TY - JOUR

T1 - New double nonlinear-optical borate Rb3SmB6O12: Synthesis, structure and spectroscopic properties

AU - Atuchin, Victor

AU - Subanakov, Alexey

AU - Aleksandrovsky, Aleksandr

AU - Bazarov, Bair

AU - Bazarova, Jibzema

AU - Krylov, Alexander

AU - Molokeev, Maxim

AU - Oreshonkov, Aleksandr

AU - Pugachev, Alexey

N1 - Funding Information: This work was supported by the Ministry of Science and Higher Education of Russia (project 0273-2021-0008 ) and the Russian Science Foundation (project 21-19-00046 , in part of conceptualization). Also, this study was partly funded by RFBR (project No. 20–33-90188а ) and State assignment Basic Project of IA&E SB RAS No 121032400052-6 . The X-ray powder diffraction and thermal analysis were obtained using the equipment of the Collective Use Center BINM SB RAS. The Raman and luminescence experiments were performed in the Krasnoyarsk Regional Center of Research Equipment of Federal Research Center «Krasnoyarsk Science Center SB RAS. Publisher Copyright: © 2022 Elsevier B.V.

PY - 2022/4/5

Y1 - 2022/4/5

N2 - New noncentrosymmetric alkali rare-earth double borate Rb3SmB6O12 was found in the ternary system Rb2O–Sm2O3–B2O3. The Rb3SmB6O12 powder was prepared by the solid state reaction method at 750 °C for 40 h and the crystal structure was obtained by the Rietveld method. Rb3SmB6O12 crystallized in space group R32 with unit cell parameters a = 13.4874 (3) and c = 30.9398 (6) Å, V = 4874.2 (2) Å3, Z = 15. In the three-dimensional framework structure of Rb3SmB6O12, each [B5O10]5− group is linked to four different Sm-O polyhedra and, likewise, each Sm-O polyhedron is connected to four neighboring [B5O10]5− groups. The Sm-O polyhedra are formed by the face-sharing linked SmO6 octahedra. Rb+ cations are located in large cavities of the framework structure. From the thermal stability measurements, the incongruent melting of Rb3SmB6O12 is observed at 1104 K with as high melting enthalpy as Hm = –161.5 J/g. The nonlinear optical response of Rb3SmB6O12 tested via SHG is estimated to be similar to that of K3YB6O12. The Raman spectrum of Rb3SmB6O12 is mainly governed by the vibrations of BO4 and BO3 borate groups observed over the wavenumber range of 287–1550 cm–1. The spectral bands below 270 cm–1 were attributed to rotational, translational and mixed vibrations of Rb3SmB6O12 structural units. The luminescence spectrum of Sm3+ ions in the specific local environment of the Rb3SmB6O12 crystal lattice shows the ability to control the individual band intensity ratio originating from 4G5/2 level.

AB - New noncentrosymmetric alkali rare-earth double borate Rb3SmB6O12 was found in the ternary system Rb2O–Sm2O3–B2O3. The Rb3SmB6O12 powder was prepared by the solid state reaction method at 750 °C for 40 h and the crystal structure was obtained by the Rietveld method. Rb3SmB6O12 crystallized in space group R32 with unit cell parameters a = 13.4874 (3) and c = 30.9398 (6) Å, V = 4874.2 (2) Å3, Z = 15. In the three-dimensional framework structure of Rb3SmB6O12, each [B5O10]5− group is linked to four different Sm-O polyhedra and, likewise, each Sm-O polyhedron is connected to four neighboring [B5O10]5− groups. The Sm-O polyhedra are formed by the face-sharing linked SmO6 octahedra. Rb+ cations are located in large cavities of the framework structure. From the thermal stability measurements, the incongruent melting of Rb3SmB6O12 is observed at 1104 K with as high melting enthalpy as Hm = –161.5 J/g. The nonlinear optical response of Rb3SmB6O12 tested via SHG is estimated to be similar to that of K3YB6O12. The Raman spectrum of Rb3SmB6O12 is mainly governed by the vibrations of BO4 and BO3 borate groups observed over the wavenumber range of 287–1550 cm–1. The spectral bands below 270 cm–1 were attributed to rotational, translational and mixed vibrations of Rb3SmB6O12 structural units. The luminescence spectrum of Sm3+ ions in the specific local environment of the Rb3SmB6O12 crystal lattice shows the ability to control the individual band intensity ratio originating from 4G5/2 level.

KW - Borate

KW - Crystal structure

KW - Photoluminescence

KW - Raman

UR - http://www.scopus.com/inward/record.url?scp=85124573994&partnerID=8YFLogxK

U2 - 10.1016/j.jallcom.2022.164022

DO - 10.1016/j.jallcom.2022.164022

M3 - Article

AN - SCOPUS:85124573994

VL - 905

JO - Journal of Alloys and Compounds

JF - Journal of Alloys and Compounds

SN - 0925-8388

M1 - 164022

ER -