基于能量传递的稀土掺杂微纳米发光材料的制备及其发光特性研究
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摘要
在过去的几十年里，关于纳米发光材料特别是掺杂稀土离子的纳米发光材料研究，已经成为热门课题之一。因为稀土离子独特的4f电子层结构，使其广泛应用于高性能磁铁、发光设备、催化剂和其他功能材料等方面。稀土掺杂纳米发光材料作为一类重要的无机材料因其具有独特的光学和电学特性已经引起研究者越来越多的关注。本论文采用溶剂热法和高温固相法合成出不同体系的稀土掺杂微纳米荧光材料，并对其进行表征和发光特性研究，主要研究内容如下：
1.使用一种简单的一步溶剂热法成功地合成出新型单分散BaCeF_5、BaCeF_5:Tb~（3+）和BaCeF_5:Tb~（3+）/Sm~（3+）纳米晶体。分别利用X射线衍射（XRD）、场发射扫描电子显微镜（FE-SEM）、透射电镜（TEM）、光致发光（PL）和衰减曲线等对40nm球形纳米晶体和75~80nm的八面体纳米晶进行表征。结果表明，由于Ce~(3+)离子可以把能量传递给Tb~（3+）离子，所以BaCeF_5:Tb~（3+）显示出很强的绿色光发射，峰值中心位于546nm，归属于~5D_4—~7F_5能级跃迁。Tb~（3+）的发光衰减寿命随着浓度的增加而减少。利用猝灭浓度和光谱重叠法计算出Ce~(3+)和Tb~（3+）的临界能量传递距离。实验分析和理论计算表明，Ce~(3+)和Tb~（3+）之间的能量传递是偶极-四极相互作用占主导作用。不仅如此，在该体系中掺杂Sm~（3+）离子后发现，在紫外光激发下，BaCeF_5:Tb~（3+）/Sm~（3+）样品显示出典型的Tb~（3+）离子绿色光发射带和Sm~（3+）离子橙红色光和红色光发射带，这是因为Tb~（3+）和Sm~（3+）离子之间同样存在高效能量传递，这一点也可以通过荧光光谱和荧光衰减曲线来验证。另外，通过改变Sm~（3+）离子的浓度可以很容易调节BaCeF_5:Tb~（3+）/Sm~（3+）纳米发光材料的发射光颜色。这些实验结果表明，BaCeF_5:Tb~（3+）/Sm~（3+）纳米晶体可以在三维显示器和白色光源等方面具有潜在的应用价值。
2.利用溶剂热法成功合成出CeF_3:Er~(3+)/Yb~（3+）和CeF_3:Tm~（3+）/Yb~（3+）纳米片。使用X射线衍射（XRD），场发射扫描电子显微镜（FE-SEM），X射线光电子能谱（XPS）和上转换发光（UCL）对样品的晶相组成、尺寸、形貌以及光学特性进行表征与研究。在980nm激发下，CeF_3:Er~(3+)/Yb~（3+）样品显示出蓝光（487nm）、绿光（523，546nm）和红光（654nm）发射，这是因为Yb~（3+）离子激发态和Er~(3+)离子激发态之间存在能量传递过程。类似地，在980nm激发下，CeF_3:Tm~（3+）/Yb~（3+）样品显示出蓝光（450，475nm）和红光（649nm）发射，这也是由于Yb~（3+）离子激发态与Tm~（3+）离子激发态之间存在能量传递过程。实验结果表明，它们在光电子器件和光电应用材料方面拥有巨大潜力。
3.使用高温固相法合成出一种新型、颜色可调谐的上转换发光材料GdPO_4:Yb~（3+）/Ln~(3+)(Ln=Er, Ho,Tm)。在980nm激发下，样品发射光谱同时存在红光、绿光和蓝光发射（RGB）。通过改变掺杂稀土的浓度，可以实现从多色光到白光发射的调节，直到制备出色坐标为(0.328,0.327)的发光样品，这与白光标准色坐标（0.333，0.333）匹配得很好。这种上转换荧光粉因为具有颜色可调、发光强和亮度好等优点，因而它完全有可能应用在白光LED_s和生物荧光标记等领域。
4.使用高温固相法合成出新型CaEuAl_3O_7荧光粉，并对其光致发光（PL）特性进行了研究。光谱结果表明，在空气中制备的CaEuAl_3O_7荧光粉中Eu~(3+)离子显示红光发射，在碳粉还原气氛中制备的CaEuAl_3O_7样品因其部分三价铕离子被还原成二价铕离子，所以其发射光谱显示出宽带蓝光发射，发射主峰位于445nm。上述实验结果表明，在近紫外光激发下，CaEuAl_3O_7荧光粉可以同时发射红光和蓝光，所以它在固体照明领域具有潜在的应用前景。
Over the past decades, the study of nanometric luminescent materials,especially lanthanide ion-doped luminescent nanomaterials, has become one of thehottest topics in nanoscience because of their potential applications in highperformance magnets, luminescent devices, catalysts, and other functional materialsarising from4f electrons. As an important class of inorganic materials with uniqueoptical, electrical properties of nano-and micron material has caused more and moreattention. This paper used solvothermal and high temperature solid state synthesis ofthe different systems of fluorescent material, and were characterized, the maincontents are as follows:
1. A novel monodisperse BaCeF5and BaCeF5: Tb~(3+), Sm3+nanocrystals have beensuccessfully synthesized by a simple one step solvothermal synthesis. Uniformlydistributed nanocrystals with spherical morphology and an average diameter of40nm and an octahedral morphology and particle size of75-80nm were observed.X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM), photoluminescence (PL) and decay studies were employed to characterize thesamples. The results reveal that Tb~(3+)-doped BaCeF_5sample shows strong greenemission centered at546nm corresponding to