Synthesis and characterization of novel blue emitting Na2CaSiO4:Ce3+ phosphor

The blue phosphors Na_(2?x)Ca_(1?x)SiO₄:xCe³⁺ were synthesized by the sol–gel method and their luminescence characteristics were investigated for the first time. Structural information about prepared samples is obtained by analyzing the XRD patterns and SEM micrographs. The photoluminescence (PL) excitation spectra indicate that the Na_(2?x)Ca_(1?x)SiO₄:xCe³⁺ phosphors can be effectively excited by ultraviolet (360 nm) light. The PL emission spectra exhibit tunable blue broadband emission with the dominant wavelength of 427–447 nm under excitation of 360 nm by controlling the doping concentration of Ce³⁺. The concentration quenching effect for Ce³⁺ was found at the optimum doping concentration of 4 mol%. The Commission Internationale de l’Eclairage 1931 chromaticity coordinates of Na_1.96Ca_0.96SiO₄:0.04Ce³⁺ are (0.1447, 0.0787), which are better color purity compared to the commercial Eu²⁺-doped BaMgAl₁₀O₁₇ phosphor. Na_1.96Ca_0.96SiO₄:0.04Ce³⁺ composition shows intense blue emission (peak wavelength, 439 nm) with relative intensity versus commercial BaMgAl₁₀O₁₇:Eu²⁺ blue phosphor (Nichia) 65 and 158 % under 254 and 365 nm excitation, respectively. All the results indicate that Na_(2?x)Ca_(1?x)SiO₄:xCe³⁺ phosphors are potential candidate as a blue emitting phosphor for UV-converting white light-emitting diodes.     

Luminescence properties of Cu-activated BaZnOS phosphor

Cu-activated BaZnOS was studied for the first time as a novel and efficient blue-emitting phosphor. Under the excitation of UV radiation, the phosphor can efficiently give a blue emission centered at 430 nm, corresponding to the transition from conduction band edge to the excited state of Cu²⁺ in the BaZnOS host. The maximum emission intensity occurs at 0.08 mol% of the Cu doping content for both photoluminescence (PL) and X-ray excited luminescence. The optimized blue-emitting BaZnOS:Cu phosphor has a larger PL intensity than the well-known green-emitting ZnO:Cu and blue-emitting ZnS:Cu phosphors. The excellent luminescence properties are tightly related to the appropriate direct band gap and the unique crystal structure of BaZnOS host. These results strongly indicate that the Cu-activated BaZnOS is a potential material used as a new high-brightness blue phosphor for UV light-emitting diode and display devices.     

Strong upconversion–downshifting green emission from Tb<Superscript>3+</Superscript> ions in core/shell/shell-structured nanophosphors

Efficient upconversion (UC)–downshifting (DS), dual-mode-emitting NaGdF₄:Yb,Tm/NaGdF₄:Tb/NaYF₄ core/shell/shell (C/S/S) nanophosphors (NPs) were synthesized. The UC luminescence color changed from blue to sky blue after doping Tb³⁺ into NaGdF₄ shell because Tb³⁺ emission peaks via ⁵D₄ → ⁷F_J transition were observed with Tm³⁺ emission peaks via ¹D₂ → ³F₄ and ¹G₄ → ³H₆ transitions through the energy migration UC process of Yb³⁺ → Tm³⁺ → Gd³⁺ → Tb³⁺. Upon increasing the Tb³⁺ concentration in the NaGdF₄ shell from 5 to 15%, the Commission Internationale de l’Éclairage (CIE) color coordinates changed from (0.2188, 0.2390) to (0.2616, 0.3654). When NaGdF₄:Yb(49%),Tm(1%)/NaGdF₄:Tb(15%)/NaYF₄ NPs were excited using 273 nm ultraviolet light, the C/S/S NPs exhibited bright green light with CIE color coordinates of (0.3354, 0.5090) as a result of energy transfer from Gd³⁺ to Tb³⁺. These bright UC–DS, dual-mode-emitting C/S/S NPs could be applied in various applications, including multiplexed imaging and anticounterfeiting.     

