Laser-induced breakdown spectroscopy of BaF₂-Tm³⁺

Our recent study was focused on the emission from Laser Induced Plasma (LIP) at the delay times of tenths of microseconds after the laser pulse. At these long delays, the spectrum is dominated by the broadband molecular emission and plasma induced luminescence (PIL) produced by a luminescent matrix; only solitary atomic emission lines can be seen. Barium fluoride BaF₂ activated by thulium (Tm) is a famous scintillator that presents the promising object for LIP in terms of both the potential for BaF molecular emission and Tm³⁺ PIL. The detection of molecular and PIL bands presents a new opportunity for analysis of halogens and rare-earth elements, which are the difficult objects for LIBS. In this paper, we show that the UV, Green, Extreme Red, and Infrared molecular bands from BaF and blue luminescence from Tm³⁺ are present in the LIP emission spectra while the detection of atomic emission from F I and Tm I was impossible with the same experimental setup. Thus, the detection of molecular emission and PIL can be more sensitive than the traditional detection of emission from atoms and ions.