几种稀土化合物粉体的制备及其显微组织与发光的调控
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摘要
稀土因其独特的发光性能而在颜色显示、照明、光纤通讯、防伪等领域有着广泛的应用，始终是材料学与物理学的一个研究热点。尤其是稀土红外上转换发光材料，除具有光化学稳定性好、荧光寿命长、吸收和发射带窄、生物毒性小这些特点之外，还因使用红外光激发而拥有更深的光穿透能力、对生物组织损伤小、无荧光背景等优点，使得能将其构建成生物荧光探针，在生物医学荧光成像上显示出巨大的现实与潜在应用前景。另外，很多稀土发光材料还具有较好的顺磁性能，从而使得该类材料在磁共振成像、生物分离方面具有潜在应用价值。为探寻这类材料的制备合成方法，实现这类材料在形貌、尺寸及发光颜色的可控，并开发新型稀土荧光材料。本文采用不同方法，制备了几种稀土化合物粉体。系统地研究了制备工艺对稀土化合物组织、形貌及其发光性能的影响。成功地实现了对这些稀土化合物组织和发光特性的调控。论文的主要研究内容及其结论如下：
(1)采用燃烧法成功地合成了Yb_3Al_5O_(12)(YbAG)与YbAG/Yb_2O_3粉体材料，并通过Er~(3+)掺杂，实现了该粉体材料的红色上转换发光，尤其是在掺铒YbAG/Yb_2O_3粉体材料中实现了纯红色上转换发光，系统讨论了纯红色上转换发光的发光机制；
(2)采用不同的氟源，用沉淀法合成了YF_3纳米颗粒，研究结果表明NH_4~+及其浓度对正八面体纳米颗粒的合成具有控制作用，NH_4~+在YF_3正八面体纳米颗粒的特定晶面(111)的吸附是合成八面体颗粒的决定因素。同时使用HF作为氟源时，可合成YF_3纳米束，对该纳米束在空气中进行退火处理，将YF_3完全脱氟氧化生成氟氧化物，这种氟氧化物具有很好的上转换发光性能；
(3)以油酸/油酸钠/酒精/水为反应体系，采用溶剂热法控制合成了具有各种形貌特征的LaF_3纳米晶，研究发现仅通过调整反应参数与反应条件无法实现LaF_3向NaLaF_4纳米晶的转变。但通过引入Ca~(2+)，并延长反应时间与增加反应前驱体氟源的用量，可以生成不同长径比的NaLaF_4纳米晶。同时当以其它的碱取代NaOH从而改变反应体系中的表面活性剂时可以控制合成具有不同粒径的其它稀土氟化物纳米晶，如当用LiOH取代NaOH时，合成了四方相LiYF_4、LiYbF_4和LiLuF_4纳米晶，当以氨水取代NaOH时，合成出了正交相YF_3和面心立方相的GdF_3纳米晶。在适当光源的激发下，可实现这些纳米晶的光致发光；
(4)使用溶剂热法控制合成出了几种近单分散性碱土稀土氟化物超细纳米晶，包括BaYF_5、Sr_2YF_7和Ba_2Er_(1-x)Yb_xF_7。这些纳米晶均具有面心立方结构，通过合理掺杂实现了这些纳米晶的发光颜色调控，而且其中Ba_2Er_(1-x)Yb_xF_7纳米晶具有很好的顺磁性能。
Rare earth with the phosphors of unique photoluminescent properties always is a hotresearch topic in materials and physics for their wide applications in color display,lighting, fiber-optic communications, anti-fake and so on. In particular, the rare earthinfrared-excited upconversion luminescent phosphors possess not only advantages ofthe photochemical stability, long fluorescence lifetime, narrow absorption andemission bands, and low biotoxicity, but also the virtues of deeper light penetration,lack of photodamage to the living organisms and no autofluorescent of biologicaltissue for using the infrared as excitation resource. The rare earth phosphors, whichcan be built as bioprobes based on these characteristics, present real and potentialapplications in bioimaging. Furthermore, many rare earth phosphors with niceparamagnetism have potential applications in magnetic resonance imaging andbioseparation. Several kinds of rare earth compound powders were synthesized withvarious approaches in this dissertation to explore the synthetic method of thesematerials, to achieve the control of their morphology, size and emission color, and todevelop new rare-earth fluorescent materials. This dissertaton studied systematicallythe effects of the synthesis on the structure, morphology and photoluminescentproperties of rare earth composites, and achieved successfully the control on them.The main contents and conclusions are listed as follows:
(1) Yb_3Al_5O_(12)(YbAG) and YbAG/Yb_2O_3powders were prepared successfully bycombustion route. Red upconversion emission can be realized by Er~(3+)-doping.Especially the pure red upconversion emission was realized in YbAG/Yb_2O_3powders.And the emission mechanism of pure red emission was discussed.
(2) YF_3nanoparticles were synthesized via precipitation by using different fluorinesources. It is found the ammonium ions are responsible to YF_3octahedrananoparticles and the adsorption of NH_4~+on specific crystalline face (111) was thedetermining factor to synthesize the octrahedra nanoparticles. YF_3nanobundles willbe defluorinated and oxidized to oxyfluorites which had nice upconversion property.
(3) A series of LaF_3nanocrystals were synthesized with the solvothermal method inwhich the system of oleic acid, eunatrol, alcohol and water are mixed together to formthe microemulsion. Their crystalline structures and Synthetic Conditions were studied.For example, Tetragonal LiYF_4、LiYbF_4and LiLuF_4nanocrystals were prepared whenNaOH were displaced by LiOH. It is confirmed that these series of nanocrystals maybe used as host matrix materials for luminescence.
