Solvothermal Synthesis, Cathodoluminescence, and Field‐Emission Properties of Pure and N‐Doped ZnO Nanobullets

Homogenous crystallization in solution, in the absence of external influences, is expected to lead to growth that is symmetric at least in two opposite facets. Such was not the case when we attempted to synthesize ZnO nanostructures by employing a solvothermal technique. The reaction product, instead, consisted of bullet‐shaped tiny single crystals with an abrupt hexagonal base and a sharp tip. A careful analysis of the product and the intermediate states of the synthesis reveals that one of the reaction intermediates with sheet‐like morphology acts as a self‐sacrificing template and induces such unexpected and novel growth. The synthesis was further extended to dope the nanobullets with nitrogen as previous studies showed this can induce p‐type behavior in ZnO, which is technologically complementary to the naturally occurring n‐type ZnO. Herein, a soft‐chemical approach is used for the first time for this purpose, which is otherwise accomplished with high‐temperature techniques. Cathodoluminesce (CL) investigations reveal stable optical behavior within a pure nanobullet. On the other hand, the CL spectra derived from the surfaces and the cores of the doped samples are different, pointing at a N‐rich core. Finally, even though N‐doped ZnO is known to have high electrical conductivity, the study now demonstrates that the field‐emission properties of ZnO can also be greatly enhanced by means of N doping.