Synthesis of CaWO4:Er3+@SiO2 and CaWO4:Tm3+@SiO2 nano-particles via a combustion pathway and study of their optical properties

Use of citric acid as a chelating agent and fuel, ammonium nitrate as fuel, boric acid as flux material and silica as supports, CaWO₄:Ln³⁺@SiO₂ (Ln = Er and Tm) nanoparticles were synthesized via a combustion reaction at 800 °C. Characterization of the samples was performed by X-ray diffractometer (XRD), reflectance UV–Vis spectrophotometer, fluorescence spectrophotometer (PL) and transmission electron microscope (TEM). XRD patterns showed that tetragonal crystalline structure of scheelite and silica supports were formed, and that the formation of a silica support could enhance the luminescence intensity of CaWO₄:Ln³⁺. The reflectance UV–Vis and PL spectra indicated the broad absorption band of WO₄ ^2? groups about 240 nm, the WO₄ ^2? wide excitation band with maximum at 240 nm, a broad emission band of WO₄ ^2? with maximum about 420 nm, and characteristic emissions of Ln³⁺ ions. According to the TEM analysis, CaWO₄:Er³⁺@SiO₂ and CaWO₄:Tm³⁺@SiO₂ nanoparticles have almost the same morphology with average particle sizes about 50 nm.     

Strong Single‐Band Blue Emission from Colloidal Ce3+/Tm3+‐Doped NaYF4 Nanocrystals for Light‐Emitting Applications

An intense single‐band blue emission at λ=450 nm is observed from Tm³⁺ ions through Ce³⁺ sensitization, for the first time, in colloidal Ce³⁺/Tm³⁺‐doped NaYF₄ nanocrystals. The intense Tm³⁺ emission through broad‐band excitation is advantageous for developing luminescent nanocomposites because they can be easily incorporated into polymers. The composites can easily be coated over UV light‐emitting diodes (LEDs) to develop phosphor‐based blue LEDs.     

Synthesis and luminescent properties of a new blue light-emitting phosphor KBa<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>Tm<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>P<Subscript>5</Subscript>O<Subscript>15</Subscript>

A new blue phosphor KBa_2?xTm _x P₅O₁₅ for white light-emitting diodes (W-LEDs) was prepared by the high-temperature solid-state synthesis method. Its structure, morphology, elementary composition, and luminescent properties were investigated. The phosphor KBa_1.96Tm_0.04P₅O₁₅ exhibits an irregular morphology with a diameter of about 10 μm. The emission spectra consisted of two emission peaks centered at 451 and 477 nm due to the ¹D₂ → ³F₄ and ¹G₄ → ³H₆ transitions of Tm³⁺ activator, respectively. The optimum dopant concentration of Tm³⁺ activator in KBa₂P₅O₁₅ host matrix is about 4 mol%. The critical distance is calculated to be 25 Å, and the concentration quenching mechanism of Tm³⁺ ions in KBa₂P₅O₁₅ was confirmed to be d–q interaction. The CIE coordinates of KBa_1.96Tm_0.04P₅O₁₅ phosphor was calculated to be (0.1503, 0.0542), corresponding to blue color with a high color purity of about 92%. Hence, we may expect that the obtained phosphor KBa_2?xTm _x P₅O₁₅ would be potentially used as a blue phosphor for W-LEDs.     

White luminescence of Tm-Dy ions co-doped aluminoborosilicate glasses under UV light excitation

Tm³⁺ and Dy³⁺ ions co-doped aluminoborosilicate glasses were prepared in this study. The luminescence properties of the glasses were analyzed. A combination of blue, green, yellow, and red emission bands was shown for these glasses, and white light emission could be observed under UV light excitation. White light luminescence color could be changed by varying the excitation wavelength. Concentration quenching effect was investigated in this paper. Furthermore, the dependence of luminescence properties on glass compositions was studied. Results showed that the luminescence intensity changed with different network modifier oxides, while the white color luminescence was not affected significantly.     

Confining Excitation Energy in Er3+‐Sensitized Upconversion Nanocrystals through Tm3+‐Mediated Transient Energy Trapping

A new class of lanthanide‐doped upconversion nanoparticles are presented that are without Yb³⁺ or Nd³⁺ sensitizers in the host lattice. In erbium‐enriched core–shell NaErF₄:Tm (0.5 mol %)@NaYF₄ nanoparticles, a high degree of energy migration between Er³⁺ ions occurs to suppress the effect of concentration quenching upon surface coating. Unlike the conventional Yb³⁺‐Er³⁺ system, the Er³⁺ ion can serve as both the sensitizer and activator to enable an effective upconversion process. Importantly, an appropriate doping of Tm³⁺ has been demonstrated to further enhance upconversion luminescence through energy trapping. This endows the resultant nanoparticles with bright red (about 700‐fold enhancement) and near‐infrared luminescence that is achievable under multiple excitation wavelengths. This is a fundamental new pathway to mitigate the concentration quenching effect, thus offering a convenient method for red‐emitting upconversion nanoprobes for biological applications.     

