Anisotropy of the Electric Field Gradient in Two-Dimensional α-MoO<sub>3</sub> Investigated by <sup>57</sup>Mn(<sup>57</sup>Fe) Emission Mössbauer Spectroscopy
Van der Waals α-MoO<sub>3</sub> samples offer a wide range of attractive catalytic, electronic, and optical properties. We present herein an emission Mössbauer spectroscopy (eMS) study of the electric-field gradient (EFG) anisotropy in crystalline free-standing α-MoO<sub>3</sub&...
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MDPI AG
2022-07-01
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| Series: | Crystals |
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| author | Juliana Schell Dmitry Zyabkin Krish Bharuth-Ram João N. Gonçalves Carlos Díaz-Guerra Haraldur P. Gunnlaugsson Aitana Tarazaga Martín-Luengo Peter Schaaf Alberta Bonanni Hilary Masenda Thien Thanh Dang Torben E. Mølholt Sveinn Ólafsson Iraultza Unzueta Roberto Mantovan Karl Johnston Hafliði P. Gíslason Petko B. Krastev Deena Naidoo Bingcui Qi |
| author_facet | Juliana Schell Dmitry Zyabkin Krish Bharuth-Ram João N. Gonçalves Carlos Díaz-Guerra Haraldur P. Gunnlaugsson Aitana Tarazaga Martín-Luengo Peter Schaaf Alberta Bonanni Hilary Masenda Thien Thanh Dang Torben E. Mølholt Sveinn Ólafsson Iraultza Unzueta Roberto Mantovan Karl Johnston Hafliði P. Gíslason Petko B. Krastev Deena Naidoo Bingcui Qi |
| author_sort | Juliana Schell |
| collection | DOAJ |
| description | Van der Waals α-MoO<sub>3</sub> samples offer a wide range of attractive catalytic, electronic, and optical properties. We present herein an emission Mössbauer spectroscopy (eMS) study of the electric-field gradient (EFG) anisotropy in crystalline free-standing α-MoO<sub>3</sub> samples. Although α-MoO<sub>3</sub> is a two-dimensional (2D) material, scanning electron microscopy shows that the crystals are 0.5–5-µm thick. The combination of X-ray diffraction and micro-Raman spectroscopy, performed after sample preparation, provided evidence of the phase purity and crystal quality of the samples. The eMS measurements were conducted following the implantation of <sup>57</sup>Mn (<i>t</i><sub>1/2</sub> = 1.5 min), which decays to the <sup>57</sup>Fe, 14.4 keV Mössbauer state. The eMS spectra of the samples are dominated by a paramagnetic doublet (D1) with an angular dependence, pointing to the Fe<sup>2+</sup> probe ions being in a crystalline environment. It is attributed to an asymmetric EFG at the eMS probe site originating from strong in-plane covalent bonds and weak out-of-plane van der Waals interactions in the 2D material. Moreover, a second broad component, D2, can be assigned to Fe<sup>3+</sup> defects that are dynamically generated during the online measurements. The results are compared to ab initio simulations and are discussed in terms of the in-plane and out-of-plane interactions in the system. |
| first_indexed | 2024-03-09T10:20:45Z |
| format | Article |
| id | doaj.art-df04a760a38943e5bf402682fc167b61 |
| institution | Directory Open Access Journal |
| issn | 2073-4352 |
| language | English |
| last_indexed | 2024-03-09T10:20:45Z |
| publishDate | 2022-07-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Crystals |
| spelling | doaj.art-df04a760a38943e5bf402682fc167b612023-12-01T22:02:31ZengMDPI AGCrystals2073-43522022-07-0112794210.3390/cryst12070942Anisotropy of the Electric Field Gradient in Two-Dimensional α-MoO<sub>3</sub> Investigated by <sup>57</sup>Mn(<sup>57</sup>Fe) Emission Mössbauer SpectroscopyJuliana Schell0Dmitry Zyabkin1Krish Bharuth-Ram2João N. Gonçalves3Carlos Díaz-Guerra4Haraldur P. Gunnlaugsson5Aitana Tarazaga Martín-Luengo6Peter Schaaf7Alberta Bonanni8Hilary Masenda9Thien Thanh Dang10Torben E. Mølholt11Sveinn Ólafsson12Iraultza Unzueta13Roberto Mantovan14Karl Johnston15Hafliði P. Gíslason16Petko B. Krastev17Deena Naidoo18Bingcui Qi19European Organization for Nuclear Research (CERN), 1211 Geneva, SwitzerlandChair Materials for Electrical Engineering and Electronics, Institute of Materials Science and Engineering, Institute of Micro and Nanotechnologies MacroNano<sup>®</sup>, TU Ilmenau, Gustav-Kirchhoff-Strasse 5, 98693 Ilmenau, GermanySchool of Chemistry and Physics, University of KwaZulu-Natal, Durban 4001, South AfricaCICECO—Aveiro Institute of Materials and Departamento de Física, Universidade de Aveiro, 3810-193 Aveiro, PortugalDepartmento Física de Materiales, Facultad de Ciencias Físicas, Universidad Complutense de Madrid, 28040 Madrid, SpainScience Institute, University of Iceland, Dunhaga 3, 107 Reykjavík, IcelandQuantum Materials Group, Institute for Semiconductor and Solid State Physics, Johannes Kepler University, Altenbergerstr. 