A new class of metal-cluster sensitizers has been explored for designing high-efficiency solar cells. Thiol-protected gold clusters which exhibit molecular-like properties have been found to inject electrons into TiO2 nanostructures under visible excitation. Mesoscopic TiO2 films modified with gold clusters deliver stable photocurrent of 3.96 mA/cm(2) with power conversion efficiencies of 2.3% under AM 1.5 illumination. The overall absorption features and cell performance of metal-cluster-sensitized solar cells (MCSCs) are comparable to those of CdS quantum-dot-based solar cells (QDSCs). The relatively high open-circuit voltage of 832 mV and fill factor of 0.7 for MCSCs as compared to QDSCs show the viability of these new sensitizers as alternatives to semiconductor QDs and sensitizing dyes in the next generation of solar cells. The superior performance of MCSCs discussed in this maiden study lays the foundation to explore other metal clusters with broader visible absorption.

Neighboring metal nanoparticles influence photovoltaic and photocatalytic behavior of semiconductor nanostructures either through Fermi level equilibration by accepting electrons or inducing localized surface plasmon effects. By employing SiO(2)- and TiO(2)-capped Au nanoparticles we have identified the mechanism with which the performance of dye-sensitized solar cells (DSSC) is influenced by the neighboring metal nanoparticles. The efficiency of an N719 dye-sensitized solar cell (9.3%) increased to 10.2% upon incorporation of 0.7% Au@SiO(2) and to 9.8% upon loading of 0.7% Au@TiO(2) nanoparticles. The plasmonic effect as monitored by introducing Au@SiO(2) in DSSC produces higher photocurrent. However, Au nanoparticles undergo charge equilibration with TiO(2) nanoparticles and shift the apparent Fermi level of the composite to more negative potentials. As a result, Au@TiO(2) nanoparticle-embedded DSSC exhibit higher photovoltage. A better understanding of these two effects is crucial in exploiting the beneficial aspects of metal nanoparticles in photovoltaics.

No abstract

The photoresponse of quantum dot solar cells (QDSCs) has been successfully extended to the near-IR (NIR) region by sensitizing nanostructured TiO(2)-CdS films with a squaraine dye (JK-216). CdS nanoparticles anchored on mesoscopic TiO(2) films obtained by successive ionic layer adsorption and reaction (SILAR) exhibit limited absorption below 500 nm with a net power conversion efficiency of ~1% when employed as a photoanode in QDSC. By depositing a thin barrier layer of Al(2)O(3), the TiO(2)-CdS films were further modified with a NIR absorbing squaraine dye. Quantum dot sensitized solar cells supersensitized with a squariand dye (JK-216) showed good stability during illumination with standard global AM 1.5 solar conditions, delivering a maximum overall power conversion efficiency (η) of 3.14%. Transient absorption and pulse radiolysis measurements provide further insight into the excited state interactions of squaraine dye with SiO(2), TiO(2), and TiO(2)/CdS/Al(2)O(3) films and interfacial electron transfer processes. The synergy of combining semiconductor quantum dots and NIR absorbing dye provides new opportunities to harvest photons from different regions of the solar spectrum.

A new series of stable, unsymmetrical squaraine near-IR sensitizers (JK-216 and JK-217), which are assembled using both thiophenyl pyrrolyl and indolium groups, exhibit a panchromatic light harvesting up to 780 nm. The JK-216 based cell exhibited a record efficiency of 6.29% for near-IR DSSCs. In addition, the JK-217 device showed an excellent stability under a light soaking test at 60 °C for 1000 h.