In this study, Y3Al5O12:Eu3+ red phosphors were synthesized at different temperatures using a solid state reaction method. The crystal structures, surface and optical properties of the Y3Al5O12:Eu3+ red phosphors were investigated using Xray diffraction (XRD), field emission scanning electron microscope (FE-SEM), and photoluminescence (PL) analyses. From XRD results, the crystal structure of the Y3Al5O12:Eu3+ red phosphors was determined to be cubic. The maximum emission spectra were observed for the Y3Al5O12:Eu3+ red phosphor prepared by annealing for 4h at 1,700 oC. The 565~590 nm photoluminescent spectra of the Y3Al5O12:Eu3+ red phosphors is associated with the 5D0 → 7F2 magnetic dipole transition of the Eu3+ ions. The intensity of the photoluminescent spectra in the red phosphors is more dominant for the magnetic dipole transition than the electric dipole transition with increasing annealing temperature. The International Commission on Illumination (CIE) coordinates of Y3Al5O12:Eu3+ red phosphors prepared by 1,700 oC annealing temperature are X = 0.5994, Y = 0.3647.
Y2O3:Eux (x = 0.005, 0.01, 0.02, 0.03, 0.05, 0.1 mol) phosphors are synthesized with different concentrations of Eu3+ ions by solvothermal method. The crystal structure, surface and optical properties of the Eu doped Y2O3 phosphors are investigated using X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and photoluminescence (PL) and photoluminescence excitation (PLE) analyses. From X-ray diffraction (XRD) results, the crystal structure of the Eu doped Y2O3 phosphor is found to be cubic. The maximum emission spectra of the Eu doped Y2O3 phosphors are observed at 0.05 mol Eu3+ concentration. The photoluminescence of 615 nm in the Eu doped Y2O3 phosphors is associated with 5D0 → 7F2 transition of Eu3+ ions. The decrease in emission intensity of 0.1 mol Eu doped Y2O3 is interpreted by concentration quenching. The International Commission on Illumination (CIE) coordinates of 0.05 mol Eu doped Y2O3 phosphor are X = 0.6547, Y = 0.3374.
The co-doping effect of aliovalent metal ions such as Mg2+, Ca2+, Sr2+, Ba2+, and Zn2+ on the photoluminescence of the Y2O3:Eu3+ red phosphor, prepared by spray pyrolysis, is analyzed. Mg2+ metal doping is found to be helpful for enhancing the luminescence of Y2O3:Eu3+. When comparing the luminescence intensity at the optimum doping level of each Mg2+ ion, the emission enhancement shows the order of Zn2+ Ba2+ > Ca2+ > Sr3+> Mg2+. The highest emission occurs when doping approximately 1.3% Zn2+, which is approximately 127% of the luminescence intensity of pure Y2O3:Eu3+. The highest emission was about 127% of the luminescence intensity of pure Y2O3:Eu3+ when doping about 1.3% Zn2+. It is determined that the reason (Y, M)2O3:Eu3+ has improved luminescence compared to that of Y2O3:Eu3+ is because the crystallinity of the matrix is improved and the non-luminous defects are reduced, even though local lattice strain is formed by the doping of aliovalent metal. Further improvement of the luminescence is achieved while reducing the particle size by using Li2CO3 as a flux with organic additives.
Lu(Nb,Ta)O4:Eu3+ powders are synthesized by a solid-state reaction process using LiCl and Li2SO4 fluxes. The photoluminescence (PL) excitation spectra of the synthesized powders consist of broad bands at approximately 270 nm and sharp peaks in the near ultraviolet region, which are assigned to the Nb5+-O2− charge transfer of [NbO4]3− niobates and the f-f transition of Eu3+, respectively. The PL emission spectra exhibit red peaks assigned to the 5D0 → 7FJ transitions of Eu3+. The strongest peak is obtained at 614 nm (5D0 → 7F2), indicating that the Eu3+ ions are incorporated into the Lu3+ asymmetric sites. The addition of fluxes causes the increase in emission intensity, and Li2SO4 flux is more effective for enhancement in emission intensity than is LiCl flux. The substitution of Ta5+ for Nb5+ results in an increase or decrease in the emission intensity of LuNb1-xTaxO4:Eu3+ powders, depending on amount and kind of flux. The findings are explained using particle morphology, modification of the [NbO4]3− structure, formation of substructure of LuTaO4, and change in the crystal field surrounding the Eu3+ ions.
