Εξειδίκευση τύπου :	Άρθρο σε επιστημονικό περιοδικό
Τίτλος:	Tailoring the Electronic and Structural Properties of Lead-Free A2ZrX6 "Defect" Perovskites: A DFT Study on A-Site Cation and Halogen Substitutions
Δημιουργός/Συγγραφέας:	Kolokytha, Christina [EL] Τζέλη, Δήμητρα[EN] Tzeli, Demeter [EL] Λαθιωτάκης, Νεκτάριος N.[EN] Lathiotakis, Nektarios N.
Ημερομηνία:	2025-08-25
Γλώσσα:	Αγγλικά
ISSN:	1996-1944
DOI:	10.3390/ma18173976
Άλλο:	40942399
Περίληψη:	Lead-free A2ZrX6 "defect" perovskites hold significant potential for many optoelectronic applications due to their stability and tunable properties. Extending a previous work, we present a first-principles density functional theory (DFT) study, utilizing PBE and HSE06 functionals, to systematically investigate the impact of A-site cation and X-site halogen substitutions on the structural and electronic properties of these materials. We varied the A-site cation, considering ammonium, methylammonium, dimethylammonium, trimethylammonium, and phosphonium, and the X-site halogen, trying Cl, Br, and I. Our calculations reveal that both these substitutions significantly affect the band gap and the lattice parameters. Increasing A-site cation size generally enlarges the unit cell, while halogen electronegativity directly correlates with the band gap, yielding the lowest values for iodine-containing systems. We predict a broad range of band gaps (from ~4.79 eV for (PH4)2ZrCl6 down to ~2.11 eV for MA2ZrI6 using HSE06). The (PH4)2ZrX6 compounds maintain cubic crystal symmetry, unlike the triclinic of the ammonium-derived systems. Finally, our calculations show that the MA cation yields the smallest band gap among the ones studied, a result that is attributed to its size and the charges of the hydrogen atoms attached to nitrogen. Thus, our findings offer crucial theoretical insights into A2ZrX6 structure-property relationships, demonstrating how A-site cation and halogen tuning enables control over electronic and structural characteristics, thus guiding future experimental efforts for tailored lead-free perovskite design.
Τίτλος πηγής δημοσίευσης:	Materials (Basel, Switzerland)
Τόμος/Κεφάλαιο:	18
Τεύχος:	17
Θεματική Κατηγορία:	[EL] Ανόργανη χημεία[EN] Inorganic chemistry [EL] Φυσική και θεωρητική χημεία[EN] Physical and theoretical chemistry
Λέξεις-Κλειδιά:	hybrid DFT calculations hybrid organic–inorganic perovskites materials for energy applications optoelectronic properties
Χρηματοδότης:	European Union
Χρηματοδοτικό πρόγραμμα:	Flagship Research Projects in challenging interdisciplinary sectors with practical applications in Greek Industry
Αναγνωριστικό χρηματοδοτικού προγράμματος:	TAEDR-0537347
Κάτοχος πνευματικών δικαιωμάτων:	© 2025 by the authors. Licensee MDPI, Basel, Switzerland.
Όροι και προϋποθέσεις δικαιωμάτων:	This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/ licenses/by/4.0/).
Ηλεκτρονική διεύθυνση στον εκδότη (link):	https://doi.org/10.3390/ma18173976
Εμφανίζεται στις συλλογές:	Ινστιτούτο Θεωρητικής και Φυσικής Χημείας (ΙΘΦΧ) - Επιστημονικό έργο