Temperature dependence of excited-state relaxation processes of Pr in Pr-doped and Pr, Gd-doped CsCdBr3

The temperature dependence and mechanisms for relaxation of the ¹D₂ and ³P₁ states of Pr³⁺ in symmetrical Pr-Pr and Pr-Gd pairs in 0.12% Pr:CsCdBr₃ and 0.025% Pr:1.5% Gd:CsCdBr₃, respectively, are presented. Both single-ion and pair relaxation mechanisms are considered. The temperature dependences of the energy-transfer processes in Pr-Pr pairs are all well-explained in terms of resonance considerations for the donor and acceptor zero-phonon crystal-field transitions.     

Luminescence of Ce doped LaPO4 nanophosphors upon Ce 4f-5d and band-to-band excitation

Luminescence spectral-kinetic studies have been performed for pure and Ce-doped LaPO₄ micro- and nanosized phosphates using synchrotron radiation for the excitation within 5-20 eV energy range at T=8-300 K. Mechanisms for the excitation of Ce³⁺ 5d-4f emission as well as the quenching processes are discussed. The influence of surface defects has been considered to modify considerably the luminescent properties of nanosized phosphors upon the excitation in the energy range of Ce³⁺ 4f-5d transitions and LaPO₄ host absorption.     

Synthesis, structure and luminescence of LaSi3N5:Ce phosphor

In this work, new LaSi₃N₅:Ce³⁺ phosphors have been synthesized by solid-state reaction. Rietveld refinement of the crystal structure of La_1−xCe_xSi₃N₅ reveals that Ce atoms substituted for La atoms occupy 4a crystallographic positions. Broad emission and excitation bands observed were attributed to the transitions between the doublet ground state of the 4f¹ configuration and the crystal field components of the 5d¹ excited state. At 77 K, the centroid and crystal field splitting ε_cfs of the 5d levels of Ce³⁺ in LaSi₃N₅:Ce³⁺ compounds were valuated at 33.4×10³ and 11.3×10³ cm⁻¹, respectively. The zero-phonon line and the Stokes shift were measured to be 26.0×10³ and 5.0×10³ cm⁻¹, respectively.     

Charge transfer transitions in the excitation spectra of PrX3:Ce (X=Cl, Br) scintillators

The Cl⁻→Pr³⁺ charge transfer transition is identified to occur in the excitation spectrum of PrCl₃:Ce³⁺ at 211 nm (47,393 cm⁻¹). A model based on the dissociation of the charge transfer state is proposed to explain the presence of the ligand-to-Pr³⁺ charge transfer transition band in the excitation spectrum of PrX₃:Ce³⁺ (X=Cl, Br) when the Ce³⁺ emission is monitored.     

Spectral-kinetic characteristics of Pr luminescence in LiLuF4 host upon excitation in the UV-VUV range

Spectral-kinetic study of Pr³⁺ luminescence has been performed for LiLuF₄:Pr(0.1 mol%) single crystal upon the excitation within 5-12 eV range at T=8 K. The fine-structure of Pr³⁺ 4f ²→4f 5d excitation spectra is shown for LiLuF₄:Pr(0.1 mol%) to be affected by the efficient absorption transitions of Pr³⁺ ions into 4f 5d involving 4f ¹ core in the ground state. Favourable conditions have been revealed in LiLuF₄:Pr(0.1 mol%) for the transformation of UV-VUV excitation quanta into the visible range. Lightly doped LiLuF₄:Pr crystals are considered as the promising luminescent materials possessing the efficient Pr³⁺³P₀ visible emission upon UV-VUV excitation. The mechanism of energy transfer between Lu³⁺ host ion and Pr³⁺ impurity is discussed.     

Photoluminescence investigations on the nanoscale phase transition in Pb(Mg1/3Nb2/3)O3

The temperature dependence of the photoluminescence spectra of the relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃ has been reported. The temperature behaviours of the 1.57, 1.67 and 1.73 eV bands indicate a phase transition at 110 K. This is attributed to a structural phase transition in the charged nanoshell. Analysis of the temperature dependence of 1.67 eV band intensity with a thermal quenching model indicated the existence of a phonon mode at 1153 cm⁻¹. This mode is identified in the Raman spectra measurement. The intensity of the 1.73 eV band showing an anomalous behaviour at 210 K is attributed to a transition from a crystalline phase to an amorphous phase in the charged nanoshell.     

