embedded in silica

The structural evolution of cobalt nanoclusters synthesized in silica glass by ion implantation has been investigated upon thermal annealing. The samples were characterized by in-situ grazing incidence X-ray diffraction, exploiting a synchrotron radiation beam and following their evolution during thermal treatments in vacuo up to T = 800 °C. Before heating, the system is composed of hcp Co nanocrystals; we have not detected the transition from hcp to fcc structure that in the bulk phase occurs around 420 °C; nevertheless, the differences in the diffraction pattern recorded at T = 800 °C with respect to the corresponding one at room temperature suggest the presence of a second crystalline phase.     

General synthesis of manganese-doped II-VI and III-V semiconductor nanowires

A general approach for the synthesis of manganese-doped II-VI and III-V nanowires based on metal nanocluster-catalyzed chemical vapor deposition has been developed. High-resolution transmission electron microscopy and energy-dispersive X-ray spectroscopy studies of Mn-doped CdS, ZnS, and GaN nanowires demonstrate that the nanowires are single-crystal structures and homogeneously doped with controllable concentrations of manganese ions. Photoluminescence measurements of individual Mn-doped CdS and ZnS nanowires show characteristic pseudo-tetrahedral Mn2+ ((4)T1-->(6)A1) transitions that match the corresponding transitions in bulk single-crystal materials well. Photoluminescence studies of Mn-doped GaN nanowires suggest that manganese is incorporated as a neutral (Mn3+) dopant that partially quenches the GaN band-edge emission. The general and controlled synthesis of nanowires doped with magnetic metal ions opens up opportunities for fundamental physical studies and could lead to the development of nanoscale spintronic devices.     

Colloidal synthesis of ultrathin two-dimensional semiconductor nanocrystals

2D semiconductor quantum wells have been recognized as potential candidates for various quantum devices. In quantum wells, electrons and holes are spatially confined within a finite thickness and freely move in 2D space. Much effort has focused on shape control of colloidal semiconductor nanocrystals(NCs), and synthesis of 2D colloidal NCs has been achieved very recently. Here, recent advances in colloidal synthesis of uniform and ultrathin 2D CdSeNCs are highlighted. Structural and optical property characterization of these quantum-sized 2D CdSe NCs is discussed. Additionally, 2D CdSe NCs doped with Mn 2+ ions for dilute magnetic semiconductors (DMS) are presented.These 2D CdSe-based NCs can be used as model systems for studying quantum-well structures.     

Track membranes with embedded semiconductor nanocrystals: structural and optical examinations

We studied the optical properties of poly(ethylene terephthalate) ion track membranes of 1.5, 0.5 and 0.05?μm?pores impregnated with luminescent semiconductor CdSe/ZnS nanocrystals of different diameters (2.5 and 5?nm). The nanocrystals were embedded from their colloidal solutions in toluene by the immersion of a membrane in a colloidal solution. Localization of quasi-isolated weakly interacting CdSe/ZnS nanocrystals in a loosened layer on the track pore wall surface along with the existence of empty pores was demonstrated. We observed also the spatial separation of nanocrystals of 2.5 and 5?nm in size along the 50?nm pores.     

Mesoporous silica beads embedded with semiconductor quantum dots and iron oxide nanocrystals: dual-function microcarriers for optical encoding and magnetic separation

Mesoporous beads are promising materials for embedding functional nanoparticles because of their nanometer-sized pores and large surface areas. Here we report the development of silica microbeads embedded with both semiconductor quantum dots (QD) and iron oxide (Fe3O4) nanocrystals as a new class of dual-function carriers for optical encoding and magnetic separation. The embedding (doping) process is carried out by either simultaneous or sequential addition of quantum dots and iron oxide (Fe3O4) nanocrystals in solution. The doping process is fast and quantitative, but the incorporated iron oxide strongly attenuates the signal intensity of QD fluorescence. We find that this attenuation is not due to conventional fluorescence quenching but is caused by the broad optical absorption spectrum of mixed-valence Fe3O4. For improved biocompatibility and reduced nonspecific binding, the encoded beads are further coated with amphiphilic polymers such as octylamine poly(acrylic acid). The results indicate that the polymer-coated beads are well suited for target capturing and enrichment, yielding magnetic separation efficiencies higher than 99%. By combining the multiplexing capability of QDs with the superparamagnetic properties of iron oxide nanocrystals, this class of encoded beads is expected to find broad applications in high-throughput and multiplexed biomolecular assays.     

