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Physical review. B, Solid state

Theoretical Study of the Raman Relaxation of Ni2+ and Cr3+ Ions in MgO Crystals

D. K. Ray, Tuhina Ray, Michael J. L. Sangster, Sanjeev Kumar Gupta

Published Jul 1, 1970• 14 citations
Publisher

Abstract

The Raman relaxation rates for ${\mathrm{Ni}}^{2+}$ and ${\mathrm{Cr}}^{3+}$ ions in MgO crystals have been calculated using a shell model of phonons which is in good agreement with the results of neutron scattering experiments. These shell-model results are compared with those obtained with the Debye model for the phonons and, also, with the available experimental results for ${\mathrm{Ni}}^{2+}$ and ${\mathrm{Cr}}^{3+}$ in MgO. In the case ${\mathrm{Ni}}^{2+}$, 50\ifmmode^\circ\else\textdegree\fi{}K is the highest temperature for which the relaxation time is sufficiently long to be directly measureable. As might be expected, in this low-temperature region the results based on the shell model and the Debye model of phonons are not significantly different. However, the values of relaxation rates at 123 and 136\ifmmode^\circ\else\textdegree\fi{}K obtainable from the recent line-shape measurements for ${\mathrm{Ni}}^{2+}$ in MgO are in good agreement with those calculated on the basis of the shell model of phonons. In the case of ${\mathrm{Cr}}^{3+}$ ions, the relaxation time can be measured directly up to temperatures as high as 200\ifmmode^\circ\else\textdegree\fi{}K, and in this range of temperature the two sets of results differ considerably. With the shell model, we obtain good agreement with the experimental results on the functional dependence of the relaxation rate $\frac{1}{{T}_{1}}$ on temperature. However, the absolute values of $\frac{1}{{T}_{1}}$ for ${\mathrm{Cr}}^{3+}$ obtained with this phonon model are on the average less than the experimental measurements by a factor of 5. The possible sources which might be important in bridging the gap between the theoretical and experimental results are discussed.