Confining Excitation Energy in Er3+-Sensitized Upconversion Nanocrystals through Tm3+-Mediated Transient Energy Trapping

A new class of lanthanide-doped upconversion nanoparticles are presented that are without Yb³⁺ or Nd³⁺ sensitizers in the host lattice. In erbium-enriched core–shell NaErF₄:Tm (0.5 mol %)@NaYF₄ nanoparticles, a high degree of energy migration between Er³⁺ ions occurs to suppress the effect of concentration quenching upon surface coating. Unlike the conventional Yb³⁺-Er³⁺ system, the Er³⁺ ion can serve as both the sensitizer and activator to enable an effective upconversion process. Importantly, an appropriate doping of Tm³⁺ has been demonstrated to further enhance upconversion luminescence through energy trapping. This endows the resultant nanoparticles with bright red (about 700-fold enhancement) and near-infrared luminescence that is achievable under multiple excitation wavelengths. This is a fundamental new pathway to mitigate the concentration quenching effect, thus offering a convenient method for red-emitting upconversion nanoprobes for biological applications.     

Characterizations of white-light ZnWO4 phosphor prepared by blending complementary phosphor

In the preparation of ZnWO₄ phosphor, crystalline ZnWO₄ was created, even though the concentration of WO₃ was only 10 mol%. ZnWO₄ was the dominant crystallization phase when the concentration of WO₃ exceeded 40 mol%. The optimal crystallization of ZnWO₄ phosphor was obtained when the composition molar ratio of ZnO to WO₃ was 1:1, and sintering was carried out at 1,100°C for 3 h. In this condition, a bluish-green emission with a peak at 460 nm was observed. For Y₂O₃:Eu³⁺,Li⁺, the complementary phosphor of ZnWO₄, the Li flux improved phosphor crystallization. The red emission peak of the Y₂O₃:Eu³⁺,Li⁺ phosphor was measured at about 612 nm. The optimal photoluminescence intensity of the Y₂O₃:Eu³⁺,Li⁺ phosphor was obtained when it was sintered at 1,200°C for 5 h and was mixed with 11 mol% Eu₂O₃ and 70 mol% Li₂CO₃. When the weight ratio of Y₂O₃:Eu³⁺,Li⁺ to ZnWO₄ was 1:4, the Y₂O₃:Eu³⁺,Li⁺-blended ZnWO₄ phosphor showed white-light emission with Commission Internationale de l’Eclairage coordinates at (0.34, 0.30). The luminance of the white-light phosphor excited by a 6-W UV lamp was around 160 cd/m².     

Single red up-conversion luminescence of Er sensitized layered Y2Ti2O7 phosphor

High color purity red emission with single band successfully achieved in a new Er³⁺, Tm³⁺ co-doped Y₂Ti₂O₇ system under 1550 nm excitation, value of red to green emission ratio of the samples is more than 10³. Efficient up-conversion luminescence can be obtained while the ⁴I_13/2 level of Er³⁺ pumped by 1500 nm directly based on the large absorption section and long luminescence lifetime, and red emission composition will greatly enhanced by co-doping with Tm³⁺ ions, color purity of red emission under 1550 nm excitation is much higher than that of 980 nm. The quenching concentration of Er³⁺ ions is up to 28 mol% in Y₂Ti₂O₇ rely on the layer distribution of cations, which can further improve the red emission color purity.     

Tunable white light-emission of a CaW1?x Mo x O4:Tm3+, Tb3+, Eu3+ phosphor prepared by a Pechini sol–gel method

A white light-emitting CaW_1?x Mo _x O₄:Tm³⁺, Tb³⁺, Eu³⁺ phosphor was prepared by a Pechini sol?Cgel method. The incorporation of Mo⁶⁺ into the CaWO₄ host matrix can broaden its excitation range and promote tunability to its emission. When the CaW_1?x Mo _x O₄ system is triply-doped with Tm³⁺, Tb³⁺, and Eu³⁺ ions, energy transfer occurs from both WO₄ ^2? and MoO₄ ^2? groups to Tm³⁺ and Tb³⁺ ions. A significant red-shift in the excitation of Eu³⁺ allows the resulting emission to be tunable between cool, natural, and warm white light by varying the excitation wavelength. The undoped and triply-doped CaW_1?x Mo _x O₄ phosphors were characterized by X-ray diffraction, scanning electron microscopy, photoluminescence excitation and emission spectra, and CIE chromaticity (x, y) coordinates.     