pH selective synthesis of ZnS nanocrystals and their growth and photoluminescence

ZnS nanocrystals with sizes of 3.0 ± 0.5 and 6.5 ± 0.5 nm have been prepared, that were selectively dependent upon the pH values (pH ≈ 7 and ≈ 1.7, respectively) of the synthetic aqueous solutions; where environmental friendly β-cyclodextrine was used as a stabilizer. Two different growth processes were observed depending on the pHs. For an aqueous solution with a pH of 7, the growth process was analogous to the thermodynamically controlled discontinuous growth, whereas, for an aqueous solution with a pH 1.7, the growth process was analogous to continuous growth followed by Ostwald ripening. The growth of the nanocrystals proceeds faster in pH 1.7 than in pH 7, where the interaction between stabilizer and core nanocrystals is stronger in pH 7 than in pH 1.7. The PL of the nanocrystals demonstrated that the band-edge emissions are dominant for both crystallites, where red shifts of 75 meV were observed for smaller nanocrystals as compared to the larger ones.     

Effect of size non-uniformity on photoluminescence from ensembles of InAs quantum dots embedded in GaAs

The photoluminescence (PL) spectrum from ensembles of InAs/GaAs quantum dots (QDs) is calculated. The effect of the dot size distribution and the variation of the associated confining potentials on the PL spectra are estimated. It is found that the intermixing of the interfaces causes an increase of the PL spectra energy. The size distribution determines the spectrum width and makes the PL line shape asymmetric with a high-energy tail. Moreover, the non-uniform size distribution also results in a redshift of the PL peak. The experimental PL spectrum is well explained by the size distribution and intermixing effect within the effective mass approximation.     

Sol-gel synthesis, microstructure and adsorption properties of hollow silica spheres

Spherical colloidal particles with a hollow interior and a mesoporous shell are particularly useful for drug delivery and release because such spheres combine the unique properties of hollow interior (for storing the drug) with mesoporous shell (for controlled release). Hollow silica spheres (HSS) with a mesoporous shell were prepared via a sol-gel process in the presence of dual templates polystyrene spheres and cetyltrimethylammonium bromide for creating the hollow core and mesopore shell. The effect of the ratio of silica precursor over polystyrene spheres on particle morphology and pore structure of the HSS was investigated. The adsorption kinetics of methyl blue on the HSS was evaluated and correlated with the mesoporous shell structure.     

Solvothermal synthesis,characterization and photoluminescence studies of ZnS:Eu nanocrystals

Europium doped zinc sulfide nanocrystals (ZnS:Eu) are prepared by solvothermal method. Crystallite size and lattice constant of the prepared samples are calculated from the X-ray diffraction patterns. The as-prepared samples are found to be a mixture of complex chemical groups. Heat treatment of the samples at 300 °C resulted in ZnS:Eu state. The crystal structure is not affected by the increase in the concentration of Eu from 1 mol% to 5 mol%. Fourier Transform Infrared Spectroscopy (FTIR) studies showed that characteristic absorption bands of hydroxyl groups and the acetate bands increased with increase in Eu concentration. The morphological results studied using Scanning Electron Microscopy (SEM) indicate agglomeration of nanoparticles and a marginal increase in the particle size. Photoluminescence (PL) spectra of the samples showed a prominent emission band peaked at ∼400 nm besides three weak ones at ∼422, 485 and 530 nm. The PL intensity increased with increase in Eu concentration.     

