Naphthoquinoneoxime-Sensitized Titanium Dioxide Photoanodes: Photoelectrochemical Properties.

Abstract

Naphthoquinoneoxime derivatives, viz., LwOx, 3-hydroxy-4-(hydroxyimino)naphthalen-1 (4H)-one; PthOx, 3-hydroxy-4-(hydroxyimino)-2-methylnaphthalen-1(4H)-one; and Cl_LwOx, 2-chloro-3-hydroxy-4-(hydroxyimino)naphthalen-1(4H)-one, are used in fabrication of dye-sensitized solar cells (DSSCs). The photophysical and electrochemical properties of the sensitizers were studied. The HOMO-LUMO energy gaps of the sensitizers (LwOx, PthOx, and Cl_LwOx) calculated by using the intersection of UV-visible and fluorescence spectra are 2.85, 2.71, and 2.87 eV, respectively. The energy band alignment energy level of the sensitizer, that is, the lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO), should match with the energy level of the TiO2 conduction band and the redox potential of iodine/triiodide electrolyte to allow smooth electron transfer. The electrochemical characterization of sensitizers was done to find the LUMO and HOMO level of the sensitizer. It shows that the LUMO level of (LwOx, PthOx, and Cl_LwOx) is above the conduction band position of TiO2. Electrochemical impedance spectroscopy was used to study the charge transport resistance and electron lifetime of DSSCs. The charge transport resistance at the TiO2 |electrolyte|counter electrode interface was reduced in the Cl_LwOx device; thus, the electron lifetime of Cl_LwOx was enhanced compared to LwOx and PthOx sensitizers. The fabricated device was characterized using photocurrent density-voltage (J-V) measurement. It is observed that there was an enhancement in the overall power conversion efficiency (η) of the DSSCs fabricated by using Cl_LwOx sensitizers as compared to LwOx and PthOx sensitizer-loaded photoanodes. Enhancement in power conversion efficiency, that is, photovoltage and photocurrent, is achieved due to the chlorine substituent. Thus, the chlorine substituent naphthoquinoneoxime pushes the electron density, enhancing the pushing nature and facilitating the lone pair present in the N-OH moiety to attach to TiO2 more strongly.