Luminescence properties and energy transfer studies of a color tunable BaY2Si3O10:Tm3+,Dy3+ phosphor

A series of color-tunable and white light emitting phosphors BaY₂Si₃O₁₀:Tm³⁺,Dy³⁺ were synthesized by a high temperature solid-state reaction, and their phase structure, photoluminescence properties, and energy transfer processes between rare-earth ions were investigated in detail. Upon UV excitation, white light emission depending on dopant concentrations could be achieved by integrating a blue emission band located at 458 nm and an orange one located at 576 nm attributed to Tm³⁺ and Dy³⁺ ions, respectively. In addition, the energy transfer process between Tm³⁺ and Dy³⁺ ions was demonstrated to be a resonant type via a dipole–quadrupole mechanism. Preliminary studies showed that the phosphor might be promising as a single-phased white-light-emitting phosphor for UV chip pumped white-light LEDs.     

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.     

On the relationship between emission color and Ce3+ concentration in garnet phosphors

It is known that the emission color of Ce³⁺ doped garnets is strongly redshifted at higher Ce³⁺ concentrations. In this report, we study the cause of this redshift in Lu₃Al₅O₁₂:Ce³⁺ (LuAG:Ce) phosphors. These changes in emission color with Ce³⁺ concentration are mainly attributed to a combination of inhomogenous broadening for Ce³⁺ in LuAG and energy transfer from high energy Ce³⁺ ions to low energy Ce³⁺ ions. Evidence for inhomogenous broadening and energy transfer is given through time resolved measurements. Potential reasons for inhomogenous broadening of Ce³⁺ in these phosphors are also discussed.     

Luminescent properties of Sr2Al2SiO7:Ce3+,Eu2+ phosphors for near UV-excited white light-emitting diodes

The Sr₂Al₂SiO₇:Eu²⁺, Ce³⁺ phosphors were synthesized by a high temperature solid-state reaction. Effective energy transfer occurs in Ce³⁺ and Eu²⁺ co-doped Sr₂Al₂SiO₇ due to large spectral overlap between the emission of Ce³⁺ and excitation of Eu²⁺ ions. Co-doping of Ce³⁺ enhances the emission intensity of Eu²⁺ greatly by transferring its excitation energy to Eu²⁺ ions. The critical distance has been estimated to be about 1.83 nm by spectral overlap method. Furthermore, the developed phosphors can generate lights from blue to green region under the excitation of UV radiation by appropriately tuning the activator content. The Sr₂Al₂SiO₇:Eu²⁺,Ce³⁺ phosphors are promising phosphors for warm-white-light-emitting diode because of its effective excitation in the near ultraviolet range.     

Luminescence properties and energy transfer investigations of Ce3+/Tb3+ co-doped BaY2Si3O10 phosphor

A novel phosphor BaY₂Si₃O₁₀ (BYSO): Ce³⁺, Tb³⁺ was synthesized by the conventional solid-state reaction, which displays tunable color emission from blue to blue-green under ultraviolet excitation by adjusting the radio of Ce³⁺ and Tb³⁺ appropriately. Photoluminescence characteristics were carefully investigated. We demonstrate the existence of efficient energy transfer from Ce³⁺ to Tb³⁺ in BaY₂Si₃O₁₀: Ce³⁺, Tb³⁺ phosphor. The energy transfer Ce³⁺ → Tb³⁺ was proved to be governed by dipole–quadrupole interaction.     

Co-existence phenomenon of Ce3+/Ce4+ and Tb3+ in Ce/Tb co-doped Zn2(BO3)(OH)0.75F0.25 phosphor: Luminescence and energy transfer

A serials of Zn₂(BO₃)(OH)_0.75F_0.25 (ZBF), Tb³⁺, Ce^3+/4+ single-doped ZBF and Tb³⁺/Ce^3+/4+ co-doped ZBF novel phosphors with belt-like morphology were obtained through hydrothermal reaction without any surfactant. The obtained samples were characterized by XRD, SEM, EDS, TEM, TGA, XPS, DR, PL, and DT. The TGA curve shows that the phosphor is thermal stability. XPS results show that Tb³⁺ is present in the Tb-doped phosphor, and the Ce³⁺/Ce⁴⁺ mixed valence is present in the Ce-doped phosphor. The PL results indicate that ZBF host material and ZBH:Ce^3+/4+ can emit blue light, ZBF:Tb³⁺ can emit green light. Compared with the Tb³⁺ single doped phosphor, the Tb³⁺/Ce^3+/4+ co-doped phosphors shown stronger emission and shorter decay time, which is attributed to the effective energy transfer from the Ce^3+/4+ to Tb³⁺ ions.     

