J. Mater. Sci. Technol. ›› 2020, Vol. 42: 212-219.DOI: 10.1016/j.jmst.2019.10.015
• Orginal Article • Previous Articles Next Articles
Yuchen Liuab, Yu Zhoua, Dechang Jiaa, Juanli Zhaob, Banghui Wangb, Yuanyuan Cuib, Qian Lib, Bin Liub*(
)
Received:2019-09-14
Revised:2019-10-09
Accepted:2019-10-10
Published:2020-04-01
Online:2020-04-16
Contact:
Liu Bin
Yuchen Liu, Yu Zhou, Dechang Jia, Juanli Zhao, Banghui Wang, Yuanyuan Cui, Qian Li, Bin Liu. Composition dependent intrinsic defect structures in ASnO3 (A = Ca, Sr, Ba)[J]. J. Mater. Sci. Technol., 2020, 42: 212-219.
Fig. 1. Chemical potential diagram of (a) BaSnO3, (b) SrSnO3, (c) CaSnO3, where in the quadrangle ABCD is stable area of ASnO3.
| ASnO3 | A = Ba | A = Sr | A = Ca | ||||||
|---|---|---|---|---|---|---|---|---|---|
| -μBa | -μSn | -μO | -μSr | -μSn | -μO | -μCa | -μSn | -μO | |
| A: Sn-&SnO2-rich | 3.59 | 0 | 3.69 | 3.81 | 0 | 3.69 | 4.02 | 0 | 3.69 |
| B: O-&SnO2-rich | 7.28 | 7.38 | 0 | 7.50 | 7.38 | 0 | 7.74 | 7.38 | 0 |
| C: O-&AO-rich | 5.93 | 8.73 | 0 | 6.70 | 8.17 | 0 | 7.20 | 7.93 | 0 |
| D: Sn-&AO-rich | 1.56 | 0 | 4.37 | 2.60 | 0 | 4.10 | 3.23 | 0 | 3.96 |
Table 1 Chemical potentials (-μA, -μSn, -μO) of A, Sn and O at the corner points, as A, B, C and D in Fig. 1.
| ASnO3 | A = Ba | A = Sr | A = Ca | ||||||
|---|---|---|---|---|---|---|---|---|---|
| -μBa | -μSn | -μO | -μSr | -μSn | -μO | -μCa | -μSn | -μO | |
| A: Sn-&SnO2-rich | 3.59 | 0 | 3.69 | 3.81 | 0 | 3.69 | 4.02 | 0 | 3.69 |
| B: O-&SnO2-rich | 7.28 | 7.38 | 0 | 7.50 | 7.38 | 0 | 7.74 | 7.38 | 0 |
| C: O-&AO-rich | 5.93 | 8.73 | 0 | 6.70 | 8.17 | 0 | 7.20 | 7.93 | 0 |
| D: Sn-&AO-rich | 1.56 | 0 | 4.37 | 2.60 | 0 | 4.10 | 3.23 | 0 | 3.96 |
Fig. 2. Interstitial configurations of cubic perovskite BaSnO3 with (a) Bai (orange ball), (b) Sni (blue ball) and (c) Oi (brown ball), orthorhombic perovskite SrSnO3 and CaSnO3 with (d) Sri or Cai (black ball), (e) Sni (blue ball) and (f) Oi (brown ball).
Fig. 3. Electron Fermi level dependent defect formation energies for charged isolated point defects under (a) Sn- & SnO2-rich, (b) O- & SnO2- rich, (c) O- & AO-rich, and (d) Sn- & AO-rich conditions.
Fig. 4. Thermodynamic transition levels of Oi, Bai and Sni for BaSnO3, VO, Oi, Sni and SnSr for SrSnO3, Oi and SnCa for CaSnO3.
| C-defect complex | Ef(eV) | ||
|---|---|---|---|
| Ba | Sr | Ca | |
| 0↔$V^{2-}_{A}$+$V^{4-}_{Sn}$+$3V^{2+}_{O}$+ASnO3 | 2.02 | 2.28 | 2.91 |
| $A^{0}_{A}$↔$V^{2-}_{A}$+$V^{2+}_{i}$ | 5.64 | 3.73 | 4.17 |
| $Sn^{0}_{Sn}$↔$V^{4-}_{Sn}$+$Sn^{4+}_{i}$ | 5.50 | 4.37 | 4.89 |
| $O^{0}_{O}$↔$V^{2+}_{O}$+$O^{2-}_{i}$ | 3.85 | 3.52 | 3.95 |
| $A^{0}_{A}$+$Sn^{0}_{Sn}$↔$A^{2-}_{Sn}$+$Sn^{2+}_{A}$ | 5.04 | 2.29 | 2.15 |
Table 2 Native defect complex mechanisms and their formation energies (Ef in eV per defect), where nominally charged isolated point defects are denoted as C-defect complexes.
