Novel blue-emitting phosphor NaMg4(PO4)3:Eu, Ce with energy transfer

A blue-emitting phosphor of NaMg₄(PO₄)₃:Eu²⁺, Ce³⁺ was prepared by a combustion-assisted synthesis method. The phase formation was confirmed by X-ray powder diffraction measurement. Photoluminescence excitation spectrum measurements show that the phosphor can be excited by near UV light from 230 to 400 nm and presents a dominant luminescence band centered at 424 nm due to the 4f⁶5d¹ → 4f⁷ transition of Eu²⁺ ions at room temperature. Effective energy transfer occurs in Ce³⁺/Eu²⁺ co-doped NaMg₄(PO₄)₃ due to large spectral overlap between the emission of Ce³⁺ and excitation of Eu²⁺. Co-doping of Ce³⁺ enhances the emission intensity of Eu²⁺ greatly by transferring its excitation energy to Eu²⁺, and Ce³⁺ plays a role as a sensitizer. Ce³⁺-Eu²⁺ co-doped NaMg₄(PO₄)₃ powders can possibly be applied as blue phosphors in the fields of lighting and display.     

A novel red phosphor NaLa4(SiO4)3F: Eu

A novel red phosphor NaLa₄(SiO₄)₃F: Eu³⁺ was synthesized by the conventional solid-state reaction at 950 °C for the first time. The luminescence properties of NaLa₄(SiO₄)₃F: Eu³⁺ were investigated, and the critical concentration of the activator concentration (Eu³⁺) was found to be 0.1 mol per formula unit. The phosphor presented red luminescence under the ultraviolet excitation of 254 or 395 nm, attributed to the transitions from ⁵D₀ excited states to ⁷F_J ( J = 0-4) ground states of Eu³⁺ ions. The results indicated that this newly-developed phosphor could find applications in tricolor fluorescent lamp, phosphor-liquid crystal displays and white lighting devices utilizing GaN-based excitation in the near UV.     

Preparation and characterization of Co-doped ZnO-Al2O3-SiO2 glass-ceramics by the sol-gel method

Transparent glass-ceramics containing Co²⁺:ZnAl₂O₄ nanocrystals were obtained by the sol-gel process for the first time. The gels of composition 89SiO₂-5.9Al₂O₃-4.9ZnO-0.2CoO (ZAS) were prepared at room temperature, and heat-treated at different temperatures. The microstructure and optical properties of the heated samples were studied by using X-ray diffraction (XRD), transmission electron microscopy (TEM), infrared spectroscopy, and optical absorption spectra. Co²⁺:ZnAl₂O₄ nanocrystals were precipitated from ZAS system and dispersed in the SiO₂-based glass during heat-treatment in the temperature range 900-1100 °C. Co²⁺ ions were located in tetrahedral sites in ZnAl₂O₄ nanocrystals. The Co²⁺:ZnAl₂O₄ crystallite size was in the range of 4-15 nm.     

Enhanced G4 emission in NaLaF4: Pr, Yb and charge transfer in NaLaF4: Ce, Yb studied by fourier transform luminescence spectroscopy

A high resolution luminescence study of NaLaF₄: 1%Pr³⁺, 5%Yb³⁺ and NaLaF₄: 1%Ce³⁺, 5%Yb³⁺ in the UV to NIR spectral range using a InGaAs detector and a fourier transform interferometer is reported. Although the Pr³⁺(³P₀ → ¹G₄), Yb³⁺(²F_7/2 → ²F_5/2) energy transfer step takes place, significant Pr³⁺¹G₄ emission around 993, 1330 and 1850 nm is observed. No experimental proof for the second energy transfer step in the down-conversion process between Pr³⁺ and Yb³⁺ can be given. In the case of NaLaF₄: Ce³⁺, Yb³⁺ it is concluded that the observed Yb³⁺ emission upon Ce³⁺ 5d excitation is the result of a charge transfer process instead of down-conversion.     

