Site-occupancy scheme in disordered Ca₃RE₂(BO₃)₄: a dependence on rare-earth (RE) ionic radius

Abstract

The structures of polycrystalline Ca3RE2(BO3)4 (RE = La, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Y; space group Pnma) orthoborates were determined using powder X-ray diffraction. Trends in the unit-cell dimensions and yet unreported trends in other structural properties (interatomic distances and the fractional occupation of three Ca/RE sites) for these compounds are demonstrated as a function of RE ionic radius. The unit-cell volume and a unit-cell parameter present a linear dependence, while the b and c unit-cell parameters change in a nonlinear manner. For the whole series, the RE atoms are present at all three cationic sites (labelled as M1, M2 and M3), but the fractional occupancies depend on the RE ionic radius. The small rare-earth atoms tend to enter mainly the M3 site; for the larger rare earths, the occupancy of this site decreases sharply. The occupancy of the M1 site by RE atoms is around 0.5 and tends to increase with increasing RE ionic radius. The M2 site is the least preferentially occupied by RE ions, but the occupancy discernibly increases with rising radius as well. These findings are assembled with properties of isostructural strontium and barium borates, allowing prediction of occupancy schemes for not yet investigated compounds from the A 3RE2(BO3)4 (A = Ca, Ba, Sr).

Synthesis of a mixed‐valent europium(II, III)‐borate and its optical and magnetic behavior

“…The crystal structure of Eu 5 (BO 3 ) 4 , which is Eu II 3 Eu III 2 (BO 3 ) 4 , can be regarded as a superstructure a =3 a sub of the Ba 3 La 2 (BO 3 ) 4 [14] structure type. For several combinations of an alkaline earth metal ion with a lanthanoid ion borates with isotypic structure were so far reported (Ba/Pr, [14] Ba/Nd, [15] Sr/Ho, [10] Sr/Er, [10] Ca/Y, [15a] Ca/La, [15a] Ca/Gd [15a] ). In all these structures alkaline earth and lanthanoide ions are disordered with occupancies frequently close to 1/3 and 2/3, suggesting that in a superstructure ordering of di‐ and trivalent cations could be possible.…”

SESAM Mode-Locked Yb:Ca3Gd2(BO3)4 Femtosecond Laser

“…Thus, a Yb 3+ -doped Ca 3 Gd 2 (BO 3 ) 4 crystal (abbreviated Yb:GdCB) with high optical quality has been successfully grown with the Czochralski method and laser performance in the CW regime was characterized [11,15,16]. In the GdCB structure, the Ca 2+ and Gd 3+ cations statistically occupy three non-equivalent crystallographic sites, forming M-oxygen distorted polyhedrons [17] (the dopant Yb 3+ ions are expected to replace the Gd 3+ ones). This leads to a "glassy-like" spectroscopic behaviour of Yb:GdCB crystals at the expense of a relatively low thermal conductivity of 0.92 W/mK at room temperature [18].…”