High sensitive Ln3+/Tm3+/Yb3+ (Ln3+ = Ho3+, Er3+) tri-doped Ba3Y4O9 upconverting optical thermometric materials based on diverse thermal response from non-thermally coupled energy levels

Upconversion (UC) optical thermometers using the fluorescence intensity ratio (FIR) technique arising from the thermally coupled energy levels (TCLs) are still suffering from low sensitivity owing to the restriction of small energy gap. In the present study, a strategy to strive for superior temperature sensitivity and signal discriminability is employed with the help of non-thermally coupled energy levels (NTCLs). A novel tri-doped Ba₃Y₄O₉: Ho³⁺/Tm³⁺/Yb³⁺ phosphor with rhombohedral symmetry was successfully prepared via a solid-state reaction method, and the temperature sensing performance was evaluated by analyzing temperature-dependent upconversion emission spectra. The emission intensities of both Ho³⁺ and Tm³⁺ activators can be almost completely restored to their original values when the temperature of the sample is cooled to room temperature. The temperature-dependent FIR between NTCLs can be fitted well by a derived three-term equation with the correlation coefficient above 99.6%, and the FIR of NTCLs exhibits high temperature sensitivity over a wide temperature range owing to the different temperature responses of the NTCLs. The maximum absolute sensitivity S_A and relative sensitivity S_R values reaches as high as 0.0552?K^?1 and 1.49% K^?1, respectively, which are much higher than those of the previously reported bulk UC optical temperature sensing materials. Moreover, the emission bands of NTCLs are well separated, which endows the material a good signal discriminability for temperature detection. Excellent temperature sensing performance is also demonstrated in Er³⁺/Tm³⁺/Yb³⁺ tri-doped Ba₃Y₄O₉, evidencing the validity of this strategy. These results indicate that the present UC materials can be potential candidates for optical temperature sensors, and the present strategy will provide a thought for developing other innovative UC temperature sensing materials.     

Upconversion luminescence properties of NaBi(MoO4)2:Ln3+, Yb3+ (Ln = Er,Ho) nanomaterials synthesized at room temperature

Studies on lanthanide ions doped upconversion nanomaterials are increasing exponentially due to their widespread applications in various fields such as diagnosis, therapy, bio-imaging, anti-counterfeiting, photocatalysis, solar cells and sensors, etc. Here, we are reporting upconversion luminescence properties of NaBi(MoO₄)₂:Ln³⁺, Yb³⁺ (Ln = Er, Ho) nanomaterials synthesized at room temperature by simple co-precipitation method. Diffraction and spectroscopic studies revealed that these nanomaterials are effectively doped with Ln³⁺ ions in the scheelite lattice. DR UV–vis spectra of these materials exhibit two broad bands in the range of 200–350 nm correspond to MoO₄²⁻ charge transfer, s-p transition of Bi³⁺ ions and sharp peaks due to f-f transition of Ln³⁺ ions. Upconversion luminescence properties of these nanomaterials are investigated under 980 nm excitation. Doping concentration of Er³⁺ and Yb³⁺ ions is optimized to obtain best upconversion photoluminescence in NaBi(MoO₄)₂ nanomaterials and is found to be 5, 10 mol % for Er³⁺, Yb³⁺, respectively. NaBi(MoO₄)₂ nanomaterials co-doped with Er³⁺, Yb³⁺ exhibit strong green upconversion luminescence, whereas Ho³⁺, Yb³⁺ co-doped materials show strong red emission. Power dependent photoluminescence studies demonstrate that emission intensity increases with increasing pump power. Fluorescence intensity ratio (FIR) and population redistribution ability (PRA) of ²H_11/2 → ⁴I_15/2, ⁴S_3/2 → ⁴I_15/2 transitions of Er³⁺ increases with increasing the Yb³⁺ concentration. Also, these values increase linearly with increasing the pump power up to 2 W. It reveal that these thermally coupled energy levels are effectively redistributed in co-doped samples due to local heating caused by Yb³⁺.     

