Application of highly-ordered TiO2 nanotube-arrays in heterojunction dye-sensitized solar cells

Abstract

Highly-ordered TiO2 nanotube arrays are made by potentiostatic anodization of a titanium film in a fluoride containing electrolyte. Here we describe the application of this unique material architecture in both front-side and back-side illuminated dye-sensitized solar cells (DSSCs). The back-side illuminated solar cells are based on the use of 6.2 µm long (110 nm pore diameter, 20 nm wall thickness) highly-ordered nanotube-array films made by anodization of a 250 µm thick Ti foil in a KF electrolyte. Front-side illuminated solar cells use a negative electrode composed of optically transparent nanotube arrays, approximately 3600 nm in length (46 nm pore diameter, 17 nm wall thickness), grown on a fluorine doped tin oxide coated glass substrate by anodic oxidation of a previously deposited RF-sputtered titanium thin film in a HF electrolyte. After crystallization by oxygen annealling the nanotube-arrays are treated with TiCl4 to enhance photocurrent amplitudes. The arrays are then sensitized by a self-assembled monolayer of bis(tetrabutylammonium)-cis-(dithiocyanato)-N, N′- bis(4-carboxylato-4′-carboxylic acid-2, 2′-bipyridine)ruthenium(II) (commonly called ‘N719’). Superior photoresponse is obtained using acetonitrile as the dye solvent. Voltage decay measurements indicate that the highly-ordered TiO2 nanotube-arrays, in comparison with nanoparticulate systems, provide excellent pathways for electron percolation with superior electron lifetimes. The front-side illuminated DSSCs, show a typical AM 1.5 photocurrent of 10.3 mA cm−2, open circuit voltage of 0.84 V, 0.54 fill factor, and 4.7% efficiency although the transparent nanotube-array negative electrode is only 360 nm thick. The back-side illuminated DSSCs show an AM 1.5 short-circuit current density of 10.6 mA cm−2, 0.82 V open circuit potential and a 0.51 fill factor yielding a solar conversion efficiency of 4.4%.