Commensurate Stacking Phase Transitions in an Intercalated Transition Metal Dichalcogenide.

Yang, Xiaohui; Bao, Jin-Ke; Lou, Zhefeng; Li, Peng; Jiang, Chenxi; Wang, Jialu; Sun, Tulai; Liu, Yabin et al. · Adv Mater · 2022

basic_science · Level V

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Abstract

Intercalation and stacking-order modulation are two active ways in manipulating the interlayer interaction of transition metal dichalcogenides (TMDCs), which lead to a variety of emergent phases and allow for engineering material properties. Herein, the growth of Pb-intercalated TMDCs-Pb(Ta<sub>1+x</sub> Se<sub>2</sub> )<sub>2</sub> , the first 124-phase, is reported. Pb(Ta<sub>1+x</sub> Se<sub>2</sub> )<sub>2</sub> exhibits a unique two-step first-order structural phase transition at around 230 K. The transitions are solely associated with the stacking degree of freedom, evolving from a high-temperature (high-T) phase with ABC stacking and R3m symmetry to an intermediate phase with AB stacking and P3m1, and finally to a low-temperature (low-T) phase again with R3msymmetry, but with ACB stacking. Each step involves a rigid slide of building blocks by a vector [1/3, 2/3, 0]. Intriguingly, gigantic lattice contractions occur at the transitions on warming. At low-T, bulk superconductivity with T<sub>c</sub>  ≈ 1.8 K is observed. The underlying physics of the structural phase transitions are discussed from first-principle calculations. The symmetry analysis reveals topological nodal lines in the band structure. The results demonstrate the possibility of realizing higher-order metal-intercalated phases of TMDCs and advance the knowledge of polymorphic transitions, and may inspire stacking-order engineering in TMDCs and beyond.