Development of rare-earth ion-doped oxide phosphors upon band gap excitation and elucidation of their emission mechanism

带隙激发稀土离子掺杂氧化物荧光粉的开发及其发射机制的阐明

• 批准号: 17560598
• 负责人: INAGUMA Yoshiyuki
• 金额: $ 2.24万
• 依托单位: Gakushuin University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2005
• 资助国家: 日本
• 起止时间: 2005 至 2006
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-17560598/
• 关键词: Phosphor; Perovskite; Praseodymium; Band gap; Site symmetry; Covalency; 蛍光; 希土類; 発光; プラセオジウム

(1) Photoluminescence of Pr^3+-doped Ruddlesden-Popper-type titanates, Sr_<n+1>Ti_nO_<3n+1>:Pr^<3+> (n=1, 2, ∞) and Ca_<n+1>Ti_nO_<3n+1>:Pr^<3+> (n=2)Perovskite-related Ruddlesden-Popper-type compounds, Sr_<n+1>Ti_nO_<3n+1>:Pr^<3+> (n=1, 2, ∞) and Ca_<n+1>Ti_nO_<3n+1>:Pr^<3+> (n=2) were prepared by a Pechini-type polymerizable complex method using a citric metal complex or conventional solid state reaction, and their photoluminescence properties were investigated. The compounds show distinct emission corresponding to the f-f transitions of Pr^<3+>. The excitation process is consistent with the transition between the valence band and the conduction band in host materials. Ca_3Ti_2O_7:Pr^<3+> exhibits red emission more than ten times stronger than Sr_3Ti_2O_7:Pr^<3+>. The differences in luminescent properties among the compounds originate from the structure dependence of the energy transfer from host to activator Pr^<3+>, and the site symmetry of Pr^<3+>.(2) Photoluminescence upon band g … More ap excitation in perovskite-type titanates R_<1/2>Na_<l/2>TiO_3:Pr (R=La, Gd, Lu, and Y)Pr^<3+>-doped perovskites R_<1/2>Na_<1/2>TiO3:Pr (R=La, Gd, Lu, and Y) were synthesized, and their structures, optical absorption and luminescent properties were investigated, and the relationship between structures and optical properties was discussed. Optical band gap of R_<1/2>Na_<1/2>TiO3 increases in the order R=La, Gd, Y, and Lu, which is primarily due to a decrease in band width accompanied by a decrease in Ti-O-Ti bond angle. Intense red emission assigned to f-f transition of Pr^<3+> from the excited ^1D_2 level to the ground ^3H_4 state upon the band gap photo-excitaion (UV) was observed for all compounds. The wavelength of emission peaks was red-shifted in the order R=La, Gd, Y, and Lu, which originates from the increase in crystal field splitting of Pr^<3+>. This is attributed to the decrease in inter-atomic distances of Pr-O together with the inter-atomic distances (R, Na)-O, i.e., increase in covalency between Pr and O. The results indicate that the luminescent properties in R_<1/2>Na_<1/2>TiO_3:Pr are governed by the relative energy level between the ground and excited state of 4f^2 for Pr^<3+>, and the conduction and valence band, which is primarily dependent on the structure, e.g., the tilt of TiO6 octahedra and the Pr-Ti inter-atomic distance and the site symmetry of Pr ion.(3) Occupation site of Pr and luminescent properties in Pr-doped perovskite-type lithium ion-conducting oxides, A_0.6Li_0.3Ti_0.5Ta_0.5O_3 : Pr (A=Ca, Sr)We investigated the lattice parameters and luminescent properties of Pr-doped perovskite-type lithium ion conductors, A_<0.6-3x/2>Pr_xLi_0.3Ti_0.5Ta_0.5O_3 (A=Ca and Sr, 0≦x≦0.05). Ca_<0.6>Li_0.3Ti_0.5Ta_0.5O_3:Pr shows the intense red emission corresponding to the f-f transition of Pr^<3+> (^1D_2 → ^3H_4) on the ultraviolet photo-excitation with the energy corresponding to the band-gap of host. In contrast, Sr_<0.6>Ti_<0.5>Ta_0.5O_3:Pr exhibites blue-green and red emission on the excitation with blue light corresponding to the f-f transition of Pr^<3+> (^3H_4 →^3P_4) . It was found that these differences in luminescent properties primarily originate from the occupation site of Pr in these perovskite-type oxides. Less

