Lithium Ion Intercalation‐Induced Metal‐Insulator Transition in Inclined‐Standing Grown 2D Non‐Layered Cr 2 S 3 Nanosheets

Gate-controlled ionic intercalation in the van der Waals gap of 2D layered materials can induce novel phases and unlock new properties. However, this strategy is often unsuitable for densely packed 2D non-layered materials. The non-layered rhombohedral Cr₂S₃ is an intrinsic heterodimensional superlattice with alternating layers of 2D CrS₂ and 0D Cr_1/3. Here an innovative chemical vapor deposition method is reported, utilizing strategically modified metal precursors to initiate entirely new seed layers, yields ultrathin inclined-standing grown 2D Cr₂S₃ nanosheets with edge instead of face contact with substrate surfaces, enabling rapid all-dry transfer to other substrates while ensuring high crystal quality. The unconventional ordered vacancy channels within the 0D Cr_1/3 layers, as revealed by cross-sectional scanning transmission electron microscope, permitting the insertion of Li⁺ ions. An unprecedented metal-insulator transition, with a resistance modulation of up to six orders of magnitude at 300 K, is observed in Cr₂S₃-based ionic field-effect transistors. Theoretical calculations corroborate the metallization induced by Li-ion intercalation. This work sheds light on the understanding of growth mechanism, structure-property correlation and highlights the diverse potential applications of 2D non-layered Cr₂S₃ superlattice.