Theoretical limits of multiple exciton generation and singlet fission tandem devices for solar water splitting

Photoelectrochemical (PEC) water splitting is one of the most important approaches being investigated for solar fuel generation. In this study, we determine the maximum thermodynamic power conversion efficiencies (PCEs) of PEC water splitting two-bandgap tandem devices that produce multiple carriers per photon absorbed via Multiple Exciton Generation (MEG) or Singlet Fission (SF) and in the presence of solar concentration. Here, we employ a detailed balance thermodynamic analysis to determine the effects of top cell thickness, solar concentration, carrier multiplication, electrode overvoltage (V_O), and water absorption on PEC power conversion efficiency for water splitting cells. We have found a maximum PEC power conversion efficiency of 62.9% in cells using two ideal tandem MEG absorbers with bandgaps of 0.3 and 1.2 eV at 1000-suns solar concentration and 0 overvoltage; the maximum PCE for two tandem SF absorbers under the same conditions is nearly the same at 59% with the same values for the absorption thresholds. A very interesting and important result was that, upon thinning the top cell, the range of viable bandgaps for both the top and bottom cells is extended by as much as 0.5-1 eV while still maintaining high maximum conversion efficiency (60-63%). The effects of imposing different solar concentrations from 1X to 1000X and having different tandem configurations of SF and MEG layers were also studied.