• Accepted Paper

Coherent phonon motions and ordered vacancy compound mediated quantum path interference in Cu-poor CuInxGa(1−x)Se2 (CIGS) with attosecond transient absorption

Hugo Laurell, Jonah R. Adelman, Elizaveta Yakovleva, Carl Hägglund, Kostiantyn Sopiha, Axel Stenquist, Han K. D. Le, Peidong Yang, Marika Edoff, and Stephen R. Leone

Phys. Rev. X - Accepted 29 September, 2026

DOI: https://doi.org/10.1103/btyv-jrrx

Abstract

In this study, coherent phonon motion is observed in bandgap excited CuInxGa(1−x)Se2 (CIGS) extreme-ultraviolet (XUV) attosecond transient absorption spectroscopy across the Se M4,5 absorption edge. Two frequencies of coherent phonon motion are resolved, a low frequency mode attributed through Raman measurements to the A1g phonon motion of a Cu-deficient ordered vacancy compound (OVC), while the high frequency mode originates from the A1g phonon motion in the chalcopyrite phase. The two oscillations lead to modulations in the XUV differential absorption ΔA(ϵ,τ) due to energy shifts of the Se M4,5 edge, with a minimum of the coherent-phonon amplitude occurring approximately 1 ps after band-gap excitation. The picosecond recoveries of the valence-band state-opening and conduction-band state-blocking signals are separately retrieved. The valence- and conduction-band signals recover with time constants of 1.4(1) ps and 2.2(1) ps, respectively. The conduction-band value agrees well with the approximately 3-ps carrier-cooling time previously reported for comparable co-evaporated CIGS. These constants characterize the recovery of the XUV state-blocking amplitudes and are not direct measurements of the total carrier densities or unique microscopic cooling times. Most importantly, 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, providing a femtosecond probe of interfacial electronic coherence in a photovoltaic absorber. The complex interplay between the chalcopyrite and OVC phases is revealed in this investigation through both coherent vibrational and electronic motions.

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