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Chemical Interaction of Hydrogen Radicals (H*) with Transition Metal Nitrides

[Image: see text] Transition metal nitrides (TMNs) are reported as protective coatings in reactive hydrogen environments. Although the permeation of H(2) through TMN coatings is well reported, their reducibility in H* environments is less investigated. In this work, we categorize the interaction of...

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Autores principales: Rehman, Abdul, van de Kruijs, Robbert W. E., van den Beld, Wesley T. E., Sturm, Jacobus M., Ackermann, Marcelo
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10510390/
https://www.ncbi.nlm.nih.gov/pubmed/37736296
http://dx.doi.org/10.1021/acs.jpcc.3c04490
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author Rehman, Abdul
van de Kruijs, Robbert W. E.
van den Beld, Wesley T. E.
Sturm, Jacobus M.
Ackermann, Marcelo
author_facet Rehman, Abdul
van de Kruijs, Robbert W. E.
van den Beld, Wesley T. E.
Sturm, Jacobus M.
Ackermann, Marcelo
author_sort Rehman, Abdul
collection PubMed
description [Image: see text] Transition metal nitrides (TMNs) are reported as protective coatings in reactive hydrogen environments. Although the permeation of H(2) through TMN coatings is well reported, their reducibility in H* environments is less investigated. In this work, we categorize the interaction of H* with ambient exposed TiN, ZrN, HfN, VN, NbN, and TaN thin films at 700 °C into three classes. We find that in TiN and VN samples, H*-induced reduction was limited to the surface (≈ top 2 nm). Significant denitridation was observed in ZrN and HfN samples beneath the surface, along with an increase in the transition metal oxide (TMO(x)) fraction. Denitridation was observed in NbN and TaN samples as well, but the increase in the TMO(x) content was less than for ZrN and HfN. We propose a model in three steps: hydrogenation, formation of volatile species, and diffusion of subsurface atoms to the surface. We show that the interaction of H* with TiN, ZrN, HfN, VN, NbN, and TaN with partially oxidized surfaces can be explained using the preferred hydrogenation pathway (based on the work functions) and the thermodynamic driver for forming volatile species (NH(3) and H(2)O; based on the change in Gibbs free energy).
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spelling pubmed-105103902023-09-21 Chemical Interaction of Hydrogen Radicals (H*) with Transition Metal Nitrides Rehman, Abdul van de Kruijs, Robbert W. E. van den Beld, Wesley T. E. Sturm, Jacobus M. Ackermann, Marcelo J Phys Chem C Nanomater Interfaces [Image: see text] Transition metal nitrides (TMNs) are reported as protective coatings in reactive hydrogen environments. Although the permeation of H(2) through TMN coatings is well reported, their reducibility in H* environments is less investigated. In this work, we categorize the interaction of H* with ambient exposed TiN, ZrN, HfN, VN, NbN, and TaN thin films at 700 °C into three classes. We find that in TiN and VN samples, H*-induced reduction was limited to the surface (≈ top 2 nm). Significant denitridation was observed in ZrN and HfN samples beneath the surface, along with an increase in the transition metal oxide (TMO(x)) fraction. Denitridation was observed in NbN and TaN samples as well, but the increase in the TMO(x) content was less than for ZrN and HfN. We propose a model in three steps: hydrogenation, formation of volatile species, and diffusion of subsurface atoms to the surface. We show that the interaction of H* with TiN, ZrN, HfN, VN, NbN, and TaN with partially oxidized surfaces can be explained using the preferred hydrogenation pathway (based on the work functions) and the thermodynamic driver for forming volatile species (NH(3) and H(2)O; based on the change in Gibbs free energy). American Chemical Society 2023-09-06 /pmc/articles/PMC10510390/ /pubmed/37736296 http://dx.doi.org/10.1021/acs.jpcc.3c04490 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Rehman, Abdul
van de Kruijs, Robbert W. E.
van den Beld, Wesley T. E.
Sturm, Jacobus M.
Ackermann, Marcelo
Chemical Interaction of Hydrogen Radicals (H*) with Transition Metal Nitrides
title Chemical Interaction of Hydrogen Radicals (H*) with Transition Metal Nitrides
title_full Chemical Interaction of Hydrogen Radicals (H*) with Transition Metal Nitrides
title_fullStr Chemical Interaction of Hydrogen Radicals (H*) with Transition Metal Nitrides
title_full_unstemmed Chemical Interaction of Hydrogen Radicals (H*) with Transition Metal Nitrides
title_short Chemical Interaction of Hydrogen Radicals (H*) with Transition Metal Nitrides
title_sort chemical interaction of hydrogen radicals (h*) with transition metal nitrides
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10510390/
https://www.ncbi.nlm.nih.gov/pubmed/37736296
http://dx.doi.org/10.1021/acs.jpcc.3c04490
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