A p‑Type Zinc-Based Metal–Organic Framework

An original concept for the property tuning of semiconductors is demonstrated by the synthesis of a p-type zinc oxide (ZnO)-like metal–organic framework (MOF), (ZnC2O3H2) n , which can be regarded as a possible alternative for ZnO, a natural n-type semiconductor. When small oxygen-rich organic linkers are introduced to the Zn–O system, oxygen vacancies and a deep valence-band maximum, the two obstacles for generating p-type behavior in ZnO, are restrained and raised, respectively. Further studies of this material on the doping and photoluminescence behaviors confirm its resemblance to metal oxides (MOs). This result answers the challenges of generating p-type behavior in an n-type-like system. This concept reveals that a new category of hybrid materials, with an embedded continuous metal–oxygen network, lies between the MOs and MOFs. It provides concrete support for the development of p-type hybrid semiconductors in the near future and, more importantly, the enrichment of tuning possibilities in inorganic semiconductors.