白光LED用Mn<sup>4+</sup>激活红光荧光粉中锰离子价态表征研究进展

Mn4+激活红光荧光粉是白光发光二极管(LED)用荧光粉的研究热点之一。过渡金属锰元素具有未充满的d轨道, 可形成Mn4+/Mn3+/Mn2+等多种价态, 而其他价态的存在会影响Mn4+的吸收/辐射跃迁。目前, 多数研究论文对所制备荧光粉中锰离子价态未进行表征, 或采用的表征手段难以定性或定量确定多种共存价态锰离子的相对含量。本文对Mn4+激活红光荧光粉中锰离子价态表征手段进行综述, 包括漫反射光谱、荧光光谱、X射线光电子能谱、电子顺磁共振谱、阴极射线发光谱、X射线精细吸收谱、变温磁化率谱等。对其测试结果在定性或定量表征锰离子价态方面的可靠性以及测试便易性进行对比评述。最后总结了影响锰离子价态的因素和调控其价态的实验方法, 以期对新型高效Mn4+激活红光荧光粉的研发有所裨益。

Abstract

The development of Mn4+ activated red phosphor for white LEDs is one of the current research hotspots. Manganese, as a transition metal element, has partially filled d orbitals and can form various valence states other than Mn4+ in the prepared phosphors. The existence of other valence states, however, can affect the absorption and luminescence of the Mn4+ ions. In many related papers, the valence state of manganese ions of the as-prepared phosphors is not analyzed, or the adopted techniques are difficult to characterize various valence states of manganese ions qualitatively or quantitatively. This article reviews the valence-state characterization techniques of manganese ions, including the diffuse reflectance spectrum, the photoluminescence spectrum, the X-ray photoelectron spectroscopy, the electron paramagnetic resonance spectrum, the cathodoluminescence spectrum, the X-ray absorption fine structure spectrum, and the temperature-dependent magnetic susceptibility. The reliability of these techniques to qualitatively or quantitatively characterize the manganese valence is comparatively discussed. The influencing factors of the valence state of manganese ions and the regulating method of Mn4+ in phosphors are also summarized, with a view to benefiting the development of new efficient Mn4+ activated red phosphors.

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王兆武, 姬海鹏, 徐坚, 易莎莎, 侯星慧, 陈德良, 解荣军. 白光LED用Mn⁴⁺激活红光荧光粉中锰离子价态表征研究进展[J]. 发光学报, 2020, 41(10): 1195. WANG Zhao-wu, JI Hai-peng, XU Jian, YI Sha-sha, HOU Xing-hui, CHEN De-liang, XIE Rong-jun. Advances in Valence State Analysis of Manganese in Mn⁴⁺-activated Red Phosphors for White LEDs[J]. Chinese Journal of Luminescence, 2020, 41(10): 1195.

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