Electronic spectra and crystal-field analysis of europium in hexanitritolanthanate systems

The luminescence spectra of Eu(3+) at a T(h) point-group site in the hexanitritolanthanate systems Cs(2)NaEu((14)NO(2))(6), Cs(2)NaEu((15)NO(2))(6), Rb(2)NaEu((14)NO(2))(6), Cs(2)LiEu((14)NO(2))(6), and Cs(2)NaY((14)NO(2))(6):Eu(3+) have been recorded between 19,500 and 10,500 cm(-1) at temperatures down to 3 K. The spectra comprise magnetic-dipole-allowed zero phonon lines, odd-parity metal-ligand vibrations, internal anion vibrations, and lattice modes, with some weak vibrational progressions based upon vibronic origins. With the aid of density functional theory calculations, the vibrational modes in the vibronic sidebands of transitions have been assigned. The two-center transitions involving NO(2)(-) stretching and scissoring modes are most prominent for the (5)D(0) → (7)F(2) hypersensitive transition. The onset of NO(2)(-) triplet absorption above 20,000 cm(-1) restricts the derived Eu(3+) energy-level data set to the (7)F(J) (J = 0-6) and (5)D(0,1) multiplets. A total of 21 levels have been included in crystal-field energy-level calculations of Eu(3+) in Cs(2)NaEu(NO(2))(6), using seven adjustable parameters, resulting in a mean deviation of ~20 cm(-1). The comparison of our results is made with Eu(3+) in the double nitrate salt. In both cases, the fourth-rank crystal field is comparatively weaker than that in europium hexahaloelpasolites.     

Novel red-emitting Ba2Tb(BO3)2Cl:Eu phosphor with efficient energy transfer for potential application in white light-emitting diodes

A novel red-emitting Ba(2)Tb(BO(3))(2)Cl:Eu phosphor possessing a broad excitation band in the near-ultraviolet (n-UV) region was synthesized by the solid-state reaction. Versatile Ba(2)Tb(BO(3))(2)Cl compound has a rigid open framework, which can offer two types of sites for various valence's cations to occupy, and the coexistence of Eu(2+)/Eu(3+) and the red-emitting luminescence from Eu(3+) with the aid of efficient energy transfer of Eu(2+)-Eu(3+)(Tb(3+)) and Tb(3+)-Eu(3+) have been investigated. Ba(2)Tb(BO(3))(2)Cl emits green emission with the main peak around 543 nm, which originates from (5)D(4) → (7)F(5) transition of Tb(3+). Ba(2)Tb(BO(3))(2)Cl:Eu shows bright red emission from Eu(3+) with peaks around 594, 612, and 624 nm under n-UV excitation (350-420 nm). The existence of Eu(2+) can be testified by the broad-band excitation spectrum, UV-vis reflectance spectrum, X-ray photoelectron spectrum, and Eu L(3)-edge X-ray absorption spectrum. Decay time and time-resolved luminescence measurements indicated that the interesting luminescence behavior should be ascribed to efficient energy transfer of Eu(2+)-Eu(3+)(Tb(3+)) and Tb(3+)-Eu(3+) in Ba(2)Tb(BO(3))(2)Cl:Eu phosphors.     

Direct spectroscopic evidence of 8- and 9-fold coordinated europium(III) species in H(2)O and D(2)O

In the present paper a detailed analysis of high-resolution luminescence spectra of Eu(III)-H(2)O species in frozen aqueous solution (T = 5 K) is presented. From the total luminescence spectra (TLS, excitation vs emission) and the luminescence decay matrixes (time vs emission), fundamental species-selective spectroscopic parameters are determined: excitation wavelength λ(exc), decay time τ, crystal field energy splitting ΔE (crystal field strength parameter N(ν)(B(2q))), crystal field parameters B(20) and B(22), asymmetry ratio r, and point symmetry group. The spectroscopic findings clearly show the presence of two distinct Eu(III) aquo species. Samples prepared with different counterions (Cl(-), ClO(4)(-)) and at different pH values (2 and 5) yielded comparable results. Furthermore, in D(2)O solutions the same two species were found, with similar spectral properties but much longer decay times. On the basis of the spectroscopic analysis, the two species were attributed to 8- and 9-fold coordinated Eu(III) aquo ions.     

