Rare‐earth materials for use in the dark

Abstract— Recently, it was found that some materials doped with rare‐earth ions show bright and long‐lasting phosphorescence. They do not include radioactive elements and can be safely used as luminous paints for use in the dark. Some of them are better than the traditional zinc sulfide doped with copper (ZnS:Cu). The most important rare‐earth materials with long‐lasting phosphorescence are aluminates such as alkaline‐earth aluminates MAl₂O₄:Eu²⁺, Dy³⁺ (M = Sr, Ca) and garnets Y₃Ga₅O₁₂:Tb³⁺, Gd₃Ga₅O₁₂:Tb³⁺, Cd₃Al₂Ge₃O₁₂:Tb³⁺, Cd₃M₂Ge₃O₁₂:Pr³⁺ (M = Al, Ge), Y₃Al_5?xGa_xO₁₂:Ce³⁺ (x = 3, 3.5). Some oxides such as InBO₃:Tb³⁺, Ba₂SiO₄:Dy³⁺ also show long‐lasting phosphorescence properties. Other sulfide materials include ZnS:Eu, Ca_xSr_1?x S:Bi, Tm, Cu or Ca_xSr_1?xS:Eu. Alkaline‐earth aluminates MAl₂O₄:Eu²⁺ (M = Mg, Ca, Sr, Ba) codoped with RE³⁺ (RE = Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were synthesized by using homogeneous precipitation method.     

Quantum chemistry and QSPR study on relationship between crystal structure and emission wavelength of Eu2+‐doped phosphors

Abstract— The relationship between crystal structures and emission properties has been computationally investigated for Eu²⁺‐doped phosphors. The electronic structure of the Eu²⁺‐doped BaMgAl¹⁰O¹⁷ phosphor was analyzed by using the quantum chemistry method. The different effects of O and Ba atoms on the Eu 5d states were determined. The presence of O and Ba atoms increases and decreases the energy level of the Eu 5d orbital by forming anti‐bonding and bonding interactions, respectively. According to the electronic‐structure analysis, the structure index that represents the local geometrical information of the Eu atom was defined. The relationship between the crystal structures and the emission wavelengths of the 1 6 Eu²⁺‐doped oxide phosphors were studied by using the quantitative structure‐property relationship (QSPR). The QSPR model suggested that the both O and alkaline‐earth atoms around the Eu atom are of importance in the determination of the emission wavelength. The interaction between the Eu and the nearest O atoms make the Eu²⁺ emission wavelength short. On the other hand, the interaction from the alkaline‐earth atoms around the Eu atom lengthens the Eu²⁺emission wavelength. This evaluation method is useful in selecting the host material that indicates a desirable emission wavelength of the Eu²⁺‐doped phosphors.     

Enhanced PL and VUV absorption of BaZr(BO3)2:Eu3+ by Al3+ incorporation

Abstract— The photoluminescence (PL) and vacuum‐ultraviolet excitation (VUV) properties of BaZr(BO₃)₂ doped with the Eu³⁺ activator ion were studied as a new red phosphor for PDP applications. The excitation spectrum shows strong absorption in the VUV region with an absorption band edge at 200 nm. The charge‐transfer excitation band of Eu³⁺ was enhanced by co‐doping with an Al³⁺ ion into the BaZr(BO₃)₂ lattices. The PL spectrum shows the strongest emission at 615 nm, corresponding to the electric dipole ⁵D₀ → ⁷F₂ transition of Eu³⁺ in BaZr(BO₃)₂, which results in good red‐color purity.     

Development of a new blue CaMgSi2O6:Eu2+ phosphor for PDPs

Abstract— A blue‐light‐emitting Eu²⁺‐doped CaMgSi₂O₆ phosphor having a long lifetime for a plasma‐display panel (PDP) was developed. The CaMgSi₂O₆:Eu²⁺(CMS:Eu) phosphors show no luminance degradation during the baking process, and an equivalent photoluminescence peak intensity compared to that of the conventional blue‐phosphor BaMgAl₁₀O₁₇:Eu²⁺ (BAM) after baking. CMS: Eu shows a poor luminescent characteristic for the Xe excimer band excitation due to the lack of absorption. To introduce the absorption center for the Xe excimer band, we performed Gd‐codoping of CMS: Eu as a sensitizer and found a new excitation band around 172 nm, which originated from Gd³⁺. The test PDPs panels using synthesized CMS: Eu phosphor and CMS: Eu, Gd phosphor were examined to investigate the luminescent and aging characteristics of a Xe‐discharge excitation source. The CMS: Eu panel shows an emission peak intensity comparable to that of the BAM panel (i.e., a comparable stimuli L/CIEy, 93% of BAM), while the CMS: Eu, Gd panel shows poorer blue emission intensity compared to the BAM panel (up to 53% of total stimuli of BAM). The CMS: Eu panel and the CMS: Eu, Gd panel show less luminance degradation than the BAM panel under the aging test, and the panel retains 90% of its luminance after 300 hours of driving. It was found that CMS: Eu appears to be a candidate for a new blue PDP phosphor because of its longevity in a Xe‐discharge plasma environment.     

