Surface modification by high-energy heavy-ion irradiation in various crystalline ZnO facets

Phys Chem Chem Phys. 2021 Oct 13;23(39):22673-22684. doi: 10.1039/d1cp02388h.

Abstract

Self-assembled surface nanoscale structures on various ZnO facets are excellent templates for the deposition of semiconductor quantum dots and manipulation with surface optical transparency. In this work, we have modified the surface of c-, m- and a-plane ZnO single-crystals by high-energy W-ion irradiation with an energy of 27 MeV to observe the aspects of surface morphology on the optical properties. We kept ion fluences in the range from 5 × 109 cm-2 to 5 × 1011 cm-2 using the mode of single-ion implantation and the overlapping impact mode to see the effect of various regimes on surface modification. Rutherford backscattering spectroscopy in the channeling mode (RBS-C) and Raman spectroscopy have identified a slightly growing Zn-sublattice disorder in the irradiated samples with a more significant enhancement for the highest irradiation fluence. Simultaneously, the strong suppression of the main Raman modes and the propagation of the modes corresponding to polar Zn-O vibrations indicate disorder mainly in the O-sublattice in non-polar facets. The surface morphology, analysed by atomic force microscopy (AFM), shows significant changes after ion irradiation. The c- and a-plane ZnO exhibit the formation of small grains on the surface. The m-plane ZnO forms a sponge-like surface for lower fluences and grains for the highest fluence. The surface roughness itself increases with the irradiation fluence as shown by AFM measurement as well as spectroscopic ellipsometry (SE) analysis. The damage caused by high-energy irradiation leads to non-radiative processes and suppression of the near-band-edge peak as well as the deep-level emission peak in the photoluminescence spectra. Furthermore, the refraction index n and the extinction coefficient k of irradiated samples, determined by SE, have features corresponding to the particular exciton states blurred and are slightly lower in the optical bandgap region especially for the polar c-plane ZnO facet.