Blue and white light emission in Tm3+ and Tm3+/Dy3+ doped zinc phosphate glasses upon UV light excitation

A spectroscopic study based on photoluminescence spectra and decay time profiles in Tm³⁺ and Tm³⁺/Dy³⁺ doped Zn(PO₃)₂ glasses is reported. The Tm³⁺ doped Zn(PO₃)₂ glass, upon 357 nm excitation, exhibits blue emission with CIE1931 chromaticity coordinates, x = 0.157 and y = 0.030, and color purity of about 96%. Under excitations at 348, 352 and 363 nm, which match with the emissions of AlGaN and GaN based LEDs, the Tm³⁺/Dy³⁺ co-doped Zn(PO₃)₂ glass displays natural white, bluish white and cool white overall emissions, with correlated color temperature values of 4523, 10700 and 7788 K, respectively, depending strongly on the excitation wavelength. The shortening of the Dy³⁺ emission decay time in presence of Tm³⁺ suggests that Dy³⁺→Tm³⁺ non-radiative energy transfer occurs. By using the Inokuti-Hirayama model, it is inferred that an electric quadrupole-quadrupole interaction might be the dominant mechanism involved in the energy transfer. The efficiency and probability of this energy transfer are 0.12 and 126.70 s⁻¹, respectively.     

Luminescence properties and energy transfer of co-doped Ba<Subscript>3</Subscript>GdNa(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>F:Ce<Superscript>3+</Superscript>,Tb<Superscript>3+</Superscript> green-emitting phosphors

Phase pure Ce³⁺ and Tb³⁺ singly doped and Ce³⁺/Tb³⁺ co-doped Ba₃GdNa(PO₄)₃F samples have been synthesized via the high temperature solid-state reaction. The crystal structures, photoluminescence properties, fluorescence lifetimes, thermal properties and energy transfer of Ba₃GdNa(PO₄)₃F:Ce³⁺,Tb³⁺ were systematically investigated. Rietveld structure refinement indicates that Ba₃GdNa(PO₄)₃F crystallizes in a hexagonal crystal system with the space group P-6. For the co-doped Ba₃GdNa(PO₄)₃F:Ce³⁺,Tb³⁺ samples, the emission color can be tuned from blue to green by varying the doping concentration of the Tb³⁺ ions. The intense green emission was realized in the Ba₃GdNa(PO₄)₃F:Ce³⁺,Tb³⁺ phosphors on the basis of the highly efficient energy transfer from Ce³⁺ to Tb³⁺. Also the energy transfer mechanism has been confirmed to be quadrupole–quadrupole interaction, which can be validated via the agreement of critical distances obtained from the concentration quenching (13.84 Å). These results show that the developed phosphors may possess potential applications in near-ultraviolet pumped white light-emitting diodes.     

Single-component and white light-emitting phosphor BaAl2Si2O8: Dy3+, Eu3+ synthesis,luminescence, energy transfer,and tunable color