Investigation on luminescence of Na3Ca6(PO4)5:Eu2+ phosphor for LEDs

In this paper, a series of Na₃Ca_6(1−x)(PO₄)₅:xEu²⁺ (NCP:xEu²⁺, 0 ≤ x ≤ 4%) phosphors were prepared by conventional solid-state reaction method, and their photoluminescence properties were studied. Upon 365 nm excitation, the typical NCP:2%Eu²⁺ phosphor shows an asymmetric bluish green emission band with the dominant peak at 498 nm which could be attributed to the 4f⁶5d¹-4f⁷ transition of Eu²⁺. By measuring the time-resolved photoluminescence spectra, it reveals more than one Eu²⁺ emission center in the Eu²⁺-activated NCP phosphors. By monitoring 498 nm, the excitation spectrum of NCP:2%Eu²⁺ demonstrates a broad excitation band ranging from 240 to 450 nm, which can match well with the emission wavelength of the NUV LED chip. The SEM image shows that the average particle size of NCP:2%Eu²⁺ is about 19.4 µm. The above results imply that the NCP:Eu²⁺ phosphor could have potential application in LEDs.     

A new long-lasting phosphor Zr and Eu co-doped SrMg2(PO4)2

Zr⁴⁺- and Eu³⁺-codoped SrMg₂(PO₄)₂ phosphors were prepared by conventional solid-state reaction. Under the excitation of ultraviolet light, the emission spectra of Sr_0.95Eu_0.05Mg_2−2xZr_2xP₂O₈ (x = 0.0005-0.07) are composed of a broad emission band peaking at 500 nm from Zr⁴⁺-emission and the characteristic emission lines from the ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3 and 4) transitions of Eu³⁺ ions. These phosphors show the long-lasting phosphorescence. The emission color varies from red to white with increasing Zr⁴⁺-content. The white-light emission is realized in single-phase phosphor of Sr_0.95Eu_0.05Mg_2−2xZr_2xP₂O₈ (x = 0.07) by combining the Zr⁴⁺- and Eu³⁺-emission. The duration of the persistent luminescence of Sr_0.95Eu_0.05Mg_2−2xZr_2xP₂O₈ (x = 0.07) reaches nearly 1.5 h. The time at which the long-lasting phosphorescence intensity is 50% of its original value (T_0.5) is 410 s. The afterglow decay curves and the thermoluminescence spectra were measured to discuss this long-lasting phosphorescence phenomenon. The co-doped Zr⁴⁺ ions act as both the luminescence centers and trap-creating ions.     

Red emitting MTiO3 (M = Ca or Sr) phosphors doped with Eu3+ or Pr3+ with some cations as co-dopants

Ca (or Sr)TiO₃:Eu³⁺, M (Li⁺ or Na⁺ or K⁺) and CaTiO₃:Pr³⁺, M (Li⁺ or Na⁺ or Ag⁺ or K⁺ or Gd³⁺ or La³⁺) powders were prepared by combustion synthesis method and the samples were further heated to ～1000 °C to improve the crystallinity. The structure and morphology of materials were examined by X-ray diffraction (XRD) and a scanning electron microscopy (SEM). The morphologies of SrTiO₃:Eu³⁺, CaTiO₃:Eu³⁺ or CaTiO₃:Pr³⁺ powders co-doped with other metal ions were very similar. Small and coagulated particles of nearly cubical shapes with small size distribution having smooth and regular surface were formed. Photo-luminescence spectra of CaTiO₃:Pr³⁺ and co-doped either with Li⁺, Na⁺, K⁺, Ag⁺, La³⁺ or Gd³⁺ ions showed red emissions at 613 nm due to the ¹D₂ → ³H₄ transition of Pr³⁺. The variation of intensity of emission peak with different co-doping follows the order: K⁺ > Ag⁺ > Na⁺ > Li⁺ > La³⁺ > Gd³⁺. The characteristic emissions of CaTiO₃:Eu³⁺ lattices had strong emission at 614 and 620 nm for ⁵D₀ → ⁷F₂ with other weak transitions observed at 580, 592, 654, 705 nm for ⁵D₀ → ⁷F_n transitions where n = 0, 1, 3, 4 respectively in all host lattices. Photoluminescence intensity in SrTiO₃:Eu³⁺ is more than CaTiO₃:Eu³⁺ lattices. A remarkable increase of photoluminescence intensity (in ⁵D₀ → ⁷F₂ transition) was observed if co-doped with Li⁺ ions in CaTiO₃:Eu³⁺ and SrTiO3:Eu³⁺.     

