Zinc oxide has been actively investigated since it has a number of interesting physical properties as a widegap ( E g = 3.4376 eV at 4.2 K) semiconductor with a significant ionic-bonding component [1]. The prospects of application of ZnO and ZnO:Ga in short-wavelength optoelectronics and laser and scintillation technique were considered in [2][3][4]. Photoluminescence investigations, performed on thin films [2,3], ceramics [4], nanopowders [5], and single crystals [6][7][8] showed that zinc oxide exhibits a narrow UV line peaking near 3.3 eV and a wide long-wavelength ( ~2.2 eV) emission band. The narrow UV line has an exciton nature, while the long-wavelength band is attributed to recombination of electrons with oxygen vacancies [5]. Most investigations of the ZnO photoluminescence were performed upon excitation by a He-Cd laser (325 nm) [5][6][7][8]. In this study, the spectral-kinetic characteristics of a ZnO:Ga single crystal excited by vacuum UV (VUV) radiation were investigated.Measurements were performed on a small (approximately 4 × 1.5 × 1 mm) ZnO:Ga single crystal with a gallium concentration of 10 18 cm -3 . The excitation and emission spectra of ZnO:Ga were measured at temperatures of 8 and 300 K at the Synchrotron Radiation Laboratory HASYLAB (DESY, Hamburg), using the experimental equipment of the SUPERLUMI station. The luminescence spectra were recorded using a monochromator with the best resolution (for low-temperature measurements): 2 meV. The luminescence excitation spectra were measured in the range from 4 to 12.5 eV (resolution 3.2 Å) using an R6358P photomultiplier (Hamamatsu) on a secondary monochromator. In measurements of kinetic curves, the excitation pulse width was 290 ps. Figure 1 shows the crystal luminescence spectra measured upon excitation by 6.89-eV photons at temperatures of 8 and 300 K (Figs. 1a and 1b, respectively). The low-temperature spectrum contains a very narrow (width at half-maximum 7.2 meV) line peaking at 3.356 eV (Fig. 1 ‡, inset) and a wide band peaking near 2.0 eV. The narrow 3.356-eV UV line is due to free excitons in zinc oxide. The weak peak at 3.214 eV should be attributed to the superposition of a free exciton and two longitudinal optical (LO) phonons, since the energy of LO phonons in ZnO is 72 meV [7]. The wide band is red-shifted in comparison with the similar band in ZnO nanocrystals. It is believed that this band is due to several types of electron recombination: at oxygen and zinc vacancies and at interstitial zinc [8].At room temperature, the UV line is red-shifted ( h ν max = 3.3 eV) and broadened (Fig. 1b). These changes are due to the change in the luminescence mechanism: the exciton luminescence is suppressed at room temperature and emission occurs between donor (gallium) levels and valence-band holes [3,9]. The wide band in the visible spectral range (Fig. 1b) peaks at 2.1 eV and has a feature near 2.3 eV.The reflection and luminescence excitation spectra of a ZnO:Ga crystal are shown in Fig. 2. The excitation spectra exhibit peaks near 6.0, 7.8, ...