Field emission measurements of current-voltage characteristics are reported for tetrapod structures of ZnO. The nonlinear Fowler-Nordheim (FN) plot is analyzed according to a model of calculation based on saturation of conduction band current and predominance of valence band current at high-field values. The simulated FN plot exhibits similar features to those observed experimentally. The model of calculation suggests that the slope variation of the FN plot, in the high-field and low-field regions, does not depend on the magnitude of saturation. Instead, it is a characteristic of the energy band structure and voltage-to-barrier-field conversion factor of the emitting material.

Summary High‐energy ball milling is performed on Li1.1Mn1.95Fe0.05O4 spinel material, synthesized by sol‐gel method for lithium rechargeable battery, at different durations to obtain nanopowders of finite size distributions. The powders are investigated by means of scanning electron microscopy, particle size distribution, and X‐ray diffraction (XRD) measurements. The structural analysis of the powders is performed to investigate the effect of milling on the particle size, crystallite size, and lattice strain. The scanning electron micrographs and size distribution measurements show that the particle size decreases with the increase in milling duration. The XRD results show that the widths of the diffraction peaks increase with the decrease of particle size (increase of milling duration). This broadening is analyzed according to Scherrer, Williamson‐Hall, and Halder‐Wagner methods. Peak broadening is attributed to contributions of crystallite size and lattice strain. While reducing the particle and crystallite sizes is desirable to achieve higher specific capacity and energy density of the battery active material, lattice strain leads to material degradation and a reduced capacity retention. Thus, when performing mechanical milling, lattice strain should be taken seriously into consideration to optimize the milling parameters and to enhance the materials electrochemical performance.

The experimental total energy distribution (TED) of the field emitted electrons from a single pod of a ZnO tetrapod has been obtained, exhibiting a two-peak feature. The energy difference between the two peaks in the TED is found to be nearly equal to the band gap of the bulk ZnO. The results show that field emitted electrons originate from both the conduction and valence bands. The peak position dependence on the applied voltage has also been observed. In the present case, the size of the ZnO tetrapod is not small enough to reflect the quantum confinement effects.

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