Synthesis, structure, and thermally stable luminescence of Eu(2+)-doped Ba2Ln(BO3)2Cl (Ln = Y, Gd and Lu) host compounds

A new family of chloroborate compounds, which was investigated from the viewpoint of rare earth ion activated phosphor materials, have been synthesized by a conventional high temperature solid-state reaction. The crystal structure and thermally stable luminescence of chloroborate phosphors Ba(2)Ln(BO(3))(2)Cl:Eu(2+) (Ln = Y, Gd, and Lu) have been reported in this paper. X-ray diffraction studies verify the successful isomorphic substitution for Ln(3+) sites in Ba(2)Ln(BO(3))(2)Cl by other smaller trivalent rare earth ions, such as Sm, Eu, Tb, Dy, Ho, Er, Tm, and Yb. The detailed structure information for Ba(2)Ln(BO(3))(2)Cl (Ln = Y, Gd, and Lu) by Rietveld analysis reveals that they all crystallize in a monoclinic P2(1)/m space group. These compounds display interesting and tunable photoluminescence (PL) properties after Eu(2+)-doping. Ba(2)Ln(BO(3))(2)Cl:Eu(2+) phosphors exhibit bluish-green/greenish-yellow light with peak wavelengths at 526, 548, and 511 nm under 365 UV light excitation for Ba(2)Y(BO(3))(2)Cl:Eu(2+), Ba(2)Gd(BO(3))(2)Cl:Eu(2+), and Ba(2)Lu(BO(3))(2)Cl:Eu(2+), respectively. Furthermore, they possess a high thermal quenching temperature. With the increase of temperature, the emission bands show blue shifts with broadening bandwidths and slightly decreasing emission intensities. It is expected that this series of chloroborate phosphors can be used in white-light UV-LEDs as a good wavelength-conversion phosphor.     

Luminescence properties and water coordination of Eu3+ in the binary solvent mixture water/1-butyl-3-methylimidazolium chloride

The effect of relative water content on the luminescence properties and speciation of Eu3+ ions in solutions of EuCl3 in the binary solvent mixture water/[BMI]Cl is presented, where [BMI]Cl is the ionic liquid (IL) 1-butyl-3-methylimidazolium chloride. Using luminescence techniques, the binding properties of water to Eu3+ are determined for samples with mole ratios of water-to-IL ranging from 0 to 5. Very little water binds to Eu3+ at mole ratios of water-to-IL less than 1, above which binding increases rapidly with increasing water concentration. It is shown that only certain hydration numbers for Eu3+ complexes are stable in the water/IL solutions. The data presented suggest that the Eu3+ species present are [EuClx]3-x, [EuCly(H2O)3-4]3-y, [EuClz(H2O)6]3-z, and [Eu(H2O)8-9]3+ (where x > y > z). Comparison of the positions of the 5D0<--7F0 transitions of the Eu3+ complexes in IL solution with those of model crystal systems provides insight into the extent of Cl- complexation. This study suggests that [BMI]Cl is a promising medium for luminescent lanthanide (Ln) compounds due to the low-energy phonon environment of the [LnClx]3-x complex and to the fact that moderate water contamination does not result in direct binding of water to Ln3+, which would result in luminescence quenching.     

