At interfaces with inversion symmetry breaking, Rashba effect couples the motion of electrons to their spin; as a result, spin-charge interconversion mechanism can occur. These interconversion mechanisms commonly exploit Rashba spin splitting at the Fermi level by spin pumping or spin torque ferromagnetic resonance. Here, we report evidence of significant photoinduced spin to charge conversion via Rashba spin splitting in an unoccupied state above the Fermi level at the Cu(111)/$alpha$-Bi$_{2}$O$_{3}$ interface. We predict an average Rashba coefficient of $1.72times 10^{-10}eV.m$ at 1.98 eV above the Fermi level, by fully relativistic first-principles analysis of the interfacial electronic structure with spin orbit interaction. We find agreement with our observation of helicity dependent photoinduced spin to charge conversion excited at 1.96 eV at room temperature, with spin current generation of $J_{s}=10^{6}A/m^{2}$. The present letter shows evidence of efficient spin-charge conversion exploiting Rashba spin splitting at excited states, harvesting light energy without magnetic materials or external magnetic fields.
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