(INVITED) Energy transfer processes in Sr3Tb(PO4)3 eulytite-type materials singly doped with Nd3+ and Sm3+

In this study the optical spectroscopy, the excited state dynamics and in particular the energy transfer Tb3+→Ln3+ (Ln = Nd or Sm), have been investigated in detail in eulytite double phosphate hosts of the type Sr3Tb(PO4)3 doped with 1 mol% Ln3+. It has been found that for Ln=Nd and Sm, the energy transfer efficiency (ηT) is 0.76 and 0.73, respectively, thanks to the assistance of fast migration in the Tb3+ 5D4 level. The pathway responsible for the transfer of excitation has been unambiguously identified in the case of Sr3Tb0.99Nd0.01(PO4)3, whilst the situation is more complex for Sr3Tb0.99Sm0.01(PO4)3, due to high density of the final Sm3+ states that could be involved. The Tb3+→Nd3+ energy transfer has been tentatively attributed to the exchange interaction on the basis of the short transfer distance and multipolar selection rules

Phase transition, radio- and photoluminescence of K3Lu(PO4)2 doped with Pr3+ ions

Luminescent characteristics of K3Lu(PO4)2:Pr3+ (1 and 5 mol.%) microcrystalline powders, a promising optical material for scintillation applications, were investigated using various experimental techniques. The material shows emission features connected with both high intensity interconfigurational 4f15d→4f2 transitions (broad UV emission bands) and intraconfigurational 4f2→4f2 transitions (weak emission lines in the visible range). The output of X-ray excited 4f15d→4f2 emission of Pr3+ increases with a temperature rise from 90 K to room tem- perature and higher depending on the Pr3+ ions concentration. The high 5% concentration of Pr3+ ions is found to be favourable for the stabilization of a monoclinic phase (P21/m space group) over a trigonal one (P3 space group) while emission properties of the material reveal that a phase transition occurs at higher temperatures. Decay kinetics of Pr3+ 4f15d→4f2 emission are recorded upon excitation with high repetition rate X-ray syn- chrotron excitation and pulse cathode ray excitation. Issues related to a non-exponential decay of luminescence and presence of slow decay components are discussed in terms of energy transfer dynamics. The presence of defects was revealed with thermoluminescence measurements and these are suggested to be the mainly responsible for delayed recombination of charge carriers on the Pr3+ 4f15d states. Some peculiarities of host-to- impurity energy transfer are discusse

Understanding the Efficiency of Mn4+ Phosphors: Study of the Spinel Mg2Ti1-xMnxO4

We present a spectroscopic study of Mn-doped Mg2TiO4 as a function of pressure and temperature to check its viability as a red-emitting phosphor. The synthesis following a solid-state reaction route yields not only the formation of Mn4+ but also small traces of Mn3+. Although we show that Mn4+ photoluminescence is not appreciably affected by the presence of Mn3+, its local structure at the substituted Ti4+ host site causes a reduction of the Mn4+ pumping efficiency yielding a drastic quantum-yield reduction at room temperature. By combining Raman and time-resolved emission and excitation spectroscopies, we propose a model for explaining the puzzling nonradiative and inefficient pumping processes attained in this material. In addition, we unveil a structural phase transition above 14 GPa that worsens their photoluminescence capabilities. The decrease of emission intensity and lifetime with increasing temperature following different thermally activated de-excitation pathways is mostly related to relatively small activation energies and the electric−dipole transition mechanism associated with coupling to odd-parity vibrational modes. A thorough model based on the configurational energy level diagram to the A1g normal mode fairly accounts for the observed excitation and emissionthe quantum yieldof this material

The effect of cation substitution on the local coordination of protons in Ba2In1.85M0.15O6H2 (M = In, Ga, Sc and Y)

