Luminescence study of the 4f5d configuration of Nd in LiYF4, LiLuF4 and BaY2F8 crystals

Ultraviolet fluorescence of Nd³⁺ ions induced by triphotonic excitation process was studied in Nd-doped LiYF₄, LiLuF₄ and BaY₂F₈ crystals using a technique of time-resolved spectroscopy. The observed ultraviolet luminescence was due to transitions between the bottom of 4f²5d configuration and 4f³ states of Nd³⁺ ions. Narrow emission lines superposed to the broadband emissions were observed. A detailed analysis of luminescence spectrum revealed that the narrow emissions are due to parity and spin allowed radiative transitions from the Stark levels of ⁴K_11/2(5d) state created by the electrostatic interaction between the 5d electron and the two electrons of the 4f² configuration. The narrow emissions are related to the high spin state (S=3/2) which gives f-f characteristics to the f-d broadband emissions. The narrow emissions superposed to the wide emission correspond to 18%, 34% and 43% of the integrated broadband emission at 262 nm observed in LiYF₄, LiLuF₄ and BaY₂F₈ crystals, respectively. Although the 5d-4f² interaction is observed to be weaker than 5d-crystal field interaction, it is stronger enough to select only the radiative transitions from 4f²5d configuration to 4f³ states that preserves the total spin S=3/2.     

Resonant photoemission from SmS(100)

A strong, sharp resonance enhancement of 4f photoemission has been observed on SmS(100) surfaces for photon energies in the region of the 4d-4f transitions at about 126 eV. The discrete final state reached via the excitation hν+4d¹⁰4f⁶→4d⁹4f⁷ autoionizes primarely via a super Coster-Kronig transition of the type 4d⁹4f⁷→4d¹⁰4f⁵ + unbound electron. Other decay channels, e.g, Sm 5p emission, as well as a surface induced binding energy shift in the Sm³⁺ final state are identified and discussed.     

High-temperature VUV spectroscopy of KYF4 crystals doped with Nd3+, Er3+ and Tm3+ ions

Thermal quenching of 5d-4f luminescence from Nd³⁺, Er³⁺ and Tm³⁺ ions doped into KYF₄ crystals has been investigated in the temperature range up to ∼750 K where this luminescence is completely quenched. The obtained temperatures of thermal quenching (T_q) are ∼270, 495, 450 K for Nd³⁺, Er³⁺, Tm³⁺, respectively. At high temperatures, thermal quenching of 5d-4f luminescence from Nd³⁺ and Er³⁺ is accompanied by the appearance of 4f-4f luminescence from the lower-energy 4f levels. It has been shown that the dominating mechanism of thermal quenching for Nd³⁺ and Er³⁺ ions is thermally stimulated non-radiative transitions (intersystem crossing) from the 5d states to lower-energy 4f levels, namely ²G(2)_9/2 and ²F(2)_7/2, respectively, whereas for the Tm³⁺ ion, thermally stimulated ionization of 5d electrons to the conduction band states is responsible for thermal quenching of 5d-4f luminescence. The energy gap between the lowest Tm³⁺ 5d level and the bottom of the KYF₄ conduction band has been estimated to be 0.66 eV.     

Radiative constants in the spectra of ions of the erbium isoelectronic sequence

The probabilities of the 4f ¹³6p→4f ¹³5d lectric dipole transitions and the lifetimes of levels of the 4f ¹³6p and 4f ¹³5d configurations are calculated for spectra of ions Yb III, Lu IV, Hf V, and Ta VI of the erbium isoelectronic sequence. The wave functions of the intermediate coupling scheme, necessary for calculating the relative line strengths, are obtained semiempirically from experimentally measured energy intervals between fine-structure levels. To pass to the absolute values, the radial integrals of transitions, evaluated with the Hartree-Fock functions, are used.     

Intra- and inter-configurational luminescence spectroscopy of Pr3+ -doped YPO4 nanophosphors

Nanopowders of YPO₄ phosphors with different Pr³⁺doping were successfully prepared by a sol gel method under different synthesis conditions. The crystallite size and strain show a strong dependence on the Pr³⁺ doping concentration and on the annealing temperature. By annealing at 300 °C one can obtain the xenotime structure of the pure YPO₄. The crystallite size can be controlled by controlling the annealing temperature and it increases with increasing the annealing temperature. The room temperature inter-configurational 4f² ↔ 4f5d and intra-configurational 4f²↔ 4f² emission-excitation transitions spectra are measured and investigated. Upon 4f² → 4f5d excitation transition, all the samples present broad intense emission bands attributed to 4f5d → 4f² emission transitions and peaks in red region assigned to ¹D₂→³H₄ transition as photon cascade emission phenomena (PCE). The presence of only ¹D₂→³H₄ transition is discussed. In addition, the ¹D₂ energy level lifetimes as well as the refractive indexes were determined and discussed.     

