Characterization of the VUV excitation spectrum of BaZr(BO3)2:Eu

The excitation spectra of M (M=Si⁴⁺, Ti⁴⁺) and Eu³⁺ co-doped BaZr(BO₃)₂, BaZrO₃:Eu and La₂Zr₂O₇:Eu in the vacuum ultraviolet (VUV) regions of 110-300 nm are investigated and the host-lattice absorption are characterized. The result indicated that BaZr(BO₃)₂:Eu³⁺ phosphor has a strong absorption under the VUV excitation, and in the host-lattice excitation, the strong band at 130-160 nm could be due to the BO₃ atomic groups; the band at 160-180 nm is related to the excitation of Ba-O; 180-200 nm corresponds to the charge transfer (CT) transition of Zr-O. The band at 200-235 nm due to the CT band of Eu³⁺-O²⁻ and a bond valence study explained the observed weak CT band of Eu³⁺-O²⁻ in the excitation spectra of BaZr(BO₃)₂:Eu³⁺. The emission results show that Si⁴⁺ can sensitize luminescence in the host of BaZr(BO₃)₂:Eu but Ti⁴⁺ has no improvement effect on luminescence.     

Excitation energy dependent chromaticity of BaZr(BO3)2:Eu

The luminescence properties of BaZr(BO₃)₂:5% Eu were investigated under ultraviolet (UV) and vacuum ultraviolet (VUV) excitation and different luminescence behaviors were observed by different excitation energies. After the analyses of the luminescence spectra, the result indicates that Eu³⁺ occupying non-centrosymmetric sites Ba²⁺ can be excited preferentially under 254 nm excitation, while Eu³⁺ occupying centrosymmetric sites Zr⁴⁺ can be excited preferentially under 147 nm excitation.     

Photoluminescence properties of Sr(Y, Gd)2O4:Euunder VUV excitation

Vacuum ultraviolet (VUV) excitation and photoluminescence (PL) properties of Sr(Y, Gd)₂O₄ doped with Eu³⁺ were studied. The excitation spectra of SrY_1.9Eu_0.1O₄ and SrY_1.0Gd_0.9Eu_0.1O₄ had absorption in the VUV region with the absorption band edge at 149 nm, while the absorption of SrGd_1.9Eu_0.1O₄ in the VUV region was weak, which could be due to the narrow host band gap and no efficient energy transfer occurred in the VUV region. The PL spectra of all samples exhibited the characteristic emission of Eu³⁺ with the red ⁵D₀-⁷F₂ transition (611 nm) being the most prominent group.     

Synthesis and luminescence properties of Eu, Ce and Tb-activated Sr3La2(BO3)4 under UV excitation

The spectroscopic properties in UV-excitable range for the phosphors of Sr₃La₂(BO₃)₄:RE³⁺ (RE³⁺=Eu³⁺, Ce³⁺, Tb³⁺) were investigated. The phosphors were synthesized by conventional solid-state reactions. The photoluminescence (PL) spectra and commission international de I'Eclairage (CIE) coordinates of Sr₃La₂(BO₃)₄:RE³⁺ were investigated. The f-d transitions of Eu³⁺, Ce³⁺ and Tb³⁺ in the host lattices are assumed and corroborated. The PL and PL excitation (PLE) spectra indicate that the main emission wavelength of Sr₃La₂(BO₃)₄:Eu³⁺ is 611 nm, and Sr₃La₂(BO₃)₄:Ce³⁺ shows dominating emission peak at 425 nm, while Sr₃La₂(BO₃)₄:Tb³⁺ displays green emission at 487, 542, 582 and 620 nm. These phosphors were prepared by simple solid-state reaction at 1000 °C. There are lower reactive temperature and more convenient than commercial phosphors. The Sr₃La₂(BO₃)₄:Tb³⁺ applied to cold cathode fluorescent lamp was found to emit green light and have a major peak wavelength at around 542 nm. These phosphors may provide a new kind of luminescent materials under ultraviolet excitation.     

