Formation and optical properties of CdSSe semiconductor nanocrystals in the silicate glass matrix

Technological conditions providing the formation of CdS _x Se_1−x semiconductor crystal grains with sizes ranging from 2 to 8 nm in a silicate glass matrix have been determined. As the temperature of forming annealing increases, the size of crystal grains increases without changes in their crystal structure and composition. The observed short-wavelength shift of the optical absorption edge indicates that the quantum confinement affects the energy band structure of the nanocrystals. Intense luminescence of the samples is due to radiative transitions involving defects at the semiconductor nanocrystal-silicate matrix interface or intrinsic defects of nanocrystals.     

Characterization of chemically synthesized CdS nanoparticles

II-VI semiconductor nanoparticles are presently of great interest for their practical applications such as zero-dimensional quantum confined materials and for their applications in optoelectronics and photonics. The optical properties get modified dramatically due to the confinement of charge carriers within the nanoparticles. Similar to the effects of charge carriers on optical properties, confinement of optical and acoustic phonons leads to interesting changes in the phonon spectra. In the present work, we have synthesized nanoparticles of CdS using chemical precipitation technique. The crystal structure and grain size of the particles are studied using XRD. The UV-visible absorption, photoluminescence and Raman spectra of the sample are recorded and discussed briefly     

Surface-enhanced Raman spectroscopy of semiconductor nanostructures

We review our recent results concerning surface-enhanced Raman scattering (SERS) by confined optical and surface optical phonons in semiconductor nanostructures including CdS, CuS, GaN, and ZnO nanocrystals, GaN and ZnO nanorods, and AlN nanowires. Enhancement of Raman scattering by confined optical phonons as well as appearance of new Raman modes with the frequencies different from those in ZnO bulk attributed to surface optical modes is observed in a series of nanostructures having different morphology located in the vicinity of metal nanoclusters (Ag, Au, and Pt). Assignment of surface optical modes is based on calculations performed in the frame of the dielectric continuum model. It is established that SERS by phonons has a resonant character. A maximal enhancement by optical phonons as high as 730 is achieved for CdS nanocrystals in double resonant conditions at the coincidence of laser energy with that of electronic transitions in semiconductor nanocrystals and localized surface plasmon resonance in metal nanoclusters. Even a higher enhancement is observed for SERS by surface optical modes in ZnO nanocrystals (above 10⁴). Surface enhanced Raman scattering is used for studying phonon spectrum in nanocrystal ensembles with an ultra-low areal density on metal plasmonic nanostructures.     

Quantum confinement effect in the vibrational spectrum of CdSxSe1−x quantum dots in a fluorophosphate glass matrix

The vibrational spectra of mixed cadmium sulfoselenide nanocrystals in a fluorophosphate glass matrix are investigated by Raman spectroscopy. The asymmetry of the lines of the fundamental modes of nanocrystals is experimentally observed in the region of lattice vibrations, which is interpreted as a quantum confinement effect. In the framework of the model of confined phonons, the contribution of the band states to the Raman scattering spectrum is calculated and the size of nanocrystalline regions is estimated. The results obtained are in good agreement with the data on the low-frequency Raman scattering in these objects.     

Nanostructuring-induced modification of optical properties of p-GaAs (1 0 0)

A pulsed anodic etching method has been utilized for nanostructuring of p-type GaAs (1 0 0) surface, using HCl-based solution as electrolyte. The resulting porous GaAs layer is characterized by atomic force microscopy (AFM), room temperature photoluminescence (PL), Raman spectroscopy and optical reflectance measurements. AFM imaging reveals that the porous GaAs layer is consisted of a pillar-like of few nm in width distributed between more-reduced size nanostructures. In addition to the “infrared” PL band of un-etched GaAs, a strong “green” PL band is observed in the etched sample. The broad visible PL band of a high-energy (3.82 eV) excitation is found to compose of two PL band attributed to excitons confinement in two different sizes distribution of GaAs nanocrystals. The quantum confinement effects in GaAs nanocrystallites is also evidenced from Raman spectroscopy through the pronounced appearance of the transverse optical (TO) phonon line in the spectra of the porous sample. Porosity-induced a significant reduction of the specular reflection, in the spectral range (400–800 nm), is also demonstrated.     

