Synthesis and luminescence properties of broad band greenish-yellow emitting LnVO4:Bi3+ and (Ln1, Ln2)VO4:Bi3+ (Ln=La,Gd and Y) as down conversion phosphors

Ln_0.97VO₄:Bi_0.03³⁺ and (Ln1_0.5, Ln2_0.5)_0.97VO₄:Bi_0.03³⁺ (where Ln=La, Gd and Y) down conversion (DC) phosphors have been synthesized by a novel co-precipitation technique followed by heat-treatment. The influence of lanthanide host composition on crystal structure, luminescence and pertinent optical properties have been investigated by various spectroscopic techniques: XRD, SEM, FT-IR and PL. The produced phosphors have exhibited an intense greenish-yellow emission, upon UV-irradiation. A broad band excitation (280–350 nm) ascribed to ¹S₀→³P₁ and an intense broad greenish-yellow emission band (400–700 nm) attributed to ³P₁→¹S₀ transition, owing to Bi³⁺ ions have been observed. PL spectra revealed that the phosphors with Gd – containing host has exhibited a better luminescence among the others. The luminescence intensity sequence in descending order was as follows: GdVO₄→(Gd, Y)VO₄→(La, Gd)VO₄→(La, Y)VO₄→YVO₄→LaVO₄: Bi³⁺. These phosphors can efficiently convert the UV-photons in a broad range from 280–350 nm of feckless UV-rays into the absorbable visible emission for c-Si solar cells, based on the spectral matching phenomena. In view of the better fluorescence and pertinent optical properties, the phosphor with composition Gd_0.97VO₄: Bi_0.03³⁺ is a suggestible sought UV-absorbing spectral converter, in its thin transparent DC form for c-Si solar cells for better harvesting the solar energy.     

Luminescence and temperature-sensing properties of Y4GeO8:Bi3+,Eu3+ phosphor

In this paper, Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor with dual emission centers was elaborated via conventional solid-state reaction technology. Thorough research on the structure, morphology, and luminous properties of Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor, the potential applications in optical thermometry were investigated by means of fluorescence intensity ratio and thermochromic techniques. Under 290 and 347 nm excitation, Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor presents broadband emission from ³P₁ → ¹S₀ transition of Bi³⁺ ions and characteristic emission peaks from 4f–4f transition of Eu³⁺ ions. Outstanding temperature-sensing capabilities are acquired from Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor. The maximum relative sensitivity (S_r) can attain 1.51% K⁻¹ (λ_ex = 290 nm). With temperature raising (303–513 K), the emitted color of Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor (λ_ex = 290 nm) shifts from faint yellow to red with a high chromaticity shift (0.180), which can be distinguished by the unaided eye clearly. Our results indicate that Y₄GeO₈:Bi³⁺,Eu³⁺ phosphor has potential applications in optical temperature measurement and high-temperature safety marker.     

Energy transfer and color-tunable emission in Ba2Y2Si4O13:Bi3+,Eu3+ phosphors

Single-composition Ba₂Y₂Si₄O₁₃:Bi³⁺,Eu³⁺ (BYSO:Bi³⁺,Eu³⁺) phosphors with color-tunable and white emission were prepared by conventional high temperature solid-state reaction method. The structural and luminescent properties of these phosphors were thoroughly investigated through X-ray diffraction, photoluminescence, and decay curves. BYSO:Bi³⁺ phosphors show two excitation peaks at 342 and 373 nm, and give two emission peaks at 414 and 503 nm, respectively, indicating that there are two sites of Bi³⁺ in BYSO. The energy transfer from Bi³⁺ to Eu³⁺ was investigated in detail. Varied hues from blue (chromaticity coordinate [0.219, 0.350]) to white (0.288, 0.350) and orange-red light (0.644, 0.341) can be generated by adjusting the content of Eu³⁺. Pure white light emission (0.311, 0.338) can be obtained under the excitation of 355 nm in BYSO:3%Bi³⁺,20%Eu³⁺ phosphor. Besides, BYSO:Bi³⁺,Eu³⁺ phosphors exhibit distinct thermal quenching properties, whose emission intensity at 473 K is 82.6% of that at 298 K. Our results indicate that BYSO:Bi³⁺,Eu³⁺ may be applied as conversion phosphors for n-UV-based W-LEDs.     

