Fine tuning of emission through the engineering of colloidal crystals

Université Bordeaux 1, Centre de Recherche Paul Pascal, 115 avenue Dr Schweitzer, 33600 Pessac, France.
Physical Chemistry Chemical Physics (Impact Factor: 4.49). 10/2010; 12(38):11993-9. DOI: 10.1039/c0cp00129e
Source: PubMed


We describe the preparation and characterization of photonic colloidal crystals from silica spheres with incorporated luminescent [Mo(6)Br(14)](2-) cluster units. These structures exhibit strong angle-dependent luminescent properties. The incorporation of one or several planar defects in the periodic structures gives rise to the creation of a passband in the stopband. In the energy range of this passband, an increase of the emission intensity has been found.

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    ABSTRACT: Metal atom clusters constitute very promising candidates as luminophores for applications in biotechnology because they are nanosized entities offering robust luminescence in the near-infrared field (NIR). However, they cannot be used as prepared for biological applications because of potential toxic effects and quenching of the clusters' luminescence in aqueous media, and they therefore need to be dispersed in a biocompatible matrix. We describe herein the encapsulation of octahedral rhenium clusters, denoted as A(4)[Re(6)Q(8)L(6)] (A = Cs or K, Q = S or Se, and L = OH or CN), in silica nanoparticles by a water-in-oil microemulsion process, paying particular attention to the clusters' stability. The obtained A(4)[Re(6)Q(8)L(6)]@SiO(2) nanoparticles are 30 nm in size with good monodispersity and a perfectly spherical shape, as shown by scanning electron microscopy (SEM). The presence of cluster units inside the silica matrix was evidenced by scanning transmission electron microscopy in annular dark-field mode (ADF-STEM). From the point of view of their optical properties, the A(4)[Re(6)Q(8)L(6)]@SiO(2) nanoparticles show red and NIR emission under UV excitation, even when dispersed in water. The evolution of the structural and luminescence properties of clusters before and after encapsulation was followed by Raman and photoluminescence spectroscopy.
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    ABSTRACT: The enhancement of the capillarity fabrication of well-ordered two-dimensional (2D) and three-dimensional (3D) opal photonic crystal is described herein. The quality enhancement and the reduction of the fabrication time are improved by using core@soft adhesive shell (Silica@PolyButylAcrylate) particles dispersed in an organic solvent with a high boiling point. The hybridization by an elastomeric corona polymer, grafted from the SiO(2) surface, has offered adhesive properties naturally tunable by changing the polymer state from a solvated to a dry one. Such properties involve drastic changes of the self-assembly behavior and qualities. Their use, as elementary building blocks, for colloidal crystal fabrication have required a high withdrawal rate (up to 4000 μm s(-1)), i.e. involving a three order of magnitude reduction in time compared to a classic vertical deposition method (1 to 10 μm s(-1)) and a good control/prediction of the coating thickness can be tuned by varying the withdrawal rate and the particle concentration. In addition, an analysis of the 2D synthetic iridescence of the hybrid photonic crystal was performed under white light, revealing the adhesive shell bridge influence on the dissipation energy of cracks linked to the crystal quality and the photonic properties.
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    ABSTRACT: Engineering spontaneous emission by means of photonic crystals (PHC) is under extensive study. However PHC modification of line emissions of rare earth (RE) ions has not been thoroughly understood, especially in cases of weak opal PHCs and while emitters are well dispersed into dielectric media. In this study, poly-methyl methacrylate (PMMA) opal PHCs containing uniformly dispersed europium chelate were fabricated with finely controlled photonic stop band (PSB) positions. Measurements of luminescent dynamics and angle resolved/integrated emission spectra as well as numerical calculations of total densities of states (DOS) were performed. We determined that in weak opals, the total spontaneous emission rate (SER) of Σ(5)D(0)-(7)F(J) for Eu(3+) was independent of PSB positions but was higher than that of the disordered powder sample, which was attributed to higher effective refractive indices in the PHC rather than PSB effect. Branch SER of (5)D(0)-(7)F(2) for Eu(3+) in the PHCs, on the other hand, was spatially redistributed, suppressed or enhanced in directions of elevated or reduced optical modes, keeping the angle-integrated total unchanged. All the results are in agreement with total DOS approximation. Our paper addressed two unstudied issues regarding modified narrow line emission in weak opal PHCs: firstly whether PSB could change the SER of emitters and whether there exist, apart from PSB, other reasons to change SERs; secondly, while directional enhancement and suppression by PSB has been confirmed, whether the angle-integrated overall effect is enhancing or suppressing.
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