The persistent phosphor SrAl_(2)O_(4):Eu^(2+),Dy^(3+)is the subject of numerous investigations.One often neglected aspect is that in this phosphor,as well as in Sr_(4)Al_(14)O_(25):Eu^(2+),Dy^(3+),there are two differ...The persistent phosphor SrAl_(2)O_(4):Eu^(2+),Dy^(3+)is the subject of numerous investigations.One often neglected aspect is that in this phosphor,as well as in Sr_(4)Al_(14)O_(25):Eu^(2+),Dy^(3+),there are two different Sr^(2)+sites which can be occupied by the dopant Eu^(2+)ions,We first introduce a general scheme of possible energy transfers in these persistent phosphor materials including explicitly both europium ions,This scheme is used as a generic starting point to study experimentally specific pathways.We illustrate this application with the study of the effect of excitation wavelength(444 and 382 nm)on the afterglow of differently doped SrAl_(2)O_(4):Eu^(2+),Dy^(3+)samples,as well as on the emission decay curves.With the same excitation intensity under 444 nm excitation,the resulting afterglow intensity is stronger than under near UV excitation.At 382 nm,Eu^(2+)ions on both Sr^(2)+s ites in SrAl_(2)O_(4)are excited,but at room temperature the blue emission is quenched,leading to a loss of photons.The observed effects can further be associated with the ratio of Eu^(2+)ions and trap states which are modulated by the concentrations of Eu^(2+)and Dy^(3+)in SrAl_(2)O_(4),as well as by temperature,Increasing the nominal Dy^(3+)content from 0.1 mol%to 0.5 mol%with respect to Sr results in the doubling of the integrated afterglow intensity and confirms thus that Dy^(3+)ions are indeed involved in the trapping process,The concentration of trap states is much lower than the concentration of Eu^(2+)ions,as even with low excitation densities,a plateau of integrated afterglow intensity(corresponding to the total number of accessible traps)is reached.We postulate that an important fraction of excited Eu^(2+)ions can potentially transfer their energy to trap states.Once that all traps are filled or in a dynamical filling-depletion process under illumination(with thermal and/or optical depletion processes),for the remaining Eu^(2+)a"normal"steady-state emission is observed.The luminescence decay curves at 520 nm measured at 77 K show a mono-exponential decay with a common lifetime of about 1140 ns for all 5 samples under 437 nm excitation,while under 375 nm excitation,a feed process originating from the energy transfer between Eu^(2+)ions is demonstrated.Under 375 nm excitation,the non-exponential decay observed at 440 nm can be quantitatively associated to a Forster energy transfer process with R_(0)=1.58(8)nm.For the overall understanding of the afterglow processes,it appears that one has to consider the individual contributions of all active ions on different lattice sites.展开更多
基金Project supported by the Swiss National Science Foundation(200020_182494,200021_169033)Innosuisse(25902.1 PFNM-NM,15217.1PFIW-IW)。
文摘The persistent phosphor SrAl_(2)O_(4):Eu^(2+),Dy^(3+)is the subject of numerous investigations.One often neglected aspect is that in this phosphor,as well as in Sr_(4)Al_(14)O_(25):Eu^(2+),Dy^(3+),there are two different Sr^(2)+sites which can be occupied by the dopant Eu^(2+)ions,We first introduce a general scheme of possible energy transfers in these persistent phosphor materials including explicitly both europium ions,This scheme is used as a generic starting point to study experimentally specific pathways.We illustrate this application with the study of the effect of excitation wavelength(444 and 382 nm)on the afterglow of differently doped SrAl_(2)O_(4):Eu^(2+),Dy^(3+)samples,as well as on the emission decay curves.With the same excitation intensity under 444 nm excitation,the resulting afterglow intensity is stronger than under near UV excitation.At 382 nm,Eu^(2+)ions on both Sr^(2)+s ites in SrAl_(2)O_(4)are excited,but at room temperature the blue emission is quenched,leading to a loss of photons.The observed effects can further be associated with the ratio of Eu^(2+)ions and trap states which are modulated by the concentrations of Eu^(2+)and Dy^(3+)in SrAl_(2)O_(4),as well as by temperature,Increasing the nominal Dy^(3+)content from 0.1 mol%to 0.5 mol%with respect to Sr results in the doubling of the integrated afterglow intensity and confirms thus that Dy^(3+)ions are indeed involved in the trapping process,The concentration of trap states is much lower than the concentration of Eu^(2+)ions,as even with low excitation densities,a plateau of integrated afterglow intensity(corresponding to the total number of accessible traps)is reached.We postulate that an important fraction of excited Eu^(2+)ions can potentially transfer their energy to trap states.Once that all traps are filled or in a dynamical filling-depletion process under illumination(with thermal and/or optical depletion processes),for the remaining Eu^(2+)a"normal"steady-state emission is observed.The luminescence decay curves at 520 nm measured at 77 K show a mono-exponential decay with a common lifetime of about 1140 ns for all 5 samples under 437 nm excitation,while under 375 nm excitation,a feed process originating from the energy transfer between Eu^(2+)ions is demonstrated.Under 375 nm excitation,the non-exponential decay observed at 440 nm can be quantitatively associated to a Forster energy transfer process with R_(0)=1.58(8)nm.For the overall understanding of the afterglow processes,it appears that one has to consider the individual contributions of all active ions on different lattice sites.