TiO2 Conduction Band Modulation with In2O3 Recombination Barrier Layers in Solid-State Dye-Sensitized Solar Cells

Atomic layer deposition (ALD) was used to grow subnanometer indium oxide recombination barriers in a solid-state dye-sensitized solar cell (DSSC) based on the spiro-OMeTAD hole-transport material (HTM) and the WN1 donor-pi-acceptor organic dye. While optimal device performance was achieved after 3-10 ALD cycles, 15 ALD cycles (similar to 2 angstrom of In2O3) was observed to be optimal for increasing open-circuit voltage (V-oc) with an average improvement of over 100 mV, including one device with an extremely high V-oc of 1.00 V. An unexpected phenomenon was observed after 15 ALD cycles: the increasing V-oc trend reversed, and after 30 ALD cycles V-oc dropped by over 100 mV relative to control devices without any In2O3. To explore possible causes of the nonmonotonic behavior resulting from In2O3 barrier layers, we conducted several device measurements, including transient photovoltage experiments and capacitance measurements, as well as density functional theory (DFT) studies. Our results suggest that the V-oc gains observed in the first 20 ALD cycles are due to both a surface dipole that pulls up the TiO2 conduction band and recombination suppression. After 30 ALD cycles, however, both effects are reversed: the surface dipole of the In2O3 layer reverses direction, lowering the TiO2 conduction band, and mid-bandgap states introduced by In2O3 accelerate recombination, leading to a reduced V-oc.