不同掺杂浓度Tm3+：LiLuF4单晶的1800 nm荧光发射

采用坩埚下降法生长了Tm³⁺掺杂浓度为0.45%,0.90%,1.63%与3.25%（摩尔分数,x）的LiLuF₄单晶.测试了样品的电感耦合等离子体原子发射光谱（ICP-AES）、X射线衍射（XRD）谱、吸收光谱（1400-2000 nm）,并且分析比较了808 nm半导体激光器（LD）激发下荧光光谱. 结果表明：当Tm³⁺的浓度从0.45%变化到3.25%时,1800 nm处的荧光强度呈现了先增后减的趋势,当掺杂浓度约为0.90%时达到最大值,而位于1470 nm处的荧光强度则呈现了相反的趋势. Tm³⁺：³F₄能级的荧光衰减寿命随着掺杂浓度的增加不断减小. 1800 nm处的这种荧光强度变化归结于Tm³⁺离子间的交叉驰豫效应（³H₆,³H₄→³F₄,³F₄）和自身的浓度猝灭效应. 同时计算得到了浓度为0.90%的样品在1890 nm处的最大发射截面为0.392×10^-20 cm². 并且根据Judd-Ofelt 理论所得寿命和测定的荧光寿命计算得到了³F₄→³H₆的最大量子效率约为120%.     

Er3+-Tm3+-Yb3+ tri-doped CaMoO4 upconverting phosphors in optical devices applications

The structural and optical properties of the Er³⁺-Tm³⁺-Yb³⁺codoped CaMoO₄ phosphors prepared by chemical route have been explored. The crystalline structures of the prepared phosphors have been investigated with the help of X-ray diffraction analysis. The presence of different vibrational modes and absorption bands arising due to the transitions from the ground state to different excited states of rare earth ions have been identified using the Raman and UV-VIS-NIR absorption spectra of the developed phosphor, respectively. The concentration quenching effect on the luminescence property of the prepared materials has been explained in detail. The upconversion luminescence property of the Er³⁺-Tm³⁺-Yb³⁺codoped CaMoO₄ phosphor annealed at different temperatures under 980 nm and 808 nm excitations have been reported. The energy transfer Er³⁺ → Tm³⁺, Yb³⁺ → Er³⁺ and Tm³⁺ has been found to be responsible for efficient UC emission. The dipole-dipole interaction is observed to be responsible for the concentration quenching of the luminescence intensity. The effect of annealing temperature on the upconversion luminescence property has been explained in detail. The results suggest that the developed tri-doped phosphor may be suitable in making the efficient NIR to visible upconverter and lighting based optical devices.     

Intrinsic Time‐Tunable Emissions in Core–Shell Upconverting Nanoparticle Systems

Color‐tunable luminescence has been extensively investigated in upconverting nanoparticles for diverse applications, each exploiting emissions in different spectral regions. Manipulation of the emission wavelength is accomplished by varying the composition of the luminescent material or the characteristics of the excitation source. Herein, we propose core–shell β‐NaGdF₄: Tm³⁺, Yb³⁺/β‐NaGdF₄: Tb³⁺ nanoparticles as intrinsic time‐tunable luminescent materials. The time dependency of the emission wavelength only depends on the different decay time of the two emitters, without additional variation of the dopant concentration or pumping source. The time‐tunable emission was recorded with a commercially available camera. The dynamics of the emissions is thoroughly investigated, and we established that the energy transfer from the ¹D₂ excited state of Tm³⁺ ions to the higher energy excited states of Tb³⁺ ions to be the principal mechanism to the population of the ⁵D₄ level for the Tb³⁺ ions.     

