Single-layer CrI₃ grown by molecular beam epitaxy

Single- and few-layer chromium triiodide (CrI₃), which has been intensively investigated as a promising platform for two-dimensional magnetism, is usually prepared by the mechanical exfoliation. Here, we report direct growth of single-layer CrI₃ using molecular beam epitaxy in ultrahigh vacuum. Scanning tunneling microscopy (STM), together with density functional theory (DFT) calculation, revealed that the iodine trimers, each of which consists of three I atoms surrounding a three-fold Cr honeycomb center, are the basic units of the topmost I layer. Different superstructures of single-layer CrI₃ with periodicity around 2-4 nm were obtained on Au(1 1 1), while only the 1 × 1 structure was observed on the graphite substrate. At an elevated temperature of 423 K, single-layer CrI₃ began to decompose and transformed into single-layer chromium diiodide. Our bias-dependent STM images suggest that the unoccupied and occupied states are spatial-separately distributed, consistent with the results of our DFT calculation. We also discussed the role of charge distribution in the super-exchange interactions among Cr atoms in single-layer CrI₃.