The effect of Al2O3 barrier layers in TiO2/dye/CuSCN photovoltaic cells explored by recombination and DOS characterization using transient photovoltage measurements.

Solid-state dye-sensitized solar cells of the type TiO(2)/dye/CuSCN have been made with thin Al(2)O(3) barriers between the TiO(2) and the dye. The Al(2)O(3)-treated cells show improved voltages and fill factors but lower short-circuit currents. Transient photovoltage and photocurrent measurements have been used to find the pseudo-first-order recombination rate constant (k(pfo)) and capacitance as a function of potential. Results show that k(pfo) is dependent on V(oc) with the same form as in TiO(2)/dye/electrolyte cells. The added Al(2)O(3) layer acts as a "tunnel barrier", reducing the k(pfo) and thus increasing V(oc). The decrease in k(pfo) also results in an increased fill factor. Capacitance vs voltage plots show the same curvature (approximately 150 mV/decade) as found in TiO(2)/dye/electrolyte cells. The application of one Al(2)O(3) layer does not cause a significant shift in the shape or position of the capacitance curve, indicating that changes in band offset play a lesser role in the observed V(oc) increase. Cells made with P25 TiO(2) have, on average, 2.5 times slower recombination rate constants (longer lifetimes) than those made with colloidal TiO(2). The cells with P25 also show 2.3 times higher trap density (DOS), which results in little change in the V(oc) between the two types of TiO(2). It is further noted that the recombination current in these cells cannot be calculated from the total charge times the first order rate constant.