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.     

Tunable emission color of Li2SrSiO4:Tb3+ due to cross‐relaxation process and optical thermometry investigation

A series of Li₂SrSiO₄:xTb³⁺ (0.2%, 0.4%, 0.6%, 0.8%, 2%, 4%, and 6%) phosphors were prepared by conventional solid‐state reaction. It was found that this silicate phosphor has a wide excitation band at near‐ultraviolet region (230‐300 nm) due to spin‐allowed 4f ⁸→4f⁷5d¹ transitions of Tb³⁺ ions, with the exact position dependent on the crystal field of the lattice. The cross‐relaxation process originating from ⁵D₃→⁵D₄ and ⁷F₆→⁷F₀ happened between different Tb³⁺ ions. It leads to the luminescence color of Li₂SrSiO₄: xTb³⁺ tuning from blue to green just by controlling Tb³⁺ concentrations. Furthermore, concentration quenching mechanism, energy migration type, cross‐relaxation rate and efficiency, are discussed in detail. Finally, optical thermometry properties were investigated via temperature‐dependent emission spectra. The results show that low‐concentration‐doped sample (Li₂SrSiO₄:0.4%Tb³⁺) shows remarkable optical thermometry based on fluorescence intensity ratio (FIR) between the blue and green emission of Tb³⁺ ions, whereas the high‐concentration‐doped sample (Li₂SrSiO₄:4%Tb³⁺) demonstrates small emission intensity loss. It illustrates that terbium‐doped silicate phosphor is a multifunctional material with potential application for display field and optical thermometry .     

Toward temperature-dependent Bi3+-related tunable emission in the YVO4:Bi3+ phosphor

Up until now, many previous works have indicated us that the photoluminescence (PL) properties of phosphors sometimes can be changed with the change in the external temperature, resulting in the anomalous PL phenomena and correlated new applications that are difficult to achieve at room temperature. In this work, we report the temperature-dependent Bi³⁺-related PL properties in the YVO₄:Bi³⁺ phosphor. Our findings show that increasing the temperature from 10 to 300 K enables manipulating the energy interaction from groups to Bi³⁺, thereby leading to the temperature-induced color tuning from blue (0.183, 0.212) to yellow (0.418, 0.490). Upon this heating process, we further reveal that the dynamic Bi³⁺ luminescence has experienced a regular transition from double-exponential to single-exponential decay, which results in the decrease in the average Bi³⁺ lifetime from 122.606 to 0.376 μs. Discussions on the PL results imply that the tunable PL observations are due to the interplay of temperature-dependent energy transfer from groups to Bi³⁺ and redistribution of the excited ³P₀ and ³P₁ states of Bi³⁺ upon the thermal stimulation. This work not only presents the temperature-triggered Bi³⁺ tunable properties in the well-studied YVO₄ host lattice but also can provide new insights into revealing Bi³⁺-related PL mechanism in other Bi³⁺-doped photonic materials in the future and, in the meanwhile, gives some directive ideas for us to explore previously unnoticed applications for rare-earth (RE; eg, Eu³⁺, Pr³⁺, Tb³⁺, Eu²⁺, Er³⁺, etc) and other non-RE (eg, Bi³⁺, Mn⁴⁺, Mn²⁺, Cr³⁺, etc) doped phosphors.     

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.     

Tunable luminescence and energy transfer properties of MgY4Si3O13: Ce3+, Tb3+, Eu3+ phosphors

The tricolor-emitting MgY₄Si₃O₁₃: Ce³⁺, Tb³⁺, Eu³⁺ phosphors for ultraviolet-LED have been prepared via a high-temperature solid-state method. X-ray diffraction, photoluminescence emission, excitation spectra and fluorescence lifetime were utilized to characterize the structure and the properties of synthesized samples. Two different lattice sites for Ce³⁺ are occupied from the host structure and the normalized PL and PLE spectra. The emissions of single-doped Ce³⁺/Tb³⁺/Eu³⁺ are located in blue, green and red region, respectively. The energy transfer from Ce³⁺ to Tb³⁺ and from Tb³⁺ to Eu³⁺ has been validated by spectra and decay curves and the energy transfer mode from Tb³⁺ to Eu³⁺ was calculated to be electric dipole-dipole interactions. By adjusting the content of Tb³⁺ and Eu³⁺ in MgY₄Si₃O₁₃: Ce³⁺, Tb³⁺, Eu³⁺, the CIE coordinates can be changed from blue to green and eventually generate white light under UV excitation. All the results indicate that the MgY₄Si₃O₁₃: Ce³⁺, Tb³⁺, Eu³⁺ phosphors are potential candidates in the application of UV-WLEDs.     