Red,green and blue-violet emission coexistence in white-light-emitting Ca3SiO4Cl2:Bi3+, Li+, Eu2+, Eu3+ phosphor

A series of emission-tunable Ca₃SiO₄Cl₂:Bi³⁺, Li⁺, Euⁿ⁺(n =2, 3) (CSC:Bi³⁺, Li⁺, Euⁿ⁺) phosphors have been synthesized via sol-gel method. The X-ray diffraction results indicate that the as-synthesized phosphors crystallize in a low temperature phase with the space group of P21/c. Energy transfer from Bi³⁺ to Eu³⁺/Eu²⁺ exists in CSC:Bi³⁺, Li⁺, Euⁿ⁺ phosphors. Under the excitation of 327 or 365 nm, the Ca_2.98−ySiO₄Cl₂:0.01Bi³⁺, 0.01Li⁺, yEuⁿ⁺(y=0.0001–0.002) phosphors show an intense green emission band around 505 nm, while under the excitation of 264 nm, three emission bands centered around 396 nm (Bi³⁺), 505 nm (Eu²⁺) and 614 nm (Eu³⁺) are observed and tunable colors from blue-violet to green or white are achieved in these phosphors by varying the content of Eu. White-light emission with the color coordinate (0.312, 0.328) is obtained in Ca_2.978SiO₄Cl₂:0.01Bi³⁺, 0.01Li⁺, 0.002Euⁿ⁺(n =2, 3). Based on these results, the as-prepared CSC:Bi³⁺, Li⁺, Eu²⁺, Eu³⁺ phosphors can act as color-tunable and single-phase white emission phosphors for potential applications in UV-excited white LEDs.     

Photoluminescent properties and site occupation preference in Bi3+, Eu3+ doped CaY4(SiO4)3O phosphor

Bi³⁺, Eu³⁺ doped CaY₄(SiO₄)₃O phosphors were synthesized through high temperature solid state reaction. Their photoluminescent properties were investigated and site occupation preference of Bi³⁺ in cationic sites was analyzed. The structure of CaY₄(SiO₄)₃O is characterized by three non-equivalent cationic sites with different coordination and cation-oxygen distances. By means of dielectric theory of the chemical bond for complex crystals, several kinds of chemical bond parameters like fractional covalence of CaY₄(SiO₄)₃O were calculated and integrated to yield environmental factor h_e. According to quantitative equations between the transition energy of Bi³⁺ and environmental factor h_e, the excitation bands at 308 and 226 nm were assigned to ¹S₀→³P₁ transition of Bi³⁺ in Y(6h) and Y(4f) site, respectively. Another excitation band centered at 210 nm should be the overlap of Bi³⁺ A-band in Ca site and C-band in Y(6h) site. Optical band gap of pure CYSO was calculated using Kubelka–Munk method from diffuse reflectance spectra. Red emission can be realized in CaY₄(SiO₄)₃O:Bi³⁺, Eu³⁺ under UV light excitation because of efficient energy transfer from Bi³⁺ to Eu³⁺ and decay behaviors of Bi³⁺ and Eu³⁺ emission were investigated. Without optimization, the internal quantum efficiency of CYSO:2%Bi³⁺, 7%Eu³⁺ at 310 and 393 nm excitations were 31.563%, 74.252%, respectively.     

