Chromaticity Shift Research Articles

Crystal structure and spectral tuning of Eu2+/Eu3+ co-activated Na2Ba1-xSrxCa(PO4)2 phosphors with high thermal stability

The coupling of UV LED chips with phosphors to produce white or color-tunable light is still a challenge. In this work, we propose a simple rare earth occupation site engineering method to adjust the valence of doped Eu ions. Based on the Ba2+ substituted by Sr2+, new Eu2+/Eu3+ co-activated Na2Ba1-xSrxCa(PO4)2 (NB1-xSxCP) phosphors were designed and successfully synthesized. In NB1-xSxCP, the Ba2+/Sr2+ site is occupied by Eu2+, while the Ca2+ site is occupied by Eu3+. The coupled broad blue 448 nm and sharp red 619 nm luminescence under 321 nm excitation has demonstrated the coexistence of Eu2+ and Eu3+. This double emission phenomenon is studied in terms of the fluorescence lifetime as well as lattice distortion induced by the substitution ions. With the increased substitution of Sr, the luminescence of NB1-xSxCP:0.03Eu2+/3+ can be tuned from blue to red crossing the warm-white region. When x = 0.3, the chromaticity coordinates is located at (0.3779, 0.2495). The integrated intensity of Na2Ba0.7Sr0.3Ca(PO4)2:0.03Eu2+/3+ at 150℃ remains 90.9 % of that at room temperature, while the chromaticity shift (ΔE) can be calculated as 15 ×10−3. The Eu2+/Eu3+ co-activated NB1-xSxCP is a potential candidate for single-phase color-tunable phosphors used for light-tunable applications due to the combining contributions from both Eu3+ and Eu2+ ions.

A red-emitting phosphor Na3AlF6:Mn4+: Green synthesis, optical characteristics, thermal stability and application in high-performance warm WLED

Mn4+-doped fluoride red phosphors have been widely used in warm WLEDs, but the preparation of such phosphor requires the use of a large amount of HF as a fluorine source and an acidic environment. How to reduce the excessive use of highly toxic HF in the preparation process and achieve green synthesis has become a hot research topic. Therefore, a simple green synthesis strategy is proposed in this work to synthesize a series of red-emitting phosphors Na3AlF6:Mn4+. The highly toxic HF solution is replaced by using a low toxicity reaction system (HCl/HNO3 + NH4F), which reduces the direct use of HF. X-ray powder diffraction, energy-dispersive X-ray spectrometer and scanning electron microscope are employed to determine the crystal structure, composition and morphology of all samples. Optical properties are characterized using excitation spectra, emission spectra and fluorescence lifetime curves. The calculation results indicate that the red-light has low correlated color temperature and the excellent color purity, and Na3AlF6 host can provide a strong crystal field environment for Mn4+. In addition, different aluminum sources and Mn4+ doping concentrations are used to explore the optimal preparation condition. The mechanisms of concentration quenching and thermal quenching have also been systematically explored. The stabilities of red-light emission intensity and color are investigated under the high temperature. The integral PL intensity at 423 K is 47 % of the initial value at 298 K. The activation energy, the chromaticity shift and the chromaticity coordinate variation are also systematically calculated. More importantly, a high-performance warm WLED with low correlated color temperature (CCT = 3296 K) and high color rendering index (Ra = 94.7) is achieved by using Na3AlF6:Mn4+ as a red-emitting material. Not only that, the warm WLED exhibits strong output stability under high driving current. The discovery of this work provides a comprehensive understanding for the rational design of high-performance Mn4+-activated fluoride red phosphors via a simple green synthesis strategy.

