The luminescence of Tm2+ in strontium tetraborate

The 4f¹²5d→4f¹³ emission of Tm²⁺ is observed for the first time. It consists of a red band emission with vibronic structure. For a parity-allowed 4f-5d transition its decay time is long, viz. 230 μs. In addition intraconfigurational 4f¹³ line emission is observed. The results are compared to 4f-5d emissions of other divalent lanthanides in SrB₄O₇.     

Non-radiative relaxation processes of the Pr3+ ion

Conclusions The³P₀→¹D₂ non-radiative decay rates A_NR of Pr³⁺ and the transition probabilities A_VIB for the vibronic³H₄→³P₀ excitation transitions of Pr³⁺ were measured at 4.2 K in several host lattices. Besides the well-known dependence on the number of phonons involved in the radiationless transition, the multiphonon relaxation rates are observed to be greatly enhanced by increasing covalency and/or decreasing Pr-ligand distances. The enhanced multiphonon relaxation is ascribed to a stronger electron-phonon coupling. The increase in the electron-phonon coupling strength is confirmed by the increase of the vibronic transition probabilities A_VIB in the same sequence as the A_NR rates. The observed host lattice dependence of A_NR can be qualitatively accounted for by a non-linear multiphonon relaxation mechanism. Under certain conditions (viz. low-lying 4f5d states, and a force constant stronger in the 4f5d than in the 4f² states) fast³P₀→¹D₂ non-radiative relaxation via intersystem crossing through the 4f5d state becomes the dominant relaxation mechanism, even at 4.2 K. Debye Institute, Utrecht University P. O. Box 80000, 3508 TA Utrecht, The Netherlands. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 62, No. 4, pp. 63–71, July–August, 1995.     

Optical transitions of Eu2+ IONS in RbMgF3 crystals

Because of the need for tunable solid state lasers in the blue region of the spectrum, a number of recent studies have been on the optical properties of Eu²⁺ in various crystals lattices. The absorption and emission from Eu²⁺ ions in fluoride hosts arise from both 5d→4f and 4f→4f transitions. The absorption is in the ultra-violet and the emission is in the blue. The 4f-4f transitions are very sharp and are located around 360 nm. The 5d→4f emission bands at 405 nm and 525 nm are broad and host lattice dependent. We have studied the temperature dependence of the optical properties of RbMgF₃:Eu²⁺ including absorption, emission, and excitation. In the case of the emission studies both temperature dependence and the lifetimes of the transitions have been measured. These transitions are discussed in detail.     

Vibronic Transitions of Trivalent Er and Ce in BaY2F8 Single Crystals

High resolution (0.02 cm^?1) Fourier transform spectroscopy was applied in the 9–300 K and 100–24,000cm^?1 ranges, respectively, to detect in Er^3? and Ce^3? doped BaY₂F₈ single crystals (1) the narrow line spectra due to the intraconfigurational 4f→4f transitions of the rare earths (RE) and (2) the possible vibronic tails accompanying the zero-phonon lines. The ²F_5/2→²F_7/2 transition was monitored for the Ce^3?-doping and the crystal field splitting of the initial and final manifold was determined. Weak vibronic spectra accompanying six among the nine investigated 4f→4f transitions of Er^3? and the ²F_5/2→²F_7/2 transition of Ce^3? were detected. The vibronic spectra amplitude was found to scale with the RE contents. On the basis of the IR- and Raman-active vibrational modes, either measured or quoted in the literature, most of the vibronic lines could be successfully assigned to the lattice modes. Violations of the selection rules were envisaged and discussed.     

Absolute oscillator strengths of 5f-5f transitions of U4+ in ThBr4 and in hydrobromic acid solutions

Absolute oscillator strengths of 5f² transitions of U⁴⁺ in ThBr₄ and in hydrobromic acid solutions are found to be about 10^-4 which is two orders of magnitude larger than those for 4f-4f transitions (lanthanide series) and one order of magnitude larger than 5f³ ones (U³⁺). Applicability of Judd's theory to 5f² transitions is discussed with particular attention to the roles played by reduced matrix elements of odd rank tensor U^λ and by the proximity of the 6d configuration.     

Intra and inter-ionic multiphonon transitions in rare earth doped crystals

A theory has been developed for non-radiative multiphonon transitions in ionic crystals doped by RE-impurities. The degeneration of final electronic states has been taken into account in the framework of the first cumulant approximation. An analytical expression has been obtained for the rate of non-resonant energy transfer caused by electrostatic inter-ionic interaction and numerical estimations for Yb → Tm and Yb → Ho transitions in YAlO₃ and YLiF₄ crystals are listed. The intra-center multiphonon non-radiative relaxation has been considered in the case where acoustical modes of lattice vibrations are the promoting ones.     

