Size dependent photodegradation of CdS particles deposited onto TiO2 mesoporous films by SILAR method

The properties of CdS nanoparticles incorporated onto mesoporous TiO2 films by a successive ionic layer adsorption and reaction (SILAR) method were investigated by Raman spectroscopy, UV-visible spectroscopy, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). High resolution TEM indicated that the synthesized CdS particles were hexagonal phase and the particle sizes were less than 5 nm when SILAR cycles were fewer than 9. Quantum size effect was found with the CdS sensitized TiO2 films prepared with up to 9 SILAR cycles. The band gap of CdS nanoparticles decreased from 2.65 eV to 2.37 eV with the increase of the SILAR cycles from 1 to 11. The investigation of the stability of the CdS/TiO2 films in air under illumination (440.6 µW/cm2) showed that the photodegradation rate was up to 85% per day for the sample prepared with 3 SILAR cycles. XPS analysis indicated that the photodegradation was due to the oxidation of CdS, leading to the transformation from sulphide to sulphate (CdSO4). Furthermore, the degradation rate was strongly dependent upon the particle size of CdS. Smaller particles showed faster degradation rate. The size-dependent photo-induced oxidization was rationalized with the variation of size-dependent distribution of surface atoms of CdS particles. Molecular Dynamics (MD) simulation has indicated that the surface sulphide anion of a large CdS particle such as CdS made with 11 cycles (CdS11, particle size = 5.6 nm) accounts for 9.6% of the material whereas this value is increased to 19.2% for (CdS3) based smaller particles (particle size: 2.7 nm). Nevertheless, CdS nanoparticles coated with ZnS material showed a significantly enhanced stability under illumination in air. A nearly 100% protection of CdS from photon induced oxidation with a ZnS coating layer prepared using four SILAR cycles, suggesting the formation of a nearly complete coating layer on the CdS nanoparticles.

Influência da concentração das partículas cristalinas nas propriedades dielétricas do híbrido PVAl/Cds

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Photoluminescence of ZnS clusters in zeolite-Y

Two obvious emissions are observed from the ZnS clusters encapsulated in zeolite-Y. The emission around 355 nm is sharp and weak, locating at the onset of the absorption edge. The band around 535 nm is broad, strong and Stokes-shifted. Both the two emissions shift to blue and their intensities firstly increase then decrease as the loading of ZnS in zeolite-Y or clusters size decreases. Through investigation, the former is attributed to the excitonic fluorescence, and the latter to the trapped luminescence from surface states. The cluster size-dependence of the luminescence may be explained qualitatively by considering both the carrier recombination and the nonradiative recombination rates. Four peaks appearing in the excitation spectra are assigned to the transitions of 1S-1S, 1S-1P, 1S-1D and surface state, respectively. The excitation spectra of the clusters do not coincide with their absorption spectra. The states splitted by quantum-size confinement are detected in the excitation spectra, but could not be differentiated in the optical absorption spectra due to inhomogeneous broadening. The size-dependence of the excitation spectra is similar to that of the absorption spectra. Both the excitation spectra of excitonic and of trapped emissions are similar, but change in relative intensity and shift in position are observed.

Absorption and luminescence of the surface states in ZnS nanoparticles

A broad absorption band around 500 nm is observed in ZnS nanoparticles. The absorption becomes more intensive and shifts to the blue as the particle size is decreased. The absorption energy is lower than the band gap of the particles and is considered to be caused by the surface states. This assignment is supported by the results of the fluorescence and of the thermoluminescence of the surface states. Both the absorption and the fluorescence reveal that the surface states are size dependent. The glow peak of the semiconductor particles is not varied as much upon decreasing size, indicating the trap depth of the surface states is not sensitive to the particle size. Considering these results, a new model on the size dependence of the surface states is proposed, which may explain our observations reasonably. (C) 1997 American Institute of Physics.

Thermoluminescence of ZnS nanoparticles

The thermoluminescence (TL) of ZnS nanoparticles is reported. The TL intensity increases as the particle size is decreased. The consistency of the size dependence of the TL with that of the surface fluorescence indicates that the TL may be related to the surface states. TL may be caused by the recombination of carriers released from the surface states or defect sites by heating. Smaller particles have higher surface/volume ratio and more surface states, therefore contain more accessible carriers for TL. Besides, the carrier recombination rate increases upon decreasing size due to the increase of the overlap between the electron and hole wave functions. These two effects may make the TL increase upon decreasing size of the particles. The appearance of TL prior to any radiation reveals that trapped carriers have pre-existed. The investigation of TL may provide some useful information about the surface states that may explain the size dependence of the surface fluorescence. (C) 1997 American Institute of Physics.

