Journal of the Optical Society of America B

Spectroscopic investigations of the 4ƒ5d energy levels of Pr^3+ in fluoride crystals by excited-state absorption and two-step excitation measurements

Mathieu Laroche, Alain Braud, Sylvain Girard, Jean‐Louis Doualan, R. Moncorgé, M. Thuau, Larry D. Merkle

Published Dec 1, 1999• 54 citations

Abstract

Excited-state absorption spectra obtained by a pulsed pump–probe technique specially designed for the near-UV spectral domain were recorded in three Pr3+-doped fluoride crystals (KY3F10,LiYF4, and BaY2F8). These excited-state absorption spectra correspond to optical transitions from the 3P0 or the 1D2 metastable levels of the 4f2 configuration up to the first energy levels of the 4f5d electronic configuration. The position, the anisotropic behavior, and the line shape of the observed excited-state absorption bands are discussed and compared with ground-state absorption (from level 3H4) or direct excitation spectra available in the literature. Subsequently, two-step excitation into the 4f5d high-lying energy levels of Pr3 by means of 3P0 and 1D2 is shown to be an efficient way to produce broadband UV fluorescence by use of pump beams in the blue and the near UV.

DOI: 10.1364/josab.16.002269

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Experimental and theoretical investigations of the 4ƒ^2→ 4ƒ5d ground-state and excited-state absorption spectra of Pr^3+ in LiYF_4

Mathieu Laroche, J.L. Doualan, Sylvain Girard +2 more

Journal of the Optical Society of America BJul 1, 200052 citations

4f2to 4f5d excited state absorption in Pr3+:YAlO3

S Nicolas, Mathieu Laroche, S Girard +5 more

Excited-state absorption spectra, from the 3 P J - 1 I 6 or 1 D 2 manifold to 4f5d levels, recorded in the 23000 - 42000 cm -1 range and calibrated in units of cross sections, are reported and discussed in the case of Pr 3+ -doped YAlO 3 . The 4f5d 4f 2 Pr 3+ emission between 30000 and 44000 cm -1 is then observed, showing the possibility of UV laser operation following two-step excitation pumping using near-UV-visible pump photons.

Journal of Physics Condensed MatterSep 24, 199935 citations

Excitation of the 1S0 State of Pr3+ in Crystal Hosts

Christopher G. Levey, Thomas J. Glynn, William M. Yen

International Conference on Luminescence - 1984Jan 1, 19840 citations

Single-frequency continuous-wave diode-pumped Pr3+:BaY2F8 orange laser

David Pabœuf, Oussama Mhibik, Fabien Bretenaker +3 more

Conference on Lasers and Electro-Optics Europe & European Quantum Electronics Conference (CLEO/Europe-EQEC)May 1, 20110 citations

Excited-state absorption in Pr3+ : Y3 Al5 O12

Y. M. Cheung, Swapan Kumar Gayen

Physical review. B, Condensed matterJun 1, 199450 citations

Revisiting the luminescence properties of Pr3+: YAG within the framework of an extended approach of Judd-Ofelt theory

Maxence Lepers, G. Hovhannesyan, Y. Guyot +2 more

physics.atom-phCross-listedarXiv:2604.21374Apr 24, 2026

Journal of the Optical Society of America B

Spectroscopic investigations of the 4ƒ5d energy levels of Pr^3+ in fluoride crystals by excited-state absorption and two-step excitation measurements

Mathieu Laroche, Alain Braud, Sylvain Girard, Jean‐Louis Doualan, R. Moncorgé, M. Thuau, Larry D. Merkle

Published Dec 1, 1999• 54 citations

Publisher

Abstract

DOI: 10.1364/josab.16.002269

Related papers

Experimental and theoretical investigations of the 4ƒ^2→ 4ƒ5d ground-state and excited-state absorption spectra of Pr^3+ in LiYF_4

