Connection between Unusual Lattice Thermal Expansion and Cooperative Jahn–Teller Effect in Double Perovskites LaPbMSbO6(M = Mn, Co, Ni)

Lattice thermal expansion (LTE) has been investigated in double perovskites LaPbMSbO6(M = Mn, Co, Ni). Ordinary LTE behavior with good thermal stability is identified for the Mn sample, whereas unusual LTE with a preferably expanded interplanar distance of (040) is revealed for Co and Ni samples. Temperature-dependent X-ray diffraction patterns (T-XRD), Raman spectra (T-Raman), and specific heat capacities (T-Cp) consistently indicate that a rare isostructural displacive phase transition (IDPT) with a second-order phase transition nature is predominant near the critical temperature. Refinements of neutron powder diffraction (NPD) and in situ T-XRD data present temperature-sensitive bond parameters which are relevant to planar oxygen O1. X-ray photoelectron spectra (XPS) further confirm the Jahn–Teller (J-T) activated Co2+(HS) or Ni3+(HS/LS) cations at the B-site sublattice. This unusual LTE behavior could be understood by the cooperative J-T effect contributed by a Pb2+ion and Co2+/Ni3+ion from A- and B-site sublattices, respectively. The importance of 6s(Pb)-2p(O)-3d(Co/Ni) extended orbital hybridization on affecting thermal expansion behavior is highlighted on the basis of temperature-induced phonon mode softening. This study presents a microscopic description of connection between anisotropic thermal expansion and a cooperative J-T effect, which inspired exploration of thermal–mechanical coupled functional materials based on LaPbMSbO6double perovskites.