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The Journal of Physical Chemistry C

Persistent Photochemical Hole-Burning in the R-Lines of Tetravalent Manganese in Submicron α-Al2O3

Norfadira Binti Wahib, Hans Riesen

Published Aug 24, 2023• 0 citations
Publisher

Abstract

Persistent spectral hole-burning in the R-lines of tetravalent manganese in X-irradiated submicron corundum powder is reported for the first time. Two samples were investigated, namely, nominally 0.4 atom % Mn 3+ -doped and 0.4 atom % Mn 4+, Mg 2+ -codoped α-Al 2 O 3 . The samples were produced by a simple combustion reaction method at 600 °C. Spectral hole-burning properties of Mn 4+ ions burned via the R 1 and R 2 lines were measured either by the photoluminescence excitation mode via monitoring the luminescence signal of a vibrational sideband at ∼694 nm or in luminescence, with blue light excitation after the burn period. The hole widths were studied as a function of burn fluence and temperature in the range from 2 to 90 K. We propose a photochemical hole-burning mechanism for both samples based on photoionization and photoreduction of the tetravalent manganese ion. Interestingly, the 0.4 atom % Mn 4+, Mg 2+ sample displayed a higher hole-burning efficiency than the Mn 3+ sample. The hole widths obtained for the persistent spectral holes in the present powder samples were approximately 300 times broader at 2.2 ± 0.1 GHz compared to the ∼6 MHz width observed in transient hole-burning in a macroscopic crystal [ Riesen, H. Chem. Phys. Lett. 2011, 515 (44), 241−244]. We assign this effect to the disruption of the crystal lattice upon the valence state change of the Mn 4+ ion in the hole-burning process. From the hole width, we obtained a decay time of 0.72 ns for the 2 A̅ → E̅ one-phonon relaxation process within the split 2 E excited state. The stability of the spectral holes burned via the R 1 and R 2 lines was investigated for both samples, and we observed a decay of about 20% within 2 h, indicating slow spontaneous hole-filling. A hole area recovery of ∼70 and ∼64% was observed after a temperature cycle from 2.5 to 70 and 90 K for the 0.4 atom % Mn 3+ and 0.4 atom % Mn 4+, Mg 2+ samples, respectively.