69, 4040 Linz, AustriaChair Materials for Electrical Engineering and Electronics, Institute of Materials Science and Engineering, Institute of Micro and Nanotechnologies MacroNano<sup>®</sup>, TU Ilmenau, Gustav-Kirchhoff-Strasse 5, 98693 Ilmenau, GermanyQuantum Materials Group, Institute for Semiconductor and Solid State Physics, Johannes Kepler University, Altenbergerstr. 69, 4040 Linz, AustriaSchool of Physics, University of the Witwatersrand, Johannesburg 2050, South AfricaInstitute for Materials Science and Center for Nanointegration Duisburg-Essen (CENIDE), University of Duisburg-Essen, 45141 Essen, GermanyEuropean Organization for Nuclear Research (CERN), 1211 Geneva, SwitzerlandScience Institute, University of Iceland, Dunhaga 3, 107 Reykjavík, IcelandDepartment of Applied Mathematics, University of the Basque Country (UPV/EHU), Torres Quevedo Ingeniaria Plaza 1, 48013 Bilbao, SpainCNR-IMM, Unit of Agrate Brianza, Via Olivetti 2, 20864 Agrate Brianza (MB), ItalyEuropean Organization for Nuclear Research (CERN), 1211 Geneva, SwitzerlandScience Institute, University of Iceland, Dunhaga 3, 107 Reykjavík, IcelandInstitute for Nuclear Research and Nuclear Energy, Bulgarian Academy of Sciences, 72 Tsarigradsko Chaussee Boulevard, 1784 Sofia, BulgariaSchool of Physics, University of the Witwatersrand, Johannesburg 2050, South AfricaScience Institute, University of Iceland, Dunhaga 3, 107 Reykjavík, IcelandVan der Waals α-MoO<sub>3</sub> samples offer a wide range of attractive catalytic, electronic, and optical properties. We present herein an emission Mössbauer spectroscopy (eMS) study of the electric-field gradient (EFG) anisotropy in crystalline free-standing α-MoO<sub>3</sub> samples. Although α-MoO<sub>3</sub> is a two-dimensional (2D) material, scanning electron microscopy shows that the crystals are 0.5–5-µm thick. The combination of X-ray diffraction and micro-Raman spectroscopy, performed after sample preparation, provided evidence of the phase purity and crystal quality of the samples. The eMS measurements were conducted following the implantation of <sup>57</sup>Mn (<i>t</i><sub>1/2</sub> = 1.5 min), which decays to the <sup>57</sup>Fe, 14.4 keV Mössbauer state. The eMS spectra of the samples are dominated by a paramagnetic doublet (D1) with an angular dependence, pointing to the Fe<sup>2+</sup> probe ions being in a crystalline environment. It is attributed to an asymmetric EFG at the eMS probe site originating from strong in-plane covalent bonds and weak out-of-plane van der Waals interactions in the 2D material. Moreover, a second broad component, D2, can be assigned to Fe<sup>3+</sup> defects that are dynamically generated during the online measurements. The results are compared to ab initio simulations and are discussed in terms of the in-plane and out-of-plane interactions in the system.https://www.mdpi.com/2073-4352/12/7/942α-MoO<sub>3</sub>emission Mössbauer spectroscopytwo-dimensional (2D) materialab initio simulations |
| spellingShingle | Juliana Schell Dmitry Zyabkin Krish Bharuth-Ram João N. Gonçalves Carlos Díaz-Guerra Haraldur P. Gunnlaugsson Aitana Tarazaga Martín-Luengo Peter Schaaf Alberta Bonanni Hilary Masenda Thien Thanh Dang Torben E. Mølholt Sveinn Ólafsson Iraultza Unzueta Roberto Mantovan Karl Johnston Hafliði P. Gíslason Petko B. Krastev Deena Naidoo Bingcui Qi Anisotropy of the Electric Field Gradient in Two-Dimensional α-MoO<sub>3</sub> Investigated by <sup>57</sup>Mn(<sup>57</sup>Fe) Emission Mössbauer Spectroscopy Crystals α-MoO<sub>3</sub> emission Mössbauer spectroscopy two-dimensional (2D) material ab initio simulations |
| title | Anisotropy of the Electric Field Gradient in Two-Dimensional α-MoO<sub>3</sub> Investigated by <sup>57</sup>Mn(<sup>57</sup>Fe) Emission Mössbauer Spectroscopy |
| title_full | Anisotropy of the Electric Field Gradient in Two-Dimensional α-MoO<sub>3</sub> Investigated by <sup>57</sup>Mn(<sup>57</sup>Fe) Emission Mössbauer Spectroscopy |
| title_fullStr | Anisotropy of the Electric Field Gradient in Two-Dimensional α-MoO<sub>3</sub> Investigated by <sup>57</sup>Mn(<sup>57</sup>Fe) Emission Mössbauer Spectroscopy |
| title_full_unstemmed | Anisotropy of the Electric Field Gradient in Two-Dimensional α-MoO<sub>3</sub> Investigated by <sup>57</sup>Mn(<sup>57</sup>Fe) Emission Mössbauer Spectroscopy |
| title_short | Anisotropy of the Electric Field Gradient in Two-Dimensional α-MoO<sub>3</sub> Investigated by <sup>57</sup>Mn(<sup>57</sup>Fe) Emission Mössbauer Spectroscopy |
| title_sort | anisotropy of the electric field gradient in two dimensional α moo sub 3 sub investigated by sup 57 sup mn sup 57 sup fe emission mossbauer spectroscopy |
| topic | α-MoO<sub>3</sub> emission Mössbauer spectroscopy two-dimensional (2D) material ab initio simulations |
| url | https://www.mdpi.com/2073-4352/12/7/942 |
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