(1)Pr^3+掺杂Ruddlesden-Popper型钛酸盐Sr_（n+1）Ti_nO_（3 n +1）：Pr^（3+）的光致发光（n=1，2，∞）和Ca_<n+1>Ti_nO_<3 n +1>：Pr^<3 +>（n=2）钙钛矿类Ruddlesden-Popper型化合物Sr_<n+1>Ti_nO_<3 n +1>：采用Pechini型可聚合络合法，通过柠檬酸金属络合物或传统固相反应制备了Pr^<3+>（n=1，2，∞）和Ca <n+1>Ti_nO_<3 n +1>：Pr^<3+>（n=2），并研究了它们的光致发光性能。这些化合物显示出明显的荧光，对应于Pr^<3+>的f-f跃迁。激发过程与主体材料中价带和导带之间的跃迁一致。Ca_3Ti_2O_7：Pr^<3+>的红光发射强度是Sr_3Ti_2O_7：Pr^<3+>的10倍以上。这些化合物发光性质的差异源于主体到激活剂Pr^<3+>的能量传递的结构依赖性和Pr^<3+>的位置对称性。(2)G带光致发光 ...更多信息 合成了钙钛矿型钛酸盐R_（1/2）Na_（1/2）TiO_3：Pr（R=La，Gd，Lu，Y）中的ap激发，研究了Pr ~（3+）掺杂的钙钛矿型钛酸盐R_（1/2）Na_（1/2）TiO_3：Pr（R=La，Gd，Lu，Y）的结构、光吸收和发光性能，并讨论了结构与光学性能的关系。R_（1/2）Na_（1/2）TiO_3的光学带隙按R=La，Gd，Y，Lu的顺序增大，这主要是由于Ti-O-Ti键角减小而导致的带隙减小。所有化合物在紫外光激发下均观察到Pr^<3+>从激发态^1D_2到基态^3H_4的f-f跃迁。发射峰的波长按R=La，Gd，Y，Lu的顺序发生红移，这是由于Pr^<3+>的晶场分裂增加所致。这归因于Pr-O的原子间距离与（R，Na）-O的原子间距离一起减小，即，Pr和O之间的共价性增加。结果表明，R_（1/2）Na_（1/2）TiO_3：Pr的发光性质主要受Pr^<3+>的基态和激发态4f^2的相对能级以及导带和价带的影响，而导带和价带的相对能级主要取决于结构，如：TiO_6八面体的倾斜和Pr-Ti原子间距以及Pr离子的位对称性。(3)Pr掺杂钙钛矿型锂离子导电氧化物A_（0.6）Li_（0.3）Ti_（0.5）Ta_（0.5）O_3：Pr（A=Ca，Sr）中Pr的占位位置及发光性能研究了Pr掺杂钙钛矿型锂离子导电氧化物A_（0.6-3x/2）Pr_xLi_（0.3）Ti_（0.5）Ta_（0.5）O_3（A=Ca，Sr，0 × x ≤ 0.05）的晶格参数和发光性能。Ca_<0.6>Li_（0.3）Ti_（0.5）Ta_（0.5）O_3：Pr在紫外光激发下产生强的红光发射，对应于Pr^&lt;3+&gt;（^1D_2 → ^3H_4）的f-f跃迁，其能量对应于基质的带隙。而Sr_<0.6>Ti_<0.5>Ta_（0.5）O_3：Pr在蓝光激发下呈现蓝绿色和红色发光，对应于Pr^&lt;3+&gt;（^3H_4 →^3P_4）的f-f跃迁。结果发现，这些发光性能的差异主要源于这些钙钛矿型氧化物中的Pr的占据位置。少

项目成果

Crystal Structure and Diffusion Path in the Fast Lithium-lon Conductor La_0.62Li_0.16TiO_3

快速锂离子导体La_0.62Li_0.16TiO_3的晶体结构和扩散路径

• 发表时间: 2005
• 期刊: Journal of the American Chemical Society 127(10)
• 作者: Yue Jin Shan;Yoshiyuki Inaguma;Hiroyuki Tetsuka;Tetsuro Nakamura;Ludwig J. Gaulder;Yoshiyuki Inaguma;Yoshiyuki Inaguma;Yoshiyuki Inaguma;Masatomo Yashima
• 通讯作者: Masatomo Yashima

Structure and Mossbauer studies of F-O ordering in antiferromagnetic perovskite PbFeO2F

• DOI: 10.1021/cm048125g
• 发表时间: 2005-03-22
• 期刊: CHEMISTRY OF MATERIALS
• 影响因子: 8.6
• 作者: Inaguma, Y;Greneche, JM;Fourquet, JL
• 通讯作者: Fourquet, JL

Structural investigations of migration pathways in lithium ion-conducting La2/3−xLi3xTiO3 perovskites

• DOI: 10.1016/j.ssi.2006.08.012
• 发表时间: 2006-11
• 期刊: Solid State Ionics
• 影响因子: 3.2
• 作者: Y. Inaguma;T. Katsumata;M. Itoh;Y. Morii;T. Tsurui

Systematic study of photoluminescence upon band gap excitation in perovskite-type titanates R1/2Na1/2TiO3:Pr (R = La, Gd, Lu, and Y)

• DOI: 10.1016/j.jssc.2007.03.017
• 发表时间: 2007-05-01
• 期刊: JOURNAL OF SOLID STATE CHEMISTRY
• 影响因子: 3.3
• 作者: Inaguma, Yoshiyuki;Tsuchiya, Takeshi;Katsumata, Tetsuhiro
• 通讯作者: Katsumata, Tetsuhiro

Photoluminescence of praseodymium-doped Srn+1+TinO3n+1 (n=1, 2, ∞)

• DOI: 10.1143/jjap.44.761
• 发表时间: 2005-01-01
• 期刊: JAPANESE JOURNAL OF APPLIED PHYSICS PART 1-REGULAR PAPERS BRIEF COMMUNICATIONS & REVIEW PAPERS
• 作者: Inaguma, Y;Nagasawa, D;Katsumata, T
• 通讯作者: Katsumata, T