Sol-gel processing of carbidic glasses

Carbon incorporation into the silicate network results in the formation of rigid carbidic glasses with improved physical, mechanical and thermal properties. This generated great interest in the development of these heteroatom structured materials through different processing routes. In the present studies, sol-gel processing has been used to prepare silicon based glasses, especially oxycarbides through organic-inorganic hybrid gels by hydrolysis-condensation reactions in silicon alkoxides, 1,4-butanediol and furfuryl alcohol with an aim to introduce Si-C linkages in the precursors at sol level. The incorporation of these linkages has been studied using IR and NMR spectroscopy. These bonds, so introduced, are maintained throughout the processing, especially during pyrolysis to high temperatures. In FFA-TEOS system, copolymerization with optimized mol ratio of the two results in resinous mass. This precursor on pyrolysis to 1000°C results in Si-O-C type amorphous solid black mass. XRD studies on the materials heated to 1400°C exhibit presence of crystalline Si-C and cristobalites in amorphous Si-O-C mass. In organic-inorganic gel system, the pyrolysed mass exhibits phase stability up to much higher temperatures. The carbidic materials so produced have been found to exhibit good resistance against oxidation at 1000°C. Paper presented at the 5th IUMRS ICA98, October 1998, Bangalore     

Novel nano-structured glasses containing semiconductor quantum dots: controlling the photoluminescence with phonons and photons

Effects of temperatures and excitation intensities on the photoluminescence properties of PbS quantum dots precipitated in the glass were investigated. Peak wavelength of the near-infrared photoluminescence shifted towards the short wavelength side with an increase in temperature and excitation intensity. The largest shift in the peak wavelength of the photoluminescence bands was approximately 90 nm. The temperature coefficient of band gap energy (deduced from the photoluminescence wavelength) of quantum dots varied from 230 to 28 μeV/K under the excitation intensity of 50–600 mW. The integrated photoluminescence intensity also showed similar dependencies on temperature and excitation intensity. The shifts of the photoluminescence with changes in the temperature and excitation intensity were associated with the trapping and re-activation of charge carriers at defect sites located at the QDs/glass interface and inside the glass matrix.     

Exciton polarizability in semiconductor nanocrystals

The response of charge to externally applied electric fields is an important basic property of any material system, as well as one critical for many applications. Here, we examine the behaviour and dynamics of charges fully confined on the nanometre length scale. This is accomplished using CdSe nanocrystals of controlled radius (1-2.5 nm) as prototype quantum systems. Individual electron-hole pairs are created at room temperature within these structures by photoexcitation and are probed by terahertz (THz) electromagnetic pulses. The electronic response is found to be instantaneous even for THz frequencies, in contrast to the behaviour reported in related measurements for larger nanocrystals and nanocrystal assemblies. The measured polarizability of an electron-hole pair (exciton) amounts to approximately 10(4) A(3) and scales approximately as the fourth power of the nanocrystal radius. This size dependence and the instantaneous response reflect the presence of well-separated electronic energy levels induced in the system by strong quantum-confinement effects.     

Sol-gel preparation of silica glass

This paper is a preliminary report on the preparation of silica glass containing very low amount of hydroxyl by the sol-gel processing technique. Gels were prepared from optimized amounts of tetraethyl orthosilicate, fumed silica and water. Acids and bases in small quantities were added for catalysing hydrolysis and adjusting the pH. Dried gels were heated up to 1400°C in various atmospheres to obtain transparent silica glass of the required density and very low (<5 ppm) hydroxyl content.     

Ⅳ-Ⅵ族半导体纳米晶的液相法合成

Ⅳ-Ⅵ族半导体纳米晶独特的物理化学性质引起了业界广泛关注.以PbS,PbSe和PbTe纳米晶为例,着重阐述了液相法合成该族纳米晶的实验方法和制备技术,主要包括溶胶一凝胶法、共沉淀法、有机金属法、模板法和微乳法等几个方面;展望了今后的研究和发展方向.