Eu^2+/Eu^3+ mixed-valence couple co-doped material holds great potential for ratiometric temperature sensing owing to its different electronic configurations and electron-lattice interaction. Here, the correlation of ...Eu^2+/Eu^3+ mixed-valence couple co-doped material holds great potential for ratiometric temperature sensing owing to its different electronic configurations and electron-lattice interaction. Here, the correlation of nonstoichiometry in chemical composition, phase structures and luminescence propertis of Ca2 Al2 Si1-xO7:Eu is discussed, and controlled Eu^2+/Eu^3+ valence and tunable emission appear with decreasing Si content. It is found that the 2 Ca^2++ Si^4+←→ Eu^2++ Eu^3++ Al^3+ cosubstitution accounts for the structural stability and charge balance mechanism. Benefiting from the diverse thermal dependent emission behaviors of Eu^2+ and Eu^3+, Ca2 Al2 Si1-xO7:Eu thermometer exhibits excellent temperature sensing performances with the maximum absolute and relative sensitivity being 0.024 K-1(at 303 K) and 2.46% K-1(at 443 K) and good signal discriminability. We propose that the emission quenching of Eu^2+ is ascribed to 5 d electrons depopulation through Eu^2+/Eu^3+ intervalence charge transfer state, while the quenching of Eu^3+ comes from multiphonon relaxation. Our work demonstrates the potential of Ca2 Al2 Si1-xO7:Eu for noncontact optical thermometry, and also highlights mixed-valence europium-containing compounds toward temperature sensing.展开更多
基金supported by the National Natural Science Foundation of China (51722202, 51972118 and 51572023)the Guangdong Provincial Science & Technology Project (2018A050506004)Innovation Projects of Department of Education of Guangdong Province (2018KQNCX265)
文摘Eu^2+/Eu^3+ mixed-valence couple co-doped material holds great potential for ratiometric temperature sensing owing to its different electronic configurations and electron-lattice interaction. Here, the correlation of nonstoichiometry in chemical composition, phase structures and luminescence propertis of Ca2 Al2 Si1-xO7:Eu is discussed, and controlled Eu^2+/Eu^3+ valence and tunable emission appear with decreasing Si content. It is found that the 2 Ca^2++ Si^4+←→ Eu^2++ Eu^3++ Al^3+ cosubstitution accounts for the structural stability and charge balance mechanism. Benefiting from the diverse thermal dependent emission behaviors of Eu^2+ and Eu^3+, Ca2 Al2 Si1-xO7:Eu thermometer exhibits excellent temperature sensing performances with the maximum absolute and relative sensitivity being 0.024 K-1(at 303 K) and 2.46% K-1(at 443 K) and good signal discriminability. We propose that the emission quenching of Eu^2+ is ascribed to 5 d electrons depopulation through Eu^2+/Eu^3+ intervalence charge transfer state, while the quenching of Eu^3+ comes from multiphonon relaxation. Our work demonstrates the potential of Ca2 Al2 Si1-xO7:Eu for noncontact optical thermometry, and also highlights mixed-valence europium-containing compounds toward temperature sensing.