Optical property evaluation of thoria doped with heavier rare-earth oxides LnO1.5 (Ln = Er3+, Ho3+, Tm3+, and Yb3+)

To address the existing gap in the literature of upconversion studies involving thoria, samples of thoria doped with Ho³⁺-Yb³⁺, Er³⁺-Yb³⁺, and Tm³⁺-Yb³⁺ were synthesized following epoxide gel method and were characterized. Fluorite structure of the doped samples was evident for the calcined samples from the corresponding xerogels as noticed in their powder X-ray diffraction patterns. The presence of a sharp band near 460 cm⁻¹ in the Raman spectra of all these samples supported the results from diffraction experiments. Intraconfigurational f-f transitions of Ho³⁺, Er³⁺, and Tm³⁺ were present in the UV-visible absorbance spectra of these samples. Both normal emission and upconversion emission from these samples have been studied. Emissions in all three basic colors were observed in the upconversion emission spectra. Two-photon process was found to be responsible for the upconversion in these systems. Decay time measurements for these emissions were analyzed. This synthetic process was further extended to determine the extent of dissolution of heavier lanthanides and found that up to 50 mol% of Ho³⁺, Er³⁺ and 60 mol% of Tm³⁺, Yb³⁺ could be dissolved retaining fluorite structure. Creation of oxygen vacancies for these heavily doped specimens was quite encouraging and it could be useful as solid electrolytes in fuel cells.     

Sr3GdLi(PO4)3F:Eu2+, Mn2+: A tunable blue-white color emitting phosphor via energy transfer for near-UV white LEDs

A series of Eu²⁺ and Mn²⁺ co-doping Sr₃GdLi(PO₄)₃F phosphors have been synthesized through high temperature solid state reaction. Eu²⁺ single doped Sr₃GdLi(PO₄)₃F phosphors have an efficient excitation in the range of 230–430 nm, which is in good agreement with the commercial near-ultraviolet (n-UV) LED chips, and gives intense blue emission centering at 445 nm. The critical distance of the Eu²⁺ ions in Sr₃GdLi(PO₄)₃F is computed and demonstrated that the concentration quenching mechanism of Eu²⁺ is mostly caused by the dipole-dipole interaction. By co-doping Eu²⁺ and Mn²⁺ ions in the Sr₃GdLi(PO₄)₃F host, the energy transfer from Eu²⁺ to Mn²⁺ that can be discovered. With the increase of Mn²⁺ content, emission color can be adjusted from blue to white under excitation of 380 nm, corresponding to chromatic coordinates change from (0.189, 0.108) to (0.319, 0.277). The energy transfer from Eu²⁺ to Mn²⁺ ions is proven to be a dipole-dipole mechanism on the basis of the experimental results and analysis of photoluminescence spectra and decay curves. This study infers that the obtained Sr₃GdLi(PO₄)₃F:Eu²⁺, Mn²⁺ phosphors may be a potential candidate for n-UV LEDs.     

Synthesis,structure and luminescence of a high-purity and thermal-stable Sr9LiMg(PO4)7: Eu3+ red phosphor

Eu³⁺-activated Sr₉LiMg(PO₄)₇ phosphors, which presented bright red emissions mainly from the ⁵D₀→⁷F₂ transition of Eu³⁺ ions upon the near-ultraviolet excitation, were successfully synthesized in ambient atmosphere. The crystal structure, phase constitution, photoluminescent behaviors, decay time, internal quantum efficiency and thermal stability of the resultant phosphors were investigated in detail. Eu³⁺ ions are found to tend to occupy multiple Sr²⁺ sites, which are 7, 8 and 10-coordinated. The optimal doping concentration is 7 mol% and the electrical multipolar interaction contributed to the non-radiative energy transfer between Eu³⁺ ions in Sr₉LiMg(PO₄)₇ host lattices. Temperature-dependent PL spectra indicated Sr₉LiMg(PO₄)₇: Eu³⁺ possess excellent emission and color stability at elevated temperature. Fabricated single-chromatic LED prototype emit bright red light under 20 mA bias current, which demonstrates that Sr₉LiMg(PO₄)₇: Eu³⁺ phosphor is of great potential as converted phosphor in NUV LED application.     