Unusual luminescence of octahedrally coordinated divalent europium ion in Cs2MP2O7 (M=Ca, Sr)

The excitation and emission spectra of octahedrally coordinated europium ion (Eu²⁺) ions in Cs₂M²⁺P₂O₇ (M²⁺=Ca, Sr) are reported and discussed. The remarkable features of the Eu²⁺ luminescence in these phosphate materials include (a) very large Stokes shift of emission (∼1 eV), (b) high luminescence quenching temperature, and (c) unusually low energy of the emitted photons for Eu²⁺ luminescence in phosphate-based materials. The broad emission bands of Eu²⁺ in Cs₂CaP₂O₇ and Cs₂SrP₂O₇ peak at 607 and 563 nm, respectively. The Stokes shift, crystal field splitting, centroid shift and the red shift of the Eu²⁺ 4f⁶5d¹ electronic configuration have been estimated from the relevant optical data. The radiative lifetime of the Eu²⁺ emission in Cs₂M²⁺P₂O₇ is ∼1.2 μs. The nature of the Eu²⁺ emission in Cs₂M²⁺P₂O₇ is discussed and arguments are presented to associate the luminescence with an extreme case of normal 4f⁶5d¹→4f⁷[⁸S_7/2] emission.     

Cr-related centers in Gd3Ga5O12 polycrystals

The luminescence excitation spectra, emission spectra under photo- and X-ray excitation, luminescence decay kinetics and thermostimulated luminescence (TSL) of Gd₃Ga₅O₁₂ garnet (GGG) polycrystalline samples have been investigated. It was established that the spectrum of Cr³⁺ ion emission were present in all TSL peaks. The activation energies of traps that are responsible for appearance of TSL in the region 295-600 K were estimated. It is shown that delocalization of electrons from the Cr³⁺e traps leads to the appearance of thermoluminescence (TL) glow peak at 390 K. The nature of other TSL peaks is discussed. The influence of visible light on the TSL intensity of the preliminary X-ray-irradiated samples is shown.     

4-benzyl pyridinium dihydrogenmonophosphate C6H5CH2C5H4NHH2PO4 : Single-crystal structure and its conductivity in polycrystalline form

The salt 4-benzyl pyridinium dihydrogenmonophosphate is monoclinic P2₁/c with the following unit cell dimensions: ; ; ; and β=97.328(11). Also, , D_x=1.403, , F(000)=560; ; and R=0.0495 and R_w=0.0964 for 3733 independent reflections. The structure consists of infinite parallel two-dimensional planes built of H₂PO₄⁻ anions and C₆H₅CH₂C₅H₄NH⁺ cations mutually connected by strong O-H ?O and N-H ?O hydrogen bonding. There are no contacts other than the normal Van der Waals interactions between the layers. The conductivity relaxation parameters associated with some H⁺ conduction have been determined from an analysis of the spectrum measured in a wide temperature range.     

Luminescence and Tb-Ce-Eu ion energy transfer in single-crystalline films of Tb3Al5O12:Ce,Eu garnet

The paper is devoted to investigation of the processes of excitation energy transfer between the host cations (Tb³⁺ ions) and the activators (Ce³⁺ and Eu³⁺ ions) in single-crystalline films of Tb₃Al₅O₁₂:Ce,Eu (TbAG:Ce,Eu) garnet which is considered as a promising luminescent material for the conversion of LED's radiation. The cascade process of excitation energy transfer is shown to be realized in TbAG:Ce,Eu: (i) from Tb³⁺ ions to Ce³⁺ and Eu³⁺ ions; (ii) from Ce³⁺ ions to Eu³⁺ ions by means of dipole-dipole interaction and through Tb³⁺ ion sublattice.     

