Ionization of helium-like ions with excitation of nl states by high-energy photon scattering

The kinetic and spectral characteristics of the complex dielectric constant of a Ce: YAG crystal under laser irradiation in 250–275 nm spectral range are investigated. The lifetimes of free charge carriers and charge carriers, localized at the lattice defects (color centers), are estimated. It was established that photoconductivity signal of the sample is essentially caused by one-photon ionization processes from the ² F _5/2 ground state of Ce³⁺ ions.     

Photoconductivity and photodielectric effect in LiY1 − x Lu x F4 crystals doped with Ce3+ and Yb3+ ions

Time and spectral dependences of the dielectric permittivity of the LiY_{1 ? x} Lu _x F₄ (x = 0, 0.5, and 1) crystals doped with Ce³⁺ and co-doped with Yb³⁺ ions under UV laser excitation were studied by the 8-mm microwave resonant technique at room temperature. The obtained photoconductivity spectrum in 240–310 nm spectral range was interpreted as a stepwise photoionization spectrum of the Ce³⁺ ions due to sequential 4f–5d and 5d–6s transitions. Average lifetimes of free and defect trapped (color centers) charge carriers were estimated.     

Two-step photoconductivity in LiY<Subscript> <Emphasis Type="Italic">x</Emphasis> </Subscript>Lu<Subscript>1 – <Emphasis Type="Italic">x</Emphasis> </Subscript>F<Subscript>4</Subscript>:Ce,Yb crystals

Photoconductivity of LiY_xLu_1–xF₄:Ce,Yb (x = 0–1) crystals is measured under one- and two-step excitation. It is established that the photoconductivity is due to intra-center transitions from excited states of Ce³⁺ ions. The position of the ground 4 f-state of Ce³⁺ ion relative to the bottom of the conduction band is determined. The choice of pumping conditions to obtain the lasing on the 5d–4f transitions of trivalent cerium in these active media is substantiated.     

Near infrared fluorescence and energy transfer in Ce/Nd Co-doped CaxSr1−xS

Novel near infrared (NIR) phosphors Ca_xSr_1−xS:Ce³⁺,Nd³⁺ were synthesized by a solid state reaction. The NIR emission was realized through an efficient absorption by the allowed 4f-5d transition of Ce³⁺ and efficient energy transfer to Nd³⁺ via well-matched energy levels. Ce³⁺ and Nd³⁺ content in CaS/SrS was optimized. It was found that CaS:Ce³⁺,Nd³⁺ gave much stronger NIR emission than that of SrS:Ce³⁺,Nd³⁺. Further studies on Ca_xSr_1−xS:Ce³⁺,Nd³⁺ indicated that both visible emission of Ce³⁺ and NIR emission of Nd³⁺ were observably affected by Ca/Sr ratio. The energy transfer efficiency, which can be estimated from fluorescence lifetime of Ce³⁺, increased from 52% to 74% for the Ca_xSr_1−xS:Ce³⁺,Nd³⁺ (x=0 to 1) series, accompanied with a shift of maximal emission wavelength of Ce³⁺ from 482 to 505 nm. The results showed that overlap between emission spectrum of Ce³⁺ and excitation spectrum of Nd³⁺ plays an important role in the energy transfer efficiency, and Ce³⁺ emitting in green or blue-greenish region sensitized the Nd³⁺ NIR fluorescence emission more efficiently than that in blue region.     

Self-compensation characteristics of Eu ions in BaTiO3

In order to clarify whether the mixed valence of Eu²⁺/Eu³⁺ exists in a self-compensation mode in Eu-doped BaTiO₃, the site occupation and valence state of Eu ions in barium titanate were investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), electron spin resonance (ESR), Raman spectroscopy (RS), and dielectric measurements. The results indicate that Eu ions may enter both Ba- and Ti-sites as Eu³⁺, forming a self-compensation mode with the amphoteric behavior. Self-compensation characteristics of Eu ions in BaTiO₃ are reflected by an expansion in unit cell volume, evolution of the 830 cm^− 1 Raman band, strong diffusion of the dielectric peak, disappearance of the Eu²⁺ ESR broad signal, and a g = 2.004 signal independent of temperature.     