Nanosized Gd2O3:Eu3+ red phosphor is prepared using a template method from metal salt impregnated into a crystalline cellulose and is dispersed using a bead mill wet process. The driving force of the surface coating between Gd2O3:Eu3+ and mica is induced by the Coulomb force. The red phosphor nanosol is effectively coated on mica flakes by the electrostatic interaction between positively charged Gd2O3:Eu3+ and negatively charged mica above pH 6. To prepare Gd2O3:Eu3+-coated mica (Gd2O3:Eu/mica), the coating conditions are optimized, including the stirring temperature, pH, calcination temperature, and coating amount (wt%) of Gd2O3:Eu3+. In spite of the low luminescence of the Gd2O3:Eu/mica, the luminescent property is recovered after calcination above 600℃ and is enhanced by increasing the Gd2O3:Eu3+ coating amount. The Gd2O3:Eu/mica is characterized using X-ray diffraction, field emission scanning electron microscopy, zeta potential measurements, and fluorescence spectrometer analysis.
Gd2O3:Eu3+ red phosphors were prepared by template method from crystalline cellulose impregnated by metal salt. The crystallite size and photoluminescence(PL) property of Gd2O3:Eu3+ red phosphors were controlled by varying the calcination temperature and Eu3+ mol ratio. The nano dispersion of Gd2O3:Eu3+ was also conducted with a bead mill wet process. Dependent on the time of bead milling, Gd2O3:Eu3+ nanosol of around 100 nm (median particle size : D50) was produced. As the bead milling process proceeded, the luminescent efficiency decreased due to the low crystallinity of the Gd2O3:Eu3+ nanoparticles. In spite of the low PL property of Gd2O3:Eu3+ nanosol, it was observed that the photoluminescent property was recovered after re-calcination. In addition, in the dispersed nanosol treated at 85 oC, a self assembly phenomenon between particles appeared, and the particles changed from spherical to rod-shaped. These results indicate that particle growth occurs due to mutual assembly of Gd(OH)3 particles, which is the hydration of Gd2O3 particles, in aqueous solvent at 85 oC.
Inorganic phosphors based on ZrO2:Eu3+ nanoparticles were synthesized by a salt-assisted ultrasonic spray pyrolysis process that is suitable for industrially-scalable production because of its continuous nature and because it does not require expensive precursors, long reaction time, physical templates or surfactant. This facile process results in the formation of tiny, highly crystalline spherical nanoparticles without hard agglomeration. The powder X-ray diffraction patterns of the ZrO2:Eu3+ (1-20 mol%) confirmed the body centered tetragonal phase. The average particle size, estimated from the Scherrer equation and from TEM images, was found to be approximately 11 nm. Photoluminescence (PL) emission was recorded under 266 nm excitation and shows an intense emission peak at 607 nm, along with other emission peaks at 580, 592 and 632 nm which are indicated in red.
Dy3+ and Eu3+-codoped SrWO4 phosphor thin films were deposited on sapphire substrates by radio frequency magnetron sputtering by changing the growth and thermal annealing temperatures. The results show that the structural and optical properties of the phosphor thin films depended on the growth and thermal annealing temperatures. All the phosphor thin films, irrespective of the growth or the thermal annealing temperatures, exhibited tetragonal structures with a dominant (112) diffraction peak. The thin films deposited at a growth temperature of 100 oC and a thermal annealing temperature of 650 oC showed average transmittances of 87.5% and 88.4% in the wavelength range of 500-1100 nm and band gap energy values of 4.00 and 4.20 eV, respectively. The excitation spectra of the phosphor thin films showed a broad charge transfer band that peaked at 234 nm, which is in the range of 200-270 nm. The emission spectra under ultraviolet excitation at 234 nm showed an intense emission peak at 572 nm and several weaker bands at 479, 612, 660, and 758 nm. These results suggest that the SrWO4: Dy3+, Eu3+ thin films can be used as white light emitting materials suitable for applications in display and solid-state lighting.