A dual functional near infrared fluorescent probe based on the bodipy fluorophores for selective detection of copper and aluminum ions

A new near infrared (NIR) fluorescent 4,4-Difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) dye with dual functionality was synthesized and characterized. The compound 1 responds to copper ion in NIR region with high selectivity through a photo-induced electron transfer process established between the substituted benzene group in the meso position and the BODIPY core when Cu²⁺ binds with the four oxygen atoms in the structure, and results in the quenching of the fluorescence. The response range to copper ions was from 10 to 50 μM, and other metal ions including Li⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Pb²⁺, Fe³⁺, Ag⁺, Hg²⁺, Co²⁺, Zn²⁺, Mn²⁺, Cd²⁺, Ni²⁺ and Al³⁺ had no interference. When excited at 520 nm, a new emission peak at 568 nm of compound 1 was used to detect Al³⁺ selectively from 30 μM to 110 μM without any interference from other metal ions including copper ions.     

Eu2+‐doped AlN—SiC solid‐solution phosphors: Synthesis and cathodoluminescence properties

Abstract— Eu and Si co‐doped AlN was reported to be an interesting blue phosphor for field‐emission displays (FEDs). In this paper, SiC instead of Si³N⁴ was used as the Si source. Eu²⁺‐doped AlN—SiC phosphors were prepared by firing the powder mixtures of AlN, SiC, and Eu²O³ at 2050°C for 2 hours under 1‐MPa N². Solid solutions between AlN and SiC were formed in a wide range, promoting the solution of Eu²⁺ in AlN. The phosphors showed intense blue emissions under electron‐beam excitation, indicative of potential phosphors for FEDs.     

Red phosphor Li2Mg2(WO4)3: Eu3+ with lyonsite structure for near ultraviolet light-emitting diodes

A series of Eu³⁺-activated Li₂Mg₂(WO₄)₃ (LMW) materials were synthesized by high temperature solid state reactions. The phosphor can be effectively excited by 394 nm near ultraviolet light and emit intense red light with high color purity. Prepared phosphors can be indexed to LMW with particular lyonsite structure. The occupation of Eu³⁺ in LMW is selective. Most of Eu³⁺ comes into ¹A sites without inversion symmetry. The present research suggests that LMW is a suitable host for luminescence applications and Eu³⁺-activated LMW is a promising phosphor for phosphor-converted white light-emitting diodes.     

Enhancement of red fluorescence and afterglow in CaWO4:Eu3+ by addition of MoO3

In this study, Eu³⁺ doped Ca(WO₄)_1?x(MoO₄)_x phosphors were synthesized via high temperature solid-state reaction. Compared with the Eu³⁺ activated CaWO₄ sample, an increment of MoO₃ doping concentration could improve the emission intensity. Improved red afterglow originating from the ⁵D₀ to ⁷F_J (J = 0, 1, 2, 3, 4) transitions of Eu³⁺ was observed after appropriate amount of MoO₃ was added, and the optimal MoO₃ doping concentration was experimentally determined to be 0.02. The proposed explanation for the afterglow property was also discussed.     

