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.     

Photoluminescence properties of Eu and Mn-activated BaMgP2O7 as a potential red phosphor for white-emission

A phosphate compound, BaMgP₂O₇ was co-doped with Eu²⁺ and Mn²⁺ for making a red-emitting phosphor. The phosphor was prepared by a solid-state reaction at high temperature. The photoluminescence properties were investigated under ultraviolet (UV) ray excitation. From a powder X-ray diffraction (XRD) analysis, the formation of single-phased BaMgP₂O₇ with a monoclinic structure was confirmed. In the photoluminescence spectra, the BaMgP₂O₇:Eu,Mn phosphor emits two distinctive colors: a blue band centered at 409 nm originating from Eu²⁺ and a red band at 615 nm caused by Mn²⁺. Also, efficient energy transfer from Eu²⁺ to Mn²⁺ in the BaMgP₂O₇:Eu,Mn system was verified by observing that the excitation spectra of BaMgP₂O₇:Eu,Mn emitted at 409 and 615 nm by Eu²⁺ emission and Mn²⁺ emission, respectively, are almost the same as that of BaMgP₂O₇:Eu monitored at 409 nm. The optimum concentration of Eu²⁺ ions in BaMgP₂O₇:0.015Eu excited at 309 nm wavelength is 1.5 mol%. With an increase of Mn²⁺ content up to 17.5 mol%, a systematic decline in the intensity of the excitation spectrum by Eu²⁺ and a gradual growth in the intensity of emission band by Mn²⁺ were observed. Accordingly, the optimum concentration of Mn²⁺ in BaMgP₂O₇:0.015Eu,Mn is 17.5 mol%. The maximum spectral overlap between emission of Eu²⁺ and excitation of Mn²⁺ is achieved in a composition of BaMgP₂O₇:0.015Eu,0.175Mn, resulting in considerable red-emission at 615 nm.     

Charge states of the activator and size effects in BaF2: Eu nanophosphors

ABSTRACT

According to the spectra of stationary X-ray excited luminescence (XEL) of BaF₂: Eu nanophosphors at 80 and 294 K, it was revealed that the thermal annealing of fine-grained nanoparticles (d?=?35?nm) in the range of 400–1000°C, which is accompanied by an increase of their sizes in the range of 58–120?nm, does not result in effective changes of the charge state of Eu^{3 +} → Eu^{2 +} activator, in contrast to CaF₂: Eu nanoparticles. The maximum light output of X-ray excited luminescence of BaF₂: Eu nanophosphors in the 590?nm emission band of Eu³⁺ ion was observed at an annealing temperature of 600°C with the average size of nanoparticles 67?nm. The subsequent growth of annealing temperatures, especially in the range of 800–1000°C, causes decrease in the light output of X-ray excited luminescence due to the increase of defect concentration in the lattice as a result of sharp increase of nanoparticle sizes and their agglomeration. In BaF₂: Eu nanoparticles of 58?nm size, according to the thermostimulated luminescence (TSL) spectrum, transformation of Eu³⁺ → Eu²⁺ under the influence of long-time X-ray irradiation was revealed for the peak of 151?K. Thus, X-ray excited luminescence spectra of BaF₂: Eu nanophosphors are formed predominantly due to the emission of Eu³⁺ ions, while emission of Eu²⁺ ions is observed in the TSL spectra.     

Combined Rietveld refinement of BaMgAl10O17:Eu using X-ray and neutron powder diffraction data

The phosphor, BaMgAl₁₀O₁₇:Eu²⁺, showing a blue emission band at about 450 nm was prepared by a normal solid-state reaction using BaCO₃, Al₂O₃, MgO and Eu₂O₃ as starting materials with AlF₃ as a flux. The study of combined Rietveld refinement and photoluminescence spectra was carried out to determine the structural parameters, such as lattice constants, the valence state of Eu, the site preference of Mg and site fractions of Mg and Eu. The occupancies of Eu and Mg were 0.022 and 0.526, respectively. The valence state of Eu was the divalent state because there was only one broad line at about 450 nm in the photoluminescence spectrum. The site preference of Mg atoms was the tetrahedral site of Al atoms surrounded by oxygen atoms in the spinel block. Lattice parameters decreased due to the difference of two ionic radii, Eu²⁺(1.09 Å) and Ba²⁺(1.34 Å), compared with those of BaMgAl₁₀O₁₇.     

