Lithium Ion Intercalation‐Induced Metal‐Insulator Transition in Inclined‐Standing Grown 2D Non‐Layered Cr2S3 Nanosheets

Abstract 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 Cr 2 S 3 is an intrinsic heterodimensional superlattice with alternating layers of 2D CrS 2 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 Cr 2 S 3 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 Cr 2 S 3 ‐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 Cr 2 S 3 superlattice.