Efficient and tunable Mn2+ sensitized luminescence via energy transfer of a novel red phosphor Ca19Mn2(PO4)14: Eu2+ for white LED

The exploration of efficient and high-purity red phosphors is an urgent need in LED development. Due to the compact and compositional-tunable structure of whitlockite compound, manganese-based Ca₁₉Mn₂(PO₄)₁₄ is chosen as phosphor host for Eu²⁺ sensitization. Rietveld refinement, steady-state spectra, decay lifetime analysis and temperature-dependent emission spectra were investigated and clearly discussed. Under 360 nm excitation, Ca₁₉Mn₂(PO₄)₁₄: Eu²⁺ shows a strong Mn²⁺ sensitized emission at 655 nm with FWHM of 82 nm, benefiting from the short-distance-induced high-efficient Eu² -Mn²⁺ energy transfer. Emission engineering of Ca₁₉Mn₂(PO₄)₁₄: Eu²⁺ is achieved by Sr²⁺ co-doping, leading to both tunable peak wavelength (ranging from 650 to 610 nm) and improved intensity (130% of original value). Moreover, Ca₁₉Mn₂(PO₄)₁₄: Eu²⁺ exhibits a promising thermal stability where only 40% of emission intensity is lost at 200 °C. Finally, we explored the working performance of the fabricated RGB phosphor-converted white LED. The present work indicates that Ca₁₉Mn₂(PO₄)₁₄: Eu²⁺ phosphor is of great potential as a promising and efficient red phosphor in phosphor-converted white LED.     

Photoluminescence and energy transfer of efficient and thermally stable white-emitting Ca9La(PO4)7:Ce3+, Tb3+, Mn2+ phosphors

The development of novel single-component white-emitting phosphors with high thermal stability is essential for improving the illumination quality of white light-emitting diodes. In this work, we synthesized a series of Ce³⁺, Tb³⁺, Mn²⁺ single- and multiple-doped Ca₉La(PO₄)₇ (CLPO) phosphors with β-Ca₃(PO₄)₂-type structure by the simple high-temperature solid-state reaction. The crystallization behavior, crystal structure, surface morphology, photoluminescence performance, decay lifetime and thermal stability were systematically investigated. The PL spectra and decay curves have evidenced the efficient energy transfer from Ce³⁺ to Tb³⁺ and from Ce³⁺ to Mn²⁺ in the CLPO host, and corresponding energy transfer efficiency reaches 41.8% and 54.1%, respectively. The energy transfer process of Ce³⁺→Tb³⁺ and Ce³⁺→Mn²⁺ can be deduced to the resonant type via dipole-dipole and dipole-quadrupole interaction mechanism, and corresponding critical distance were determined to be 12.23 and 14.4 Å, respectively. Based on the efficient energy transfer, the white light emission can be successfully achieved in the single-component CLPO:0.15Ce³⁺, 0.10Tb³⁺, 0.04Mn²⁺ phosphor, which owns CIE chromaticity coordinates of (0.3245, 0.3347), CCT of 5878 K, internal and external quantum efficiency of 84.51% and 69.32%. Especially, compared with the emission intensity at 25 °C, it still remains 98.5% at 150 °C and 92.0% at 300 °C. Based on these results, the single-component white light emission phosphor CLPO:0.15Ce³⁺, 0.10Tb³⁺, 0.04Mn²⁺ is a potential candidate for UV-converted white LEDs.     

White light emission from novel host-sensitized single-phase Y2WO6: Ln3+ (Ln3+=Eu3+, Dy3+) phosphors