稀土离子电声子耦合S因子的计算

本文给出了计算多声子跃迁中电声子耦合最小S因子的公式,它具有不依赖晶格振动具体模式的优点,在此基础上具体估算了LaF₃晶体中Ho³⁺稀土杂质在 ⁵F₁,⁵F₄,⁵F₅,⁵G₄,⁵G₅能级之间的多声子跃迁的S因子,得到S为0.05左右,这是与通常的实验结果相符的。 关键词：     

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.     

An example of concentration sensitive electron-phonon coupling in {(C4H9)4N}3 EuxY1−x(NCS)6 and a new hypothesis for self-quenching

The strong vibronic one-phonon side-bands of the ⁵D₀ → ⁷F₀ emission of Eu³⁺ in {(C₄H₉)₄N}₃ Eu_xY_1?x(NCS)₆ are used to compute the Huang-Rhys electron-phonon coupling factor (S₀) of Eu³⁺ with the mode at 35 cm^-1. Increasing concentration from 1 to 100 is found to lead to a doubling of the electron-phonon coupling strength. Generalization of such an effect is proposed as a new hypothesis for part of the self-quenching process of rare-earth ions.     

Electron-vibrational interaction in 4f-5d optical transitions in Ba, Ca, Sr thiogallates doped with Eu ions

This study is devoted to the problem of the electron-vibrational interaction in 4f-5d optical transitions. We analyze the room temperature experimental data on the vibronically assisted broad bands arising from the 4f-5d transitions in Ba, Ca, and Sr thiogallates doped with Eu²⁺ ions. An approximate simple expression is given for the shape function of the broad vibronic bands with allowance for the terms corresponding to the emission (absorption) from both ground and first excited vibrational levels. We estimate the vibronic coupling parameters and the Stokes shifts for these systems. The theoretical results are in a good agreement with the experimental data.     

Giant natural circular dichroism of vibronic transitions in HoAl3(BO3)4

The giant natural optical activity of vibronic replicas of the f–f ⁵ I ₈ → ⁵ F ₂ transition in HoAl₃(BO₃)₄ is observed. It exceeds the optical activity related to purely electronic transitions by two orders of magnitude and corresponds to the almost complete circular polarization of the transitions. This effect is explained by the local distortions of the crystal in the excited electronic state, which lead to the mixing of electron and vibrational wavefunctions and, as a consequence, to the delocalization of the vibronic wavefunction and the enhancement of spatial dispersion, which is responsible for the optical activity.     

Dynamic studies on the time-resolved fluorescence of Sm in BaCl2

The time dependence of Sm²⁺ fluorescence in orthorhombic BaCl₂ was investigated between 77 and 300 K. The thermal quenching mechanism of the 4f-4f emissions of Sm²⁺ was examined. The position of the lowest level of Sm²⁺ 4f⁵5d states was calculated from the temperature dependence of ⁵D₁ lifetime by the two-step quenching model and was estimated in good approximation from the emission and excitation peaks by the electron-phonon coupling theory. A growing process of ⁵D₀-⁷F₀ emission and a double-decay process of 5d-4f emission were observed in the time-resolved fluorescence. They show clearly the population transfer among the Sm²⁺ excited states via thermal transition.     

Study of the d-f Emission,and f-d Ground-State and Excited-State Absorption of Nd3+ in Crystals Using the Simple Model

The simplified model for 4f-5d transitions is applied to obtain the line strengths for emission, ground-state absorption and excited states absorption involving 4f-5d transitions of Nd³⁺ in crystals. The results are host independent for the usual case where 5d crystal-field interaction can be considered as strong, in the sense that the calculated 5d-4f emission relative line strengths will be the same for Nd³⁺ in any host. Also the calculated 4f-5d absorption line strengths can be grouped by the 5d crystal-field components. For each 5d crystal-field component, the group of absorption line strengths for different 4f²5d transition final states forms a pattern independent of the 5d crystal-field component and the host. For practical cases, due to strong but still limited 5d crystal-field splitting, the transitions to different 5d crystal-field components may overlap each other. The theoretical results are used to interpret available experimental data.     

Photoluminescence in MgxSr1−xAl2O4:Eu, Ndand electron-vibrational interaction in the Eu 5d states

Green phosphor compositions Mg_xSr_1−xAl₂O₄:Eu, Nd (with x=0.05-0.25) were prepared by solid state reaction method. The effect of Mg substitution on photoluminescence characteristics was investigated. The photoluminescence show intense green emission for MgSrAl₂O₄:Eu²⁺, Nd³⁺ with long persistence. This green emission corresponds to transitions from 4f⁶5d¹ to 4f⁷ of Eu²⁺ ion. Comparative analysis of the excitation and emission spectra were used to evaluate the crystal field splitting of the 5d states of Eu²⁺ and the parameters of electron-vibrational interaction, such as Huang-Rhys factor, effective phonon energy, and zero-phonon line position.     