the~5D_4–~7F_5transition of Tb~(3+)due toan efficient energy transfer from Ce~(3+)to Tb~(3+). The decay lifetime of Tb~(3+)monotonically decreases with increase of Tb~(3+)concentration. The critical energytransfer distance between Ce~(3+)and Tb~(3+)was also calculated by methods ofconcentration quenching and spectral overlapping. Experimental analysis andtheoretical calculations reveal that the dipole–dipole interaction should be thedominant mechanism for the Ce~(3+)-Tb~(3+)energy transfer. Under ultraviolet irradiation,the BaCeF_5: Tb~(3+), Sm~(3+)samples exhibit the typical green emission band of the Tb~(3+)ions, as well as an orange-red and red emission bands of the Sm~(3+)ions in thepresence of Ce~(3+)ions. The highly intense orange-red and red emission bands of theSm~(3+)ions were attributed to the effective energy transfer from the Tb~(3+)to Sm~(3+)ions,which has been justified through the luminescence spectra and the fluorescencedecay dynamics. The luminescence colours of BaCeF_5: Tb~(3+), Sm~(3+)nanophosphorscan be easily tuned by changing the concentration of Sm~(3+)ions. These resultssuggest that BaCeF_5: Tb~(3+), Sm~(3+)nanocrystals can be explored for three dimensionaldisplays, white light sources, and so on.
2. CeF_3: Er~(3+), Yb~(3+)；Tm~(3+),Yb~(3+)nanoplates have been successfully synthesized by asolvothermal method with further calcinations. The crystalline phase, size and opticalproperties were characterized using powder X-ray diffraction (XRD), fieldemission-scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), Energy dispersive spectroscopy (EDS) and upconversion luminescence (UCL).The CeF_3: Er~(3+), Yb~(3+)samples showed blue emission (487nm), green emissions (523,546nm) and red emission (654nm) under980nm excitation. The main mechanism ofupconversion is attributed to the energy transfer (ET) among Yb~(3+)and Er~(3+)ions inexcited states. The CeF_3: Tm~(3+),Yb~(3+)samples showed blue emissions (450,475nm)and red emission (649nm) under980nm excitation. The main mechanism that allowsfor upconversion is attributed the energy transfer (ET) among Yb~(3+)and Tm~(3+)ions inexcited states. The results illustrate the large potential of this new class of material forphotonic applications involving optoelectronics devices.
3. A novel and tunable upconversion luminescent material GdPO_4: Yb~(3+), Ln~(3+)(Ln=Er, Ho, Tm) has been synthesized by conventional solid-state reaction method.Simultaneous red, green and blue (RGB) emissions were obtained after excitation at980nm. Color emission was tuned from multicolor to white light with colorcoordinate (0.328,0.327) matching very well with the white reference (0.333,0.333).Changes in color emissions were obtained by varying the intensity ratios betweenRGB bands that were strongly concentration dependent because of the interaction ofco-dopants. The color tunability, high quality of white light and high intensity of theemitted signal make these upconversion (UC) phosphors excellent candidates forapplications in white light LEDs and biological fluorescent tags.