Improving the dielectric constant of Al2O3 by cerium substitution for high-k MIM applications

Process compatible high-k dielectric thin films are one of the key solutions to develop high performance metal–insulator–metal (MIM) structures for future microelectronic devices. Engineered cerium–aluminate (Ce_xAl_2–xO₃) thin films were deposited on titanium nitride metal electrodes by electron-beam co-evaporation of ceria and alumina in a molecular beam deposition chamber. X-ray photoelectron spectroscopy clearly reveals that Ce cations can be stabilized in the 3+ valence state in Ce_xAl_2–xO₃ up to x = 0.7 by accommodation in the alumina host matrix. Higher Ce content was observed to result in cerium dioxide segregation in cerium aluminate matrix, probably due to the chemical tendency of Ce cations to exist rather in the 4+ than in the 3+ state. Electrical characterization of the X-ray amorphous Ce_0.7Al_1.3O₃ films reveals a dielectric constant value of about 11 and leakage current lower than 10^?4 A/cm². No parasitic low-k interface formation between the high-k Ce_0.7Al_1.3O₃ film and the TiN metal electrode is detected.     

Highly efficient cooperative energy transfer from Ho3+ and Tm3+ ions to Ce3+ ions in crystals

A phenomenon of highly efficient cooperative energy transfer from Ho³⁺ and Tm³⁺ ions to two-particle (2Ce³⁺) cooperative acceptors in crystals of solid solutions of La_1?x Ce _x F₃ is revealed. The rates of cooperative energy transfer in Ho³⁺→2Ce³⁺, Tm³⁺→2Ce³⁺, and Tb³⁺→ 2Yb³⁺ systems are measured, as well as their dependence on the magnitude of the matrix elements of donor transition.     

Energy transfer from Ce3+toNd3+ in pentaphosphate crystals

An excitation band at 300 nm corresponding to Ce³⁺absorption is observed in pentaphosphate crystals containing Ce³⁺ and Nd³⁺ when the Nd³⁺ luminescence is monitored. The decay of excitation of Ce³⁺ in crystals of pure cerium pentaphosphate, CeP₅O₁₄, follows single exponential kinetics with a 22 ± 2 nsec lifetime. In Ce_0.5Nd_0.5P₅O₁₄ crystals, the Ce³⁺ lifetime is shortened to 3.8 ± 0.4 nsec as a result of efficient nonradiative energy transfer to the Nd³⁺ ions.     

A novel high-k ‘Y5V’ barium titanate ceramics co-doped with lanthanum and cerium

Structural, dielectric, and ferroelectric properties of a novel high-k ‘Y5V’ (Ba_1−xLa_x)(Ti_1−x/4−yCe_y)O₃ ceramics (where x=0.03 and y=0.05, denoted by BL3TC5) with the highest ‘Y5V’ dielectric response (ε′>10 000) among rare-earth-doped BaTiO₃ ceramics to date are investigated in detail using SEM, TEM, XRD, DSC, EPR, Raman spectroscopy (RS), temperature and frequency, electric field dependences of dielectric permittivity (ε′), and temperature and electric field dependences of ferroelectric hysteresis loops. The BL3TC5 diffusion of ferroelectric phase transition occurs around dielectric peak temperatures (T_m) near a room temperature characteristic of dielectric thermal relaxation. Powder XRD data and defect complex model were given. “Relaxor” behavior associated with an order/disorder model and formation of a solid solution were discussed. The EPR results provided the evidence of Ti vacancies as compensating for lattice defects. High-k relaxor nature of BL3TC5 is characterized by an average cubic structure with long-range lattice disordering and local polar ordering; a slow change of the ε′ (T) and P_r(T) curves around T_m; no phase transition observed by DSC; and a broad, red-shifted A₁ (TO₂) Raman phonon mode at 251 cm⁻¹ accompanying the disappearance of the “silent” mode at 305 cm⁻¹ and a clear anti-resonance effect at 126 cm⁻¹ at room temperature.     