Investigation of 515 nm green-light emission for full color emission LaAlO3 phosphor with varied valence Eu

Photoluminescence and lifetime decay properties of varied valence Eu were employed to investigate the luminescence mechanism of green-light emission positioned at ∼515 nm for full color emission LaAlO₃ phosphor co-doped with Eu²⁺ and Eu³⁺. The enhanced ⁵D₂→⁷F₃ transition emission of Eu³⁺ was assigned for this green emission. Energy transfer between Eu²⁺ and ⁵D₂ level of Eu³⁺ was proposed, which results in the enhancement of ⁵D₂→⁷F₃ transition emission. In addition, energy transfer relations between host-Eu and charge transfer state (CTS)-Eu were also discussed associated with the PLE spectra and band schemes.     

A-site and B-site substitutions and the emission properties of Eu3+ ions in ABO3 –type cubic perovskite: A case study of BaZrO3

The emission properties of the rare earth (RE) elements have been found to be sensitive to the local lattice environment around them, and could be employed for probing the local lattice environment. Because each constituent ion of a material should have its own particular structural environment, the emission profiles in RE elements depend strongly on the doping sites of RE elements inside the host crystals. We investigated the emission properties of the Eu³⁺ ion doped BaZrO₃ (BaZrO₃:Eu) with doping site dependence (A-site vs. B-site), as well as ambient dependence in the post-annealing process. The site-selective doping was identified from the Rietveld refinement analysis on the XRD patterns of our BaZrO₃:Eu samples. Photoluminescence and photoluminescence excitation measurements showed that the emission properties of the samples with the Eu³⁺ ions substituted at Zr sites revealed much greater emission properties than those at the Ba sites. This behavior was found to accord with the change in intensity ratio of ⁵D₀ → ⁷F_0,2 to ⁵D₀ → ⁷F₁ in Eu ions, which should be a measure of the local lattice asymmetry around the Eu ions. We also found that with post-annealing in H₂ atmosphere, the emission intensities of the Eu ions increased significantly, while with post-annealing in O₂ atmosphere, they were suppressed. Our findings indicated that the cation/oxygen vacancies could change the local lattice environment around the Eu ions, as well as the valence states of Eu ions, depending on the doping site in the cubic perovskite.     

Photoluminescence and radioluminescence study of NaMgF3:Eu nanoparticles

Photoluminescence (PL) and radioluminescence (RL) measurements were made on small (∼25 nm) NaMgF₃ nanoparticles doped with Eu concentrations ranging from 0.1% to 5%. We find that they contained Eu³⁺, Eu²⁺, and an additional unidentified defect with a broad PL emission ∼470 nm. Similar to previous measurements on larger (57 nm–77 nm) NaMgF₃:Eu nanoparticles with 1% Eu and 5% Eu, we find that the PL lifetime decreases with increasing Eu concentration that can be attributed to Eu energy transfer to non-radiative recombination sites. However, there is no change in the fraction of Eu³⁺ distorted sites. The ∼470 nm PL defect peak was also reported for larger nanoparticles, which suggests that this peak arises from similar unidentified point defects. However, the activated non-radiative decay for the small nanoparticles has a significantly lower activation energy. The Eu³⁺ RL decreases by only 2.3% at 10 kGy for low Eu concentrations.     

Development of zeolite-derived novel aluminosilicate phosphors

In this research, zeolite-derived aluminosilicate phosphors were synthesized through the ion exchange route. Red light-emitting property of Eu³⁺-doped aluminosilicate phosphors were discussed from a view point of the Eu content, heat-treatment condition and the oxidation state of Eu ions. The crystalline phase of the host aluminosilicates could be successfully controlled as designed based on the published NaAlO₂–SiO₂ binary phase diagram. Orange-red emission peaks derived from the ⁵D₀→⁷F_j (j=0, 1, 2, 3, 4) transition of Eu³⁺ were observed around 590–700 nm, and 4f⁶5d→4f⁷ transition of Eu²⁺ was observed at around 400–500 nm. The relative intensity I(⁵D₀→⁷F₂) of the dominant emission peak at 612 nm increased consistently with the Eu content. The results of the XANES spectroscopy analysis revealed that Eu²⁺ ion in the 1400 °C as heat-treated host aluminosilicate were successfully converted to Eu³⁺ by the additional annealing at 1100 °C. The Eu contents and heat-treatment conditions were determined to exhibit the best performance as a red phosphor, which were 10 wt% and 1500 °C, respectively     

