Inter- and Intraconfigurational Transitions of Nd³⁺ in Hexafluoroelpasolite Lattices

Abstract

Excitation of the 4f3 ion Nd3+ in hexafluoroelpasolite lattices by synchrotron radiation of wavelength approximately 185 nm leads to fast 4f(2)5d --> 4f3 emission below 52,630 cm(-1) and slower 4f3 --> 4f3 emission from the luminescent states (4)F(3/2) gamma8u (11 524 cm(-1)) and 2G2(9/2) gamma8u (approximately 47,500 cm(-1)). The near-infrared emission is well-resolved, and a clear interpretation of the 4I(9/2) crystal field levels and of the one-phonon vibronic sideband is given. The excitation spectrum of the 2G2(9/2) emission enables clarification of the structure of the 4f(2)5d configuration (which extends from approximately 52,000 to 128,000 cm(-1)). Detailed energy level and intensity calculations have been performed, which provide simulations of the d-f emission and the f-d excitation spectra in good agreement with experiment. It is interesting that although the 4f3 2G2(9/2) gamma8u --> 4f3 4I(J) transitions are very weak in intensity compared with transitions terminating upon higher multiplet terms, most of the 4f(2)5d (3H) 4I(9/2) gamma8g --> 4f3 emission intensity resides in the transitions to 4I(J).

Luminescence and excitation spectra of YAG:Nd3+ excited by synchrotron radiation

“…in Cs 2 NaYF 6 , in which almost all of the intensity is concentrated in transitions to the 4 I J multiplets [17]. The excitation spectrum of this fast emission coincides with that of the Nd 3+ 4f-4f emission, as shown in Fig.…”

“…5 3 crystal-field levels from these emission spectra are in agreement with previous studies. As in the case of Cs 2 NaYF 6 :Nd 3+ [17], the interconfigurational emission transitions to 4 I J are more intense than to other multiplet terms, but the intraconfigurational transitions to 4 I J from 2 F(2) 5/2 are relatively weak.…”

“…The five crystalfield parameters of the 5d electron, B [16]. The f-d interaction parameters were estimated using the standard atomic computer program [15] but were reduced to 74% of the calculated free-ion values [17,18]. In addition, the D E (fd) parameter, which accounts for the difference between the average energies of 4f 2 5d and 4f 3 configurations, was adjusted to obtain the best agreement between experiment and calculation.…”

Vacuum ultraviolet excitation spectra of lanthanide-doped hexafluoroelpasolites

“…The 4f N -4f N −1 5d spectra of Nd 3+ [89], Er 3+ [102] and Tm 3+ [102,103] in the Cs 2 NaYF 6 host have been previously reported and are subsequently referred to with respect to the spectra obtained herein.…”

“…The magnetic properties [87], vibrational spectra [88] and intraconfigurational 4f N -4f N spectra of Nd 3+ [89], Eu 3+ [90,91], Tb 3+ [92], Er 3+ [93], Tm 3+ [94] and Yb 3+ [95,96] [3,101]) although a spectral interpretation was not given [3,99]. The 4f N -4f N −1 5d spectra of Nd 3+ [89], Er 3+ [102] and Tm 3+ [102,103] in the Cs 2 NaYF 6 host have been previously reported and are subsequently referred to with respect to the spectra obtained herein.…”