Size-dependent photo-induced shift of the first exciton band in CdTe quantum dots in glass prepared by a two-stage heat-treatment process

CdTe nanocrystals were grown from commercially available RG850 Schott filter glass by two-step heat-treatment process which almost doubles the particle to matrix volume fraction. A calculation shows that a quantized-state effective mass model in the strong confinement regime might be used to deduce the average radius for the nanocrystals larger than 2 nm in radius from the energetic position of the first exciton peak in optical absorption spectrum. Size-induced shift of ∼360 meV in the first exciton peak position was observed. The steady state photoluminescence spectra exhibit a broad band red shifted relative to the first exciton band, which indicates the existence of shallow trap states. The non-linear optical properties of CdTe nanocrystals were studied by room temperature resonant photoabsorption spectroscopy. The differential absorption spectra had three-lobed structure whose size-dependent evolution was explained by bleaching of the absorption, red shift and broadening in the Gaussian absorption band used to fit the first exciton peak. A maximum red shift of 2.32 meV for the average nanocrystal radius of 4.65 nm was estimated by fitting the photomodulation spectra with a combination of first and second derivative Gaussian absorption bands. We presume that the red shift is induced by the electric field of trapped charges in surface states. Internal electric field strengths of 23 and 65 kV/cm were predicted for the average nanocrystal radii of 3.95 and 4.65 nm, respectively, with the help of second-order perturbation theory in the strong confinement limit.     

Quantum confinement effects on the optical phonons of CdTe quantum dots

We present Raman-scattering results for CdTe nanocrystals in doped glasses which clearly show the confinement effects on the phonon spectra as a function of the quantum-dot size. We observed optical phonon modes, surface phonons and some of their overtone combinations. We show that the surface-phonon scattering intensity increases as the quantum-dot size decreases. Our results also show a decrease in the electron–phonon coupling as the nanocrystal size is decreased. These confinement effects are observed by changing the laser excitation energy, and thus by tuning to resonance with the optical transitions for quantum dots of different sizes within their broad size distribution in semiconductor-doped glasses.     

Controlled synthesis, characterization and optical properties of CdS nanocrystalline thin films via chemical bath deposition (CBD) route

In this study, the CdS nanocrystalline thin films obtained from an ammonia-free chemical bath deposition process. The crystallites with a size range of 10–20 nm in diameter with zinc blend (cubic) and wurtzite (hexagonal) crystal structure and strong photoluminescence were prepared from the mixture solutions of: cadmium chloride dihydrate as a cadmium source, thiourea as a sulfur source and sodium citrate dihydrate as a complexing agent for cadmium ions. The well-cleaned glass used as a substrate for thin films deposition. The obtained samples were characterized by the techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), atomic force microscopy (AFM) and fluorescence spectroscopy. Also, the effect of two parameters such as pH and temperature of reaction on the synthesis of CdS nanocrystals was studied. Finally, it was found the CdS nanocrystals showed sharp excitation features and strong “band-edge” emission.     

Raman properties embeddedof GaSb nanoparticlesin SiO2 films

The Raman shifts of nanocrystalline GaSb excited by an Ar^ ion laser at wavelengths 514.5, 496.5, 488.0, 476.5,and 457.9nm are studied by an SPEX-1403 laser Raman spectrometer respectively, and they are explained by phonon confinement, tensile stress, resonant Raman scattering and quantum size effects. The Stokes and anti-Stokes Raman spectra of GaSb nanocrystals strongly support the Raman feature of GaSb nanocrystals. The calculated optical spectra compare well with experimental data on Raman scattering GaSb nanocrystals.     

Auger relaxation processes in semiconductor nanocrystals and quantum wells

Auger recombination rates in mesoscopic semiconductor structures have been studied as a function of energy band parameters and heterostructure size. It is shown that nonthreshold Auger processes stimulated by the presence of heteroboundaries become the dominant nonradiative recombination channel in nanometer size semiconductor structures. The size dependence of luminescence quantum yields in nanostructures and microcrystals are discussed. Auger-like collisions of electrons and heavy holes are shown to serve as “accelerators” of thermalization processes in semiconductor quantum dots.     