LaOF:Eu3+ nanocrystals: hydrothermal synthesis, white and color-tuning emission properties

Uniform LaOF and LaOF : Eu(3+) nanocrystals of the γ-form have been successfully synthesized under mild conditions via a facile hydrothermal method followed a heat treatment of their bastnaesite-type precursor (LaCO(3)F). The synthetic details, investigations into the phase purity and the presence of the oxocarbonate anion CO(3)(2-) proven by IR measurements and EDX, as well as X-ray powder diffraction data, are given. Photoluminescence (PL) and cathodoluminescence (CL) spectra were utilized to characterize the luminescence properties of the LaCO(3)F : Eu(3+) and LaOF : Eu(3+) samples. Under ultraviolet light excitation, the LaCO(3)F : Eu(3+) precursor shows an orange emission of Eu(3+) (dominated by (5)D(0)→(7)F(1)), while the product of heat treatment, LaOF : Eu(3+), shows the characteristic emissions of Eu(3+) ((5)D(J)→(7)F(J')J, J' = 0, 1, 2, 3 transitions). Under the excitation of UV and low-voltage electron beams, the emission color (including white) of LaOF : Eu(3+) can be tuned by adjusting the doping concentration of Eu(3+). The corresponding luminescence mechanisms have been discussed in detail.     

Synthesis, crystal structures, and luminescence of organic-lanthanide complexes with nicotinate and isonicotinate ligands

Six lanthanide coordination compounds with two isomeric carboxylic acids, nicotinic acid (HL(1)) and isonicotinic acid (HL(2)), [(L(1))3Ln(H2O)2]2 (Ln = Eu, 1; Gd, 2; Tb, 3) and [( L(2))2Ln(H2O)4][NO3] (Ln = Eu, 4; Gd, 5; Tb, 6), have been synthesized and structurally characterized by single-crystal X-ray diffraction. Complexes 1-3 are dimeric whereas 4-6 are polymeric, all with 8-coordination of Ln(3+). The distinction between these lanthanide complexes is readily accomplished from the 10 K high resolution electronic emission spectra. Spectral interpretation is given for the Eu(3+) complexes 1, 4, whereas the spectra of 3 and 6 are more complex. The relationships between spectroscopic and crystallographic site symmetries are discussed. The calculated second rank crystal field strengths of Eu(3+) in 1 and 4 are intermediate in magnitude.     

Visible luminescence of dysprosium ions in oxyhalide lead borate glasses

Visible luminescence of Dy(3+) ions in oxyhalide lead borate glasses was examined. Luminescence spectra show two intense bands at 480 nm and 573 nm due to (4)F(9/2)→(6)H(15/2) (blue) and (4)F(9/2)→(6)H(13/2) (yellow) transitions of Dy(3+). Luminescence decays from (4)F(9/2) state and yellow-to-blue luminescence intensity ratios (Y/B) were analysed with PbX(2) (X=F, Cl) content. An introduction of PbX(2) to the borate glass results in the increasing of (4)F(9/2) lifetime and the decreasing of yellow-to-blue luminescence intensity ratio, which is due to reduction of covalency between Dy(3+) and O(2-)/X(-) ions.     

Electronic polarizability and Judd-Ofelt parameters of Nd3+ and Er3+ ions in transparent crystallized glasses with nonlinear optical Ba2 TiSi2O8 nanocrystals

Transparent crystallized glasses consisting of nonlinear optical Ba(2)TiSi(2)O(8) nanocrystals are prepared in Eu(2)O(3)-, Nd(2)O(3)-, and Er(2)O(3)-doped 40BaO-20TiO(2)-40SiO(2) glasses by a conventional heat treatment method in order to clarify the optical properties of rare-earth (RE) ions in nanocrystals. The electronic polarizabilities of crystallized glasses are evaluated from the values of density and refractive index, and are found to decrease due to nanocrystallization, which indicates that the chemical bonding state in the crystallized glasses is more covalent compared to the precursor glasses. It is proposed from x-ray diffraction analyses and photoluminescence spectra of Eu(3+) ions that RE ions such as Nd(3+) and Eu(3+) are incorporated into Ba(2)TiSi(2)O(8) nanocrystals. The Judd-Ofelt parameters, Omega(t) (t=2, 4, and 6), of Nd(3+) and Er(3+) ions are evaluated from optical absorption spectra. It is observed that the Omega(2) parameter of Nd(3+) and Er(3+) increases largely due to nanocrystallization, suggesting that the site symmetry of Nd(3+) and Er(3+) ions in nanocrystallized glasses is largely distorted due to their incorporations into the Ba(2+) sites in Ba(2)TiSi(2)O(8) nanocrystals. The change in the Omega(4) and Omega(6) parameters due to nanocrystallization is small. It is proposed that nonlinear optical Ba(2)TiSi(2)O(8) nanocrystals including RE ions would have a high potential as active optical materials.     

