Ho~(3+)/Tm~(3+)/Yb~(3+)等离子掺杂氟氧化物玻璃及硅酸盐玻璃的荧光特性
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摘要
由于稀土荧光材料在固体激光器、传感器、太阳电池、光存储、光学探测器和三维立体演示等领域有着广泛的应用前景，因此稀土荧光材料的研究受到了人们的重视。同时稀土离子掺杂的基质材料成了目前研究的热点之一，本论文主要研究了Ho~(3+)/Yb~(3+)，Tm~(3+)/Yb~(3+)，Ho~(3+)/Tm~(3+)/Yb~(3+)掺杂NaYF_4玻璃陶瓷的上转换荧光特性和发光机制及Ho~(3+)/Yb~(3+)掺杂硅酸盐的上转换荧光特性，通过改变稀土离子浓度和泵浦光功率等参数，观测到了白光发射。论文主要工作和结果如下：
首先用高温固相法制备了Ho~(3+)/Yb~(3+)，Tm~(3+)/Yb~(3+)，Ho~(3+)/Tm~(3+)/Yb~(3+)掺杂NaYF4玻璃陶瓷和Ho~(3+)/Yb~(3+)掺杂硅酸盐玻璃陶瓷。利用XRD表征玻璃中微晶的存在。在980nm的红外泵浦光的激发下，观测了稀土离子Ho~(3+)、Tm~(3+)的荧光光谱。其中，观测到绿光发光中心在520nm~580nm来自Ho~(3+)的5F4/5S2→5I8的跃迁绿光衍射分有明显的Stark劈裂，626nm~680nm nm的红光部分来自Ho~(3+)的~5F_5→~5I_8的辐射跃迁，蓝光是由于Tm~(3+)离子~1G_4→~3H_6跃迁中心波长475nm，红光是部分由Tm~(3+)离子1G4→~3H_4跃迁中心波长651nm，红外光是Tm~(3+)由3H4→3H6跃迁中心波长790nm。通过荧光光谱和泵浦光激发功率关系及稀土离子的能级图解释了Ho~(3+)/Tm~(3+)/Yb~(3+)共掺杂NaYF_4玻璃陶瓷的上转换发光机制，其中蓝光上转换荧光主要是三光子过程，绿光和红光及红外光上转换荧光主要是双光子过程。另外通过改变稀土离子浓度和泵浦光功率等参数，最终实现白光发射。同时还制备了Ho~(3+)/Yb~(3+)共掺杂的硅酸盐玻璃陶瓷，通过对荧光光谱的观测得出Li~+稀土离子Ho~(3+)具有荧光增强的作用。
最后利用Judd-Oflet计算了Ho~(3+)在NaYF_4玻璃陶瓷中的J-O强度参数λ。解释了Yb~(3+)与Li~+对稀土里子的荧光增强作用与实验结果一致。
Over the past two decades, the rare earth fluorescent material has received a greatamount of attention due to its potential applications in solid laser, sensors, solar cell, lightstorage device,3-dimensional display and so on. At present, special attention has beengiven to rare earth ions co-doped matrix materials owing to their unique properties forfuture photonics device. In this thesis, we systematically studied the spectrum propertiesand up-conversion luminescent mechanism of NaYF_4glass ceramics dopingHo~(3+)/Yb~(3+)-Tm~(3+)/Yb~(3+)-Ho~(3+)/Tm~(3+)/Yb~(3+)and the up-conversion fluorescence properties ofHo~(3+)/Yb~(3+)co-doped silicate, achieved white-light. The rest and contents of the thesis isorganized as follows:
In the first section, the Ho~(3+)/Yb~(3+)-Tm~(3+)/Yb~(3+)-Ho~(3+)/Tm~(3+)/Yb~(3+)co-doped NaYF_4glassceramic and Ho~(3+)/Yb~(3+)doping silicate glass ceramics were fabricated usinghigh-temperature melting method. The existence of nanocrystal within glass sample wasconfirmed by X-ray Diffraction (XRD). Under the980nm infrared light pumping, thefluorescence spectra of the rare earth ions Ho~(3+), Tm~(3+)were characterized. The results showthat the green-light emission peak within520~580nm has obvious Stark fracturing and isoriginated from Ho~(3+)(~5F_4/~5S_2→~5I_8) radiation. The red-light emission within626~680nm isoriginated from Ho~(3+)(~5F_5→~5I_8) radiation. The blue-ray was due to Tm~(3+)ion (~1G_4→~3H_6)with the light center475nm, the red-ray in part by Tm~(3+)ion (~1G_4→~3H_4) with the lightcenter651nm, the infrared-ray was from Tm~(3+)(~3H_4→~3H_6) with the light center790nm.The up-conversion mechanism of NaYF_4glass ceramics is explained through the ln-lnrelations between fluorescence spectra intensity and pump power and rare earth ionsenergy level. The results show that the main conversion fluorescent blue-ray is three-photon process, while the green, red and infrared-ray conversion fluorescence is mainlytwo-photon process. White-light emission was finally achieved by changing the parameterssuch as rare earth ions concentration and pump power. In the second section, the Ho~(3+)/Yb~(3+)co-doped silicate glass ceramics was fabricated and characterized. The experimental resultsof fluorescence spectrum demonstrate the fluorescence enhancement effect of Li~+ion onrare earth ions Ho~(3+).