Optical properties of (ZnO)0.5(P2O5)0.5 glasses doped with Gd2O3:Eu nanoparticles and Eu2O3

Binary (ZnO)_0.5(P₂O₅)_0.5 glasses doped with Eu₂O₃ and nanoparticles of Gd₂O₃:Eu were prepared by conventional melt-quench method and their luminescence properties were compared. Undoped (ZnO)_0.5(P₂O₅)_0.5 glass is characterized by a luminescent defect centre (similar to L-centre present in Na₂O-SiO₂ glasses) with emission around 324 nm and having an excited state lifetime of 18 ns. Such defect centres can transfer the energy to Eu³⁺ ions leading to improved Eu³⁺ luminescence from such glasses. Based on the decay curves corresponding to the ⁵D₀ level of Eu³⁺ ions in both Gd₂O₃:Eu nanoparticles incorporated as well as Eu₂O₃ incorporated glasses, a significant clustering of Eu³⁺ ions taking place with the latter sample is confirmed. From the lifetime studies of the excited state of L-centre emission from (ZnO)_0.5(P₂O₅)_0.5 glass doped with Gd₂O₃:Eu nanoparticles, it is established that there exists weak energy transfer from L-centres to Eu³⁺ ions. Poor energy transfer from the defect centres to Eu³⁺ ions in Gd₂O₃:Eu nanoparticles doped (ZnO)_0.5(P₂O₅)_0.5 glass has been attributed to effective shielding of Eu³⁺ ions from the luminescence centre by Gd-O-P type of linkages, leading to an increased distance between luminescent centre and Eu³⁺ ions.     

A Mössbauer study of La1−xEuxB6 compounds synthesized at high pressure and temperature

A series of hexaborides La_1?xEu_xB₆ (x=0.0–1.0) were synthesized under a pressure of 3.5 GPa and at a temperature of 1600^○C using La₂O₃, Eu₂O₃ and amorphous boron as the starting materials. The products were characterized by X‐ray Diffraction (XRD) and Mössbauer spectroscopy. XRD data analysis shows that all samples crystallize in a cubic CsCl‐type structure, and the cell volume increases with x. Room temperature ¹⁵¹Eu Mössbauer measurements reveal that Eu ions in all samples are in the divalent state, except for the x=1.0 sample where a small amount of Eu³⁺ ions was detected. The quadrupole splitting of the Eu²⁺ ions is positive. Eu ions were reduced from trivalent to divalent during the high‐pressure and ‐temperature processes. The isomer shifts of the Eu²⁺ ions are all smaller than ?12.5 mm/s, suggesting that there is no valence fluctuation in the samples. The hexaborides doped by divalent Eu are not metallic.     

Enhanced UV-excited luminescence of europium ions in silver/tin-doped glass

Glasses containing silver, tin and europium were prepared by the melt-quenching technique with silver nanoparticles (NPs) being embedded upon heat treatment (HT). An intensification of Eu³⁺ ions emission was observed for non-resonant excitation around 270 nm, corresponding to UV absorption in the material. Optical measurements suggest that light absorption occurs at single Ag⁺ ions and/or twofold-coordinated Sn centers followed by energy transfer to europium which results in populating the ⁵D₀ emitting state in Eu³⁺. After HT at 843 K, a quenching effect is observed on Eu³⁺ luminescence with increasing holding time in the 350–550 nm excitation range. The quenching effect shows with the presence of Ag NPs which may provide multipole radiationless pathways for excitation energy loss in europium ions.     

Development of new elasticoluminescent material SrMg2(PO4)2:Eu

We have succeeded in developing a new elasticoluminescent (elastico-L) material SrMg₂(PO₄)₂:Eu (SMPE), which emits purple light clearly observable with the naked eye. SMPE can be synthesized at a firing temperature, which is several hundred degrees Kelvin lower than that for other materials of this group. Based on a comparison between elastico-L emission spectrum and photoluminescence spectrum, the emission was identified to be due to electron transition from an excited state 4f⁶5d¹ to the ground state 4f⁷ in Eu²⁺ ions. While the emission gradually decayed as stress was applied repeatedly, it recovered completely upon irradiation with UV light (365 nm). This behavior, characteristic to elastico-L materials of the defect-controlled type, suggests that deep charge traps are involved in the emission process. In this paper, the elastico-L mechanism in SMPE is discussed in detail with reference to its thermoluminescence and electroluminescence spectra.     