A series of Eu³⁺- or Dy³⁺-doped and Eu³⁺/Dy³⁺ co-doped Y₂WO₆ in pure phase was synthesized via high-temperature solid-state reaction. X-ray diffraction, diffuse reflection spectra, photoluminescence excitation and emission spectra, the CIE chromaticity coordinates and temperature-dependent emission spectra were exploited to investigate the phosphors. Upon UV excitation at 310 nm, efficient energy transfer from the host Y₂WO₆ to dopant ions in Eu³⁺ or Dy³⁺ single-doped samples was demonstrated and those phosphors were suitable for the UV LED excitation. The intense red emission was observed in Y₂WO₆: Eu³⁺, and blue and yellow ones were observed in Y₂WO₆: Dy³⁺. Concentration quenching in Y₂WO₆: Dy³⁺ phosphors could be attributed to the electric dipole-dipole interaction. In Eu³⁺/Dy³⁺ co-doped Y₂WO₆ phosphors energy transfer process only took place from the host to Eu³⁺/Dy³⁺ ions and warm white-light emission can be obtained by adjusting the dopant concentrations. The temperature-dependent luminescence indicated Eu³⁺/Dy³⁺ co-doped Y₂WO₆ was thermally stable. Our overall results suggested that Y₂WO₆: Ln³⁺ (Ln³⁺=Eu³⁺, Dy³⁺) as warm white-light emitting host-sensitized phosphor might be potentially applied in WLEDs.     

Host sensitized photoluminescence in Sr2.9-3x/2LnxAlO4F: 0.1Eu3+ (Ln = Gd,Y) for innovative flexible lighting applications

Tetragonal structured Sr₃AlO₄F is highly strained as reported from its global instability index estimation. Moreover, our results of X-ray photoelectron spectroscopy (XPS) also ascertained that the structure of Sr₃AlO₄F is highly strained with oxygen vacancies. Herein, aliovalent substitutions of divalent Sr ions with trivalent Ln (Ln = Gd/Y) ions were carried out to improve the stability of Sr₃AlO₄F lattice, which subsequently enhanced the photoluminescence in a series of Sr_2.9-3x/2Ln_xAlO₄F: 0.1Eu³⁺ phosphors. All the phosphors showed intense red-orange emission (⁵D₀ → ⁷F_1,2) at excitation with UV and near-UV light. The critical concentrations of Gd³⁺ and Y³⁺ up to which the Eu³⁺ emission intensities increased linearly were observed to be x = 0.09 and x = 0.07, respectively. Nevertheless, further enhancement in the Eu³⁺ luminescence of the optimized phosphors was realized by subsequently annealing in low oxygen atmospheres. The enhancement in oxygen deficiency during the post-annealing in Ar or vacuum led the energy transfer (O^2--Eu³⁺) to a greater extent which afterward increased the Eu³⁺ luminescence. The optimized Sr_2.765Gd_0.09AlO₄F: 0.1Eu³⁺ and Sr_2.795Y_0.07AlO₄F: 0.1Eu³⁺ phosphors showed high red color purity (~99%), as well as CIE coordinates of (0.62, 0.38), indicated that these phosphors could be appropriate red-emitting components for making flexible optical films for many lighting devices. Therefore, flexible polydimethylsiloxane based films were also fabricated using optimized Sr_2.765Gd_0.09AlO₄F: 0.1Eu³⁺ phosphor. The electroluminescence of a flexible PDMS-phosphor composite film showed an intense and pure red color with good thermal stability suggesting its suitability in flexible lighting and display devices.     

Broadband emission of single-phase Ca3Sc2Si3O12:Cr3+/Ln3+ (Ln = Nd,Yb, Ce) phosphors for novel solid-state light sources with visible to near-infrared light output

Novel single-component phosphors Ca₃Sc₂Si₃O₁₂:Cr³⁺/Ln³⁺ (CSS:Cr³⁺/Ln³⁺, Ln = Nd, Yb, Ce) with broadband near-infrared (NIR) emissions are synthesized. Their phase structure, photoluminescence properties and energy transfer between Cr³⁺ and Ln³⁺ ions are investigated. In the CSS host, Cr³⁺ ions occupy Sc³⁺ sites with low-field octahedral coordination, and thus show a broadband emission in 700–900 nm under the blue light excitation. Nd³⁺, Yb³⁺ and Ce³⁺ ions substitute Ca²⁺ sites in CSS, where Nd³⁺ and Yb³⁺ ions emit the NIR light in 900–1100 nm and their excitation efficiencies at ∼450 nm are greatly enhanced by utilizing the energy transfer from Cr³⁺ to Nd³⁺/Yb³⁺ ions. Ce³⁺ ions can further enhance the absorption of CSS:Cr³⁺/Ln³⁺ phosphors to the blue light, and at the same time contribute to the visible emission in 480–650 nm. Furthermore, CSS:Cr³⁺/Ln³⁺ phosphors show good thermal stability, and approximately 79% of the initial emission intensity is sustained at 150 °C. A phosphor-converted LED (pc-LED) prototype is fabricated by integrating the as-prepared phosphor CSS:Cr³⁺/Ln³⁺ and the commercial phosphor CaAlSiN₃:Eu²⁺ with the blue LED chip, showing a super broadband emission ranging from 450 to 1100 nm. This finding shows the potential application of CSS:Cr³⁺/Ln³⁺ phosphors in broadband NIR pc-LEDs or super broadband LED sources with visible to NIR light output.     

