Enhanced conductivity and stability of Co_(0.98)Cu_(x)Mn_(2.02−x)O_(4)ceramics with dual phases and twin structures

Semiconductor materials with heterogeneous interfaces and twin structures generally demonstrate a higher concentration of carriers and better electrical stability.A variety of Cu-doped Co_(0.98)Cu_(x)Mn_(2.02−x)O_(4)(0≤x≤0.5)negative temperature coefficient(NTC)ceramics with dual phases and twin structures were successfully prepared in this study.Rietveld refinement indicates that the content of a cubic spinel phase increases with increasing Cu content.The addition of Cu can promote grain growth and densification.Atomic-level structural characterization reveals the evolution of twin morphology from large lamellae with internal fine lamellae(LIT lamellae)to large lamellae without internal fine lamellae(L lamellae)and the distribution of twin boundary defects.First-principles calculations reveal that the dual phases and twin structures have lower oxygen-vacancy formation energy than those in the case of the pure tetragonal and cubic spinel,thereby enhancing the transmission of carriers.Additionally,the three-dimensional charge-density difference shows that metal ions at the interface lose electrons and dwell in high valence states,thereby enhancing electrical stability of the NTC ceramics.Furthermore,the additional Cu ions engage in electron-exchange interactions with Mn and Co ions,thereby reducing resistivity.In comparison to previous Cu-containing systems,the Co_(0.98)Cu_(x)Mn_(2.02−x)O_(4)series exhibit superior stability(aging value≤2.84%),tunable room-temperature resistivity(ρ),and material constant(B)value(17.5Ω·cm≤ρ≤7325Ω·cm,2836 K≤B≤4315 K).These discoveries lay a foundation for designing and developing new NTC ceramics with ultra-high performance.