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CaTiO₃:Pr红色荧光粉的溶胶-凝胶合成法:为发光和余辉应用定制合成参数

Sol-Gel Synthesis of CaTiO:Pr Red Phosphors: Tailoring the Synthetic Parameters for Luminescent and Afterglow Applications.

作者信息

Meroni Daniela, Porati Luca, Demartin Francesco, Poelman Dirk

机构信息

Dipartimento di Chimica, Università degli Studi di Milano, Via Golgi 19, 20133 Milano, Italy.

Consorzio Interuniversitario Nazionale per la Scienza e la Tecnologia dei Materiali (INSTM), Via Giusti 9, 50121 Firenze, Italy.

出版信息

ACS Omega. 2017 Aug 31;2(8):4972-4981. doi: 10.1021/acsomega.7b00761. Epub 2017 Aug 28.

Abstract

Two sol-gel synthetic routes for the preparation of CaTiO:Pr red emitting phosphors were compared, with the aim of producing nanostructured materials with tailored luminescence/afterglow properties. The effect of the synthetic parameters, such as the addition of a stabilizer and calcination temperature, on the structural, morphological, and optical properties was investigated. The desired perovskite phase was obtained at a calcination temperature of 800 °C or higher. Although the use of acetic acid as the chelating agent leads to micrometric particles with heterogeneous composition, the presence of hydroxypropylcellulose (HPC) results in smaller, less aggregated particles as well as in a high phase purity. At the highest HPC content, surface Ca-rich impurities were detected, although no segregated Ca-rich phases were detectable by X-ray powder diffraction analyses. Luminescence properties were found to be positively related to the phase purity of the oxide, with the highest quantum yields at temperatures equal to or higher than 1000 °C. On the contrary, persistent luminescence properties were highest at intermediate calcination temperatures and for samples synthesized with acetic acid. Overall, a notable role of oxygen vacancies resulting from local Ca excess was observed, acting as trap levels promoting longer relaxation pathways. Thanks to the small-sized particles and best steady-state luminescent properties due to a substantial decrease of lattice defects, the HPC synthesis is a promising strategy for light-emitting diode applications. On the other hand, the acetic acid synthesis promoted a higher defect density, which is required for an efficient yield of light emission in the long time range and is thus more suitable for afterglow applications.

摘要

比较了两种用于制备CaTiO:Pr红色发光磷光体的溶胶-凝胶合成路线,目的是制备具有定制发光/余辉特性的纳米结构材料。研究了合成参数,如稳定剂的添加和煅烧温度对结构、形态和光学性能的影响。在800°C或更高的煅烧温度下获得了所需的钙钛矿相。虽然使用乙酸作为螯合剂会导致组成不均一的微米级颗粒,但羟丙基纤维素(HPC)的存在会导致颗粒更小、团聚更少,且相纯度更高。在HPC含量最高时,检测到表面富含钙的杂质,尽管通过X射线粉末衍射分析未检测到分离的富钙相。发现发光性能与氧化物的相纯度呈正相关,在等于或高于1000°C的温度下量子产率最高。相反,余辉性能在中间煅烧温度下以及用乙酸合成的样品中最高。总体而言,观察到局部钙过量导致的氧空位起了显著作用,作为陷阱能级促进了更长的弛豫路径。由于颗粒尺寸小以及晶格缺陷大幅减少而具有最佳的稳态发光性能,HPC合成是发光二极管应用的一种有前景的策略。另一方面,乙酸合成促进了更高的缺陷密度,这对于长时间范围内高效的发光产率是必需的,因此更适合余辉应用。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e663/6644088/4b4fdb58f094/ao-2017-00761u_0003.jpg

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