A map of the inorganic ternary metal nitrides

Sun, Wenhao; Bartel, Christopher J.; Arca, Elisabetta; Bauers, Sage R.; Matthews, Bethany E.; Orvañanos, Bernardo; Chen, Bor Rong; Toney, Michael F.; Schelhas, Laura T.; Tumas, William; Tate, Janet; Zakutayev, Andriy; Lany, Stephan; Holder, Aaron M.; Ceder, Gerbrand

doi:10.1038/s41563-019-0396-2

Cited by 349 publications

(399 citation statements)

References 83 publications

(62 reference statements)

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“…The design and discovery of new materials are being rapidly accelerated by the growing availability of density functional theory (DFT) calculated property data in open materials databases, which allow users to systematically retrieve computed results for experimentally known and yet-to-be-realized solid compounds. [1][2][3][4][5][6] The primary properties of interest are the optimized structure and corresponding total energy, E, with, for example, ~50,000,000 compiled structures and energies available via the NOMAD repository. 7 Given E for a set of structures, one can routinely obtain the reaction energy, Erxn, to convert between structures.…”

Section: Introductionmentioning

confidence: 99%

The role of decomposition reactions in assessing first-principles predictions of solid stability

et al. 2019

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The performance of density functional theory (DFT) approximations for predicting materials thermodynamics is typically assessed by comparing calculated and experimentally determined enthalpies of formation from elemental phases, ΔHf. However, a compound competes thermodynamically with both other compounds and their constituent elemental forms, and thus, the enthalpies of the decomposition reactions to these competing phases, ΔHd, determine thermodynamic stability. We evaluated the phase diagrams for 56,791 compounds to classify decomposition reactions into three types: 1. those that produce elemental phases, 2. those that produce compounds, and 3. those that produce both. This analysis shows that the decomposition into elemental forms is rarely the competing reaction that determines compound stability and that approximately two-thirds of decomposition reactions involve no elemental phases. Using experimentally reported formation enthalpies for 1,012 solid compounds, we assess the accuracy of the generalized gradient approximation (GGA) (PBE) and meta-GGA (SCAN) density functionals for predicting compound stability. For 646 decomposition reactions that are not trivially the formation reaction, PBE [mean absolute difference between theory and experiment (MAD) = 70 meV/atom] and SCAN (MAD = 59 meV/atom) perform similarly, and commonly employed correction schemes using fitted elemental reference energies make only a negligible improvement (~2 meV/atom). Furthermore, for 231 reactions involving only compounds (Type 2), the agreement between SCAN, PBE, and experiment is within ~35 meV/atom and is thus comparable to the magnitude of experimental uncertainty.

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Section: Introductionmentioning

confidence: 99%

The role of decomposition reactions in assessing first-principles predictions of solid stability

et al. 2019

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“…Possible reasons are the strength of the nitrogen triple bond, making nitrides generally more difficult to synthesize than oxides, and the relative metal-nitrogen bond strength, making them more metastable than any other material family [6] [7]. As a result, there are a large number of nitride materials that have yet to be experimentally synthesized, many of which are predicted to have favorable optical, electronic, thermal, and mechanical properties [8] [9]. Several predicted ternary nitrides have recently been synthesized [10].…”

Section: Introductionmentioning

confidence: 99%

Thin Film Synthesis of Semiconductors in the Mg–Sb–N Materials System

et al. 2019

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Nitrides feature many interesting properties, such as a wide range of bandgaps suitable for optoelectronic devices including light-emitting diodes (LEDs), and piezoelectric response used in microelectromechanical systems (MEMS). Nitrides are also significantly underexplored compared to oxides and other chemistries, with many being thermochemically metastable, sparking interest from a basic science point of view. This paper reports on experimental and computational exploration of the Mg-Sb-N material system, featuring both metastable materials and interesting semiconducting properties. Using sputter deposition, we discovered a new Mg2SbN3 nitride with a wurtzite-derived crystal structure and synthesized the antimonide-nitride Mg3SbN with an antiperovskite crystal structure for the first time in thin film form. Theoretical calculations indicate that Mg2SbN3 is metastable and has properties relevant to LEDs and MEMS, whereas Mg3SbN has a large dielectric constant (28e0) and low hole effective masses (0.9m0), of interest for photovoltaic solar cell absorbers. The experimental solar-matched 1.3 eV optical absorption onset of the Mg3SbN antiperovskite agrees with the theoretical prediction (1.3 eV direct, 1.1 eV indirect), and with the measurements of room-temperature near-bandgap photoluminescence. These results make an important contribution towards understanding semiconductor properties and chemical trends in the Mg-Sb-N materials system, paving the way to future practical applications of these novel materials.

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“…Under high pressure, metal nitrides have attractive physical and chemical characteristics, such as good superconductivity, good magnetism, good hardness, and a particular catalytic performance [5][6][7][8] . Metallic nitrides are conducive to optoelectronic and defect-tolerance characteristics and have strong metal-nitrogen bonds for structural stability and mechanical stiffness 9 . Particularly, the compression of N-rich nitrides has been recommend as an alternative method to obtain metallic atomic nitrogen states as high-energy density materials since the laser-heated diamond anvil cell, which is a powerful tool, has been used to synthesize a series of stable monatomic forms of solid nitrogen [10][11][12][13] .…”

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Formation mechanism of insensitive tellurium hexanitride with armchair-like cyclo-N6 anions

Liu

Zhuang

et al. 2020

Commun Chem

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The lower decomposition barriers of cyclo-N 6 anions hinder their application as high-energydensity materials. Here, first-principles calculations and molecular dynamics simulations reveal that enhancing the covalent component of the interaction between cyclo-N 6 anions and cations can effectively improve the stability of cyclo-N 6 anions. Taking tellurium hexanitride as a representative, the exotic armchair-like N 6 anions of tellurium hexanitride exhibit resistance towards electronic attack and gain extra stability through the formation of covalent bonds with the surrounding elemental tellurium under high pressures. These covalent bonds effectively improve the chemical barrier and insensitivity of tellurium hexanitride during blasting, which prevents the decomposition of solid cyclo-N 6 salts into molecular nitrogen. Furthermore, the high-pressure induced covalent bonds between cyclo-N 6 anions and tellurium enable the high bulk modulus, remarkable detonation performance, and hightemperature thermodynamic stability of tellurium hexanitride.

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A map of the inorganic ternary metal nitrides

Cited by 349 publications

References 83 publications

The role of decomposition reactions in assessing first-principles predictions of solid stability

The role of decomposition reactions in assessing first-principles predictions of solid stability

Thin Film Synthesis of Semiconductors in the Mg–Sb–N Materials System

Formation mechanism of insensitive tellurium hexanitride with armchair-like cyclo-N6 anions

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