Multiscale Computational Design of Functionalized Photocathodes for H₂ Generation

We present an integrated computational approach combining first-principles density functional theory (DFT) calculations with wxAMPS, a solid-state drift/diffusion device modeling software, to design functionalized photocathodes for high-efficiency H₂ generation. As a case study, we have analyzed the performance of p-type Si(111) photocathodes functionalized with a set of 20 mixed aryl/methyl monolayers, which have a known synthetic route for attachment to Si(111). DFT is used to screen for high-performing monolayers by calculating the surface dipole induced by the functionalization. The trend in the calculated surface dipoles was validated using previously published experimental measurements. We find that the molecular dipole moment is a descriptor of the surface dipole. wxAMPS is used to predict the open-circuit voltage (efficiency) of the photocathode by calculating the photocurrent versus voltage behavior using the DFT surface dipole calculations as inputs to the simulation. We find that V_oc saturates beyond a surface dipole of ∼0.3 eV, suggesting an upper limit for achievable device performance. This computational approach provides a possibility for the rational design of functionalized photocathodes for enhanced H₂ generation by combining the angstrom-scale results obtained using DFT with the micron-to-nanometer scale capabilities of wxAMPS.