Crystal structure and luminescence properties of Lu3+ and Mg2+ incorporated silicate garnet [Ca3−(x+0.06)LuxCe0.06](Sc2−yMgy)Si3O12

The yellow-emitting phosphor [Ca_3?(x+0.06)Lu_xCe_0.06](Sc_2?yMg_y)Si₃O₁₂ obtained from Lu³⁺ and Mg²⁺ co-modified green-emitting silicate garnet Ca₃Sc₂Si₃O₁₂:Ce³⁺ (CSS:Ce³⁺) exhibits promising applications for white LEDs. In this paper, we discuss the effect of charge balance on the garnet structure formation. The changes of bond length and covalence caused by the replacement of Lu³⁺ and Mg²⁺ for Ca²⁺ and Sc³⁺ are analyzed. The shift of the Ce³⁺ emission and excitation can be attributed to the combined results from crystal field splitting effect and centroid shift of Ce³⁺ 5d levels. Thermal stability is analyzed according to configurational coordinate diagram.     

Enhanced luminescent properties of Y3Al5O12:Tb,Ce phosphor prepared by spray pyrolysis

Yttrium aluminum garnet (YAG) particles doped with Tb³⁺ or double doped with Tb³⁺ and Ce³⁺ were prepared by spray pyrolysis and characterized by photo- and cathode-luminescence. It was tried to incorporate a broad band of Ce³⁺ activator into the line peaks of Tb³⁺ in YAG host without the reduction of emission intensity. Ce-codoped YAG:Tb particles showed a broad band emission due to the d-f transition of Ce³⁺ and a reduction in the intensity of emission peaks due to ⁵D₃-⁷F_j (j=3, 4, 5, 6) transition of Tb³⁺ when they were excited by the ultraviolet light of 270 nm. These results supported that an effective energy transfer occurs from Tb³⁺ to Ce³⁺ in YAG host. Codoping Ce³⁺ ions greatly intensified the excitation peak at 270 nm for the emission at 540 nm of Tb³⁺, which means that more lattice defects, involving in the energy absorption and transfer to Tb³⁺, are formed by the Ce³⁺ codoping. The finding gives a promising approach for enhancing the luminescence efficiency.     

Energy transfer mechanisms in the KCaLa1−x−yCexTby(PO4)2 phases

The various mechanisms involved in the green emission of KCaLa_1?x?yCe_xTb_y(PO₄)₂ under UV excitation are analyzed for a weak terbium concentration (y = 0.05). Ce³⁺ → Tb³⁺ transfer can be described by the Dexter model, but only for a weak cerium concentration. For higher cerium contents the cerium lifetime temperature dependence can be fitted by using a model involving energy migration between Ce³⁺ ions before Ce³⁺ → Tb³⁺ transfer. The investigation of the variation of the terbium emission vs temperature involves the presence of energy-trapping defects in the material.     

Luminescence properties of LiPrxCe1−xP4O12

LiPr_1−xCe_xP₄O₁₂ (x=0, 0.002, 0.02; 0.1) powder samples were prepared using the melt solution technique. Luminescent parameters of LiPr_1−xCe_xP₄O₁₂ phosphors have been investigated under ultraviolet-vacuum ultraviolet (3-12 eV) synchrotron radiation and X-rays excitation at room and near liquid He temperatures. Excitation luminescence spectra of Ce³⁺ emission, luminescent spectra and decay curves from the lower excited state levels of the 4f¹5d¹ and 5d¹ electronic configuration of the Pr³⁺ and Ce³⁺, respectively, clearly indicate energy transfer from Pr³⁺ to Ce³⁺. Energy migration proceeds via the Pr-sublattice followed by nonradiation transfer from Pr³⁺ to Ce³⁺ ions.     