Mathieu Laroche, J.L. Doualan, Sylvain Girard +2 more

Near-UV excited-state absorption spectra obtained with a pulsed pump–probe technique were recorded in LiYF4:Pr3+ at 77 and at 8 K and revealed a detailed structure of the 4f2 1D2→4f5d and 4f2 (3P0+1I6)→4f5d optical transitions. These experimental results, together with those previously obtained at room temperature, are compared with the numerical predictions of a full calculation of the 4f5d sublevels and of the electric dipole transitions toward these sublevels from different states of the 4f2 configuration. The agreement is good, provided that the four adjustable parameters of the theory are taken as B20(5d)=7290 cm-1,B40(5d)=-14 900 cm-1,F0=60 557 cm-1, and 〈r〉fd=0.245 Å. The level structure of the 4f5d configuration of LiYF4:Pr3+ is shown to be dominated, as expected, by the crystal field coupling of the 5d electron but also, to a noticeable extent, by the spin–orbit coupling of the 4f electron and the Coulomb repulsion of both electrons. The former of these two interactions is somewhat more efficient than the latter in the low-energy part of the 4f5d configuration, i.e., in the spectral region where the largest amount of experimental data is currently available.Near-UV excited-state absorption spectra obtained with a pulsed pump–probe technique were recorded in LiYF4:Pr3+ at 77 and at 8 K and revealed a detailed structure of the 4f2 1D2→4f5d and 4f2 (3P0+1I6)→4f5d optical transitions. These experimental results, together with those previously obtained at room temperature, are compared with the numerical predictions of a full calculation of the 4f5d sublevels and of the electric dipole transitions toward these sublevels from different states of the 4f2 configuration. The agreement is good, provided that the four adjustable parameters of the theory are taken as B20(5d)=7290 cm-1,B40(5d)=-14 900 cm-1,F0=60 557 cm-1, and 〈r〉fd=0.245 Å. The level structure of the 4f5d configuration of LiYF4:Pr3+ is shown to be dominated, as expected, by the crystal field coupling of the 5d electron but also, to a noticeable extent, by the spin–orbit coupling of the 4f electron and the Coulomb repulsion of both electrons. The former of these two interactions is somewhat more efficient than the latter in the low-energy part of the 4f5d configuration, i.e., in the spectral region where the largest amount of experimental data is currently available.

Journal of the Optical Society of America BJul 1, 200052 citations

4f2to 4f5d excited state absorption in Pr3+:YAlO3

S Nicolas, Mathieu Laroche, S Girard +5 more

Journal of Physics Condensed MatterSep 24, 199935 citations

Excitation of the 1S0 State of Pr3+ in Crystal Hosts

Christopher G. Levey, Thomas J. Glynn, William M. Yen

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.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.

International Conference on Luminescence - 1984Jan 1, 19840 citations

Single-frequency continuous-wave diode-pumped Pr3+:BaY2F8 orange laser

David Pabœuf, Oussama Mhibik, Fabien Bretenaker +3 more

The optical transition (3H4→1D2) of trivalent praseodymium embedded in crystalline matrices is a promising candidate for the realization of optically controlled quantum memories. This application requires a specific laser source emitting at 606 nm whose short-term linewidth is smaller than the linewidth of the considered ion, i.e., in the kHz range. Currently, this can only be addressed with a highly frequency stabilized dye laser [1]. In order to develop a simpler all-solid-state laser source suitable for coherent processing of Pr3+, we have explored Pr3+-doped fluoride materials which are well-known to offer a large range of available laser transitions in the visible spectrum ranging from blue to red [2] including an orange one around 600 nm, the pumping transitions lying in the blue between 445 and 480 nm. The recent developments of high power blue laser diodes emitting around 445 nm enable now the pumping of Pr-doped lasers in a compact setup. We present, here, the results we obtained with the diode pumping of a Pr3+:BaY2F8(Pr:BYF) crystal which emits at 607 nm.The optical transition (3H4→1D2) of trivalent praseodymium embedded in crystalline matrices is a promising candidate for the realization of optically controlled quantum memories. This application requires a specific laser source emitting at 606 nm whose short-term linewidth is smaller than the linewidth of the considered ion, i.e., in the kHz range. Currently, this can only be addressed with a highly frequency stabilized dye laser [1]. In order to develop a simpler all-solid-state laser source suitable for coherent processing of Pr3+, we have explored Pr3+-doped fluoride materials which are well-known to offer a large range of available laser transitions in the visible spectrum ranging from blue to red [2] including an orange one around 600 nm, the pumping transitions lying in the blue between 445 and 480 nm. The recent developments of high power blue laser diodes emitting around 445 nm enable now the pumping of Pr-doped lasers in a compact setup. We present, here, the results we obtained with the diode pumping of a Pr3+:BaY2F8(Pr:BYF) crystal which emits at 607 nm.