Preparation and upconversion property of TeO2:Er/Yb nanoparticles

Different crystal structure of TeO₂ nanoparticles were used as the host materials to prepare the Er³⁺/Yb³⁺ ions co-doped upconversion luminescent materials. The TeO₂ nanoparticles mainly kept the original morphology and phase after having been co-doped the Er³⁺/Yb³⁺ ions. All the as-prepared TeO₂:Er³⁺/Yb³⁺ nanoparticles showed the green emissions (525 nm, 545 nm) and red emission (667 nm) under 980 nm excitation. The green emissions at 525 nm, 545 nm and red emission at 667 nm were attributed to the ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions of the Er³⁺ ions, respectively. For the α-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles, three-photon process involved in the green (²H_11/2 → ⁴I_15/2) emission, while two-photon process involved in the green (⁴S_3/2→⁴I_15/2) and red (⁴F_9/2 → ⁴I_15/2) emissions. For the β-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles, two-photon process involved in the green (²H_11/2 → ⁴I_15/2), green (⁴S_3/2 → ⁴I_15/2) and red (⁴F_9/2 → ⁴I_15/2) emissions. It suggested that the crystal structure of TeO₂ nanoparticles had an effect on transition processes of the Er³⁺/Yb³⁺ ions. The emission intensities of the α-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles and β-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles were much stronger than those of the (α + β)-TeO₂:Er³⁺/Yb³⁺ (3/10 mol%) nanoparticles.     

White light generation in Al2O3:Ce:Tb:Mn films deposited by ultrasonic spray pyrolysis

Aluminium oxide (Al₂O₃) films doped with CeCl₃, TbCl₃ and MnCl₂ were deposited at 300 °C with the ultrasonic spray pyrolysis technique. The films were analysed using the X-ray diffraction technique and they exhibited a very broad band without any indication of crystallinity, typical of amorphous materials. Sensitization of Tb³⁺ and Mn²⁺ ions by Ce³⁺ ions gives rise to blue, green and red simultaneous emission when the film activated by such ions is excited with UV radiation. The overall efficiency of such energy transfer results to be about 85% upon excitation at 312 nm. Energy transfer from Ce³⁺ to Tb³⁺ ions through an electric dipole-quadrupole interaction mechanism appears to be more probable than the electric dipole-dipole one. A strong white light emission for the Al₂O₃:Ce³⁺(1.3 at.%):Tb³⁺(0.2 at.%):Mn²⁺(0.3 at.%) film under UV excitation is observed. The high efficiency of energy transfer from Ce³⁺ to Tb³⁺ and Mn²⁺ ions, resulting in cold white light emission (x = 0.30 and y = 0.32 chromaticity coordinates) makes the Ce³⁺, Tb³⁺ and Mn²⁺ triply doped Al₂O₃ film an interesting material for the design of efficient UV pumped phosphors for white light generation.     

Crystal growth and spectral properties of Pr:La2(WO4)3

Pr³⁺-doped La₂(WO₄)₃ single crystal with dimensions up to Ø 20 mm × 35 mm has been grown by the Czochralski method. The structure of the Pr³⁺:La₂(WO₄)₃ crystal was determined by the X-ray powder diffraction and the Pr³⁺ concentration in this crystal was determined. The absorption and fluorescence spectra of Pr³⁺:La₂(WO₄)₃ crystal were measured at room temperature, and the fluorescence lifetime of main emission multiplets were estimated from the recorded decay curves. The spectral properties related to laser performance of the crystal were evaluated.     

Crystal growth and optical properties of the Nd doped LuF3 single crystals

Thirty millimeter diameter single crystal of Nd³⁺ doped LuF₃ was grown using LiF as solvent. The single phase crystallization was confirmed by the powder X-ray diffraction, and high structural perfection was demonstrated by X-ray rocking curve (XRC) measurements. FWHM of XRC for 220 reflection was 32 arcsec. No remarkable absorption due to unfavorable impurities was observed from optical absorption measurements in the VUV spectral region. The crystal showed the VUV luminescence peaking around 178 nm that is consistent with the 4f²5d-4f³ transition of Nd³⁺ ion. The luminescence intensity of Nd:LuF₃ under X-ray irradiation was significantly higher than that of reported VUV scintillators such as Nd:LaF₃ or Nd:LiLuF₄.     

Luminescence properties of Ca4Y6(SiO4)6O:RE (RE = Eu, Tb, Dy, Sm and Tm) under vacuum ultraviolet excitation

The vacuum ultraviolet excited luminescent properties of Eu³⁺, Tb³⁺, Dy³⁺, Sm³⁺ and Tm³⁺ in the matrices of Ca₄Y₆(SiO₄)₆O were investigated. The bands at about 173 nm in the vacuum ultraviolet excited spectra were attributed to host lattice absorption of the matrix Ca₄Y₆(SiO₄)₆O. For Eu³⁺-doped samples, the O²⁻ → Eu³⁺ CTB was identified at 258 nm. Typical 4f-5d absorption bands in the region of 195-300 nm were observed in Tb³⁺-doped samples. For Dy³⁺-doped and Sm³⁺-doped samples, the broad excitation bands consisted of host absorptions, CTB and f-d transition. For Tm³⁺-doped samples, the O²⁻ → Tm³⁺ CTB was located at 191 nm. About the color purity and emission intensity, Ca₄Y₆(SiO₄)₆O:Tb³⁺ is an attractive candidate of green light PDP phosphor, and Ca₄Y₆(SiO₄)₆O:Dy³⁺ has potential application in the field of mercury-free lamps.     