New apatite-type phosphor Ca9La(PO4)5(SiO4)F2:Tb3+,Dy3+ with improved color rendering index

Ca₉La(PO₄)₅(SiO₄)F₂:Tb³⁺,Dy³⁺ (CLPSF:Tb³⁺,Dy³⁺) phosphors were successfully prepared using the traditional solid-state technique. The crystal structure was refined and the luminescence properties have been examined in detail. The band gap and electronic structure of Ca₉La(PO₄)₅(SiO₄)F₂ were performed by the periodic density functional theory (DFT) calculation. The spectral and fluorescence decay dynamics of CLPSF:Tb³⁺,Dy³⁺ show that the energy transfer behavior between Tb³⁺ and Dy³⁺ ions is observed. The CLPSF:Tb³⁺,Dy³⁺ phosphors can be efficiently excitable at the wavelengths range from 300 to 500 nm. The emission spectrum covers the whole visible part of the spectra with the sharp emission bands in red, green, and blue regions. The correlated color temperature (CCT) and color rendering index (CRI) of white light emission could be improved by the fine-tuning of the Tb³⁺ and Dy³⁺ ions ration in accordance with the energy transfer behavior. Thus, the CLPSF:Tb³⁺,Dy³⁺ phosphor could be used as a material for the near-ultraviolet (n-UV) and white light-emitting diodes (w-LEDs).     

Synthesis and luminescence study of Zn3V2O8: Bi3+ yellow phosphor for solar spectral conversion

A yellow phosphor Zn₃V₂O₈: Bi³⁺ was synthesized by solid‐state method. It can efficiently absorb UV photons of 250‐400 nm, and convert into strong yellow emission with maximum at 550 nm, which can be absorbed by dye‐sensitized solar cells (DSSCs). VO₄→Bi³⁺ energy transfer is discussed. The critical Bi³⁺ concentration is 0.04 with critical distance of 13.25 Å. The CIE coordinates of Zn₃V₂O₈: Bi³⁺ are (0.421, 0.518). Zn₃V₂O₈: Bi³⁺ phosphor exhibits good thermal stability with T_1/2=150°C. The results indicate that Zn₃V₂O₈: Bi³⁺ phosphor is a promising UV‐absorbing spectral converter to enhance power conversion efficiency and photochemical stability of DSSCs.     

Sr8Si4O12Cl8:Eu3+,M3+(M3+=Bi3+,Gd3+)中Eu3+的敏化发光

以Na2CO3为电荷补偿剂,采用高温固相法合成了碱土氯硅酸盐Sr8Si4O12Cl8:(Eu3 M3 )(M=Bi3 ,Gd3 )荧光材料.X射线衍射分析结果表明:合成的Sr8Si4O12Cl8:(Eu3 ,M3 )为纯四方相.Eu3 的发射主峰位于614 nm,为5D0→7F2的电偶极跃迁,表明Eu3 处于非中心对称格位,即取代Sr2 的位置.通过对其激发光谱和发射光谱研究,发现敏化剂Bi3 ,Gd3 的掺入对Eu3 的发射具有较强的敏化作用,当Bi3 和Gd3 的掺杂量(摩尔分数)分别为5.0%时,Eu3 的相对发光强度分别提高了29.4%和23.6%.     

Ca3MgSi2O8:RE(RE=Eu2+,Ce3+,Tb3+)的发光性能

采用高温固相法在还原气氛下合成了Ca3MgSi2O8:RE(RE=Eu2 ,Ce3 ,Tb3 )系列样品.用荧光光谱仪研究了样品掺杂Eu2 ,Ce3 ,Tb3 后的光谱性质.样品Ca3MgSi2O8:Ce3 在紫外光激发下呈蓝紫色发射;样品Ca3MgSi2O8:Eu2 在紫外光激发下则呈绿色发射.分别讨论了Ce3 ,Eu2 和Ce3 ,Tb3 共激活焦硅酸钙盐在紫外光激发下的光谱特性和其中存在的能量传递机理,发现Ce3 分别对Eu2 和Tb3 有敏化作用.     