Dysprosium doped di-strontium magnesium di-silicate white light emitting phosphor by solid state reaction method

Dysprosium doped di-strontium magnesium di-silicate namely Sr₂MgSi₂O₇:Dy³⁺ phosphor was prepared by the solid state reaction method. The phase structure, surface morphology, particle size, elemental analysis was analyzed by using XRD, TEM, EDX and FTIR techniques. The EDX and FTIR spectra confirm the present elements in Sr₂MgSi₂O₇:Dy³⁺ phosphor. The optical properties of Sr₂MgSi₂O₇:Dy³⁺ phosphor was investigated utilizing thermoluminescence (TL), photoluminescence (PL), long lasting phosphorescence and mechanoluminescence (ML). Under the ultraviolet excitation, the emission spectra of Sr₂MgSi₂O₇:Dy³⁺ phosphor are composed of a broad band and the characteristic emission of Dy³⁺ peaking at 470 nm (blue), 575 nm (yellow) and 678 nm (red), originating from the transitions of ⁴F_9/2 → ⁶H_15/2, ⁴F_9/2 → ⁶H_13/2 and ⁴F_9/2 → ⁶H_11/2. CIE color coordinates of Sr₂MgSi₂O₇:Dy³⁺ are suitable as white light emitting phosphor. Decay graph indicate that this phosphor also contains fast decay and slow decay process. The peak of ML intensity increases linearly with increasing impact velocity of the moving piston. The possible mechanism of this white light emitting long lasting phosphor is also investigated.     

Experimental and theoretical luminous efficacies of phosphors used in combination with blue‐emitting LEDs for lighting and backlighting

Abstract— Phosphors that absorb blue light and emit in the green, yellow, and red have been synthesized, and their experimental and theoretical luminous efficacies are compared. It is proposed that a blue‐emitting LED in combination with red‐emitting Sr₂Si₅N₈: Eu²⁺ and green‐emitting SrGa₂S₄: Eu²⁺ phosphors is used as an energy‐efficient white‐light source for display backlighting applications.     

Identification of charge‐transfer transition between Gd3+ to O2− in gadolinium‐containing oxide phosphors in VUV region

Abstract— The broad bands at around 155 nm for GdAl₃(BO₃)₄:Eu, at 184 nm for Ca₄GdO(BO₃)₃:Eu, at 183 nm for Gd₂SiO₅:Eu, and at 170 nm for GdAlO₃:Eu were observed. These bands were assigned to the charge‐transfer (CT) transition of Gd³⁺‐O^2?. In the excitation spectrum of (Gd,Y)BO₃:Eu, a broadened excitation band was observed in VUV region. It could be considered that this band was composed of two bands at about 160 and 166 nm. The preceding band was assigned to the BO₃ group absorption. The later one at about 166 nm could be assigned to the CT transition of Gd³⁺‐O^2?, according to the result of GdAl₃(BO₃)₄:Eu, Ca₄GdO(BO₃)₃:Eu, Gd₂SiO₅:Eu, and GdAlO₃:Eu. The excitation spectra overlapped between the CT transition of Gd³⁺‐O^2? and BO₃ groups absorption. It caused the emission of Eu³⁺ to take place effectively in the trivalent europium‐doped (Gd,Y)BO₃ host lattice under 147‐nm excitation.     

Eu2+‐doped barium thioaluminate EL devices prepared by two‐target pulsed‐electron‐beam evaporation

Abstract— New blue‐emitting thin‐film‐electroluminescent (TFEL) devices that satisfy the requirements for full‐color TFEL displays were developed. Eu²⁺‐doped BaAl²S⁴ thin films were used for the emission layer. BaAl²S⁴:Eu thin films were prepared by two‐target pulsed‐electron‐beam evaporation suitable for the deposition of multinary compounds that have difficulty in obtaining stoichiometoric thin films. The EL spectrum only had a peak at around 470 nm. The Commission Interantionale de l'Eclairge (CIE) color coordinates were x = 0.12 and y = 0.10. The luminance level from a 50‐Hz pulses voltage was 65 cd/m².     

Design and characterization of new lanthanide fluorides and their optical properties

Three kinds of lanthanide phosphors (La_xLu_1−xF₃: Eu³⁺, LaF₃–CaF₂:Eu³⁺ and LaF₃: Eu³⁺) have been successfully synthesized based on three different ways such as molten salts, co-precipitation, supersonic and microwave irradiations. The as-prepared powder materials all exhibited red luminescence. Their crystal structures or morphologies were studied by means of X-ray powder diffraction and scanning electronic microscope. Eu³⁺-doped LaF₃–CaF₂ phosphor can be emissive under excitation at longer wavelengths (466 and 533 nm) excitations. Supersonic and microwave irradiations have shortened the reaction time of LaF₃: Eu³⁺ crystals in 40 min under very low temperature (50 °C).     