Surface photovoltage spectra and photoelectrochemical properties of semiconductor-sensitized nanostructured TiO2 electrodes

Three kinds of TiO2 nanostructured thin films and their CdS-sensitized films, consisting of different sizes of TiO2 nanoparticles prepared with different methods, have been investigated. The surface photovoltage spectra (SPS) measurements indicate that the density of surface states on TiO2 is likely dependent upon the details of prepared methods. TiO2 particles prepared from basic sol have more surface states than that prepared from acidic sol. When the TiO2 thin films prepared using the TiO2 sols were sensitized by CdS particles, the SPS responses relative to the surface states on TiO2 from 350 to 800 nm were decreased. The photoelectrochemical properties of nanostructured TiO2 electrodes suggest that the fewer the surface states and the smaller the particle sizes of TiO2, the larger the photocurrent response. For CdS sensitized TiO2 thin film electrode, it is shown that the semiconductor sensitization is an efficient way to decrease the influence of surface states on the charge separation, and can improve the intensity of photocurrent response. (C) 2001 Elsevier Science B.V. All rights reserved.

Room temperature ferromagnetism and white light emissive CdS:Cr nanoparticles synthesized by chemical co-precipitation method

Undoped and Cr (3% and 5%) doped CdS nanoparticles were synthesized by chemical co-precipitation method. The synthesized nanocrystalline particles are characterized by energy dispersive X-ray analysis (EDAX), scanning electron microscope (SEM), X-ray Diffraction (XRD), transmission electron microscopy (TEM), diffuse reflectance spectroscopy (DRS), photoluminescence (PL), Electron paramagnetic resonance (EPR), vibrating sample magnetometer (VSM) and Raman spectroscopy. XRD studies indicate that Cr doping in host CdS result a structural change from Cubic phase to mixed (cubic + hexagonal) phase. Due to quantum confinement effect, widening of the band gap is observed for undoped and Cr doped CdS nanoparticles compared to bulk CdS. The average particle size calculated from band gap values is in good agreement with the TEM study calculation and it is around 4-5 nm. A strong violet emission band consisting of two emission peaks is observed for undoped CdS nanoparticles, whereas for CdS:Cr nanoparticles, a broad emission band ranging from 420 nm to 730 nm with a maximum at similar to 587 nm is observed. The broad emission band is due to the overlapped emissions from variety of defects. EPR spectra of CdS:Cr samples reveal resonance signal at g = 2.143 corresponding to interacting Cr3+ ions. VSM studies indicate that the diamagnetic CdS nanoparticles are transform to ferromagnetic for 3% Cr3+ doping and the ferromagnetic nature is diminished with increasing the doping concentration to 5%. (C) 2015 Elsevier B.V. All rights reserved.

Photorefractive performance of a novel multifunctional inorganic-organic hybridized nanocomposite sensitized by CdS nanoparticles

A novel multifunctional inorganic-organic photorefractive (PR) poly(N-vinyl)-3-[p-nitrophenylazolcarbazolyl-CdS nanocomposites with different molar ratios of US to poly(N-vinyl)-3-[p-nitrophenylazo]carbazolyl (PVNPAK) were synthesized via a postazo-coupling reaction and chemically hybridized approach, respectively. The nanocomposites are highly soluble and could be obtained as film-forming materials with appreciably high molecular weights and low glass transition temperature (T,) due to the flexible spacers. The PVNPAK matrix possesses a highest-occupied molecular orbital value of about -5.36 eV determined from cyclic voltammetry. Second harmonic generation (SHG) could be observed in PVNPAK film without any poling procedure and 4.7 pm/V of effective second-order nonlinear optical susceptibility is obtained. The US particles as photosensitizers had a nanoscale size in PVNPAK adopting transmission electron microscopy. The improvement of interface quality between US and polymer matrix is responsible for efficient photoinduced charge generation efficiency in the nanocomposites. An asymmetric optical energy exchange between two beams on the polymer composites PVNPAK-CdS/ECZ has been found even without an external field in two-beam coupling (TBC) experiment, and the TBC gain and diffraction efficiency of 14.26 cm(-1) and 3.4% for PVNPAK-5-CdS/ECZ, 16.43 cm(-1) and 4.4% for PVNPAK-15-CdS/ECZ were measured at a 647.1 nm wavelength, respectively.

