Experimental and numerical analysis of Tm2+excited-states dynamics and luminescence in CaX2(X= Cl, Br, I).

The prospect of using Tm2+-doped halides for luminescence solar concentrators (LSCs) requires a thorough understanding of the temperature dependent Tm2+excited states dynamics that determines the internal quantum efficiency (QE) and thereby the efficiency of the LSC. In this study we investigated the dynamics in CaX2:Tm2+(X= Cl, Br, I) by temperature- and time-resolved measurements. At 20 K up to four distinct Tm2+emissions can be observed. Most of these emissions undergo quenching via multi-phonon relaxation below 100 K. At higher temperatures, only the lowest energy 5d-4f emission and the 4f-4f emission remain. Fitting a numerical rate equation model to the data shows that the subsequent quenching of the 5d-4f emission is likely to occur initially via multi-phonon relaxation, whereas at higher temperatures additional quenching via interband crossing becomes thermally activated. At room temperature only the 4f-4f emission remains and the related QE becomes close to 30%. Possible reasons for the quantum efficiency not reaching 100% are provided.

Reprint of experiments and theory of (138)La radioactive decay.

We measured with unprecedented accuracy key features of the (138)La radioactive decays as ß particle energy distribution from 0.5keV to the end-point and ratios of electron capture probabilities PL/PK, PM/PK and PM/PL. This was achieved by making use of LaBr3:Ce and CeBr3 scintillator detectors. The advantage of the presented technique relies on the double role of LaBr3:Ce as source of (138)La and detector medium resulting in a relatively efficient counting statistics and unaltered ß energy detection. The experimental results are compared to advanced computational techniques and significant deviation is found below 20keV with the computational spectrum showing a 5% excess of ß particle relative to the experimental spectrum at 10keV.

Experiments and theory of ¹³8La radioactive decay.

We measured with unprecedented accuracy key features of the (138)La radioactive decays as ß particle energy distribution from 0.5 keV to the end-point and ratios of electron capture probabilities PL/PK, PM/PK and PM/PL. This was achieved by making use of LaBr3:Ce and CeBr3 scintillator detectors. The advantage of the presented technique relies on the double role of LaBr3:Ce as source of (138)La and detector medium resulting in a relatively efficient counting statistics and unaltered ß energy detection. The experimental results are compared to advanced computational techniques and significant deviation is found below 20 keV with the computational spectrum showing a 5% excess of ß particle relative to the experimental spectrum at 10 keV.

Experimental study of the 4fn → 4fn and 4fn → 4fn-15d1 transitions of the lanthanide diiodides LnI2 (Ln=Nd, Sm, Eu, Dy, Tm, Yb).

The diffuse reflectance and photoluminescence (PL) spectra of NdI(2), SmI(2), EuI(2), DyI(2), TmI(2) and YbI(2) were measured between 225 and 12 500 nm in order to determine their 4f(n) â†’ 4f(n-1)5d(1) optical bandgaps. The results were compared with those obtained using an empirical model of the electronic structure of LnI(2). The results can be used to explain the lanthanide valency and crystalline structure changes of other lanthanide diiodides such as PrI(2).

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.

The thermally induced metal-semiconducting phase transition of samarium monosulfide (SmS) thin films.

High quality phase pure samarium monosulfide (SmS) thin films were prepared by electron beam evaporation using a samarium metal source in a H(2)S atmosphere. The optical properties (reflection, transmission, absorption) of the films in the semiconducting and metallic phase were analysed from the UV to the mid-IR and explained in terms of the electronic structure of SmS. In this paper it will be shown that metallic SmS thin films exhibit an apparently continuous thermally induced metallic to semiconducting phase transition when studied optically. Temperature dependent x-ray diffraction measurements, however, indicate that the metallic to semiconductor phase transition is in fact first order at a single grain level. The apparently continuous optical behaviour is therefore due to the polycrystalline nature of the films.

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).

Crystal structure and luminescence properties of LiYP4O12:Ce3+ phosphor.

