Down-shifting in Ce3+–Tb3+ co-doped SiO2–LaF3 nano-glass–ceramics for photon conversion in solar cells

95SiO₂–5LaF₃ sol–gel derived nano-glass–ceramics single doped with Ce³⁺ or Tb³⁺ and co-doped with Ce³⁺–Tb³⁺ were synthesized by thermal treatment of precursor glasses. Precipitation of LaF₃ nanocrystals during ceramming process was confirmed by X-ray diffraction with mean size ranging from 12 to 15 nm. An exhaustive spectroscopic analysis has been carried out. As a result, it was found that the green emission of Tb³⁺ ions was greatly enhanced through down shifting process, due to efficient energy transfer from Ce³⁺ to Tb³⁺ ions in the glass–ceramics, which is favored by the reduction of the interionic distances when the dopant ions are partitioned into LaF₃ nanocrystals. These results suggest the use of these materials to improve the efficiency of solar cells.     

Effects of ultraviolet excitation on the spectroscopic properties of Sm3+ and Tb3+ doped aluminophosphate glasses

Li₂O–BaO–Al₂O₃–La₂O₃–P₂O₅ glasses optically activated with rare earth ions with the 4f⁵, and 4f⁸ electronic configuration (Sm³⁺ and Tb³⁺, respectively) were analyzed by Raman spectroscopy, absorption, excitation photoluminescence, decay curves and temperature dependent photoluminescence. The spectroscopic characteristics of the as-prepared and heat treated samples at temperatures below and above T_g were studied as well as their room temperature photometric properties under ultraviolet excitation. All the doped glasses exhibit typical signatures of the lanthanides in their trivalent charge state. For the samarium doped glass heat treated at 250 °C (<T_g) the Sm²⁺ luminescence was also observed. The analysis of the luminescence efficiency was performed in the interval range of 14 K to room temperature, where the integrated intensity of the luminescence was found to decrease for the Sm³⁺ and Tb³⁺ ions in the studied temperature range. Luminescence decay curves were found to be non-exponential for the ⁴G_5/2 → ⁶H_7/2 and ⁵D₃ → ⁷F₄ transitions of the Sm³⁺ and Tb³⁺ ions, respectively. The results strongly suggest the occurrence of energy transfer processes through cross relaxation phenomena, mediated by dipole–dipole interaction in all the studied samples. The decay of the ⁵D₄ → ⁷F₅ emission of the Tb³⁺ ions was found to be single exponential with a time constant of ∼3.1 ms. Based on the spectroscopic characteristics, models for recombination processes are proposed. The room temperature luminance photometric properties with ultraviolet excitation show that the samarium doped glasses have much lower luminance intensity (around 0.3 Cd/m²) when compared with the 6–7 Cd/m² observed for the terbium doped ones.     

RE3+ (RE = Ce3+, Tb3+) doped BaGdF5 nanocrystals: Synthesis,optical and magnetic properties,and energy transfer

Through a citric acid assisted hydrothermal method, the RE³⁺ (RE³⁺ = Ce³⁺, Tb³⁺) doped cubic phase BaGdF₅ nanocrystals with a sphere-like morphology and an average size of 30 nm have been synthesized. The samples show paramagnetic properties at 300 K. The photoluminescence spectra of the obtained samples suggest that the existence of Ce³⁺ can dramatically enhance the emission intensity of Tb³⁺ due to an efficient energy transfer from Ce³⁺ to Tb³⁺. The energy transfer efficiency from Ce³⁺ to Tb³⁺, the critical energy transfer distance between Ce³⁺ and Tb³⁺, and the energy transfer mechanism of Ce³⁺–Tb³⁺ are discussed based on the experimental data and the theoretical analysis.     

Cold white light generation through the simultaneous emission from Ce3+ and Tb3+ in sodium germanate glass

A spectroscopic investigation of sodium germanate glasses activated with Ce³⁺, Tb³⁺ and Ce³⁺/Tb³⁺ is carried out by analyzing their photoluminescence spectra and decay times. Non-radiative energy transfer from Ce³⁺ to Tb³⁺ is observed upon near-UV excitation at 310 nm (peak emission wavelength of AlGaN-based LEDs). The non-radiative nature of this energy transfer is inferred from the increase in the decay rate of the Ce³⁺ emission when the glass is co-doped with Tb³⁺. From an analysis of the Ce³⁺ emission decay time curve it is inferred that an electric dipole–quadrupole interaction might to be the dominant mechanism for the Tb³⁺ emission sensitized by Ce³⁺. Energy transfer from Ce³⁺ to Tb³⁺ leads to a simultaneous emission of these ions in the blue, green, yellow and red, resulting in white light with CIE1931 chromaticity coordinates, x = 0.30 and y = 0.32, which correspond to cold white light with a colour temperature of 7320 K and very small deviation from the Planckian black-body radiator locus (0.005).     

