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Doping of TiO2 nanotubes with nitrogen by annealing in ammonia for visible light activation: Influence of pre- and post-annealing in air

Authorized Users Only
2019
Authors
Bjelajac, Anđelika
Petrović, Rada
Popović, Maja
Rakočević, Zlatko Lj.
Socol, Gabriel
Mihailescu, Ion N.
Janaćković, Đorđe
Article (Published version)
Metadata
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Abstract
The similar to 60 nm wide and similar to 2 mu m long TiO2 nanotubes were obtained by anodization of Ti films sputtered on F-doped tin oxide glass. For N-doping the samples were annealed in ammonia atmosphere. The effect of pre- and post-annealing in air on the nature and amount of incorporated N was studied by X-ray photoelectron spectroscopy. By measuring the absorption spectra of the obtained samples and interpreting the corresponding Tauc plots it was shown that the sample annealed just in ammonia showed the highest visible light absorption even after sputtering cleaning and a decrease of N amount from 3.8% to 1%. Pre and/or post annealing in air led to smaller amount of incorporated N, that caused less pronounced absorption enhancement and smaller band gap narrowing compared to the sample annealed only in ammonia. By fitting of N 1 s line, the contribution that was assigned to substitutional N was detected only in the samples that did not sustained post-annealing. The study showed ...that post-annealing in air might lead to partial conversion of N atoms in TiO2 to oxidized nitrogen species that are easily removed with sputtering. It is also possible that substitutional nitrogen was suppressed by oxygen from air to move to interstitial site. Weakly bonded NOx surface species, which are cleaned away by sputtering, can be removed by post-annealing in air. Those surface species could act as sensitizers and when their amounts are reduced, the core absorption properties, as a result of interstitial incorporation of N in TiO2 structure, were revealed. Much lower visible light sensitization was achieved in the case of pre-annealed sample in comparison to sample without pre-annealing, regardless the same quantity and type of incorporated nitrogen.

Keywords:
Titania / Nanotubes / Nitrogen doping / Thermal annealing / X-ray photoelectron spectroscopy / Diffuse reflectance spectroscopy / Band gap
Source:
Thin Solid Films, 2019, 692
Publisher:
  • Elsevier Science Sa, Lausanne
Funding / projects:
  • UEFISCDI [304/2011]
  • Synthesis, processing and applications of nanostructured multifunctional materials with defined properties (RS-45019)
  • Functional, Functionalized and Advanced Nanomaterials (RS-45005)
Note:
  • Peer-reviewed manuscript: http://TechnoRep.tmf.bg.ac.rs/handle/123456789/5027
Related info:
  • Version of
    http://TechnoRep.tmf.bg.ac.rs/handle/123456789/5027