High-efficiency RbASiF6:Mn4+ (A = K, Cs) phosphors obtained by one-step green synthesis method

Red-emitting Mn4+-doped fluoride phosphors are recognized as promising materials for high-performance warm white light-emitting diodes (WLEDs). However, the extensive use of toxic hydrofluoric acid in traditional synthesis methods hinders their development and commercialization. Furthermore, the traditional solid-phase method often has cumbersome sintering steps, high temperature, long holding time, and certain safety hazards, so it is very necessary to develop a green synthesis method with simple steps and low energy consumption. In this study, a low-temperature solid-state method is proposed to synthesize RbASiF6:Mn4+ (A = K, Cs) phosphors by one step. Optimal emission intensities were observed at Mn4+ concentrations of 1.2 % in RbKSiF6 and 2.1 % in RbCsSiF6. These phosphors demonstrated high thermal stability. At 423 K, the photoluminescence intensities of RbKSiF6:1.2 %Mn4+ and RbCsSiF6:2.1 %Mn4+ reached 114 % and 87 % of their respective values at room temperature. Meanwhile, the chromaticity shifts were almost negligible, and high color purity was achieved for both phosphors. The electro-optical performance of WLED devices utilizing these phosphors, in combination with YAG:Ce3+ and GaN chips, showed high color rendering indices (CRI) and low correlated color temperatures (CCT) across varying currents. Specifically, under a driving current of 20 mA, the device incorporating RbKSiF6:1.2 %Mn4+ exhibited a CRI of 94 and a CCT of 3732 K, with a luminous efficacy of 61 lm/W. These findings highlight the potential of green-synthesized RASFM phosphors in advancing the application of warm WLEDs.

Crystal field optimization, luminescence enhancement and thermal stability of novel K2NaAl0.4Ga0.6F6:Mn4+ solid solution red phosphor for high-performance warm WLED

Mn4+-doped fluoride phosphors have important application value in the background light and WLED lighting fields. Therefore, the synthesis of efficient and stable Mn4+-doped red phosphor is of great application value. In this study, a series of red-emitting K2NaAl1-yGayF6:xMn4+ (y = 0, 0.2, 0.4, 0.6, 0.8 and 1) (x = 0.01, 0.03, 0.05, 0.07 and 0.09) solid solution phosphors are successfully synthesized by simple coprecipitation method. The synthesis strategy of simple crystal structure optimization is proposed to realize simultaneously the crystal field optimization, luminescence enhancement and thermal stability of red phosphor. The calculation and theoretical analysis of crystal field strength are used to prove that solid solution matrix K2NaAl0.4Ga0.6F6 is the most ideal matrix material. X-ray powder diffraction, energy-dispersive X-ray spectrometer and scanning electron microscope are employed to determine the crystal structure, composition and morphology of all samples. Optical properties are characterized using excitation spectra, emission spectra and fluorescence lifetime curves. Moreover, the CIE coordinates of red-light show that the phosphor has low correlated color temperature and excellent color purity. Intriguingly, the as-prepared K2NaAl0.4Ga0.6F6:Mn4+ phosphor possesses admirable thermal quenching behavior and color stability at high temperature. At a temperature of 423 K, the photoluminescence intensity can be maintained at 52 % of the original intensity (298 K). The activation energy, the chromaticity shift and chromaticity coordinate variation are also systematically calculated. More importantly, A high-performance warm WLED with low correlated color temperature (CCT = 3982 K) and high color rendering index (Ra = 93.7) is achieved by using K2NaAl0.4Ga0.6F6:Mn4+ as a red-emitting material. These results demonstrate that K2NaAl0.4Ga0.6F6:Mn4+ red phosphor provides a novel choice for the warm WLED required for indoor lighting.

A novel white Y2(Ti0.8Hf0.2)2O7: Eu phosphors regulated by HfO2 exhibiting low color shifting for high temperature

The development of white phosphors that can be activated in near-ultraviolet light is highly important in the field of LED lighting. In this work, a series of color-tunable Y2(Ti1-xHfx)2O7:Eu phosphors were prepared by adjusting the HfO2 and Eu3+ concentrations. In particular, white Y2(Ti0.8Hf0.2)2O7:Eu phosphors were successfully synthesized and emitted a broad band covering the entire visible light region upon excitation with 340 nm UV light. The white banded materials were composed of Eu2+ and Eu3+ emissions and HfO2 defect emission. The formation of Eu2+ ions was caused by the introduction of HfO2, which causes self-reduction of Eu3+ ions but does not require additional reducing agents. The white Y2(Ti0.8Hf0.2)2O7:Eu phosphors exhibit low color shifting at high temperature, which is very important for LED applications. The chromaticity shift of the Y2(Ti0.8Hf0.2)2O7:0.2Eu phosphor is 2.83 × 10−2 at 503 K, which is only 54.8 % that of commercial three-color white phosphors at the same temperature. The Ra value did not decrease significantly with increasing temperature and reached 90.2 at 383 K. Y2 (Ti0.8Hf0.2)2O7:0.2Eu phosphors were assembled with a 365 nm LED chip to fabricate a WLED device that showed excellent white-colored coordinates (0.345, 0.358) and a high Ra value of 90.1 under a 300 mA current.

