Prediction and identification of point defect fingerprints in
X-ray photoelectron spectra of TiNx with 1.18  ≤ x ≤ 1.37

J 2025

Prediction and identification of point defect fingerprints in X-ray photoelectron spectra of TiNx with 1.18 ≤ x ≤ 1.37

ONDRAČKA, Pavel; Pauline KÜMMERL; Marcus HANS; Stanislav MRÁZ; Daniel PRIMETZHOFER et al.

Základní údaje

Originální název

Prediction and identification of point defect fingerprints in X-ray photoelectron spectra of TiNx with 1.18 ≤ x ≤ 1.37

Autoři

ONDRAČKA, Pavel ; Pauline KÜMMERL; Marcus HANS; Stanislav MRÁZ; Daniel PRIMETZHOFER; David HOLEC; Petr VAŠINA a Jochen M. SCHNEIDER

Vydání

MATERIALS & DESIGN, ELSEVIER SCI LTD, 2025, 0264-1275

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10305 Fluids and plasma physics

Stát vydavatele

Velká Británie a Severní Irsko

Utajení

není předmětem státního či obchodního tajemství

Odkazy

URL

Impakt faktor

Impact factor: 7.900 v roce 2024

Označené pro přenos do RIV

Ano

Kód RIV

RIV/00216224:14310/25:00143599

Organizační jednotka

Přírodovědecká fakulta

Klíčová slova anglicky

TiN; Point defects; XPS; Vacancy quantification; N 1s and Ti2p binding energies; DFT

Štítky

14312030, rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 28. 1. 2026 11:11, Mgr. Marie Novosadová Šípková, DiS.

Anotace

V originále

We investigate the effect of selected N and Ti point defects in B1 TiN on N 1s and Ti 2p3/2 binding energies (BE) through experiments and ab initio calculations. X-ray photoelectron spectroscopy (XPS) measurements of TiNx films with 1.18 ≤ x ≤ 1.37 reveal additional N 1s spectral components at lower binding energies. Ab initio calculations predict that these components are caused by either Ti vacancies, which induce an N 1s BE shift of -0.54 eV in their first N neighbors, and/or N tetrahedral interstitials, which have their N 1s BE shifted by-1.18 eV and shift the BE of their first N neighbors by -0.53 eV. However, based on ab initio data the tetrahedral N interstitial is estimated to be unstable at room temperature. We, therefore, unambiguously attribute the N 1s spectral components at lower BE in Ti-deficient TiNx thin films to the presence of Ti vacancies. Furthermore, it is demonstrated that the vacancy concentration in Al-capped Ti-deficient TiNx can be quantified with the proposed correlative method based on measured and predicted BE data. Our work highlights the potential of ab initio-guided XPS measurements for detecting and quantifying point defects in B1 TiNx.

Návaznosti

LM2023039, projekt VaV

Název: Centrum výzkumu a vývoje plazmatu a nanotechnologických povrchových úprav

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, R&D centre for plasma and nanotechnology surface modifications

90254, velká výzkumná infrastruktura

Název: e-INFRA CZ II

Citovat

ONDRAČKA, Pavel; Pauline KÜMMERL; Marcus HANS; Stanislav MRÁZ; Daniel PRIMETZHOFER; David HOLEC; Petr VAŠINA a Jochen M. SCHNEIDER. Prediction and identification of point defect fingerprints in X-ray photoelectron spectra of TiNx with 1.18 ≤ x ≤ 1.37. MATERIALS & DESIGN. ELSEVIER SCI LTD, 2025, roč. 259, November, s. 1-11. ISSN 0264-1275. Dostupné z: https://doi.org/10.1016/j.matdes.2025.114752.

@article{2550865,
   author = {Ondračka, Pavel and Kümmerl, Pauline and Hans, Marcus and Mráz, Stanislav and Primetzhofer, Daniel and Holec, David and Vašina, Petr and Schneider, Jochen M.},
   article_number = {November},
   doi = {https://doi.org/10.1016/j.matdes.2025.114752},
   keywords = {TiN; Point defects; XPS; Vacancy quantification; N 1s and Ti2p binding energies; DFT},
   language = {eng},
   issn = {0264-1275},
   journal = {MATERIALS & DESIGN},
   title = {Prediction and identification of point defect fingerprints in X-ray photoelectron spectra of TiNx with 1.18 ≤ x ≤ 1.37},
   url = {https://doi.org/10.1016/j.matdes.2025.114752},
   volume = {259},
   year = {2025}
}

TY  - JOUR
ID  - 2550865
AU  - Ondračka, Pavel - Kümmerl, Pauline - Hans, Marcus - Mráz, Stanislav - Primetzhofer, Daniel - Holec, David - Vašina, Petr - Schneider, Jochen M.
PY  - 2025
TI  - Prediction and identification of point defect fingerprints in X-ray photoelectron spectra of TiNx with 1.18 ≤ x ≤ 1.37
JF  - MATERIALS & DESIGN
VL  - 259
IS  - November
SP  - 1-11
EP  - 1-11
PB  - ELSEVIER SCI LTD
SN  - 02641275
KW  - TiN
KW  - Point defects
KW  - XPS
KW  - Vacancy quantification
KW  - N 1s and Ti2p binding energies
KW  - DFT
UR  - https://doi.org/10.1016/j.matdes.2025.114752
N2  - We investigate the effect of selected N and Ti point defects in B1 TiN on N 1s and Ti 2p3/2 binding energies (BE) through experiments and ab initio calculations. X-ray photoelectron spectroscopy (XPS) measurements of TiNx films with 1.18 ≤ x ≤ 1.37 reveal additional N 1s spectral components at lower binding energies. Ab initio calculations predict that these components are caused by either Ti vacancies, which induce an N 1s BE shift of -0.54 eV in their first N neighbors, and/or N tetrahedral interstitials, which have their N 1s BE shifted by-1.18 eV and shift the BE of their first N neighbors by -0.53 eV. However, based on ab initio data the tetrahedral N interstitial is estimated to be unstable at room temperature. We, therefore, unambiguously attribute the N 1s spectral components at lower BE in Ti-deficient TiNx thin films to the presence of Ti vacancies. Furthermore, it is demonstrated that the vacancy concentration in Al-capped Ti-deficient TiNx can be quantified with the proposed correlative method based on measured and predicted BE data. Our work highlights the potential of ab initio-guided XPS measurements for detecting and quantifying point defects in B1 TiNx.
ER  -

ONDRAČKA, Pavel; Pauline KÜMMERL; Marcus HANS; Stanislav MRÁZ; Daniel PRIMETZHOFER; David HOLEC; Petr VAŠINA a Jochen M. SCHNEIDER. Prediction and identification of point defect fingerprints in X-ray photoelectron spectra of TiNx with 1.18 ≤ x ≤ 1.37. \textit{MATERIALS \&{} DESIGN}. ELSEVIER SCI LTD, 2025, roč.~259, November, s.~1-11. ISSN~0264-1275. Dostupné z: https://doi.org/10.1016/j.matdes.2025.114752.

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