White light emitting from YVO4/Y2O3:Eu3+,Bi3+ composite phosphors for UV light-emitting diodes

A series of (1−x)YVO₄/xY₂O₃:Eu³⁺_0.006,Bi³⁺_0.006 (0≤x≤0.54) composite phosphors was synthesized in one step by high temperature solid state reaction and the photoluminescence properties were investigated. By means of co-doping Eu³⁺ and Bi³⁺ ions into the composite matrices composed of YVO₄ and Y₂O₃ crystals, the YVO₄/Y₂O₃:Eu³⁺,Bi³⁺ phosphor exhibits simultaneously the blue (418 nm), green (540 nm) and orange-red (595, 620 nm) emissions. The broad blue and green emissions are attributed to the ³P₁–¹S₀ transitions of Bi³⁺ ion both in Y₂O₃ and in YVO₄ matrices. Moreover, the sharp orange-red emissions are attributed to the ⁵D₀–⁷F_1,2 transitions of Eu³⁺ ion in YVO₄ matrix. By tuning the mole ratio of YVO₄/Y₂O₃ matrices the white light-emitting could be obtained. The results indicated that when the mole ratio of Y₂O₃ (x) is at 0.11–0.54 mol, the (1−x)YVO₄/xY₂O₃:Eu³⁺_0.006,Bi³⁺_0.006 phosphors emit white light by combining the blue, green and orange-red emissions under the excitation of 360–370 nm wavelength which matches the emission of the commercial UV-LED diode. This implies that the phosphors may be the promising white light materials with broad absorption band for white light-emitting diodes.     

A novel single-phase Na3.6Y1.8(PO4)3:Bi3+,Eu3+ phosphor for tunable and white light emission

A new type of Bi³⁺,Eu³⁺ single- and co-doped Na_3.6Y_1.8(PO₄)₃ phosphate phosphors were manufactured using conventional high-temperature solid-state reaction technique to explore their application for solid-state lighting. The crystal structure, luminescent properties, luminescent mechanism and quantum efficiency were thoroughly explored. Results show that there are two crystallization sites for Bi³⁺ and Eu³⁺ ions. Upon the excitation of 342 and 373 nm, Bi³⁺ single-doped phosphors exhibit green and blue emission, derived from the ³P₁ to ¹S₀ transition of Bi³⁺ located in different occupancy sites. Thanks to radiative energy transfer process from Bi³⁺ to Eu³⁺, adjustable emission could be acquired by altering Eu³⁺ content in co-doped phosphors. Pure white-light emission with quantum efficiency value of 22.9% can be realized in Na_3.6Y_1.8(PO₄)₃:0.01Bi³⁺,0.1Eu³⁺ sample and the integrated intensity of white light emission at 417 K remains 85% of that at room temperature. Our results indicate that Na_3.6Y_1.8(PO₄)₃:Bi³⁺,Eu³⁺ phosphors have feasible application in high-power ultraviolet driven solid-state lighting.     

Tunable Emission Phosphor Ca4Y6O(SiO4)6:Ce3+, Eu2+: Luminescence and Energy Transfer

A series of Ca_4–yY_6–xO(SiO₄)₆: xCe³⁺, yEu²⁺ samples are synthesized by a high‐temperature solid‐state method. Under 356 nm excitation, Ca₄Y₆O(SiO₄)₆:Ce³⁺ presents a strong blue emission band at 426 nm which are assigned to 4f⁰5d¹→4f¹ transition of Ce³⁺ ion. Ca₄Y₆O(SiO₄)₆:Eu²⁺ shows green emission under 380 nm radiation excitation, and the peak locates at 527 nm which is mainly due to transitions of Eu²⁺ from 4f⁷ ground state to 4f⁶5d¹ excited state. Under 356 nm excitation, a remarkable energy transfer from Ce³⁺ to Eu²⁺ exists in Ca₄Y₆O(SiO₄)₆, and the result reveals that the mechanism of energy transfer is a resonant type via a nonradiative dipole–dipole interaction. The hues of Ca₄Y₆O(SiO₄)₆:Ce³⁺, Eu²⁺ can be adjusted by the energy transfer from Ce³⁺ to Eu²⁺ ions, and a white emission can be achieved by tuning the ratio of Ce³⁺ to Eu²⁺. The results mean that Ce³⁺ may be the effective sensitizer for Eu²⁺‐doped Ca₄Y₆O(SiO₄)₆.     

