A systematic study of the negative thermal expansion in zinc-blende and diamond-like semiconductors

Upon heating, almost all zinc-blende (ZB) and diamond-like semiconductors undergo volume contraction at low temperature, i.e. negative thermal expansion (NTE), instead of commonly expected expansion. Specifically, CuCl has the largest NTE among these semiconductors with a coefficient comparable with the record value of ZrW _2 O _8 . So far, underlying physical mechanism remains ambiguous. Here, we present a systematic and quantitative study of the NTE in ZB and diamond-like semiconductors using first-principles calculations. We clarified that the material ionicity, which renders the softening of the bond-angle-bending and thus, the enhancement of excitation of the transverse acoustic (TA) phonon, is responsible for the NTE of ZB and diamond-like semiconductors. With the increase in the ionicity from the groups IV, III-V, IIB-VI to IB-VII ZB semiconductors, the coefficient of the maximum NTE increases due to the weakness in bond-rotation effect, which makes the relative motion between cation and anion transverse to the direction of the bond more feasible and the mode Grüneisen parameters of the TA modes more negative. Since CuCl has the highest ionicity among all ZB and diamond-like semiconductors, it is expected to have the largest NTE, in good agreement with the experimental observation. This understanding would be beneficial for tetrahedral materials with specific applications.