Photoluminescence and gamma-ray irradiation of SrAl2O4:Euand Y2O3:Eu phosphors

Y₂O₃:Eu³⁺ phosphor is a very attractive material for use as a red phosphor in many fields. SrAl₂O₄:Eu²⁺ belongs to long lasting phosphor (LLP) and it is a useful bluish-green luminescence material, which can also be a promising candidate as a simple and easy-to-use radiation detection element for visual display of two dimensional radiation distributions. In the present study, both these two kinds of phosphors were synthesized using high temperature solid state reactions. In our work, the influence of gamma-ray irradiation on the properties of these two kinds of phosphors was studied by comparing photoluminescence, brightness and the decay curve of unirradiated and gamma-ray-irradiated samples. Conclusions from the present work can be briefly summarized as follows. In irradiated samples, the brightness is decreased without sensible change in the wavelength distribution of the luminescence spectrum and in the decay kinetic upon gamma exposure. Moreover, the emission due to Eu³⁺→Eu²⁺ conversion in Y₂O₃:Eu³⁺ phosphors was not observed in our sample after irradiation to high exposure. Also the brightness of SrAl₂O₄:Eu²⁺ phosphor turned out to decrease after the exposition to ionizing radiation while the luminescence wavelength distribution remained unchanged. The reason for the effect of gamma-ray irradiation on the properties of phosphors is also discussed in the paper.     

Preparation of novel phosphor using intercalation of tobermorite

The emission intensity of phosphors is often subject to concentration quenching after doping of the activator in the host crystal rises above a certain limit. This study describes the preparation of novel phosphors based on tobermorite that do not exhibit concentration quenching. In the preparation of phosphors, Eu³⁺ ions are exchanged with intercalated Ca²⁺ ions within the tobermorite by dipping in EuCl₃ solution. The emission intensity of the Eu³⁺ doped tobermorite increased with increasing Eu/Ca atomic ratio and attained a maximum value of 8.6% for a Eu/Ca atomic ratio of 0.22. Heating of the phosphor at 800 °C resulted in a three-fold improvement in emission intensity.     

Photoelectron spectra and surface valence fluctuation of Eu in the misfit-layer compound {(EuS)1.15}1.5NbS2

The 1.5Q/1 H type of the misfit layer compound {(EuS)_1.15}_1.5NbS₂ has been studied by X-ray photoelectron spectroscopy. Eu 3d, 4d, 4f and 5p spectra are measured with Al and MgKα radiation. Their intensities are analyzed, taking the escape depth of photoelectrons emitted from the core levels into account. The results indicate that valence transfer of nearly-half Eu²⁺ ions to Eu³⁺ happens in the outermost surface layer and a reduced Eu–S distance brings about surface rearrangement. It is confirmed that Eu²⁺ and Eu³⁺ coexist in a bulk, in consistency with bond valence calculations and Mössbauer spectra. The XPS spectra are well interpreted in terms of the multiplet structures of Eu²⁺ and Eu³⁺.     

Characterization and photoluminescence studies of Eu<Superscript>2+</Superscript>-doped BaSO<Subscript>4</Subscript> phosphor prepared by the recrystallization method

Eu doped BaSO₄ was prepared by the recrystallization method and characterization of the material was done by using X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and Fourier transform infrared spectroscopy (FTIR) techniques. From the XRD pattern of Eu doped BaSO₄ compound, it was found that the prominent phase formed was BaSO₄ and traces of other phases were very weak and the result of FTIR spectrum of BaSO₄:Eu shows that the sulfur-oxygen stretch was found at around 1100 cm⁻¹. The room-temperature PL spectra of the Eu doped BaSO₄ sample showed one peak centered at 374 nm, which is the characteristic emission of Eu²⁺ ion. This emission band at 374 nm corresponds to the 4f⁶ 5d→4f⁷ (⁸S_7/2) transitions of Eu²⁺ ions. The excitation spectrum taken at the wavelength 374 nm extends over a wide range of wavelengths from 220–350 nm with a strong peak at around 260 nm. Furthermore, the present sample shows good crystal quality and high photoluminescence sensitivity. Hence our results suggest possible potential applications of Eu doped BaSO₄ phosphor in optoelectronic devices.     