Enhancement of oxygen/pressure sensing performance of Eu3+-doped YSZ phosphors via Bi3+ sensitization

The effects of the incorporation of a Bi³⁺ sensitizer on the phosphorescence properties and oxygen partial pressure sensitivity of the Eu³⁺ doped yttria stabilized zirconia (YSZ) phosphors were studied using a lifetime-based optical measurement system. Two series of YSZ: Eu phosphors were investigated in this work: Eu_0.01Bi_xY_0.07-xZr_0.92O_1.96 substitutional series and Eu_0.01Bi_xY_0.07Zr_0.92-xO_1.96-0.5x additive series. The phosphorescence intensity of the additive-series phosphors was enhanced by 47% excited at 405 nm with a Bi³⁺ concentration of 2 mol% due to the energy transfer between Bi³⁺ and Eu³⁺. In contrast, the phosphorescence intensity of the substitutional-series phosphors decreased as the Bi³⁺ concentration increased. The phosphorescence lifetimes for both series phosphors were highly sensitive to oxygen partial pressure at elevated temperatures. With increasing Bi³⁺ concentration, the oxygen sensitivities of both series were enhanced initially, which was related to the increment of concentration dependent non-radiative decay via cross-relaxation between Bi³⁺ and Eu³⁺. With 1 mol% Bi³⁺ doping, the oxygen sensitivity was enhanced by 28% and 12% for substitutional-series and additive-series phosphors, respectively. As the Bi³⁺ concentration further increased, the oxygen sensitivities of both series declined, which was attributed to the energy transfer between Bi³⁺, the formation of Bi³⁺ aggregates as well as the increase of the Eu³⁺ site symmetry. The results of this study not only provided valuable references for phosphor thermometry, but also offered new ideas for developing high-temperature non-contact pressure sensors.     

Tuning the luminescence properties of blue and far-red dual emitting Gd2MgTiO6: Bi3+, Cr3+ phosphor for LED plant lamp

Blue and far-red light play a key role in plant growth, so it is necessary to develop blue and far-red dual emitting phosphors. However, the match between phosphors and plant pigments is not satisfactory. In this work, we synthesized a series of blue and far-red dual emission Gd₂MgTiO₆: Bi³⁺, Cr³⁺ (GMTO: Bi³⁺, Cr³⁺) phosphors and discussed the luminescence performance. The blue emission at 430 nm is ascribed to ³P₁ → ¹S₀ transition of Bi³⁺ and the far-red emission is ascribed to ⁴T₂ → ⁴A₂ and ²E → ⁴A₂ transitions of Cr³⁺. Notably, because of the energy competition between Cr³⁺ ions and host materials, the luminescence tuning realized with the content of Cr³⁺ doping. In addition, an energy-transfer performance occurred from Bi³⁺ ions to Cr³⁺ ions and the photoluminescence intensity of Cr³⁺ can be enhanced by Bi³⁺. The pc-LEDs devices were synthesized by GMTO: Bi³⁺, Cr³⁺ phosphor, and ultraviolet (UV) chips. Finally, the emission of GMTO: Bi³⁺, Cr³⁺ phosphor matched well with the absorption spectra of plant pigments which indicated the potential applications in LED plant lamp.     

