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Physical review. B, Condensed matter

Excited-state absorption in Pr3+ : Y3 Al5 O12

Y. M. Cheung, Swapan Kumar Gayen

Published Jun 1, 1994• 50 citations
Publisher

Abstract

The optical-absorption transitions originating from the lowest 4f5d excited state of ${\mathrm{Pr}}^{3+}$ in ${\mathrm{Y}}_{3}$${\mathrm{Al}}_{5}$${\mathrm{O}}_{12}$ have been studied. The experimental arrangement uses a 7-ns 266-nm light pulse to populate the lowest 4f5d state, and a spatially overlapped, time-sequenced pulse from a frequency-tunable dye laser to induce transitions from that excited state. The excited-state-absorption (ESA) spectrum covering the 900--300-nm probe wavelength range is characterized by two broad peaks centered at 700 and 350 nm on a slowly rising background. The peak ESA cross section at 355 nm is (1\ifmmode\pm\else\textpm\fi{}0.1)\ifmmode\times\else\texttimes\fi{}${10}^{\mathrm{\ensuremath{-}}17}$ ${\mathrm{cm}}^{2}$. The position, shape, and strength of the spectrum suggest that the terminal states of the ESA transitions are the second 4f5d state of ${\mathrm{Pr}}^{3+}$ and the conduction band of the host lattice. The ESA measurements have been extended to transitions from the $^{3}$${\mathit{P}}_{0}$ and $^{1}$${\mathit{D}}_{2}$ excited states of the 4${\mathit{f}}^{2}$ configuration of ${\mathrm{Pr}}^{3+}$ as well. The ESA cross sections at a probe wavelength of 532 nm are (8\ifmmode\pm\else\textpm\fi{}1)\ifmmode\times\else\texttimes\fi{}${10}^{\mathrm{\ensuremath{-}}19}$ ${\mathrm{cm}}^{2}$ and (5.7\ifmmode\pm\else\textpm\fi{}0.6)\ifmmode\times\else\texttimes\fi{}${10}^{\mathrm{\ensuremath{-}}19}$ ${\mathrm{cm}}^{2}$ for transitions from the $^{3}$${\mathit{P}}_{0}$ and $^{1}$${\mathit{D}}_{2}$ excited states, respectively. The terminal state of ESA transitions from these two levels is the lowest 4f5d state. The strong ESA completely inhibits the potential laser action based on emission from these states in this crystal.

DOI
10.1103/physrevb.49.14827

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Broad bandwidth 5d→4f transitions in Ce3+ have been considered for tunable laser action. In this letter, optical probe measurements of excited Ce3+ ions in Y3Al5O12 show that stimulated emission in the 550–610-nm region is not possible at 295 K because of excited-state absorption. Transient measurements demonstrate that part of this loss has ≈75-ns lifetime and is associated with absorption from the lowest 5d level; a longer-lifetime loss is also observed. The excited-state-absorption loss is reduced at lower temperatures.