Y2O3–H3BO3:Eu3+ powders are synthesized using a mechanical alloying method, and their photoluminescence (PL) properties are investigated through luminescence spectrophotometry. For samples milled for 300 min, some Y2O3 peaks ([222], [440], and [622]) and amorphous formations are observed. The 300-min-milled mixture annealed at 800°C for 1 h with Eu = 8 mol% has the strongest PL intensity at every temperature increase of 100°C (increasing from 700 to 1200°C in 100°C increments). PL peaks of the powder mixture, as excited by a xenon discharge lamp (20 kW) at 240 nm, are detected at approximately 592 nm (orange light, 5Do → 7F1), 613 nm, 628 nm (red light, 5Do → 7F2), and 650 nm. The PL intensity of powder mixtures milled for 120 min is generally lower than that of powder mixtures milled for 300 min under the same conditions. PL peaks due to YBO3 and Y2O3 are observed for 300-min-milled Y2O3–H3BO3 with Eu = 8 mol% after annealing at 800°C for 1 h.
NaLa1-x(MoO4)2:Eu3+/Yb3 phosphors with doping concentrations of Eu3+ and Yb3+ (x=Eu3++Yb3+, Eu3+=0.05, 0.1,0.2 and Yb3+=0.2, 0.45) were successfully synthesized by the microwave-modified sol-gel method, and the upconversion andspectroscopic properties were investigated. Well-crystallized particles showed a fine and homogeneous morphology with particlesizes of 2-5µm. Under excitation at 980nm, NaLa0.5(MoO4)2:Eu0.05Yb0.45 particles exhibited a strong 525-nm emission bandand a weak 550-nm emission band in the green region, and a very weak 665-nm emission band in the red region. The strong525-nm emission in the green region corresponds to the 7F1→5D1 transition and the weak 550-nm emission in the green regioncorresponds to the 7F0→5D2 transition, while the very weak emission 665-nm band in the red region corresponds to the5D0→7F3 transition. The Raman spectra of the doped particles indicated the domination of strong peaks at higher frequenciesof 762, 890, 1358 and 1430cm−1 and weak peaks at lower frequencies of 323, 388 and 450cm−1 induced by the disorder ofthe [MoO4]2− groups with the incorporation of the Eu3+ and Yb3+ elements into the crystal lattice or by a new phase formation.
SrSnO3 phosphor powders were synthesized with two different contents of activator ions Eu3+ and Tb3+ using thesolid-state reaction method. The structural, morphological, and optical properties of the phosphors were investigated using X-ray diffractometry, field-emission scanning electron microscopy, and fluorescence spectrophotometry, respectively. All thephosphors showed a cubic structure, irrespective of the type and the content ratio of activator ions. For Eu3+-doped SrSnO3phosphors, the intensity of the 620nm red emission spectrum resulting from the 5D0→7F2 transition of Eu3+ was stronger thanthat of the 595nm orange emission signal due to the 5D0→7F1 transition in the range 0.01-0.05mol of Eu3+, but the ratio ofthe intensity was reversed in the range 0.10-0.20mol of Eu3+. The variation in the emission intensity indicates that the sitesymmetry of the Eu3+ ions around the host crystal was changed from non-inversion symmetry to inversion. For the Tb3+-dopedSrSnO3 phosphors under excitation at 281nm, one strong green emission band at 550nm and several weak bands wereobserved. These results suggest that the optimum red and green emission signals can be realized when the activator ion contentfor Eu3+- or Tb3+-doped SrSnO3 phosphors is 0.20mol and 0.15mol, respectively.
Red phosphors Ca1-1.5xWO4:Eux3+ were synthesized with different concentrations of Eu3+ ions by using a solid-statereaction method. The crystal structure of the red phosphors was found to be a tetragonal system. X-ray diffraction (XRD) resultsshowed the (112) main diffraction peak centered at 2θ=28.71o, and the size of crystalline particles exhibited an overalldecreasing tendency according to the concentration of Eu3+ ions. The excitation spectra of all the phosphors were composedof a broad band centered at 275nm in the range of 230-310nm due to O2−→W6+ and a narrow band having a peak at 307nmcaused by O2−→Eu3+. Also, the excitation spectrum presents several strong lines in the range of 305-420nm, which areassigned to the 4f-4f transitions of the Eu3+ ion. In the case of the emission spectrum, all the phosphor powders, irrespectiveof Eu3+ ion concentration, indicated an orange emission peak at 594nm and a strong red emission spectrum centered at 615nm,with two weak lines at 648 and 700nm. The highest red emission intensity occurred at x=0.10mol of Eu3+ ion concentrationwith an asymmetry ratio of 12.5. Especially, the presence of Eu3+ in the Ca1-1.5xWO4:Eux3+ shows very effective use of excitationenergy in the range of 305-420nm, and finally yields a strong emission of red light.
