Multifunctional two-dimensional semiconductors SnP₃: universal mechanism of layer-dependent electronic phase transition

Two-dimensional (2D) semiconductors SnP₃ are predicted, from first-principles calculations, to host moderate band gaps (0.72 eV for monolayer and 1.07 eV for bilayer), ultrahigh carrier mobility (∼10⁴ cm² V⁻¹ s⁻¹ for bilayer), strong absorption coefficients (∼10⁵ cm⁻¹) and good stability. Moreover, the band gap can be modulated from an indirect character into a direct one via strain engineering. For experimental accessibility, the calculated exfoliation energies of monolayer and bilayer SnP₃ are smaller than those of the common arsenic-type honeycomb structures GeP₃ and InP₃. More importantly, a semiconductor-to-metal transition is discovered with the layer number N  >  2. We demonstrate, in remarkable contrast to the previous understandings, that such phase transition is largely driven by the correlation between lone-pair electrons of interlayer Sn and P atoms. This mechanism is universal for analogues phase transitions in arsenic-type honeycomb structures (GeP₃, InP₃ and SnP₃). (paper)