Excitation density effects have a pronounced influence on relaxation processes in solids. They come into play in scintillating
and dosimetric materials exposed to ionizing radiation or in laser materials operating in intense ultraviolet light
fields. The scientific understanding of the underlying process is poor, mainly because most of the studies of light emitting
materials under short wavelength excitation have been performed at weak and moderate excitation intensities due to
limited availability of powerful light sources. Disembodied data on excitation density effects have been reported for
wide-gap dielectrics studied by luminescence spectroscopy, by using such excitation sources as powerful ion beams,1,2pulsed electron beams,2,3 and wide-band hard X-ray synchrotron radiation.4 It is obvious that such non-selective excitation
is a good tool for revealing density-related phenomena in these materials in general, but for investigating specific
features of relaxation processes in insulators, light sources with well defined parameters are necessary. Since the shortwavelength
free electron laser (FEL) technology has been devised by an international consortium at HASYLAB of
DESY, resulting in the development of TESLA Test facility (TTF)5 and later in the construction of a dedicated FEL
source FLASH in Hamburg,6 more advanced studies became possible. The range of interests towards this light source
covers the fields from material science and various other branches of physics to structural biology. The pioneering luminescence
study revealed excitation density effects in the decay of Ce3+ 5d-4f luminescence in Y3Al5O12 crystals and luminescence
of BaF2 crystals in UV-visible range.7 These results motivated systematic investigations of excitation density
effects in wide gap crystals using FEL8,9 and high-harmonic-generated VUV radiation,10 and, at lower energies, femtosecond
laser pulses in the UV.11,12 The main goal of the present work is to analyze the same phenomenon in wide-band
gap BaF2 crystals, where luminescence centres of different origin (self-trapped excitons and cross-luminescence) are
present. Using models developed for explaining the non-linear behaviour of luminescence and exciton-exciton interaction
effects causing scintillator non-proportionalities,10,13 simulations of luminescence decay curves are performed. Possible
quenching effects in the cross-luminescence decay of BaF2 under XUV excitation have been analyzed by Terekhin
et al.14
Photoluminescence of scintillator materials based on intrinsic excitonic luminescence (PbWO4), and on extrinsic
luminescence from doped trivalent rare earth ions (RE3+), such as Y3Al5O12:Ce 3+ and Lu3Al5O12:Pr3+ was studied under
excitation with free electron laser (FEL) light in the 50-100 eV energy range. In case of PbWO4, non-exponential
behavior in the initial part of decay curves was observed depending on the FEL pulse energy, and modeled in terms of
the bimolecular self-quenching process. For the RE3+ doped samples, a reduction in light yield with increasing pulse
energy is observed, which can be traced to saturation of the available RE3+ sites in the crystal due to the initial high
concentration of electron-hole pairs after FEL excitation.
The new XUV sources, which deliver spatially coherent pulses of high peak power, allow to study elementary
processes in the light/solid interaction in the high intensity regime (⩾1011W/cm2). Here, we report two
studies which have used high-order laser harmonics (HH) generated in gas as the excitation source. Firstly, we
have investigated the dynamics of electron relaxation in the wide gap CdWO4 dielectric crystal, an efficient
scintillator material, using time-resolved luminescence spectroscopy. The kinetics decay of luminescence shows
evidence of non radiative relaxation of the self-trapped excitons at the &mgr;s damage to surfaces of poly(methyl
methacrylate) - PMMA, induced by a multi-shot XUV-irradiation (1 kHz reprate) for given fluence, below
damage threshold range of ≈mJ/cm2. The main processes participating in the surface modification, polymer
chain scission followed by the blow up of the volatile, molecular fragments and cross-linking in the near-surface
layer of remaining material, are tentatively identified and associated to, crater formation for short-time exposure
(< 1min) and surface hardening for long-time exposure (⩾1min).
The optical properties of as-grown and electron-irradiated α-Al203 (corundum) single crystals were investigated at low
temperatures, using vacuum-W (VUV) time-resolved luminescence spectroscopy under the synchrotron radiation
excitation. It has been shown that in the electron-irradiated crystals the excitation of self-shrunk exciton emission extends
to the region of interband transitions. The decay time of the 7.6-eV emission of the self-shrunk excitons in as-grown
crystals was found to be about 7 and 23.8 ns respectively for the excitations in the excitonic band and at energies at
which several electron-hole pairs are generated. In the irradiated crystals, these lifetimes were by about 2 ns longer than
in the as-grown ones. For both crystal states, the nature and dynamics of the electronic excitations are discussed.
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