Red-emitting Eu3+-activated (Y0.95-xAlx)VO4 (0<x≤0.12) nanophosphors with the particle size of ~30nm and thehigh crystallinity have been successfully synthesized by a hydrothermal reaction. In the synthetic process, deionized water asa solvent and ethylene glycol as a capping agent were used. The crystalline phase, particle morphology, and thephotoluminescence properties of the excitation spectrum, emission intensity, color coordinates and decay time, of the prepared(Y0.95-xAlx)VO4:Eu3+ nanophosphors were compared with those of the YVO4:Eu3+. Under 147nm excitation, (Y0.95-xAlx)VO4nanophosphors showed strong red luminescence due to the 5D0-7F2 transition of Eu3+ at 619nm. The luminescence intensityof YVO4:Eu3+ enhanced with partial substitution of Al3+ for Y3+ and the maximum emission intensity was accomplished at theAl3+ content of 10mol%. By the addition of Al3+, decay time of the (Y,Al)VO4:Eu3+ nanophosphor was decreased in comparisonwith that of the YVO4:Eu3+ nanophosphor. Also, the substitution of Al3+ for Y3+ invited the improvement of color coordinatesdue to the increase of R/O ratio in emission intensity. For the formation of transparent layer, the red nanophosphors werefabricated to the paste with ethyl celluloses, anhydrous terpineol, ethanol and deionized water. By screen printing method, atransparent red phosphor layer was formed onto a glass substrate from the paste. The transparent red phosphor layer exhibitedthe red emission at 619nm under 147nm excitation and the transmittance of ~80% at 600nm.
A3-2x/3Al1-zInzO4F: Eux3+ (A=Ca, Sr, Ba, x=-0.15, z=0, 0.1) oxyfluoride phosphors were simply prepared by thesolid-state method at 1050oC in air. The phosphors had the bright red photoluminescence (PL) spectra of an A3-2x/3Al1-zInzO4Ffor Eu3+ activator. X-ray diffraction (XRD) patterns of the obtained red phosphors were exhibited for indexing peak positionsand calculating unit-cell parameters. Dynamic excitation and emission spectra of Eu3+ activated red oxyfluoride phosphors wereclearly monitored. Red and blue shifts gradually occurred in the emission spectra of Eu3+ activated A3AlO4F oxyfluoridephosphors when Sr2+ by Ca2+ and Ba2+ ions were substituted, respectively. The concentration quenching as a function of Eu3+contents in A3-2x/3AlO4F:Eu3+ (A=Ca, Sr, Ba) was measured. The interesting behaviors of defect-induced A3-2x/3Al1-zInzO4-αF1-δphosphors with Eu3+ activator are discussed based on PL spectra and CIE coordinates. Substituting In3+ into the Al3+ positionin the A3-2x/3AlO4F:Eu3+ oxyfluorides resulted in the relative intensity of the red emitted phosphors noticeably increasing byseven times.
Red-orange phosphors Gd1-xPO4:Eux3+ (x=0, 0.05, 0.10, 0.15, 0.20) were synthesized with changing theconcentration of Eu3+ ions using a solid-state reaction method. The crystal structures, surface morphology, and optical propertiesof the ceramic phosphors were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), andphotoluminescence (PL) spectrophotometry. The XRD results were in accordance with JCPDS (32-0386), and the crystalstructures of all the red-orange phosphors were found to be a monoclinic system. The SEM results showed that the size ofgrains increases and then decreases as the concentration of Eu3+ ionincreases. As for the PL properties, all of the ceramicphosphors, irrespective of Eu3+ ion concentration, had orange and red emissions peaks at 594nm and 613nm, respectively. Themaximum excitation and emission spectra were observed at 0.10mol of Eu3+ ion concentration, just like the grain size. Anorange color stronger than the red means that 5D0→7F1 (magnetic dipole transition) is dominant over the 5D0→7F2 (electricdipole transition), and Eu3+ is located at the center of the inversion symmetry. These properties contrasted with those of a redphosphor Y1-xPO4:Eux3+, which has a tetragonal system. Therefore, we confirm that the crystal structure of the host materialhas a major effect on the resulting color.