Ueda Kazushige, Tanaka Syuto, Yoshino Takuma, Shimizu Yuhei, Honma Tetsuo
Department of Materials Science, Graduate School of Engineering , Kyushu Institute of Technology , 1-1 Sensui , Tobata, Kitakyushu 804-8550 , Japan.
National Metrology Institute of Japan (NMIJ) , National Institute of Advanced Industrial Science and Technology (AIST) , 1-1-1 Umezono , Tsukuba , Ibaraki 305-8563 , Japan.
Inorg Chem. 2019 Aug 19;58(16):10890-10897. doi: 10.1021/acs.inorgchem.9b01273. Epub 2019 Aug 2.
Eu and Tb ions were site-selectively doped into LaLuO with the orthorhombic perovskite-type structure (ABO), and their luminescence properties were examined considering the doping sites (A or B sites). The X-ray diffraction analysis revealed the expansion or contraction of the unit cell volumes of the materials depending on the doping sites. The spectra of X-ray absorption near edge structure for the Eu and Tb L edge exhibited different shapes for the ions at A and B sites, confirming the site-selective doping of Eu and Tb in LaLuO. The photoluminescence (PL) and PL excitation (PLE) spectra of the materials also showed some differences caused by the doping sites. The intensities of the Eu PL peaks derived from the D-F transitions and those from the D-F transitions were markedly different between Eu at A sites and those at B sites because of the different site symmetries. The splitting of the intense Tb PL peaks originating from the D-F transitions and the absence of PL peaks from D-F transitions were found only for Tb at B sites because of the strong crystal field at B sites. In addition to the PL spectra, the positions of PLE peaks originating from charge transfer transitions in Eu and the 4f-5d transitions in Tb depended on the doping sites. The successful site-selective doping enabled us to clarify the site-sensitive luminescence properties of Eu and Tb doped in the perovskite-type LaLuO.
将铕（Eu）和铽（Tb）离子选择性地掺杂到具有正交钙钛矿型结构（ABO）的LaLuO中，并根据掺杂位点（A或B位点）研究了它们的发光特性。X射线衍射分析表明，材料的晶胞体积会根据掺杂位点而膨胀或收缩。Eu和Tb L边的X射线吸收近边结构光谱对于A位点和B位点的离子呈现出不同的形状，证实了Eu和Tb在LaLuO中的位点选择性掺杂。材料的光致发光（PL）和PL激发（PLE）光谱也因掺杂位点而显示出一些差异。由于位点对称性不同，A位点的Eu和B位点的Eu源自D-F跃迁的PL峰强度以及源自D-F跃迁的PL峰强度明显不同。仅在B位点的Tb中发现了源自D-F跃迁的强烈Tb PL峰的分裂以及D-F跃迁的PL峰的缺失，这是因为B位点的晶体场很强。除了PL光谱外，源自Eu中电荷转移跃迁和Tb中4f-5d跃迁的PLE峰的位置也取决于掺杂位点。成功的位点选择性掺杂使我们能够阐明掺杂在钙钛矿型LaLuO中的Eu和Tb的位点敏感发光特性。