Crystal growth and scintillation properties of Nd-doped Lu3Al5O12 single crystals with different Nd concentrations

Nd 0.1%, 0.5%, 1% and 3% doped Lu₃Al₅O₁₂ (Nd:LuAG) single crystals were grown in the nitrogen atmosphere by the micro-pulling down (μ-PD) method. The grown crystals had a single-phase confirmed by powder XRD analysis. In absorption spectra, some weak absorption lines due to Nd³⁺ 4f-4f transitions were observed and their intensity increased with the increase of Nd concentration. When excited by ²⁴¹Am α-ray, a broad emission peak due to defects in the host lattice at 320 nm and some sharp lines due to Nd³⁺ 4f-4f transitions at wavelength longer than 400 nm were observed. The decay time profiles of Nd:LuAG under γ-ray excitation were well approximated by two exponential function of 340-760 ns and 3-5 μs for each sample. By pulse height measurement using ¹³⁷Cs, Nd 0.5%:LuAG showed the highest light yield of 7600 ± 760 photons/MeV.     

Photon-avalanche upconversion of Ho in NaYF4 and enhancement of violet, blue and green emissions induced by sensitization of Tm

Ho³⁺ singly doped and Ho³⁺/Tm³⁺ co-doped hexagonal NaYF₄ powders have been synthesized by a solid-state reaction method. Under excitation of 671 nm diode laser, upconverted blue, green and red emission bands are observed in Ho³⁺ singly doped sample. Temporal evolution and excitation power dependent behavior for the green emission are explored, indicating that a photon-avalanche mechanism is responsible for the upconversion processes in Ho³⁺ singly doped hexagonal NaYF₄ sample. With the introduction of Tm³⁺, the intensities of both blue and green emissions of Ho³⁺ are efficiently enhanced, which are attributed to two energy transfer processes from Tm³⁺ to Ho³⁺, i.e., ³F₄ (Tm³⁺) + ⁵I₈(Ho³⁺) → ³H₆ (Tm³⁺) + ⁵I₇(Ho³⁺) and ¹G₄ (Tm³⁺) + ⁵I₈(Ho³⁺) → ³H₆ (Tm³⁺) + ⁵F₃(Ho³⁺). The result offers a new sensitization approach to enhance the upconversion efficiency of Ho³⁺ under 671 nm excitation.     

Effect of crystallization quality on ferromagnetism in Zn1 − xCoxO nanopowders

In this paper, a series of Zn_1 − xCo_xO nanocrystals with different cobalt percentages were fabricated by a simple chemical method, which were intensively explored for spintronics applications. X-ray diffraction (XRD), ultraviolet-visible (UV-Vis) spectrophotometer, transmission electron microscope (TEM) and vibrating sample magnetometer (VSM) were used to characterize the structures and magnetic properties of prepared samples. It was concluded that Co²⁺ was well inserted into ZnO wurtzite structure. The ferromagnetism of Zn_1 − xCo_xO nanopowders was observed at room temperature. The relation between crystallization quality and magnetism of Zn_1 − xCo_xO nanopowders was discussed in detail. It was demonstrated the crystallization quality of Zn_1 − xCo_xO nanocrystals had a strong effect on the ferromagnetism.     

The microwave-assisted synthesis and characterization of Zn1 − xCoxO nanopowders

In this paper, we present a simple microwave-assisted synthesis of Zn_1 − xCo_xO nanopowders. With the advantages of the microwave-assisted method, we have successfully synthesized good crystalline quality and good surface morphology Zn_1 − xCo_xO nanopowders. The nanopowders are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-VIS absorption, and micro-Raman spectroscopy. We found, in the synthesis process, the surfactant Triethanolamine (TEA) plays an important role on the morphology of Zn_1 − xCo_xO nanoparticles. The XRD study shows that for Co doping up to 5%, Co²⁺ ions are successfully incorporated into the ZnO host matrix. The absorption spectra of Zn_1 − xCo_xO (x = 1-5%) nanopowders show several peaks at 660, 611 and 565 nm, indicating the presence of Co²⁺ ions in the tetrahedral sites. The Raman study shows that the linewidth of E₂^low mode increases with Co concentration, which further indicates the incorporation of Co²⁺ ions into the ZnO host matrix.     