Conference on Lasers and Electro-Optics Europe & European Quantum Electronics Conference (CLEO/Europe-EQEC)May 1, 20110 citations

Excited-state absorption in Pr3+ : Y3 Al5 O12

Y. M. Cheung, Swapan Kumar Gayen

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.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.

Physical review. B, Condensed matterJun 1, 199450 citations

Revisiting the luminescence properties of Pr3+: YAG within the framework of an extended approach of Judd-Ofelt theory

Maxence Lepers, G. Hovhannesyan, Y. Guyot +2 more

We show in this article the improvements which can be obtained in the description of the luminescence properties of Pr3+ doped materials by using an extension of the Judd-Ofelt theory in order to relax some strong selection rules and approximations of the standard formalism and to better account for the influence of the 4f5d excited electronic configuration. The demonstration is made by re-examining the case of Pr3+:YAG, a well known luminescent and laser crystal with a very low energy 4f5d absorption band. Our extension thus provides a better agreement between calculated and measured absorption intensities, especially for the hypersensitive 3 H4 $\rightarrow$ 3 P2 transition. A comparison is made with the results obtained in the case of Pr3+:ZBLAN, a laser fluoride glass with much higher 4f5d absorption levels. Our investigation also gives the opportunity, in the case of Pr3+:YAG, to provide more complete and more reliable absorption and emission data than reported in the past literature and to exploit these data to better address the question of laser operation at various emission wavelengths. It is thus demonstrated that laser operation should be possible with improved laser performance at 488 nm, 616 nm and 744 nm, as it was already achieved in the past, but also at 566 nm and 931 nm by using appropriate laser cavities and laser mirrors.We show in this article the improvements which can be obtained in the description of the luminescence properties of Pr3+ doped materials by using an extension of the Judd-Ofelt theory in order to relax some strong selection rules and approximations of the standard formalism and to better account for the influence of the 4f5d excited electronic configuration. The demonstration is made by re-examining the case of Pr3+:YAG, a well known luminescent and laser crystal with a very low energy 4f5d absorption band. Our extension thus provides a better agreement between calculated and measured absorption intensities, especially for the hypersensitive 3 H4 $\rightarrow$ 3 P2 transition. A comparison is made with the results obtained in the case of Pr3+:ZBLAN, a laser fluoride glass with much higher 4f5d absorption levels. Our investigation also gives the opportunity, in the case of Pr3+:YAG, to provide more complete and more reliable absorption and emission data than reported in the past literature and to exploit these data to better address the question of laser operation at various emission wavelengths. It is thus demonstrated that laser operation should be possible with improved laser performance at 488 nm, 616 nm and 744 nm, as it was already achieved in the past, but also at 566 nm and 931 nm by using appropriate laser cavities and laser mirrors.

physics.atom-phCross-listedarXiv:2604.21374Apr 24, 2026

The optical-absorption transitions originating from the lowest 4f5d excited state of

{\mathrm{Pr}}^{3+}

{\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.

\rightarrow

3 P2 transition. A comparison is made with the results obtained in the case of Pr3+:ZBLAN, a laser fluoride glass with much higher 4f5d absorption levels. Our investigation also gives the opportunity, in the case of Pr3+:YAG, to provide more complete and more reliable absorption and emission data than reported in the past literature and to exploit these data to better address the question of laser operation at various emission wavelengths. It is thus demonstrated that laser operation should be possible with improved laser performance at 488 nm, 616 nm and 744 nm, as it was already achieved in the past, but also at 566 nm and 931 nm by using appropriate laser cavities and laser mirrors.