A series of Dy³⁺ - Eu³⁺ co-doped BaAl₂Si₂O₈ phosphors were prepared via the conventional solid-state reaction method. Their crystal structure, luminescent characteristic and lifetime were investigated. The optimum doping concentrations of Dy³⁺and Eu³⁺ are both 0.05 for Dy³⁺ or Eu³⁺ singly doped BaAl₂Si₂O₈. Furthermore, BaAl₂Si₂O₈: 0.05Dy³⁺ and BaAl₂Si₂O₈: 0.05Eu³⁺ emits yellow and red light. The emission color of BaAl₂Si₂O₈: Dy³⁺, Eu³⁺ could be tuned from yellow to white due to the energy transfer. This energy transfer from Dy³⁺ to Eu³⁺ was confirmed and investigated by photoluminescence spectra and the decay time of energy donor Dy³⁺ ions. With constantly increasing Eu³⁺ concentration, the energy transfer efficiency from Dy³⁺ to Eu³⁺ in BaAl₂Si₂O₈ host increased gradually and reached as high as 81%, the quantum yield was about 47.43%. BaAl₂Si₂O₈: Dy³⁺, Eu³⁺ phosphors can be effectively excited by UV (about 348 nm) light and emit visible light from yellow to white by altering the concentration ratio of Dy³⁺ and Eu³⁺, indicating that the phosphors have potential applications as a white light-emitting phosphor for display and lighting.     

Synthesis and luminescent properties of Eu3+ and Dy3+ doped BiPO4 phosphors for near UV-based white LEDs

The phosphors BiPO₄:Eu³⁺ co-doped with Dy³⁺ were synthesized by the conventional solid-state reaction method. XRD and scanning electron microscopy results showed that the crystalline phase of the samples BiPO₄:Eu³⁺ transforms from high-temperature monoclinic phase to low-temperature monoclinic phase with the increase of Dy³⁺ concentration. The photoluminescence properties of the samples showed that the colors shifting from red–orange area to blue–green area are close to those of ideal white light by readjusting the doping concentration ratio of Eu³⁺ and Dy³⁺. The Eu³⁺and Dy³⁺ doped BiPO₄ phosphors may be potential applications in white light near-UV light-emitting diodes.     

Controllable white light emission from Dy<Superscript>3+</Superscript>–Eu<Superscript>3+</Superscript> co-doped KCaBO<Subscript>3</Subscript> phosphor

Potassium calcium borate, KCaBO₃:Eu³⁺ phosphors with various Dy³⁺ concentrations (0–3 wt%) were synthesized by solid state reaction and studied for the first time. Under various UV–violet excitations, the obtained single monoclinic phased Dy³⁺–Eu³⁺ co-doped KCaBO₃ polycrystalline phosphors emit a combination of yellow–blue and red–orange wavelength giving intense white light, which can easily be controlled by varying the concentration of Dy³⁺. The increase in white light emission with the increase of Dy³⁺ concentration indicates the efficient energy inter-ion transfer from Dy³⁺ to Eu³⁺ ions. Furthermore, the observed emission lifetimes and the intense white light emission are suggestive exploration for the present phosphor for potential optoelectronic applications such as white light-emitting phosphor for blue LEDs chips.     

Luminescence properties of Ce-Dy codoped aluminium oxide films

Photoluminescence properties of CeCl₃ and DyCl₃ codoped aluminium oxide films deposited by the ultrasonic spray pyrolysis technique were characterized by excitation, emission and decay time spectroscopy. When excited by ultraviolet radiation the films emit a combination of blue and yellow wavelengths through an efficient energy transfer from Ce³⁺ to Dy³⁺ ions (up to around 77%). From spectroscopic data it is inferred that such energy transfer is nonradiative in nature taking place between Ce³⁺ and Dy³⁺ clusters through a short-range interaction mechanism. In the Ce³⁺ doped single film the chromaticity coordinates are in the purplish blue region, whereas that in the cerium and dysprosium codoped films the coordinates move toward the white light emission region.     

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).     

Luminescent characteristics of LiSrBO3:M (M = Eu, Sm, Tb, Ce, Dy) phosphor for white light-emitting diode

LiSrBO₃:M (M = Eu³⁺, Sm³⁺, Tb³⁺, Ce³⁺, Dy³⁺) phosphors which have been developed for white light-emitting diodes (LEDs) were synthesized by a normal solid-state reaction. The emission and excitation spectra indicate that these phosphors can be effectively excited by near-ultraviolet light-emitting diodes (UVLED), and exhibit satisfactory red, green and blue performances, respectively, nicely fitting in with the widely applied UV chip. Under the condition of doping charge compensation Li⁺, Na⁺ and K⁺, the luminescence intensities of these phosphors were increased.     

