中国物理B ›› 2009, Vol. 18 ›› Issue (10): 4386-4392.doi: 10.1088/1674-1056/18/10/048

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Structural phase transition behaviour of Zn4Sb3 and its substitutional compounds (Zn1.98M0.02)4Sb3 (M= Al, Ga and In) at low temperatures

秦晓英1, 刘冕1, 刘峰2   

  1. (1)Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031, China; (2)Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031, China;Department of Applied Mathematics and Physics, Anhui University of Science and Technology, Wuhu 241000, China
  • 收稿日期:2008-04-27 修回日期:2009-04-28 出版日期:2009-10-20 发布日期:2009-10-20
  • 基金资助:
    Project supported by the National Natural Science Foundation of China (Grant No 10774145).

Structural phase transition behaviour of Zn4Sb3 and its substitutional compounds (Zn1.98M0.02)4Sb3 (M= Al, Ga and In) at low temperatures

Liu Feng(刘峰)a)b), Qin Xiao-Ying(秦晓英)a)†, and Liu Mian (刘冕)a)   

  1. a Key Laboratory of Materials Physics, Institute of Solid State Physics, Chinese Academy of Sciences, Hefei 230031, China; b Department of Applied Mathematics and Physics, Anhui University of Science and Technology, Wuhu 241000, China
  • Received:2008-04-27 Revised:2009-04-28 Online:2009-10-20 Published:2009-10-20
  • Supported by:
    Project supported by the National Natural Science Foundation of China (Grant No 10774145).

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摘要： Structural phase transitions of Zn4Sb3 and its substitutional compounds (Zn1.98M0.02)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 Al doping, Al substitution for Zn causes E1 to increase to 4.6~eV, implying its suppression of β ≤ftrightarrow α transition to a great extent. Moreover, it is found that both β ≤ftrightarrow α and α ≤ftrightarrow α ' transitions are completely prohibited by substitution of either In or Ga for Zn in Zn4Sb3. The underlying mechanisms for these phenomena are discussed.

Abstract: Structural phase transitions of Zn4Sb3 and its substitutional compounds (Zn1.98M0.02)4Sb3 (M= Al, Ga and In) are investigated by electrical transport measurement and differential scanning calorimetry below room temperature. The results indicate that both $\beta$ → $\alpha$  and $\alpha$ → $\alpha'$ 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 $\beta$  → $\alpha$ and $\alpha$ → $\alpha'$ phase transition processes for Zn4Sb3 are $E_1=3.9$ eV and $E_2=4.1$ eV, respectively. Although no remarkable influence on activation energy $E_2$ is observed after Al doping, Al substitution for Zn causes $E_1$ to increase to 4.6 eV, implying its suppression of $\beta  \leftrightarrow \alpha$  transition to a great extent. Moreover, it is found that both $\beta \leftrightarrow \alpha$  and $\alpha  \leftrightarrow \alpha'$ transitions are completely prohibited by substitution of either In or Ga for Zn in Zn4Sb3. The underlying mechanisms for these phenomena are discussed.

Key words: Zn4Sb3, differential scanning calorimetry, phase transition

中图分类号: 

  • 64.70.K-
61.66.Fn (Inorganic compounds) 61.72.J- (Point defects and defect clusters) 72.20.Pa (Thermoelectric and thermomagnetic effects) 72.80.Jc (Other crystalline inorganic semiconductors)