Sensitive optical thermometer via efficient energy transfer in dual-emitting thermochromic YNbO4:Bi3+, Eu3+ phosphor

The remote and non-invasive optical thermometer exploiting fluorescence intensity ratio technology is of great importance in various intelligent optoelectronic sensors. Dual-emitting YNbO₄:Bi³⁺, Eu³⁺ phosphor is synthesized and investigated for the development of temperature sensing materials. The phosphor excited at 318 nm shows a blue broad band emission and several red sharp peaks. The value of Bi³⁺→Eu³⁺ energy transfer can reach 98.2% when Eu³⁺ doping content is 0.14. Benefiting from diverse thermal response behaviors due to Bi³⁺ and Eu³⁺ ions completely different electronic configurations, a dual-emitting optical thermometer is designed. The maximum values of absolute and relative sensitivities are as high as 2.51% K^?1 at 473 K and 1.43% K^?1 at 423 K, respectively. The thermochromic phosphor possesses a great chromaticity shift (ΔE = 317×10^?3) with temperature. Based on superior color discriminability, visual colorimetry temperature measurement relied on thermal characteristic is proposed. All the results demonstrate that YNbO₄:0.01Bi³⁺, 0.005Eu³⁺ phosphor as a sensitive and reliable optical thermometer has great potentials in temperature measurement.     

White‐emitting phosphor Ba2B2O5:Ce3+, Tb3+, Sm3+: Luminescence,energy transfer,and thermal stability

A series of Ba₂B₂O₅: RE (RE=Ce³⁺/Tb³⁺/Sm³⁺) phosphors were synthesized using high‐temperature solid‐state reaction. The X‐ray diffraction (XRD), luminescent properties, and decay lifetimes are utilized to characterize the properties of the phosphors. The obtained phosphors can emit blue, green, and orange‐red light when single‐doped Ce³⁺, Tb³⁺, and Sm³⁺. The energy can transfer from Ce³⁺ to Tb³⁺ and Tb³⁺ to Sm³⁺ in Ba₂B₂O₅, but not from Ce³⁺ to Sm³⁺ in Ce³⁺ and Sm³⁺ codoped in Ba₂B₂O₅. However, the energy can transfer from Ce³⁺ to Sm³⁺ through the bridge role of Tb³⁺. We obtain white emission based on energy transfer of Ce³⁺→Tb³⁺→Sm³⁺ ions. These results reveal that Ce³⁺/Tb³⁺/Sm³⁺ can interact with each other in Ba₂B₂O₅, and Ba₂B₂O₅ may be a potential candidate host for white‐light‐emitting phosphors.     

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.     

Tunable chromaticity and high color rendering index of WLEDs with CaAlSiN3:Eu2+ and YAG:Ce3+ dual phosphor-in-silica-glass

Phosphors-in-glass (PiG), which serves as a potential bi-replacement of both phosphors and organic encapsulants in high-power white light-emitting diodes (WLEDs), has captured much attention due to its high thermal stability and excellent luminescent properties. However, due to the high-temperature sensitivity and the chemical reactions between phosphors with glass matrix, a variety of phosphors, especially red phosphors could be hardly dispersed into the glass without thermal quenching and decomposition, which greatly limits the improvement of color rendering index and chromaticity tunability of the WLEDs. In this study, adopting the mesoporous silica (FDU-12) and commercial phosphors as raw materials, the phosphors-in-silica-glasses (PiSGs) embedded with red phosphor CaAlSiN₃:Eu²⁺ and yellow phosphor YAG:Ce³⁺ have been successfully prepared at low sintering temperature (950°C) and short preparation time (10 minutes) using spark plasma sintering. Owing to the well preservation of the originally emissive properties of the embedded phosphors, the warm WLEDs with tunable chromaticity and exhibited a superior performance with LE of 133 lm/W, CCT of 3970 K and CRI of 81 were fabricated by encapsulating the as-prepared PiSGs on the blue chips. Moreover, the PiSG composite exhibits a high thermal conductivity up to 1.6 W/m·K.     