We report on an investigation of the local structure and vibrational dynamics in the brownmillerite-based proton conductors Ba2In1.85M0.15O6H2 with M = In, Ga, Sc and Y. The aim is to determine the effect of the cation (M) substitution on the local coordination environment of the protons. The techniques used are infrared spectroscopy and inelastic neutron scattering. The materials are characterized by two main types of proton sites, denoted as H (1) and H(2), which are featured by different local structures. We establish that the relative population of these two proton sites varies as a function of M. Specifically, it is found that, with respect to Ba2In2O6H2, the relative population of H(1) protons increases upon the substitution of In with any of the three different cations. The strongest effect is observed for M = Ga and Sc, whereas the effect observed for M = Y is minor. This new insight motivates efforts to unravel the mobility of the two types of protons, since then cation modification would offer a rational route for improving the proton conductivity of these types of materials

Breeding for black rot resistance in grapevine: advanced approaches for germplasm screening

Crop improvement by means of traditional or molecular breeding is a key strategy to accomplish the European Green Deal target of reducing pesticides by 50% by 2030. Regarding viticulture, this is exacerbated by the massive use of chemicals to control pathogen infections. Black rot is an emergent disease caused by the ascomycete Phyllosticta ampelicida, and its destructiveness is alarming vine growers. Implementing and improving effective phenotyping strategies are fundamental preliminary steps to breed disease resistant varieties and this work suggests good practices adopted for this purpose. Primarily, the pedigree of black rot resistance donors was reconstructed based on the collection of phenotypic historical data, highlighting unexplored sources of black rot resistance. Strains used for artificial infections were isolated, genetically characterized and mixed to avoid race-specific resistance selection. A new inoculation protocol based on the use of leaf mature lesions was developed. Ex vivo inoculation on detached leaves was effective for the evaluation of conidia germination and hyphal growth, but not for disease progression. Finally, the pedigree was used for the identification of 23 genotypes to be tested. Two breeding selections (NY39 and NY24) resulted symptomless in all assessments and a third one (F25P52) also showed very high resistance, although with a greater variability. Other two genotypes (F12P19 and ‘Charvir’) fell within the medium resistance category, making them good candidates in a regime of well-timed preventive treatments. In conclusion, this work was effective to a comprehensive parental line characterization and preparatory towards grapevine breeding programs for black rot resistanc

Efficient optical pumping of Zeeman spin levels in Nd3+:YVO4

We demonstrate that Zeeman ground-state spin levels in Nd3+:YVO4 provides the possibility to create an efficient lambda-system for optical pumping experiments. The branching ratio R in the lambda-system is measured experimentally via absorption spectroscopy and is compared to a theoretical model. We show that R can be tuned by changing the orientation of the magnetic field. These results are applied to optical pumping experiments, where significant improvement is obtained compared to previous experiments in this system. The tunability of the branching ratio in combination with its good coherence properties and the high oscillator strength makes Nd3+:YVO4 an interesting candidate for various quantum information protocols.Comment: 8 pages, 6 figure

Photoluminescence Properties and Fabrication of Red-Emitting LEDs based on Ca9Eu(VO4)(7) Phosphor

We study the photoluminescence properties of the red-emitting phosphor Ca9Eu(VO4)(7) and establish a strong red emission centered at 613 nm under excitation at 395 nm (near ultra violet light, near-UV light) due to the intra-configurational D-5(0) -> F-7(2) transition within the 4f(6) configuration of the Eu3+ ions. The intensity of the emitted light decreases with increasing temperature and at T = 470 K about 50% of the intensity of the emitted light at room temperature is lost. Five different red-LED prototypes were constructed by applying a mixture of Ca9Eu(VO4)(7) phosphor and silicone gel on the headers of near-UV LED chips. The prototypes showed a color output from violet for the lowest phosphor concentration (133 g phosphor /l silicone gel), reaching an almost pure red-light output for the highest phosphor concentration (670 g phosphor /l silicone gel). The luminous efficiency of optical radiation (LER) was found to decrease slightly with increasing applied current. For the highest phosphor concentration, the LER decreases from 238 lmW(-1) for 1 mA current supply to 235 lmW(-1) for 18 mA current supply. The external quantum efficiency decreased from 7.33% for the lowest phosphor containing LED prototype to 4.13% for the highest one. (C) The Author(s) 2019. Published by ECS