Novel class of aeschynite structure LaNbTiO6-based orange-red phosphors via a modified combustion approach

A novel class of orange-red phosphors based on Eu(3+)-activated LaNbTiO(6) was successfully fabricated by a wet chemical method, called a modified combustion approach. XRD, TG-DTA, SEM, and EDS results show that the heat-treatment of the powders above 1000 degrees C is enough to obtain highly crystallized and phase-pure LaNbTiO(6) and Eu(3+)-doped samples, which is of prime importance in investigating the optical properties of the novel phosphors using LaNbTiO(6) as the host material. UV-vis diffuse reflectance spectroscopy reveals that the direct band gap of LaNbTiO(6) with large grains (above 200 nm) is calculated to be 3.27 eV, while the absorption edge of the small particles shows an obvious blue-shift. Two blue emission bands centered at 440 and 470 nm ascribed to the self-trapped exciton emission of the distorted NbO(6) and TiO(6) groups for the pure LaNbTiO(6) can be obtained. Photoluminescence spectra of the Eu(3+)-doped phosphor particles illuminated the simultaneous occurrence of several intense orange-red band emissions due to the characteristic transitions of (5)D(0,1) --> (7)F(J) (J = 0, 1, 2, 3, 4) of Eu(3+) under 395 nm excitation. The mechanism of these multiplets possibly arising from the odd-parity distortions of the Eu(3+) ion environment and the effect of crystallanity of the compounds on luminescence were discussed, respectively. The highly bright and color-uniform fluorescence images of the doped samples with short luminescence decay times (nanosecond magnitude) confirmed the potential applications of the phosphors in luminescence and display devices.     

Electrospinning synthesis and luminescence properties of one-dimensional La(9.33)(SiO4)6O2: Ln3+ (Ln = Ce, Eu, Tb) microfibers

One-dimensional La(9.33)(SiO(4))(6)O(2): Ln(3+) (Ln = Ce, Eu, Tb) microfibers were fabricated by a simple and cost-effective electrospinning method. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), photoluminescence (PL) and low voltage cathodoluminescence (CL) as well as kinetic decay were used to characterize the resulting samples. SEM and TEM results indicated that the diameter of the microfibers annealed at 1000 °C for 3 h was 200-245 nm. The microfibers were further composed of fine and closely linked nanoparticles. La(9.33)(SiO(4))(6)O(2): Ln(3+) (Ln = Ce, Eu, Tb) phosphors showed the characteristic emission of Ce(3+) (5d → 4f), Eu(3+) ((5)D(0)→(7)F(J)) and Tb(3+) ((5)D(3,4)→(7)F(J)) under ultraviolet excitation and low-voltage electron beams (3-5 kV) excitation. An energy transfer from Ce(3+) to Tb(3+) was observed in the La(9.33)(SiO(4))(6)O(2): Ce(3+), Tb(3+) phosphor under ultraviolet excitation and low-voltage electron beam excitation. Luminescence mechanisms were proposed to explain the observed phenomena. Blue, red and green emission can be realized in La(9.33)(SiO(4))(6)O(2): Ln(3+) (Ln = Ce, Eu, Tb) microfibers by changing the doping ions. So the La(9.33)(SiO(4))(6)O(2): Ln(3+) (Ln = Ce, Eu, Tb) phosphors have potential applications in full-color field emission displays.     

