Excitation and emission thermal shifts in ABF<sub>3</sub>:Mn<sup>2+</sup> perovskites: coupling with impurity vibrational modes
M C Marco de Lucas; F Rodriguez; M Moreno; M C Marco de Lucas; Dept. de Ciencias de la Tierra y Fisica Materia Condensada, Cantabria Univ., Santander, Spain; F Rodriguez; Dept. de Ciencias de la Tierra y Fisica Materia Condensada, Cantabria Univ., Santander, Spain; M Moreno; Dept. de Ciencias de la Tierra y Fisica Materia Condensada, Cantabria Univ., Santander, Spain
Журнал:
Journal of Physics: Condensed Matter
Дата:
1995-09-18
Аннотация:
The thermal shifts undergone by the first moment of the <sup>6</sup>A<sub>1g</sub>(S) to <sup>4</sup>T<sub>1g</sub>(G) excitation band and the associated emission band of Mn<sup>2+</sup>-doped ABF<sub>3</sub> perovskites are investigated in the 9-300 K temperature range. It is found that these shifts are similar for the whole series and have average values of +150 and +450 cm<sup>-1</sup> for excitation and emission, respectively. Both the sign and the magnitude of these different thermal shifts are explained in terms of (i) the phonon assistance mechanism required to gain intensity of the parity-forbidden transitions, (ii) the quadratic electron-phonon coupling and (iii) thermal expansion effects. To achieve this analysis a previous discussion upon the nature of the vibrational modes seen in the optical spectra is carried out. It is stressed that the impurity vibrational mode displaying h(cross) omega <sub>g</sub>=570 cm<sup>-1</sup> in the emission spectrum of KMgF<sub>3</sub>:Mn<sup>2+</sup> exhibits a value of 540 cm<sup>-1</sup> in the corresponding excitation spectrum. This situation, which is also found for other modes seen in the optical spectra of KMgF<sub>3</sub>:Mn<sup>2+</sup>, indicates that the mode (though associated with the LO<sub>3</sub> branch of KMgF<sub>3</sub>) is not a pure mode of the lattice but displays a kind of resonant character. As a salient feature the calculated thermal shifts are based on the experimental shifts experienced by the frequencies of the optical and acoustic modes on going from the ground <sup>6</sup>A<sub>1g</sub> to the excited <sup>4</sup>T<sub>1g</sub> state of MnF<sub>6</sub><sup>4-</sup>. At variance with findings for the R lines in Cr<sup>3+</sup> and V<sup>2+</sup>, it is clearly demonstrated that the explicit and implicit contributions to the thermal shift of the zero-phonon line in MnF<sub>6</sub><sup>4-</sup> are similar and both induce red shifts upon heating. Moreover the present analysis reveals that the explicit contribution to the thermal shift undergone by the zero-phonon line of KMgF<sub>3</sub>:Mn<sup>2+</sup> is mainly dominated by the odd-parity low-energy modes. The calculated thermal shifts reproduce reasonably well the experimental data.
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