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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 BaF 2 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. Unlabelled Image • We studied LIBS of BaF 2 activated by Tm3+. • Emission and temporal behavior of BaF molecules were determined. • Plasma Induced Luminescence of Tm3+ was found. [ABSTRACT FROM AUTHOR]