Spectral and kinetic characteristics of trivalent praseodymium in LaF3-LiF and SrAl12O19

Recent data on cascade transitions in the 4f shell of the Pr³⁺ ion in various matrices are analyzed. Spectral and kinetic characteristics of LaF₃-LiF:Pr and SrAl₁₂O₁₉:Pr phosphors, which show photon cascade emission, were investigated. The emission intensities in the first (¹ S→¹ I ₆ transitions) and the second (transitions from the ³ P ₀ level to the ³ H and ³ F multiplets) cascade stages were measured and the temperature dependences of the intensities of the main emission lines and their kinetic characteristics were determined. The following parameters of SrAl₁₂O₁₉:Pr were found: the band gap width (7.5 eV), the energy gap between the ¹ S ₀, 4f and 5d levels (0.24 eV), and the characteristics of the 4f→5d band (6.0–7.5 eV) of the Pr³⁺ luminescence excitation. It is shown that the LaF₃-LiF:Pr compound has a number of specific features in comparison with other Pr³⁺-doped phosphors.     

Vacuum ultraviolet 5d14f9-4f10 emission of Ho3+ ions in alkaline-earth fluorides

Time-resolved emission and excitation spectra as well as emission decay kinetics of CaF₂, SrF₂, BaF₂ doped with HoF₃ were investigated. Intensive emission bands near 168 nm, having long decay time, are caused by the spin-forbidden transitions from the 5d¹4f⁹ high-spin states to the ground ⁵I₈ states of Ho³⁺ ions. Weak spin allowed 5d¹4f⁹(low-spin)-4f¹⁰ emission band at 158 nm was observed only in CaF₂–Ho crystals. Spin allowed and spin-forbidden excitation bands were observed near 166 and 155 nm, respectively, in all studied crystals. Fast component of spin-forbidden emissions due to multiphonon relaxation to low-lying 4f¹⁰ Ho³⁺ level also was observed for all crystals.     

Luminescence from the Pr 4f5d and S0 states in LiLaP4O12

The photoluminescence and excitation spectra of Pr³⁺ activated LiLaP₄O₁₂ has been investigated in the 10-300 K temperature region. At all temperatures, the luminescence consists of optical transitions emanating from both the Pr³⁺ 4f¹5d¹ and the ¹S₀ states. However, at low temperatures the emission spectrum is dominated by the intraconfiguration emission transitions emanating from the Pr³⁺¹S₀ state. With increasing temperature, there is an exchange of intensity between the two emitting states; emission transitions from the ¹S₀ state exhibit strong intensity quenching while the 4f¹5d¹→4f² emission transitions reveal intensity gain. These results are explained on the basis of thermal population of the 4f¹5d¹ state by the ¹S₀ state. The energy barrier of 0.05 eV (403 cm⁻¹) for the nonradiative process is determined from the temperature dependence of the ¹S₀ lifetime.     

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.     

Preparation and photoluminescence properties of the Eu2+, Sm3+ co-doped Li2SrSiO4 phosphors

A series of Eu²⁺ and Sm³⁺ co-doped Li₂SrSiO₄ phosphors are prepared by the high temperature solid-state reaction. The morphology, structure and spectroscopic properties of the prepared samples are characterized by scanning electron microscopy, X-ray diffraction, diffuse reflection spectra, photoluminescence spectra and electron paramagnetic resonance spectra, respectively. The effect of Sm³⁺ doping concentration on the photoluminescence intensity of the prepared samples is also investigated. The results indicate that the crystal structure of Li₂SrSiO₄ is not changed with the Eu²⁺, Sm³⁺ co-doping. The spherical-like particle size of the obtained product is about 20–30 nm in diameter. When the Sm³⁺ concentration is 0.3 mol% and the Eu²⁺ concentration is 0.7 mol%, the phosphors show the maximum emission intensity, which is 50% higher than that of Eu²⁺ doped Li₂SrSiO₄. Excited at 420 nm, the phosphor presents a single broad emission band peaking at 558 nm, which is ascribed to the 4f⁶5d¹ → 4f⁷ transitions of Eu²⁺ and ⁴G_5/2 → ⁶H_5/2 and ⁴G_5/2 → ⁶H_7/2 transitions of Sm³⁺. The Commission International de I′Eclairage chromaticity coordinates of Li₂SrSiO₄:0.7 mol% Eu²⁺, 0.3 mol% Sm³⁺ are x = 0.28, y = 0.28.     