Luminescence characteristics of SrZnSO:M (M = Bi3+, Mn2+ and Tb3+) phosphors

Bi³⁺/Tb³⁺/Mn²⁺-activated SrZnSO phosphors were prepared to investigate their luminescence characteristics. The SrZnSO:Bi³⁺, SrZnSO:Mn²⁺ and SrZnSO:Tb³⁺ phosphors, excited by the NUV/blue light, show blue, orange and green emissions, respectively. The Bi³⁺ → Tb³⁺, Tb³⁺ → Mn²⁺ and Bi³⁺ → Mn²⁺ energy transfer processes take place in Bi³⁺/Tb³⁺-, Tb³⁺/Mn²⁺-, Bi³⁺/Mn²⁺- and Bi³⁺/Tb³⁺/Mn²⁺-activated SrZnSO phosphors, which result in tunable luminescence of these phosphors. The CIE coordinates were calculated on the basis of the emission spectra, and they reflect the emission color changes of phosphors. For the Bi³⁺/Tb³⁺-, Tb³⁺/Mn²⁺- and Bi³⁺/Mn²⁺- activated SrZnSO phosphors, the emission points are located in the cyan, yellow and white light regions, respectively. For the Bi³⁺/Tb³⁺/Mn²⁺-activated SrZnSO phosphors, the light is in warm white light region.     

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.     

Site construction of Eu2+ and sensitized luminescence of Eu3+ in LaF3:Eu nanophosphor

LaF₃:Eu nanophosphors were prepared by a traditional hydrothermal method with citric acid as a reducing agent. X-ray diffraction, scanning electronic microscopy, and luminescence spectroscopy were used to study the nanophosphors. The formation of three different luminescence centers of Eu²⁺ and two different luminescence centers of Eu³⁺ is attributed to the existence of abundant surface defects in this nanophosphor. Eu³⁺ is effectively excited by energy transfer from Eu²⁺ to Eu³⁺. The excitation wavelength of Eu³⁺ covers a broad spectral range from 250 to 480 nm. The nanophosphor shows a tunable luminescence color varying from blue to white and then to red, which is explained from three aspects of Eu concentration, energy transfer, and concentration quenching. Utilizing the surface defect of nanoparticles to control the reduction of Eu³⁺ is considered a promising strategy for exploring Eu²⁺ and Eu³⁺ codoped phosphor suitable for the lighting and display application.     

Ba3Tb(BO3)3:Eu3+的制备与发光性质

采用高温固相法合成了Ba3Tb(BO3)3:Eu3+红色荧光粉,并研究了Ba3Tb(BO3)3:Eu3+的发光特性。Ba3Tb(BO3)3:Eu3+的激发光谱包含250nm～330nm和350nm～400nm的2个宽带,最大峰值位于383nm,可以被紫外-近紫外发光二极管(light-emitting diodes,LED)有效激发。Ba3Tb(BO3)3:Eu3+的发射谱显示出4组发射峰,其主发射峰位于620nm,对应Eu3+的5D0→7F2跃迁;Eu3+掺杂摩尔分数为2%时,Ba3Tb(BO3)3:Eu3+发光亮度最高。经分析发现Ba3Tb(BO3)3:Eu3+存在Tb3+→Eu3+的能量传递。     

The Energy Transfer and Thermal Stability of a Blue‐Green Color Tunable K2CaP2O7:Ce3+,Tb3+ Phosphor

Novel blue‐green emitting Ce³⁺‐ and Tb³⁺‐activated K₂CaP₂O₇ (KCPO) luminescent materials were synthesized via a solid‐state reaction method. X‐ray diffraction, luminescence spectroscopy, decay time, and fluorescent thermal stability tests have been used to characterize the prepared samples. The KCPO:Ce³⁺,Tb³⁺ luminescence spectra show broad band of Ce³⁺ ions and characteristic line of Tb³⁺ ion transition (⁵D₄–⁷F₅). The color variation in the light emitting from blue to green under UV excitation can be obtained by tailoring the Tb³⁺ content in KCPO:Ce³⁺. Besides, Ce³⁺ ions obviously intensify Tb³⁺ ion emission through an effective energy transfer process, which was confirmed from decay curves. The energy transfer efficiency was determined to be 82.51%. A resonant type mechanism via the dipole–quadrupole interaction can be proposed for energy transfer. As a whole, the KCPO:Ce³⁺,Tb³⁺ phosphor exhibits excellent performance in the range from 77 to 673 K, indicating the phosphors are highly potential candidates for solid‐state lighting.     

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.     

Strong energy transfer and color tunable emission in Eu2+ and Mn2+ co-doped Na2BaSr(PO4)2 phosphor

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