Effect of crystal structures on energy transfer behavior from Bi3+ to Eu3+ in alkaline earth metalstannates

A single phased color-tunable phosphor via energy transfer has drawn much attention, whereas it is still a question that how to choose a suitable host to realize an efficient energy transfer. In this work, novel single Bi³⁺ or Eu³⁺ doped and Bi³⁺, Eu³⁺ co-activated Ca₂SnO₄ (CSO) and Sr₂SnO₄ (SSO) phosphors have been prepared through a high temperature solid state reaction. The energy transfer happening from hosts to Eu³⁺ has been confirmed. By co-doping of Bi³⁺, a brighter red light is realized which is attributed to the much more efficient energy transfer from Bi³⁺ to Eu³⁺. After comparison, the energy transfer efficiency from Bi³⁺ to Eu³⁺ is much higher in CSO:Bi³⁺, Eu³⁺ than that in SSO:Bi³⁺, Eu³⁺. Furthermore, the experiment reveals that the single-phased color-tunable phosphors exhibit excellent resistance against thermal quenching, suggesting that they can be potential candidates in UV-pumped white light emitting diodes (LEDs).     

Luminescence and self-referenced optical temperature sensing performance in Ca2YZr2Al3O12:Bi3+,Eu3+ phosphors

Ca₂YZr₂Al₃O₁₂:Bi³⁺,Eu³⁺ phosphors were elaborated by a traditional solid-state reaction method. The luminescence of Ca₂YZr₂Al₃O₁₂:Bi³⁺ samples, energy transfer from Bi³⁺ to Eu³⁺, and the temperature sensing properties of Ca₂YZr₂Al₃O₁₂:Bi³⁺,Eu³⁺ samples have been systematically researched. Under the excitation of ultraviolet light, Bi³⁺ single doped phosphors give 313 and 392 nm emission bands, which origin from the substitutions of Bi³⁺ instead of Ca²⁺ and Y³⁺ sites, respectively. And the color-adjustable emission from blue to red were observed by increasing Eu³⁺ content in Ca₂YZr₂Al₃O₁₂:Bi³⁺,Eu³⁺ samples. Relying on different temperature dependent variation tendency, the fluorescence intensity ratio (FIR) values present outstanding temperature sensing properties. The absolute and relative sensitivity can be up to 0.826 %K^-1 and 0.664 %K^-1, respectively. All above results suggest that Ca₂YZr₂Al₃O₁₂:Bi³⁺,Eu³⁺ phosphor is a potential alternative for optical thermometer.     

Broad band down conversion from ultra violet light to near infrared emission in YVO4:Bi3+, Yb3+ as spectral conversion phosphor for c-Si solar cells

Vanadate based down conversion phosphors have been synthesized by a novel co-precipitation technique. The effect of pH on crystal structure, particle size, morphology and luminescence properties were investigated by XRD, SEM-EDAX, FT-IR and PL measurements. As different from other reports (blue, green emission) the produced phosphors have shown greenish–yellow emission, owing to their fine particle size. A broad band excitation (280–370 nm), ascribed to ¹S₀→³P₁ and an intense greenish–yellow band emission (410–700 nm) attributed to ³P₁→¹S₀ transition of Bi³⁺ were observed. A strong greenish–yellow emission was measured with 3 mol. % of Bi³⁺ ions, as an optimum dopant concentration. The characteristic NIR emission of Yb³⁺, owing to ²F_5/2→²F_7/2 was recorded at 1039 nm, as a result of efficient energy transfer from Bi³⁺ to Yb³⁺, ions. The phosphors with chemical composition as Y_0.96VO₄: Bi_0.03³⁺, Yb_0.01³⁺ and Y_0.87VO₄: Bi_0.03³⁺,Yb_0.1³⁺ are suggested to be the novel candidates for the efficient down conversion of broad band ultra violet (UV) light into visible/near infrared (NIR) emission, as DC layers on c-Si solar cells for better harvesting the solar spectrum via spectral matching phenomena.     

