Abstract
A large uniaxial negative thermal expansion (NTE) along the c-axis has recently been observed in the transition metal (Tr) zirconides TrZr(2) with a tetragonal CuAl(2)-type structure. A recent study on FeZr₂ [M. Xu et al., Nat. Commun. 14, 4439 (2023)] suggests that optical phonons play a critical role in inducing the NTE along the c-axis. In this study, we investigate the thermophysical properties of TrZr₂ compounds (Tr = Fe and Co(1- x)Ni(x)(x = 0, 0.2, 0.4, 0.6, 0.8, 1)) using specific heat measurements, sound velocity data, and theoretical phonon calculations to achieve our aim of clarifying the contribution of optical phonons to the uniaxial NTE along the c-axis observed in both FeZr₂ and CoZr₂. We found that FeZr(2) shows a lattice-specific heat peak structure at 8.90 meV, which corresponds to optical phonon energy with a high population of negative Grüneisen parameter along the c-axis in the phonon dispersion curves in FeZr(2). In an examination of a chemical substitution effect on the Co(1- x)Ni(x)Zr(2), we found that the lattice-specific heat peak structure disappeared for x ≥ 0.4 and the oscillator intensity decreased. Phonon calculations revealed the existence of low-energy optical phonon branches at the Γ point for CoZr(2) and FeZr(2) with uniaxial NTE along the c-axis. However, the low-energy phonon branches were not found in NiZr(2) with uniaxial positive thermal expansion along the c-axis. The increase in phonon density of states near the above optical phonon energy in CoZr(2) and FeZr(2) is consistent with the lattice-specific heat analyses, and we propose that low-energy optical phonons are essential for the exhibiting of uniaxial NTE along the c-axis in TrZr(2).