Dipolar studies in CaF2 with Ce3+

Dielectric relaxation in CaF₂ doped with various amounts of Ce³⁺ (0·01 to 1·0 mol%) was measured. The value of the activation energy for orientation of the dipoles {Ce³⁺-F^? interstitial} was determined to be H = (0·46 ± 0·01) eV. The frequency factor was found to have the value τ_o = (5 ± 1) × 10^?15 sec, giving for the vibrational frequency of the interstitial the value ν_o = (5 ± 1) × 10¹³ sec^?1.The number of dipoles contributing to the dielectric loss peak was determined to be between 10¹⁷ and 8 × 10¹⁷ cm^?3 for the different doping amounts of Ce³⁺. Optical absorption measurements showed the existence of large aggregate bands. We could verify that there exists a second-order reaction of aggregation, which is responsible for the non-linearity found between optical absorption at 305 nm and the nominal concentration of Ce³⁺ in the samples. On the other hand, if we assume that the centers which contribute to optical absorption at 305 nm are those also responsible for the relaxation peak, we find that the number contributing to each process is not the same. We can define an interaction radius R as the minimum separation between two dipoles allowing them to contribute to the relaxation peak. From our experimental data R ? 3·8 × 10^?7 cm.     

Luminescence enhancement by energy transfer from Ce ions in Ba1.6Ca0.4P2O7:Ce:Tb phosphor

The optical properties of Ba_1.6Ca_0.4P₂O₇ doped with Ce³⁺ and Tb³⁺ are investigated. Under excitation at 280 nm the emission spectrum of Ba_1.6Ca_0.4P₂O₇:Ce³⁺ consists of a peak at 370 nm and a shoulder at the longer wavelength side. The emission spectra of Ba_1.6Ca_0.4P₂O₇:Tb³⁺ shows the well-known emission lines due to ⁵D₄-⁷F_J transitions of Tb³⁺. The green emissions of Tb³⁺ ions are enhanced upon UV excitation through energy transfer from Ce³⁺ to Tb³⁺ ions. The efficiency of such an energy transfer is estimated based on spectroscopic data. The dependence of photoluminescence (PL) intensities of Ce³⁺ and Tb³⁺ emissions on Ce³⁺ or Tb³⁺ concentrations in the systems (Ba_1.6Ca_0.4P₂O₇:0.04Ce³⁺,xTb³⁺ and Ba_1.6Ca_0.4P₂O₇:xCe³⁺,0.04Tb³⁺) and the temperature dependence of PL emission spectra of Ba_1.6Ca_0.4P₂O₇:0.06Ce³⁺,0.04Tb³⁺ is also investigated.     

Ferroelectric and pyroelectric properties of Ce3+ modified tetragonal tungsten bronze structured lead barium niobate-55 ceramics

In this work, Lead Barium Niobate-55 tetragonal tungsten bronze structured ceramics modified with Ce³⁺ with the stoichiometric formula Pb_0.55?(3y/2)Ce_yBa_0.45Nb₂O₆, where y=0–10 mol% Ce³⁺, were fabricated through the solid state reaction method and investigated for ferroelectric and pyroelectric properties. Pb_0.55?(3y/2)Ce_yBa_0.45Nb₂O₆ (PBN55) exhibited tetragonal (4mm) tungsten bronze structure. The ferroelectric properties (spontaneous polarization, P_s, remanent polarization, P_r and coercive field, E_c), as a function of Ce³⁺ concentration, have been reported. The influence of Ce³⁺ on pyroelectric properties of the PBN55 system has been evaluated. The pyroelectric properties were characterized and discussed as a function of Ce³⁺. The 6 mol% Ce³⁺ modified tetragonal PBN55 composition exhibited optimum pyroelectric properties in the series which could be suitable for possible pyroelectric applications.     