Realizing broadband spectral conversion in novel Ce3+,Cr3+,Ln3+ (Ln = Yb,Nd, Er) tridoped near-infrared phosphors via multiple energy transfers

The solar spectral converters mainly involve the energy transfer between two codoped ions. Here, we report a series of Ce³⁺, Cr³⁺, Ln³⁺ (Ln = Yb, Nd, Er) tridoped Gd₃Sc₂Ga₃O₁₂ (GSGO) phosphors with improved absorption and increasing near infrared (NIR) emission. We observed the multiple energy transfer behaviors of Cr³⁺→Ln³⁺, Ce³⁺→Ln³⁺, Ce³⁺→Cr³⁺, and Ce³⁺→Cr³⁺→Ln³⁺ in GSGO matrix. When Ce³⁺ is introduced into the GSGO:Cr³⁺,Ln³⁺ phosphors, the energy transfer of Ce³⁺→Cr³⁺→Ln³⁺ has been realized by utilizing the energy transfer bridge of the Cr³⁺ ion. Consequently, GSGO:Ce³⁺,Cr³⁺,Ln³⁺ can absorb almost all ultraviolet and visible (UV–Vis) light and produce strong NIR light thanks to the synergistic effect of Ce³⁺→Cr³⁺→Ln³⁺, improving the photovoltaic conversion efficiency of c-Si solar cells. Our results show that the prepared GSGO:Ce³⁺,Cr³⁺,Ln³⁺ have the potential application in the solar spectral material for c-Si solar cells. Meanwhile, the strategy of multiple energy transfers gives a new way to design the spectral conversion materials with wider absorption for c-Si solar cells.     

Rapid green preparation of Lu7O6F9:RE (RE = Eu3+/Gd3+, Yb3+/Er3+) phosphors using ionic liquids

Rare earth oxyfluoride materials are a fascinating class of host matrixes for various applications. However, rapid green preparation of multifunctional rare earth oxyfluoride phosphors remains a huge challenge. In this work, we report the fast synthesis of Lu₇O₆F₉ using ionic liquids (ILs), which enables the precursors to be obtained at 10 min. The effects of calcination temperature, reaction temperature, reaction time and fluorine source on the phase and morphology of precursors and products are elaborated and the growth mechanism is put forward. Eu³⁺ alone and Yb³⁺, Er³⁺ co-doped samples were prepared to investigate the down-conversion (DC) and up-conversion (UC) properties, respectively. Besides, Gd³⁺ ions were introduced to the Eu³⁺ doped products, endowing the phosphors more intense luminescence and paramagnetic properties. The proposed facile synthesis route, excellent luminescence, thermal stability and paramagnetic properties open up the way to obtain rare earth fluoride and oxyfluoride for multifunctional applications.     

