Tunable dielectric response and electronic conductivity of potassium-ion-doped tunnel-structured manganese oxides

Abstract

Potassium-ion-doped MnO2 has been successfully synthesized using the hydrothermal method, and the influence of the doped potassium ions on the electrical conductivity and permittivity is studied. X-ray powder diffraction, scanning electron microscopy, electron-probe micro-analysis, and a vector network analyzer are used to perform characterization. The densities of states of doped and undoped MnO2 tunnel structures are also discussed based on first-principles calculations. Results show that the conductivity and dielectric resonance of MnO2 can be elevated by means of K+ doping. The conductivity of K+-doped MnO2 prepared at different reaction times shows a decreasing trend and is generally 1 order of magnitude higher than that of pure MnO2. The electrical conductivity of K+-doped MnO2 (R3) shows the highest value of 3.33 × 10−2 S/cm at the reaction time of 24 h, while that of pure MnO2 is 8.50 × 10−4 S/cm. When treated with acid, the conductivity of samples remains basically stable along with the increase of treatment time. In addition, acid treatment plays a very significant role in controlling the amount of K+ ions in crystals. The K+ contents of acid-treated samples are 5 times lower than that of the untreated R1. The dielectric losses of the samples with different reaction times are enhanced markedly with frequency increment. The complex permittivity of pure MnO2 only exhibits a resonance at ∼12 GHz, while K+-doped MnO2 exhibits another resonance behavior at ∼9 GHz. The capacity of the dielectric property in the net structure is enhanced by the interfacial polarization, dielectric relaxation, multiple internal reflections, and multiple scattering benefiting.