Solvent composition regulates the Se : Sb ratio in antimony selenide nanowires deposited from thiol-amine solvent...

Antimony selenide (Sb₂Se₃), a V₂VI₃ semiconductor with an intriguing crystal structure, has demonstrated improved power conversion and solar-to-hydrogen efficiencies in recent years. Depositing antimony selenide nanowires (NWs) from a solution such as a thiol : amine "alkahest" ink is a low-cost and facile route to deposit high surface area photocathodes. However, little is known about the correlations between the solvent composition and the crystallites' structure and optoelectronic properties, which are crucial for photovoltaic and photoelectrochemical applications. We found that the Se : Sb ratio in the NWs decreases from 3 : 2 to less than 1 : 1 with decreasing thiol : amine ratio in the ink used for deposition but not in the solvent mixture used for dissolving the metals. The reduced Se : Sb ratio in the solid NWS correlates with an optical bandgap wider by ∼0.3 eV in comparison to stoichiometric NWs, a decrease of the NWs diameter from 180 to 30 nanometers, and a ∼0.2 eV larger work function. In addition, we found that the Se : Sb ratio is not uniform along the NWs, which causes a surface potential increase near the tips of the NWs due to a lower Se : Sb ratio near the NWs tips. The increased surface potential near the tips corresponds to a driving force, due to doping or graded bandgap broadening, that facilitates the migration of photoexcited electrons towards the NW tips. Our findings unlock a path for fine-tuning the optoelectronic properties of antimony selenide towards improving the performance of antimony selenide solar cells and photocathodes.