A series of chlorotricarbonyl rhenium (I) bis(phenylimino)acenaphthene (Re-DIAN-X) complexes were used as the photosensitizers for photovoltaic cells. Unlike other transition-metal-based photovoltaic sensitizers that can only be prepared by solution method, these complexes are sublimable. Compared to other rhenium diimine complexes based on bipyridine or 1,4-diaza-1,3-butadiene ligands, these complexes have lower band gaps, which can be modified easily by changing the structure of the ligand. It allows the preparation of blend of metal complexes in order to broaden the sensitization region in UV-vis absorption spectrum. One of the complexes also shows bipolar charge transport character with relatively high charge carrier mobilities in the order of 10-3 cm2V-1s-1. Multilayer heterojunction and bulk heterojunction devices with fullerene as the electron accepting molecule were prepared. For the bulk heterojunction devices, the fill factor and power conversion efficiency under AM 1.5 simulated solar light illumination were 0.51 and 1.29 %, respectively. The effects of changing the Re-DIAN/C60 film thickness, Re-DIAN/C60 ratio and variation of ligand structures in the bulk heterojunction devices were studied. The amount of photosensitizer and electron transport molecules may strongly affect the balance between the photon absorption, exciton formation, dissociation, and charge transport processes. Atomic force microscopic images showed that the complex dispersed evenly with fullerene molecules in solid state.
Multilayer photovoltaic devices were fabricated by the sequence adsorption of different polyelectrolytes. A ruthenium terpyridine complex containing poly(p-phenylenevinylene) was used as the polycation layer. This polymer has been shown to exhibit large photo-sensitivity due to the presence of the ruthenium complex, which has relatively long-lived excited state. This polymer absorbs strongly in the visible region at ca. 480 - 550 nm and it can act as the electron transporter. Sulfonated polyaniline was used as the hole-transporting polyanion layer. The ITO/(polyanion/polycation)n/Al devices were found to exhibit photovoltaic properties under the illumination of AM1 solar radiation. The short-circuit current Isc, open-circuit voltage Voc, and the fill factor FF were measured to be 14 μA/cm2, 0.84 V and 0.16 respectively. It was found that the power conversion efficiencies of the devices were dependent on the device thickness. This simple layer-by-layer self-assembly method allowed us to control the devices thickness accurately.
Photovoltaic devices were fabricated using rhenium bis(arylimino)acenaphthene (DIAN) complex containing poly(p-phenylenevinylene). These polymers absorb strongly in the visible region at ca. 440-550 nm. In addition, this type of transition metal based polymers have been shown to exhibit large photo-sensitivity due to the presence of the rhenium complex, which has a relatively long-lived Metal-to-Ligand Charge Transfer (MLCT) character. By using this type of polymers, the metal content can be adjusted easily by simply changing the monomer feed ratio. Moreover, the excited state properties and electronic absorption properties can be modified by varying the structure of the diimine ligand coordinated to the metal. This approach allows us to fine-tune the absorption spectra of the polymers by employing different types of rhenium complex derivatives. PEDOT:PSS and PTCDI were used as the hole and electron transport layers, respectively. The ITO/PEDOT:PSS/DIAN-PPV/PTCDI/Al devices were found to exhibit photovoltaic response under the illumination of AM1 solar radiation. The short-circuit current Isc, open-circuit voltage Voc, and the fill factor FF were measured to be 38 μA/cm2, 0.93 V and 0.21 respectively. Another photovoltaic device was prepared with the structure ITO/PEDOT:PSS/DIAN-PPV:TiO2/PTCDI/Al and its photovoltaic properties were studied. The presence of TiO2 will assist the electron transport of the DIAN-PPV to the PTCDI, in which the electrons can be collected at the aluminium electrode. The short-circuit current Isc, open-circuit voltage Voc, and the fill factor FF were measured to be 51 μA/cm2, 1.18 V and 0.12 respectively. It was observed that the power conversion efficiency of photovoltaic devices related closely to the rhenium content and the structure of the rhenium complex used.