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Journal of Applied Physics

Nonradiative Relaxation Time between 4T1, 2 and 2E States in Ruby

S. A. Pollack

Published Dec 1, 1967• 25 citations
Publisher

Abstract

The R-line fluorescence in ruby was excited with the nanosecond light pulses, and the slope of the rise curve was studied as a function of the pulse width at room temperature. The purpose of the experiment was to determine the value or the upper limit of the nonradiative relaxation time between the pump bands 4T1, 2 and the fluorescence state 2E. The upper limit of 5 nsec was determined. A brief review of previous work is given.

DOI
10.1063/1.1709279

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Experimental studies of non-radiative relaxation rates in solid state laser materials

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Techniques for the measurement of non-radiative decay rates between the optically excited states in solid-state laser materials are described. Two crystals have been investigated, ruby (Cr3+:Al2O3) and Sm2+:CaF2. A review of the spectroscopy of these materials is presented with particular emphasis on aspects relevant to non-radiative decay. An experiment is described using a second harmonic Nd3+ Nd:glass Q-switched laser to pump ruby crystals. Limiting non-radiative relaxation times were derived from the rise of fluorescence. Rubies varying in concentration between 0.05% and 0.4% were studied over a range of temperatures, 77 -> 7000 K. 4T2 -> 2E(E + 2A), 4T2 -> 2T1 (Eb) and 4T2 -> 2T1 (2A + Ea) non-radiative relaxations were all found to be <4ns in good agreement with the experimental results of other workers. Two experiments employing a ruby laser to pump Sm2+ :CaF2 are described. The first used a Q-switched laser and, apart from some improvements was similar to the ruby experiment. An upper limit of 4f5 5d pump -> metastable non-radiative decay of 2ns was found for Sm2+:CaF2, The fluorescence decay constant at 295 K was also measured to be 63ns. The second experiment employed a mode-locked laser and the Sm2+:CaF2 non-radiative decay time was <0.5ns. A new effect - provisionally called 'surface emission' - discovered during the ruby measurements, has been examined in detail and the results of this investigation are presented. A phase-shift technique for the measurement of non-radiative decay times is examined in detail. A pilot experiment using a self-mode-locked He-Ne laser at 633 nm to pump Sm2+:CaF2 is described. The non-radiative relaxation time found by this method was <33ps. Suggestions for improved experiments, both pulsed and phase-shifts, are made and the application of the techniques to other materials is discussed.

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7B4 - Absorption and emission properties of optically pumped ruby

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Several experiments on optically excited ruby are described. First, absorption transitions initiated from the metastable states,t\min{2}\max{3}2Eandt\min{2}\max{3}2T1, are investigated in the photon energy range from 5500 to 45 000 cm-1. The absorption spectrum of these excited states is determined in both\pi-and σ-polarizations and assignments for the observed absorption bands are achieved. Obtained results are compared with other experiments reported in the literature. Next, emission properties of pink ruby are studied in the region near theRlines. The emission spectrum is determined point by point by means of intense flash excitation. The observed weak bands are ascribed to theR'and phonon assistedRtransitions. Laser actions in these bands are discussed and experimental results on phonon terminated laser amplification are presented. An experiment using a giant pulse as an excitation source reveals that the transition time fromt\min{2}\max{3}2Etot\min{2}\max{3}2T1is shorter than a fraction of 1μs at room temperature.

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Two‐Stage Excitation of the Phosphorescence of Ruby

Z. L. Morgenshtern, Vladimir B. Neustruev

Abstract A long‐time phosphorescence of ruby is found under intense optical excitation in the spectral region of the R‐lines. From the initial brightness decay, as a function of the intensity and wavelength of the exciting light, it is suggested that the phosphorescence has a recombination character. The long‐wavelength limit of excitation corresponds to about 2 eV. These results indicate a complex character for the phosphorescence excitation (two‐photon or two‐step). To differentiate between these two possibilities experiments are performed using two excitation pulses with various time delays between them. These experiments show that two‐step excitation of electrons into the conduction band of ruby takes place over 2E levels of the Cr ions. From the results, and absorption data of ruby and corundum, a band scheme is proposed which explains the long‐wavelength limit of phosphorescence excitation in terms of indirect transitions.