4. A novel CaEuAl_3O_7phosphor was synthesized by a high temperature solid-statereaction method. the photoluminescence (PL) properties were investigated toexamine its application in the development of white light-emitting diodes (w-LED_s). The red emission was observed from Eu~(3+)ions in the CaEuAl3O7phosphor. TheCaEuAl_3O_7:Eu~(3+)/Eu~(2+)prepared in a thermal-carbon reducing atmosphere whichshows good absorption ranging from ultraviolet to a blue region centered at445nm.The above results indicate that the CaEuAl_3O_7is a good candidate as red and bluecomponent for near UV-excited w-LED_s
1.使用一种简单的一步溶剂热法成功地合成出新型单分散BaCeF_5、BaCeF_5:Tb~（3+）和BaCeF_5:Tb~（3+）/Sm~（3+）纳米晶体。分别利用X射线衍射（XRD）、场发射扫描电子显微镜（FE-SEM）、透射电镜（TEM）、光致发光（PL）和衰减曲线等对40nm球形纳米晶体和75~80nm的八面体纳米晶进行表征。结果表明，由于Ce~(3+)离子可以把能量传递给Tb~（3+）离子，所以BaCeF_5:Tb~（3+）显示出很强的绿色光发射，峰值中心位于546nm，归属于~5D_4—~7F_5能级跃迁。Tb~（3+）的发光衰减寿命随着浓度的增加而减少。利用猝灭浓度和光谱重叠法计算出Ce~(3+)和Tb~（3+）的临界能量传递距离。实验分析和理论计算表明，Ce~(3+)和Tb~（3+）之间的能量传递是偶极-四极相互作用占主导作用。不仅如此，在该体系中掺杂Sm~（3+）离子后发现，在紫外光激发下，BaCeF_5:Tb~（3+）/Sm~（3+）样品显示出典型的Tb~（3+）离子绿色光发射带和Sm~（3+）离子橙红色光和红色光发射带，这是因为Tb~（3+）和Sm~（3+）离子之间同样存在高效能量传递，这一点也可以通过荧光光谱和荧光衰减曲线来验证。另外，通过改变Sm~（3+）离子的浓度可以很容易调节BaCeF_5:Tb~（3+）/Sm~（3+）纳米发光材料的发射光颜色。这些实验结果表明，BaCeF_5:Tb~（3+）/Sm~（3+）纳米晶体可以在三维显示器和白色光源等方面具有潜在的应用价值。
2.利用溶剂热法成功合成出CeF_3:Er~(3+)/Yb~（3+）和CeF_3:Tm~（3+）/Yb~（3+）纳米片。使用X射线衍射（XRD），场发射扫描电子显微镜（FE-SEM），X射线光电子能谱（XPS）和上转换发光（UCL）对样品的晶相组成、尺寸、形貌以及光学特性进行表征与研究。在980nm激发下，CeF_3:Er~(3+)/Yb~（3+）样品显示出蓝光（487nm）、绿光（523，546nm）和红光（654nm）发射，这是因为Yb~（3+）离子激发态和Er~(3+)离子激发态之间存在能量传递过程。类似地，在980nm激发下，CeF_3:Tm~（3+）/Yb~（3+）样品显示出蓝光（450，475nm）和红光（649nm）发射，这也是由于Yb~（3+）离子激发态与Tm~（3+）离子激发态之间存在能量传递过程。实验结果表明，它们在光电子器件和光电应用材料方面拥有巨大潜力。
3.使用高温固相法合成出一种新型、颜色可调谐的上转换发光材料GdPO_4:Yb~（3+）/Ln~(3+)(Ln=Er, Ho,Tm)。在980nm激发下，样品发射光谱同时存在红光、绿光和蓝光发射（RGB）。通过改变掺杂稀土的浓度，可以实现从多色光到白光发射的调节，直到制备出色坐标为(0.328,0.327)的发光样品，这与白光标准色坐标（0.333，0.333）匹配得很好。这种上转换荧光粉因为具有颜色可调、发光强和亮度好等优点，因而它完全有可能应用在白光LED_s和生物荧光标记等领域。
4.使用高温固相法合成出新型CaEuAl_3O_7荧光粉，并对其光致发光（PL）特性进行了研究。光谱结果表明，在空气中制备的CaEuAl_3O_7荧光粉中Eu~(3+)离子显示红光发射，在碳粉还原气氛中制备的CaEuAl_3O_7样品因其部分三价铕离子被还原成二价铕离子，所以其发射光谱显示出宽带蓝光发射，发射主峰位于445nm。上述实验结果表明，在近紫外光激发下，CaEuAl_3O_7荧光粉可以同时发射红光和蓝光，所以它在固体照明领域具有潜在的应用前景。
Over the past decades, the study of nanometric luminescent materials,especially lanthanide ion-doped luminescent nanomaterials, has become one of thehottest topics in nanoscience because of their potential applications in highperformance magnets, luminescent devices, catalysts, and other functional materialsarising from4f electrons. As an important class of inorganic materials with uniqueoptical, electrical properties of nano-and micron material has caused more and moreattention. This paper used solvothermal and high temperature solid state synthesis ofthe different systems of fluorescent material, and were characterized, the maincontents are as follows:
1. A novel monodisperse BaCeF5and BaCeF5: Tb~(3+), Sm3+nanocrystals have beensuccessfully synthesized by a simple one step solvothermal synthesis. Uniformlydistributed nanocrystals with spherical morphology and an average diameter of40nm and an octahedral morphology and particle size of75-80nm were observed.X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM), photoluminescence (PL) and decay studies were employed to characterize thesamples. The results reveal that Tb~(3+)-doped BaCeF_5sample shows strong greenemission centered at546nm corresponding to the~5D_4–~7F_5transition of Tb~(3+)due toan efficient energy transfer from Ce~(3+)to Tb~(3+). The decay lifetime of Tb~(3+)monotonically decreases with increase of Tb~(3+)concentration. The