Evolution and Eu~(3+) Doping of Sol-Gel Derived Ternary Zn_xTi_yO_z - Nanocrystals

Jan Mrazek; Lubomir Spanhel; Genevieve Chadeyron

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Evolution and Eu~(3+) Doping of Sol-Gel Derived Ternary Zn_xTi_yO_z - Nanocrystals

机译：溶胶-凝胶衍生的三元Zn_xTi_yO_z纳米晶的演化和Eu〜（3+）掺杂

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Alloyed Zn_xTi_yO_z nanostructures were prepared by a thermal condensation process employing ethanolic mixtures of zinc acetate dihydrate and titanium alkoxide, without additional use of additives. It has been found that the nanocrystal growth takes place at temperatures above 350 °C yielding cubic spinel Zn2TiO4, cubic ZnTio3, or hexagonal ilmenite ZnTiO3. Their preferential appearance and size tuning between 5 and 80 nm was possible by varying the starting sol condensation conditions, Zn/Ti-ratio and sintering temperature. The electronic transitions in these ternary oxide semiconductor nanocrystals were observed at photon energies between 3.6 and 3.8 eV that reflects the presence of a wider optical gap than that known for the corresponding binary oxides ZnO and TiO2. We also noticed a strong influence of Eu~(3+) doping on the resulting structural and optical properties. Despite its large ionic size, this lanthanide efficiently intervenes in the evolution process by blocking the nanocrystal growth and the cubic-to-hexagonal transformation in ZnTiO3. Its preferential incorporation into spinel phase is manifested by the activation of a strong red intrashell fluorescence and a significant Stark splitting of the ~5F_J states. The comparison of the spectral response and asymmetry ratio values deduced from the experimental Eu~(3+) luminescence data collected on structurally similar Zn2TiO4 and ZnTiO3 nanophases suggests the hypothesis that cubic ZnTiO3 has a structure of an inverse defect spinel. Our study has not confirmed the existence of the previously reported and often recalled defect spinel Zn2Ti3O8.

机译：合金化的Zn_xTi_yO_z纳米结构是通过热缩合工艺制备的，该工艺使用二水合乙酸锌和醇钛的乙醇混合物，无需额外使用添加剂。已经发现，纳米晶体生长在高于350℃的温度下发生，产生立方尖晶石Zn 2 TiO 4，立方ZnTio 3或六角钛铁矿ZnTiO 3。通过改变起始溶胶的缩合条件，Zn / Ti比和烧结温度，可以在5至80 nm之间实现其优先的外观和尺寸调节。这些三元氧化物半导体纳米晶体中的电子跃迁是在3.6至3.8 eV的光子能量下观察到的，反映出存在比对应的二元氧化物ZnO和TiO2更大的光学间隙。我们还注意到Eu〜（3+）掺杂对所得结构和光学性能的强烈影响。尽管其离子尺寸很大，但这种镧系元素通过阻止ZnTiO3中的纳米晶体生长和立方到六方相转变，有效地干预了演化过程。其优先掺入尖晶石相的过程通过强烈的红色壳内荧光的激活和〜5F_J状态的显着Stark分裂来证明。从在结构相似的Zn2TiO4和ZnTiO3纳米相上收集的实验Eu〜（3+）发光数据得出的光谱响应和不对称比值的比较表明，立方ZnTiO3具有逆缺陷尖晶石结构。我们的研究尚未证实先前报道并经常被召回的尖晶石Zn2Ti3O8的存在。

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《The journal of physical chemistry, C. Nanomaterials and interfaces》 |2010年第7期|共10页
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Jan Mrazek; Lubomir Spanhel; Genevieve Chadeyron;
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1. Evolution and Eu~(3+) Doping of Sol-Gel Derived Ternary Zn_xTi_yO_z - Nanocrystals [J] . Jan Mrazek, Lubomir Spanhel, Genevieve Chadeyron The journal of physical chemistry, C. Nanomaterials and interfaces . 2010,第7期

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Evolution and Eu~(3+) Doping of Sol-Gel Derived Ternary Zn_xTi_yO_z - Nanocrystals

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