Band gap tuning of ZnO nanoparticles via Mg doping by femtosecond laser ablation in liquid environment

► Femtosecond laser ablation synthesis of Mg doped ZnO nanoparticles. ► Electronic properties of ZnO are modified by Mg. ► Band gap and exciton energy shifts to the blue. ► The exciton energy shift is saturated at Mg content of about 20%. ► Phase separation at Mg content is at more than 25%. ► Mechanism of exciton pinning – recombination via new surface states. We use multiphoton IR femtosecond laser ablation to induce non-thermal non-equilibrium conditions of the nanoparticle growth in liquids. Modifications of the electronic properties of ZnO NP were achieved by Mg ion doping of targets prepared from mixtures of Zn and Mg acetylacetonates. The nanoparticle sizes were 3–20nm depending on the ablation conditions. X-ray fluorescence indicates that stoichiometric ablation and incorporation of Mg in nanocrystalline ZnO occurs. HRTEM observations show that nanoparticles retain their wurtzite structure, while at high Mg concentrations we detect the MgO rich domains. Exciton emissions exhibit relatively narrow bands with progressive and controlled blue shifts up to 184meV. The exciton energy correlates to band edge absorption indicating strong modification of the NP band gaps. Stabilisation of the exciton blue shift is observed at high Mg concentration. It is accompanied by the formation of structure defects and ZnO/MgO phase separation within the nanoparticles.