Tunable luminescence properties and energy transfer of single-phase Ca<Subscript>4</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>O: Dy<Superscript>3+</Superscript>, Eu<Superscript>2+</Superscript> multi-color phosphors for warm white light

The novel Ca_4?x(PO₄)₂O: xDy³⁺ and Ca_4?x?y(PO₄)₂O: xDy³⁺, yEu²⁺ multi-color phosphors were synthesized by traditional solid-state reaction. The crystal structure, particle morphology, photoluminescence properties and energy transfer process were investigated in detail. The X-ray diffraction (XRD) results demonstrate that the products showed pure monoclinic phase of Ca₄(PO₄)₂O when x < 0.1. The scanning electron microscopy (SEM) indicated that the phosphors were grain-like morphologies with diameters of ~ 3.7–7.0 μm. Under excitation of 345 nm, Dy³⁺-doped Ca₄(PO₄)₂O phosphors showed multi-color emission bands at 410, 481 and 580 nm originated from oxygen vacancies and Dy³⁺. Interestingly, Ca₄(PO₄)₂O: Dy³⁺, Eu²⁺ phosphors exhibited blue emission band at 481 nm and broad emission band from 530 to 670 nm covering green to red regions. The energy transfer process from Dy³⁺ to Eu²⁺ was observed for the co-doped samples, and the energy transfer efficiency reached to 60% when Eu²⁺ molar concentration was 8%. In particular, warm/cool/day white light with adjustable CCT (2800–6700 K) and high CRI (R_a > 85) can be obtained by changing the Eu²⁺ co-doping contents in Ca₄(PO₄)₂O: Dy³⁺, Eu²⁺ phosphors. The optimized Ca_3.952(PO₄)₂O: 0.04Dy³⁺, 0.008Eu²⁺ phosphor can achieve the typical white light with CCT of 4735 K and CRI of 87.     

Synthesis,tunable luminescence and thermal stability of Mg<Subscript>2</Subscript>Al<Subscript>4</Subscript>Si<Subscript>5</Subscript>O<Subscript>18</Subscript>:Ce<Superscript>3+</Superscript>/Mn<Superscript>2+</Superscript> phosphors

Ce³⁺/Mn²⁺ singly doped and codoped Mg₂Al₄Si₅O₁₈ phosphors were synthesized by a solid state reaction. The phase, luminescent properties and thermal stability of the synthesized phosphors were investigated. Ce³⁺ and Mn²⁺ singly doped Mg₂Al₄Si₅O₁₈ phosphors show emission bands locating in blue and yellow–red regions, respectively. In Ce³⁺ and Mn²⁺ codoped Mg₂Al₄Si₅O₁₈, tunable luminescence was obtained because of the energy transfer from Ce³⁺ to Mn²⁺. In Mg₂Al₄Si₅O₁₈:Ce³⁺/Mn²⁺ phosphors with a fixed Ce³⁺ concentration, energy transfer efficiency increases with the increasing Mn²⁺ concentration, which is confirmed by the continually decreasing intensity and shortening decay time of Ce³⁺ emission. Moreover, the luminescent properties and thermal stability provide a great significance on the applications in the field of light emitting diodes.     

Near-infrared downconversion in Ce<Superscript>3+</Superscript>–Yb<Superscript>3+</Superscript> co-doped YAG

The phosphors YAG co-doped with Ce³⁺–Yb³⁺ ion pair were successfully synthesized by solid state reaction method varying the concentration of Yb³⁺ ions from 1 to 15 % mol. The phosphors were characterized by powder X-ray powder diffraction and surface morphology was studied by scanning electronic microscope. The photoluminescence (PL) properties were studied by spectrophotometers in near infra red (NIR) and ultra violet visible region. The synthesized phosphors can convert a photon of blue region (469 nm) into photons of NIR region (979 and 992 nm). The co-operative energy transfer was studied by time decay curve and PL spectra. The theoretical value of quantum efficiency was calculated from steady time decay measurement and the maximum efficiency approached up to 145.19 %. Hence this phosphor could be used as a downconversion luminescent convertor in front of crystalline silicon solar cell (c-Si) panels to reduce thermalization loss due to spectral mismatch of the solar cells.     

