Communication: Effect of Oxidation on Excited State Dynamics of Neutral TinO2n-x (n<10, x<4) Clusters

Abstract

Excited state lifetimes of neutral titanium oxide clusters (TinO2n-x, n < 10, x < 4) were measured using a sequence of 400 nm pump and 800 nm probe femtosecond laser pulses. Despite large differences in electronic properties between the closed shell stoichiometric TinO2n clusters and the suboxide TinO2n-x (x = 1-3) clusters, the transient responses for all clusters contain a fast response of 35 fs followed by a sub-picosecond excited state lifetime. In this non-scalable size regime, subtle changes in the sub-ps lifetimes are attributed to variations in the coordination of Ti atoms and localization of charge carriers following UV photoexcitation. In general, clusters exhibit longer lifetimes with increased size and also with addition of O atoms. This suggests that removal of O atoms develops stronger Ti-Ti interactions as the system transitions from a semiconducting character into a fast metallic electronic relaxation mechanism.

Oxygen Deficiencies in Titanium Oxide Clusters as Models for Bulk Defects

“…The neutral cluster distribution was subsequently measured using a home-built Wiley–McLaren type time-of-flight mass spectrometer coupled to a femtosecond laser (<35 fs) for ionization. Detailed information on the experimental setup was previously described. , Briefly, the ionic clusters produced through laser ablation are deflected from the fs laser pulse interaction area through the use of electrostatic fields. Neutral clusters are ionized using temporally overlapped 400 nm (3.1 eV) and 800 nm (1.55 eV) pulses from a Ti:sapphire laser at intensities of 9.9 × 10 14 and 3.1 × 10 15 W/cm 2 respectively.…”