Charge transfer effects on the luminescent properties of Eu3+ in oxysulfides

Energy shifts of 4f⁶ states of Eu³⁺ in matrices, and phonon sidebands, linewidths and luminescence decay of Eu³⁺ in Ln₂O₂S (Ln=Lu, Y, Gd and La) have been studied. The charge transfer state (CTS) of Eu³⁺ is described by a model in which a hole is transferred from Eu³⁺ to ligands. Septet states obtained from the 4f⁷(⁸S) + hole configuration of CTS interact with the ⁷F term of the 4f⁶ configuration. This effect causes downward shifts of ⁷F_J states in matrices. Diffuse charge distributions for ⁷F_J states due to the mixing with CTS make the curvatuve of their adiabatic potential curves be smaller than that for ⁵D_J'. Such a difference in the potential curves between ⁷F_J and ⁵D_J' causes broadening of the absorption lines compared with the corresponding emission linewidths in Y₂O₂S. A dynamic Jahn-Teller model is proposed for the concentration-enhanced phonon sidebands accompanying 4f-4f transitions. The vibronics appear only in the excitation spectra and not in the emission spectra. Spectral distributions of the effective density of phonon states are obtained from the observed phonon sidebands for Ln₂O₂S: 5%Eu. The phonon spectra indicate delocalization of the 4f orbitals of Eu³⁺ with increasing the host-cation radius. The observed lifetimes of ⁵D₀ show a decrease in the same order due to decrease in the 4f-CTS mixing.     

Upconverted 5d-4f luminescence from Er and Nd ions doped into fluoride hosts excited by ArF and KrF excimer lasers

We report on observation of upconverted VUV luminescence due to 5d-4f radiative transitions in Er³⁺ and Nd³⁺ ions doped into some fluoride crystals, under excitation by ArF and KrF excimer lasers, respectively. Only spin-forbidden 5d-4f luminescence of Er³⁺ (at 165 nm) was detected from the LiYF₄:Er³⁺ crystal whereas both spin-forbidden (at 169 nm) and spin-allowed (at 160.5 nm) components are observed from the BaY₂F₈:Er³⁺ crystal, the latter being much weaker than in the case of one-photon excitation. Nd³⁺ 5d-4f luminescence at 180 and 173 nm has been detected from the LiYF₄:Nd³⁺ and LaF₃:Nd³⁺ crystals, respectively. The shift of short-wavelength edge of 5d-4f emission spectra towards longer wavelengths is observed under temperature increase from 15 to 293 K. The observed effects in the spectra of Er³⁺ and Nd³⁺ doped crystals were interpreted as a result of reabsorption of 5d-4f luminescence escaping from the bulk of the crystals.     

Low-temperature time-resolved VUV luminescence spectroscopy of SrF<Subscript>2</Subscript>: Er<Superscript>3+</Superscript> crystals

Time-resolved excitation and emission spectra of SrF₂: Er³⁺ upon selective excitation with synchrotron radiation in the VUV and ultrasoft x-ray ranges at T = 8 K were studied. The VUV luminescence of SrF₂: Er³⁺ derives from high-energy interconfiguration 4f¹⁰5d-4f¹¹ transitions in the Er³⁺ ion. The VUV emission spectrum revealed, in addition to the 164.5-nm band (millisecond-range kinetics), a band at 146.4 nm (with a decay time of less than 600 ps). The formation of excitation spectra for the f-f and f-d transitions in the Er³⁺ ion is discussed.     

Multiphonon relaxations in Ho3+:LaF3 single crystal

The mulliphonon transition rates in Ho³⁺:LaF₃ are estimated from the observed fluorescence decay rates of the states ⁵F₃ and (⁵F₄, ⁵S₂), in the temperature interval 80–675°K. The data is analyzed in terms of the existing theoretical models. The analysis indicates that the high energy phonons play a dominant role in these multiphonon transitions.     

High pressure luminescence study of Sm3+: K–Ba–Al fluorophosphate glass

The luminescence spectra and decay curves for the ⁴G_5/2 level of Sm³⁺ ions in 55.95P₂O₅+14K₂O+6KF+14.95BaO+9Al₂O₃+0.1Sm₂O₃ glass, referred to as PKFBASm01, have been studied as a function of pressure up to 40.5 GPa at room temperature. With the increase in pressure, a continuous red shift of the ⁴G_5/2→⁶H_{9/2, 7/2, 5/2} transitions and a progressive increase in the magnitude of the crystal-field splittings for these transitions are observed. The decay curves for the ⁴G_5/2 level of the Sm³⁺ ions in PKFBASm01 glass are found to exhibit single exponential behavior at ambient pressure and become non-exponential at higher pressures, accompanied by shortening of lifetimes. A generalized Yokoto–Tanimoto model has been used to explain the pressure-induced non-exponential nature of the decay curves.     

