Re-Engineering Hematite: Synergistic Co-Doping Routes to Efficient Solar Water Splitting

Solar-driven water electrolysis requires high-performance photoelectrodes that exhibit excellent photoabsorption, superior charge transport, and optimized thermal management. In this work, we conducted a first-principles investigation to explore optimized doping conditions for hematite ($\alpha$-Fe${}_2$O${}_3$) by incorporating boron (B), yttrium (Y), and niobium (Nb) mono-dopants, as well as (B, Y) and (B, Nb) co-dopants. To identify the optimal dopant elements and concentrations, we evaluated electronic charge transport, thermal properties, and magnetic susceptibility over a temperature ($T$) range of 300 to 900 K and doping densities ($N$) from ${10}^{19}$ to ${10}^{21}$ cm${}^{-3}$. The B-doped, (B, Y)-doped, and (B, Nb)-doped $\alpha$-Fe${}_2$O${}_3$ photoelectrodes showed significantly reduced band gap energy ($E_g$) relative to $\alpha$-Fe${}_2$O${}_3$. In comparison, Y and Nb dopants only slightly reduced $E_g$ relative to $\alpha$-Fe${}_2$O${}_3$. While B doping introduced impurity states near the Fermi level that limited thermoelectric charge transport, $\alpha$-Fe${}_2$O${}_3$ photoelectrodes doped by other elements exhibited notable improvements, including enhanced visible-light absorption, increased carrier concentration, improved electrical conductivity ($\sigma$), and efficient thermal management. Additionally, these doped photoelectrodes exhibited a remarkable increase in Pauli magnetic susceptibility ($\chi$) by two orders of magnitude compared to pristine $\alpha$-Fe${}_2$O${}_3$, indicating exciting potential for generating spin-selective polarized currents. Overall, our findings revealed that the co-doping conditions are the most effective for enhancing the performance of $\alpha$-Fe${}_2$O${}_3$, providing a low-cost and high-efficiency solution for sustainable green hydrogen (H${}_2$) generation in photocatalytic water splitting.