We designed a stepwise approach for co-sensitization of a zinc porphyrin sensitizer (LD12) with a spirally configured organic dye (CD5) for dye-sensitized solar cells. The co-sensitized LD12 + CD5 device showed significantly enhanced VOC and JSC relative to its individual single-dye sensitized devices. Upon optimization, the device made of the LD12 + CD5 system yielded JSC/mA cm-2 = 16.7, V OC/V = 0.74, FF = 0.73 and η = 9.0%; this performance is superior to that of either individual device made from LD12 (η = 7.5%) and CD5 (η = 5.7%) under the same conditions of fabrication. To understand the effects of the potential shift and charge recombination on the cell performance, we measured charge-extraction (CE) and intensity-modulated photovoltage spectra (IMVS). Upon sensitization with each dye, the TiO2 potentials are similar, but co-sensitization causes the potential to shift down (cathodic shift). Charge recombination was significantly retarded for the co-sensitized system relative to each individual dye-sensitized system, to account for the enhanced VOC for the former relative to the latter. A test of stability indicates a systematic trend between the LD12 + CD5 and LD12 devices; the performance of the co-sensitized device degraded only ∼15% and remained stable during the period of 500-1000 h near 295 K.
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