Structural Effects on the Incident Photon-to-Current Conversion Efficiency of Zn Porphyrin Dyes on the Low-Index Planes of TiO(2)

[Image: see text] The structural effects of substrates on the incident photon-to-current conversion efficiency (IPCE) of Zn porphyrin (ZnP) dyes (ZnP-ref, YD2, and ZnPBAT) have been studied on well-defined single-crystal surfaces of rutile TiO(2) (TiO(2)(111), TiO(2)(100), and TiO(2)(110)). IPCE of ZnP-ref depends on the structure of the substrates remarkably: TiO(2)(100) < TiO(2)(110) < TiO(2)(111). IPCE of ZnP-ref/TiO(2)(111) is 13 times as high as that of ZnP-ref/TiO(2)(100) at 570 nm. YD2 and ZnPBAT also give the highest IPCE on TiO(2)(111). The relative coverages of the porphyrin dyes give the following order: TiO(2)(111) < TiO(2)(110) < TiO(2)(100). This order is opposite to that of IPCEs. The orientation of the dyes is predicted using density functional theory calculations on simplified models of TiO(2) surfaces. The highest IPCE on TiO(2)(111) is attributed to the high rate of electron transfer through the space due to the fluctuation of the tilt angle of the adsorbed dyes.