Applied Physics Letters•Sep 1, 1978•203 citations
The optical-absorption transitions originating from the lowest 4f5d excited state of Pr3+{\mathrm{Pr}}^{3+}Pr3+ in {\mathrm{Y}}_{3}$${\mathrm{Al}}_{5}$${\mathrm{O}}_{12} have been studied. The experimental arrangement uses a 7-ns 266-nm light pulse to populate the lowest 4f5d state, and a spatially overlapped, time-sequenced pulse from a frequency-tunable dye laser to induce transitions from that excited state. The excited-state-absorption (ESA) spectrum covering the 900--300-nm probe wavelength range is characterized by two broad peaks centered at 700 and 350 nm on a slowly rising background. The peak ESA cross section at 355 nm is (1\ifmmode\pm\else\textpm\fi{}0.1)\ifmmode\times\else\texttimes\fi{}10\ensuremath−17{10}^{\mathrm{\ensuremath{-}}17}10\ensuremath−17 cm2{\mathrm{cm}}^{2}cm2. The position, shape, and strength of the spectrum suggest that the terminal states of the ESA transitions are the second 4f5d state of Pr3+{\mathrm{Pr}}^{3+}Pr3+ and the conduction band of the host lattice. The ESA measurements have been extended to transitions from the ^{3}$${\mathit{P}}_{0} and ^{1}$${\mathit{D}}_{2} excited states of the 4f2{\mathit{f}}^{2}f2 configuration of Pr3+{\mathrm{Pr}}^{3+}Pr3+ as well. The ESA cross sections at a probe wavelength of 532 nm are (8\ifmmode\pm\else\textpm\fi{}1)\ifmmode\times\else\texttimes\fi{}10\ensuremath−19{10}^{\mathrm{\ensuremath{-}}19}10\ensuremath−19 cm2{\mathrm{cm}}^{2}cm2 and (5.7\ifmmode\pm\else\textpm\fi{}0.6)\ifmmode\times\else\texttimes\fi{}10\ensuremath−19{10}^{\mathrm{\ensuremath{-}}19}10\ensuremath−19 cm2{\mathrm{cm}}^{2}cm2 for transitions from the ^{3}$${\mathit{P}}_{0} and ^{1}$${\mathit{D}}_{2} excited states, respectively. The terminal state of ESA transitions from these two levels is the lowest 4f5d state. The strong ESA completely inhibits the potential laser action based on emission from these states in this crystal.
The two-photon absorption cross section for transitions from the 3^{3}3H4{\mathit{H}}_{4}H4​ ground-state manifold to the second excited state of the 4f5d configuration of Pr3+{\mathrm{Pr}}^{3+}Pr3+ in Y3{\mathrm{Y}}_{3}Y3​Al5{\mathrm{Al}}_{5}Al5​O12{\mathrm{O}}_{12}O12​ is observed to be enhanced by about two orders of magnitude when the excitation frequency happens to be resonant with the 3^{3}3PJ{\mathit{P}}_{\mathit{J}}PJ​ (J=0,1,2) and 1^{1}1I6{\mathit{I}}_{6}I6​ intermediate states of the 4f2{\mathit{f}}^{2}f2 configuration. The structure and line shape of the two-photon excitation spectrum spanning the 39 600--46 950 ${\mathrm{cm}}^{\mathrm{\ensuremath{-}}1}$ transition-energy range are entirely dominated by these resonantly enhanced transitions, while the contributions from nonresonant transitions appear as a slowly varying background beneath the strong resonance peaks. A two-photon absorption cross section as high as 4\ifmmode\times\else\texttimes\fi{}${10}^{\mathrm{\ensuremath{-}}50}$ cm4{\mathrm{cm}}^{4}cm4 s is measured at the peak of the resonantly enhanced transition at 44 246 ${\mathrm{cm}}^{\mathrm{\ensuremath{-}}1}$, which involves a level of the 3^{3}3P2{\mathit{P}}_{2}P2​ manifold as the intermediate state. The spectrally integrated cross section over that manifold is 3.3\ifmmode\times\else\texttimes\fi{}${10}^{\mathrm{\ensuremath{-}}38}$ cm4{\mathrm{cm}}^{4}cm4.
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High-power, picosecond-pulse excitation was used to study the dynamics of the pumping and decay processes in Y3{\mathrm{Y}}_{3}Y3​Al5{\mathrm{Al}}_{5}Al5​O12{\mathrm{O}}_{12}O12​:Nd3+{\mathrm{Nd}}^{3+}Nd3+. The observed fluorescence spectral lines are assigned to transitions from three different metastable states excited by both single-photon and two-photon absorption. The branching ratios, lifetimes, and quantum efficiencies of the metastable states are obtained from the data as well as the two-photon absorption cross sections. The results provide useful information concerning ultraviolet pumping efficiencies of the Nd-YAG (Nd-doped yttrium aluminum garnet) laser transition and the $5d\ensuremath{-}4f$ nonradiative decay rate for this material. In addition, the time-resolved spectroscopy method employed here is shown to be an extremely sensitive technique for obtaining two-photon absorption cross sections.
We excite the (4f2)1s0 state directly through a two photon excited state absorption (from the 1D2 level) and indirectly through excitation of the 4f5d band (using an ArF excimer laser). In Pr3+:LaF3 the 1S0 state lies below the band, and only 1S0 emission is observed. In most hosts examined, it is above the band, and only 4f5d emission is observed. In Pr3+:CaF2 there are sites with each of these properties, and both 1S0 and 4f5d emission are observed, with a relative strength that is concentration dependent.
Broad bandwidth 5d→4f transitions in Ce3+ have been considered for tunable laser action. In this letter, optical probe measurements of excited Ce3+ ions in Y3Al5O12 show that stimulated emission in the 550–610-nm region is not possible at 295 K because of excited-state absorption. Transient measurements demonstrate that part of this loss has ≈75-ns lifetime and is associated with absorption from the lowest 5d level; a longer-lifetime loss is also observed. The excited-state-absorption loss is reduced at lower temperatures.