The luminescence of Cs2NaSbCl6 AND Cs2NaSbBr6: a transition from a localized to a delocalized excited state

doi:10.1016/0009-2614(87)80336-6

Chemical Physics Letters

Volume 138, Issue 1, 10 July 1987, Pages 23-28

https://doi.org/10.1016/0009-2614(87)80336-6 Get rights and content

Abstract

The luminescences of Cs₂NaSbCl₆ and Cs₂NaSbBr₆ are reported. For Cs₂NaSbBr₆ the luminescence properties are described in terms of a band model. For Cs₂NaSbCl₆ the luminescence is interpreted in terms of isolated Sb³⁺ centres, comparable with Cs₂NaMCl₆−Sb³⁺ (M = Sc, Y, La). The radius of the Sb³⁺ ion is larger in the chloro- than in the bromo-elpasolite.

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Citation Excerpt :
Note that a rough estimation of EA can be obtained by substituting he to BVS in Eqn. (5). The model looks meaningful and discriminates well the behavior of localized and delocalized states, as exemplified by Cs2NaSbCl6 (localized state) that is well predicted and Cs2NaSbBr6 (delocalized state) that is not (and should not !) [36]. This holds for stoichiometric Sb or Bi halides.
The Duffy's model is reformulated for Sb³⁺ and Bi³⁺ in cubic chloro- and bromo-elpasolites with « 0D » perovskite structure. The new equation allows calculating the energy of the first s² → s¹p¹ electron transition from crystal structure data. The Stokes shift pertaining to the Sb³⁺ emission in Cs₂B^IM^IIICl₆ double perovskites is rationalized based on Waber-Cromer orbital radii, in the approximation of the symmetrically breathing quasi-molecular (SbCl₆)^3- octahedron. This constitutes a preliminary structure-property descriptor to be implemented in machine learning algorithms for further computer-assisted design of double halide perovskites doped with Sb³⁺.
Infrared and Raman spectra of the elpasolites Cs<inf>2</inf>NaSbCl<inf>6</inf> and Cs<inf>2</inf>NaBiCl<inf>6</inf>: Evidence for a pseudo Jahn-Teller distorted ground state
1990, Journal of Physics and Chemistry of Solids
The infrared and Raman spectra of the elpasolites Cs₂NaSbCl₆ and Cs₂NaBiCl₆ provide evidence for a dynamically distorted electronic ground state of the MCl³⁻₆ (M = Sb³⁺, Bi³⁺) octahedra. Broad T_1u absorption bands in the infrared (IR) spectra indicate that vibronic coupling between the A_1g ground state and the lower T_1u excited states leads to structural fluctuations with a time scale of the order of the vibrational time scale. The Raman spectrum of Cs₂NaBiCl₆ shows that on the time scale of electronic transitions the structure of the BiCl³⁻₆ anion is (nearly) octahedral, whereas in the case of Cs₂NaSbCl₆ the Raman spectrum reveals a more strongly distorted octahedral structure for the SbCl³⁻₆ anion with C_2x and C_3v characteristics which are easily generated by linear combinations of the T_1u stretching and bending coordinates. The pseudo Jahn-Teller distortions are induced by the s² electronic configuration of the Sb³⁺ and Bi³⁺ ions. The tendency to accommodate the s² electrons in a lone pair orbital seems to be counteracted by the high symmetry crystal field which forces the s² electrons to occupy an s-type antibonding orbital. This is reflected by the relatively large values for the effective Sb³⁺ and Bi³⁺ ionic radii in these compounds.
On the luminescence of Te4+ in A<inf>2</inf>ZrCl<inf>6</inf> (A = Cs, Rb) and A<inf>2</inf>ZrCl<inf>6</inf> (A = Cs, Rb, K)
1989, Journal of Physics and Chemistry of Solids
