Structure–Composition–Property Relationships in Antiperovskite Nitrides: Guiding a Rational Alloy Design

Abstract

ABX3 perovskites have attracted intensive research interest in recent years due to their versatile composition and superior optoelectronic properties. Their counterparts, antiperovskites (X3BA), can be viewed as electronically inverted perovskite derivatives, but they have not been extensively studied for solar applications. Therefore, understanding their composition-property relationships is crucial for future photovoltaic application. Here, taking six antiperovskite nitrides +2 3-3-3 X N A (X = Mg, Ca, Sr; A = P, As, Sb, Bi) as an example, we investigate the effect of X-and A-sites on the electronic, dielectric, and mechanical properties from the viewpoint of the first-principles calculations. Our calculation results show that the X-site dominates the conduction band, and the A-site has a non-negligible contribution to the band edge. These findings are completely different from traditional halide perovskites.Interestingly, when changing X-or A-site elements, a linear relationship between the tolerance factor and physical quantities, such as electronic parameters, dielectric constants, and Young's modulus, is observed. By designing the Mg3NAs1-xBix alloys, we further verify this power of the linear relationship, which provides a predictive guidance for experimental preparation of antiperovskite alloys. Finally, we make a comprehensive comparison between the antiperovskite nitrides and conventional halide perovskites for pointing out the future device applications.

Antiperovskite Sr3MN and Ba3MN (M = Sb or Bi) as promising photovoltaic absorbers for thin‐film solar cells: A first‐principles study

“…Inorganic antiperovskite nitrides with X 3 AN formula (X is a divalent cation and A is a trivalent anion) are emerging compound semiconductors with a potential application in solar‐energy conversion 24,32,33 . To enable the potential application, an understanding of the fundamental properties relevant for PV applications is important, but it has not been established yet.…”

“…31 Inorganic antiperovskite nitrides with X 3 AN formula (X is a divalent cation and A is a trivalent anion) are emerging compound semiconductors with a potential application in solar-energy conversion. 24,32,33 To enable the potential application, an understanding of the fundamental properties relevant for PV applications is important, but it has not been established yet. In this study, using density functional theory (DFT) calculations, we scrutinize the crystal structure, electronic band structure, and optical absorption of Sr 3 MN and Ba 3 MN (M = Sb or Bi), potential PV absorbers.…”

Anti-perovskite carbides Ca6CSe4and Sr6CSe4for photovoltaics with similar optoelectronic properties to MAPbI3

“…The desired band-edge electronic dispersion is caused by the strong orbital-hybridization nature, resulting in a small carrier effective mass. The strong dielectric screening owing to the large dielectric constant (17)(18)(19)(20)(21)(22)(23)(24)(25)(26)(27)(28)(29)(30)(31)(32)(33)(34) and small exciton binding energy (30-76 meV) are favorable for the photo-induced carrier transport. Therefore, their estimated room-temperature carrier mobility can reach up to 300 cm 2 V −1 s −1 .…”

“…Recently, anti-perovskite nitrides M 3 NX (M = Mg, Ca, Sr, Ba; X = N, P, As, Sb, Bi) have been extensively explored, and they could be used as photovoltaic cell absorbers, thermoelectric materials, and topological insulators. 28 Among them, Mg(Ca) 3 NSb and Mg(Ca, Sr) 3 NP show suitable direct bandgap and high optical absorption coefficient, displaying great potential as photovoltaic absorbers. 29–31 Using sputter deposition, Mg 3 NSb has been synthesized as a thin film.…”

Understanding of Layer-Dependent Stability and Rashba Spin Splitting of Two-Dimensional Organic–Inorganic Halide Perovskites α-FABX3 (B = Ge, Sn, and Pb; X = Cl, Br, and I)

“…Three-dimensional (3D) organic–inorganic halide perovskites (OIHPs) have attracted tremendous interest in photovoltaic applications owing to their exceptional optoelectronic properties. − Recently, the recorded highest power conversion efficiency of single-junction 3D OIHP solar cells has been up to 25.5%, , which is quite competitive with traditional solar cells such as Si (26.1%) and GaAs (27.8%) . However, the stability is an essential issue limiting the commercialization of 3D OIHPs .…”