An efficient far-red emission Sr2InSbO6:Mn4+, M (M = Li+, Na+, and K+) phosphors for plant cultivation LEDs

High-efficiency and far-red light phosphors based on Mn⁴⁺-doped inorganic luminescence materials are beneficial to plant cultivation. However, Mn⁴⁺-doped oxide phosphors have a common problem of low quantum efficiency. Alkali metal ion codoping can effectively improve the luminescence properties of Mn⁴⁺-activated oxide phosphors. Herein, a series of Sr₂InSbO₆:Mn⁴⁺, M (SISO:Mn⁴⁺, M) (M = Li⁺, Na⁺, and K⁺) far-red-emitting phosphors codoped alkali metal ions were first synthesized. Density functional theory calculation indicated that SISO is a kind of indirect bandgap material with a bandgap of ∼1.60 eV. The SISO:Mn⁴⁺ samples showed a far-red light at 698 nm upon 365 nm, which perfectly matched the absorption spectrum of the far-red-phytochrome (Pfr) of plants. The doping concentration of the SISO:Mn⁴⁺ samples was optimized to be 0.006 mol. The concentration quenching mechanism was defined as dipole–dipole interaction by combining the Dexter theory and the Inokuti–Hirayama model. Optimizing the sintering temperature and codoped with alkali metal ions (Li⁺, Na⁺, and K⁺) could improve the luminescent intensity of SISO:Mn⁴⁺. The optimum sintering temperature was 1300°C. The internal quantum efficiencies of SISO:0.006Mn⁴⁺ and SISO:0.006Mn⁴⁺, 0.006Li⁺ phosphors are 22.67% and 60.56%, respectively. SISO:Mn⁴⁺, Li⁺ phosphors-based plant growth light-emitting diodes (LEDs) demonstrate excellent optical stability and long lifetime. Thus, these phosphors are promising candidates for plant cultivation LEDs.     

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.     

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.     

Synthesis and thermophysical performances of complex Ca3Ln3Ti7Ta2O26.5 (Ln=Dy and Er) oxides

Ca₃Dy₃Ti₇Ta₂O_26.5 and Ca₃Er₃Ti₇Ta₂O_26.5 oxides were synthesized using a high-temperature solid-state fritting technique, and the thermophysical performances of these two oxides were investigated. Both Ca₃Dy₃Ti₇Ta₂O_26.5 and Ca₃Er₃Ti₇Ta₂O_26.5 show a monophasic pyrochlore-type lattice. The thermal conductivity of Ca₃Er₃Ti₇Ta₂O_26.5 is lower than that of Ca₃Dy₃Ti₇Ta₂O_26.5. The oxides exhibit lower thermal conductivities than YSZ owing to their complex elemental compositions, large number of ions, and high oxygen vacancy concentrations. The thermal expansion coefficients of the obtained oxides are similar to that of YSZ.     

Cation vacancy repair towards a new yellow Ca7Sr3Na(PO4)7:Eu2+ phosphor

Cationic substitution is a prevalent strategy to tune the luminescence spectra of phosphors. In this work, we reported a series of Eu²⁺-activated whitlockite type Ca₇Sr_3.5-0.5xA_x(PO₄)₇ (CSPA; A =Li, Na, K) (x = 0–1.00) phosphors. The substitution by Na⁺ for both half occupied/vacant M(4) site was verified via Raman spectra, Reitveld refinement and HR-TEM, whereas a similar accommodation of K⁺ into the Ca₂Sr(PO₄)₂ (CSP) host cannot be realized due to the significant size mismatch. A continuous increase of Na⁺ contents led to the progressively structural contraction, promoting the migration of Eu²⁺ activator from looser M(4) to other sites, and regulating the luminescence behaviors. Consequently, the gradual red-shift of emission band terminated at a new yellow phosphor Ca₇Sr₃Na(PO₄)₇:0.04Eu²⁺. The cation vacancy repair developed in this work can not only migrate the Eu²⁺ activator among different cation sites, but also serves as a new strategy for tuning the luminescence properties of phosphor.     