Red emission in B- and Li-doped SrAl2O4:Eu phosphor under UV excitation

Samples of SrAl₂O₄:Eu³⁺ doped with B³⁺ and SrAl₂O₄:Eu³⁺ co-doped with B³⁺ and Li⁺ have been prepared by the solid-reaction method. The influence of B³⁺ and Li⁺ contents on luminescence property has been investigated. It is found that the substitution of B³⁺ for Al³⁺ greatly improves red emission intensity at 591, 615 and 701 nm. The dopant Li⁺ as charge compensator in SrAl₂O₄:Eu³⁺, B³⁺ can further enhance luminescence intensity. The strongest red emission is obtained in the Sr(Al_1.9, B_0.1)O₄:Eu_0.02³⁺, Li⁺_0.02 sample. The developed phosphors can be efficiently excited by ultraviolet (UV) light from 350 to 480 nm, which indicates that B³⁺ and Li⁺ co-doped SrAl₂O₄:Eu³⁺ is a good candidate phosphor applied in solid-state lighting in conjunction with white UV light-emitting diodes (LEDs).     

Eu3+ emission in SrAl2B2O7 based phosphors

Eu³⁺ doped SrAl₂B₂O₇ phosphors were fabricated by the wet method. The structures of the phosphors were characterized by XRD. The doping content of Eu³⁺ ions in SrAl₂B₂O₇:Eu³⁺ phosphors are 1%, 4%, 6%, 8%, 10% (molar fraction), respectively. Luminescence properties were analyzed by measuring the excitation and photoluminescence spectra. The luminescent properties of SrAl₂B₂O₇:Eu³⁺ phosphors are discussed. It is shown that from 4% to 6% of doping content of Eu³⁺ ions under 392 nm excitation in SrAl₂B₂O₇:Eu³⁺ phosphors is optimum.     

Synthesis and optical properties of Er and Eu doped SrAl2O4 phosphor ceramic

We report, for the first time on luminescence from a Er³⁺ doped SrAl₂O₄ phosphor. Effects of Eu³⁺ doping were also studied. The influence of rare-earth doping in crystal structure and its optical properties were analysed by means of X-ray diffraction (XRD), Raman scattering, optical absorption, excitation and emission (PL) spectroscopy, thermally stimulated luminescence (TSL) and scanning electron microscope (SEM). Luminescence spectra and luminescence decay curves for Er³⁺ transitions in the near infrared region were recorded. The PL maximum for Eu doped SrAl₂O₄ is obtained at 620 nm and corresponds to the orange region of the spectrum. Diffraction patterns reveal a dominant phase, characteristic of the monoclinic SrAl₂O₄ compound and the presence of dopants has no effect on the basic crystal structure of SrAl₂O₄. The shapes of the glow curves are different for each dopant irradiated with either a ⁹⁰Sr-⁹⁰Y beta source, or UV light at 311 nm, and in detail the TL signals differ somewhat between Er and Eu dopants.     

PHASE DEPENDENCE OF LUMINESCENT EMISSION OF Eu2+ DOPED SrAl2O4

In this work, we made five samples of SrAl₂O₄: Eu²⁺, Dy³⁺, the α phase and β phase SrAl₂O₄:Eu²⁺,Dy³⁺ powder and pellet samples, and α phase single crystal. We have measured the emission spectra of all the samples. All the emission peaks are around 520 nm, which correspond to the transition from 4f⁶5d¹(²E_g) to 4f⁷(⁸S_7/2) of Eu²⁺ in SrAl₂O₄ host. The intensity of emission of the β phase is stronger than that of the α phase. We believe that it is because the Eu²⁺ ions have occupied the two types of sites in the α phase SrAl₂O₄ host and the lifetime of the transition of Eu²⁺ in the A site is longer than that in the B site. This result also proves that the β phase of the material is brighter than the α phase. In addition, the β phase can be achieved by quenching technique.     

Luminescent properties of SrAl2B2O7: Ce, Tb

By using metal nitrates as starting materials, SrAl₂B₂O₇: Tb³⁺ and SrAl₂B₂O₇: Ce³⁺, Tb³⁺ powder phosphors were prepared by sol-gel method. X-ray diffraction (XRD), photoluminescence excitation and emission, as well as kinetic decays were employed to characterize the resulting samples. The results show that energy transfers from Ce³⁺ to Tb³⁺ ions. The emission intensity of Tb³⁺ ions in SrAl₂B₂O₇ could be greatly intensified when Ce³⁺ ions are doped into SrAl₂B₂O₇: Tb³⁺. The decay times of SrAl₂B₂O₇: Tb³⁺ were prolonged when Ce³⁺ ions were doped. The doping of Ce³⁺ ions not only improved the luminescent intensity, but also made the materials gets stable luminescent properties.     