Splitting of X-ray diffraction peak in (Ge:SiO2)/SiO2 multilayers

(Ge:SiO₂)/SiO₂ multilayers were fabricated for exploring the influence of the stress on the structure of Ge nanocrystals. When annealed at 800 °C, the multilayers show a clear splitting (fine structure) of the Ge (220) X-ray diffraction peak and have a preferred orientation. Similar effects cannot take place in the multilayers annealed at higher or lower temperature. Analyses of Raman scattering, X-ray diffraction spectroscopy, and transmission electron microscope observations suggest that the observed phenomena arise from compressive stress exerted on Ge nanocrystals, which is induced by the confinement of both the SiO₂ matrix in the cosputtered layer and neighboring SiO₂ layers. The stress may cause an orthorhombic distortion of the diamond structure of bulk Ge. This will lead to the disappearance of the (111) and (311) diffraction peaks and the splitting of the (220) peak. This kind of (Ge:SiO₂)/SiO₂ multilayers enables us to control the sizes of the Ge crystallites and enhance the stress, and is thus promising in forming new nanocrystal structures.     

Preparation and characterization of LiAEAlF6:Eu (AE=Mg, Ca, Sr or Ba) phosphors

Wet chemical synthesis of LiAEAlF₆:Eu (AE=Mg, Ca, Sr or Ba) phosphors is described. Formation of single-phase compounds LiCaAlF₆ and LiSrAlF₆ was confirmed by XRD. LiCaAlF₆:Eu and LiSrAlF₆:Eu phosphors exhibited broadband emission corresponding to intraconfigurational transition 4f⁶5d¹→4f⁷(⁸S_7/2). LiMgAlF₆:Eu exhibits a narrow line emission corresponding to ⁶P_J→⁸S_7/2 transition of 4f⁷ configuration besides the band emission. LiBaAlF₆:Eu, on the other hand, was found to yield predominantly line emission.     

Luminescence characteristics of Pb centres in undoped and Ce-doped Lu3Al5O12 single-crystalline films and Pb→Ce energy transfer processes

At 4.2-350 K, the steady-state and time-resolved emission and excitation spectra and luminescence decay kinetics were studied under excitation in the 2.5-15 eV energy range for the undoped and Ce³⁺-doped Lu₃Al₅O₁₂ (LuAG) single-crystalline films grown by liquid phase epitaxy method from the PbO-based flux. The spectral bands arising from the single Pb²⁺-based centres were identified. The processes of energy transfer from the host lattice to Pb²⁺ and Ce³⁺ ions and from Pb²⁺ to Ce³⁺ ions were investigated. Competition between Pb²⁺ and Ce³⁺ ions in the processes of energy transfer from the LuAG crystal lattice was evidenced especially in the exciton absorption region. Due to overlap of the 3.61 eV emission band of Pb²⁺ centres with the 3.6 eV absorption band of Ce³⁺ centres, an effective nonradiative energy transfer from Pb²⁺ ions to Ce³⁺ ions takes place, resulting in the appearance of slower component in the luminescence decay kinetics of Ce³⁺ centres and decrease of the Ce³⁺-related luminescence intensity.     

Ionic conductivity of the perovskites NaMgF3, KMgF3, KMgK3 and KZnF3 at high temperatures

We have carried out a study of the ionic conductivity of NaMgF₃, KMgF₃ and KZnF₃ up to temperatures close to the melting point. Our results, in contrast to previous reports in the literature, show no abnormal ionic conductivity at high temperatures. Care in interpretation of results is required because of surface electronic conduction.     

Reduction effect on the optical properties of Sm doped in SrB4O7 and SrB6O10 crystals

Reduction effects on the optical properties of Sm²⁺ ions doped in SrB₄O₇ and SrB₆O₁₀ crystals were studied by measurements of luminescence intensity decay as a function of time, X-ray irradiation and laser power effects on the photoluminescence. The fluorescence intensity of Sm²⁺ doped in SrB₄O₇ and SrB₆O₁₀ crystals decreased upon excitation at 488 nm of Ar⁺ laser and this so-called photo-bleaching effect was highly dependent on the sample preparation conditions. The fluorescence intensity of Sm²⁺ doped in SrB₄O₇ decreased about 13%, while it decreased about 55% in the SrB₆O₁₀ crystal irradiated with X-ray for 10 h. Differences of photo-beaching effect and other optical properties of Sm²⁺ doped in SrB₄O₇ and SrB₆O₁₀ are discussed.     

