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physica status solidi (b)

Two‐Stage Excitation of the Phosphorescence of Ruby

Z. L. Morgenshtern, Vladimir B. Neustruev

Published Jan 1, 1966• 9 citations
Publisher

Abstract

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.

DOI
10.1002/pssb.19660140206

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Absorption Spectrum of Optically Pumped Ruby I. Experimental Studies of Spectrum in Excited States

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Absorption transitions between two excited optical states in ruby have been studied by comparing the absorption coefficients measured under optically pumped and unpumped conditions. The spectrum has been determined in the π-and σ-polarizations in the photon energy range from 5,500 to 45,000 cm -1 . Several absorption bands have been found which arise from the transitions from the excited states t 2g 3 2 E g and t 2g 3 2 T 1g of the Cr 3+ ion. From the locations and intensities of these bands, the terminal states of the observed transitions are assigned to the charge transfer state, the t 2g 3 2 T 2g state, and the doublet states belonging to the electron configuration t 2g 3 e g . Calculated energies between these states and the metastable states, t 2g 3 2 E g and t 2g 3 2 T 1g , are in good agreement with the peak energies of the observed absorption bands. The present experiment gives new information inaccessible by the ordinary ground state absorption measurement, such as the locations of several doublet states with the configuration t 2g 2 e g and the intensities of doublet-doublet transitions in ruby.

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Many existing advanced laboratory experiences associated with the metastable 2E term of Cr3+ in ruby, which gives rise to the R-lines at 692.7 and 694.3 nm, focus on a room-temperature measurement of the radiative lifetime of the 2E term. In our local work developing a laboratory experience in atomic phosphorescence, we noted a lack of consistency in the literature for the lifetime of the Cr3+ 2E term. These projects typically use commercially available ruby spheres for which the manufacturer(s) only state an ∼2% Cr concentration. The uncertainty in chromium concentration represents one major source of systematic error for this laboratory experience, as does the neglect of reabsorption of R-line photons within the respective sample. We present our results and corrections for systematic issues that make this project a more rewarding experience for students. Our result for the room temperature radiative-lifetime for the 2E term is 3.3 ± 0.1 ms; which, unlike some more recent reports1, compares favorably with that of Nelson and Sturge3.

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physica status solidi (a)•Apr 16, 1979•36 citations

7B4 - Absorption and emission properties of optically pumped ruby

T. Kushida

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.

IEEE Journal of Quantum Electronics•Sep 1, 1966•26 citations
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.
Absorption transitions between two excited optical states in ruby have been studied by comparing the absorption coefficients measured under optically pumped and unpumped conditions. The spectrum has been determined in the π-and σ-polarizations in the photon energy range from 5,500 to 45,000 cm -1 . Several absorption bands have been found which arise from the transitions from the excited states t 2g 3 2 E g and t 2g 3 2 T 1g of the Cr 3+ ion. From the locations and intensities of these bands, the terminal states of the observed transitions are assigned to the charge transfer state, the t 2g 3 2 T 2g state, and the doublet states belonging to the electron configuration t 2g 3 e g . Calculated energies between these states and the metastable states, t 2g 3 2 E g and t 2g 3 2 T 1g , are in good agreement with the peak energies of the observed absorption bands. The present experiment gives new information inaccessible by the ordinary ground state absorption measurement, such as the locations of several doublet states with the configuration t 2g 2 e g and the intensities of doublet-doublet transitions in ruby.
Many existing advanced laboratory experiences associated with the metastable 2E term of Cr3+ in ruby, which gives rise to the R-lines at 692.7 and 694.3 nm, focus on a room-temperature measurement of the radiative lifetime of the 2E term. In our local work developing a laboratory experience in atomic phosphorescence, we noted a lack of consistency in the literature for the lifetime of the Cr3+ 2E term. These projects typically use commercially available ruby spheres for which the manufacturer(s) only state an ∼2% Cr concentration. The uncertainty in chromium concentration represents one major source of systematic error for this laboratory experience, as does the neglect of reabsorption of R-line photons within the respective sample. We present our results and corrections for systematic issues that make this project a more rewarding experience for students. Our result for the room temperature radiative-lifetime for the 2E term is 3.3 ± 0.1 ms; which, unlike some more recent reports1, compares favorably with that of Nelson and Sturge3.
A spatially periodic distribution of excited electronic states is produced in ruby which is placed into the interference region of two light beams derived from a pulsed laser (wavelength 530 nm). The spatially modulated population density acts like an optical grating and is detected by diffraction of a quasi-cw laser beam (488 nm). The lifetimes of the population density gratings are measured for ruby crystals with 0.05 to 5% Cr-doping and compared with the fluorescence lifetimes of the R-lines (694 nm). For the 0.05% ruby both lifetimes are nearly equal. At higher Cr-concentrations the grating decay is considerably faster than the fluorescent decay. The grating lifetimes are independent of the grating period A = 1 to 100 μm. From this observation an upper limit of the diffusion constant for energy transfer between excited electronic states in ruby is estimated.
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.