Luminescence excitation spectra of TbX3 (X = Cl, Br, I)

A systematic study of the excitation spectrum of TbX₃ (X = Cl⁻, Br⁻, I⁻) is presented in this work. In general, the excitation spectra of TbX₃ can be divided into three major regions: (1) the short-wave host lattice absorption region, (2) the intermediate absorption region where the Tb³⁺ 4f⁸ → 4f⁷5d¹ interconfigurational excitation transition are located, and (3) the long-wave excitation region where the Tb³⁺ 4f⁸ → 4f⁸ intraconfigurational excitation transition are located. The high spin and the low spin components of the Tb³⁺ interconfigurational excitation transition are clearly identified in the case of TbCl₃. The luminescence of TbX₃ (X = Cl⁻, Br⁻, I⁻) is dominated by emission transitions emanating from the Tb³⁺⁵D₄ state. A comparative study of the optical properties of TbX₃ (X = Cl⁻, Br⁻, I⁻) with the properties of the Tb³⁺ ion in several halide host lattices is presented. Further, a comparative study of the fundamental host lattice optical transitions in terbium halides and other halide materials is also presented.     

Growth and spectral properties of Cr:KAl(MoO4)2 crystal

The Cr³⁺:KAl(MoO₄)₂ single crystal was grown by top seeding solution growth method (TSSG). Based on the absorption and emission spectra, the crystal field strength Dq, the Racah parameters B and C, the effective phonon energy ?ω and the Huang-Rhys factor S were calculated: Dq = 1494.8 cm^− 1, B = 585.5 cm^− 1 and C = 3049 cm^− 1, ?ω = 373.8 cm^− 1 and the Huang-Rhys factor S = 3.74, respectively. The value Dq/B = 2.55 indicates that Cr³⁺ ion occupies the strong crystal field site in KAl(MoO₄)₂ crystal. A comparison of crystal field parameters for Cr³⁺:KAl(MoO₄)₂ with other Cr³⁺-doped crystals was presented. The results of spectral measurement show that Cr³⁺:KAl(MoO₄)₂ may be a potential candidate for broadband laser applications.     

Thermal stability against reduction of LaMn1−yCoyO3 perovskites

Thermal and reduction-oxidation stability of substituted LaMn_1−yCo_yO₃ perovskite-type oxides (0.0 ≤ y_Co ≤ 1.0) prepared by the citrate route have been studied by means of surface area, X-ray diffraction, FTIR spectroscopy and magnetic properties. The perovskite orthorhombic structure is found for y_Co ≤ 0.5, with the exception of y_Co = 0.1, which corresponds better to rhombohedral LaMnO_3.15. For y_Co > 0.5 the diffraction profiles are quite similar to the cobaltite’s rhombohedral structure. Magnetic iso-field studies (ZFC-FC) reveal that, for y_Co ≤ 0.50, the system presents an antiferromagnetic canted-like ordering of the Mn/Co sublattice, in which the presence of divalent Co ion creates Mn³⁺-Mn⁴⁺ pairs that interact ferromagnetically through the oxygen orbital. This interpretation is confirmed by the magnetization loops, in which the magnetic moment increases when substituting Mn for Co. Therefore, the general trend is: for y_Co ≤ 0.5, the Co ions are inserted in the manganite structure and for y_Co > 0.5, the Mn ions are inserted in cobaltite structure. The enhancement of the ferromagnetic properties and the thermal stability against reduction for y_Co = 0.5 is attributed to optimized Co²⁺-Mn⁴⁺ interactions.     