Controllable morphology, excellent stability and non-equivalent doping-induced optical properties of Mn4+-activated K2NaScF6 red phosphor for high-quality warm WLED

Currently, Mn4+ activated fluoride red phosphor has been widely studied to improve the optical performance of white light-emitting diode (WLED) in the field of high-efficiency lighting and wide color gamut backlight display. In this paper, a series of red-emitting K2NaScF6:Mn4+ phosphors are synthesized by a simple co-precipitation method with a non-equivalent substitution of Mn4+ for Sc3+ at room temperature. The crystal structure, morphology and elemental composition of K2NaScF6:Mn4+ phosphors prepared using different reaction conditions are systematically investigated. Interestingly, the K2NaScF6:Mn4+ phosphors exhibit narrowband red emission with low correlated color temperature (CCT), high color purity and short fluorescence lifetime. Compared to equivalent doping, the mechanism of short fluorescence lifetime caused by non-equivalent doping has also been systematically discussed. The optimal doping concentration is determined by setting a series of Mn4+ doping concentrations and the concentration quenching mechanism is analyzed. The crystal field strength (Dq), Racah parameters (B and C) and nephelauxetic ratio (β1) are calculated in detail to evaluate the crystal field environment of Mn4+ in K2NaScF6. The good water resistance of the as-prepared sample K2NaScF6:Mn4+ is verified by comparing with the commercially available phosphor K2SiF6:Mn4+. Moreover, the thermal stability is also analyzed by calculating the activation energy (Ea), chromaticity shift (ΔE) and chromaticity coordinate variation (CCV). Importantly, the as-packaged warm WLED (InGaN chip + YAG:Ce3+ + K2NaScF6:Mn4+) has excellent optical properties (CCT = 4082 K, color rendering index (CRI, Ra = 91.2) and luminous efficiency (LE) = 78.86 lm/W), and it exhibits good output stability at high drive currents. In summary, our work demonstrates that K2NaScF6:Mn4+ red phosphors possess a great potential application in warm WLED for the indoor lighting.

Five-Surface Phosphor-in-Glass for Enhanced Illumination and Superior Color Uniformity in Large-View Scale LEDs.

A novel five-surface phosphor-in-glass (FS-PiG) structure for high illumination and excellent color uniformity in large-view scale LEDs for sensor light source application is demonstrated. YAG phosphor (Y3Al5O12:Ce3+) was uniformly mixed with ceramic and sintered at 680 °C to form a phosphor wafer. Sophisticated laser engraving was employed on the phosphor wafer to form saddle-shaped large-view scale FS-PiG LEDs. The performance of the FS-PiG LEDs exhibited an illumination of 401 lm, average color temperature (CCT) of 5488 K ± 110 K, and color coordinates (CIE) of (0.3179 ± 0.003, 0.3352 ± 0.003). In contrast to convention single-surface phosphor-in-glass (SS-PiG) LEDs, the performance exhibited an illumination of 380 lm, average CCT of 5830 K ± 758 K, and CIE of (0.3083 ± 0.07, 0.3172 ± 0.07). These indicated that the performance of the FS-PiG LEDs was higher than the SS-PiG LEDs for illumination, CCT, and CIE by 1.7, 7, and 23 times, respectively. Furthermore, the FS-PiG LEDs demonstrate a lower lumen loss of 2% and a reduced chromaticity shift of 5.4 × 10-3 under accelerated aging at 350 °C for 1008 h, owing to the high ceramic melting temperature of up to 510 °C. In this study, the proposed FS-PiG large-view scale LEDs with excellent optical performance and high reliability may be promising candidates to replace the conventional phosphor-in-organic silicone material used in high-power LEDs for the next generation of sensor light sources, display, and headlight applications.