Luminescence properties and energy transfer of a novel bluish-green tunable NaBa4(BO3)3:Ce3+, Tb3+ phosphor

A series of single-phased emission tunable NaBa₄(BO₃)₃:Ce³⁺, Tb³⁺ phosphors were synthesized by solid-state reaction. The crystal structure, photoluminescence properties, concentration quenching and energy transfer of NaBa₄(BO₃)₃:Ce³⁺, Tb³⁺ were systematically investigated. The wavelength-tunable bluish-green light can be realized by coupling the emission bands centered at 425 and 543 nm ascribed to the contribution from Ce³⁺ and Tb³⁺, respectively. The energy transfer from Ce³⁺ to Tb³⁺ in NaBa₄(BO₃)₃ host was studied and demonstrated to be a resonant type via a dipole–dipole interaction mechanism. The energy transfer efficiency (Ce³⁺ → Tb³⁺) obtained by decay curves was consistent with the result calculated by the emission intensity, which gradually increased from 0% to 84.5% by increasing the Tb³⁺ doping content from 0 to 0.45. The results indicate that the NaBa₄(BO₃)₃:Ce³⁺, Tb³⁺ phosphors have potential applications as an ultraviolet-convertible phosphor due to its effective excitation in the ultraviolet rang.     

Investigation on the luminescence of RE3+ (RE = Ce,Tb, Eu and Tm) in KMGd(PO4)2 (M = Ca,Sr) phosphates

The VUV excited luminescent properties of Ce³⁺, Tb³⁺, Eu³⁺ and Tm³⁺ in the matrices of KMGd(PO₄)₂ (M = Ca, Sr) were investigated. The bands at about 165 nm and 155 nm in the VUV excitation spectra are attributed to host lattice absorptions of the two matrices. For Ce³⁺-doped samples, the Ce³⁺ 5d levels can be identified. As for Tb³⁺-doped samples, typical 4f–5d absorption bands in the region of 175–250 nm were observed. For Eu³⁺ and Tm³⁺-doped samples, the O²⁻–Eu³⁺ and O²–Tm³⁺ CTBs are observed to be at about 229 nm and 177 nm, respectively. From the standpoints of color purity and luminescent efficiency, KCaGd(PO₄)₂:Tb³⁺ is an attractive candidate of green light PDP phosphor.     

VUV–UV luminescence of Ce3+, Tb3+, Eu3+, and Dy3+ doped GdOCl

The vacuum ultraviolet spectroscopic properties of GdOCl:Re³⁺ (Re³⁺ = Ce³⁺, Tb³⁺, Eu³⁺, and Dy³⁺) are investigated in detail for the first time. The host absorption band is determined to be around 179 nm, and the f–d transition bands as well as the charge transfer bands are assigned. Upon 179 nm excitation, Re³⁺ (Re³⁺ = Ce³⁺, Tb³⁺, Eu³⁺, Dy³⁺) ions shown their characteristic emissions. Energy transfers from Gd³⁺ to Re³⁺ ion were observed. A broad band ranging from 350 to 400 nm corresponding to the d–f transition of Ce³⁺ is observed. Eu³⁺ has typical red emission with the strongest peak at 620 nm; Tb³⁺ shows characteristic transition of ⁵D_3,4 → ⁷F_j, and its spin-forbidden and spin-allowed f–d transitions in VUV region are calculated with Dorenbos’ equations, these calculated values agree well with the experimental results. Dy³⁺ presents yellow emission (⁴F_9/2 → ⁶H_13/2) with the strongest peak at 573 nm.     

