High energy excitations in ion-induced electron emission from AlF3

► We measure energy spectra of electrons ejected from AlF3 by keV ions. ► The spectra show a peak around 7 eV. ► Factor analysis separates components due to different excitation mechanisms. ► The peak in the spectra is due to autoionization of F− 2p4nl n′l′. ► Autoionizing states are excited by electron promotion in close collisions.