An analytical and machine learning model for SPD estimation and its prediction for lumen and chromaticity shift based LED lifetime performance analysis

The LED lifetime is commonly estimated by manufacturers using an exponential model to evaluate L70 criteria. However, it ignores colour characteristic variation and does not explain the root cause of LED failure. In this paper, a spectral power distribution (SPD) based approach is proposed to estimate lifetime performance of cool white LED considering both colour characteristics and lumen maintenance, as all the lighting performance parameters are extracted from SPD. The exponential model does provide the lifetime using only lumen data and does not explain the colour characteristics. As an alternate to the exponential model, a quadratic polynomial, and machine learning (ML) models with hours and temperature as input factors, is proposed to determine SPD for experimental conditions as well as to predict for other operating conditions. Further, the lifetime performance analysis is performed for reliability assessment conditions through both lumen and colorimetric performances. The outcomes of all the models are analysed and it is found that the results are comparable. As ML models are simpler than analytical models for more than two inputs, further it is used to predict SPD at different temperatures and the LED performance is validated. Further analysis shows that a decrease in blue light is the primary cause of the overall decrease in light output and decrease in yellow emission due to phosphor degradation is the reason for chromaticity shift.

Novel single phase warm white-emitting phosphor BaLaGaO4:Dy3+,Sm3+ with high thermal stability and color stability

In this study, new phosphors BaLaGaO4 (BLGO) doped with dysprosium (Dy3+) and samarium (Sm3+) ions were created using a high-temperature solid-state method. Characterizations with X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDS), and elemental mapping revealed successful doping and uniform elemental distribution. Then the samples were tested for photoluminescence (PL) spectra, the results indicated that the BaLaGaO4:xDy3+ (BLGO:xDy3+) phosphors emitted strong blue and yellow light upon excitation at 350 nm. The emission peaks were located at 480 and 572 nm, respectively. By introducing different proportions of Sm3+ ions, the BaLaGaO4:0.04Dy3+,ySm3+ (BLGO:0.04Dy3+,ySm3+) samples could be excited at 365 nm, and enhancing the red emission component of the phosphor. Meantime, with increasing Sm3+ content, the correlated color temperature (CCT) decreased from 5507 to 3767 K. And the emission spectrum and decay lifetime of BLGO:0.04Dy3+,ySm3+ confirmed the energy transfer from Dy3+ to Sm3+. Furthermore, at 423 K, the luminous intensity of BLGO:0.04Dy3+,0.04Sm3+ retained 86 % of its strength at 298 K, and the chromaticity shift (ΔS) was only 0.00574, which indicated that the sample had excellent thermal stability and excellent color stability. Finally, using the prepared sample and a 365 nm light-emitting diode (LED) chip, a white light-emitting diode (WLED) was fabricated. The CCT of the manufactured WLED also showed a corresponding reduction (from 3423 to 2814 K). Moreover, under the working conditions of 3.4 V and 0.6A, the thermal imaging obtained after 90 min of WLED operation shows the stability of the packaged WLED at high temperature. These researches show that the phosphor has potential application value in indoor lighting technologies.

Probing multifunctional applications of LiCa2Mg2V3O12: Sm3+ phosphor using Judd-Ofelt analysis and dual mode non-contact optical thermometry

