Molecular Beam Epitaxy of Transition Metal (Ti-, V-, and Cr-) Tellurides: From Monolayer Ditellurides to Multilayer Self-Intercalation Compounds.

Material growth by van der Waals epitaxy has the potential to isolate monolayer (ML) materials and synthesize ultrathin films not easily prepared by exfoliation or other growth methods. Here, the synthesis of the early transition metal (Ti, V, and Cr) tellurides by molecular beam epitaxy (MBE) in the mono- to few-layer regime is investigated. The layered ditellurides of these materials are known for their intriguing quantum- and layer dependent- properties. Here we show by a combination of sample characterization and comparison with computational predictions that ML ditellurides with octahedral 1T structure are readily grown, but for multilayers, the transition metal dichalcogenide (TMDC) formation competes with self-intercalated compounds. CrTe, a TMDC that is known to be metastable in bulk and easily decomposes into intercalation compounds, has been synthesized successfully in the ML regime at low growth temperatures. At elevated growth temperatures or for multilayers, only the intercalation compound, equivalent to a bulk CrTe, could be obtained. ML VTe is more stable and can be synthesized at higher growth temperatures in the ML regime, but multilayers also convert to a bulk-equivalent VTe compound. TiTe is the most stable of the TMDCs studied; nevertheless, a detailed analysis of multilayers also indicates the presence of intercalated metals. Computation suggests that the intercalation-induced distortion of the TMDC-layers is much reduced in Ti-telluride compared to V-, and Cr-telluride. This makes the identification of intercalated materials by scanning tunneling microscopy more challenging for Ti-telluride. The identification of self-intercalation compounds in MBE grown multilayer chalcogenides may explain observed lattice distortions in previously reported MBE grown early transition metal chalcogenides. On the other hand, these intercalation compounds in their ultrathin limit can be considered van der Waals materials in their own right. This class of materials is only accessible by direct growth methods but may be used as "building blocks" in MBE-grown van der Waals heterostructures. Controlling their growth is an important step for understanding and studying the properties of these materials.