The present paper details the preparation of CaAl12-xO19: xMn4+ (CAO: Mn4+) red phosphors based on CaAl12O19 using a high-temperature solid-state method through Mn ion doping. A range of analytical techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM) and fluorescence spectroscopy, to comprehensively investigate the crystal structure, microstructure and photoluminescence characteristics of the samples. The results demonstrate that the doped Mn4+ ions enter the octahedral sites of Al3+, and the lattice constants of the matrix does not change significantly because the ionic radius of the doped Mn4+ ions is equivalent to the size of the Al3+ ions. On this basis, the lattice size and lattice strain were calculated using the W-H equation. The results show that as the doping concentration gradually increases, both the lattice size and strain exhibit a slowly increasing trend. The prepared phosphor exhibited a polyhedral morphology, characterised by two hexagonal prisms with irregular hexagonal end faces, a substantial particle size, and optimal dispersion. When exposed to near ultraviolet light at a wavelength of 349 nm, the photoluminescence spectrum displays narrow-band emission characteristics, with the central wavelength of the emission peak at 654 nm and the full width at half maximum (FWHM) of 40.706 nm. The emission peak is attributed to the transition from 2Eg to 4A2g of Mn4+ in a strong crystal field. With the increase of Mn4+ doping concentration, the fluorescence intensity first increases and then decreases, and the fluorescence intensity is the highest when the doping concentration is 1.2 mol%. The analysis yielded three emission peaks, which were separated by the peak separation method. These peaks correspond to the emission of Mn4+ at three different octahedral points of Al3+. The integrated area ratio of the three peaks indicates that Mn4+ is predominantly present on the symmetrical sites. Thermal stability analysis demonstrates that the emission intensity of the phosphor decreases rapidly due to three factors. Firstly, the size of the Mn4+ ions is smaller than the octahedral gap size. Secondly, the energy is higher. Thirdly, no radiation transition intensifies with the increase of temperature. The colour purity calculation indicates that the red phosphor prepared has a colour purity of over 99%. At the same time, the color temperature is below 6000k, which renders it suitable for indoor plant cultivation.

Preparation and Luminescence Properties of Mn⁴⁺ Ions Doped CaAl₁₂O₁₉ Red Phosphors

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发表日期：

2025年11月28日

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Chuheng Guan,
Yumeng Jia,
Zhongxiang Shi,
Jing Wang,
Yingnan Dong,
Zhihui Wang

摘要

The present paper details the preparation of CaAl_12-xO₁₉: xMn⁴⁺ (CAO: Mn⁴⁺) red phosphors based on CaAl₁₂O₁₉ using a high-temperature solid-state method through Mn ion doping. A range of analytical techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM) and fluorescence spectroscopy, to comprehensively investigate the crystal structure, microstructure and photoluminescence characteristics of the samples. The results demonstrate that the doped Mn⁴⁺ ions enter the octahedral sites of Al³⁺, and the lattice constants of the matrix does not change significantly because the ionic radius of the doped Mn⁴⁺ ions is equivalent to the size of the Al³⁺ ions. On this basis, the lattice size and lattice strain were calculated using the W-H equation. The results show that as the doping concentration gradually increases, both the lattice size and strain exhibit a slowly increasing trend. The prepared phosphor exhibited a polyhedral morphology, characterised by two hexagonal prisms with irregular hexagonal end faces, a substantial particle size, and optimal dispersion. When exposed to near ultraviolet light at a wavelength of 349 nm, the photoluminescence spectrum displays narrow-band emission characteristics, with the central wavelength of the emission peak at 654 nm and the full width at half maximum (FWHM) of 40.706 nm. The emission peak is attributed to the transition from ²E_g to ⁴A_2g of Mn⁴⁺ in a strong crystal field. With the increase of Mn⁴⁺ doping concentration, the fluorescence intensity first increases and then decreases, and the fluorescence intensity is the highest when the doping concentration is 1.2 mol%. The analysis yielded three emission peaks, which were separated by the peak separation method. These peaks correspond to the emission of Mn⁴⁺ at three different octahedral points of Al³⁺. The integrated area ratio of the three peaks indicates that Mn⁴⁺ is predominantly present on the symmetrical sites. Thermal stability analysis demonstrates that the emission intensity of the phosphor decreases rapidly due to three factors. Firstly, the size of the Mn⁴⁺ ions is smaller than the octahedral gap size. Secondly, the energy is higher. Thirdly, no radiation transition intensifies with the increase of temperature. The colour purity calculation indicates that the red phosphor prepared has a colour purity of over 99%. At the same time, the color temperature is below 6000k, which renders it suitable for indoor plant cultivation.

Preparation and Luminescence Properties of Mn4+ Ions Doped CaAl12O19 Red Phosphors

摘要

Preparation and Luminescence Properties of Mn⁴⁺ Ions Doped CaAl₁₂O₁₉ Red Phosphors