57Fe Mössbauer study of epitaxial TiN thin film grown on MgO(100) by magnetron sputtering

B. Qi*, H.P. Gunnlaugsson, A. Mokhles Gerami, H.P. Gislason, S. Ólafsson, F. Magnus, Torben Esmann Mølholt, H. Masenda, A. Tarazaga Martín-Lueugo, A. Bonanni, P.B. Krastev, V. Masondo, I. Unzueta, K. Bharuth-Ram, K. Johnston, D. Naidoo, J. Schell, P. Schaaf

*Corresponding author for this work

    Research output: Contribution to journalJournal articleResearchpeer-review

    Abstract

    The properties and performance of TiN thin films are closely related to the concentration and mobility of lattice defects in the thin film structures of TiN. This makes a local atomic scale study of TiN thin films an ever-growing demand. Emission 57Fe Mössbauer spectroscopy (eMS) is a powerful tool in this regard, which we apply here to study an ultrathin TiN film epitaxially grown on MgO (100). With the help of theoretical calculations, our results show that most implanted Fe ions adopt a 2+ valence state and locate at the Ti sublattice in the bulk-like single crystalline grains, with the rest Fe residing at the grain boundaries as interstitials. A small percentage of nitrogen point defects (vacancy VN and interstitial NI) are observed in the bulk-like crystalline grains. A temperature-dependent, interstitial NI mediated site-exchange between NI and VN inside the crystal grain are deduced via a N2 dimmer like diffusion of NI through the crystal grains in the temperature range of 540 - 620 K. This is interesting in the perspective of exploring the catalytic property of TiN nanostructures. The titanium vacancy (VTi) is only detected at the grain boundaries. Annealing up to 813 K, both the VN and NI are annihilated in the crystalline grains and the VTi is fully recovered with healing of the grain boundaries. However, no evidence of ferromagnetism due to dilute implantation of 57Mn/57Fe and or structural defects in the film is obtained. This suggests that the so far reported dilute magnetism and defect-induced ferromagnetism in TiN nanostructures requires a further systematic investigation.
    Original languageEnglish
    JournalApplied Surface Science
    Volume464
    Pages (from-to)682-691
    ISSN0169-4332
    DOIs
    Publication statusPublished - 2019