| C-defect complex | Ef(eV) | ||
|---|---|---|---|
| Ba | Sr | Ca | |
| 0↔$V^{2-}_{A}$+$V^{4-}_{Sn}$+$3V^{2+}_{O}$+ASnO3 | 2.02 | 2.28 | 2.91 |
| $A^{0}_{A}$↔$V^{2-}_{A}$+$V^{2+}_{i}$ | 5.64 | 3.73 | 4.17 |
| $Sn^{0}_{Sn}$↔$V^{4-}_{Sn}$+$Sn^{4+}_{i}$ | 5.50 | 4.37 | 4.89 |
| $O^{0}_{O}$↔$V^{2+}_{O}$+$O^{2-}_{i}$ | 3.85 | 3.52 | 3.95 |
| $A^{0}_{A}$+$Sn^{0}_{Sn}$↔$A^{2-}_{Sn}$+$Sn^{2+}_{A}$ | 5.04 | 2.29 | 2.15 |
Fig. 5. Temperature dependent concentrations of various charged native defect complexes of (a) BaSnO3, (b) SrSnO3 and (c) CaSnO3.
| Nonstoichiometric mechanisms | ΔH(eV) | |||
|---|---|---|---|---|
| AO-rich | A = Ba | A = Sr | A = Ca | |
| AO↔$A^{2+}_{i}$+$O^{2-}_{i}$ | (R1) | 14.33 | 10.05 | 10.23 |
| AO+$\frac{1}{2}Sn^{0}_{Sn}$+$\frac{1}{2}O^{0}_{O}$↔$\frac{1}{2}$ASnO3+$\frac{1}{2}V^{2+}_{O}$+$\frac{1}{2}A^{2-}_{Sn}$ | (R2) | 2.17 | 1.75 | 2.39 |
| AO+$\frac{1}{3}Sn^{0}_{Sn}$↔$\frac{1}{3}$ASnO3+$\frac{1}{3}A^{2-}_{Sn}$+$\frac{1}{2}A^{2+}_{i}$ | (R3) | 3.66 | 2.17 | 2.37 |
| AO+$Sn^{0}_{Sn}$+$2O^{0}_{O}$↔ASnO3+$V^{4-}_{Sn}$+$2V^{2+}_{O}$ | (R4) | 5.45 | 6.98 | 8.51 |
| AO+$\frac{1}{3}Sn^{0}_{Sn}$↔$\frac{1}{3}$ASnO3+$\frac{1}{3}V^{4-}_{Sn}$+$\frac{2}{3}A^{2+}_{i}$ | (R5) | 6.24 | 4.34 | 4.40 |
| SnO2-rich | ||||
| SnO2↔$Sn^{4+}_{i}$+$2O^{2-}_{i}$ | (R6) | 19.60 | 15.02 | 16.51 |
| SnO2+$\frac{1}{2}A^{0}_{A}$↔$\frac{1}{2}$ASnO3+$\frac{1}{2}Sn^{2+}_{A}$+$\frac{1}{2}O^{2-}_{i}$ | (R7) | 5.37 | 3.25 | 3.17 |
| SnO2+$\frac{2}{3}A^{0}_{A}$↔$\frac{2}{3}$ASnO3+$\frac{1}{3}Sn^{2+}_{A}$+$\frac{1}{3}V^{2-}_{A}$ | (R8) | 2.11 | 1.03 | 1.31 |
| SnO2+$A^{0}_{A}$+$O^{0}_{O}$↔ASnO3+$V^{2-}_{A}$+$V^{2+}_{O}$ | (R9) | 3.30 | 3.62 | 5.48 |
| SnO2+$\frac{2}{3}A^{0}_{A}$↔$\frac{2}{3}$ASnO3+$\frac{2}{3}Sn^{4+}_{i}$+$\frac{2}{3}V^{2-}_{A}$ | (R10) | 3.60 | 2.74 | 3.90 |
Table 3 Reaction enthalpies (∆H in eV) of ASnO3 nonstoichiometric mechanisms under AO- (line CD in Fig. 1) and SnO2- (line AB in Fig. 1) rich conditions (R: reaction).