Green and red up-conversion emissions of Er-Yb-codoped Al2O3 powders prepared by the nonaqueous sol-gel method

The 1 mol% Er³⁺- and 0-20 mol% Yb³⁺-codoped Al₂O₃ powders have been prepared by the nonaqueous sol-gel process using aluminum isopropoxide as precursor, acetylacetone as chelating agent, nitric acid as catalyzer, and hydrated erbium and ytterbium nitrate as dopant under isopropanol environment. The two crystalline types of doped Al₂O₃, γ and θ, and a stoichiometric compound, (Yb,Er)₃Al₅O₁₂, were obtained for all the Er³⁺-Yb³⁺-codoped Al₂O₃ powders at the sintering temperature of 1000 °C. The maximal intensity of both the green and red up-conversion emissions centered at about 523, 545, and 660 nm was observed for the 1 mol% Er³⁺- and 10 mol% Yb³⁺-codoped Al₂O₃ powders. The intensity ratio of the red to green up-conversion emission (I_red/I_green) increased with increasing the Yb³⁺ doping concentration for the Er³⁺-Yb³⁺-codoped Al₂O₃ powders. Furthermore, the intensity ratio of the green up-conversion emission at about 523 to 545 nm (I₅₂₃/I₅₄₅) was proportional to the Yb³⁺ doping concentration and pump electric current, which was associated with the elevated temperature of powders.     

Photoluminescence in amorphous (PbLa)TiO3 thin films deposited on different substrates

Pb_1−XLa_XTiO₃ thin films, (X=0.0; 13 and 0.27 mol%) were prepared by the polymeric precursor method. Thin films were deposited on Pt/Ti/SiO₂/Si (1 1 1), Si (1 0 0) and glass substrates by spin coating, and annealed in the 200-300°C range in an O₂ atmosphere. X-ray diffraction, scanning electron microscopy and atomic force microscopy were used for the microstructural characterization of the thin films. Photoluminescence (PL) at room temperature has been observed in thin films of (PbLa)TiO₃. The films deposited on Pt/Ti/SiO₂/Si substrates present PL intensity greater than those deposited on glass and silicon substrates. The intensity of PL in these thin films was found to be dependent on the thermal treatment and lanthanum molar concentration.     

Spectroscopic features of Pr, Nd, Sm and Er ions in Li2O-MO (Nb2O5, MoO3 and WO3)-B2O3 glass systems

Li₂O-MO (Nb₂O₅, MoO₃ and WO₃)-B₂O₃ glasses doped with four rare earth ions, viz., Pr³⁺, Nd³⁺, Sm³⁺ and Er³⁺ (of 1.0 mol% each) were prepared. The glasses were characterized by X-ray diffraction, differential scanning calorimetry, ESR, optical absorption and photoluminescence spectra. From the measured intensities of various absorption bands of these glasses, the Judd-Ofelt parameters Ω₂, Ω₄ and Ω₆ have been evaluated. The Judd-Ofelt theory could successfully be applied to characterize the absorption and luminescence spectra of these glasses. From this theory, various radiative properties like transition probability A, branching ratio β_r, the radiative life time τ_r and the emission cross-section σ^E for various emission levels of these glasses have been determined and reported. An attempt has also been made to throw some light on the relationship between the structural modifications and luminescence efficiencies of all the three glasses. The analysis of the data indicated high non-radiative losses in Nb₂O₅ mixed glasses.     

New measurements of the emission spectra of Sm2+ in KMgF3 and NaMgF3 crystals

The fluorescence of divalent samarium in KMgF₃ and NaMgF₃ crystals is investigated. The emission is observed to originate from transitions between the ⁵D_J, and ⁷F_J multiplets of the 4?⁶ configuration. More precisely, the lowest ⁵D_J level, ⁵D₀, appears to be the most efficient emitting level in the temperature range 4–300K. Contrary to what has been reported elsewhere, the Sm²⁺ fluorescence in both crystals does not exhibit any broad band emission even at room temperature. The great number of lines in the ⁵D₀→⁷F_J patterns gives evidence of the multiple-center origin of the fluorescence.