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Raffaele Tommasi
Ruolo
Professore Associato
Organizzazione
Università degli Studi di Bari Aldo Moro
Dipartimento
DIPARTIMENTO DI SCIENZE MEDICHE DI BASE, NEUROSCIENZE ED ORGANI DI SENSO
Area Scientifica
AREA 02 - Scienze fisiche
Settore Scientifico Disciplinare
FIS/07 - Fisica Applicata (a Beni Culturali, Ambientali, Biologia e Medicina)
Settore ERC 1° livello
Non Disponibile
Settore ERC 2° livello
Non Disponibile
Settore ERC 3° livello
Non Disponibile
The relaxation dynamics of charge carriers of organic capped TiO2 nanorods dispersed in chloroform was investigated by femtosecond transient absorption in a weak-excitation regime. Anisotropic TiO2 nanocrystals were excited in the UVvis range, using different pump wavelengths, namely above (300 nm), close to (350 nm), and below (430 nm) the direct band gap of anatase TiO2. We show that the ultrafast dynamics strongly depends on excitation wavelength and determine the time constants of all the processes entering the relaxation. Moreover, we demonstrate that two transient absorption bands at 500 and 700 nm, typically attributed to trapped h(+) and e, respectively, are accessible only when TiO2 is photoexcited well above the band gap, while there is no evidence of such bands when TiO2 is photoexcited close to or below its band gap. In such cases the observed dynamics are attributed to trapped excitons.
A growing interest is devoted to the study of imidazolium-based ionic liquids as innovative materials to combine with functional elements for advanced technological applications. Materials based on semiconductor and oxide nanocrystals in ionic liquids can be promising for their integration in lithium batteries, as well as in innovative solar cells. Although the physical chemical properties and the solvation dynamics of bare ionic liquids have been extensively studied, their combination with colloidal nanocrystals still remains almost unexplored. Here, the optical properties of organic-capped luminescent cadmium selenide nanocrystals coated by a shell of zinc sulfide (CdSe(ZnS)) dispersed in 1,3-dialkyl imidazolium ionic liquids have been investigated, also in dependence of the alkyl chain length on the imidazolium ring and of the anion nature, by using both time-integrated and time-resolved optical spectroscopy. The observed variations in decay profiles of the ionic liquid in presence of colloidal nanocrystals suggest that the dispersion of the nanostructures induces modifications in the ionic liquid structural order. Finally, atomic force microscopy analysis has provided insight into the topography of the investigated dispersions deposited as film, confirming the organization of the ionic liquids in super-structures, also upon nanocrystal incorporation.
Room temperature ionic liquids are currently used as functional materials in several application and their optical investigation can provide a better understanding of their physical and chemical behavior. Absorption and emission properties of imidazolium-based ILs have been attributed to the imidazolium moiety and related to the presence of energetically different aggregates. Here, time-integrated and time-resolved investigation has been carried out on 1-alkyl-3-methylimidazolium tetrafluoroborate and hexafluorophosphate ionic liquids with different chain lengths in order to probe the occurrence of energy transfer processes, and hence to disclose the presence of various states with different energy. Such a study contributes to provide relevant insight on the effect of alkyl chain and anion type on the emission characteristics, and, hence, on the presence of associated structures.
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