Molecular valve consisting of poly(acrylic acid) gel

A molecular valve, consisting of poly(acrylic acid) gel-coated Au mesh, was developed based on volume change of the gel in response to cation concentration. The valve closed when concentration of cations such as H⁺, Na⁺, K⁺, Ca²⁺, Cu²⁺, or Al³⁺ was low, whereas opened upon increase in its concentration. The valve re-closed when water was flowed. The concentration where the valve opens was found to increase in the order of Al³⁺, Ca²⁺, and Na⁺ (2 × 10⁻⁴, 5 × 10⁻⁴, and 6 × 10⁻³ M, respectively). The response to Cu²⁺ ion showed similar behaviour, but the opening concentration was ca. 2 × 10⁻⁴ M, which is lower than that of Ca²⁺ ion. The valve appeared to close over the pH range from 3 to 12, whereas to open below and above it. The fastest response time to open the valve (less than 1 min) was obtained for a solution of pH 1–2. The valve showed repeatability at least 25 cycles upon successive loading of a solution of pH 2 and water. Effects of anions and pressure were also studied.     

Potentiometric solid-state sensor for DO measurement in water using sub-micron Cu0.4Ru3.4O7 + RuO2 sensing electrode

The dissolved oxygen (DO) sensing electrode (SE) concept utilizing sub-micron-sized ruthenium oxide (RuO₂), doped with other nanostructured oxides, has been extended to investigate the possibility of employing copper (II) oxide (Cu₂O) as a dopant in order to improve sensor's characteristics and meet long term antifouling needs for SEs. In this work, a thin-film SE made of RuO₂ was constructed on the alumina sensor substrate, and a range of dopants and their concentrations was added to it in order to optimize SE properties. The Cu₂O-doped RuO₂ SE had shown a linear response to DO between 0.5 and 8.0 ppm at various temperatures, with two sensitivity maxima of 47.4 and 46.0 mV per decade for Cu₂O concentrations of 10 and 20 mol%, respectively. The maximum sensitivity for Cu_0.4Ru_3.4O₇ + RuO₂-SE was obtained at a dopant concentration of 10%. Selectivity measurements revealed that the presence of Ca²⁺, Mg²⁺, Li⁺, Na⁺, NO³⁻, PO₄³⁻, SO₄²⁻, F⁻, K⁺ and Cl⁻ in the solution had no significant effect on the sensor's emf. The sensor allows overcoming the problem of an insufficient selectivity of semiconductor-based water sensors. It was also found that the doping of RuO₂-SE by Cu₂O allowed it to function at full capacity in a natural outdoor water body with no obvious effects of biofouling.     

Facile synthesis of lanthanide vanadates and their luminescent properties

GdVO₄:Eu³⁺, Bi³⁺ with tetragonal phase has been successfully synthesized by employing efficient irradiations. The assembly of composites with fine grains based on acoustic energy and microwave radiation requires low temperature (90 °C) and short reaction time (60 min). All the compounds exhibited red emissions and they can be sensitized through the doped Bi³⁺ ions. The dependence of pH changes and doping concentration on the fluorescence features has been discussed. The photoluminescence measurements show that the optical properties achieved the best results at pH = 9 for GdVO₄:Eu³⁺(5 mol%), Bi³⁺(1 mol%) or pH = 7 for GdVO₄:Eu³⁺.     

A study on the chromaticity shifts of blue phosphor for color plasma displays

The dependency of the chromaticity shifts on the concentration of Eu²⁺ doped in BaMgAl₁₀O₁₇ (BAM) was investigated under heat‐treatment and vacuum ultraviolet (VUV) irradiation. The Eu²⁺ ions in BAM show an asymmetrical broad emission band with a maximum at ～452 nm under excitation of VUV light at room temperature, showing that multiple crystalline cationic sites exist in the host. It was found that the chromaticity shifts greatly decrease with increasing heat‐treatment temperature. Regardless of the Eu²⁺ concentration, the chromaticity shifts caused by heat‐treatment are greater than that caused by VUV irradiation. Compared with conventional BAM, a solid solution of BAM with barium aluminate as a powder and film was also studied, and very few chromacity shifts were observed. It is suggested that the distribution of Eu²⁺ ions in different sites in a BAM lattice results in different chromaticity coordinates. By increasing the Eu²⁺ concentration in BAM, or under heat‐treatment and VUV irradiation, the emission band shifts towards longer wavelengths.