Luminescence spectroscopy of Eu3+ and Mn2+ ions in MgGa2O4 spinel

Photoluminescence and excitation spectra of the spinel-type MgGa₂O₄ with 0.5 mol. % Mn²⁺ ions and Eu³⁺ content from 0 to 8 mol. % have been investigated in this work at room temperature. Polycrystalline samples were synthesized via high-temperature solid-state reaction method. Photoluminescence spectra of all samples exhibit host emission presented by a broad “blue” band peaking ∼430 nm, which consists of at least three elementary bands that correspond to different host defects. Excitation of the host luminescence showed the broad band with a maximum at 360 nm. Characteristic bands of d–d transitions of Mn²⁺ ions and f–f transitions of Eu³⁺ ions together with charge-transfer bands (CTB) of these ions were also found on the excitation spectra. Mn²⁺ and Eu³⁺ co-doped samples emit in green and red spectral regions. Mn²⁺ ions are responsible for the green emission band at 505 nm (⁴Т₁→⁶А₁ transition). The studies of photoluminescence spectra of activated samples with different Eu³⁺ ions content show characteristic f–f luminesecence of Eu³⁺ ions. The maximum of Eu³⁺ emission was found at 618 nm (⁵D₀→⁷F₂) and optimal concentration of activator ions was around 4 mol. %.     

Stability of divalent/trivalent oxidation state of europium in some Sr-based inorganic compounds

This work investigates the stability of Eu²⁺ and Eu³⁺ in some Sr-based inorganic compounds. Generally reducing condition is adopted in order to obtain Eu²⁺, however, the Eu doped SrAl₂O₄/SrLaAlO₄ case indicates that for some compounds Eu³⁺ is stabilized even in reducing atmosphere. Bond valence method is applied to explain this phenomenon and it reveals that crystal structure also determines the valence state of europium cations along with reducing/oxidizing condition. An analysis of other Eu doped Sr-based materials is performed which shows the relationship between Eu²⁺/Eu³⁺ stability and the Global Instability Index (GII). This research provides a guideline for synthesizing specific novel Eu²⁺/Eu³⁺ phosphors.     

Optical and structural properties of Eu-diffused and doped ZnO nanowires

Single crystal ZnO nanowires diffused with europium (Eu) from a solid source at 900 °C for 1 h or doped with Eu during growth have been characterized. The ZnO nanowires were grown by chemical vapor deposition on Si substrates employing Au as a catalyst. The diameter of the resulting nanowires was 200 nm with a length of 1 μm. Photoluminescence spectra excited by a He–Cd laser at room temperature showed the green luminescence at 515 nm in Eu-diffused nanowires. A small red shift of near-band-edge emission of ZnO nanowires was observed in the diffused wires, but sharp emission from Eu³ ions was not present. Transmission electron microscopy shows crystalline Eu₂O₃ formation on the diffused nanowire surface, which forms a coaxial heterostructure system. When Eu was incorporated during the nanowire growth, the sharp ⁵D_O–⁷F₂ transition of the Eu³⁺ ion at around 615 nm was observed.     

A study of the luminescence properties of Eu -doped borate crystal and glass

Eu³⁺-doped La₂O₃-3B₂O₃ crystal and glass were prepared by solid state reaction under different calcination temperature. The emission spectrum, phonon sideband (PSB), charge transfer band (C.T.B.) and lifetime of the Eu³⁺ ion in the two materials, with the same composition but with different phase, were investigated. With excitation at 394 nm light, the glass presented intense 618 nm red luminescence; however, the crystal gave 696 nm red luminescence. This difference is ascribed to the discrepancy of the local structure around the Eu³⁺ ion in the crystal and glass. To clarify the discrepancy, the coordination of Eu³⁺ in the borate glass and crystal was investigated. The results show that Eu³⁺ ions formed a complex Eu³⁺-O²⁻-B³⁺ bond in glass; however, in the crystal, it formed a complex Eu³⁺-O²⁻-La³⁺ bond. The lifetime of Eu³⁺ ions in the crystal and the glass is 3.08 ms and 1.98 ms, respectively. This indicates that the discrepancy in the local structure around the Eu³⁺ ions between the crystal and the glass leads to different fluorescence properties.