Development of Conductive Delafossite-type Oxide Phosphor Co-doped with Rare-earth and Acceptor Cations

以二元氧化物为源，采用常规固相反应法制备了CuR_xY_(1-x) O_2和CuR_xLa_(1-x) O_2 （R: Eu, Tb, Tm）样品的delafoste型氧化物。考虑到稀土离子半径，晶格常数对稀土阳离子浓度的依赖意味着R^（3+）阳离子在Y^（3+）或La^（3+）位点上掺杂。CuYO_2和CuLaO_2中由于Cu^+从3d^94s到3d^（10）的互组态跃迁而出现了较宽的发射带，而CuR_xY_(1-x) O_2和CuR_xLa_(1-x) O_2中由于R^（3+）的f-f跃迁而出现了明显的锐利发射线，表明通过R掺杂成功地控制了CuYO_2和CuLaO_2的发光性能，CuCa_yY_(1-y) O_2的p型电导率随着Ca浓度的增加而增加。CuCa_yLa_(1-y) O_2和CuSr_yLa_(1-y) O_2则没有。在CuCa_yY_(1-y) O_2中p型电导率的增加被认为是由Ca^（2+）取代引起的，更多的受体阳离子取代了Y^（3+）。R和Ca共掺杂的CuR_xCa_yY_(1-x-y) O_2样品，以及CuR_xY_(1-x) O_2和CuCa_yY_(1-y) O_2样品，由于R^（3+）的f-f跃迁和Ca^（2+）受体的作用，表现出明显的锐利发射线和良好的p型电导率。以金属硝酸盐为源，采用溶液法制备了delafoste型CuYO_2和CuR_xY_(1-x) O_2（R: Eu, Tb）薄膜。晶格参数对R浓度的依赖意味着用R^（3+）取代Y^（3+）。CuYO_2薄膜中由于Cu^+的组态跃迁形成了绿色发射带，而cub_xy_ (1-x) O_2和CuEu_xY_(1-x) O_2薄膜中由于Tb^（3+）和Eu^（3+）的f-f跃迁形成了明显的锐利发射线。这些结果与常规固相反应制备的CuR_xY_(1-x) O_2体样品的数据吻合较好，表明溶液法制备CuYO_2和CuR_xY_(1-x) O_2膜是成功的。少

Delafossite-type oxides of CuR_xY_(1-x) O_2 and CuR_xLa_(1-x) O_2 (R: Eu, Tb, Tm) samples were prepared by the conventional solid state reactions using binary oxides as sources. Taking account of the rare-earth ionic radii, the lattice-constant dependence on the concentration of the rare-earth cation implied doping with the R^(3+) cation on the Y^(3+) or La^(3+) site. A broad emission band due to the Cu^+ interconfiguration transition from 3d^94s to 3d^(10) was observed in CuYO_2 and CuLaO_2, while noticeable sharp emission lines due to the f-f transitions of R^(3+) were observed in respective CuR_xY_(1-x) O_2 and CuR_xLa_(1-x) O_2, indicating successful control of luminescence property of CuYO_2 and CuLaO_2 by doping with R. P-type conductivity of CuCa_yY_(1-y) O_2 increased with increasing Ca concentration, but those of CuCa_yLa_(1-y) O_2 and CuSr_yLa_(1-y) O_2 did not. The increase of the p-type conductivity in CuCa_yY_(1-y) O_2 is considered to be caused by substitution of Ca^(2+) … More acceptor cation for the Y^(3+) site. CuR_xCa_yY_(1-x-y) O_2 samples co-doped with R and Ca, as well as the CuR_xY_(1-x) O_2 and CuCa_yY_(1-y) O_2 samples, exhibited noticeable sharp emission lines due to the f-f transitions of R^(3+) and good p-type conductivity due to Ca^(2+) acceptor. This fact demonstrates controllability of luminescence and conductive properties of CuYO_2 by co-doping with R and Ca. Delafossite-type CuYO_2 and CuR_xY_(1-x) O_2(R: Eu, Tb)films were prepared by solution method using metal nitrates as sources. The lattice-parameter dependence on R concentration implies substitution of R^(3+) for Y^(3+) site. A green emission band due to the Cu^+ interconfiguration transition was observed in CuYO_2 films, while noticeable sharp emission lines due to the f-f transitions of Tb^(3+) and Eu^(3+) were observed in respective CuTb_xY_(1-x) O_2 and CuEu_xY_(1-x) O_2 films. These results for the films correspond well to the data for the CuR_xY_(1-x) O_2 bulk samples prepared by the conventional solid state reactions, indicating successful preparation of CuYO_2 and CuR_xY_(1-x) O_2 films via the solution method. Less