Luminescence emission from metastable Sm2+ defects in Y PO4:Ce,Sm.

Ce(3+) and Sm(3+) both form stable defect centres in Y PO(4), and their emission properties are well known. However, by irradiating co-doped Y PO(4):Ce,Sm with x-rays or UV light the charge states of the defects can be modified to become Ce(4+) and Sm(2+), which are metastable, and their behaviour acts as a model system for understanding carrier dynamics in charge storage phosphors. Here we report on the luminescence emission behaviour of the Sm(2+) defects that can be observed after x-irradiation. Under suitable excitation conditions, emission from both the stable Sm(3+) and metastable Sm(2+) can be monitored simultaneously. The Sm(2+) luminescence is found to be comprised of a series of narrow lines in the energy range 1.5-1.8 eV, identifiable as internal 4f-4f transitions, accompanied by a series of phonon replicas (phonon energy, 20.4 meV). The intensity of the metastable Sm(2+) emission increases in proportion to the x-irradiation time as their population is increased; under 1.92 eV laser stimulation, the PL is found to fully quench at temperatures above 150 K due to photo-thermal ionization of the defect.

Probing electron transfer processes in YPO(4):Ce, Sm by combined synchrotron-laser excitation spectroscopy.

Yttrium phosphate co-doped with cerium and samarium acts as a charge storage phosphor, but in highly doped material (0.5% co-doping levels), the proximity of defects leads to the uncontrolled non-radiative loss of stored charge through tunnelling. In order to characterize these defects, their mutual interactions and intra-pair charge transfer routes, experiments have been undertaken in which a laser probe is deployed during luminescence excitation using a synchrotron. Two modes of operation are described; in each case, the laser (2.8 eV) probes only Sm(2+) ions, and the detection is set to monitor exclusively Ce(3+) 5d-4f emission. Mode 1: the sample is pumped with monochromatic synchrotron photons in the range 4.5-12 eV, and the resultant charge populations probed with the laser 30 s later; this has the effect of sampling electrons trapped at Sm(2+) that are in quasi-equilibrium. Here, a clear transition between a sub-bandgap Urbach tail region and excitations above the mobility edge is especially apparent, enabling an accurate value of the conduction band energy of YPO(4) to be determined, 9.20 eV. Furthermore, the Sm(2+) and Ce(3+) ground state energies can be positioned within the bandgap (6.8 eV and 3.85 eV above the top of the valence band, respectively). Mode 2: the sample is pumped with monochromatic synchrotron photons in the range 4.5-12 eV and, during this pumping process, the laser probe is activated. This more dynamic process probes direct electron transfer excitation processes between spatially correlated Sm-Ce defect pairs, via their excited states; the laser probe enhances the Ce(3+) emission if direct electron transfer from the Ce(3+) ground state to the excited states of Sm(2+) is being pumped, or quenches the luminescence if the Ce(3+) excited states are pumped. The experiments allow for a precise measure of the difference in energy between the Sm(2+) and Ce(3+) ground states (2.98 eV).

Direct evidence for the participation of band-tails and excited-state tunnelling in the luminescence of irradiated feldspars.

The significance and extent of band-tail states in the luminescence and dosimetry properties of natural aluminosilicates (feldspars) is investigated by means of studies using low temperature (10 K) irradiation and optically stimulated luminescence (OSL) stimulation spectroscopy, and thermoluminescence (TL) in the range 10-200 K, made in comparison with high temperature (300 K) irradiation and photo-transferred OSL and TL investigations undertaken at low temperature. These measurements allow mappings of the band-tails to be made; they are found to be ∼0.4 eV in extent in the typical materials studied. Furthermore, by populating charge trapping centres at high temperature (300 K) and monitoring the OSL stimulation spectra at temperatures in the range 10-300 K, clear evidence is presented for the presence of both thermally activated and non-thermally activated OSL processes; it is argued that the former result from thermally activated hopping through the band-tail states, whilst the latter are due to tunnelling processes, either from the excited state of the OSL centres or through the tail states. The spectral measurements are supported by analysis of the temporal dependence of the OSL signals, which correspond to either tunnelling or general order kinetic decay processes.

Electronic and optical properties of magnesium phthalocyanine (MgPc) solid films studied by soft X-ray excited optical luminescence and X-ray absorption spectroscopies.

In a study to link the optical and structural properties of solid films of magnesium Phthalocyanine (MgPc), a range of synchrotron based spectroscopic methods have been used. These include X-ray excited optical luminescence (XEOL) together with X-ray absorption spectroscopy (XAS) measured both by total electron yield methods (TEY) and by using the optically detected photoluminescence yield method (PLY). XEOL spectra below K shell threshold show a broad emission peak at approximately 860 nm which can be attributed to the optical Q-band of these organic systems, which is then suppressed above the threshold. The shift to higher wavelength compared to optical emission spectra from MgPc in solution is consistent with intermolecular coupling of the excited states in the loosely intermolecular bonded phthalocyanine crystal structure. Zero order total PLY spectra at both C and N K edges are compared to TEY spectra where at the C K edge an inversion of intensity ratios between features is observed. Wavelength-specific PLY absorption spectra taken at 860 nm at the N K edge show a role for sigma* states participating in the luminescence process possibly through the sigma-like lone pair of bridging nitrogen atom, denoted the n --> pi* transition.

Enhancements in luminescence measurement techniques.

New developments in the Risø TL/OSL system includes a software controlled heater fitted underneath the beta source to enable irradiation of samples at an elevated temperature. This allows investigations of competition effects from thermally shallow traps and centres. Significant additional software developments include the facility to vary linearly the stimulation power during stimulation (linearly modulated OSL). The elevated temperature irradiator facility has been further expanded to allow the measurement of radioluminescence (RL) during beta irradiation. This additional facility allows the measurement of TL, OSL and RL in the same software controlled automatic sequence. This paper provides a description of the capabilities of the new combined automatic TL/OSL/RL reader, and illustrates the application of the elevated temperature irradiator facility, and the RL unit. The new measurement facilities have provided preliminary information about possible trap competition during storage, and changes in recombination processes.