    Keywords

    • Mössbauer spectroscopy
    • Epitaxial thin film
    • Defects

    Cite this

    Qi, B., Gunnlaugsson, H. P., Mokhles Gerami, A., Gislason, H. P., Ólafsson, S., Magnus, F., ... Schaaf, P. (2019). 57Fe Mössbauer study of epitaxial TiN thin film grown on MgO(100) by magnetron sputtering. Applied Surface Science, 464, 682-691. https://doi.org/10.1016/j.apsusc.2018.09.107
    Qi, B. ; Gunnlaugsson, H.P. ; Mokhles Gerami, A. ; Gislason, H.P. ; Ólafsson, S. ; Magnus, F. ; Mølholt, Torben Esmann ; Masenda, H. ; Tarazaga Martín-Lueugo, A. ; Bonanni, A. ; Krastev, P.B. ; Masondo, V. ; Unzueta, I. ; Bharuth-Ram, K. ; Johnston, K. ; Naidoo, D. ; Schell, J. ; Schaaf, P. / 57Fe Mössbauer study of epitaxial TiN thin film grown on MgO(100) by magnetron sputtering. In: Applied Surface Science. 2019 ; Vol. 464. pp. 682-691.
    @article{f7f2da664e384d78a1a943515abb485b,
    title = "57Fe M{\"o}ssbauer study of epitaxial TiN thin film grown on MgO(100) by magnetron sputtering",
    abstract = "The properties and performance of TiN thin films are closely related to the concentration and mobility of lattice defects in the thin film structures of TiN. This makes a local atomic scale study of TiN thin films an ever-growing demand. Emission 57Fe M{\"o}ssbauer spectroscopy (eMS) is a powerful tool in this regard, which we apply here to study an ultrathin TiN film epitaxially grown on MgO (100). With the help of theoretical calculations, our results show that most implanted Fe ions adopt a 2+ valence state and locate at the Ti sublattice in the bulk-like single crystalline grains, with the rest Fe residing at the grain boundaries as interstitials. A small percentage of nitrogen point defects (vacancy VN and interstitial NI) are observed in the bulk-like crystalline grains. A temperature-dependent, interstitial NI mediated site-exchange between NI and VN inside the crystal grain are deduced via a N2 dimmer like diffusion of NI through the crystal grains in the temperature range of 540 - 620 K. This is interesting in the perspective of exploring the catalytic property of TiN nanostructures. The titanium vacancy (VTi) is only detected at the grain boundaries. Annealing up to 813 K, both the VN and NI are annihilated in the crystalline grains and the VTi is fully recovered with healing of the grain boundaries. However, no evidence of ferromagnetism due to dilute implantation of 57Mn/57Fe and or structural defects in the film is obtained. This suggests that the so far reported dilute magnetism and defect-induced ferromagnetism in TiN nanostructures requires a further systematic investigation.",
    keywords = "M{\"o}ssbauer spectroscopy, Epitaxial thin film, Defects",
    author = "B. Qi and H.P. Gunnlaugsson and {Mokhles Gerami}, A. and H.P. Gislason and S. {\'O}lafsson and F. Magnus and M{\o}lholt, {Torben Esmann} and H. Masenda and {Tarazaga Mart{\'i}n-Lueugo}, A. and A. Bonanni and P.B. Krastev and V. Masondo and I. Unzueta and K. Bharuth-Ram and K. Johnston and D. Naidoo and J. Schell and P. Schaaf",
    year = "2019",
    doi = "10.1016/j.apsusc.2018.09.107",
    language = "English",
    volume = "464",
    pages = "682--691",
    journal = "Applied Surface Science",
    issn = "0169-4332",
    publisher = "Elsevier",

    }

    Qi, B, Gunnlaugsson, HP, Mokhles Gerami, A, Gislason, HP, Ólafsson, S, Magnus, F, Mølholt, TE, Masenda, H, Tarazaga Martín-Lueugo, A, Bonanni, A, Krastev, PB, Masondo, V, Unzueta, I, Bharuth-Ram, K, Johnston, K, Naidoo, D, Schell, J & Schaaf, P 2019, '57Fe Mössbauer study of epitaxial TiN thin film grown on MgO(100) by magnetron sputtering', Applied Surface Science, vol. 464, pp. 682-691. https://doi.org/10.1016/j.apsusc.2018.09.107

    57Fe Mössbauer study of epitaxial TiN thin film grown on MgO(100) by magnetron sputtering. / Qi, B.; Gunnlaugsson, H.P.; Mokhles Gerami, A.; Gislason, H.P.; Ólafsson, S.; Magnus, F.; Mølholt, Torben Esmann; Masenda, H.; Tarazaga Martín-Lueugo, A.; Bonanni, A.; Krastev, P.B.; Masondo, V.; Unzueta, I.; Bharuth-Ram, K.; Johnston, K.; Naidoo, D.; Schell, J.; Schaaf, P.

    In: Applied Surface Science, Vol. 464, 2019, p. 682-691.

    Research output: Contribution to journalJournal articleResearchpeer-review

    TY - JOUR

    T1 - 57Fe Mössbauer study of epitaxial TiN thin film grown on MgO(100) by magnetron sputtering

    AU - Qi, B.

    AU - Gunnlaugsson, H.P.

    AU - Mokhles Gerami, A.

    AU - Gislason, H.P.

    AU - Ólafsson, S.

    AU - Magnus, F.

    AU - Mølholt, Torben Esmann

    AU - Masenda, H.

    AU - Tarazaga Martín-Lueugo, A.

    AU - Bonanni, A.

