Engineering Highly Emissive Tetra(t‐Butyl)rubrene/off‐Stoichiometry Thiol‐Ene Hybrids Toward Flexible Luminescent Solar Concentrator‐Integrated Photovoltaics with Excellent Stability

Luminescent solar concentrators (LSCs) are highly valued in transparent photovoltaics for their versatility and adaptability as effective large‐area sunlight collectors. However, constructing LSCs as efficient, long‐term stable, and easily malleable power‐generating units still remains a challenge. Herein, high photostability, high photoluminescence quantum yield (ΦPL), and Stokes‐shifted emission are achieved in tetra(t‐butyl)rubrene/off‐stoichiometry thiol‐ene (TBRb/OSTE) hybrids by incorporating TBRb molecules into OSTE polymers. To demonstrate their potentials in LSCs, a luminescent solar concentrator integrated photovoltaics (LSCIPV) is created using a one‐step synthesis that combines the preparation of TBRb/OSTE hybrids, coupling with the silicon solar cell, and the encapsulation of both components. The LSCIPV demonstrates remarkable flexibility and the integration of an ethylene tetrafluoroethylene film contributes to a hydrophobic surface and antireflection effect, resulting in an external photon efficiency (ηext) of 4.9% and a power conversion efficiency of 1.04% for the 100 cm2 device. The LSCIPV exhibits good photostability over 800 h of UV light exposure. Monte Carlo ray‐tracing simulations indicate that an optimized TBRb‐based LSCIPV can potentially achieve an ηext of 1.3%, even for a large device with an area of 1 m2.