Site selective 4f5d spectroscopy of CaF2 : Pr

Spectroscopic investigations were performed on a single crystal of CaF₂ doped with 0.05% Pr³⁺. Three different Pr³⁺ sites with different luminescent properties were identified. The 4f² →4f¹5d¹ excitation spectrum of the first site has a sharp maximum at 221.3 nm. Excitation in the 4f5d bands of this site yields strong 4f5d emissions in the UV/VIS part of the spectrum and also weaker intraconfigurational 4f² emissions. By comparing the intraconfigurational 4f emissions and their decay times with data from the literature, these 4f5d bands are assigned to transitions on Pr³⁺ ions on a site with C_4V symmetry. The fd excitation spectrum of the second site has a zero phonon line at 223.3 nm. Upon selective excitation in this band, only 4f5d emission is observed. Probably, these 4f5d bands correspond to Pr³⁺ ions on a O_h site. The third set of 4f5d bands has a 4f5d onset at 208 nm. By comparison of the luminescence spectra of the intraconfigurational 4f² transitions with literature data, these transitions are assigned to Pr³⁺ on an L site. Excitation in these 4f5d band yields ¹S₀ emission followed by emission from the ³P₀ state. The present results clarify some contradictions reported in the literature.     

Energy level scheme and the effect of magnetic order on the optical transitions in europium chalcogenides

The optical constants of Eu-chalcogenide single crystals have been determined at room temperature for photon energies from 1 to 6 eV. In the same energy range the transmission of thin evaporated films (except for EuO) has been measured with polarized light above and below the magnetic ordering temperature. The observed polarization-dependent splittings of the two main absorption maxima in the region of magnetic order suggest transitions from the 4f⁷-level into the crystal field split 5dt_2g- and 5de_g-states. An attempt has been made to relate the maxima of the absorption coefficient to interband transitions and transitions from the localized 4f-states. With this assumption we derived a consistent energy level scheme of the four Eu-chalcogenides. From the scheme we gained useful information about the width of the 5d-states, the crystal field splitting and the possible type of conductivity. Finally we tried to explain theoretically the splittings observed in the region of magnetic order. For this purpose a one-particle model has been used to calculate the transition probabilities for the 4f⁷?4f⁶(⁷F _J ) 5dt_2g and the 4f⁷?4f⁶(⁷F _J ) 5de_g transition, taking into account an exchange interaction as well as a spin-orbit coupling. Although this simple model can explain the splittings of the excited 4f⁶(⁷F _J ) 5de_g-state, a complete explanation of the effect of magnetic order on the 4f⁶(⁷F _J ) 5dt_2g-state fails up to now.     

掺杂三价铽离子的碱土金属钨酸盐的光谱特性研究

本文合成了一系列掺杂三价铽离子的碱土金属钨酸盐,测定了晶体的X射线粉末衍射数据及发射光谱和激发光谱.所合成的化合物均属四方晶系,I41/a空间群,晶胞多数随金属离子半径的增大而增大.研究了在这些晶体中三价铽离子5D3→7Fi和5D4→7Fi跃迁发射的激发态及其能量传递机理和浓度猝灭机制.讨论了发射光谱和激发光谱与铽离子浓度、金属离子半径及铽离子在晶体中的溶解度的关系.     

Absorption Spectra of Lanthanide Complexes in Solution

Abstract

The 4f electrons of lanthanides yield three types of transitions: (i) Internal 4f-4f transitions which give rise to sharp, narrow bands of comparatively weak intensities which are Laporte forbidden. (ii) Allowed 4fⁿ?4f^n-1 (n – l)d, which are relatively broad and intense. (iii) Broad and often intense 4fⁿ?λ^?1 fⁿ⁺¹ electron transfer bands generally occurring in the ultraviolet region (λ^? represents a hole in the orbital concentratedmainly on the ligands).     

Observation of stokes and anti-stokes vibrational sidebands in the optical emission spectrum of Eu atoms isolated in an argon matrix

The 4f⁶5d6s² → 4f⁷ 6s² emission spectrum of Eu atoms isolated in an argon matrix shows (a) zero-phonon lines and (b) Stokes vibrational sidebands due to resonance modes in the $\text{Ar}$: Eu phonon spectrum. In addition, unexpected anti-Stokes vibrational side bands are observed, which might be due to “hot luminescence”.