Concerted Photoluminescence of Electrochemically Self-Assembled CuSCN/Stilbazolium Dye Hybrid Thin Films

Hybrid thin films of crystalline CuSCN and 4-(N,N-dimethylamino)-4′-(N′-methyl)­stilbazolium (DAS) in three distinctively different nanostructures were obtained by electrochemical self-assembly from a single pot containing all the chemical ingredients. Their optical properties for UV–vis-NIR absorption, photoluminescence (PL), and PL excitation spectra were examined between 77 and 298 K, in comparison with solution and solid powder of DAS tosylate (DAST). Unlike all other dyes we tested before, PL of DAS was not quenched but rather enhanced when hybridized with CuSCN. DAST exhibited a strong exciton–phonon coupling to weaken, broaden, and red shift PL at room temperature, so that it inversely is strongly enhanced, sharpened, and blue-shifted at 77 K. The PL of the same dye in the hybrid thin film, however, shows a slight red shift and only a moderate enhancement at reduced temperatures due to strong exciton stabilization in dielectric environment of CuSCN and concerted PL by energy transfer from CuSCN to DAS luminophore, making it a unique nearly temperature-independent luminescent material

Electrochemical Self-Assembly of Nanostructured CuSCN/Rhodamine B Hybrid Thin Film and Its Dye-Sensitized Photocathodic Properties

Nanostructured hybrid thin films of CuSCN and rhodamine B (RB) are electrochemically self-assembled (ESA) by cathodic electrolysis in an ethanol/water mixture containing Cu²⁺, SCN^–, and RB. By selecting the solvent, Cu²⁺/SCN^– ratio, and the concentration of RB, we demonstrate several control parameters in the film formation. High loading of RB into the film has been achieved to reach a CuSCN:RB volume ratio of approximately 2:1. The RB solid could almost completely be extracted from the hybrid film by soaking the film in dimethylacetamide (DMA), leading to a large increase of the surface area. The crystallographic orientation of the nanostructure with respect to the substrate can be controlled. Efficient quenching of fluorescence of RB has been observed for the CuSCN/RB hybrid film, implying hole injection from RB excited state to CuSCN. Photoelectrochemical study on the porous crystalline CuSCN obtained after the DMA treatment and sensitized with RB revealed sensitized photocathodic action under visible light illumination, indicating the potential usefulness of the porous CuSCN electrodes for construction of tandem dye-sensitized solar cells