REVO4‐Based Nanomaterials (RE = Y,La, Gd,and Lu) as Hosts for Yb3+/Ho3+, Yb3+/Er3+, and Yb3+/Tm3+ Ions: Structural and Up‐Conversion Luminescence Studies

Rare‐earth vanadates of the form REVO₄ (RE = Y, La, Gd, and Lu) doped by Yb³⁺/Ho³⁺, Yb³⁺/Er³⁺_, or Yb³⁺/Tm³⁺ lanthanide ions were successfully synthesized using the sol–gel method and annealing at 600°C in an air atmosphere. The structure and morphology of the prepared nanocrystals were investigated by X‐ray diffraction, thermogravimetric analysis, transmission electron microscopy, and energy‐dispersive X‐ray spectroscopy. All prepared materials were homogenous and had nanosized dimensions. Their elemental compositions were confirmed by optical emission spectrometry. Spectroscopic analysis of the materials was carried out by measuring excitation and emission spectra, luminescence decays, and dependence between the intensity of the luminescence and the laser energy. Following effective excitation by NIR radiation, Ln³⁺ co‐doped vanadate matrices exhibited a strong up‐conversion (UC) luminescence. Differences in spectroscopic properties between monoclinic LaVO₄ and tetragonal YVO₄, GdVO₄, or LuVO₄ doped by Ln³⁺ ions were observed, indicating the influence of the crystal structure on the UC emission. Drawing conclusions from these spectroscopic investigations, the UC mechanisms were proposed, including energy‐transfer processes between Yb³⁺ ions and emitting ions.     

Synthesis,crystal structure,optical and adsorption properties of BaAl2O4: Eu2+, Eu2+/ L3+ (L = Dy,Er, Sm,Gd, Nd,and Pr) phosphors

In this work, the BaAl2O4: Eu²⁺, Eu²⁺/L³⁺ (L= Dy, Er, Sm, Gd, Nd, and Pr) phosphors were synthesized via a facile solid-state reaction method using LiCl as a flux material at 1100 °C. The structural properties, microstructure, adsorption and photoluminescence characteristics of products were evaluated by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), Uv–vis adsorption and photoluminescence (PL) analyses. The observation of XRD patterns showed that even 10% LiCl is not able to produce any impurity phase in BaAl₂O₄: Eu²⁺ crystal structure, although the microstructure morphology is considerably affected. The particle size of BaAl₂O₄: Eu²⁺ phosphors was about 220 nm while the use of LiCl flux resulted in a remarkable decrease of this parameter to about 120 nm. Furthermore, the PL patterns disclosed that Eu²⁺ ions have occupied one type of Ba²⁺ sites while larger quantities of lanthanides (L³⁺) occupied the second type of Ba²⁺ sites. The strongest photoluminescence emission intensity at the wavelength of 495 nm was achieved when 5 wt% LiCl was added to BaAl₂O₄: Eu²⁺. Also, the absorption analysis revealed that the addition of flux enriches the adsorption of Congo red (CR) dye on the phosphor powders. The use of 5 wt% flux material led to noticeable improvement of CR adsorption capacity from 38.53 to 48.3 mg g⁻¹.     

Synthesis and photoluminescence properties of Sr3(PO4)2:Re3+, Li+ (Re = Eu,Sm) red phosphors for white light-emitting diodes

Sr₃(PO₄)₂:Re³⁺, Li⁺ (Re = Eu, Sm) red phosphors were prepared via a high temperature solid state reaction, and their structure and luminescence properties were investigated. X-ray diffraction patterns indicate that the phase of as-prepared samples is in good agreement with standard Sr₃(PO₄)₂ structure. Under 395 nm excitation, the emission of Sr₃(PO₄)₂:Eu³⁺ consists of a strong peak centered at 622 nm and two weak peaks centered at 598 nm and 660 nm, which correspond to ⁵D₀→⁷F₂, ⁵D₀→⁷F₁ and ⁵D₀→⁷F₃ transitions, respectively. Also, the emission spectrum of Sr₃(PO₄)₂:Sm³⁺ shows three main peaks at 568 nm, 603 nm and 651 nm, which are attributed to ⁴G_5/2→⁶H_I/2 (I = 5, 7, 9) transitions of Sm³⁺. Furthermore, luminescence properties of Sr₃(PO₄)₂:Re³⁺, Li⁺ (Re = Eu, Sm) samples are enhanced significantly by Li⁺ ions doping as charge compensator. Results indicate that as-prepared Sr₃(PO₄)₂:Re³⁺, Li⁺ (Re = Eu, Sm) could be the potential red phosphors used in white light-emitting diodes.