Enhancing the anti-oxidation stability of vapor-crystallized arsenic crystals via introducing iodine

The oxidation of arsenic restricts its application in high-performance electronic devices and functional materials. Herein, a removable iodine-regulation method was proposed for the first time to enhance the anti-oxidation behavior of arsenic. In a gradient of 500–650 ℃, the introduction of 0.6–5.0 at% iodine into arsenic vapor could regulate an arsenic crystal. The oxygen content on the regulated arsenic crystal surface was lowered below 2.5 at% after exposure to ambient conditions for 96 h, reducing over 90% compared with the control group. The residual iodine barrier, which was mainly in the As-I2 state, suppressed the long-term oxidation of arsenic. First-principles calculation suggested that the adsorbed I2 weakened the delocalization of lone-pair electrons and inhibited charge transfer from the arsenic surface. Iodine regulation stabilized arsenic surface, which preferred (003) or (012) facets. Their surface energies were 22.4 meV and 47.6 meV, respectively. The synergistic effect of surface stabilization and I2 passivation lowered the surface energy and continuously slowed the oxidation of arsenic. Therefore, iodine regulation comprehensively enhanced the anti-oxidation properties of arsenic. Moreover, heating at 200 ℃ left the arsenic surface iodine content below 0.1 at% with little variation in structure. The improved anti-oxidation property of arsenic preserves resources for further advanced applications.