Enhancement of blue-green photoluminescence in B2O3 fritted ZrO2:Ce3+ phosphor

Blue-green emission of ZrO₂:Ce³⁺ phosphor, prepared by solid-state reaction, is demonstrated. The phosphor presents a strong and broad photoluminescence band centered at 496 nm with excitation at 291 nm. The optimized Ce content is 2.5 mol% for the strongest emission of ZrO₂:Ce³⁺ phosphors prepared without B₂O₃. The PL intensity is enhanced by at least 3 dB by adding 5.0 mol% B₂O₃ within the ZrO₂:Ce³⁺ containing 5.0 mol% Ce during synthesis. Increase of the B₂O₃ flux effectively induces the Ce ions to substitute the Zr ions in ZrO₂ lattice and causes the ZrO₂ lattice distortion. The formation of Ce_0.75Zr_0.25O₂ compound within the ZrO₂:Ce³⁺ occurred when the Ce content is greater than or equal to 2.5 mol% for the phosphors prepared without B₂O₃ and leads to a degradation of the phosphor PL intensity due to the host effect. The addition of B₂O₃ during the preparation of phosphors containing Ce ions lower than or equal to 5.0 mol% essentially restrains the Ce_0.75Zr_0.25O₂ formation and then enhances the blue-green PL.     

Phase structure evolution and thermal expansion variation of Sc2O3 doped Nd2Zr2O7 ceramics

(Nd_1−xSc_x)₂Zr₂O₇ (x = 0, 0.1, 0.3, 0.5, 0.7) compounds were synthesized by solid state reaction at 1700 °C for 10 h, and characterized by XRD, Raman spectroscopy, SEM and high-temperature dilatometer. Nd₂Zr₂O₇ exhibited pyrochlore phase, and its lattice parameter increased after Sc₂O₃ doping, which could be attributed to the presence of Sc³⁺ interstitial ions in pyrochlore lattice. Fluorite phase formed in the doped Nd₂Zr₂O₇, and (Nd_0.3Sc_0.7)₂Zr₂O₇ exhibited pure fluorite phase. The thermal expansion coefficient (TEC) of Nd₂Zr₂O₇ was significantly enhanced by 10 mol% Sc₂O₃ doping, but higher Sc₂O₃ doping decreased the TEC. The reduced crystal energy due to the presence of Sc³⁺ interstitial ions could cause the initial increase in the TEC, and the formation of fluorite phase might contribute to the reduced TEC. Considering the alleviation of the thermal expansion mismatch stress for the high-temperature applications of Nd₂Zr₂O₇, Sc₂O₃ was an excellent dopant and there existed an optimal Sc₂O₃ content for the optimization design of compound compositions.     

The effect of AlN and flux addition on luminescence properties of Ce doped TAG phosphor for white light emitting diodes

A series of Ce³⁺-activated Tb₃Al₅O₁₂ green-yellow phosphors were synthesized using solid state reaction method. The X-ray diffraction peaks of the synthesized phosphor were well matched to the Tb₃Al₅O₁₂ reference peak data. As the addition amount of AlN increase, the relative intensity of diffraction peak increase. But, the addition amount of AlN is over 0.3 mol, the second phase TbAlO₃ diffraction peaks increase. When the addition amount of AlN is 0.3 mol, PL shows the highest emission efficiency. These results were explained by the reducing atmosphere made using AlN. The highest emission intensity was observed when the Ce³⁺ concentration is 0.25 mol. The emission intensity of the Tb_2.75Al₅O₁₂:Ce_0.25³⁺ phosphors were increased by adding BaF₂ and KNO₃ as a flux. The yellow emitting Tb₃Al₅O₁₂:Ce³⁺ phosphors obtained could be applied as white LEDs.     

Al2O3:Cr3+ microfibers by hydrothermal route: Luminescence properties

Uniform Al₂O₃:Cr³⁺ microfibers were synthesized by using a hydrothermal route and thermal decomposition of a precursor of Cr³⁺ doped ammonium aluminum hydroxide carbonate (denoted as AAHC), and characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), photoluminescence (PL) spectra and decay curves. XRD indicated that Cr³⁺ doped samples calcined at 1473 K were the most of α-Al₂O₃ phase. SEM showed that the length and diameter of these Cr³⁺ doped alumina microfibers were about 3–9 μm and 300 nm, respectively. PL spectra showed that the Al₂O₃:Cr³⁺ microfibers presented a broad R band at 696 nm. It is shown that the 0.07 mol% of doping concentration of Cr³⁺ ions in α-Al₂O₃:Cr³⁺ was optimum. According to Dexter's theory, the critical distance between Cr³⁺ ions for energy transfer was determined to be 38 Å. It is found that the curve followed the single-exponential decay.     