(4) BaYF_5、Sr_2YF_7和Ba_2Er_(1-x)Yb_xF_7rare earth fluoride nanocrystals containingalkaline earth ions were synthesized with the solvothermal method. Their crystallinestructures and controllable photoluminescence were studied. And the paramagneticproperty of Ba_2Er_(1-x)Yb_xF_7nanocrystals were studied.
(1)采用燃烧法成功地合成了Yb_3Al_5O_(12)(YbAG)与YbAG/Yb_2O_3粉体材料，并通过Er~(3+)掺杂，实现了该粉体材料的红色上转换发光，尤其是在掺铒YbAG/Yb_2O_3粉体材料中实现了纯红色上转换发光，系统讨论了纯红色上转换发光的发光机制；
(2)采用不同的氟源，用沉淀法合成了YF_3纳米颗粒，研究结果表明NH_4~+及其浓度对正八面体纳米颗粒的合成具有控制作用，NH_4~+在YF_3正八面体纳米颗粒的特定晶面(111)的吸附是合成八面体颗粒的决定因素。同时使用HF作为氟源时，可合成YF_3纳米束，对该纳米束在空气中进行退火处理，将YF_3完全脱氟氧化生成氟氧化物，这种氟氧化物具有很好的上转换发光性能；
(3)以油酸/油酸钠/酒精/水为反应体系，采用溶剂热法控制合成了具有各种形貌特征的LaF_3纳米晶，研究发现仅通过调整反应参数与反应条件无法实现LaF_3向NaLaF_4纳米晶的转变。但通过引入Ca~(2+)，并延长反应时间与增加反应前驱体氟源的用量，可以生成不同长径比的NaLaF_4纳米晶。同时当以其它的碱取代NaOH从而改变反应体系中的表面活性剂时可以控制合成具有不同粒径的其它稀土氟化物纳米晶，如当用LiOH取代NaOH时，合成了四方相LiYF_4、LiYbF_4和LiLuF_4纳米晶，当以氨水取代NaOH时，合成出了正交相YF_3和面心立方相的GdF_3纳米晶。在适当光源的激发下，可实现这些纳米晶的光致发光；
(4)使用溶剂热法控制合成出了几种近单分散性碱土稀土氟化物超细纳米晶，包括BaYF_5、Sr_2YF_7和Ba_2Er_(1-x)Yb_xF_7。这些纳米晶均具有面心立方结构，通过合理掺杂实现了这些纳米晶的发光颜色调控，而且其中Ba_2Er_(1-x)Yb_xF_7纳米晶具有很好的顺磁性能。
Rare earth with the phosphors of unique photoluminescent properties always is a hotresearch topic in materials and physics for their wide applications in color display,lighting, fiber-optic communications, anti-fake and so on. In particular, the rare earthinfrared-excited upconversion luminescent phosphors possess not only advantages ofthe photochemical stability, long fluorescence lifetime, narrow absorption andemission bands, and low biotoxicity, but also the virtues of deeper light penetration,lack of photodamage to the living organisms and no autofluorescent of biologicaltissue for using the infrared as excitation resource. The rare earth phosphors, whichcan be built as bioprobes based on these characteristics, present real and potentialapplications in bioimaging. Furthermore, many rare earth phosphors with niceparamagnetism have potential applications in magnetic resonance imaging andbioseparation. Several kinds of rare earth compound powders were synthesized withvarious approaches in this dissertation to explore the synthetic method of thesematerials, to achieve the control of their morphology, size and emission color, and todevelop new rare-earth fluorescent materials. This dissertaton studied systematicallythe effects of the synthesis on the structure, morphology and photoluminescentproperties of rare earth composites, and achieved successfully the control on them.The main contents and conclusions are listed as follows:
(1) Yb_3Al_5O_(12)(YbAG) and YbAG/Yb_2O_3powders were prepared successfully bycombustion route. Red upconversion emission can be realized by Er~(3+)-doping.Especially the pure red upconversion emission was realized in YbAG/Yb_2O_3powders.And the emission mechanism of pure red emission was discussed.
(2) YF_3nanoparticles were synthesized via precipitation by using different fluorinesources. It is found the ammonium ions are responsible to YF_3octahedrananoparticles and the adsorption of NH_4~+on specific crystalline face (111) was thedetermining factor to synthesize the octrahedra nanoparticles. YF_3nanobundles willbe defluorinated and oxidized to oxyfluorites which had nice upconversion property.
(3) A series of LaF_3nanocrystals were synthesized with the solvothermal method inwhich the system of oleic acid, eunatrol, alcohol and water are mixed together to formthe microemulsion. Their crystalline structures and Synthetic Conditions were studied.For example, Tetragonal LiYF_4、LiYbF_4and LiLuF_4nanocrystals were prepared whenNaOH were displaced by LiOH. It is confirmed that these series of nanocrystals maybe used as host matrix materials for luminescence.
(4) BaYF_5、Sr_2YF_7和Ba_2Er_(1-x)Yb_xF_7rare earth fluoride nanocrystals containingalkaline earth ions were synthesized with the solvothermal method. Their crystallinestructures and controllable photoluminescence were studied. And the paramagneticproperty of Ba_2Er_(1-x)Yb_xF_7nanocrystals were studied.
引文
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