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The degree of buckling of two-dimensional (2D) materials can have a dramatic impact on their corresponding electronic structures. Antimonene (β-phase), a new 2D material with air stability and promising electronic properties, has been engineered to adopt flat or two-heights-buckling geometries by employing different supporting substrates for epitaxial growth. However, studies of the antimonene monolayer with a more buckled configuration are still lacking. Here, we report the synthesis of an antimonene monolayer with a three-heights-buckl