Synthesis and photoluminescence enhancement of Ca3Sr3(VO4)4:Eu3+ red phosphors by co-doping with La3+

In this study, a series of red-emitting Ca₃Sr₃(VO₄)₄:Eu³⁺ phosphors co-doped with La³⁺ was prepared using the combustion method. The microstructures, morphologies, and photoluminescence properties of the phosphors were investigated. All Ca₃Sr₃(VO₄)₄:Eu³⁺, La³⁺ samples synthesized at temperatures greater than 700 ℃ exhibited the same standard rhombohedral structure of Ca₃Sr₃(VO₄)₄. Furthermore, the Ca₃Sr₃(VO₄)₄:Eu³⁺, La³⁺ phosphor was effectively excited by near-ultraviolet light of 393 nm and blue light of 464 nm. The strong excitation peak at 464 nm corresponded to the ⁷F₀→⁵D₂ electron transition of Eu³⁺. The strong emission peak observed at 619 nm corresponded to the ⁵D₀→⁷F₂ electron transition of Eu³⁺. Co-doping with La³⁺ significantly improved the emission intensity of Ca₃Sr₃(VO₄)₄:Eu³⁺ red phosphors. The optimum luminescence of the phosphor was observed at Eu³⁺ and La³⁺ concentrations of 5% and 6%, respectively. Moreover, co-doping with La³⁺ also improved the fluorescence lifetime and thermal stability of the Ca₃Sr₃(VO₄)₄:Eu³⁺ phosphor. The CIE chromaticity coordinate of Ca₃Sr₃(VO₄)₄:0.05Eu³⁺, 0.06La³⁺ was closer to the NTSC standard for red phosphors than those of other commercial phosphors; moreover, it had greater color purity than that of all the samples tested. The red emission intensity of Ca₃Sr₃(VO₄)₄:0.05Eu³⁺, 0.06La³⁺ at 619 nm was ~1.53 times that of Ca₃Sr₃(VO₄)₄:0.05Eu³⁺ and 2.63 times that of SrS:Eu²⁺. The introduction of charge compensators could further increase the emission intensity of Ca₃Sr₃(VO₄)₄:Eu³⁺, La³⁺ red phosphors. The phosphors synthesized herein are promising red-emitting phosphors for applications in white light-emitting diodes under irradiation by blue chips.     

Synthesis and luminescence enhancement of red-emitting Sr9Y(PO4)7:Eu3+ phosphor through Gd3+ co-doping for white light-emitting diodes

A series of Sr₉Y(PO₄)₇:Eu³⁺ and Sr₉Y(PO₄)₇:Eu³⁺, Gd³⁺ red-emitting phosphors were prepared via a high-temperature solid-state method, Gd³⁺ ion was co-doped in Sr₉Y(PO₄)₇:Eu³⁺ as sensitizer to enhance the luminescence property. The X-ray diffraction results verify that the structure of the as-prepared samples is consistent with the standard Sr₉Y(PO₄)₇ phase. All the Sr₉Y(PO₄)₇:Eu³⁺ samples show both characteristic emission peaks at 594 nm and 614 nm under near-ultraviolet excitation of 394 nm. The co-doping of Gd³⁺ significantly improves the luminescence intensity of the Sr₉Y(PO₄)₇:Eu³⁺ phosphors due to the crystal field environment effect and energy transfer of Gd³⁺→Eu³⁺ caused by the introduction of Gd³⁺, especially Sr₉Y(PO₄)₇:0.11Eu³⁺, 0.05Gd³⁺, which emission intensity is higher than that of Sr₉Y(PO₄)₇:0.11Eu³⁺ by 1.21 times. The color purity and lifetime of Sr₉Y(PO₄)₇:0.11Eu³⁺, 0.05Gd³⁺ phosphor are 88.26% and 3.7615 ms, respectively. A w-LED device was packaged via coating the as-prepared phosphor on n-UV chip of 395 nm with commercial phosphors. These results exhibit that the Sr₉Y(PO₄)₇:Eu³⁺, Gd³⁺ red-emitting phosphor can be used as a red component in the w-LEDs application.     

