On the Crystal Chemistry of RE₂Si₂O₇: Revisited Structures, Group–Subgroup Relationship, and Insights of Ce³⁺-Activated Radioluminescence

Polymorphic rare-earth disilicates RE 2 Si 2 O 7 (RE = La–Lu, Y, and Sc) are attractive materials as thermal barrier coatings and scintillators; however, the orthorhombic E(δ)-type (RE = Eu–Ho and Y) and the triclinic F-type (RE = Sm and Eu) remain structurally controversial hitherto. In this work, we revisit the crystal structures of E(δ)-RE 2 Si 2 O 7 ( Pnma ), F-RE 2 Si 2 O 7 ( P 1̅), and the monoclinic G-La 2 Si 2 O 7 ( P 2 1 / n ) by X-ray single-crystal/powder diffraction. The second-harmonic generation (SHG) and/or the local-structure-sensitive VUV–UV–vis luminescence of Ce 3+ /Eu 3+ validate the structure determination. E(δ)-RE 2 Si 2 O 7 (RE = Eu–Ho) crystallizes in the centrosymmetric Pnma instead of the previous noncentrosymmetric Pna 2 1 (a subgroup of Pnma ). Increasing the RE 3+ radius results in structural transformations of the reconstructive-type E(δ) ↔ F and translationengleiche subgroup–group relationship F ↔ G (RE = La–Nd). More importantly, we perform a complete survey of 17 structure-types over 63 compounds of RE 2 Si 2 O 7 and their related transformations depending on the radius of RE 3+ . On the basis of these studies, one could (i) predict the potential polymorphs of RE 2 Si 2 O 7, including the high-pressure phase and the RE 2 Si 2 O 7 solid solutions; (ii) correlate the coefficient of thermal expansion (CTE) with the crystal structure, and (iii) understand the unusual radioluminescence of (Gd,La) 2 Si 2 O 7:Ce 3+ high-temperature scintillators.