The authors report the first preparation of high-density ultrafine green-emitting wool-like BaCO 3 nanowires, having an average diameter of 18.5 nm, and an average crystallite size of 13.4 nm, by an electrospinning method with a subsequent two-step calcination approach. A possible vapor-solid interaction mechanism was proposed for the finest nanowires growth, where the reactive carbon dioxide vapors were generated during the static atmosphere ambient calcination and assisted oxidization nucleation at enhanced temperatures. Our work provides new insights into electrospun fiber diameter refinement via controlled calcination, and this simple post-electrospinning controlled strategy can be generally applied to other metal carbonate ultrafine NWs families.
Unlike to the most previous reports, mixed-cation Cu(+)/Cu(2+) doping-induced novel nanoscale phenomena, including photoluminescence quenching and a correlating ferrimagnetism with Néel temperature ≈ 14 K, were found in the as-calcined (Cu2(+)/Cu1(2+))0.044Zn0.956O electrospun nanobelts (NBs). There is also high strain (up to 1.98%) and shrunk lattice distortion (ΔV/V0 ∼ 0.127%) in the (Cu2(+)/Cu1(2+))0.044Zn0.956O NBs, leading to broken lattice symmetry in conjunction with nonstoichiometry (i.e., oxygen vacancies or accurate F centers), which could be possible origins of ferrimagnetism in the Cu-doped ZnO NBs. Electron paramagnetic resonance spectra reveal that there are giant and anisotropic g factors, suggesting that there is strong anisotropic spin-orbit interaction between the Cu(2+) ion and F center (i.e., forming Cu(2+)-F(+) complexes) in the (Cu2(+)/Cu1(2+))0.044Zn0.956O NBs. The above correlation enables the potential application of tuning of the optical and ferrimagnetic properties through strain and F-center engineering.
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