Three highly efficient porphyrin sensitizers—YD2, YD2-oC8, and YD30, either sensitized on TiO2 films or embedded in PMMA films—were investigated using electrophotoluminescence (E-PL) spectra. Under both thin-film conditions, on application of an external electric field we observed the quenching of fluorescence of push–pull porphyrins (YD2 and YD2-oC8) and a slightly enhanced fluorescence of the reference porphyrin without an electron donor group (YD30). A nonfluorescent state with charge separation (CS) is proposed to be involved in both YD2 and YD2-oC8 systems so that the electron injection becomes accelerated in the presence of a strong electric field. In contrast, the retardation of the nonradiative process not involving a CS state was the reason for the field-induced enhancement of fluorescence of YD30. The extent of fluorescence quenching of YD2-oC8 was greater than that of YD2 on TiO2 films, indicating that the ortho-substituted long alkoxyl chains play a key role to accelerate the consecutive electron injection involving the CS state. Our E-PL results indicate that a field-induced variation of fluorescent intensity is related to the efficiency of conversion of solar energy and that further improvement of the performance of devices containing push–pull porphyrin dyes is achievable under an applied electric field
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