CeTaN₃ and CeNbN₃: Prospective Nitride Perovskites with Optimal Photovoltaic Band Gaps

Abstract

Perovskites constitute an exceptionally tunable materials family with diverse applications in electronics, optoelectronics, energy, and quantum technologies. Out of the thousands of known perovskites, the majority of compounds are oxides, halides, and chalcogenides. In contrast, only two nitride perovskites are currently known. In this work we perform a thorough ab initio computational screening of possible nitride perovskites, and we identify two new compounds, CeNbN 3 and CeTaN 3 , with band gaps in the near-infrared to visible range, depending on temperature. In their room-temperature orthorhombic phase, we predict that both compounds exhibit direct or quasidirect band gaps in the range 1.1−2.0 eV, with the Pnma phases matching the Shockley−Queisser limit for photovoltaic energy conversion efficiency. These compounds are also predicted to be strong light absorbers, with absorption coefficients surpassing those of high-performance semiconductors such as GaAs and CH 3 NH 3 PbI 3 . The present findings reveal a potentially new class of nitride semiconductors with promise for electronics, optoelectronics, and light harvesting and for integration with existing nitride-based lighting technology.

High-Throughput Selection and Experimental Realization of Two New Ce-Based Nitride Perovskites: CeMoN3 and CeWN3

“…LaWN 3 , which is predicted and calculated to be thermodynamically stable in this work, was successfully synthesized in a recent report . A recent computational study also reports the stabilities of CeTaN 3 , CeNbN 3 , CeWN 3 , and CeMoN 3 in perovskite structures …”

“…17 A recent computational study also reports the stabilities of CeTaN 3 , CeNbN 3 , CeWN 3 , and CeMoN 3 in perovskite structures. 6 From this evaluation, the compounds LaWN 3 , LaMoN 3 , CeWN 3 , CeMoN 3 , YWN 3 , and YMoN 3 were prioritized for experimental testing because of their calculated stabilities (ΔH d < 0) and to provide variety across both A-and B-site cations; it should be noted that perovskite LaWN 3 has already been successfully synthesized 17 and was included here for validation purposes.…”

“…As chemists and materials scientists expand the palette of available materials, interest in new nitrides continues to grow. , The perovskite structure, with the basic formula AB X 3 , underlies the properties and function of materials crucial to fields including solar research, ultrasonics, fuel cells, and many more, but there is a notable lack of reported nitrides with the perovskite structure. A few recent computational studies have predicted the stability of rare earth transition metal nitride perovskites − and interesting ferroic properties such as ferroelectricity in LaWN 3 and ferromagnetism in a broad range of RE M N 3 (RE = rare earth; M = W, Re) compounds. , Experimental reports are quite limited and frequently resulted instead in oxynitrides, though these too have been shown to exhibit a variety of interesting properties, from electrochemical activity to colossal magnetoresistance. − In contrast, a number of nitrogen-containing antiperovskites have been successfully synthesized …”

Neutron diffraction study of nitride perovskite LaReN3

“…[7,8] Moreover, prediction of properties such as ferroelectricity in LaWN 3 , suitable bandgaps for photovoltaics in CeMN 3 (M = Ta, Nb), as well as hard ferromagnetism in RReN 3 , sparked interest in these materials. [8][9][10] However, synthesized nitride perovskites ABN 3 are scarce and to date only three materials are reported: bulk-phase ThTaN 3 from 1995, thin-film LaWN 3 with a polar structure from 2021, and bulk-phase LaReN 3 from 2021. [11][12][13] These few reports reflect synthetic challenges rooted in the low formation energies of transition metal nitrides.…”

“…Nitride perovskites ABN 3 have recently gained much attention as theoretical studies have suggested stable compositions based on early heavy transition metals as B‐cations with rare‐earths (R) occupying the A‐sites [7,8] . Moreover, prediction of properties such as ferroelectricity in LaWN 3 , suitable bandgaps for photovoltaics in CeMN 3 (M=Ta, Nb), as well as hard ferromagnetism in RReN 3 , sparked interest in these materials [8–10] . However, synthesized nitride perovskites ABN 3 are scarce and to date only three materials are reported: bulk‐phase ThTaN 3 from 1995, thin‐film LaWN 3 with a polar structure from 2021, and bulk‐phase LaReN 3 from 2021 [11–13] …”