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Light-Induced Degradation in Red-Emitting ZnSiF_6 · 6H_2O:Mn~(4+) Hydrate Phosphor

机译:发光的ZnSiF_6·6H_2O:Mn〜(4+)水合物荧光粉的光致降解

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摘要

Photo-induced degradation behaviors of the red-emitting ZnSiF_6· 6H_2O:Mn~(4+) hydrate phosphor are studied using X-ray diffraction measurement, photoluminescence (PL) analysis, PL excitation spectroscopy, PL decay analysis, diffuse reflectance spectroscopy, and electron spin resonance (ESR) measurement. The ZnSiF_6 ·6H_2O:Mn~(4+) hydrate phosphor exhibits remarkable degradation in the PL intensity under Xe lamp exposure for a few minutes. Coherent laser beams also induce degradation and its degree is in the order of Ar~+ (488 nm) > He-Cd (325 nm) > He-Ne laser (632.8 nm). The degradation mechanism is found to be due to change in the valence state of manganese ions from Mn~(4+) to Mn~(5+) by the photooxidation (Mn~(4+)→ Mn~(5+)) or disproportionation reaction (2Mn~(4+)→ Mn~(3+) + Mn~(5+)). This is supported by the facts that Mn~(4+) ion has larger absorbance at 488 nm than at 325 or 632.8 nm and that the Mn~(5+)-related absorption structures appear in the diffuse reflectance spectra at wavelengths below ~700 nm. The ESR measurement also confirms the decreased Mn~+ spin density in the sample exposed with Xe lamp. A comparative discussion is given on the PL properties of the two different hydrate phosphors, ZnSiF_6? 6H_2O:Mn~(4+) and K_2SnF_6· H_2O:Mn~(4+).
机译:使用X射线衍射测量,光致发光(PL)分析,PL激发光谱,PL衰减分析,漫反射光谱和X射线分析研究了发红光的ZnSiF_6·6H_2O:Mn〜(4+)水合磷光体的光诱导降解行为。电子自旋共振(ESR)测量。 ZnSiF_6·6H_2O:Mn〜(4+)水合物荧光粉在氙灯照射几分钟后,PL强度显着下降。相干激光束也会引起降解,其程度依次为Ar〜+(488 nm)> He-Cd(325 nm)> He-Ne激光(632.8 nm)。发现降解机理是由于锰离子通过光氧化作用从Mn〜(4+)转变为Mn〜(5+)的价态或Mn〜(4+)→Mn〜(5+)或歧化反应(2Mn〜(4+)→Mn〜(3+)+ Mn〜(5+))。 Mn〜(4+)离子在488 nm处的吸光度大于325或632.8 nm处的吸光度,并且Mn〜(5+)相关的​​吸收结构出现在低于700波长的漫反射光谱中,这证明了这一点。纳米ESR测量还证实了用Xe灯曝光的样品中Mn〜+自旋密度降低。对两种不同水合物荧光粉ZnSiF_6?的PL特性进行了比较讨论。 6H_2O:Mn〜(4+)和K_2SnF_6·H_2O:Mn〜(4+)。

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