Vacancy Formation and Clustering Behavior in <i>δ</i>-MoN: A Systematic Density Functional Theory Study

Molybdenum nitrides are known to have a series of excellent physical properties owing to their unique bonding nature and electronic structure. However, the synthesized samples often exist in nonstoichiometric phases with structural defects (metal or non-metal vacancies), which may influence their pe...

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Main Authors: Jing Yu, Keda Wang
Format: Article
Language:English
Published: MDPI AG 2025-05-01
Series:Nanomaterials
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Online Access:https://www.mdpi.com/2079-4991/15/11/810
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author Jing Yu
Keda Wang
author_facet Jing Yu
Keda Wang
author_sort Jing Yu
collection DOAJ
description Molybdenum nitrides are known to have a series of excellent physical properties owing to their unique bonding nature and electronic structure. However, the synthesized samples often exist in nonstoichiometric phases with structural defects (metal or non-metal vacancies), which may influence their performance. Based on the density functional theory, we theoretically studied the vacancy formation in <i>δ</i>-MoN. Various configurations that contained one single vacancy, divacancies, or trivacancies were constructed and systematically studied. It was found that Mo vacancy leads to significant electron loss at the vacant site while N vacancy results in excess electrons being trapped, forming a uniform electron gas region. Detailed analysis revealed that four types of binding clusters are encouraged to form in <i>δ</i>-MoN. The <i>V</i><sub>Mo</sub>–<i>V</i><sub>N</sub> or <i>V</i><sub>N</sub>–<i>V</i><sub>Mo</sub>–<i>V</i><sub>N</sub> (with a sandwich structure) binding is owing to the positive and negative interaction between Mo and N vacancies. The <i>V</i><sub>N</sub>–<i>V</i><sub>N</sub> or <i>V</i><sub>N</sub>–<i>V</i><sub>N</sub>–<i>V</i><sub>N</sub> binding is attributed to the overlap of electron density, but requires N vacancies to be distributed in a specific arrangement. Both Mo and N vacancies induce the anisotropic degradation of electronic conductivity in <i>δ</i>-MoN, with the extent of degradation governed by the vacancy type and concentration.
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spelling doaj-art-779b53b2a44f4e30b2fabdd8da9bd19e2025-08-20T03:46:49ZengMDPI AGNanomaterials2079-49912025-05-01151181010.3390/nano15110810Vacancy Formation and Clustering Behavior in <i>δ</i>-MoN: A Systematic Density Functional Theory StudyJing Yu0Keda Wang1College of Food and Pharmaceutical Engineering, Suihua University, Suihua 152061, ChinaEngineering Technology Center of Corn Processing and By-Products Biochemical Utilization, Suihua University, Suihua 152061, ChinaMolybdenum nitrides are known to have a series of excellent physical properties owing to their unique bonding nature and electronic structure. However, the synthesized samples often exist in nonstoichiometric phases with structural defects (metal or non-metal vacancies), which may influence their performance. Based on the density functional theory, we theoretically studied the vacancy formation in <i>δ</i>-MoN. Various configurations that contained one single vacancy, divacancies, or trivacancies were constructed and systematically studied. It was found that Mo vacancy leads to significant electron loss at the vacant site while N vacancy results in excess electrons being trapped, forming a uniform electron gas region. Detailed analysis revealed that four types of binding clusters are encouraged to form in <i>δ</i>-MoN. The <i>V</i><sub>Mo</sub>–<i>V</i><sub>N</sub> or <i>V</i><sub>N</sub>–<i>V</i><sub>Mo</sub>–<i>V</i><sub>N</sub> (with a sandwich structure) binding is owing to the positive and negative interaction between Mo and N vacancies. The <i>V</i><sub>N</sub>–<i>V</i><sub>N</sub> or <i>V</i><sub>N</sub>–<i>V</i><sub>N</sub>–<i>V</i><sub>N</sub> binding is attributed to the overlap of electron density, but requires N vacancies to be distributed in a specific arrangement. Both Mo and N vacancies induce the anisotropic degradation of electronic conductivity in <i>δ</i>-MoN, with the extent of degradation governed by the vacancy type and concentration.https://www.mdpi.com/2079-4991/15/11/810vacancy<i>δ</i>-MoNbondingelectronic structuredensity functional theory
spellingShingle Jing Yu
Keda Wang
Vacancy Formation and Clustering Behavior in <i>δ</i>-MoN: A Systematic Density Functional Theory Study
Nanomaterials
vacancy
<i>δ</i>-MoN
bonding
electronic structure
density functional theory
title Vacancy Formation and Clustering Behavior in <i>δ</i>-MoN: A Systematic Density Functional Theory Study
title_full Vacancy Formation and Clustering Behavior in <i>δ</i>-MoN: A Systematic Density Functional Theory Study
title_fullStr Vacancy Formation and Clustering Behavior in <i>δ</i>-MoN: A Systematic Density Functional Theory Study
title_full_unstemmed Vacancy Formation and Clustering Behavior in <i>δ</i>-MoN: A Systematic Density Functional Theory Study
title_short Vacancy Formation and Clustering Behavior in <i>δ</i>-MoN: A Systematic Density Functional Theory Study
title_sort vacancy formation and clustering behavior in i δ i mon a systematic density functional theory study
topic vacancy
<i>δ</i>-MoN
bonding
electronic structure
density functional theory
url https://www.mdpi.com/2079-4991/15/11/810
work_keys_str_mv AT jingyu vacancyformationandclusteringbehaviorinidimonasystematicdensityfunctionaltheorystudy
AT kedawang vacancyformationandclusteringbehaviorinidimonasystematicdensityfunctionaltheorystudy