Electrical and optical properties of colloidal semiconductor nanocrystals in aqueous environments

Microscale and larger semiconductor crystals have electronic and optical properties that depend on their bulk band structures. When these crystals are reduced into the nanoscale, they enter a new regime in which the electrical and optical properties are no longer influenced solely by their bulk band structures, but are influenced by the crystallite size and shape. In this paper, dimensional confinement and proximity phenomena are examined for colloidal semiconductor nanocrystals in several cases of practical importance. Specifically, we determine the effective binding potentials of selected quantum dots in aqueous environments in various colloidal semiconductor nanocrystals and correlate them with experimentally obtained absorption spectra. We also study fluorescence resonance energy transfer (FRET) between semiconductor crystals connected by short peptide chains as well as the shift in photoluminescence spectra of CdTe nanowires made from a chain of CdTe quantum dots.     

Optical diffuse reflectance spectra of GaSb nanocrystals embedded in SiO2 matrix by radio-frequency magnetron co-sputtering

Nanocrystalline GaSb embedded in SiO₂ films was grown by radio-frequency magnetron co-sputtering. X-ray diffraction pattern and transmission electron microscopy (TEM) confirm the existence of GaSb nanocrystals in the SiO₂ matrix. The average size of GaSb nanoparticles is in the range of 3 to 11 nm. Diffuse reflectance spectra were used to characterize the small change of the band gap of the semiconductor. The diffuse reflectance spectra shows that the absorption peaks have a large blueshift of about 4.0 eV of the absorption relative to that of bulk GaSb. It has been explained by quantum confinement effects. Room temperature optical transmission spectra show that the absorption edge exhibits a very large blueshift of about 2.1 eV with respect to that of bulk GaSb in agreement with quantum confinement. Received: 28 July 1999 / Accepted: 27 October 1999 / Published online: 1 March 2000     

Coherent generation of acoustic phonons in an optical microcavity

Ultrafast coherent generation of acoustic phonons is studied in a semiconductor optical microcavity. The confinement of the light pulse amplifies both the generation and the detection of phonons. In addition, the standing wave character of the photon field modifies the generation and detection phonon bandwidth. Coherent generation experiments in an acoustic nanocavity embedded in an optical microcavity are reported as a function of laser energy and incidence angle to evidence the separate role of the optical and exciton resonances. Amplified signals and phonon spectra modified by the optical confinement are demonstrated.     

Polar optical phonons in semiconducting CdS nanocrystals

We have experimentally and theoretically studied IR-active optical phonons, which are spatially confined in the volume of semiconducting CdS nanocrystals of various shapes synthesized in a dielectric matrix (porous aluminum oxide). Within an approach admitting the mixing of all expected types of vibrations, the complete sets of phonon modes are determined for a spherical quantum dot (QD) and a cylindrical quantum wire (QW) in this matrix. Based on these results, the polarizability spectra of QDs and QWs, as well as the effective dielectric function of a composite material containing such nanoparticles, are calculated for the far-IR wavelength range. It is established that the spectrum of the dielectric function exhibits specific features in the region between the transverse and longitudinal optical phonon frequencies of the massive semiconductor material. These features explain the rather unusual structure of the IR spectra of the composite samples studied.     

Quantum confinement in CdSxSe1−x spherical nanocrystals in a fluorophosphate glass matrix

Differential (wavelength-modulated) absorption of sulfoselenide solid-solution nanocrystals has been studied in a glassy fluorophosphate matrix near the fundamental absorption edge at 360–620 nm. The observed oscillations in the absorption are attributed to size quantization of electrons and holes under strong quantum-confinement conditions. The sulfur content in the mixed semiconductor has been refined from Raman scattering spectra in CdS_xSe_1?x samples with x=0.30, and the nanocrystal size (R?30 Å) has been derived from low-frequency Raman scattering spectra. These data were used to calculate the energies of electron-hole transitions in nanocrystals of mixed composition, and their subsequent comparison with experiment. The calculations were found to be in a good agreement with the observed experimental absorption spectrum for nanocrystals about 45 Å in size. The applicability of band-structure simulation for a nonspherical nanocrystal grown in a fluorophosphate glass matrix is discussed.     