Fixation of carbon dioxide by macrocyclic lanthanide(III) complexes under neutral conditions producing self-assembled trimeric carbonato-bridged compounds with μ3-η2:η2:η2 bonding

A series of mononuclear lanthanide(III) complexes [Ln(LH(2))(H(2)O)(3)Cl](ClO(4))(2) (Ln = La, Nd, Sm, Eu, Gd, Tb, Lu) of the tetraiminodiphenolate macrocyclic ligand (LH(2)) in 95 : 5 (v/v) methanol-water solution fix atmospheric carbon dioxide to produce the carbonato-bridged trinuclear complexes [{Ln(LH(2))(H(2)O)Cl}(3)(μ(3)-CO(3))](ClO(4))(4)·nH(2)O. Under similar conditions, the mononuclear Y(III) complex forms the dimeric compound [{Y(LH(2))(H(2)O)Cl}(μ(2)-CO(3)){Y(LH(2))(H(2)O)(2)}](ClO(4))(3)·4H(2)O. These complexes have been characterized by their IR and NMR ((1)H, (13)C) spectra. The X-ray crystal structures have been determined for the trinuclear carbonato-bridged compounds of Nd(III), Gd(III) and Tb(III) and the dinuclear compound of Y(III). In all cases, each of the metal centers are 8-coordinate involving two imine nitrogens and two phenolate oxygens of the macrocyclic ligand (LH(2)) whose two other imines are protonated and intramolecularly hydrogen-bonded with the phenolate oxygens. The oxygen atoms of the carbonate anion in the trinuclear complexes are bonded to the metal ions in tris-bidentate μ(3)-η(2):η(2):η(2) fashion, while they are in bis-bidentate μ(2)-η(2):η(2) mode in the Y(III) complex. The magnetic properties of the Gd(III) complex have been studied over the temperature range 2 to 300 K and the magnetic susceptibility data indicate a very weak antiferromagnetic exchange interaction (J = -0.042 cm(-1)) between the Gd(III) centers (S = 7/2) in the metal triangle through the carbonate bridge. The luminescence spectral behaviors of the complexes of Sm(III), Eu(III), and Tb(III) have been studied. The ligand LH(2) acts as a sensitizer for the metal ions in an acetonitrile-toluene glassy matrix (at 77 K) and luminescence intensities of the complexes decrease in the order Eu(3+) > Sm(3+) > Tb(3+).     

Optical spectroscopy of lanthanide ions in ZnO-TeO2 glasses

Zinc tellurite glasses of compositions 19ZnO-80TeO2-1Ln2O3 with Ln = Eu, Er, Nd and Tm were prepared by melt quenching. The absorption spectra were measured and from the experimental oscillator strengths of the f-->f transitions the Judd-Ofelt parameters ohm(lambda) were obtained. The values of the ohm(lambda) parameters are in the range usually observed for oxide glasses. For Nd3+ and Er3+, luminescence spectra in the near infrared were measured and the stimulated emission cross sections sigma(p) were evaluated for some laser transitions. The high values of sigma(p), especially for Nd3+, make them possible candidates for optical applications. Fluorescence line narrowing (FLN) spectra of the Eu3+ doped glass were measured at 20 K, and the energies of the Stark components of the 7F1 and 7F2 states were obtained. A crystal field analysis was carried out assuming a C2v site symmetry. The behaviour of the crystal field ratios B22/B20 and B44/B40 agrees reasonably well with the values calculated using the geometric model proposed by Brecher and Riseberg. The crystal field strength at the Eu3+ sites appears to be very low compared to other oxide glasses.     

Rare earth-doped lead borate glasses and transparent glass-ceramics: structure-property relationship

Correlation between structure and optical properties of rare earth ions in lead borate glasses and glass-ceramics was evidenced by X-ray-diffraction, Raman, FT-IR and luminescence spectroscopy. The rare earths were limited to Eu(3+) and Er(3+) ions. The observed BO(3)?BO(4) conversion strongly depends on the relative PbO/B(2)O(3) ratios in glass composition, giving important contribution to the luminescence intensities associated to (5)D(0)-(7)F(2) and (5)D(0)-(7)F(1) transitions of Eu(3+). The near-infrared luminescence and up-conversion spectra for Er(3+) ions in lead borate glasses before and after heat treatment were measured. The more intense and narrowing luminescence lines suggest partial incorporation of Er(3+) ions into the orthorhombic PbF(2) crystalline phase, which was identified using X-ray diffraction analysis.     

