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Physical review. B, Solid state

Spectral energy transfer in Pr F3 , Pr Cl3

D. S. Hamilton, Peter M. Selzer, William M. Yen

Published Sep 1, 1977• 62 citations
Publisher

Abstract

Time-resolved fluorescence line narrowing is used to study spectral energy transfer in Pr${\mathrm{F}}_{3}$ and Pr${\mathrm{Cl}}_{3}$. The excitation spectrum of Pr${\mathrm{F}}_{3}$ in the region of the ${(^{3}H_{4})}_{1}\ensuremath{\rightarrow}^{3}P_{0}$ absorption indicates that several strong satellite lines accompany the main transition, their origin being ascribed to different ${\mathrm{Pr}}^{3+}$ ions lying in strongly perturbed lattice sites. The spectral transfer within the inhomogeneously broadened main transiton is measured, where the energy mismatch is about 2 ${\mathrm{cm}}^{\ensuremath{-}1}$. This process is characterized by a strong ($\ensuremath{\sim}{T}^{4.3}$) dependence of the transfer probability on sample temperature. The growth of the full inhomogeneous emission profile accompanies a uniform decay of the donor line shape. A transfer process between the lowest-energy satellite ions is also measured. Here the energy mismatch is 32 ${\mathrm{cm}}^{\ensuremath{-}1}$ resulting in a weak temperature dependence for the transfer rate. Both the intraline and intersatellite transfer are characterized by simple exponential rate equations. Recent calculations of phonon-assisted transfer probabilities are compared to our measurements, with the intersatellite transfer ascribed to a "one-phonon direct" process whereas the transfer within the main transition occurs by a "one-phonon second-order" mechanism. In Pr${\mathrm{Cl}}_{3}$ the transfer times are faster than the 15-nsec response time of our detection system indicating a much stronger ion-ion coupling.

DOI
10.1103/physrevb.16.1858

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Time-resolved fluorescence line narrowing is used to study spectral energy transfer in PrF3{\mathrm{F}}_{3}F3​ and PrCl3{\mathrm{Cl}}_{3}Cl3​. The excitation spectrum of PrF3{\mathrm{F}}_{3}F3​ in the region of the (3H4)1\ensuremath→3P0{(^{3}H_{4})}_{1}\ensuremath{\rightarrow}^{3}P_{0}(3H4​)1​\ensuremath→3P0​ absorption indicates that several strong satellite lines accompany the main transition, their origin being ascribed to different Pr3+{\mathrm{Pr}}^{3+}Pr3+ ions lying in strongly perturbed lattice sites. The spectral transfer within the inhomogeneously broadened main transiton is measured, where the energy mismatch is about 2 cm\ensuremath−1{\mathrm{cm}}^{\ensuremath{-}1}cm\ensuremath−1. This process is characterized by a strong (\ensuremath∼T4.3\ensuremath{\sim}{T}^{4.3}\ensuremath∼T4.3) dependence of the transfer probability on sample temperature. The growth of the full inhomogeneous emission profile accompanies a uniform decay of the donor line shape. A transfer process between the lowest-energy satellite ions is also measured. Here the energy mismatch is 32 cm\ensuremath−1{\mathrm{cm}}^{\ensuremath{-}1}cm\ensuremath−1 resulting in a weak temperature dependence for the transfer rate. Both the intraline and intersatellite transfer are characterized by simple exponential rate equations. Recent calculations of phonon-assisted transfer probabilities are compared to our measurements, with the intersatellite transfer ascribed to a "one-phonon direct" process whereas the transfer within the main transition occurs by a "one-phonon second-order" mechanism. In PrCl3{\mathrm{Cl}}_{3}Cl3​ the transfer times are faster than the 15-nsec response time of our detection system indicating a much stronger ion-ion coupling.
We report the direct observation of energy migration and spectral diffusion in the 3P0^{3}P_{0}3P0​ state of LaF3{\mathrm{F}}_{3}F3​: Pr3+{\mathrm{Pr}}^{3+}Pr3+ using the technique of time-resolved fluorescence line narrowing on the resonant $^{3}P_{0}\ensuremath{\rightarrow}^{3}H_{4}$ transition. The temperature dependence of the migration process has been measured and various possible transfer mechanisms are discussed. In addition a variation in the excited-state lifetime as a function of absorption frequency and a concentration broadening at zero delay in the nonresonant transition $^{3}P_{0}\ensuremath{\rightarrow}{(^{3}H_{6})}_{1}$ (the lowest Stark level) are reported.
We have investigated the process of quenching of fluorescence from the 3P0^{3}P_{0}3P0​ excited state of Pr3+{\mathrm{Pr}}^{3+}Pr3+ in LaF3{\mathrm{F}}_{3}F3​ due to cross relaxation among the Pr ions. The fluorescence decay of the ensemble of Pr ions after pulsed excitation is measured as a function of temperature for Pr concentration of 20 mol%. About 12% of the ions are in nonquenching sites and contribute an exponential component to the decay. The remainder of the decay originates from the bulk of the ions in quenching sites. Cross relaxation occurs directly in steps after transfer within the inhomogeneous line. Knowledge of the dynamics occurring within the inhomogeneous line derived from fluorescence line-narrowing experiments is used to analyze the cross-relaxation process from a microscopic viewpoint based on a recent model for fluorescence in the presence of traps. At 2 K the decay is consistent with an electric dipole-dipole transfer mechanism with a nearest-neighbor quenching rate of 8.9 \ifmmode\times\else\texttimes\fi{} 104{10}^{4}104 ${\mathrm{s}}^{\ensuremath{-}1}$ which is independent of temperature for T<32T<32T<32 K and which successfully predicts the observed decay rate in PrF3{\mathrm{F}}_{3}F3​. The temperature dependence of the decay for $8\ensuremath{\le}T\ensuremath{\le}32$ K is well described by a hopping model for excitation trapping. For T>35T>35T>35 K an activation process becomes dominant consistent with the onset of cross relaxation involving the 1D2(5)^{1}D_{2}(5)1D2​(5) and 3H6(1)^{3}H_{6}(1)3H6​(1) states in which a 190-${\mathrm{cm}}^{\ensuremath{-}1}$ phonon is created.
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