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中国物理学会期刊

CaLaGaO4:Eu3+的Na+掺杂红光增强及白光发光二极管应用

CSTR: 32037.14.aps.75.20260372

Enhanced red emission from CaLaGaO4:Eu3+ via Na+ doping toward white light-emitting diode applications

CSTR: 32037.14.aps.75.20260372
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  • 采用高温固相法成功合成了一系列Ca1–0.5xLa0.7Eu0.3GaO4:xNa+(CLEGO:xNa+, x = 0—1.7%)红色荧光粉. X射线衍射分析表明所有样品均为纯相, Na+的引入未改变基质的橄榄石晶体结构. 光致发光光谱分析发现, Na+掺杂显著增强了Eu3+的发光强度, 当掺杂浓度为0.9%时, 其5D07F2跃迁的红色发射强度达到未掺杂样品的1.82倍. 最优样品的量子效率为14.3%, 荧光寿命为0.93 ms, 并展现出良好的热稳定性, 在498 K下发光强度仍能维持室温下的64.9%. 将CLEGO:0.9%Na+红色荧光粉与商用蓝、绿荧光粉混合, 封装在392 nm近紫外芯片上, 成功制备出白光发光二极管(LED)器件, 其色坐标为(0.301, 0.354), 显色指数为81.8, 相对色温为6900 K. 本研究证实Na+ 掺杂是提升CLEGO荧光粉发光效率的有效策略, 该荧光粉在白光LED照明领域具有潜在的应用价值.

     

    The lack of efficient red phosphors for near-ultraviolet (n-UV) chip-based white light-emitting diodes (WLEDs) remains a major challenge. In this work, we aim to enhance the red emission of Eu3+-activated CaLaGaO4 (CLGO) phosphors via Na+ doping and to evaluate their potential for WLED applications.
    A series of Na+-doped Ca1–0.5xLa0.7Eu0.3GaO4:xNa+ (CLEGO:xNa+, x = 0–1.7%) red phosphors are synthesized by a conventional high-temperature solid-state reaction at 1246 ℃. The crystal structure and phase purity are characterized by X-ray diffraction (XRD) and Rietveld refinement. Morphology and elemental distribution are examined by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). Photoluminescence (PL) excitation and emission spectra, temperature-dependent PL (298–498 K), fluorescence decay curves, and absolute quantum yields (QY) are measured. Finally, a WLED device is fabricated by combining the optimized red phosphor with commercial BaMgAl10O17:Eu2+ (blue) and Sr2SiO4:Eu2+ (green) phosphors on a 392 nm n-UV chip.
    XRD confirms that all samples are phase-pure with an olivine-type structure. Rietveld refinement shows that Na+ substitutes for Ca2+ sites, causing lattice expansion; the cell volume increases from 423.93 to 425.58 Å3. Under 392 nm excitation, the 5D07F2 red emission at 609 nm is strongly enhanced by Na+ doping. The optimal intensity is achieved at x = 0.9%, being 1.82 times that of the undoped sample. The improvement is attributed to Na+-induced local lattice distortion, which reduces the symmetry around Eu3+ and increases the electric dipole transition probability. The CLEGO:0.9%Na+ phosphor exhibits a QY of 14.3%, which is 1.26 times that of the undoped sample. Temperature-dependent PL spectra reveal good thermal stability; at 498 K the emission intensity remains 64.9% of that at room temperature. The WLED device shows white light with chromaticity coordinates of (0.301, 0.354), a color rendering index (CRI) of 81.8, and a correlated color temperature (CCT) of 6900 K.
    In summary, Na+ doping is an effective strategy to achieve significant luminescence enhancement in CLEGO:Eu3+ red-emitting phosphors. The optimized CLEGO:0.9%Na+ phosphor combines high emission intensity, acceptable quantum efficiency, good thermal stability, and suitable color coordinates. The fabricated WLED device demonstrates satisfactory white-light performance, indicating that this red phosphor is a promising candidate for n-UV chip-based WLED applications.

     

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