Coherent phonon motions and ordered vacancy compound mediated quantum path interference in Cu-poor CuIn$_{x}$Ga$_{(1-x)}$Se$_2$ (CIGS) with attosecond transient absorption

TL;DR

This study uses attosecond transient absorption spectroscopy to observe coherent phonon motions and quantum interference effects in Cu-poor CIGS, revealing phase interactions and carrier cooling dynamics relevant for photovoltaic applications.

Contribution

It demonstrates the simultaneous observation of coherent phonons and quantum interference in CIGS, linking vibrational modes to phase composition and electronic coherence on femtosecond timescales.

Findings

Identification of two coherent phonon modes linked to different phases.

Observation of quantum path interference between conduction bands.

Disentanglement of hot carrier cooling times for electrons and holes.

Abstract

In this study, coherent phonon motion is observed in bandgap excited CuIn$_{x}$Ga$_{(1-x)}$Se$_2$ (CIGS) utilizing extreme ultraviolet (XUV) attosecond transient absorption spectroscopy across the Se M$_{4,5}$ absorption edge. Two frequencies of coherent phonon motion are resolved, a low frequency mode attributed through Raman measurements to the $A_{1g}$ phonon motion of a Cu-deficient ordered vacancy compound (OVC), while the high frequency mode originates from the $A_{1g}$ phonon motion in the chalcopyrite phase. The two oscillations lead to modulations in the XUV differential absorption $\Delta A(\epsilon,\tau)$ due to energy shifts of the Se M$_{4,5}$ edge, with a minima occuring approximately 1 ps after the band gap excitation. The hot carrier cooling time of holes and electrons are disentangled and the observed slower cooling of holes is attributed to the higher density of hole states in the valence band. We also observe fast oscillations (18.6(3) fs period) across the Se absorption edge, which are interpreted to originate from quantum path interference between the electronic conduction bands of the chalcopyrite CIGS and OVC phases, opening the possibility towards quantum coherent metrology in photovoltaics on the femtosecond timescale. The complex interplay between the chalcopyrite and OVC phases are revealed in this investigation through both coherent vibrational and electronic motions.