Influence of the Matrix Environment on the Optical Properties of Incorporated Dye Molecules

The present thesis is concerned with solid solutions of organic dyes. The organic molecules are incorporated in both optically inert or active and in rigid or flexible matrices, respectively. Exclusively thin films prepared by physical vapor deposition are studied. The optical response of the systems, in dependence on their structure and on the matrix nature, is investigated by means of absorption and luminescence spectroscopy. In the first part, perylene and 2,2-difluoro-1,3,2-dioxaborine derivatives, and Alq3 (tris(8-hydroxyquinoline) aluminium) embedded in the optically inactive SiO2 and polyimide hosts are studied. For the system dye molecules/SiO2 matrix, two sample preparation approaches, co-deposition and layer-by-layer, are compared. It is demonstrated that the luminescence properties of the mixed layers are affected by dye distribution and thin film composition. The photoluminescence quantum efficiency is strongly influenced by dye aggregation and Förster transfer. Therefore, effective separation and isolation of dye molecules in the matrix results in increased PL efficiency. Furthermore, it is established that layer-by-layer growth mode assures more homogeneous dye distribution. The spectroscopic studies also show that, since dye and matrix condense successively in time, luminescence losses due to thermal degradation of molecules are reduced. Hence, the film structure can be optimized with regard to high absorption and luminescence quantum efficiency. The experimental findings suggest that the luminescent properties of the embedded dyes are influenced by the nature of the host environment as well. In the rigid SiO2 matrix, it is possible to observe isolated facial Alq3 molecules with distinctive blue luminescence. In contrast, in the "soft" organic polyimide matrix Alq3 exhibits ordinary green luminescence. Thus, the structural properties of the host, rigidity and density, are found to be crucial for preservation of the facial Alq3 molecules. It is further demonstrated that the immobilization of molecules in the rigid SiO2 matrix in combination with layer-by-layer growth results in improved photostability. In polyimide matrix, the behavior of incorporated molecules is governed by the morphological changes of the host. These changes are defined by the curing procedure, needed for imidization, and give rise to a certain film structure. In the second part, special attention is paid on the luminescence response of dispersed DCM (4dicyanomethylene-2-methyl-6(p-dimethylaminostyril)-4H-pyran) and rubrene (5,6,11,12-tetraphenyl-naphthacene) molecules in the optically active Alq3 matrix. The observed enhancement of luminescence intensity and alteration of emitted color are favorable for application of the doped Alq3 films as converter layers in combination with commercial blue light emitting diodes in luminescence conversion devices. It is demonstrated that by optimization of the conversion layer parameters white light generation can be achieved. The devices are characterized by high conversion efficiency and Lambertian distribution of the emitted light. However, they lack sufficient stability with regard to practical applications.