DOI
10.1021/acs.jpcc.3c03771

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Persistent spectral hole-burning in the R-lines of tetravalent manganese in X-irradiated submicron corundum powder is reported for the first time. Two samples were investigated, namely, nominally 0.4 atom % Mn 3+ -doped and 0.4 atom % Mn 4+, Mg 2+ -codoped α-Al 2 O 3 . The samples were produced by a simple combustion reaction method at 600 °C. Spectral hole-burning properties of Mn 4+ ions burned via the R 1 and R 2 lines were measured either by the photoluminescence excitation mode via monitoring the luminescence signal of a vibrational sideband at ∼694 nm or in luminescence, with blue light excitation after the burn period. The hole widths were studied as a function of burn fluence and temperature in the range from 2 to 90 K. We propose a photochemical hole-burning mechanism for both samples based on photoionization and photoreduction of the tetravalent manganese ion. Interestingly, the 0.4 atom % Mn 4+, Mg 2+ sample displayed a higher hole-burning efficiency than the Mn 3+ sample. The hole widths obtained for the persistent spectral holes in the present powder samples were approximately 300 times broader at 2.2 ± 0.1 GHz compared to the ∼6 MHz width observed in transient hole-burning in a macroscopic crystal [ Riesen, H. Chem. Phys. Lett. 2011, 515 (44), 241−244]. We assign this effect to the disruption of the crystal lattice upon the valence state change of the Mn 4+ ion in the hole-burning process. From the hole width, we obtained a decay time of 0.72 ns for the 2 A̅ → E̅ one-phonon relaxation process within the split 2 E excited state. The stability of the spectral holes burned via the R 1 and R 2 lines was investigated for both samples, and we observed a decay of about 20% within 2 h, indicating slow spontaneous hole-filling. A hole area recovery of ∼70 and ∼64% was observed after a temperature cycle from 2.5 to 70 and 90 K for the 0.4 atom % Mn 3+ and 0.4 atom % Mn 4+, Mg 2+ samples, respectively.
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The temperature dependence of transient and persistent spectral holes is reported for the R-lines ( 2 E ← 4 A 2 transitions) in 4% chromium(III) doped NaMgAl(oxalate) 3 ·9H 2 O. The temperature dependence is well described by taking into account two pseudolocal vibrations in a weak electron−phonon coupling model and the direct process between the two 2 E levels. The persistent spectral hole-burning is based on a non photochemical mechanism involving mainly a rearrangement of a water molecule of crystallization. The 1.12 GHz width of the transient hole in the R 2 line provides a value for the relaxation rate within the 2 E multiplet, k (R 2 → R 1 ) = 3.5 × 10 9 s -1 at 2.5 K. The observed optical line width of Γ = 46 MHz for the R 1 -line at 2.5 K is most likely dominated by chromium(III)−chromium(III) spin−spin interactions. Spectral diffusion on the ms time scale causes persistent spectral holes to be significantly broader and holewidths of 260 MHz and 1.63 GHz for the R 1 and R 2 -line, respectively, are observed. Spontaneous hole-filling is thermally activated and spectral diffusion on the minute time scale is slow in the investigated temperature range of 2.5−30 K.
Persistent spectral hole burning is observed in Sm(2+)-doped glasses at room temperature. The holes are burned in the (7)F(0) ? (5)D(0), (5)D(1) lines of the Sm(2+) ions in three kinds of fluoride glass. The dependence of the burning efficiency on the sample and on the burning intensity is measured. The intensity dependence is approximately linear, and no antihole is observed around the burned hole. The hole-burning mechanism is discussed. The temperature dependence of the homogeneous width is also measured.
Persistent spectral hole burning in the $f\ensuremath{\rightarrow}f$ transition and changes in the $f\ensuremath{\rightarrow}d$ transition spectra upon laser irradiation were investigated in Sm2+{\mathrm{Sm}}^{2+}Sm2+-doped ${\mathrm{Al}}_{2}{\mathrm{O}}_{3}{\ensuremath{-}\mathrm{S}\mathrm{i}\mathrm{O}}_{2}$ glasses prepared by a sol-gel process. The hole was burned in the ${}^{7}{F}_{0}{\ensuremath{\rightarrow}}^{5}{D}_{0}$ line of Sm2+{\mathrm{Sm}}^{2+}Sm2+ ions using a DCM dye laser at 77 K and the dependence of the burning efficiency on laser power and burning time was measured. The hole depth increased with increasing laser irradiation time, reaching up to $\ensuremath{\sim}12%$ of the total intensity within a few hundred seconds. Neither an antihole around the burned hole nor a change in the fluorescence line narrowing spectrum were observed after hole burning. The hole depth linearly increased with increasing the incident laser power up to $\ensuremath{\sim}1{\mathrm{W}/\mathrm{m}\mathrm{m}}^{2},$ indicating a single-photon hole-burning process. On the other hand, laser irradiation with a wavelength corresponding to the energy of the ${4f}^{6}\ensuremath{\rightarrow}{4f}^{5}5d$ transition resulted in a decrease of both the absorption and fluorescence intensities but no formation of a hole. It was concluded that the electrons excited in the 4f55d{4f}^{5}5d4f55d level were further excited into the conduction band of the host matrix by a two-photon absorption process and then captured in the trapping center.
Wavelength-selective excited-state lifetime measurements and absorption, luminescence, and hole-burning spectra of a natural African emerald crystal are reported. The (2)E excited-state lifetime displays an extreme wavelength dependence, varying from 190 to 37 μs within 1.8 nm of the R(1)-line. Overall, the excited state is strongly quenched, in comparison to laboratory-created emerald (τ=1.3 ms), with an average quenching rate of ∼6 × 10(3) s(-1) at 2.5 K. This quenching is attributed to photoinduced electron transfer caused by a relatively high concentration of Fe(2+) ions. The forward electron-transfer rate, k(f), from the nearest possible Fe(2+) sites at around 5 Å is estimated to be ∼20 × 10(3) s(-1) at 2.5 K. The photoreductive quenching of the excited Cr(3+) ions by Fe(2+) is followed by rapid electron back-transfer in the ground state upon deactivation. The exchange interaction based quenching can be modeled by assuming a random quencher distribution within the possible Fe(2+) sites with the forward electron-transfer rate, k(f), given as a function of acceptor-donor separation R by exp[(R(f)-R)/a(f)]; R(f) and a(f) values of 13.5 and 2.7 Å are obtained at 2.5 K. The electron transfer/back-transfer reorganizes the local crystal lattice, occasionally leading to a minor variation of the short-range structure around the Cr(3+) ions. This provides a mechanism for spectral hole-burning for which a moderately high quantum efficiency of about ∼0.005% is observed. Spectral holes are subject to spontaneous hole-filling and spectral diffusion, and both effects can be quantified within the standard two-level systems for non-photochemical hole-burning. Importantly, the absorbance increases on both sides of broad spectral holes, and isosbestic points are observed, in accord with the expected distribution of the "photoproduct" in a non-photochemical hole-burning process.