Chemical Pressure Effects on the Stokes Shift of Bi3+ Luminescence in Orthorhombic Perovskites
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2022
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The relationship between the Stokes shift of Bi3+ emission and the volume of the unit-cell in two series of orthorhombic perovskites, LnB 3+O3 (Ln = La, Gd, Y; B 3+ = Al, In, Ga) and AB 4+O3 (A = Ca, Sr; B 4+ = Zr, Sn) is explored. The Stokes shift increases linearly with increasing cell volume. This is explained qualitatively by the lattice chemical pressure acting on the Bi3+ ion. The degree of Bi3+ ion off-centering displacement, which is due to the stereochemical activity of the lone-pair electrons (6 s2), is controlled by the chemical pressure. A small cell suppresses the off-centering displacement to produce a small Stokes shift of emission by limiting the excited state structural distortion. In large cell, the off-centering displacement is more easily accommodated. The elimination of ground state distortion in the excited state gives larger Stokes shift of emission. These qualitative arguments are supplemented by recent first-principles calculations on Bi3+ luminescence in these... perovskites. The Bi3+ luminescence in SrZrO3, previously assigned to emission from the D-state, is now assigned to the localized 3P0,1 → 1S0 transition. The energy of the 1S0 → 3P1 transition is correlated with the covalence of the BO6/2 perovskite framework. Discussion on the effective ionic radius of the Bi3+ ion in these perovskites is presented.
Извор:
ECS Journal of Solid State Science and Technology, 2022, 11, 9, 096003-Финансирање / пројекти:
- NCN [project 2018/31/B/ST4/00924]
- Program for the Foreign Experts [Grant No. W2017011]
- Chongqing University of Posts and Telecommunications and the National Foreign Experts Program for “Belt and Road Initiative” Innovative Talent Exchange [Grant No. DL2021035001L]
- Estonian Research Council [Grant PUT PRG111]
- European Regional Development Fund [TK141]
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Институција/група
VinčaTY - JOUR AU - Srivastava, Alok M. AU - Brik, Mikhail G. AU - Beers, William W. AU - Cohen, William E. PY - 2022 UR - https://vinar.vin.bg.ac.rs/handle/123456789/10601 AB - The relationship between the Stokes shift of Bi3+ emission and the volume of the unit-cell in two series of orthorhombic perovskites, LnB 3+O3 (Ln = La, Gd, Y; B 3+ = Al, In, Ga) and AB 4+O3 (A = Ca, Sr; B 4+ = Zr, Sn) is explored. The Stokes shift increases linearly with increasing cell volume. This is explained qualitatively by the lattice chemical pressure acting on the Bi3+ ion. The degree of Bi3+ ion off-centering displacement, which is due to the stereochemical activity of the lone-pair electrons (6 s2), is controlled by the chemical pressure. A small cell suppresses the off-centering displacement to produce a small Stokes shift of emission by limiting the excited state structural distortion. In large cell, the off-centering displacement is more easily accommodated. The elimination of ground state distortion in the excited state gives larger Stokes shift of emission. These qualitative arguments are supplemented by recent first-principles calculations on Bi3+ luminescence in these perovskites. The Bi3+ luminescence in SrZrO3, previously assigned to emission from the D-state, is now assigned to the localized 3P0,1 → 1S0 transition. The energy of the 1S0 → 3P1 transition is correlated with the covalence of the BO6/2 perovskite framework. Discussion on the effective ionic radius of the Bi3+ ion in these perovskites is presented. T2 - ECS Journal of Solid State Science and Technology T1 - Chemical Pressure Effects on the Stokes Shift of Bi3+ Luminescence in Orthorhombic Perovskites VL - 11 IS - 9 SP - 096003 DO - 10.1149/2162-8777/ac915b ER -
@article{ author = "Srivastava, Alok M. and Brik, Mikhail G. and Beers, William W. and Cohen, William E.", year = "2022", abstract = "The relationship between the Stokes shift of Bi3+ emission and the volume of the unit-cell in two series of orthorhombic perovskites, LnB 3+O3 (Ln = La, Gd, Y; B 3+ = Al, In, Ga) and AB 4+O3 (A = Ca, Sr; B 4+ = Zr, Sn) is explored. The Stokes shift increases linearly with increasing cell volume. This is explained qualitatively by the lattice chemical pressure acting on the Bi3+ ion. The degree of Bi3+ ion off-centering displacement, which is due to the stereochemical activity of the lone-pair electrons (6 s2), is controlled by the chemical pressure. A small cell suppresses the off-centering displacement to produce a small Stokes shift of emission by limiting the excited state structural distortion. In large cell, the off-centering displacement is more easily accommodated. The elimination of ground state distortion in the excited state gives larger Stokes shift of emission. These qualitative arguments are supplemented by recent first-principles calculations on Bi3+ luminescence in these perovskites. The Bi3+ luminescence in SrZrO3, previously assigned to emission from the D-state, is now assigned to the localized 3P0,1 → 1S0 transition. The energy of the 1S0 → 3P1 transition is correlated with the covalence of the BO6/2 perovskite framework. Discussion on the effective ionic radius of the Bi3+ ion in these perovskites is presented.", journal = "ECS Journal of Solid State Science and Technology", title = "Chemical Pressure Effects on the Stokes Shift of Bi3+ Luminescence in Orthorhombic Perovskites", volume = "11", number = "9", pages = "096003", doi = "10.1149/2162-8777/ac915b" }
Srivastava, A. M., Brik, M. G., Beers, W. W.,& Cohen, W. E.. (2022). Chemical Pressure Effects on the Stokes Shift of Bi3+ Luminescence in Orthorhombic Perovskites. in ECS Journal of Solid State Science and Technology, 11(9), 096003. https://doi.org/10.1149/2162-8777/ac915b
Srivastava AM, Brik MG, Beers WW, Cohen WE. Chemical Pressure Effects on the Stokes Shift of Bi3+ Luminescence in Orthorhombic Perovskites. in ECS Journal of Solid State Science and Technology. 2022;11(9):096003. doi:10.1149/2162-8777/ac915b .
Srivastava, Alok M., Brik, Mikhail G., Beers, William W., Cohen, William E., "Chemical Pressure Effects on the Stokes Shift of Bi3+ Luminescence in Orthorhombic Perovskites" in ECS Journal of Solid State Science and Technology, 11, no. 9 (2022):096003, https://doi.org/10.1149/2162-8777/ac915b . .