Rare earth hybrid materials of organically modified silica covalently bonded to a GaN matrix: multicomponent assembly and multi-color luminescence.
Rare earth hybrid materials of organically modified silica covalently bonded to a GaN matrix: multicomponent assembly and multi-color luminescence.
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DOI：
10.1039/c2dt12255c
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发表时间：
2012-04
影响因子：
4
通讯作者：
Yan Zhao;B. Yan
中科院分区：
文献类型：
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作者：
Yan Zhao;B. Yan
以功能化的GaN为基块，首次制备了三种具有较高热稳定性和光致发光性能的稀土杂化材料。一些硅烷偶联剂(异氰酸酯三乙氧基硅烷(ICTES)、3-氯丙基三乙氧基硅烷(CPTES)和3-氨丙基三乙氧基硅烷(APTES))作为共价键用于GaN的羟基化修饰和官能化的光活性配体(4-巯基苯甲酸(MBA)、4-羟基苯甲酸(HBA)和硝基苯甲酰氯(NBC))的修饰，得到了前驱体(MBA-ICTES-GaN、HBA-CPTES-GaN和NBC-APTES-GaN)。随后，将这三种前驱体与1，10-邻菲咯啉(Phen)组装成多组分光功能稀土杂化材料，并对其进行了FTIR光谱、UV-Vis漫反射光谱、X射线衍射谱和光致发光行为(发光、寿命、量子效率和能量转移)的表征。这些结果表明，与HBA-CPTES-GaN和NBC-APTES-GaN单元相比，具有MBA-ICTES-GaN单元的Eu(3+)杂化材料具有更好的发光强度比、更高的量子效率和更长的寿命。同时，杂化Phen-Tb-HBA-CPTES-GaN具有比其他两种杂化材料(Phen-Tb-MBA-ICTES-GaN和Phen-Tb-NBC-APTES-GaN)更强的Tb(3+)特征发射。此外，将不同摩尔比的Eu(3+)和Tb(3+)组合在同一体系(Phen-RE-MBA-ICTES-GaN)中制备了双色杂化材料，发射波长为331 nm(RE=Eu，Tb)，并可获得黄色发光。
Three kinds of rare earth hybrid materials with enhanced thermostability and photoluminescence properties have been prepared for the first time by using a functionalized GaN matrix as one of the building blocks. A number of silane coupling agents (isocyanate triethoxysilane (ICTES), 3-chloropropyl triethoxysilane (CPTES) and 3-aminopropyl triethoxysilane (APTES)) behave as the covalent linkages for modification by both hydroxylation of GaN and functionalized photoactive ligands (4-mercaptobenzoic acid (MBA), 4-hydroxybenzoic acid (HBA) and nitrobenzoyl chloride (NBC)), resulting in the precursors (MBA-ICTES-GaN, HBA-CPTES-GaN and NBC-APTES-GaN). Subsequently, multicomponent photofunctional rare earth hybrid materials with the three precursors and 1,10-phenanthroline (Phen) are assembled and characterized by their FTIR spectra, UV-vis diffuse reflectance spectra, XRD patterns, and photoluminescent behaviour (luminescence, lifetime, quantum efficiency, and energy transfer). These results reveal that the Eu(3+) hybrids with the MBA-ICTES-GaN unit have a better luminescence intensity ratio, higher quantum efficiency and longer lifetime than those with the HBA-CPTES-GaN and NBC-APTES-GaN units. Meanwhile the hybrid Phen-Tb-HBA-CPTES-GaN possesses a stronger characteristic emission of Tb(3+) ions than the other two hybrids (Phen-Tb-MBA-ICTES-GaN and Phen-Tb-NBC-APTES-GaN). Moreover, two-color-based hybrid materials are fabricated by combining different molar ratios of Eu(3+) and Tb(3+) in the same system (Phen-RE-MBA-ICTES-GaN) with emission at a wavelength of 331 nm (RE = Eu, Tb) and yellow luminescence can be achieved.