Electromagnetic absorbers with Schottky contacts derived from interfacial ligand exchanging metal-organic frameworks

[Display omitted] •ZnO/Fe Schottky junctions were fabricated in Fe(CN)63− ligand exchange method.•Rietveld refinement was employed on analyzing heterogenous interfacial structures.•Heterointerfaces with Schottky contacts can be regarded as effective polar interfaces.•The fE of S3 reached 4.88 GHz with RLmin of –33.36 dB. Various types of polycrystals have been regarded as excellent electromagnetic (EM) microwave absorbents, while differentiated heterointerfaces among grains usually manipulate conductive loss and polarization relaxation, especially interfacial polarization. Herein, polar facets that dominated the optimization of EM attenuation were clarified by carefully designing polycrystalline Schottky junctions with metal–semiconductor contacts for the first time. An ingenious ligand exchange technique was utilized to construct Zn-MOF (ZIF-L) precursors for Fe-ZnO polycrystals, in which Fe-containing Fe(CN)63− etching ligand acted as metallic source in Schottky junctions. By adjusting the Schottky contacts in polycrystals, the enhanced grain boundaries mainly induced stronger interfacial polarization and affected the microcurrent lightly. This is because Schottky barriers can cause local charge accumulation on heterointerfaces for polarization relaxation. Additionally, the coexistence of Zn and O vacancies brought a lot of lattice defects and distortions for dipole polarization. Thus, optimal EM wave absorbability was obtained by polycrystals with 8 h ligand exchange and an effective absorption band reaching 4.88 GHz. This work can provide guidance for designing advanced polycrystalline EM absorption materials and also highlight the mechanism and requirement of Schottky junctions dominating polarization.