DOI
10.1103/physrevb.2.8

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The Raman relaxation rates for Ni2+{\mathrm{Ni}}^{2+}Ni2+ and Cr3+{\mathrm{Cr}}^{3+}Cr3+ ions in MgO crystals have been calculated using a shell model of phonons which is in good agreement with the results of neutron scattering experiments. These shell-model results are compared with those obtained with the Debye model for the phonons and, also, with the available experimental results for Ni2+{\mathrm{Ni}}^{2+}Ni2+ and Cr3+{\mathrm{Cr}}^{3+}Cr3+ in MgO. In the case Ni2+{\mathrm{Ni}}^{2+}Ni2+, 50\ifmmode^\circ\else\textdegree\fi{}K is the highest temperature for which the relaxation time is sufficiently long to be directly measureable. As might be expected, in this low-temperature region the results based on the shell model and the Debye model of phonons are not significantly different. However, the values of relaxation rates at 123 and 136\ifmmode^\circ\else\textdegree\fi{}K obtainable from the recent line-shape measurements for Ni2+{\mathrm{Ni}}^{2+}Ni2+ in MgO are in good agreement with those calculated on the basis of the shell model of phonons. In the case of Cr3+{\mathrm{Cr}}^{3+}Cr3+ ions, the relaxation time can be measured directly up to temperatures as high as 200\ifmmode^\circ\else\textdegree\fi{}K, and in this range of temperature the two sets of results differ considerably. With the shell model, we obtain good agreement with the experimental results on the functional dependence of the relaxation rate 1T1\frac{1}{{T}_{1}}T1​1​ on temperature. However, the absolute values of 1T1\frac{1}{{T}_{1}}T1​1​ for Cr3+{\mathrm{Cr}}^{3+}Cr3+ obtained with this phonon model are on the average less than the experimental measurements by a factor of 5. The possible sources which might be important in bridging the gap between the theoretical and experimental results are discussed.
Paramagnetic ions in solid state crystals form the basis for many advanced technologies like lasers, masers, frequency standards, and quantum-enhanced sensors. One of the most-studied examples is the Cr3+ ion in sapphire (Al2O3), also known as ruby, which has been intensely studied in the 1950s and 1960s. However, despite decades of research on ruby, some of its fundamental optical and spin properties have not been characterized at ultra low-temperatures, yet. In this article, we present optical measurements on a ruby crystal in a dilution refrigerator at ultra-low temperatures down to 20 mK. Analysing the relative populations of its 4A2 ground state spin levels, we extract a lattice temperature of 143(7) mK under continuous laser excitation. We perform spin lattice relaxation T1 measurements in excellent agreement with the direct, one-phonon model. Furthermore, we perform optically detected magnetic resonance measurements showing magnetically driven transitions between the ground state spin levels for various magnetic fields. Our measurements characterize some of ruby's low temperature spin properties, and lay the foundations for more advanced spin control experiments.
The electron-phonon coupling for Cr 3+ in different oxide host lattices (MgO, α-Al 2 O 3 and LaAlO 3 ) was probed by performing temperature dependent line broadening measurements for zero-phonon emission lines of single ions and exchange coupled pairs. No differences in electron-phonon coupling were found comparing the results for pairs and single ions in α-Al 2 O 3 (3NN and 4NN pairs) and LaAlO 3 (NN pairs). In Cr 3+ doped MgO (Cr 3+ -V Mg -Cr 3+ pairs), it was found that the electron-phonon coupling strength parameter is larger for the pairs than for the isolated Cr 3+ ions. This is probably due to changes in the surroundings of Cr 3+ by local charge compensation by a magnesium vacancy, and not to interaction between the Cr 3+ ions.
The spin relaxation dynamics of Ce3+{\mathrm{Ce}}^{3+}Ce3+ ions in heavily cerium-doped YAG crystals is studied using pulse-electron paramagnetic resonance and time-resolved pump-probe Faraday rotation. Both techniques address the 4f4f4f ground state, while pump-probe Faraday rotation also provides access to the excited 5d5d5d state. We measure a millisecond spin-lattice relaxation time T1{T}_{1}T1​, a microsecond spin coherence time T2{T}_{2}T2​, and a $\ensuremath{\sim}10$ ns inhomogeneous spin dephasing time T2∗{T}_{2}^{*}T2∗​ for the Ce3+{\mathrm{Ce}}^{3+}Ce3+ ground state at low temperatures. The spin-lattice relaxation of Ce3+{\mathrm{Ce}}^{3+}Ce3+ ions is due to modified Raman processes involving the optical phonon mode at $\ensuremath{\sim}\phantom{\rule{0.16em}{0ex}}125\phantom{\rule{0.16em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}$. The relaxation at higher temperature goes through a first excited level of the 2F52^{2}\mathrm{F}_{\frac{5}{2}}2F25​​ term at about $\ensuremath{\hbar}\ensuremath{\omega}\ensuremath{\approx}228\phantom{\rule{4pt}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}$. Effects provided by the hyperfine interaction of the Ce3+{\mathrm{Ce}}^{3+}Ce3+ with the 27Al^{27}\mathrm{Al}27Al nuclei are observed.
Phonon-ion interactions have recently been shown to satisfactorily explain the temperature dependence of widths and positions of the RRR lines of some 3d3d3d ions in crystals. These interactions give rise to phonon relaxation processes and are investigated here as the mechanisms responsible for the widths and positions of sharp optical transitions in (4f4f4f) ions, in particular LaF3{\mathrm{F}}_{3}F3​: Pr3+{\mathrm{Pr}}^{3+}Pr3+. The widths of transitions originating or terminating in the metastable 3P0^{3}P_{0}3P0​ state and involving the 3H4^{3}H_{4}3H4​, 3H6^{3}H_{6}3H6​, 3F2^{3}F_{2}3F2​, and 3F4^{3}F_{4}3F4​ states of Pr3+{\mathrm{Pr}}^{3+}Pr3+ in LaF3{\mathrm{F}}_{3}F3​ have been investigated as a function of temperature and are found to be both qualitatively and quantitatively explainable in terms of lifetime broadening of the interacting states via nonradiative processes. Temperature-dependent shifts have also been measured for the above four groups of transitions and are shown to be in qualitative agreement with theoretical predictions. Additional features of the LaF3{\mathrm{F}}_{3}F3​: Pr3+{\mathrm{Pr}}^{3+}Pr3+ spectrum, including several unreported weak transitions and vibrational sidebands, are also reported.
Coupling between CaWO4_44​ phonons and Er3+^{3+}3+ dopants
We investigate the lattice dynamics of CaWO4_44​, a promising host crystal for erbium-based quantum memories, using inelastic neutron scattering together with density-functional perturbation theory. The measured phonon dispersion along the (100), (001), and (101) reciprocal space direction reveals phonon bands extending up to 130 meV, with a gap between 60 and 80 meV, in good agreement with our calculations. From a symmetry analysis of the phonon eigenmodes, we identify eight Raman-active modes that can couple directly to the Er3+^{3+}3+ crystal-field operators, including a low-energy BgB_gBg​ mode at 9.1 meV that is expected to play a dominant role in phonon-assisted spin-lattice relaxation. These results provide a microscopic description of the phonon bath in CaWO4_44​ and establish a basis for engineering phononic environments to mitigate the loss of stored quantum states and optimize Er-doped CaWO4_44​ for quantum-memory applications.