MAlSiN₃:Eu²⁺ (M = Ca, Sr) is commonly used in high-power phosphor-converted white-light-emitting diodes and laser diodes to promote their color-rendering index. However, the wide application of this phosphor is limited by the degradation of its luminescent properties in high-temperature, high-humidity, and high-sulfur-content environment. Here, the degradation mechanism of the (Sr,Ca)AlSiN₃:Eu²⁺ (SCASN) red phosphor under thermal-moisture-sulfur coupling conditions is investigated. Furthermore, by performing first-principles calculations, the hydrolysis mechanism on an atomic scale is assessed. The adsorption energy (E_ads) and charge transfer (ΔQ) results showed that H₂O chemically adsorbed on the (0 1 0), (3 1 0), and (0 0 1) surfaces of the CaAlSiN₃ (CASN) host lattice. The energy barrier for H₂O dissociation is only 29.73 kJ mol⁻¹ on the CASN (0 1 0) surface, indicating a high dissociation probability. The formation of NH₃, Ca(OH)₂, and CaAl₂Si₂O₈ is confirmed by H⁺ tended to combine with surface N atoms, while OH⁻ combined with the surface Al/Si or Ca atoms. Moreover, ab initio molecular dynamics simulations were performed to further understand the hydrolysis process. This work offers a guidance on the design and applications of luminescent materials in LED packages with higher reliability and stability requirements in harsh environment.

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The (Ca, Sr) AlSiN₃:Eu²⁺(CSASN:Eu) red phosphor is widely used to improve color rendering of high-power phosphor-converted lighting diode (pc-WLED), but it is always unstable under high temperature and high humidity environments. Therefore, the studies on the temperature and humidity resistance of red phosphors and their aging mechanism have become essential to evaluate its reliability in harsh applications. In this paper, the pressure cooker test (PCT) and 85°C&85% RH aging test were carried out for the CSASN:Eu red phosphors. And, its hydrolysis reaction-driven degradation mechanism was simulated and analyzed based on first-principle calculation, in which the optimized adsorption of simplified CaAlSiN3(CASN) and H2 O was simulated based on Density Function Theory (DFT) and the specific aging process was analyzed by the charge density difference and ab initio molecular dynamics (AIMD). The experimental results showed that the photoluminescence performance of CSASN:Eu red phosphor dropped gradually and finally disappeared under PCT aging, and its temperature-dependent degradation kinetics followed the Arrhenius model well. Meanwhile, the simulation results indicate that the CASN, reacted with H2 O when the H atoms had a tendency to approach N atoms. Both the temperature and humidity could accelerate the hydrolysis reaction rate.@en