Effect of iron content and potassium substitution in A$_{0.8}$Fe$_{1.6}$Se$_2$ (A = K, Rb, Tl) superconductors: a Raman-scattering investigation

TL;DR

This study uses Raman scattering and first-principles calculations to analyze how iron content and alkali metal substitution affect phonon modes in A$_{0.8}$Fe$_{1.6}$Se$_2$ superconductors, revealing key structural influences on superconductivity.

Contribution

It provides a detailed phonon mode analysis and demonstrates the impact of iron content and alkali substitution on the vibrational properties of A$_{0.8}$Fe$_{1.6}$Se$_2$ superconductors.

Findings

Frequency differences correlate with iron content and superconductivity.

Alkali metal substitution has minimal effect on high-frequency phonons.

Additional low-frequency modes relate to heavier substituted ions.

Abstract

We have performed Raman-scattering measurements on high-quality single crystals of the superconductors K$_{0.8}$Fe$_{1.6}$Se$_2$ ($T_c$ = 32 K), Tl$_{0.5}$K$_{0.3}$Fe$_{1.6}$Se$_2$ ($T_c$ = 29 K), and Tl$_{0.5}$Rb$_{0.3}$Fe$_{1.6}$Se$_2$ ($T_c$ = 31 K), as well as of the insulating compound KFe$_{1.5}$Se$_2$. To interpret our results, we have made first-principles calculations for the phonon modes in the ordered iron-vacancy structure of K$_{0.8}$Fe$_{1.6}$Se$_2$. The modes we observe can be assigned very well from our symmetry analysis and calculations, allowing us to compare Raman-active phonons in the AFeSe compounds. We find a clear frequency difference in most phonon modes between the superconducting and non-superconducting potassium crystals, indicating the fundamental influence of iron content. By contrast, substitution of K by Tl or Rb in A$_{0.8}$Fe$_{1.6}$Se$_2$ causes no substantial frequency shift for any modes above 60 cm$^{-1}$, demonstrating that the alkali-type metal has little effect on the microstructure of the FeSe layer. Several additional modes appear below 60 cm$^{-1}$ in Tl- and Rb-substituted samples, which are vibrations of heavier Tl and Rb ions. Finally, our calculations reveal the presence of "chiral" phonon modes, whose origin lies in the chiral nature of the K$_{0.8}$Fe$_{1.6}$Se$_2$ structure.