Structure, fluorescence and stability of CdS nanoparticles prepared in air

CdS nanoparticies were prepared in air and their stability by air annealing was studied. A small change in crystal structure and particle size was observed by air annealing, but a rapid reduction in fluorescence was found. Through investigation, it is revealed that it is the surface change or reconstruction rather than the variation of the size or structure that decreases the fluorescence. The emission of the particles consists with two peaks which are dependent on the excitation energy. The two peaks are considered to be arisen from "two" different sizes of nanoparticles and may be explained in terms of selectively excited photoluminescence. Finally we discuss why the discrete state of nanoparticles are able to be resolved in the photoluminescence excitation spectrum, but could not be differentiated in the absorption spectrum.

Formation, structure and fluorescence of CdS clusters in a mesoporous zeolite

CdS clusters are formed in the pores of a mesoporous zeolite in which the size of the clusters may be adjusted. The size of the clusters increases as the CdS loading is increased. X-ray diffraction investigation shows that the lattice constants of the clusters contract upon increasing size. This contraction is attributed to an increase of the static pressure exercised by the zeolite framework as the clusters grow bigger. Both the excitonic and trapped emission bands are detected and become more intensive upon decreasing size. Three absorption bands appear in the photoluminescence excitation (PLE) spectra and they shift to the blue as cluster size decreases. Based on the effective-mass approximation, the three bands are assigned to the 1S-1S, 1S-1P and 1S-1D transitions, respectively. The size-dependence of the PLE spectra can also be explained. (C) 1997 Elsevier Science Ltd.

Thermoluminescence of CdS clusters in zeolite-Y

Thermoluminescence (TL) of CdS clusters encapsulated in zeolite-Y is reported for the first time. The TL of the clusters is much stronger than that of the bulk CdS and increases as the CdS loading decreases. This inverse dependence of TL intensity upon CdS loading is caused mainly by the size-effect of the clusters. All samples exhibit almost the same glow peak position and shape, indicating that traps or surface states are not sensitive to the cluster sizes.

New observation on the luminescence of CdS clusters in zeolite-Y

The excitation spectrum of CdS dusters in zeolite-Y is consistent with their absorption spectrum, both showing two absorption bands that are assigned to the Is-is and Is-lp transitions, respectively. A new emission at 400 nn is considered to be the recombination of the bounded excitons. The emission firstly increases then decreases with increasing cluster size or loading. The emission by excitation into the Is-is band is stronger and sharper than that by excitation into the Is-lp band. This phenomenon is attributed to the size inhomogeneity and the strong electron-phonon interaction of the dusters. Copyright (C) 1996 Elsevier Science Ltd

Low-temperature synthesis of oil-soluble CdSe, CdS, and CdSe/CdS core - Shell nanocrystals by using various water-soluble anion precursors

Colloidal CdSe and CdS quantum dots were synthesized at low temperatures (60-90 degrees C) by a two-phase approach at a toluene-water interface. Oil-soluble cadmium myristate (Cd-MA) was used as cadmium source, and water-soluble Na2S, thiourea, NaHSe, Na2SeSO3, and selenourea were used as sulfur and selenium sources, respectively. When a cadmium precursor in toluene and a selenium precursor in water were mixed, CdSe nanocrystals were achieved at a toluene-water interface in the range of 1.2-3.2 nm in diameter. Moreover, we also synthesized highly luminescent CdSe/CdS core-shell quantum dots by a two-phase approach using poorly reactive thiourea as sulfur source in an autoclave at 140 degrees C or under normal pressure at 90 degrees C. Colloidal solutions of CdSe/CdS core-shell nanocrystals exhibit a photoluminescence quantum yield (PL QY) up to 42% relative to coumarin 6 at room temperature.

Controllable synthesis of highly luminescent and monodisperse CdS nanocrystals by a two-phase approach under mild conditions

Highly luminescent and monodisperse CdS nanocrystals (see Figure) have been synthesized using a two-phase approach. The synthesis of CdS nanocrystals at the liquid-liquid interface was easy, safe, and highly reproducible, and the reaction conditions were mild and controllable.