LiCa2Mg2V3O12:Sm3+ phosphors have been prepared by solid state method and analysed by X-ray diffraction, EDX-elemental mapping, UV–VIS-NIR spectroscopy, photoluminescence (PL) and temperature dependent photoluminescence (TDPL). The absorption spectra analysis using Judd-Ofelt theory provides the intensity parameters and manifest the covalent nature of Sm-O bond. The PL spectra monitored at 338 nm excitation exhibits emission peaks of Sm3+ at 567, 617 and 651 nm in addition to the broad band emission of LiCa2Mg2V3O12 host. The Commision Internationale deL’Eclairage (CIE) coordinates, correlated color temperature (CCT) and color rendering index (CRI) values elucidate the efficient yellow emission of phosphors. The radiative parameters are evaluated and have outrageous branching ratio and cross section that aids in visible laser applications. The optical thermometry of phosphor is carried out by utilizing FIR method through selecting spectral modes 6H5/2/VO43-, 6H7/2/VO43- and 6H9/2/ VO43-. The mode 6H9/2/ VO43- have higher absolute sensitivity (Sa) and relative sensitivity (Sr) values of 0.4418 K−1 and 1.6079% K−1. The temperature resolution of modes are 0.1633, 0.1677 and 0.1563 K respectively. The thermochromic study reveals the high chromaticity shift (Δs = 0.1869) of phosphor and the Sa(x) and Sr(x) values evaluated based on CIE coordinates are 0.0011 K−1 and 0.2407% K−1 respectively. The PL and TDPL characteristics of prepared phosphor suggest that it have multifunctional application in the fields of lasers, thermo-sensors, thermochromic displays and LEDs.

Enhanced thermal stability and luminous properties of Dy3+/Tm3+/Eu3+ doped glass ceramics containing Sr4Bi(PO4)3O crystalline phases based on back energy transfer

White light emitting and optical temperature sensing materials with high thermal stability have broad market development prospects. The use of substrates with excellent thermal stability is a common idea to improve thermal stability, while the modulation of dopants to enhance thermal stability has been less studied. Therefore, in this work, Tm3+/Dy3+/Eu3+ doped transparent glass ceramics containing Sr4Bi(PO4)3O crystalline-phase were prepared by melt-crystallization method to achieve warm white light emission and optical temperature sensing with good thermal stability. Since the Tm3+-Dy3+ doped samples can only achieve cold white light emission, warm white light emission is obtained by adding Eu3+, which can emit red light. The application scenario of the material is expanded. The luminous intensities of Tm3+, Dy3+, and Eu3+ were 109.4 %, 89.1 %, and 70.7 % of those at room temperature, at 473 K. The increase in the emission intensity of Tm3+ was explained by the presence of back energy transfer (BET) from Dy3+ and Eu3+ to Tm3+. The chromaticity shift (Δε) of the samples was 2.43 × 10−4 and the luminescent colour was stable. The absolute sensitivity of the material can reach 0.69 K−1 at 473 K, and the relative sensitivity of the material can reach 1.60 % K−1 at 293 K. This work provides new ideas for the study of improving the thermal stability of materials.

Photoluminescence properties of double perovskite Ca2LuTaO6:Bi3+/Sm3+ white light emitting phosphors

The high-temperature solid state reaction approach was used to successfully synthesize novel tunable-color emitting Ca2LuTaO6 phosphors with double perovskite structure that were un-doped, single-doped, and co-doped with Bi3+/Sm3+ ions. The crystal structure, microstructure, steady-state photoluminescence, time-resolved luminescence measurements, and thermal quenching features of the material were studied. The density functional theory method was used to compute the band gap of the Ca2LuTaO6, and Ca2LuTaO6: Bi3+, Sm3+ phosphors. The blue emission at 407 nm (with 313 nm excitation) is due to the host's luminescence, while the cyan emission at 480 nm (under 365 nm excitation) is related to the distinctive 3Pn − 1S0 transitions (n = 0, 1, 2) of Bi3+. Similarly, efficient red emission is observed in the case of Sm3+ single-doped Ca2LuTaO6 phosphors. In addition, the Ca2LuTaO6: 0.04Bi3+, 0.05 S m3+ phosphors exhibit energy transfer phenomena and have excellent thermal stability, the fluorescence intensity at 150 °C maintains 73% of that at 25 °C and has a small chromaticity shift. The intense blue emission at 407 nm was effectively converted to cyan, red, and white light through doping with Bi3+ and Sm3+, and the resulting energy transfer. The results obtained confirm that Ca2LuTaO6: Bi3+, Sm3+ phosphors as a single matrix have great potential for high-power WLED applications.