Some detailed investigations of optically detected Ē(2 E) →4 A 2 cross relaxation in ruby

Cross relaxation betweenē(² E) and⁴ A ₂ states of Cr³⁺ in ruby at an applied external magnetic field ofH=5336 Oe was measured by monitoring the ¦? 1/2〉_ex→ ¦? 3/2〉_g optical transition in the temperature region of 1.6 to 4.2 °K. The chromium concentration varied from 2.9· 10^?4 to 4 · 10^?6 Cr³⁺/Al³⁺. With a concentration greater than 2 · 10^?5, the light intensity of the observed transition increases when cross relaxation takes place, while below this value it decreases. By measurement of the fluorescent intensity of one transition and simultaneously inducing EPR ground state transitions, we monitored the effect of trapping. Taking the value for trapping from fluorescence decay time measurements, we have used rate equations for calculating the actual change of excited state population when cross relaxation occurs. With this phenomenological model we are able to explain our experimental data. Finally some calculations for the effective spin temperature in theē(² E) state as a function of Cr³⁺ concentration as well as for various applied magnetic fields have been done.     

The luminescence properties of Eu2+ doped Na2CaMg(PO4)2 phosphor

The blue-emitting phosphors of Eu²⁺-doped Na₂CaMg(PO₄)₂ were prepared by high-temperature solid-state reaction. The crystal phase formation was confirmed by X-ray powder diffraction measurement. The luminescence properties were investigated by photoluminescence excitation and emission spectra. The phosphor exhibited the blue luminescence due to the 4f⁶5d¹→4f⁷ transition of Eu²⁺ ions under the excitation of near UV light. The influence of temperature on the luminescence intensities and decay lifetimes of Eu²⁺ was investigated. An unusual increase of the decay lifetimes of the 4f⁶5d emission of Eu²⁺ ion is observed in Na₂CaMg(PO₄)₂ from 10 K to room temperature. The thermal stability of the luminescence of Eu²⁺-doped Na₂CaMg(PO₄)₂ was discussed.     

Magnetic circular dichroism of Pr3+ ions in yttrium—Aluminium garnet crystals

The spectra of the absorption and magnetic circular dichroism in the praseodymium-yttrium garnet-aluminate Pr³⁺:YAG have been studied within the visible and near ultraviolet (UV) spectral range for temperature T = 90 K and 300 K. Analysis of the spectral and the temperature dependences of the magnetooptical and optical spectra has made it possible to identify the optical 4f → 4f transitions occurring between the Stark sublevels of the ¹ D ₂, ³ P ₀, and ³ H ₄ multiplets in Pr³⁺:YAG. It has been shown that in the MCD mechanism in Pr³⁺:YAG within the visible and UV spectral range for the absorption bands due to both forbidden 4f → 4f and allowed 4f → 5d transitions, a significant role is being played by the effect of quantum-mechanical “mixing” of the states of the three lowest-energy Stark singlets of the ground-state ³ H ₄ multiplet of the non-Kramers RE Pr³⁺ ion.     

Broadening of the lines due to the 4f n -4f n − 15d transitions of Ce3+, Pr3+, and Tb3+ ions in the absorption spectra of CdF2 crystals

The structure of the absorption spectra of Ce³⁺, Pr³⁺, and Tb³⁺ ions in the vicinity of 4f-5d transitions has been investigated. At low temperatures the absorption spectra exhibit a weakly pronounced fine structure, in contrast to narrow-line spectra in crystals of Ca, Sr, and Ba fluorides. The spectra of Ce³⁺, Pr³⁺, and Tb³⁺ ions in CdF₂ can be considered as the absorption spectra of these ions in alkali-earth fluorides, broadened by 60–75 cm^?1. The broadening is related to the autoionization of electron from the local 5d(e _g ) level to the energy-degenerate states of the conduction band of CdF₂ crystal.     

Optical properties of BiTeI semiconductor with a strong Rashba spin-orbit interaction

We have modeled the 4f ¹-5d ¹ absorption spectrum of a LiYF₄:Ce³⁺ crystal at zero temperature using a microscopic model of the electron-phonon interaction and the real spectrum of LiYF₄ lattice vibrations. Effects caused by mixing of the wave functions of different states of the 5d ¹ excited configuration of the Ce³⁺ ion, which is induced by the electron-phonon interaction, are considered based on the calculations of the second-, third-, and fourth-order exact moments of curvature of the spectrum envelope. We have shown that the large value of the splitting between the maxima of the bands in the absorption spectrum that correspond to transitions to the third and fourth 5d ¹ levels is a result of the nonadiabatic interaction of 5d electrons with lattice vibrations.