Powder synthesis and white light-emitting properties of Eu3+ co-doped K2CaP2O7:Dy3+ phosphors with energy transfer between Dy3+ and Eu3+

A series of white-emitting K₂CaP₂O₇:Dy³⁺ and K₂CaP₂O₇:Dy³⁺, Eu³⁺ phosphors were synthesized via a solid-state method, and Eu³⁺ was co-doped in K₂CaP₂O₇:Dy³⁺ to improve its white light performance. The influences of preparation temperature and Dy³⁺/Eu³⁺ concentration on the crystal structure and photoluminescence characteristics were investigated. XRD results indicate that K₂CaP₂O₇:Dy³⁺ samples prepared above 700 °C matches the standard K₂CaP₂O₇ phase. Under excitation of 349 nm, K₂CaP₂O₇:Dy³⁺ phosphor exhibited characteristic emission peaks at 487 nm (blue) and 579 nm (yellow), and white emission was realized through combining these blue and yellow emissions. After co-doping Eu³⁺ ions, the co-luminescence of Dy³⁺/Eu³⁺ with energy transfer between Dy³⁺and Eu³⁺ were demonstrated. The chromaticity of white light was controlled by changing the ratio of Dy³⁺/Eu³⁺ concentrations, which lead to a warm white light. Therefore, the results indicate that K₂CaP₂O₇:Dy³⁺, Eu³⁺ powders have a potential application in w-LEDs as single-component white-emitting phosphor.     

Crystal structure and luminescence property of a single-phase white light emission phosphor Sr<Subscript>3</Subscript>YNa(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>F:Dy<Superscript>3+</Superscript>

A series of single-phase Sr₃YNa(PO₄)₃F:Dy³⁺ phosphors were successfully synthesized via a conventional solid state reaction process. The powder X-ray diffraction patterns were utilized to confirm the phase composite and crystal structure. The phosphor could be excited by the ultraviolet visible light in the region from 300 to 420 nm, and it shown two dominant emission bands peaking at 484 nm (blue light) and 580 nm (yellow light) which originated from the transitions of ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 of Dy³⁺, respectively. The optimum dopant concentration of Dy³⁺ ions was confirmed to be 7 mol% in Sr₃YNa(PO₄)₃F:Dy³⁺ system and the concentration quenching mechanism is dipole–dipole interaction. The lifetime values of Dy³⁺ ions at different concentrations (x?=?0.03, 0.05, 0.07, 0.09 and 0.11) were determined to be about 0.855, 0.759, 0.686, 0.606 and 0.546 ms, respectively. The thermal stability of luminescence of Sr₃YNa(PO₄)₃F:0.07Dy³⁺ phosphor was also investigated and the activated energy was deduced to be 0.228 eV, which shows good thermal stability. The chromaticity coordinates fall in the white-light region calculated by the emission spectrum. These results show that Sr₃YNa(PO₄)₃F:Dy³⁺ phosphor can be a promising white emitting phosphor for white LEDs.     

Investigation on photoluminescence properties and defect chemistry of GdAlO3:Dy3+ Ba2+ phosphors

GdAlO₃:Dy³⁺ Ba²⁺ phosphors are synthesized by citrate-based sol-gel method. Photoluminescence and positron annihilation studies are used to investigate the emission and defect chemistry of the phosphors respectively. The strong yellow (Dy³⁺) emission properties of phosphors are discussed for various concentrations of Dy³⁺ ions. Upon the addition of Ba²⁺ ion, an enhancement in emission intensity is observed due to the lattice distortions around Dy³⁺ ion. The positron studies indicate the presence of defects at crystallite boundaries, vacancy clusters and large voids in the materials. The influence of Ba²⁺ ion on the photoluminescence and lattice distortion around Dy³⁺ is also explored.