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Carbon Oxide Decomposition as a Novel Technique for Ultrahigh Quality ZnO Nanowire Crystallization

Cryst. Growth Des. 2023, 23, 9, 6442–6449

SEM images of ZnO NWs produced using the COD method on the sapphire (11–20) substrate (a) and the silicon (100) substrate (b). The average length of the NWs is 20–30 μm and the diameter is 50–500 nm. The STEM image of the edge of the ZnO NW seen along the [11–20] direction (c). Blue frames show zoomed-in areas. The low-magnification HR-TEM image of the ZnO NW acquired in diffraction contrast (d, e). A thin ZnO NW presented in HR-TEM with (1–100) and (0002) planes marked as blue and pink lines, respectively (f).

The carbothermal method of nanowire growth has been known and successfully used for a long time to cultivate various types of nanowires. It was commonly believed that in this method, carbon was utilized solely for the reduction of metal oxide, and the formation of nanowires occurred through the oxidation of metal from the gas phase, with external oxygen supplied. Through modifications to this method and by restricting the access of oxygen, we were able to produce nanowires of exceptional structural and optical quality. Furthermore, this technique is much more cost-effective due to the elimination of the need for equipment to transport carrier gases. The half-width of the optical transition of the exciton bound to the donor in the photoluminescence spectrum, determined for a single nanowire, was only 0.5 meV (measurements conducted at the Faculty of Physics, University of Warsaw). Additionally, X-ray diffraction and high-resolution transmission electron microscopy measurements confirm the excellent structural quality of the nanowires obtained. As indicated by thermodynamic calculations based on equilibrium constants and Gibbs free energies (performed at the Institute of Physical Chemistry of the Polish Academy of Sciences), the reduction of zinc oxide by carbon monoxide played a crucial role in the growth process. It is noteworthy that carbon monoxide is a product of the initial stage of the growth process, not supplied from an external source. The chemical processes occurring in our system differed from the commonly accepted reactions responsible for carbothermal growth processes. Moreover, the presented method can be applied to the growth of other nanowires, such as gallium oxide.


Wiktoria Zajkowska-Pietrzak, Jakub Turczyński, Sławomir Kret, Tomasz Andryszewski, Jan Suffczyński, Anna Reszka, Marcin Stachowicz, Aleksandra Wierzbicka, Krzysztof Fronc, and Henryk Teisseyre

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