A study on the luminescence properties of CaAl2B2O7:Eu phosphor

The blue-emitting CaAl₂B₂O₇:Eu²⁺ phosphor was prepared at 800 °C by a modified solid-state reaction. The results of X-ray powder diffraction (XRD) analysis confirmed the formation of CaAl₂B₂O₇:Eu²⁺. Photoluminescence (PL) spectroscopy showed that the phosphor could be excited efficiently by UV-vis light from 250 to 410 nm, and exhibit blue emission (460 nm). The emission intensity of CaAl₂B₂O₇:Eu²⁺ phosphor varies with the increase of Eu²⁺concentration. The mechanism of resonance-type energy transfer from Eu²⁺ to Eu²⁺ was established to be electric multipole-multipole interaction. TEM images showed that the grain size of CaAl₂B₂O₇:Eu²⁺ is about 45 nm, which is in full agreement with the theoretical calculation data from the XRD patterns.     

Luminescent properties of (Y,Gd)BO3:Bi,RE (RE=Eu, Tb) phosphor under VUV/UV excitation

Bi³⁺- and RE³⁺-co-doped (Y,Gd)BO₃ phosphors were prepared and their luminescent properties under vacuum ultraviolet (VUV)/UV excitation were investigated. Strong red emission for (Y,Gd)BO₃:Bi³⁺,Eu³⁺ and strong green emission for (Y,Gd)BO₃:Bi³⁺,Tb³⁺ are observed under VUV excitation from 147 to 200 nm with a much broader excitation region than that of single Eu³⁺-doped or Tb³⁺-doped (Y,Gd)BO₃ phosphor. Strong emissions are also observed under UV excitation around 265 nm where as nearly no luminescence is observed for single Eu³⁺-doped or Tb³⁺-doped (Y,Gd)BO₃. The luminescence enhancement of Bi³⁺- and RE³⁺-co-doped (Y,Gd)BO₃ phosphors is due to energy transfer from Bi³⁺ ion to Eu³⁺ or Tb³⁺ ion not only in the VUV region but also in the UV region. Besides, host sensitization competition between Bi³⁺ and Eu³⁺ or Tb³⁺ is also observed. The investigated phosphors may be preferable for devices with a VUV light 147-200 nm as an excitation source such as PDP or mercury-free fluorescent lamp.     

Persistent luminescence dosimetric properties of UV-irradiated SrAl2O4:Eu, Dy phosphor

Current radiation dosimetry methods involve the release of trapped charge carriers in the form of electrons-holes pairs generated by irradiation exposure of the dosimetric materials. Thermal and optical stimulations of the irradiated material freed the trapped charges that eventually recombine with interband centers producing the emission of light. The integrated intensity of the emitted light is proportional to the radiation dose exposure. In this work, we present an UV radiation dosimetry technique based on the characteristic persistence luminescence (PLUM) 4f⁶5d¹→4f⁷ electronic transition of Eu²⁺ ions in SrAl₂O₄:Eu²⁺, Dy³⁺. The dose assessment is carried out by measuring the PLUM signal integrated during a certain time. The PLUM performance of SrAl₂O₄:Eu²⁺, Dy³⁺ phosphor exhibited a linear behavior for the first 50 s of UV irradiation. For higher UV time exposure the behavior is sublinear with no apparent saturation during a 10 min period. The PLUM dosimetry response was performed at 400 nm that corresponds to the main band component of the PLUM excitation spectrum in the 250-500 nm range. The main advantage of a dosimeter device based on the PLUM of SrAl₂O₄:Eu²⁺, Dy³⁺ is that neither thermal nor optical stimulation is required, avoiding the need of cumbersome electronic photo/thermal stimulation equipment. Due to the highly efficient 250-500 nm PLUM response of SrAl₂O₄:Eu²⁺, Dy³⁺, it could have potential application as UV radiation dosimeter in the UV range of grate human health concerns caused by UV solar radiation.     