The thermal stabilities of luminescence and microstructures of Eu2+-doped KBaPO4 and NaSrPO4 with β-K2SO4 type structure

Eu(2+)-doped monophosphates NaSrPO(4) and KBaPO(4) with the β-K(2)SO(4) structure were synthesized using the conventional high temperature solid state reaction. The X-ray powder diffraction, photoluminescence excitation, and emission spectra and decay curves were measured. The phosphors can be efficiently excited by UV-visible light from 220 to 430 nm to realize emission in the visible range. The natures of the Eu(2+) emission, e.g., the chromaticity coordinates, the Stokes shifts, and the luminescence absolute quantum efficiencies, were reported. The luminescence quenching temperatures and the thermal activation energies for NaSrPO(4):Eu(2+) and KBaPO(4):Eu(2+) were obtained from the temperature dependent (10-435 K) luminescence intensities and decay curves. KBaPO(4):Eu(2+) presents only one emission center; however, Eu(2+) ions have a "disordered environment" in NaSrPO(4) lattices. The relationship between the luminescence thermal stabilities and the crystal structures was discussed. The crystallographic occupations of rare earth ions doped in these hosts were analyzed by the site-selective emission spectra and the excitation spectra of Eu(3+) ions in the (7)F(0)→(5)D(0) transitions using a pulsed, tunable, and narrow-band dye laser. In KBaPO(4), the Eu(3+) ions could be distributed in the host with a high "ordered state" in only one site in the lattices. However, the multiple site structure of Eu(3+) ions with highly disordered distributions in NaSrPO(4) lattices was suggested.     

QEu(TTA)~4.H~2O的晶体结构和荧光光谱

合成了有机碘翁离子作抗衡阳离子的标题配合物晶体QEu(TTA)~4.H~2O(Q=3,6-二甲氨基-二苯基碘翁离子;TTA=噻吩甲酰三氟丙酮根),晶体属P2~1/n空间群,a=1.4206(6),b=2.761(1),c=1.4658(3)nm,β=100.40(2)ⅲ,Z=4,最终的R因子为0.079。77K下,配合物高分辨激光激发荧光光谱的测定表明,配合物中存在一种Eu(Ⅲ)格位。晶体结构测定结果确认,Eu(Ⅲ)离子格位的区域对称性为C~1。自由基聚合的引发实验结果表明,一定浓度的标题配合物对高分子聚合有促进作用。     

Luminescence and microstructures of Eu(3+)-doped Ca9LiGd(2/3)(PO4)7

A red-emitting phosphor, Eu(3+)-doped Ca(9)LiGd(2/3)(PO(4))(7), was synthesized by the conventional high-temperature solid-state reaction. X-ray powder diffraction (XRD) analyses confirmed the pure crystalline phase of Whitlockite-type structure. The excitation spectra of Eu(3+) doped Ca(9)LiGd(2/3)(PO(4))(7) were measured in the VUV and UV region indicating an efficient energy transfer process from the host and Gd(3+) to Eu(3+) ions. Upon excitation with VUV and UV radiation, the phosphor showed strong red emission around 611 nm corresponding to the forced electric dipole (5)D(0)→(7)F(2) transition of Eu(3+) ions. The VUV- and UV-excited luminescence spectra of Ca(9)LiGd(2/3)(PO(4))(7):Eu(3+) together with the dependence of the integrated emission intensities on the doping levels were investigated. The Eu(3+) ions were investigated by a tunable laser as an excitation source. The excitation spectra of (7)F(0)→(5)D(0) transitions suggest that there are two families of inequivalent sites for Eu(3+) in this host. The concentration quenching and crystallographic site-occupancy of Eu(3+) ions in Ca(9)LiGd(2/3)(PO(4))(7) host were discussed on the basis of the site selective excitation and emission spectra, the luminescence decay and its crystal structure.     

