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 5D0→7F2 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.