A potential red phosphor LiGd(MoO4)2:Eu for light-emitting diode application

Eu³⁺-doped LiGd(MoO₄)₂ red phosphor was synthesized by solid-state reaction, and its photoluminescent properties were measured. The effect of Eu³⁺ doping concentration on PL intensity was investigated, and the optimum concentration of Eu³⁺ doped in LiGd(MoO₄)₂ was found to be 30 mol%. Compared with Y₂O₂S:0.05Eu³⁺, Na_0.5Gd_0.5MoO₄:Eu³⁺ and KGd(MoO₄)₂:Eu³⁺, the LiGd(MoO₄)₂:Eu³⁺ phosphor showed a stronger excitation band around 395 nm and a higher intensity red emission of Eu³⁺ under 395 nm light excitation. For the first time, intensive red light-emitting diodes (LEDs) were fabricated by combining phosphor and a 395 nm InGaN chip, confirming that the LiGd(MoO₄)₂:Eu³⁺ phosphor is a good candidate for LED applications.     

Fluorescence emission spectrum and energy transfer in Eu and Mn co-doped Ba2Ca(BO3)2 phosphors

Eu²⁺ and Mn²⁺ co-doped Ba₂Ca(BO₃)₂ phosphors yield two emission bands consisting of green and red components under the excitation of 360 nm, which shows a great potential for white LEDs. Effective energy transfer occurs in Eu²⁺/Mn²⁺ co-doped Ba₂Ca(BO₃)₂ host due to the large spectral overlap between the emission of Eu²⁺ and the excitation of Mn²⁺. The energy transfer from Eu²⁺ to Mn²⁺ is thoroughly investigated by their excitation, emission and photoluminescence decay behaviors, and is demonstrated to be via the dipole–quadrupole interaction.     

Luminescence optimization of Eu-doped LnAl3(BO3)4 (Ln=Y, Gd) red phosphor using spray pyrolysis

LnAl₃(BO₃)₄:Eu³⁺ (Ln=Y, Gd) red phosphor particles were prepared by spray pyrolysis and the luminescent intensity under vacuum ultraviolet (VUV) excitation was investigated by changing Eu³⁺ content, Y/Gd molar ratio, and boron content. The concentration quenching for Eu³⁺ activator was observed at 5 at%. The highest luminescent intensity at 615 nm due to the ⁵D₀→⁷F₂ transitions of Eu³⁺ was achieved when the ratio of Gd to Y was 0.55. The R/O ratio (obtained by dividing the red emission intensity at 615 nm with the orange one at 592 nm), however, was not influenced by the G/Y ratio. Using excess boron, up to 135% of the stoichiometric quantity, improved the emission intensity of LnAl₃(BO₃)₄:Eu³⁺ red phosphor. According to XRD analysis, the sample prepared using boron of a stoichiometric quantity had YBO₃ phase as a minor phase. Such YBO₃ phase progressively disappeared with an increase in the excess quantity of boron, which was responsible for the enhancement of emission intensity. In addition, the R/O ratio became larger and larger by increasing the excess content of boron due to a reduction in the symmetry of Y site. Consequently, both the emission intensity and the color coordinate of LnAl₃(BO₃)₄:Eu³⁺ red phosphors were successfully optimized in terms of the Y/Gd ratio and the excess quantity of boron in spray pyrolysis.     

Effective energy transfer between Ceand Eu in CaAl2Si2O8 host under vacuum ultraviolet illumination

We presented the energy transfer from Ce³⁺ to Eu²⁺ in CaAl₂Si₂O₈ host. The Ce³⁺-doped CaAl₂Si₂O₈ phosphor had a strong emission band at 378 nm under the vacuum ultraviolet (VUV) light. This emission spectrum of Ce³⁺ well overlapped with the excitation spectrum of Eu²⁺ under the UV illumination. As a result, the energy transfer from Ce³⁺ to Eu²⁺ in CaAl₂Si₂O₈ matrix was observed under VUV excitation, which resulted in a significant enhancement of the emission peak intensity at 446 nm. More details about the luminescent properties were presented.     