| Nonstoichiometric mechanisms | ΔH(eV) | |||
|---|---|---|---|---|
| AO-rich | A = Ba | A = Sr | A = Ca | |
| AO↔$A^{2+}_{i}$+$O^{2-}_{i}$ | (R1) | 14.33 | 10.05 | 10.23 |
| AO+$\frac{1}{2}Sn^{0}_{Sn}$+$\frac{1}{2}O^{0}_{O}$↔$\frac{1}{2}$ASnO3+$\frac{1}{2}V^{2+}_{O}$+$\frac{1}{2}A^{2-}_{Sn}$ | (R2) | 2.17 | 1.75 | 2.39 |
| AO+$\frac{1}{3}Sn^{0}_{Sn}$↔$\frac{1}{3}$ASnO3+$\frac{1}{3}A^{2-}_{Sn}$+$\frac{1}{2}A^{2+}_{i}$ | (R3) | 3.66 | 2.17 | 2.37 |
| AO+$Sn^{0}_{Sn}$+$2O^{0}_{O}$↔ASnO3+$V^{4-}_{Sn}$+$2V^{2+}_{O}$ | (R4) | 5.45 | 6.98 | 8.51 |
| AO+$\frac{1}{3}Sn^{0}_{Sn}$↔$\frac{1}{3}$ASnO3+$\frac{1}{3}V^{4-}_{Sn}$+$\frac{2}{3}A^{2+}_{i}$ | (R5) | 6.24 | 4.34 | 4.40 |
| SnO2-rich | ||||
| SnO2↔$Sn^{4+}_{i}$+$2O^{2-}_{i}$ | (R6) | 19.60 | 15.02 | 16.51 |
| SnO2+$\frac{1}{2}A^{0}_{A}$↔$\frac{1}{2}$ASnO3+$\frac{1}{2}Sn^{2+}_{A}$+$\frac{1}{2}O^{2-}_{i}$ | (R7) | 5.37 | 3.25 | 3.17 |
| SnO2+$\frac{2}{3}A^{0}_{A}$↔$\frac{2}{3}$ASnO3+$\frac{1}{3}Sn^{2+}_{A}$+$\frac{1}{3}V^{2-}_{A}$ | (R8) | 2.11 | 1.03 | 1.31 |
| SnO2+$A^{0}_{A}$+$O^{0}_{O}$↔ASnO3+$V^{2-}_{A}$+$V^{2+}_{O}$ | (R9) | 3.30 | 3.62 | 5.48 |
| SnO2+$\frac{2}{3}A^{0}_{A}$↔$\frac{2}{3}$ASnO3+$\frac{2}{3}Sn^{4+}_{i}$+$\frac{2}{3}V^{2-}_{A}$ | (R10) | 3.60 | 2.74 | 3.90 |
Fig. 6. Temperature dependent concentrations of various defect complexes under AO-rich and SnO2-rich conditions for (a, b) BaSnO3, (c, d) SrSnO3, (e, f) CaSnO3.
| ASnO3 | Stoichiometry | AO excess | SnO2 excess |
|---|---|---|---|
| A = Ba | VBa2-+VSn4-+$3V^{2+}_{O}$ | $V^{2+}_{O}$+BaSn2- | SnBa2++VBa2- |
| $V^{2+}_{O}$+$O^{2-}_{i}$ | $Ba^{2-}_{Sn}$+$Ba^{2+}_{i}$ | $V^{2-}_{Ba}$+$V^{2+}_{O}$ | |
| A = Sr | VSr2-+VSn4-+$3V^{2+}_{O}$ | $V^{2+}_{O}$+SrSn2- | SrSn2++VSr2- |
| $Sr^{2-}_{Sn}$+$Sr^{2+}_{Sr}$ | $Sr^{2-}_{Sn}$+$Sr^{2+}_{i}$ | $\frac{1}{3}Sn^{4+}_{i}$+$\frac{2}{3}V^{2-}_{Sr}$ | |
| A = Ca | CaSn2-+SnCa2+ | CaSn2-+$Ca^{2+}_{i}$ | SnCa2++VCa2- |
| $V^{2-}_{Ca}$+$V^{4-}_{Sn}$+$3V^{2+}_{O}$ | $V^{2+}_{O}$+$Ca^{2-}_{Sn}$ | $\frac{1}{2}Sn^{2+}_{Ca}$+$\frac{1}{2}O^{2-}_{i}$ |
Table 4 Predicted predominant defect structures in stoichiometric and nonstoirchiometric ASnO3 (A = Ba, Sr, Ca), where the defect complex owing the minimum formation energy is in bold.
| ASnO3 | Stoichiometry | AO excess | SnO2 excess |
|---|---|---|---|
| A = Ba | VBa2-+VSn4-+$3V^{2+}_{O}$ | $V^{2+}_{O}$+BaSn2- | SnBa2++VBa2- |
| $V^{2+}_{O}$+$O^{2-}_{i}$ | $Ba^{2-}_{Sn}$+$Ba^{2+}_{i}$ | $V^{2-}_{Ba}$+$V^{2+}_{O}$ | |
| A = Sr | VSr2-+VSn4-+$3V^{2+}_{O}$ | $V^{2+}_{O}$+SrSn2- | SrSn2++VSr2- |
| $Sr^{2-}_{Sn}$+$Sr^{2+}_{Sr}$ | $Sr^{2-}_{Sn}$+$Sr^{2+}_{i}$ | $\frac{1}{3}Sn^{4+}_{i}$+$\frac{2}{3}V^{2-}_{Sr}$ | |
| A = Ca | CaSn2-+SnCa2+ | CaSn2-+$Ca^{2+}_{i}$ | SnCa2++VCa2- |
| $V^{2-}_{Ca}$+$V^{4-}_{Sn}$+$3V^{2+}_{O}$ | $V^{2+}_{O}$+$Ca^{2-}_{Sn}$ | $\frac{1}{2}Sn^{2+}_{Ca}$+$\frac{1}{2}O^{2-}_{i}$ |
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