White light emission from Tm/Dy co-doped oxyfluoride germanate glasses under UV light excitation

In this paper, we report on the absorption and photoluminescence properties of Tm³⁺/Dy³⁺ ions co-doped oxyfluoride germanate glasses for white light emission. The X-ray diffraction (XRD) and differential thermal analysis (DTA) profiles of the host glass have been carried out to confirm its structure and thermal stability. From the measured absorption spectra, Judd-Ofelt (J-O) intensity parameters (Ω₂, Ω₄ and Ω₆) have been evaluated for Tm³⁺ and Dy³⁺ ions. A combination of blue, yellow and red emissions has emerged in these glasses, which allows the observation of bright white light when the glasses are excited by the ultraviolet light. The white light luminescence colour could be changed by varying the excitation wavelength. Also, various colours of luminescence, including white light, can be easily tuned by adjusting the concentrations of Tm³⁺ or Dy³⁺ ions in the co-doped glasses. Concentration quenching effect was also investigated and possible energy transfer mechanism from Dy³⁺→Tm³⁺ ions was explained which is also confirmed by the decay lifetime measurements.     

Novel rare earth ions-doped oxyfluoride nano-composite with efficient upconversion white-light emission

Transparent SiO₂-Al₂O₃-NaF-YF₃ bulk nano-composites triply doped with Ho³⁺, Tm³⁺ and Yb³⁺ were fabricated by melt-quenching and subsequent heating. X-ray diffraction and transmission electron microscopy measurements demonstrated the homogeneous precipitation of the β-YF₃ crystals with mean size of 20 nm among the glass matrix, and rare earth ions were found to partition into these nano-crystals. Under single 976 nm laser excitation, intense red, green and blue upconversion emissions were simultaneously observed owing to the successive energy transfer from Yb³⁺ to Ho³⁺ or Tm³⁺. Various colors of luminescence, including bright perfect white light, can be easily tuned by adjusting the concentrations of the rare earth ions in the material. The overall energy efficiency of the white-light upconversion was estimated to be about 0.2%.     

Upconversion Luminescence through Cooperative and Energy-Transfer Mechanisms in Yb3+-Metal-Organic Frameworks

Lanthanide-doped metal–organic frameworks (Ln-MOFs) have versatile luminescence properties, however it is challenging to achieve lanthanide-based upconversion luminescence in these materials. Here, 1,3,5-benzenetricarboxylic acid (BTC) and trivalent Yb³⁺ ions were used to generate crystalline Yb-BTC MOF 1D-microrods with upconversion luminescence under near infrared excitation via cooperative luminescence. Subsequently, the Yb-BTC MOFs were doped with a variety of different lanthanides to evaluate the potential for Yb³⁺-based upconversion and energy transfer. Yb-BTC MOFs doped with Er³⁺, Ho³⁺, Tb³⁺, and Eu³⁺ ions exhibit both the cooperative luminescence from Yb³⁺ and the characteristic emission bands of these ions under 980 nm irradiation. In contrast, only the 497 nm upconversion emission band from Yb³⁺ is observed in the MOFs doped with Tm³⁺, Pr³⁺, Sm³⁺, and Dy³⁺. The effects of different dopants on the efficiency of cooperative luminescence were established and will provide guidance for the exploitation of Ln-MOFs exhibiting upconversion.     

Synthesis, characterization and luminescence properties of SrLa2(MoO4)4:Eu phosphors

SrLa₂(MoO₄)₄ (SLM) phosphors doped with Eu³⁺ ions were prepared by a sol–gel combustion method using citric acid as a fuel/reductant and nitrates as oxidants. The crystallization processes were tracked by means of X-ray diffraction and thermo-gravimetric analysis and differential scanning calorimetry. The size and shape of the products were characterized using a scanning electron microscope, while the luminescent spectra of these resulting phosphors were recorded using a photoluminescence (PL) spectrophotometer. PL studies reveal that the emission intensity of SLM:Eu phosphors was strongly related to sintering temperature as well as the doping concentration of Eu³⁺ ions. The present phosphor has a strong excitation at 395 and 459 nm, indicating that it could serve as a promising red-emitting candidate for near-UV and GaN-based blue light-emitting diode chips.     

Lumineszenz und sensibilisierte Emission der dreiwertigen Seltenen Erden in Sr3La2W2O12

By activation of the new host lattice Sr₃La₂W₂O₁₂ with the trivalent rare earth ions Nd, Eu, Ho, Er, Tm, Yb an intense emission in the visible and/or infrared region is obtained. Energy transfer from Er³⁺ to Tm³⁺ and Nd³⁺ to Yb³⁺ has been found to occur. The excitation, emission, and diffuse reflectance spectra are analyzed for Sr₃La₂W₂O₁₂: Ln³⁺ (Ln = Nd, Sm, Eu, Dy, Ho, Er, Tm, Yb).