Synthesis and crystal structures and luminescent properties of divalent europium-doped Ba2ZnSi2O7 and BaZn2Si2O7

The monoclinic Ba₂ZnSi₂O₇:Eu²⁺ blue-green-emitting phosphor and the orthorhombic BaZn₂Si₂O₇:Eu²⁺ green-emitting phosphor were prepared by combustion-assisted synthesis method as the fluorescent materials for ultraviolet-light-emitting diodes (UV-LEDs) performed as a light source. The crystallinity and luminescence were investigated using X-ray diffraction (XRD) and photoluminescence (PL) spectroscopy. Pure monoclinic Ba₂ZnSi₂O₇ and orthorhombic BaZn₂Si₂O₇ crystallize completely at 1100 °C. The doped Eu²⁺ ions did not cause any significant change in the host structure. The emission spectra presented an emission position red shift of up to 16 nm from Ba₂ZnSi₂O₇:Eu²⁺ to BaZn₂Si₂O₇:Eu²⁺. The excitation spectra of Ba₂ZnSi₂O₇:Eu²⁺ and BaZn₂Si₂O₇:Eu²⁺ were broad-banding, extending from 260 to 465 nm, which match the emission of UV-LEDs.     

Synthesis and luminescence properties of needle-like SrAl2O4:Eu, Dy phosphor via a hydrothermal co-precipitation method

Needle-like SrAl₂O₄:Eu²⁺, Dy³⁺ phosphors had been prepared by calcining the precursors obtained from hydrothermal process at the temperature of 1100 °C in a weak reductive atmosphere of active carbon. The crystal structure, morphology and optical properties of the composites were characterized. X-ray diffraction (XRD) patterns illustrated that the single-phase SrAl₂O₄ was formed at 1100 °C, which is much lower than that prepared by the traditional method. The transmission electron microscope (TEM) observation revealed the precursors and the resulted SrAl₂O₄:Eu²⁺, Dy³⁺ phosphors had well-dispersed distribution and needle-like morphology with an average diameter about 150 nm at the center and the length up to 1 μm. After irradiation by ultraviolet radiation with 350 nm for 5 min, the phosphors emit green color long-lasting phosphorescence corresponding to the typical emission of Eu²⁺ ion, both the PL spectra and luminance decay revealed that the phosphors had efficient luminescent and long lasting properties.     

The effect of different gas atmospheres on luminescent properties of pulsed laser ablated SrAl2O4:Eu,Dy thinfilms

SrAl₂O₄:Eu²⁺,Dy³⁺ thin films were grown on Si (1 0 0) substrates using the pulsed laser deposition (PLD) technique to investigate the effect of vacuum, oxygen (O₂) and argon (Ar) deposition atmospheres on the structural, morphological, photoluminescence (PL) and cathodoluminescence (CL) properties of the films. The films were ablated using a 248 nm KrF excimer laser. Atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS) and fluorescence spectrophotometry were used to characterize the thin films. Auger electron spectroscopy (AES) combined with CL spectroscopy were employed for the surface characterization and electron-beam induced degradation of the films. Better PL intensities were obtained from the unannealed films prepared in Ar and O₂ atmospheres with respect to those prepared in vacuum. A stable green emission peak at 515 nm, attributed to 4f⁶5d¹→4f⁷ Eu²⁺ transitions were obtained with less intense peaks at 619 nm, which were attributed to transitions in Eu³⁺. After annealing the films prepared in vacuum at 800 °C for 2 h, the intensity of the green emission (520 nm) of the thin film increased considerably. The amorphous thin film was crystalline after the annealing process. The CL intensity increased under prolonged electron bombardment during the removal of C due to electron stimulated surface chemical reactions (ESSCRs) on the surface of the SrAl₂O₄:Eu²⁺, Dy³⁺ thin films. The CL stabilized and stayed constant thereafter.     

Surface characterization and luminescent properties of SrAl2O4:Eu,Dy nano thin films

SrAl₂O₄:Eu²⁺, Dy³⁺ thin films were grown on Si (1 0 0) substrates in different atmospheres using the pulsed laser deposition (PLD) technique. The effects of vacuum, oxygen (O₂) and argon (Ar) deposition atmospheres on the structural, morphological and photoluminescence (PL) properties of the films were investigated. The films were ablated using a 248 nm KrF excimer laser. Improved PL intensities were obtained from the unannealed films prepared in Ar and O₂ atmospheres compared to those prepared in vacuum. A stable green emission peak at 520 nm, attributed to 4f⁶5d¹→4f⁷ Eu²⁺ transitions was obtained. After annealing the films prepared in vacuum at 800 °C for 2 h, the intensity of the green emission (520 nm) of the thin film increased considerably. The amorphous thin film was crystalline after the annealing process. The diffusion of adventitious C into the nanostructured layers deposited in the Ar and O₂ atmospheres was most probably responsible for the quenching of the PL intensity after annealing.