Nonlinear and time-resolved optical study of the 112-type iron-based superconductor parent Ca$_{1-x}$La$_{x}$FeAs$_{2}$ across its structural phase transition

TL;DR

This study uses nonlinear optical techniques and density functional theory to determine the symmetry and electronic properties of the 112-type Ca$_{1-x}$La$_{x}$FeAs$_{2}$ superconductor, revealing its non-centrosymmetric structure and subtle structural changes.

Contribution

It provides the first detailed symmetry analysis of 112-type Ca$_{1-x}$La$_{x}$FeAs$_{2}$ using rotational anisotropy SHG and combines it with DFT calculations, uncovering its non-centrosymmetric point group and electronic implications.

Findings

Identified $C_2$ as the crystal point group at high temperature.

Observed a 4.6 THz phonon mode related to As atom motion.

No significant change in SHG response or phonon frequency across the structural transition.

Abstract

The newly discovered 112-type ferropnictide superconductors contain chains of As atoms that break the tetragonal symmetry between the $a$ and $b$ axes. This feature eliminates the need for uniaxial strain that is usually required to stabilize large single domains in the electronic nematic state that exists in the vicinity of magnetic order in the iron-based superconductors. We report detailed structural symmetry measurements of 112-type Ca$_{0.73}$La$_{0.27}$FeAs$_{2}$ using rotational anisotropy optical second harmonic generation. This technique is complementary to diffraction experiments and enables a precise determination of the point group symmetry of a crystal. By combining our measurements with density functional theory calculations, we uncover a strong optical second harmonic response of bulk electric dipole origin from the Fe and Ca $3d$-derived states that enables us to assign $C_2$ as the crystallographic point group. This makes the 112-type materials high-temperature superconductors without a center of inversion, allowing for the possible mixing of singlet and triplet Cooper pairs in the superconducting state. We also perform pump-probe transient reflectivity experiments that reveal a 4.6 THz phonon mode associated with the out-of-plane motion of As atoms in the FeAs layers. We do not observe any suppression of the optical second harmonic response or shift in the phonon frequency upon cooling through the reported monoclinic-to-triclinic transition at 58 K. This allows us to identify $C_1$ as the low-temperature crystallographic point group but suggests that structural changes induced by long-range magnetic order are subtle and do not significantly affect electronic states near the Fermi level.