Optical spectroscopy of pure and doped CuGeO3

TL;DR

This study provides a detailed analysis of the optical properties of pure and doped CuGeO3 crystals, revealing new insights into phonon behavior, phase transition characteristics, and magnetic excitations, including the detection of a previously unexplained optical magnetic mode.

Contribution

It presents the first detailed optical spectroscopy analysis of doped CuGeO3, highlighting the effects of doping on phonon spectra and revealing a novel optical magnetic excitation.

Findings

Detection of zone boundary folded modes below Tsp

Observation of a 44 cm^-1 singlet-triplet excitation

Strong doping effects on phonon spectra and phase transition

Abstract

We investigated in detail the optical properties of several Cu(1-delta)Mg(delta)GeO3 (with delta=0,0.01), and CuGe(1-x)B(x)O3 with B=Si (x=0,0.007,0.05,0.1), and Al (x=0,0.01) single crystals, in the frequency range 20-32000 cm^-1. We report temperature dependent reflectivity and transmission measurements, performed with polarized light in order to probe the anisotropy of the crystals along the b and c axes, and optical conductivity spectra obtained by Kramers-Kronig transformation or direct inversion of the Fresnel formula. Special emphasis is given to the far-infrared phonon spectra. The temperature dependence of the phonon parameters is presented and discussed in relation to the soft mode issue in CuGeO3. For T<Tsp we could detect zone boundary folded modes activated by the spin-Peierls phase transition. Following the temperature dependence of these modes, which shows the second order character of the phase transition, we were able to study the effect of doping on Tsp. Moreover, in transmission experiments we detected a direct singlet-triplet excitation at 44 cm^-1, across the magnetic gap, which is not understandable on the basis of the magnetic excitation spectrum so far assumed for CuGeO3. The optical activity of this excitation and its polarization dependence confirm the existence of a second (optical) magnetic branch, recently suggested on the basis of inelastic neutron scattering data. The anisotropy in the magnetic exchange constants along the b axis, necessary for the optical triplet mode to gain a finite intensity, and the strong effect of Si substitution on the phonon spectra are discussed in relation to the alternative space group P2(1)2(1)2(1), recently proposed for CuGeO3 in the high temperature uniform phase.