Eu(iii) and Tb(iii) complexes of 6-fold coordinating ligands showing high affinity for the hydrogen carbonate ion: A spectroscopic and thermodynamic study

In the present contribution, four classes of Ln(iii) complexes (Ln = Eu and Tb) have been synthesized and characterized in aqueous solution. They differ by charge, Ln(bpcd)+ [bpcd2- = N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane N,N'-diacetate] and Ln(bQcd)+ (bQcd2- = N,N'-bis(2-quinolinmethyl)-trans-1,2-diaminocyclohexane N,N'-diacetate) being positively charged and Ln(PyC3A) (PyC3A3- = N-picolyl-N,N',N'-trans-l,2-cyclohexylenediaminetriacetate) and Ln(QC3A) (QC3A3- = N-quinolyl-N,N',N'-trans-l,2-cyclohexylenediaminetriacetate) being neutral. Combined DFT, spectrophotometric and potentiometric studies reveal the presence, under physiological conditions (pH 7.4), of a couple of equally and highly stable isomers differing by the stereochemistry of the ligands (trans-N,N and trans-O,O for bpcd2- and bQcd2-; trans-O,O and trans-N,O for PyC3A3- and QC3A3-). Their high log\u2009\u3b2 values (9.97 < log\u2009\u3b2 < 15.68), the presence of an efficient antenna effect and the strong increase of the Ln(iii) luminescence intensity as a function of the hydrogen carbonate concentration in physiological solution, render these complexes as very promising optical probes for a selective detection of HCO3-in cellulo or in extracellular fluid. This particularly applies to the cationic Eu(bpcd)+, Tb(bpcd)+ and Eu(bQcd)+ complexes, which are capable of guesting up to two hydrogen carbonate anions in the inner coordination sphere of the metal ion, so that they show an unprecedented affinity towards HCO3- (log\u2009K for the formation of the adduct in the 4.6-5.9 range)

Morphology and luminescence of nanocrystalline Nb₂O₅ doped with Eu³⁺

The synthesis of nanocrystalline Nb2O5:Eu3+ has been achieved by using a Pechini procedure. The obtained materials are single-phase niobia with the orthorhombic structure, average crystallite size around 25nm and average lattice strain of about 0.002. TEM images show that the particles are rectangular and reasonably isolated. The luminescence of the Eu3+ ions in the niobia lattice is efficient and affected by a strong inhomogeneous broadening, due to an important disorder around the lanthanide ions

A chiral lactate reporter based on total and circularly polarized Tb(iii) luminescence

The coordination features and signaling of a l-lactate ion by a [Tb(bpcd)]+(bpcd = N,N′-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane-N,N′-diacetate) complex have been investigated by means of a combination of techniques, including total luminescence, calorimetry and circularly polarized luminescence. The l-lactate/[Tb(bpcd)]+association constant, determined by both luminescence titration and isothermal titration calorimetry, indicates a weak interaction (log K = 1.3-1.45) between the analyte and both enantiomers of the complex. The theoretical DFT calculations suggest that the most likely coordination of l-lactate to the possible stereoisomers of the [Tb(S,S-bpcd)]+complex (trans-O,O or trans-Npy,Npy) is one involving a hydroxyl group. The results of [Tb(rac-bpcd)]+as a chiroptical luminescent probe of l-lactate underline the peculiar role of the chiral 1,2-diaminocyclohexane (DACH) backbone. Indeed, the target anion is capable of inducing CPL activity in the racemic mixture of Tb complexes containing DACH-based ligands. The same is not observed for the achiral analogue [Tb(bped)]+(bped = N,N′-bis(2-pyridylmethyl)ethylenediamine-N,N′-diacetate) complex, likely because of the flexibility of the ethylenic group which allows an interconversion between different isomers which produces a null net CPL activity. Thanks to the differential quantum yield of the two diastereomeric species (R,R)-l and (S,S)-l, one can use the racemic complex to reveal l-lactate by measuring the induced CPL spectrum. Interestingly, this has been demonstrated in a commercial complex solution for medical use, containing several electrolytes, namely Ringer's lactate