Peak Broadening in Photoelectron Spectroscopy of Amorphous Polymers: the Leading Role of the Electrostatic Landscape

Abstract

The broadening in photoelectron spectra of polymers can be attributed to several factors, such as light source spread, spectrometer resolution, finite lifetime of the hole state, and solid-state effects. Here, for the first time, we set up a computational protocol to assess the peak broadening induced for both core and valence levels by solid-state effects in four amorphous polymers by using a combination of density functional theory, many-body perturbation theory, and classical polarizable embedding. We show that intrinsic local inhomogeneities in the electrostatic environment induce a Gaussian broadening of $0.2$-$0.7$~eV in the binding energies of both core and semi-valence electrons, corresponding to a full width at half maximum (FWHM) of $0.5$-$1.7$~eV for the investigated systems. The induced broadening is larger in acrylate- than in styrene- based polymers, revealing the crucial role of polar groups in controlling the roughness of the electrostatic landscape in the solid matrix.

References in corpus (7)

• CP2K: An Electronic Structure and Molecular Dynamics Software Package -- Quickstep: Efficient and Accurate Electronic Structure Calculations
• The GW method
• The GW compendium: A practical guide to theoretical photoemission spectroscopy
• Accurate absolute and relative core-level binding energies from $GW$
• Accurate description of charged excitations in molecular solids from embedded many-body perturbation theory
• Quantitative Predictions of Photoelectron Spectra in Amorphous Molecular Solids from Multiscale Quasiparticle Embedding
• Modeling X-ray Photoelectron Spectroscopy of Macromolecules Using GW

Cited by in corpus (2)

• Fundamental Understanding of Exposure and Process Chemistry for Enhanced Lithography and Stability of Metal Oxide Resists
• Unraveling the Reaction Mechanisms in a Chemically Amplified EUV Photoresist from a Combined Theoretical and Experimental Approach