Crystallization and solid solution attainment of samarium doped ZnO nanorods via a combined ultrasonic-microwave irradiation approach

Abstract

An advanced sol-gel method is developed via combined ultrasound-microwave irradiation and utilized for the crystallization of pristine and samarium doped zinc oxide nanorods. Organic structure directing agents directed one dimensional growth and air-annealing was applied as post-thermal treatment. Microstructural, optical, and solid state survey was pursued by PXRD, FESEM, TEM, EDS, FTIR, DRS, PL, micro-Raman, H2-TPR, and ESR techniques. Phase analysis by diffraction patterns confirmed the efficacy of irradiation strategy as it improves the crystallinity degree, expedites the hexagonal close pack morphology, and conducts lattice imperfection. Accordingly, aspect ratio and electronic evolution parallel to dopant content is favored. Electron microscopy demonstrated the flake-like rearrangement of nanorods as well as a structure-related growth where a direct proportion exists between atomic packing factor in lattice and aspect ratio. Textural investigation by EDS and FTIR rejected the presence of any impurity verifying an integrated composition. Reflectance and luminescence spectra exhibited characteristic optical behavior with shifts corresponding to dopant concentration. Also, band gap energies increased with samarium addition depicting an opposite trend with respect to unit cell variation. Finally, Raman, TPR, and ESR spectra provided detailed dopant-dependent trends on the internal solid state and defect chemistry of the nanorods. In this regard, maximum shifts in E2high and E1LO phonon modes duly correlated with the vibrations of zinc and oxygen atoms, surface oxygen and bulk ZnO reduction bands, emergence and alteration of samarium centers, along with the dominance of zinc and oxygen vacancies were all resulted due to the utmost lattice imperfection in SZO1.