Charge compensator adjusts the luminescence intensity of ZnWO4: Sm3+ full spectrum phosphors: A bifunctional phosphors for plant growth lights and FIR thermometers

Full spectrum white LED plant growth light sources are suitable for use in conditions requiring a high color rendering index. In addition to red and blue light, green light was shown to have a positive impact on plant growth in earlier studies. In this work, a series of Sm3+ doped ZnWO4 phosphors was prepared using the high-temperature solid-state reaction method. Li+ serves as a charge compensator to reduce lattice defects caused by non-equivalent isomorphism. XRD measurements and Rietveld refinement were used to investigate the phase composition and structural properties of the samples. The luminescent properties of the samples were tested using a fluorescence spectrophotometer. The Li + introduction can significantly improve the energy transfer from the matrix to Sm3+ and the luminescence intensity of Sm3+. In addition, this phenomenon was explained with non-equivalent isomorphism and the charge density difference diagram. The LED lamp was prepared using ZnWO4: 0.004Sm3+, 0.004Li + phosphor and LED chip. The emitted full spectrum light can match well with the absorption spectrum of plant pigments. The color rendering index of the LED lamp is greater than 91. And the comparative experiment of plant cultivation shows that the prepared LED plant lamp has good effects. The dependence of luminescence properties of ZnWO4: 0.004Sm3+, 0.004Li+ phosphor on temperature was determined. Based on fluorescence intensity ratio (FIR) technology, the maximum SaMAX and SrMAX are 52 % K−1 at 453 K and 9.31 % K−1 at 303 K, respectively. As the temperature increases, the chromaticity shift (Δs) value is 0.254. The benefits of the ZnWO4: 0.004Sm3+, 0.004Li+ phosphor are the straightforward synthesis process, low cost, pure phase, full spectrum, high color rendering index, tunable red-to-blue ratio, and temperature monitoring function. Therefore, this phosphor is an ideal material in plant growth and optical temperature measurement.

Luminescence properties and Judd-Ofelt analysis of Tb3+ doped Sr2YTaO6 double perovskite phosphors for white LED applications.

A series of Tb3+-doped Sr2YTaO6 double perovskite phosphors (SYT:Tb3+) were synthesized using a conventional solid-state reaction method. A strong green emission was observed in the SYT:Tb3+ phosphors, and the optimal doping concentration of Tb3+ was confirmed to be 5 mol%. The electric dipole-dipole interaction was ascribed to be the main mechanism for the luminescence concentration quenching. Analysis of the concentration-dependent fluorescence decay confirmed that the self-generated quenching model holds for the dynamic process of Tb3+ decays in SYT. Furthermore, the internal quantum efficiencies, non-radiative transition rates, and energy transfer rates of the 5D4 level for the SYT:Tb3+ samples were estimated, respectively. The luminescence thermal stability of the sample was also evaluated based on the Arrhenius model. The chromaticity shift of the SYT:5 mol% Tb3+ phosphor was examined to be 0.013 when the sample temperature was increased from 303 to 483 K, thus indicating excellent chromaticity shifting resistance under high temperature conditions. Moreover, the Judd-Ofelt parameters were calculated from the emission spectra of SYT:Tb3+ to be Ω2 = 0.29 × 10-20, Ω4 = 0.45 × 10-20, and Ω6 = 0.72 × 10-20 cm2, respectively. The fluorescence branching ratios and radiative transition rates for the 5D4 level were calculated based on the obtained Judd-Ofelt parameters. Finally, a white light-emitting diode (LED) prototype was assembled using a 310 nm LED chip combined with a prepared green SYT:Tb3+ phosphor and two other commercial blue and red phosphors. The obtained warm white light exhibits good chromaticity coordinates (0.32, 0.32) and a high color rendering index of 96.1. Based on the above results, it can be known that the prepared SYT:Tb3+ phosphors have a potential application as green emitting phosphors in white LEDs.