physica status solidi (b)•Jan 1, 1966•9 citations
The R-line fluorescence in ruby was excited with the nanosecond light pulses, and the slope of the rise curve was studied as a function of the pulse width at room temperature. The purpose of the experiment was to determine the value or the upper limit of the nonradiative relaxation time between the pump bands 4T1, 2 and the fluorescence state 2E. The upper limit of 5 nsec was determined. A brief review of previous work is given.
Techniques for the measurement of non-radiative decay rates between the optically excited states in solid-state laser materials are described. Two crystals have been investigated, ruby (Cr3+:Al2O3) and Sm2+:CaF2. A review of the spectroscopy of these materials is presented with particular emphasis on aspects relevant to non-radiative decay. An experiment is described using a second harmonic Nd3+ Nd:glass Q-switched laser to pump ruby crystals. Limiting non-radiative relaxation times were derived from the rise of fluorescence. Rubies varying in concentration between 0.05% and 0.4% were studied over a range of temperatures, 77 -> 7000 K. 4T2 -> 2E(E + 2A), 4T2 -> 2T1 (Eb) and 4T2 -> 2T1 (2A + Ea) non-radiative relaxations were all found to be <4ns in good agreement with the experimental results of other workers. Two experiments employing a ruby laser to pump Sm2+ :CaF2 are described. The first used a Q-switched laser and, apart from some improvements was similar to the ruby experiment. An upper limit of 4f5 5d pump -> metastable non-radiative decay of 2ns was found for Sm2+:CaF2, The fluorescence decay constant at 295 K was also measured to be 63ns. The second experiment employed a mode-locked laser and the Sm2+:CaF2 non-radiative decay time was <0.5ns. A new effect - provisionally called 'surface emission' - discovered during the ruby measurements, has been examined in detail and the results of this investigation are presented. A phase-shift technique for the measurement of non-radiative decay times is examined in detail. A pilot experiment using a self-mode-locked He-Ne laser at 633 nm to pump Sm2+:CaF2 is described. The non-radiative relaxation time found by this method was <33ps. Suggestions for improved experiments, both pulsed and phase-shifts, are made and the application of the techniques to other materials is discussed.
Several experiments on optically excited ruby are described. First, absorption transitions initiated from the metastable states,t\min{2}\max{3}2Eandt\min{2}\max{3}2T1, are investigated in the photon energy range from 5500 to 45 000 cm-1. The absorption spectrum of these excited states is determined in both\pi-and σ-polarizations and assignments for the observed absorption bands are achieved. Obtained results are compared with other experiments reported in the literature. Next, emission properties of pink ruby are studied in the region near theRlines. The emission spectrum is determined point by point by means of intense flash excitation. The observed weak bands are ascribed to theR'and phonon assistedRtransitions. Laser actions in these bands are discussed and experimental results on phonon terminated laser amplification are presented. An experiment using a giant pulse as an excitation source reveals that the transition time fromt\min{2}\max{3}2Etot\min{2}\max{3}2T1is shorter than a fraction of 1μs at room temperature.
Abstract A long‐time phosphorescence of ruby is found under intense optical excitation in the spectral region of the R‐lines. From the initial brightness decay, as a function of the intensity and wavelength of the exciting light, it is suggested that the phosphorescence has a recombination character. The long‐wavelength limit of excitation corresponds to about 2 eV. These results indicate a complex character for the phosphorescence excitation (two‐photon or two‐step). To differentiate between these two possibilities experiments are performed using two excitation pulses with various time delays between them. These experiments show that two‐step excitation of electrons into the conduction band of ruby takes place over 2E levels of the Cr ions. From the results, and absorption data of ruby and corundum, a band scheme is proposed which explains the long‐wavelength limit of phosphorescence excitation in terms of indirect transitions.