Hydrothermal synthesis, structural and physico-chemical characterizations of two Nasicon phosphates: M0.50Ti2(PO4)3 (M = Mn, Co)

The family of titanium Nasicon-phosphates of generic formula M_0.5^IITi₂(PO₄)₃ has been revisited using hydrothermal techniques. Two phases have been synthesized: Mn_0.5^IITi₂(PO₄)₃ (MnTiP) and Co_0.5^IITi₂(PO₄)₃ (CoTiP). Single crystal diffraction studies show that they exhibit two different structural types. Mn_0.5^IITi₂(PO₄)₃ phosphate crystallizes in the R-3 space group, with the cell parameters a = 8.51300(10) Å and c = 21.0083(3) Å (V = 1318.52(3) Å³ and Z = 6). The Co_0.5^IITi₂(PO₄)₃ phosphate crystallizes in the R-3c space group, with a = 8.4608(9) Å and c = 21.174(2) Å (V = 1312.7(2) Å³ and Z = 6). These two compounds are clearly related to the parent Nasicon-type rhombohedral structure, which can be described using [Ti₂(PO₄)₃] framework composed of two [TiO₆] octahedral interlinked via three [PO₄] tetrahedra. ³¹P magic-angle spinning nuclear magnetic resonance (MAS-NMR) data are presented as supporting data. Curie-Weiss-type behavior is observed in the magnetic susceptibility. The phases are also characterized by IR spectroscopy and UV-visible.     

Studies on optical absorption and photoluminescence of thioglycerol-stabilized ZnS nanoparticles

ZnS quantum dots of size 3 nm are prepared at 303 K using ZnSO₄ and Na₂S₂O₃ precursors with thioglycerol as stabilizing agent. Cd²⁺ doped ZnS were prepared by varying doping concentration from 1 to 8 wt.%. ZnS quantum dots were mixed with CdS quantum dots of size 4 nm in the 3:1, 2:1, 1:1, 1:2, 1:3 and 1:4 M ratio. The nanoparticles were characterized by UV–vis, photoluminescence (PL), XRD and high-resolution TEM measurements. The XRD pattern, high-resolution TEM image and SAED pattern reveal that the nanoparticles are in well-crystallized cubic phase. The band gap of ZnS has increased from the bulk value 3.7 to 4.11 eV showing quantum size effect. Excitonic transition is observed at 274 nm in UV absorption and PL emission at 411 nm. Doping with Cd²⁺ red-shifts both UV and PL spectral bands and enhances the PL band of ZnS nanoparticles. Mixing CdS and ZnS quantum dots in different molar ratios shows red-shift of the band edge in the CdS/ZnS hybrid system. In the 1:1 hybrid system of CdS/ZnS nanoparticles, PL band is red-shifted and the intensity is almost doubled with respect to that of CdS nanoparticles.     

Luminescence properties of Ba2LiB5O10:Dy phosphor

A novel warm white phosphor Ba₂LiB₅O₁₀:Dy³⁺ with various Dy³⁺ concentrations was synthesized by the conventional solid-state reaction at 800 °C. The crystal structure of the phosphor was characterized by X-ray diffraction (XRD). The photoluminescence properties of Ba₂LiB₅O₁₀:Dy³⁺ were investigated, and the critical concentration of the activator ion (Dy³⁺) was found to be 0.04 mol per formula unit. Under the ultraviolet excitation of 348 nm, the phosphor presented warm white luminescence with dominating emissions at 484.6 and 577 nm, corresponding to ⁴F_9/2-⁶H_15/2, ⁴F_9/2-⁶H_13/2 transitions, respectively. The chromatic properties of the typical sample Ba₂LiB₅O₁₀:0.04Dy³⁺ phosphor have been found to have chromaticity coordinates of x = 0.31 and y = 0.35.     

Development of “tuned microwave absorbers” using U-type hexaferrite

The paper presents that microwave absorption is tunable with sample thickness over a frequency range if electromagnetic properties of the sample do not change with frequency in that range. The work summarizes the results of polycrystalline samples of two U-type hexaferrite series: Ba₄ (Co_1−5x P_2x)₂ Fe₃₆ O₆₀ (0.0 ? x ? 0.20 in step 0.05) and (Ba_1−3x La_2x)₄ Co₂ Fe₃₆ O₆₀ (0.10 ? x ? 0.25 in step 0.05) that have been prepared through solid state reaction route. The complex permittivity, permeability and microwave absorbing properties have been discussed in detail for X-band (8.2–12.4 GHz) frequencies. The results show that the substitution of Co²⁺ ion with P⁵⁺ ion and Ba²⁺ ion with La³⁺ ion in the U-type-hexaferrite provides the desired electromagnetic properties for a “tuned microwave absorber” in samples with x = 0.05 and 0.20 of first and 0.20 sample of second series. In these samples, the microwave absorption peak (of >98%) shifts linearly from lower to upper side of X-band with sample thickness. These materials can provide significant application for reduction of radar cross section (RCS) and in electromagnetic interference (EMI) shielding.