Synthesis, optical characteristics and thermal stability of Mn4+-doped Na3GaF6 red-emitting phosphor for high-performance warm WLED

Nowadays, Mn4+-activated fluoride red phosphors with high color purity, strong zero phonon line emission and relatively short decay time are crucial for improving the optical performance of WLED and emerging applications. In this work, a series of red-emitting Mn4+-activated fluoride phosphors in consideration of the non-equivalent substitution of Mn4+ for Ga3+ in the Na3GaF6 host are synthesized via the coprecipitation method at room temperature. The use of different reaction solvents successfully regulates the morphology, size and luminescence intensity of the phosphor. Under blue light excitation, Na3GaF6:Mn4+ sample shows a bright narrow-band red emission with exceptional correlated color temperature (4029 K). Moreover, the emission of strong zero phonon line induces the outstanding color purity of red light (93%). In addition, the critical concentration of Mn4+ is determined to be 0.04 and the concentration quenching mechanism is also systematically discussed. Noticeably, when Na3GaF6:Mn4+ phosphor achieves maximum fluorescence emission, its fluorescence lifetime value is only 3.48 ms. Additionally, the theoretical calculated results demonstrate that Na3GaF6 host can provide strong crystal field strength for Mn4+, and the Racah parameters (B and C) and nephelauxetic ratio (β1) are used to evaluate the nephelauxetic effect of Mn4+, which is compared with other types of Mn4+-activated phosphors. The activation energy, chromaticity shift and chromaticity coordinate variation are systematically calculated to analyze the thermal stability of Na3GaF6:Mn4+ red phosphor. Meanwhile, by employing the as-prepared phosphor Na3GaF6:Mn4+ as a red component, a high-performance warm WLED shows a full spectrum emission, and the corresponding cold white light emission is also transformed into the warm white light emission (CCT = 4224 K, Ra = 89.1 and LE = 111.72 lm/W). Moreover, under high driving current, such WLED exhibits stable output light efficiency. These results suggest that Na3GaF6:Mn4+ as red phosphor has a stupendous potential for warm WLED in indoor lighting.

Analysis of fluorescence properties of novel Eu3+-doped ZnAl2O4-based ceramic aerogels for high-power optical device applications

A novel series of ZnAl2O4:Eu3+ aerogels (ZAE) and mullite ceramic phase reinforced ZnAl2O4:Eu3+ aerogels (MZAE) with high fluorescence thermal stability have been firstly synthesized for the encapsulation of high-power optical devices. However, due to the intrinsic structural brittleness of the aerogel, the structure of ZAE tends to collapse during the heat treatment and the fluorescence performance falls short of expectations. To this end, we propose a simple and effective strategy to enhance the structural rigidity of fluorescent aerogels by introducing the mullite ceramic phase into the network structure of ZAE. This can effectively suppress the agglomeration of Eu3+ caused by the collapse of the structure during the heat treatment, thus enhancing the optical properties of the aerogel. Compared with ZAE, MZAE has higher fluorescence thermal stability. The fluorescence intensity of MZAE at 498 K is still 75% of that at 298 K, and the chromaticity shift is only 22×10-3.

Synthesis of an efficient Mn4+-doped fluoride red phosphor with excellent fluorescence stability by green synthesis method for warm WLED

Currently, Mn4+-doped fluoride phosphors have become a research hotspot, which can help compensate for the missing red component in cold white light-emitting diodes (WLEDs). However, significant synthesis defects limit the development of such fluorescent powders due to the use of highly toxic solvent HF. To improve this situation, a simple green synthesis method should be explored to synthesize Mn4+-activated fluoride phosphor. In this study, a series of red-emitting Mn4+-activated BaTiF6 phosphors are successfully synthesized via the non-toxic reaction system (HNO3/HCl + NH4F). Its crystal structure, morphology, optical characteristics and thermal stability are systematically evaluated. Under blue light excitation, BaTiF6:Mn4+ exhibits a bright narrow-band red emission with exceptional correlated color temperature (3909 K) and color purity (90%). Additionally, the critical concentration of Mn4+ is determined to be 0.03 and the concentration quenching mechanism is also systematically discussed. By calculating the crystal field strength (Dq), Racah parameters (B and C) and nephelauxetic effect ratio parameter β1, it is confirmed that BaTiF6 host can provide a strong crystal field environment for Mn4+. Moreover, these results are compared with other matrix materials. Intriguingly, the optimal sample exists satisfactory thermal stability, whose fluorescence intensity at 423 K retains 49% of that at 298 K and the activation energy reaches up to 0.925 eV. In addition, the chromaticity shift and chromaticity coordinate variation are calculated as 17 × 10−3 and (−0.0063, 0.0063), respectively. Meanwhile, the feasibility of the as-fabricated WLEDs for interior illumination is examined. A high-performance warm WLED with low correlated color temperature (CCT = 4470 K) and high color rendering index (Ra = 88.3) is achieved by using BaTiF6:Mn4+ as a red-emitting material, moreover, WLED exhibits strong output stability under high driving current. The findings of this work provide a comprehensive understanding for rational design of high-performance Mn4+-activated fluoride red phosphors through a simple green synthesis method.