Enhanced luminescent properties and optical absorption of γ-irradiated KI: Ce, Tb crystals

This paper reports that KI doped with Ce³⁺ or double doped with Tb³⁺ and Ce³⁺ were prepared by the Bridgman-Stockbarger method and characterized by optical absorption photoluminescence (PL), thermoluminescence (TL), photostimulated emission (PSL) and TL emission. The optical absorption measurement indicates that F and V₁, V₂ centers are formed in the crystals during the γ irradiation process. It was attempted to incorporate a broad band of Ce³⁺ activator into the narrow band emission of Tb³⁺ in the KI host without the reduction of emission intensity. Ce³⁺-co-doped KI and Tb crystals showed a broad band emission due to the d-f transition of Ce³⁺ and a reduction in the intensity of emission peaks due to the ⁵D₃-⁷F_j (j=3,4,5,6) transition of Tb³⁺, when they were excited at 240 nm.These results supported that an effective energy transfer occurs from Tb³⁺ to Ce³⁺ in the KI host. Co-doping Ce³⁺ ions greatly intensified the excitation peak at 260 nm for the emission at 393 nm of Tb³⁺, which means that more lattice defects, involved in the energy absorption and transfer to Tb³⁺, are formed by the Ce³⁺ co-doping. The integrated light intensity is an order of magnitude higher as compared to the undoped samples for similar doses of irradiation and heating rates. The defects generated by irradiation were monitored by optical absorption and TSL Trap parameters for the TL process are calculated and presented.     

Tailoring of the spectral–directional characteristics of rare-earth fluorescence by metal–dielectric planar structures

It is demonstrated that the spectrum, direction and polarization of rare-earth fluorescence can be tailored by embedding the impurity ions into a planar metal–dielectric structure (MDS). The latter was designed by spin coating a rare-earth-doped oxide film (TiO₂:Sm³⁺) onto a gold-covered glass substrate. For spectral–directional investigations of Sm³⁺ fluorescence, the MDS was attached to a semi-cylindrical prism and excited by UV light from the flat side. An angular scan revealed a strongly polarized and directional emission of Sm³⁺ from the convex side of the prism. The tuning of TiO₂ film thickness in the MDS allows a control of the polarization and direction of the emission bands. A theoretical modeling of the reflectivity of the MDS suggests that the observed angular resonances in the fluorescence emission are caused by its effective coupling with surface plasmons on the gold–dielectric interface or coupling with leaky modes in sufficiently thick dielectric films working as a waveguides.     

Evolution of microstructure and dielectric properties of (LiCe)-doped Na0.5Bi2.5Nb2O9 Aurivillius type ceramics

Aurivillius type (NaBi)_0.5?x(LiCe)_xBi₂Nb₂O₉ ceramics were prepared by the standard ceramics route. The single crystal structural ceramics were achieved for all compositions and lattice distortion was decreased by (LiCe) dopants. The temperature dependent dielectric properties revealed that all compositions possess a high Curie-temperature (>780 °C). A modified Curie–Weiss relationship is used to study the diffuseness behavior of a ferroelectric phase transition indicating the degree of diffuseness of NBN-based ceramics increased with (LiCe) modifications. The degradation of resistance implied a plausible model that Ce⁴⁺ ions entered into the B-site of the pseudo-perovskite structure and acted as acceptor doping. Further investigation demonstrated that both electrical conduction and dielectric relaxation processes were associated with the oxygen vacancies produced by the substitution of Nb⁵⁺ ions by the Ce⁴⁺ ions.     

Concentration dependence of the Ce3+ and Tb3+ luminescence of Ce1-xTbxMgAl11O19

The quenching of the Ce³⁺ emission and the increase of the Tb³⁺ emission with increasing x of Ce_1-xTb_xMgAl₁₁O₁₉ for x ? 0.35 is ascribed to energy transfer from Ce³⁺ to Tb³⁺, which is restricted to nearest rare earth neighbours. This transfer is almost complete at x ? 0.35. The decrease of the Tb³⁺ emission at higher Tb³⁺ concentrations is not due to Tb³⁺ concentrational quenching, but due to the limited solubility of Tb³⁺ in the CeMgAl₁₁O₁₉ phase.