Synthesis of Ge nanocrystals by atom beam sputtering and subsequent rapid thermal annealing

Ge nanocrystals embedded in an SiO₂ matrix were prepared by the atom beam co-sputtering (ABS) method from a composite target of Ge and SiO₂. The as-deposited films were rapid thermally annealed at the temperatures 700 and 800 °C in nitrogen ambience. The structure of the films was evaluated by using X-ray diffraction (XRD) and Raman spectroscopy. XRD results reveal that as-deposited films are amorphous in nature whereas annealed samples show crystalline nature. Raman scattering spectra showed a peak of Ge–Ge vibrational mode shifted downwards to 297 cm^?1, presumably caused by quantum confinement of phonons in the Ge nanocrystals. Rutherford backscattering spectrometry has been used to measure the thickness and Ge composition of the composite films. Size variation of Ge nanocrystals with annealing temperature has been discussed. The advantages of ABS over other methods are highlighted.     

Percolation model, Sherrington-Kirkpatrick model and localization-delocalization model of spin glass transition: A comparative study

We recast the original results of our percolation model of the spin glass transition into alternative forms so as to reveal some apparent “similarities” with the Sherrington-Kirkpatrick model. However, because of the basic difference in the nature of the interactions in the two models, the reason for these “similarities” remains unclear. A close relation between the percolation model of the spin glass transition and the localization-decolization transition is also discussed qualitatively.     

Resonant Raman scattering in CdSxSe1−x nanocrystals: effects of phonon confinement,composition, and elastic strain

Optical phonon modes, confined in CdS_xSe_1−x nanocrystal (NC) quantum dots (≈2 nm in radius) grown in a glass matrix by the melting‐nucleation method, were studied by resonant Raman scattering (RRS) spectroscopy and theoretical modeling. The formation of nanocrystalline quantum dots (QDs) is evidenced by the observation of absorption peaks and theoretically expected resonance bands in the RRS excitation spectra. This system, a ternary alloy, offers the possibility to investigate the interplay between the effects of phonon localization by disorder and phonon confinement by the NC/matrix interface. Based on the concept of propagating optical phonons, which is accepted for two‐mode pseudo‐binary alloys in their bulk form, we extended the continuous lattice dynamics model, which has successfully been used for nearly spherical NCs of binary materials, to the present case. After determining the alloy composition for NCs (that was evaluated with only 2–3% uncertainty using the bulk longitudinal optical phonon wavenumbers) and the NC size (using atomic force microscopy and optical absorption data), the experimental RRS spectra were described rather well by this theory, including the line shape and polarization dependence of the scattering intensity. Even though the presence of a compressive strain in the NCs (introduced by the matrix) masks the expected downward shift owing to the phonons' spatial quantization, the asymmetric broadening of both Raman peaks is similar to that characteristic of NCs of pure binary materials. Although with some caution, we suggest that both CdSe‐like and CdS‐like optical phonon modes indeed are propagating within the NC size unless the alloy is considerably heterogeneous. Copyright © 2011 John Wiley & Sons, Ltd.     

Strength considerations of optical waveguide fibers

An important aspect of optical waveguide fiber made of glass is whether it will break under a wide variety of service and manufacturing conditions. This paper covers some of the testing in which stress, length, time, and environment were vaned. The use of Weibull statistics with these data indicates that a statistically predictable behavior exists for populations of glass fibers. Extrapolation from short lengths and short times to very long lengths and very long times must be based on an understanding of the “constants” in the prediction equation. That is, these “constants” can be shown to vary when the three basic parameters cover orders of magnitude in range.     

玻璃中CdSSe纳米晶体的光谱性能

对掺有镉、硒、硫的玻璃在650—800℃退火4?h，生长了不同尺寸的CdS0.13Se0.87纳米晶体，测量了纳米晶体的吸收光谱、光致发光（PL）谱和电调制光谱，确定了纳米晶体部分电子态的能量，讨论了CdSSe纳米晶体的光学性质与其尺寸之间的依赖关系.随着纳米晶体尺寸的增大，对应激子的吸收峰、PL峰及电吸收信号发生红移，表现出明显的量子尺寸效应.小尺寸纳米晶体的电吸收表现为量子受限的Stark效应，而大尺寸纳米晶体的电吸收线形与体材料的相似；随着纳米晶体尺寸的增大，电吸收信号增强.所有尺寸的纳米晶体都表现 关键词： CdSSe纳米晶体 吸收光谱 光致发光谱 电光响应