Intrinsic defects in primary halide perovskites: A first-principles study of the thermodynamic trends

نویسندگان

چکیده

Defects in halide perovskites play an essential role determining the efficiency and stability of optoelectronic devices based on these materials. We present a systematic study intrinsic point defects six primary metal perovskites, ${\mathrm{MAPbI}}_{3}, {\mathrm{MAPbBr}}_{3}, {\mathrm{MAPbCl}}_{3}, {\mathrm{FAPbI}}_{3}, {\mathrm{CsPbI}}_{3}$, ${\mathrm{MASnI}}_{3}$ (where MA denotes methylammonium FA formamidinium), upon density functional theory calculations. Within single computational scheme, using $\text{SCAN}+\text{rVV10}$ functional, we compare impact changing anions cations defect formation energies charge state transition levels compounds, identify physical origins underlying observed trends. Dominant lead iodide compounds are ${A}^{+}$ cation interstitials ($A=\text{Cs}$, MA, FA), charge-compensated by ${\mathrm{I}}^{\ensuremath{-}}$ or $(2\ensuremath{-})$ vacancies. In bromide chloride most prominent, for ${\mathrm{MAPbCl}}_{3}$, chlorine vacancy also becomes important. These trends can be explained terms changes electrostatic interactions chemical bonding replacing anions. Defect physics is strongly dominated tin vacancies, promoted easy oxidation tin. Intrinsically, all mildly $p$ doped, except ${\mathrm{MASnI}}_{3}$, which doped. All acceptor created shallow. Some defects, vacancies Pb Sn particular, create deep donor traps. Although such traps might hamper electronic behavior bromine- iodine-based their equilibrium concentrations too small to affect materials' properties.

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ژورنال

عنوان ژورنال: Physical Review Materials

سال: 2022

ISSN: ['2476-0455', '2475-9953']

DOI: https://doi.org/10.1103/physrevmaterials.6.055402