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Re-entrant Phase Behavior of Organic Semiconductors: A Thermodynamic Framework for Designing Stable Non-Fullerene Organic Solar Cells

Authors: PENG Zheng; GHASEMI Masoud; MICHELS Jasper J.; et al.

DOI: 10.1007/s40843-025-3735-xStatus: Verified Translated Edition
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Key Findings in This Report

• • The LF-TSB model predicts that suppressing the driving force for phase separation (e.g., by reducing molecular rigidity to lower T_g) enhances thermal stability; blends with T_g differences below 20°C maintain stable morphology after 1000 hours of thermal annealing at 85°C. • • Optimizing side-chain architecture to increase effective monomeric volume by 15% reduces the critical temperature for phase separation by 10°C, enabling stable operation at elevated temperatures. • • Molecular symmetry, which increases configurational entropy, can shift the re-entrant phase boundary by up to 30°C, allowing multi-step annealing protocols to trap kinetically stable morphologies. • • The model's parameters (effective monomeric volume, flexing energy) require fitting to experimental phase diagrams; for new blends, prediction accuracy is limited to ±5°C unless parameters are measured via calorimetry or scattering.