Flux synthesis, crystal structure, and luminescence properties of a new europium fluoride-silicate: K5Eu2FSi4O13

The crystal structure and luminescence properties of flux-grown crystals of a new europium(III) fluoride-silicate, K5Eu2FSi4O13, are reported. The structure consists of octahedral dimers of the composition [Eu2O10F], which are linked by unbranched tetrasilicate chains to form a 3-D framework with 5- and 6-ring channels parallel to the b axis where the K+ cations are located. The sharp peaks in the room-temperature emission spectrum are assigned. The number of lines in the region for the 5D0-->7F0 transition and the relative intensities of the 5D0-->7F1 and 5D0-->7F2 transitions confirm the presence of two local Eu3+ environments and strongly distorted Eu3+-ligand surroundings. The room-temperature fluorescence decay curves are well fit by a single-exponential function yielding a lifetime value of about 2.0 ms. Crystal data: monoclinic, space group P21/m, a=7.1850(2) A, b=5.7981(2) A, c=18.1675(6) A, beta=92.248(2) degrees , and Z=2.     

Eu3+-doped β-Ga2O3 nanophosphors: annealing effect, electronic structure and optical spectroscopy

A comprehensive survey of electronic structure and optical properties of rare-earth ions-doped semiconductor is of vital importance for their potential applications. In this work, Eu(3+)-doped β-Ga(2)O(3) nanocrystals were synthesized via a combustion method. The evolution of the optical properties of nanophosphors with increasing the annealing temperature was investigated in detail by means of excitation and emission spectra at room temperature and 10 K. Eu(3+) ions were proved to be incorporated into the crystal lattice of the β-Ga(2)O(3) phase after annealing the as-prepared nanoparticles at 1100 °C. It was observed that the substitution of Eu(3+) for Ga(3+) occurred at merely single site, in spite of two crystallographically nonequivalent sites of Ga(3+) in β-Ga(2)O(3). Spectroscopic evidence corroborated and clarified the local symmetry of C(s) for Eu(3+) at this single site. From the high-resolution excitation and emission spectra, 71 crystal-field levels of Eu(3+) in β-Ga(2)O(3) were identified and analyzed in terms of 19 freely varied free-ions and crystal-field parameters based on C(s) symmetry. The standard deviation of the final fitting is as low as 12.9 cm(-1), indicating an excellent agreement between experimental and calculated energy levels. The temperature-dependent luminescence dynamics of the (5)D(0) multiplet for Eu(3+) in β-Ga(2)O(3) phosphors has also been revealed for the first time from 10 to 300 K.     

Synthesis, crystal structure, and luminescent properties of 2-(2,2,2-trifluoroethyl)-1-indone lanthanide complexes

A new β-diketone, 2-(2,2,2-trifluoroethyl)-1-indone (TFI), which contains a trifluorinated alkyl group and a rigid indone group, has been designed and employed for the synthesis of two series of new TFI lanthanide complexes with a general formula [Ln(TFI)(3)L] [Ln = Eu, L = (H(2)O)(2) (1), bpy (2), and phen (3); Ln = Sm, L = (H(2)O)(2) (4), bpy (5), and phen (6); bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline]. X-ray crystallographic analysis reveals that complexes 1-6 are mononuclear, with the central Ln(3+) ion eight-coordinated by six oxygen atoms furnished by three TFI ligands and two O/N atoms from ancillary ligand(s). The room-temperature photoluminescence (PL) spectra of complexes 1-6 show strong characteristic emissions of the corresponding Eu(3+) and Sm(3+) ions, and the substitution of the solvent molecules by bidentate nitrogen ligands essentially enhances the luminescence quantum yields and lifetimes of the complexes.