    AU - Krastev, P.B.

    AU - Masondo, V.

    AU - Unzueta, I.

    AU - Bharuth-Ram, K.

    AU - Johnston, K.

    AU - Naidoo, D.

    AU - Schell, J.

    AU - Schaaf, P.

    PY - 2019

    Y1 - 2019

    N2 - The properties and performance of TiN thin films are closely related to the concentration and mobility of lattice defects in the thin film structures of TiN. This makes a local atomic scale study of TiN thin films an ever-growing demand. Emission 57Fe Mössbauer spectroscopy (eMS) is a powerful tool in this regard, which we apply here to study an ultrathin TiN film epitaxially grown on MgO (100). With the help of theoretical calculations, our results show that most implanted Fe ions adopt a 2+ valence state and locate at the Ti sublattice in the bulk-like single crystalline grains, with the rest Fe residing at the grain boundaries as interstitials. A small percentage of nitrogen point defects (vacancy VN and interstitial NI) are observed in the bulk-like crystalline grains. A temperature-dependent, interstitial NI mediated site-exchange between NI and VN inside the crystal grain are deduced via a N2 dimmer like diffusion of NI through the crystal grains in the temperature range of 540 - 620 K. This is interesting in the perspective of exploring the catalytic property of TiN nanostructures. The titanium vacancy (VTi) is only detected at the grain boundaries. Annealing up to 813 K, both the VN and NI are annihilated in the crystalline grains and the VTi is fully recovered with healing of the grain boundaries. However, no evidence of ferromagnetism due to dilute implantation of 57Mn/57Fe and or structural defects in the film is obtained. This suggests that the so far reported dilute magnetism and defect-induced ferromagnetism in TiN nanostructures requires a further systematic investigation.

    AB - The properties and performance of TiN thin films are closely related to the concentration and mobility of lattice defects in the thin film structures of TiN. This makes a local atomic scale study of TiN thin films an ever-growing demand. Emission 57Fe Mössbauer spectroscopy (eMS) is a powerful tool in this regard, which we apply here to study an ultrathin TiN film epitaxially grown on MgO (100). With the help of theoretical calculations, our results show that most implanted Fe ions adopt a 2+ valence state and locate at the Ti sublattice in the bulk-like single crystalline grains, with the rest Fe residing at the grain boundaries as interstitials. A small percentage of nitrogen point defects (vacancy VN and interstitial NI) are observed in the bulk-like crystalline grains. A temperature-dependent, interstitial NI mediated site-exchange between NI and VN inside the crystal grain are deduced via a N2 dimmer like diffusion of NI through the crystal grains in the temperature range of 540 - 620 K. This is interesting in the perspective of exploring the catalytic property of TiN nanostructures. The titanium vacancy (VTi) is only detected at the grain boundaries. Annealing up to 813 K, both the VN and NI are annihilated in the crystalline grains and the VTi is fully recovered with healing of the grain boundaries. However, no evidence of ferromagnetism due to dilute implantation of 57Mn/57Fe and or structural defects in the film is obtained. This suggests that the so far reported dilute magnetism and defect-induced ferromagnetism in TiN nanostructures requires a further systematic investigation.

    KW - Mössbauer spectroscopy

    KW - Epitaxial thin film

    KW - Defects

    U2 - 10.1016/j.apsusc.2018.09.107

    DO - 10.1016/j.apsusc.2018.09.107

    M3 - Journal article

    VL - 464

    SP - 682

    EP - 691

    JO - Applied Surface Science

    JF - Applied Surface Science

    SN - 0169-4332

    ER -

    Qi B, Gunnlaugsson HP, Mokhles Gerami A, Gislason HP, Ólafsson S, Magnus F et al. 57Fe Mössbauer study of epitaxial TiN thin film grown on MgO(100) by magnetron sputtering. Applied Surface Science. 2019;464:682-691. https://doi.org/10.1016/j.apsusc.2018.09.107