Band Engineering in Core/Shell ZnTe/CdSe for Photovoltage and Efficiency Enhancement in Exciplex Quantum Dot Sensitized Solar Cells

Even though previously reported CdTe/CdSe type-II core/shell QD sensitizers possess intrinsic superior optoelectronic properties (such as wide absorption range, fast charge separation, and slow charge recombination) in serving as light absorbers, the efficiency of the resultant solar cell is still limited by the relatively low photovoltage. To further enhance photovoltage and cell efficiency accordingly, ZnTe/CdSe type-II core/shell QDs with much larger conduction band (CB) offset in comparison with that of CdTe/CdSe (1.22 eV vs 0.27 eV) are adopted as sensitizers in the construction of quantum dot sensitized solar cells (QDSCs). The augment of band offset produces an increase of the charge accumulation across the QD/TiO₂ interface under illumination and induces stronger dipole effects, therefore bringing forward an upward shift of the TiO₂ CB edge after sensitization and resulting in enhancement of the photovoltage of the resultant cell devices. The variation of relative chemical capacitance, <i>C</i>_μ, between ZnTe/CdSe and reference CdTe/CdSe cells extracted from impedance spectroscopy (IS) characterization under dark and illumination conditions clearly demonstrates that, under light irradiation conditions, the sensitization of ZnTe/CdSe QDs upshifts the CB edge of TiO₂ by the level of ∼50 mV related to that in the reference cell and results in the enhancement of <i>V</i>_oc of the corresponding cell devices. In addition, charge extraction measurements have also confirmed the photovoltage enhancement in the ZnTe/CdSe cell related to reference CdTe/CdSe cell. Furthermore, transient grating (TG) measurements have revealed a faster electron injection rate for the ZnTe/CdSe-based QDSCs in comparison with the CdSe cells. The resultant ZnTe/CdSe QD-based QDSCs exhibit a champion power conversion efficiency of 7.17% and a certified efficiency of 6.82% under AM 1.5G full one sun illumination, which is, as far as we know, one of the highest efficiencies for liquid-junction QDSCs