DOI: 10.1016/j.tsf.2019.137598

ISSN: 0040-6090

WoS: 000499678700011

Scopus: 2-s2.0-85073690107
[ Google Scholar ]
9
10
URI
http://TechnoRep.tmf.bg.ac.rs/handle/123456789/4092
Collections
  • Radovi istraživača / Researchers’ publications (TMF)
  • Radovi istraživača (Inovacioni centar) / Researchers’ publications (Innovation Centre)
Institution/Community
Tehnološko-metalurški fakultet
TY  - JOUR
AU  - Bjelajac, Anđelika
AU  - Petrović, Rada
AU  - Popović, Maja
AU  - Rakočević, Zlatko Lj.
AU  - Socol, Gabriel
AU  - Mihailescu, Ion N.
AU  - Janaćković, Đorđe
PY  - 2019
UR  - http://TechnoRep.tmf.bg.ac.rs/handle/123456789/4092
AB  - The similar to 60 nm wide and similar to 2 mu m long TiO2 nanotubes were obtained by anodization of Ti films sputtered on F-doped tin oxide glass. For N-doping the samples were annealed in ammonia atmosphere. The effect of pre- and post-annealing in air on the nature and amount of incorporated N was studied by X-ray photoelectron spectroscopy. By measuring the absorption spectra of the obtained samples and interpreting the corresponding Tauc plots it was shown that the sample annealed just in ammonia showed the highest visible light absorption even after sputtering cleaning and a decrease of N amount from 3.8% to 1%. Pre and/or post annealing in air led to smaller amount of incorporated N, that caused less pronounced absorption enhancement and smaller band gap narrowing compared to the sample annealed only in ammonia. By fitting of N 1 s line, the contribution that was assigned to substitutional N was detected only in the samples that did not sustained post-annealing. The study showed that post-annealing in air might lead to partial conversion of N atoms in TiO2 to oxidized nitrogen species that are easily removed with sputtering. It is also possible that substitutional nitrogen was suppressed by oxygen from air to move to interstitial site. Weakly bonded NOx surface species, which are cleaned away by sputtering, can be removed by post-annealing in air. Those surface species could act as sensitizers and when their amounts are reduced, the core absorption properties, as a result of interstitial incorporation of N in TiO2 structure, were revealed. Much lower visible light sensitization was achieved in the case of pre-annealed sample in comparison to sample without pre-annealing, regardless the same quantity and type of incorporated nitrogen.
PB  - Elsevier Science Sa, Lausanne
T2  - Thin Solid Films
T1  - Doping of TiO2 nanotubes with nitrogen by annealing in ammonia for visible light activation: Influence of pre- and post-annealing in air
VL  - 692
DO  - 10.1016/j.tsf.2019.137598
ER  - 
@article{
author = "Bjelajac, Anđelika and Petrović, Rada and Popović, Maja and Rakočević, Zlatko Lj. and Socol, Gabriel and Mihailescu, Ion N. and Janaćković, Đorđe",
year = "2019",
abstract = "The similar to 60 nm wide and similar to 2 mu m long TiO2 nanotubes were obtained by anodization of Ti films sputtered on F-doped tin oxide glass. For N-doping the samples were annealed in ammonia atmosphere. The effect of pre- and post-annealing in air on the nature and amount of incorporated N was studied by X-ray photoelectron spectroscopy. By measuring the absorption spectra of the obtained samples and interpreting the corresponding Tauc plots it was shown that the sample annealed just in ammonia showed the highest visible light absorption even after sputtering cleaning and a decrease of N amount from 3.8% to 1%. Pre and/or post annealing in air led to smaller amount of incorporated N, that caused less pronounced absorption enhancement and smaller band gap narrowing compared to the sample annealed only in ammonia. By fitting of N 1 s line, the contribution that was assigned to substitutional N was detected only in the samples that did not sustained post-annealing. The study showed that post-annealing in air might lead to partial conversion of N atoms in TiO2 to oxidized nitrogen species that are easily removed with sputtering. It is also possible that substitutional nitrogen was suppressed by oxygen from air to move to interstitial site. Weakly bonded NOx surface species, which are cleaned away by sputtering, can be removed by post-annealing in air. Those surface species could act as sensitizers and when their amounts are reduced, the core absorption properties, as a result of interstitial incorporation of N in TiO2 structure, were revealed. Much lower visible light sensitization was achieved in the case of pre-annealed sample in comparison to sample without pre-annealing, regardless the same quantity and type of incorporated nitrogen.",
publisher = "Elsevier Science Sa, Lausanne",
journal = "Thin Solid Films",
title = "Doping of TiO2 nanotubes with nitrogen by annealing in ammonia for visible light activation: Influence of pre- and post-annealing in air",
volume = "692",
doi = "10.1016/j.tsf.2019.137598"
}
Bjelajac, A., Petrović, R., Popović, M., Rakočević, Z. Lj., Socol, G., Mihailescu, I. N.,& Janaćković, Đ.. (2019). Doping of TiO2 nanotubes with nitrogen by annealing in ammonia for visible light activation: Influence of pre- and post-annealing in air. in Thin Solid Films
Elsevier Science Sa, Lausanne., 692.
https://doi.org/10.1016/j.tsf.2019.137598
Bjelajac A, Petrović R, Popović M, Rakočević ZL, Socol G, Mihailescu IN, Janaćković Đ. Doping of TiO2 nanotubes with nitrogen by annealing in ammonia for visible light activation: Influence of pre- and post-annealing in air. in Thin Solid Films. 2019;692.
doi:10.1016/j.tsf.2019.137598 .
Bjelajac, Anđelika, Petrović, Rada, Popović, Maja, Rakočević, Zlatko Lj., Socol, Gabriel, Mihailescu, Ion N., Janaćković, Đorđe, "Doping of TiO2 nanotubes with nitrogen by annealing in ammonia for visible light activation: Influence of pre- and post-annealing in air" in Thin Solid Films, 692 (2019),
https://doi.org/10.1016/j.tsf.2019.137598 . .

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