Dual-mode optical thermometry based on Bi3+/Eu3+ co-activated BaGd2O4 phosphor with high sensitivity and signal discriminability

A series of BaGd₂O₄:Bi³⁺,Eu³⁺ phosphors with dual-emitting centers were prepared by high-temperature solid-state method. X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS), fluorescence spectroscopy, lifetime decay curve and variable temperature emission spectroscopy were used to systematically study the structure, luminescence performance and temperature characteristics. Under ultraviolet (UV) excitation, the BaGd₂O₄:Bi³⁺,Eu³⁺ phosphor showed a broad-band emission in the blue region corresponding to transitions of Bi³⁺ ions and the sharp red light emission corresponding to Eu³⁺ ions. The Bi³⁺ and Eu³⁺ ion emission peaks were well-separated, which meets a prerequisite for efficient temperature signal resolution measurement. The fluorescence intensity ratio (FIR) technique was used to measure the different temperature response characteristics between Bi³⁺ blue emission and Eu³⁺ red emission. When the temperature varies from 293 K to 473 K, the relative temperature sensitivity (S_r) of BaGd₂O₄:Bi³⁺,Eu³⁺ phosphors is obtained, was determined as 1.0182%K⁻¹. In addition to calculating the relative sensitivity by FIR technology, we can also obtain the value of S_r through experiments and formulas related to the decay life, and found to be 1.0651%K⁻¹. Therefore, BaGd₂O₄: Bi³⁺,Eu³⁺ phosphor is an excellent non-contact optical temperature measurement material.     

Novel color tunable LaCaGaO4:Bi3+,Eu3+ phosphors for high color rendering warm white LEDs

A series of LaCaGaO₄:xBi³⁺,yEu³⁺ (x = 0.002–0.04, y = 0.02–0.45) phosphors with adjustable emission colors were synthesized by high-temperature solid-state reaction. The samples were identified as pure phases by X-ray diffraction and Rietveld refinement, and the crystal structures were analyzed in detail. The LaCaGaO₄:xBi³⁺ phosphor shows an intense blue emission under near-ultraviolet excitation, originating from the ³P₁ → ¹S₀ transition. The spectrum analysis reveals that the Bi³⁺ ions occupy two luminescence centers in the LaCaGaO₄ host and that energy transfer can occur. A model of the energy transfer between the Bi³⁺ and Eu³⁺ ions was also created and studied in detail. As the Eu³⁺-concentration increased, the emission color of the LaCaGaO₄:0.005Bi³⁺,yEu³⁺ phosphor changed from blue to pink to red. In addition, the fluorescence lifetime, quantum yield, thermal stability, and other properties of the phosphors were characterized and analyzed. Finally, two white light-emitting diode devices with R_a values of 96.6 and 95 and correlated color temperatures of 4578 and 3324 K were fabricated, indicating the potential of phosphors for warm white lighting applications.     

Enhanced luminescence properties of Eu3+ in La2MoO6 by nonsensitization of Bi3+

It was unusual for Bi³⁺ ions to enhance the emission intensity of phosphors via nonsensitization. Here, La₂MoO₆:Eu³⁺, Bi³⁺ phosphors were successfully synthesized by a high temperature solid-state reaction method in air atmosphere. As the increase of doping concentration of Bi³⁺, the emission spectra of La₂MoO₆:Eu³⁺, Bi³⁺ phosphors had obvious shifts, splits and the enhancement of intensities, which indicated that the characteristics of the phosphors were modified. To analyze these phenomena, the crystal structure refinements, spectral characteristic analyze and Judd-Ofelt theoretical calculation were mainly performed. Bi³⁺ ions played the role of the nonsensitizer and affected the distortion of the crystal, the sites of Eu³⁺ ions, the field splitting energy and the internal quantum yield. Moreover the nephelauxetic effects of Bi³⁺ ions and the ET process caused synergistically the life times of La₂MoO₆:Eu³⁺, Bi³⁺ phosphors to increase and then gradually decrease. The CIE coordinates of phosphors changed within a small range. This study might be instrumental in promoting the further application of Bi³⁺ ions in rare earth luminescent materials.     

