Taneli Laamanen

Persistent luminescence mechanisms: human imagination at work

The present status and future progress of the mechanisms of persistent luminescence are critically treated with the present knowledge. The advantages to be achieved by a further need as well as the pitfalls of the excessive use of imagination are shown. As usual, in the beginning of the present era of persistent luminescence since the mid 1990s, the imagination played a more important role than the sparse solid experimental data and the chemical common sense and knowledge was largely ignored. Since some five years, the mechanistic studies seem to have reached the maturity and – perhaps deceivingly – it seems that there are only details to be solved. However, the development of red emitting nanocrystalline materials poses a challenge also to the more fundamental studies and interpretation. The questions still luring in the darkness include the problems how the increased surface area affects the defect structure and how the “persistent energy transfer” really works. There is still some light to be thrown onto these matters starting with agreeing on the terminology: the term phosphorescence should be abandoned altogether. The long lifetime of persistent luminescence is due to trapping of excitation energy, not to the forbidden nature of the luminescent transition. However, the technically well-suited term “afterglow” should be retained for harmful, short persistent luminescence.

Electronic structure of the SrAl2O4:Eu2+ persistent luminescence material

Abstract The electronic structure of the strontium aluminate (SrAl2O4:Eu2+) materials was studied with a combined experimental and theoretical approach. The UV-VUV synchrotron radiation was applied in the experimental study while the electronic structure of the non-optimized and optimized crystal structure were investigated theoretically by using the density functional theory. The structure of the valence and conduction bands as well as the band gap energy of the material together with the position of the Eu2+ 4f7 8S7/2 ground state were calculated. The calculated band gap energy (6.4 eV) agreed well with the experimental value of 6.6 eV. The valence band consisted mainly of oxygen states whereas the bottom of the conduction band of strontium states. In agreement with the experimental results, the calculated 4f7 8S7/2 ground state of Eu2+ lies in the energy gap of the host. The position of the 4f7 ground state depended on the Coulomb repulsion strength. The position of the 4f7 ground state with respect to the valence and conduction bands was discussed using theoretical and experimental evidence available.

The Bologna Stone: history's first persistent luminescent material

In 1603, the Italian shoemaker Vincenzo Cascariolo found that a stone (baryte) from the outskirts of Bologna emitted light in the dark without any external excitation source. However, the calcination of the baryte was needed prior to this observation. The stone later named as the Bologna Stone was among the first luminescent materials and the first documented material to show persistent luminescence. The mechanism behind the persistent emission in this material has remained a mystery ever since. In this work, the Bologna Stone (BaS) was prepared from the natural baryte (Bologna, Italy) used by Cascariolo. Its properties, e. g. impurities (dopants) and their valences, luminescence, persistent luminescence and trap structure, were compared to those of the pure BaS materials doped with different (transition) metals (Cu, Ag, Pb) known to yield strong luminescence. The work was carried out by using different methods (XANES, TL, VUV-UV-vis luminescence, TGA-DTA, XPD). A plausible mechanism for the persistent luminescence from the Bologna Stone with Cu+ as the emitting species was constructed based on the results obtained. The puzzle of the Bologna Stone can thus be considered as resolved after some 400 years of studies. (Less)

Synchrotron radiation investigations of the Sr2MgSi2O7:Eu2+,R3+ persistent luminescence materials

Abstract The electronic and defect energy level structure of polycrystalline Sr2MgSi2O7:Eu2+,R3+ persistent luminescence materials were studied with thermoluminescence and different synchrotron radiation spectroscopies (UV-VUV emission and excitation, X-ray absorption near-edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS)). Special attention was paid on the effect of the R3+ co-dopants on the persistent luminescence properties of the materials. Theoretical calculations using the density functional theory (DFT) were carried out simultaneously with the experimental work. The experimental band gap energy (Eg) value of ca. 7.1 eV agreed very well with the DFT value of 6.7 eV. The variation of the Eg value was attempted to relate with the trap structure as well as with the different properties of the R3+ co-dopants. The trap level energy distribution depended strongly on the R3+ co-dopant except for the shallowest trap energy above the room temperature remaining practically the same, however. The different processes in the mechanism of persistent luminescence from Sr2MgSi2O7:Eu2+,R3+ were assembled and their contributions discussed.

DFT and synchrotron radiation study of Eu 2+ doped BaAl 2 O 4

The structural distortions resulting from the size mismatch between the Eu2+ luminescent centre and the host Ba2+ cation as well as the electronic structure of BaAl2O4:Eu2+(,Dy3+) were studied using density functional theory (DFT) calculations and synchrotron radiation (SR) luminescence spectroscopy. The modified interionic distances as well as differences in the total energies indicate that Eu2+ prefers the smaller of the two possible Ba sites in the BaAl2O4 host. The calculated Eu2+ 4f7 and 4f65d1 ground level energies confirm that the excited electrons can reach easily the conduction band for subsequent trapping. In addition to the green luminescence, a weak blue emission band was observed in BaAl2O4:Eu2+,Dy3+ probably due to the creation of a new Ba2+ site due to the effect of water exposure on the host.