In the last section, we calculated the J-O strength parameters λHo3+in NaYF_4glassceramic using the Judd-Oflet. The experimental improved fluorescent guantum effect ofYb3+and Li~+is explained theoretically.
首先用高温固相法制备了Ho~(3+)/Yb~(3+)，Tm~(3+)/Yb~(3+)，Ho~(3+)/Tm~(3+)/Yb~(3+)掺杂NaYF4玻璃陶瓷和Ho~(3+)/Yb~(3+)掺杂硅酸盐玻璃陶瓷。利用XRD表征玻璃中微晶的存在。在980nm的红外泵浦光的激发下，观测了稀土离子Ho~(3+)、Tm~(3+)的荧光光谱。其中，观测到绿光发光中心在520nm~580nm来自Ho~(3+)的5F4/5S2→5I8的跃迁绿光衍射分有明显的Stark劈裂，626nm~680nm nm的红光部分来自Ho~(3+)的~5F_5→~5I_8的辐射跃迁，蓝光是由于Tm~(3+)离子~1G_4→~3H_6跃迁中心波长475nm，红光是部分由Tm~(3+)离子1G4→~3H_4跃迁中心波长651nm，红外光是Tm~(3+)由3H4→3H6跃迁中心波长790nm。通过荧光光谱和泵浦光激发功率关系及稀土离子的能级图解释了Ho~(3+)/Tm~(3+)/Yb~(3+)共掺杂NaYF_4玻璃陶瓷的上转换发光机制，其中蓝光上转换荧光主要是三光子过程，绿光和红光及红外光上转换荧光主要是双光子过程。另外通过改变稀土离子浓度和泵浦光功率等参数，最终实现白光发射。同时还制备了Ho~(3+)/Yb~(3+)共掺杂的硅酸盐玻璃陶瓷，通过对荧光光谱的观测得出Li~+稀土离子Ho~(3+)具有荧光增强的作用。
最后利用Judd-Oflet计算了Ho~(3+)在NaYF_4玻璃陶瓷中的J-O强度参数λ。解释了Yb~(3+)与Li~+对稀土里子的荧光增强作用与实验结果一致。
Over the past two decades, the rare earth fluorescent material has received a greatamount of attention due to its potential applications in solid laser, sensors, solar cell, lightstorage device,3-dimensional display and so on. At present, special attention has beengiven to rare earth ions co-doped matrix materials owing to their unique properties forfuture photonics device. In this thesis, we systematically studied the spectrum propertiesand up-conversion luminescent mechanism of NaYF_4glass ceramics dopingHo~(3+)/Yb~(3+)-Tm~(3+)/Yb~(3+)-Ho~(3+)/Tm~(3+)/Yb~(3+)and the up-conversion fluorescence properties ofHo~(3+)/Yb~(3+)co-doped silicate, achieved white-light. The rest and contents of the thesis isorganized as follows:
In the first section, the Ho~(3+)/Yb~(3+)-Tm~(3+)/Yb~(3+)-Ho~(3+)/Tm~(3+)/Yb~(3+)co-doped NaYF_4glassceramic and Ho~(3+)/Yb~(3+)doping silicate glass ceramics were fabricated usinghigh-temperature melting method. The existence of nanocrystal within glass sample wasconfirmed by X-ray Diffraction (XRD). Under the980nm infrared light pumping, thefluorescence spectra of the rare earth ions Ho~(3+), Tm~(3+)were characterized. The results showthat the green-light emission peak within520~580nm has obvious Stark fracturing and isoriginated from Ho~(3+)(~5F_4/~5S_2→~5I_8) radiation. The red-light emission within626~680nm isoriginated from Ho~(3+)(~5F_5→~5I_8) radiation. The blue-ray was due to Tm~(3+)ion (~1G_4→~3H_6)with the light center475nm, the red-ray in part by Tm~(3+)ion (~1G_4→~3H_4) with the lightcenter651nm, the infrared-ray was from Tm~(3+)(~3H_4→~3H_6) with the light center790nm.The up-conversion mechanism of NaYF_4glass ceramics is explained through the ln-lnrelations between fluorescence spectra intensity and pump power and rare earth ionsenergy level. The results show that the main conversion fluorescent blue-ray is three-photon process, while the green, red and infrared-ray conversion fluorescence is mainlytwo-photon process. White-light emission was finally achieved by changing the parameterssuch as rare earth ions concentration and pump power. In the second section, the Ho~(3+)/Yb~(3+)co-doped silicate glass ceramics was fabricated and characterized. The experimental resultsof fluorescence spectrum demonstrate the fluorescence enhancement effect of Li~+ion onrare earth ions Ho~(3+).
In the last section, we calculated the J-O strength parameters λHo3+in NaYF_4glassceramic using the Judd-Oflet. The experimental improved fluorescent guantum effect ofYb3+and Li~+is explained theoretically.
引文
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