Optical spectroscopy of Ce3+ ions in Gd3(AlxGa1−x)5O12 epitaxial films

Epitaxial films of Ce-doped Gd₃(Al_xGa_1−x)₅O₁₂ with x = 0.00, 0.22, 0.31, 0.38 formula units were grown using liquid-phase epitaxy method, and their optical properties were studied. The emission of Ce³⁺ ions can be observed only when Al³⁺ ions are incorporated into the garnet structure, resulting in a shift of the 5d Ce³⁺ states from the conduction band to the bandgap. It is shown that the shift is caused by the cumulative effect of gradual low-energy shift of the lowest 5d level of Ce³⁺ and the raise of the garnet bandgap energy with increasing Al³⁺ concentration.     

Microwave-assisted synthesis and characterization of LaPO4:Re (Re = Ce3+, Eu3+, Tb3+) nanorods

LaPO₄:Re (Re = Ce³⁺, Eu³⁺ and Tb³⁺) nanorods have been successfully synthesized on a large scale by a facile and rapid microwave heating method. The structure, morphology and physical properties of the as-prepared products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and photoluminescence spectroscopy (PL). XRD patterns showed that the as-prepared products had hexagonal structure and high crystallinity and purity. TEM images showed that these LaPO₄:Re nanorods have a high yield and an obvious one-dimensional structure with diameter from 6 nm to 30 nm and length up to 400 nm. The luminescence spectra of the products indicated that different rare-earth ions had been successfully doped in LaPO₄ matrix via the microwave heating method and the actual doping amounts of Re ions were determined by the inductively coupled plasma (ICP).     

Preparation and luminescence characterization of GGAG:Ce3+,B3+ for a white light-emitting diode

We prepared Gd₃Ga₂Al₃O₁₂ (GGAG) co-doped with trivalent cerium and boron ions and investigated its luminescence properties as a function of the B³⁺ concentration. The luminescence intensity was enhanced markedly by adding B³⁺ as a co-dopant. The non-boron-doped GGAG:Ce³⁺ converted less than 10% of the absorbed blue light into luminescence. As the B³⁺ concentration increased, Q increased and reached a maximum of Q = 21% at 1.5 moles in GGAG:Ce³⁺. White light closer to daylight with good color-rendering index properties was generated with the proper combination of yellow emission from GGAG:Ce³⁺,B³⁺ and blue emission from a GaN chip.     

Luminescence properties of ZnMoO4:Tb3+ green phosphor prepared via co-precipitation

Tb³⁺-doped ZnMoO₄ green phosphor was synthesized by a co-precipitation method. The morphology and structure of the phosphor were characterized by Scanning electron microscopy (SEM) and X-ray diffraction (XRD). Photoluminescence (PL) spectra were also used to characterize the ZnMoO₄:Tb³⁺ samples. The results show that ZnMoO₄:Tb³⁺ phosphor has triclinic structure with diameters ranging from 1.0 to 2.0 μm. The obtained ZnMoO₄:Tb³⁺ phosphor emits green light emission centered at 541 nm corresponding to the ⁵D₄ → ⁷F₅ transition of Tb³⁺ when excited by 378 nm or 488 nm. The optimized concentration of Tb³⁺ is 15 mol.% for the highest emission intensity at 541 nm, and the concentration quenching occurs when the Tb³⁺ concentration is beyond 15 mol.%. The concentration quenching mechanism can be interpreted by the quadrupole–quadrupole interaction of Tb³⁺ ions. The present work suggests a convenient, cost-effective method for green phosphor, which may lead to potential applications in white light-emitting diodes (WLED).     

The effect of Eu3+ concentration on the Y2O3 host lattice obtained from citrate precursors

This work presents a thermal decomposition study of the precursor resin prepared from the citrate precursor along with structural features and optical properties materials composed by Y₂O₃ and Eu³⁺ containing Y₂O₃ in 0.5, 3, 5 and 7 mol%. The microcrystallite sizes were estimated from the Scherrer equation. The structural and optical properties revealed that the addition of 5 mol% of Eu³⁺ to the Y₂O₃ matrix gave rise to the highest relative emission intensity which was evidenced by the luminescence intensity. The lifetime of the 0.5 mol% Eu³⁺-doped sample suggested two different symmetry sites for Eu³⁺ ions because two different lifetime values were acquired for this sample, while for phosphors doped with 3 or 5 mol% of Eu³⁺ ions only one similar lifetime was observed. When the concentration of Eu³⁺ is 0.5 and 3 mol%, the luminescence intensity is weak due to the low probability of the O^2? - Eu³⁺ charge transfer transition. On the other hand, when the concentration of the Eu³⁺ ions is 7 mol%, a quenching effect is evidenced.     