Defect aggregates in the Sr2MgSi2O7 persistent luminescence material

Abstract The crystal and electronic structure of the Eu 2+ doped and defect containing Sr 2 MgSi 2 O 7 persistent luminescence material were studied using the density functional theory (DFT). The defects may act as energy storage or even luminescence quenching centres in these materials, however their role is very difficult to confirm experimentally. The probability of vacancy formation was studied using the total energy of the defect containing host. Significant structural modifications in the environment of the isolated defects, especially the strontium vacancy, as well as defect aggregates were found. The experimental band gap energy of Sr 2 MgSi 2 O 7 was well reproduced by the calculations. The defect induced electron traps close to the hosts conduction band were found to act as energy storage sites contributing to its efficient persistent luminescence. The interactions between the defects were found to modify both the Eu 2+ 4f 7 ground state energy as well as the trap structure. The effect of charge compensation induced by the rare earth co-doping on the defect structure and energy storage properties of the persistent luminescence materials was discussed.

Persistent luminescence fading in Sr 2 MgSi 2 O 7 :Eu 2+ ,R 3+ materials: a thermoluminescence study

The fading of persistent luminescence in Sr2MgSi2O7:Eu2+,R3+ (R: Y, La-Nd, Sm-Lu) was studied combining thermoluminescence (TL) and room temperature (persistent) luminescence measurements to gain more information on the mechanism of persistent luminescence. The TL glow curves showed the main trap signal at ca. 80 °C, corresponding to 0.6 eV as the trap depth, with every R co-dopant. The TL measurements carried out with different irradiation times revealed the general order nature of the TL bands. The results obtained from the deconvolutions of the glow curves allowed the prediction of the fading of persistent luminescence with good accuracy, though only when using the Becquerel decay law.

Synchrotron Radiation Study of the M2MgSi2O7:Eu2+ Persistent Luminescence Materials

The synchrotron radiation luminescence and excitation spectra of the Eu doped M2MgSi2O7 (M = Ca, Sr, Ba) materials were investigated at the SUPERLUMI station of HASYLAB at DESY, Germany. The measurement of the band gap (Eg) energy of all three host lattices using the excitation spectra of Eu gave values around 7 eV. The measured band gap energies were very similar but slightly higher than those calculated with the DFT-methods. The effect of R co-doping was studied at different temperatures between 10 K and room temperature. A significant increase in the band gap energy was observed with decreasing temperature. In contrast, no noteworthy change in this value was observed as a function of the R co-doping ion.

Understanding Persistent Luminescence: Rare-Earth- and Eu2+-doped Sr2MgSi2O7

Similar to many other Eu2+,RE3+-co-doped persistent luminescence materials, for Sr2MgSi2O7:Eu2+,RE3+ the initial intensity and duration of persistent luminescence was also found to depend critically on the rare-earth (RE) co-doping. An enhancement of 1 - 2 orders of magnitude in these properties could be obtained by Dy3+ co-doping whereas total quenching of persistent luminescence resulted from the use of Sm3+ and Yb3+. To solve this drastic disparity, the effects of the individual RE3+ ions were studied with thermoluminescence (TL) spectroscopy to derive information about the formation of traps storing the excitation energy. The charge compensation defects were concluded to be the origin of the complex TL glow curve structure. The tuning of the band gap of the Sr2MgSi2O7 host and especially the position of the bottom of the conduction band due to the Eu2+,RE3+ co-doping was measured with the synchrotron radiation vacuum UV (VUV) excitation spectra of the Eu2+ dopant. The model based on the evolution of the band gap energy with RE3+ co-doping was found to explain the intensity and duration of the persistent luminescence.

Valences of dopants in Eu2+ persistent luminescence materials

The existence and effect of different rare earth (R2+/3+/IV) ions in SrAl2O4:Eu2+, R3+ and M2MgSi2O7:Eu2+, R3+ (M: Sr, Ba) persistent luminescence materials was studied with XANES (x-ray absorption near edge structure) measurements at HASYLAB/DESY (Hamburg, Germany) and MAX-lab (Lund, Sweden). The experiments were carried out at 298K for selected rare earth (co-) dopants (Eu2+; Ce3+, Nd3+, Sm3+, Dy3+ and Yb3+). The co-existence of Eu2+ and Eu3+ was observed in all materials. The co-dopants were always in the trivalent form.