LiYP(4)O(12) polyphosphate doped with Ce(3+) ions was prepared by the melt solution technique. The crystal structure, interatomic distances, and atom coordination numbers were determined using x-ray powder diffraction. A study of the spectral-kinetic luminescent properties was performed employing excitation with pulsed radiation from a synchrotron (UV-VUV range) and a laboratory x-ray source. The characteristics of Ce(3+) luminescence, namely the emission doublet maxima at 3.97 and 3.72 eV and the 4f-5d excitation maxima at 4.20, 5.11, 5.40, 5.65 and 6.55 eV, are discussed in terms of crystal field splitting in a low-symmetry site of the LiYP(4)O(12) host lattice. The location of the Ce(3+) energy levels with respect to the valence and conduction bands of the LiYP(4)O(12) host is estimated from the temperature dependence of the decay time measured for Ce(3+) 5d-4f luminescence.

Temperature dependent scintillation properties of pure LaCl(3).

The scintillation yield, scintillation decay, and x-ray excited emission of pure LaCl(3) was studied as a function of temperature between 80 and 600 K. Two broad band emissions centered around 325 nm and 400 nm were identified and correlated to emissions from two localized exciton states named STE(1) and STE(2), respectively. Different temperature dependences were observed for the short and long wavelength band intensity. From 80 to 150 K, the 400 nm band intensity increases at the expense of the 325 nm band intensity. Above 150 K almost all emission is in the 400 nm band. From 150 to 600 K, the intensity of this band decreases and its lifetime shortens. These results are analyzed and interpreted with a model that comprises the creation of STE(1) and STE(2) self-trapped excitons, thermally activated quenching of STE(1) and STE(2) emission, and thermally activated transfer of excitation energy from STE(1) to STE(2).

Luminescence properties of Ce(3+)-doped LiGdP(4)O(12) upon vacuum-ultraviolet and x-ray excitation.

Luminescent-kinetic studies for LiY(0.9)Ce(0.1)P(4)O(12), LiGd(0.9)Ce(0.1)P(4)O(12) and NaGd(0.9)Ce(0.1)P(4)O(12) phosphates which were prepared by the melt solution technique have been performed using synchrotron radiation excitation within 3-12.4 eV energy range and x-ray radiation at T = 10-300 K. The [Formula: see text] transfer at 10 K and bidirectional [Formula: see text] mechanisms of energy transfer at 300 K have been revealed based on the analysis of the excitation spectra and decay kinetic measurements of Ce(3+) luminescence. The participation of the Gd sublattice in the energy migration process to the Ce(3+) centers causes the appearance of a slow component in the decay kinetics of the x-ray-excited luminescence pulse. The luminescence efficiency of LiY(0.9)Ce(0.1)P(4)O(12), LiGd(0.9)Ce(0.1)P(4)O(12) and NaGd(0.9)Ce(0.1)P(4)O(12) upon x-ray excitation at room temperature is discussed.

Scintillation properties and anomalous Ce(3+) emission of Cs(2)NaREBr(6):Ce(3+) (RE = La,Y,Lu).

We report the optical and scintillation properties of the Ce(3+)-doped bromoelpasolites Cs(2)NaREBr(6) (RE = La,Y,Lu). The γ-ray scintillation light yield of these materials varies from 6000 to 17 000 photons per MeV absorbed γ-ray energy. At room temperature (RT), the γ-ray scintillation decay curves for all compounds show a fast component of 61 ns, whereas the intrinsic Ce(3+) decay time is 30 ns. The scintillation mechanism in elpasolites is addressed. In Cs(2)NaLuBr(6):Ce(3+) and Cs(2)NaYBr(6):Ce(3+), we observe for the first time the so-called Ce(3+) anomalous emission in bromide compounds. This emission previously observed for chloride compounds is an ultrafast Ce(3+) emission with a selective excitation mechanism. The decay time of the anomalous emission at 10 K in bromide compounds (∼7.80 ns) is faster than that in chloride compounds (∼9.90 ns). Two bands of the anomalous emission are resolved for the first time. The mechanism behind this emission is discussed.