critical energytransfer distance between Ce~(3+)and Tb~(3+)was also calculated by methods ofconcentration quenching and spectral overlapping. Experimental analysis andtheoretical calculations reveal that the dipole–dipole interaction should be thedominant mechanism for the Ce~(3+)-Tb~(3+)energy transfer. Under ultraviolet irradiation,the BaCeF_5: Tb~(3+), Sm~(3+)samples exhibit the typical green emission band of the Tb~(3+)ions, as well as an orange-red and red emission bands of the Sm~(3+)ions in thepresence of Ce~(3+)ions. The highly intense orange-red and red emission bands of theSm~(3+)ions were attributed to the effective energy transfer from the Tb~(3+)to Sm~(3+)ions,which has been justified through the luminescence spectra and the fluorescencedecay dynamics. The luminescence colours of BaCeF_5: Tb~(3+), Sm~(3+)nanophosphorscan be easily tuned by changing the concentration of Sm~(3+)ions. These resultssuggest that BaCeF_5: Tb~(3+), Sm~(3+)nanocrystals can be explored for three dimensionaldisplays, white light sources, and so on.
2. CeF_3: Er~(3+), Yb~(3+)；Tm~(3+),Yb~(3+)nanoplates have been successfully synthesized by asolvothermal method with further calcinations. The crystalline phase, size and opticalproperties were characterized using powder X-ray diffraction (XRD), fieldemission-scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), Energy dispersive spectroscopy (EDS) and upconversion luminescence (UCL).The CeF_3: Er~(3+), Yb~(3+)samples showed blue emission (487nm), green emissions (523,546nm) and red emission (654nm) under980nm excitation. The main mechanism ofupconversion is attributed to the energy transfer (ET) among Yb~(3+)and Er~(3+)ions inexcited states. The CeF_3: Tm~(3+),Yb~(3+)samples showed blue emissions (450,475nm)and red emission (649nm) under980nm excitation. The main mechanism that allowsfor upconversion is attributed the energy transfer (ET) among Yb~(3+)and Tm~(3+)ions inexcited states. The results illustrate the large potential of this new class of material forphotonic applications involving optoelectronics devices.
3. A novel and tunable upconversion luminescent material GdPO_4: Yb~(3+), Ln~(3+)(Ln=Er, Ho, Tm) has been synthesized by conventional solid-state reaction method.Simultaneous red, green and blue (RGB) emissions were obtained after excitation at980nm. Color emission was tuned from multicolor to white light with colorcoordinate (0.328,0.327) matching very well with the white reference (0.333,0.333).Changes in color emissions were obtained by varying the intensity ratios betweenRGB bands that were strongly concentration dependent because of the interaction ofco-dopants. The color tunability, high quality of white light and high intensity of theemitted signal make these upconversion (UC) phosphors excellent candidates forapplications in white light LEDs and biological fluorescent tags.
4. A novel CaEuAl_3O_7phosphor was synthesized by a high temperature solid-statereaction method. the photoluminescence (PL) properties were investigated toexamine its application in the development of white light-emitting diodes (w-LED_s). The red emission was observed from Eu~(3+)ions in the CaEuAl3O7phosphor. TheCaEuAl_3O_7:Eu~(3+)/Eu~(2+)prepared in a thermal-carbon reducing atmosphere whichshows good absorption ranging from ultraviolet to a blue region centered at445nm.The above results indicate that the CaEuAl_3O_7is a good candidate as red and bluecomponent for near UV-excited w-LED_s
引文
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