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

AbstractIn 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 (Sr) can attain 1.51% K−1 (λex = 290 nm). With temperature raising (303–513 K), the emitted color of Y4GeO8:Bi3+,Eu3+ phosphor (λex = 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.

Effect of B-site substitution on the luminescence, thermal stability and temperature sensitivity of Ba2NaNb5O15:Eu3+/Er3+ glass ceramics

Transparent glass ceramic with Ba2NaNb5O15 as the main crystal phase was prepared, and the appropriate heat treatment condition was selected as 710 °C/150 min through various characterizations. The luminous intensity and thermal stability were enhanced significantly when the glass ceramic was used as the luminous matrix. After introducing Ti4+ ions as charge compensators, the luminescence performance and thermal stability were further improved, and the reasons for this were analyzed. At 458 K, the luminous intensity of 0.5%Eu3+ doped glass ceramic containing 0.5%Ti4+ can maintain about 65% of room temperature with a chromaticity shift of 5.16 × 10−2. The relative and absolute sensitivities of 0.7%Er3+ doped glass ceramic were 4.04 × 10−3 K−1 and 1.31% K−1. Introducing Ti4+ ions would weaken the population redistribution ability of 2H11/2 and 4S3/2 levels and reduce the temperature sensitivity. However, the sample containing Ti4+ shows good thermal stability, its green emission at 458 K has a small chromaticity shift of 6.45 × 10−3. The research shows that the glass ceramic can be used as a good luminescent host material, and Eu3+/Er3+ doped glass ceramic can be used in the fields of LEDs or temperature sensing.

Thermally-stable novel NaBaBi2(PO4)3: Sm3+/Dy3+ white phosphors with tunable photoluminescence

The novel phosphors NaBaBi2(PO4)3: xDy3+ and NaBaBi2(PO4)3: 0.07Dy3+, ySm3+ were successfully synthesized using solid-state reaction method, and their microstructure, optical features and electroluminescent properties were studied. The experimental results show that the doping of Dy3+ exhibits strong yellow light emission, while Sm3+ can effectively compensate for the absent red emission in the Dy3+ emission spectrum, realize the color transition from yellow to white. In addition, the energy transfer process from Dy3+ to Sm3+ in NaBaBi2(PO4)3 was studied in details, and the light color can be adjusted by changing the ratio of Dy3+ and Sm3+, and the color temperature associated with NaBaBi2(PO4)3: 0.07Dy3+, ySm3+ can be adjusted from cool to natural. XRD and refinement results showed that Dy3+ and Sm3+ were successfully incorporated into the matrix. The morphology of NBBP: 0.07Dy3+, 0.05Sm3+ was characterized by SEM. The band gap of the NaBaBi2(PO4)3 matrix is calculated as a direct band gap by the density functional theory method, and the theoretical value (3.9534 eV) of the band gap is very similar to the experimental value (3.965 eV). By analyzing the total density of states and partial density of states, the valence band of the host is mainly composed of [PO4]. In addition, the NaBaBi2(PO4)3: 0.07Dy3+, 0.05Sm3+ phosphors have an energy transfer efficiency of 73% and exhibit excellent thermal stability, the fluorescence intensity at 428 K still maintains 81.79% of that at 303 K and has a small chromaticity shift. The correlated color temperature of the W-LEDs packaged with NaBaBi2(PO4)3: 0.07Dy3+, 0.05Sm3+ phosphor was measured as 4434K, and the color coordinates were measured as (0.3594, 0.3454). The W-LEDs driven at 3.4 V voltage and 600 mA current maintained its performance for 70 min, indicating that the packaged W-LEDs can operate continuously at high temperatures.