Ultraviolet photoelectron spectroscopy, optical transmission, fluoresc
ence excitation spectroscopy and time-resolved fluorescence spectrosco
py are used to investigate the scintillation mechanisms of cerium fluo
ride (CeF3) and of lanthanum fluoride doped with cerium in concentrati
ons between 0.01 and 50mol% cerium. In LaF3:Ce, the absorption of eith
er optical or ionizing radiation directly or indirectly results in exc
itation of the Ce3+ 4f electron to the lowest 5d level followed by 5d
--> 4f fluorescence at 284-300 nm. Whereas for optical excitation the
fluorescence has a 20 ns decay time, for ionizing radiation there is a
n additional faster (2-10 ns) initial decay component. As the cerium c
oncentration increases, another band appears that partially absorbs th
e 284 300 nm emission and re-radiates it in a broad band peaking at 34
0 nm and having a longer (approximately 30 ns) decay time. In the limi
t of 100% CeF3, radiation trapping is very pronounced. The additional
absorption and emission bands present at large Ce concentrations are a
ttributed to Ce3+ ions in perturbed sites. The relative efficiency for
excitation of unperturbed and perturbed cerium sites via the Ce3+ 5d
and 6s bands, the F- 2p valence band, and the Ce3+ or La3+ 5p core lev
els are determined from fluorescence excitation spectra.