Cubic-tetragonal phase transition in SrTiO₃ revisited: Landau theory and transition mechanism

Abstract

Existing experimental data for the antiferroelastic phase transition in strontium titanate are reviewed and analysed using a Landau free energy of the form ΔG = 1/2Aθs (cothθs/ Tc-colb.θ/T)Q² + 1/4BQ ⁴ + 1/6CQ ⁶, with A = 0·6472 J K⁻¹mol⁻¹, B = 29·12 Jmol⁻¹, C = 39·27 Jmol, T _c= 105·6 K, θ _S = 60·8 K. The temperature dependence of the critical exponent is found to be due to the delicate balance between the Q ⁴ and Q ⁶ terms in the free energy expansion, and the saturation of the order parameter at low temperatures.

The spontaneous strains observed in this phase transition are not consistent with simple rotation of the TiO₆ octahedra around [001], An alternative model is proposed, where these octahedra expand in order to preserve the volume of the twelve-fold co-ordinated Sr site and the spacing between SrO₃ pseudo-closepacked layers.

Key Words:

• Keywords:
• Landau theory
• Perovskite
• Phase transition
• SrTiO₃