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CdS nanoparticles (NPs) were synthesized using colloidal methods and incorporated within a diureasil hybrid matrix. The surface capping of the CdS NPs by 3-mercaptopropyltrimethoxysilane (MPTMS) and 3-aminopropyltrimethoxysilane (APTMS) organic ligands during the incorporation of the NPs within the hybrid matrix has been investigated. The matrix is based on poly(ethylene oxide)/poly(propylene oxide) chains grafted to a siliceous skeleton through urea bonds and was produced by sol–gel process. Both alkaline and acidic catalysis of the sol–gel reaction were used to evaluate the effect of each organic ligand on the optical properties of the CdS NPs. The hybrid materials were characterized by absorption, steady-state and time-resolved photoluminescence spectroscopy and High Resolution Transmission Electron Microscopy (HR-TEM). The preservation of the optical properties of the CdS NPs within the diureasil hybrids was dependent on the experimental conditions used. Both organic ligands (APTMS and MPTMS) demonstrated to be crucial in avoiding the increase of size distribution and clustering of the NPs within the hybrid matrix. The use of organic ligands was also shown to influence the level of interaction between the hybrid host and the CdS NPs. The CdS NPs showed large Stokes shifts and long average lifetimes, both in colloidal solution and in the xerogels, due to the origin of the PL emission in surface states. The CdS NPs capped with MPTMS have lower PL lifetimes compared to the other xerogel samples but still larger than the CdS NPs in the original colloidal solution. An increase in PL lifetimes of the NPs after their incorporation within the hybrid matrix is related to interaction between the NPs and the hybrid host matrix. [ABSTRACT FROM AUTHOR]

The incorporation of CdS nanoparticles (NPs), as prepared through colloidal methods using reverse micelles, within diureasil hybrid organic–inorganic sol–gel matrices was investigated. Several experimental conditions, namely the influence of capping agent 3-mercaptopropyltrimethoxysilane (MPTMS) or the use of tetraethoxysilane (TEOS), were studied in order to assure the preservation of the original optical properties of colloidal CdS NPs after the incorporation of the NPs within the solid diureasil hybrid matrix. The diureasil matrix is based on a siliceous network cross linked through urea bonds to poly(oxyethylene)/poly(oxypropylene) (PEO/PPO) chains. The influence of the Cd 2+ /S 2− molar ratio of the NPs in the stability and dispersion of the NPs within the diureasil matrix was also investigated. The obtained CdS doped hybrid matrix was characterized by absorption, steady-state and time-resolved photoluminescence (PL) spectroscopy and by transmission electron microscopy (TEM). The stability of the CdS NPs within the hybrid matrix showed to be dependent on the Cd 2+ /S 2− molar ratio used in the synthesis of the NPs. The use of MPTMS proved to be crucial in the preservation of the original optical properties of the colloidal CdS NPs after the incorporation of the NPs within the hybrid matrix. The effect of MPTMS was in turn influenced by the Cd 2+ /S 2− molar ratio employed in the synthesis of the CdS NPs. The use of MPTMS was less effective when Cd 2+ /S 2− molar ratio equal to 0.5 was used. In the absence of MPTMS or TEOS larger NPs size distribution and clustering of the CdS NPs were obtained after the transfer of the NPs into the hybrid matrix. [ABSTRACT FROM AUTHOR]

Abstract: Optically clear and flexible organic–inorganic hybrid materials doped with CdSe nanoparticles (NPs) were synthesized by a sol–gel method based on the hydrolysis and condensation reactions of ureasilicate precursors. The CdSe NPs were produced by a colloidal method using reverse micelles and were then transferred to the ureasilicate precursor solution followed by gelation of the mixture using ammonia/water vapours as catalyst for the sol–gel process. The influence of the NPs surface in the dispersion of the NPs within the matrix was investigated by the addition of a capping agent with both thiol and siloxane groups (3-mercaptopropyltrimethoxysilane, MPTMS). This capping agent was used in order to improve compatibility and avoid aggregation of the NPs within the matrix and to increase the preservation of the original optical properties of the NPs. The nanocomposites obtained were characterized by absorption spectroscopy, steady-state photoluminescence, time resolved photoluminescence, HRTEM and FTIR spectroscopy. The results obtained showed the influence of the use of MPTMS in the preservation of the original optical properties of the CdSe NPs after their transfer into the ureasilicate matrix. The HRTEM analysis showed the presence of well-dispersed spherical NPs with well-defined lattice fringes. The obtained nanocomposites exhibit high transparency in the visible range as a result of the good dispersion of the NPs within the matrix, showing the potentials of the developed method in the production of composite materials in which the optical properties of the NPs incorporated are crucial to the desired application. [Copyright &y& Elsevier]

Highlights: [•] In situ synthesis of CdSe nanoparticles within a hybrid ureasilicate matrix. [•] Influence of Cd/MPTMS and Cd/Se molar ratios in optical properties of nanocomposites. [•] Absorption and PL spectra of doped xerogels show features of quantum size effect. [•] PL decay profiles of doped xerogels showed to be dependent on the Cd/Se molar ratio. [ABSTRACT FROM AUTHOR]