Mechanism of monolayer to bilayer silicene transformation in CaSi2 due to fluorine diffusion

Literature Information

Publication Date 2021-04-01
DOI 10.1039/D0CP06644C
Impact Factor 3.676
Authors

Akihiro Nagoya, Ritsuko Yaokawa, Nobuko Ohba


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Abstract

Calcium disilicide (CaSi2) possesses a layered structure composed of alternating monolayers of silicene (MLSi) and calcium. Here the mechanism by which fluorine (F) diffusion into CaSi2 leads to a phase transformation from MLSi to bilayer silicene (BLSi) was investigated. Disorder in intra-layer atomic arrangements and F aggregation were observed using HAADF-STEM in areas of low F concentration. Transformation of MLSi to BLSi in CaSi2Fx was predicted to occur at x = 0.63 based on cluster expansion (CE) and density functional theory (DFT) analyses, and these results agreed well with HAADF-STEM observations. The occurrence of F aggregation at low concentrations was also confirmed by Monte Carlo simulations using the interaction parameters obtained in CE analysis. Bader charge analysis, DFT calculations of charged states, and ab initio molecular dynamics simulations indicated that the aggregated F atoms withdrew electrons from MLSi, destabilizing the buckled honeycomb structure of MLSi in CaSi2. This charge imbalance caused the transformation of MLSi to the covalent-like BLSi.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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