Structural phase transitions of Zn4Sb3 and its substitutional compounds （Zn0.98M0.02）4Sb3 （M = Al, Ga and In） are investigated by electrical transport measurement and differential scanning calorimetry below room temperature. The results indicate that both β→α and α→α′ phase transitions of Zn4Sb3 are reversible and exothermic processes, which may be explained as that both the transitions originate from the ordering of the disordered interstitial Zn and vacancies in regular sizes. The derived activation energies of β→α and α→α′ phase transition processes for Zn4Sb3 are E1 = 3.9 eV and E2 = 4.1 eV, respectively. Although no remarkable influence on activation energy E2 is observed after A1 doping, A1 substitution for Zn causes E1 to increase to 4.6 eV, implying its suppression of β←→α transition to a great extent. Moreover, it is found that both β←→α and α←→α′ transitions are completely prohibited by substitution of either In or Ga for Zn in Zn4Sb3. The underlying mechanisms for these phenomena are discussed.
