Lead sulfide (PbS) and cadmium sulfide (CdS) quantum dots (QDs) are prepared over mesoporous TiO2 films by a successive ionic layer adsorption and reaction (SILAR) process. These QDs are exploited as a sensitizer in solid‐state solar cells with 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxyphenylamine)‐9,9′‐spirobifluorene (spiro‐OMeTAD) as a hole conductor. High‐resolution transmission electron microscopy (TEM) images reveal that PbS QDs of around 3 nm in size are distributed homogeneously over the TiO2 surface and are well separated from each other if prepared under common SILAR deposition conditions. The pore size of the TiO2 films and the deposition medium are found to be very critical in determining the overall performance of the solid‐state QD cells. By incorporating promising inorganic QDs (PbS) and an organic hole conductor spiro‐OMeTAD into the solid‐state cells, it is possible to attain an efficiency of over 1% for PbS‐sensitized solid‐state cells after some optimizations. The optimized deposition cycle of the SILAR process for PbS QDs has also been confirmed by transient spectroscopic studies on the hole generation of spiro‐OMeTAD. In addition, it is established that the PbS QD layer plays a role in mediating the interfacial recombination between the spiro‐OMeTAD+ cation and the TiO2 conduction band electron, and that the lifetime of these species can change by around 2 orders of magnitude by varying the number of SILAR cycles used. When a near infrared (NIR)‐absorbing zinc carboxyphthalocyanine dye (TT1) is added on top of the PbS‐sensitized electrode to obtain a panchromatic response, two signals from each component are observed, which results in an improved efficiency. In particular, when a CdS‐sensitized electrode is first prepared, and then co‐sensitized with a squarine dye (SQ1), the resulting color change is clearly an addition of each component and the overall efficiencies are also added in a more synergistic way than those in PbS/TT1‐modified cells because of favorable charge‐transfer energetics.

Colloidal cadmium selenide (CdSe) quantum dots (QDs) have been prepared and exploited as inorganic dyes to sensitize a large-band-gap TiO2 layer for QD-sensitized solar cells. The optimized QD-sensitized solar cells exhibited an unprecedented incident photon-to-charge carrier generation efficiency of 36% and an overall conversion efficiency of over 1.7% at 0.1 sun and 1% at full sun intensity with a cobalt(II/III)-based redox system. The photovoltaic characteristics of CdSe QD-sensitized cells are compared with standard dye-sensitized solar cells, in which the former exhibited about half of the efficiency of the latter. From the kinetics of charge transfer monitored using transient spectroscopic and voltage decay measurements in the CdSe QD-sensitized cell, the regeneration yield of oxidized QDs was found to be close to almost unity, and the electron lifetime was longer in the CdSe QD-sensitized cell than in the dye-sensitized solar cell.

Nanostructured composites of inorganic and organic materials are attracting extensive interest for electronic and optoelectronic device applications. In this paper, we introduce a general method for the fabrication of metal sulfide nanoparticle/polymer films employing a low-cost and low temperature route compatible with large-scale device manufacturing. Our approach is based upon the controlled in situ thermal decomposition of a solution processable metal xanthate precursor complex in a semiconducting polymer film. To demonstrate the versatility of our method, we fabricate a CdS/P3HT nanocomposite film and show that the metal sulfide network inside the polymer film assists in the absorption of visible light and enables the achievement of high yields of charge photogeneration at the CdS/P3HT heterojunction. Photovoltaic devices based upon such nanocomposite films show solar light to electrical energy conversion efficiencies of 0.7% under full AM1.5 illumination and 1.2% under 10% incident power, demonstrating the potential of such nanocomposite films for low-cost photovoltaic devices.

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We report a transient absorption and luminescence study addressing the charge separation, recombination, and regeneration reactions at nanostructured metal oxide/PbS quantum dot/organic hole conductor heterojunctions. We show that yields of charge separation are significantly higher at PbS/SnO(2) interfaces relative to PbS/TiO(2) interfaces, and conclude that this behavior is a result of the ca. 300-500 meV lower conduction band edge in SnO(2) as compared to TiO(2). We also report a correlation between the PbS particle size and the yield of charge separation at PbS/SnO(2) interfaces, with a smaller PbS particle radius resulting a higher yield of charge separation. Finally we investigated the regeneration of the photooxidized PbS by an organic hole transporting material, namely, spiro-OMeTAD. The overall spiro-OMeTAD(+) yield is found to be 27% at a SnO(2)/PbS (approximately 3 nm diameter)/spiro-OMeTAD heterojunction. The addition of a lithium salt was found to raise the overall spiro-OMeTAD(+) yield from its initial value of 27% (where no Li(+) is present) to 50%. We believe this to be a result of an increase in the primary charge injection yield to near unity as the SnO(2) conduction band is lowered (with increasing [Li(+)]), increasing the driving force for electron injection. The present findings are discussed with relevance to the design of PbS-sensitized metal oxide layers for DSSCs.