Defect-limited efficiency of pPnictogen chalcohalide solar cells

Pnictogen chalcohalides (MChX) have recently emerged as promising nontoxic and environmentally friendly photovoltaic absorbers, combining strong light absorption coefficients with favorable low-temperature synthesis conditions. Despite these advantages and reported optimized morphologies, device eff...

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Detalles Bibliográficos
Autores: López Álvarez, Cibrán, Kavanagh, Seán R., Benítez Colominas, Pol, Saucedo Silva, Edgardo Ademar|||0000-0003-2123-6162, Walsh, Aron, Scanlon, David O., Cazorla Silva, Claudio|||0000-0002-6501-4513
Tipo de recurso: artículo
Fecha de publicación:2026
País:España
Institución:Universitat Politècnica de Catalunya (UPC)
Repositorio:UPCommons. Portal del coneixement obert de la UPC
Idioma:inglés
OAI Identifier:oai:dnet:upcommonspor::93f68c502fef4b3f7329e282dc731023
Acceso en línea:https://hdl.handle.net/2117/459902
https://dx.doi.org/10.1021/acs.chemmater.5c03275
Access Level:acceso abierto
Palabra clave:Defects
Defects in solids
Photovoltaics
Recombination
Thermodynamic properties
Descripción
Sumario:Pnictogen chalcohalides (MChX) have recently emerged as promising nontoxic and environmentally friendly photovoltaic absorbers, combining strong light absorption coefficients with favorable low-temperature synthesis conditions. Despite these advantages and reported optimized morphologies, device efficiencies remain below 10%, far from their ideal radiative limit. To uncover the origin of these performance losses, we present a systematic and fully consistent first-principles investigation of the defect chemistry across the Bi-based chalcohalide family. Our results reveal a complex defect landscape dominated by chalcogen vacancies of low formation energy, which act as deep nonradiative recombination centers. Despite their moderate charge-carrier capture coefficients, the high equilibrium concentrations of these defects reduce the theoretical maximum efficiencies by 6% in BiSeI and by 10% in BiSeBr. In contrast, sulfur vacancies in BiSI and BiSBr are comparatively benign, presenting smaller capture coefficients due to weaker electron-phonon coupling. Interestingly, despite its huge nonradiative charge-carrier recombination rate, BiSeI presents the best conversion efficiency among all four compounds owing to its most suitable bandgap for outdoor photovoltaic applications. Our findings identify defect chemistry as a critical bottleneck in MChX solar cells and propose chalcogen-rich synthesis conditions and targeted anion substitutions as effective strategies for mitigation of detrimental vacancies.