Use of LiF flux in the preparation of Ca3Sc2Si3O12:Ce3+ phosphor by sol-combustion method

LiF flux was added when prepare Ca₃Sc₂Si₃O₁₂:Ce³⁺ phosphors with sol-combustion method using urea as a fuel and chelating agent. Investigation of phase, morphology and photoluminescence of the phosphors reveals that this kind of method can decrease the phase-forming temperature by 400–500 °C and the phosphors show more uniform morphology and more excellent photoluminescence properties compared to conventional solid-state method. As one of the most important parameters for phosphors used in white light emitting diodes, the thermal quenching properties of the prepared samples are compared and discussed. The fabrication of single-color light emitting diodes show the Ca₃Sc₂Si₃O₁₂:Ce³⁺ phosphor prepared by sol-combustion method with LiF flux can be considered as a more promising high efficiency candidate used for white light emitting diodes than the phosphor made by solid-state method.     

Fabrication and luminescent properties of Ce:LaAlO3 translucent ceramics

Ce³⁺ doped LaAlO₃ translucent ceramics were fabricated with solid-state reaction method and sintered in vacuum condition. LaAlO₃ single phase was formed at 1200 °C. Their microstructures were observed and luminescent properties were investigated. The average grain size increases with the increase of sintering temperature. A dense and pore-free microstructure is displayed at 1700 °C. A band to band absorption of LaAlO₃ host is round 220 nm. Three excitation peaks at 249, 317 and 354 nm were observed in the Ce³⁺:LaAlO₃ ceramics, they were attributed to the 4f–5d transition of Ce³⁺ ions. The scintillation properties were investigated by X-ray excited radioluminescence in Ce³⁺:LaAlO₃ ceramics and the emission peak is 428 nm.     

Photoluminescence and thermoluminescence studies of Tb3+ doped ZnO nanorods

Here in, the synthesis of the terbium doped zinc oxide (ZnO:Tb³⁺) nanorods via room temperature chemical co-precipitation was explored and their structural, photoluminescence (PL) and thermoluminescence (TL) studies were investigated in detail. The present samples were found to have pure hexagonal wurtzite crystal structure. The as obtained samples were broadly composed of nanoflakes while the highly crystalline nanorods have been formed due to low temperature annealing of the as synthesized samples. The diameters of the nanoflakes are found to be in the range 50–60 nm whereas the nanorods have diameter 60–90 nm and length 700–900 nm. FTIR study shows ZnO stretching band at 475 cm^?1 showing improved crystal quality with annealing. The bands at 1545 and 1431 cm^?1 are attributed to asymmetric and symmetric CO stretching vibration modes. The diffuse reflectance spectra show band edge emission near 390 nm and a blue shift of the absorption edge with higher concentration of Tb doping. The PL spectra of the Tb³⁺-doped sample exhibited bright bluish green and green emissions at 490 nm (⁵D₄ → ⁷F₆) and 544 nm (⁵D₄ → ⁷F₅) respectively which is much more intense then the blue (450 nm), bluish green (472 nm) and broad green emission (532 nm) for the undoped sample. An efficient energy transfer process from ZnO host to Tb³⁺ is observed in PL emission and excitation spectra of Tb³⁺-doped ZnO ions. The doped sample exhibits a strong TL glow peak at 255 °C compared to the prominent glow peak at 190 °C for the undoped sample. The higher temperature peaks are found to obey first order kinetics whereas the lower temperature peaks obey 2nd order kinetics. The glow peak at 255 °C for the Tb³⁺ doped sample has an activation energy 0.98 eV and frequency factor 2.77 × 10⁸ s^?1.     

Synthesis and spectroscopic characterization of the K4BaSi3O9:Eu3+

K₄BaSi₃O₉:Eu³⁺ polycrystals were synthesized by solid state method. X-ray powder diffraction measurements confirmed structure of the samples. The excitation and the emission spectra of orthorhombic K₄BaSi₃O₉ doped with Eu³⁺ were investigated. The excitation spectrum exhibits a broad band with maximum at 220 nm corresponding to the charge transfer (CT) transition between O²⁻ and Eu³⁺ ions and smaller 4f–4f transitions. The emission of investigated phosphor was excited at 395 nm and has quantum efficiency (QE) equal 27%. The emission maximum at 616.5 nm was assigned to the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions. The luminescence decay profiles as well as the thermal quenching were measured and analyzed. K₄BaSi₃O₉:Eu³⁺has high temperature quenching of the emission T_0.5 = 335 °C.