The luminescence spectra and decay curves of Te⁴⁺-doped A₂ZrCl₆ (A = Cs, Rb) and A₂ZrCl₆ (A = Cs, Rb, K) are reported. In these lattices the Te⁴⁺ ion is octahedrally coordinated by the chloride ions. The emission consists of one band. For the compositions Cs₂ZrCl₆:Te⁴⁺, Cs₂SnCl₆Te⁴⁺ and Rb₂SnCl₆:Te⁴⁺ vibrational structure is observed in the emission band at low temperatures. The excitation spectra can be interpreted by assuming a dynamical Jahn-Teller effect in the excited state of the Te⁴⁺ ion. The vibrational frequency derived from the temperature dependence of the A band splitting is equal to the one obtained from the vibrational progression in the emission band and corresponds to the frequency of the e_g mode of the TeCl²₆− octahedron. Vibrational structure is also observed in the B excitation band of Cs₂SnCl₆: Te⁴⁺ at low temperatures. Finally, a comparison is made with the luminescence of Sn²⁺ in perovskite lattices and the luminescence of Sb³⁺ in elpasolite lattices. The Stokes shift decreases in the sequence Sn²⁺−Sb³⁺−Te⁴⁺ which can be explained by a decreasing contribution of the Jahn-Teller effect to the Stokes shift due to an increasing spin-orbit coupling.
Formation and luminescence of lower symmetrical tellurite anti-glass phases
1988, Journal of Solid State Chemistry
Two series of nonstoichiometric lanthanoid tellurite phases have been identified which are similar to cubic (Ln,Te)O_n anti-glass phases with CaF₂ defect structure. Their X-ray diagrams indicate low-symmetrical CaF₂ superstructures. Monoclinic (or pseudotetragonal) subcells were determined. Anti-glass disorder is consistent with the Eu²⁺ and Te⁴⁺ luminescence of one series, but can be excluded for the other one.
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1988, Journal of Solid State Chemistry
The luminescence of the Bi³⁺ ion (6s²) is studied in the metaphosphates LnP₃O₉ (Ln = Sc, Lu, Y, Gd, La). For Ln = Sc, Lu, Y, Gd the metaphosphates have a monoclinic structure with four slightly different sites for the trivalent cations. For Ln = Sc, Lu, Y the Stokes shift of the Bi³⁺ luminescence increased with increasing radius of the host lattice cation. Concentration quenching of the Bi³⁺ luminescence is observed. In the case of GdP₃O₉-Bi³⁺ the excitation energy is transferred to the Gd³⁺ ions. LaP₃O₉ adopts an orthorhombic structure with only one site available for the trivalent cations. The different coordination of the Bi³⁺ ion leads to a large increase of the Stokes shift of the Bi³⁺ luminescence.
Full-color and time-valve controllable long-persistent luminescence from all-inorganic halide perovskites
2024, Research Square

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Chemical Physics Letters

Abstract

References (32)

Mat. Res. Bull.

J. Solid State Chem.

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Cited by (24)

Revisiting Duffy's model for Sb<sup>3+</sup> and Bi<sup>3+</sup> in double halide perovskites: Emergence of a descriptor for machine learning

Infrared and Raman spectra of the elpasolites Cs<inf>2</inf>NaSbCl<inf>6</inf> and Cs<inf>2</inf>NaBiCl<inf>6</inf>: Evidence for a pseudo Jahn-Teller distorted ground state

On the luminescence of Te<sup>4+</sup> in A<inf>2</inf>ZrCl<inf>6</inf> (A = Cs, Rb) and A<inf>2</inf>ZrCl<inf>6</inf> (A = Cs, Rb, K)

Formation and luminescence of lower symmetrical tellurite anti-glass phases

Luminescence of Bi<sup>3+</sup> in the metaphosphates LnP<inf>3</inf>O<inf>9</inf> (Ln = Sc, Lu, Y, Gd, La)

Full-color and time-valve controllable long-persistent luminescence from all-inorganic halide perovskites