Near-UV light excited Eu3+, Tb3+, Bi3+ co-doped LaPO4 phosphors: Synthesis and enhancement of red emission for WLEDs

A series of single-phase Eu³⁺, Tb³⁺, Bi³⁺ co-doped LaPO₄ phosphors were synthesized by solid-state reaction at 800 °C. Crystal structures of the phosphors were investigated by X-ray diffraction (XRD). A monoclinic phase was confirmed. The excitation (PLE) and emission (PL) spectra showed that the phosphors could emit red light centered at 591 nm under the 392 nm excitation, which is in good agreement with the emission wavelength from near-ultraviolet (n-UV) LED chip (370–410 nm). The results of PLE and PL indicated that the co-doped Tb³⁺ and Bi³⁺could enhance emission of Eu³⁺ and the fluorescent intensities of the phosphors excited at 392 nm could reach to a maximum value when the doping molar concentration of Tb³⁺ and Bi³⁺ is about 2.0% and 2.0%, respectively. The co-doping Tb³⁺ and Bi³⁺ ions can strengthen the absorption of near UV region. They can also be efficient to sensitize the emission of Eu³⁺, indicating that the energy transfer occurs from Tb³⁺ and Bi³⁺ to Eu³⁺ ions. From further investigation it can be found that co-doping Tb³⁺ and Bi³⁺ ions can also induce excitation energy reassignment between ⁵D₀–⁷F₁ and ⁵D₀–⁷F₂ in these phosphors, and result in more energy assignment to ⁵D₀–⁷F₂ emission in LaPO₄:Eu³⁺, Tb³⁺, Bi³⁺. Our research results displayed that La_0.94PO₄:Eu³⁺_0.02, Tb³⁺_0.02, Bi³⁺_0.02 could be a new one and could provide a potential red-emitting phosphor for UV-based white LED.     

Deep blue,cyan, orange-red,and white multicolor emissions generated by Bi3+/Eu3+ activated KBaYSi2O7 luminescent materials for white light-emitting diodes

A variety of Bi³⁺ and/or Eu³⁺ doped KBaYSi₂O₇ phosphors with deep blue, cyan, orange-red, and white light multicolor emissions have been fabricated by a Pechini sol-gel (PSG) method. The KBaYSi₂O₇:Bi³⁺ phosphors exhibit an intense cyan emission or a unique narrow deep blue emission when excited by different wavelengths, which may bridge the cyan gap or act as a promising deep blue phosphor for white light-emitting diodes (WLEDs). The tunable multicolor emissions can be achieved by changing the Bi³⁺ doping concentrations. The Bi³⁺/Eu³⁺ co-doped KBaYSi₂O₇ phosphors display intrinsic emissions of Bi³⁺ and Eu³⁺ and an energy transfer process between Bi³⁺ and Eu³⁺ can be detected. The luminescence colors of KBaYSi₂O₇:Bi³⁺,Eu³⁺ regularly shift from blue, through cold and warm white, finally toward orange-red by adjusting the relative doping concentrations of Bi³⁺ and Eu³⁺. The single-phase white light-emitting material can be generated in both cold and warm white regions by simply varying the Eu³⁺ doping concentrations. Furthermore, three kinds of WLEDs devices are fabricated by KBaYSi₂O₇:Bi³⁺ or KBaYSi₂O₇:Bi³⁺,Eu³⁺ phosphors, which can exhibit dazzling white light emissions with eminent CIE coordinates, correlated color temperature, and color rendering index. The result offers direct evidence that the as-synthesized phosphors may be potentially applied in WLEDs and solid-state lighting.