TEM and DFT Study of Basal-plane Inversion Boundaries in SnO2-doped ZnO
2021
Аутори
Ribić, VesnaRecnik, Aleksander
Drazic, Goran
Podlogar, Matejka
Branković, Zorica
Branković, Goran
Чланак у часопису (Објављена верзија)
Метаподаци
Приказ свих података о документуАпстракт
In our recent study (Ribie et al. 2020) we reported the structure of inversion boundaries (IBs) in Sb2O3 -doped ZnO. Here, we focus on IBs that form in SnO2-doped ZnO. Using atomic resolution scanning transmission electron microscopy (STEM) methods we confirm that in SnO2-doped ZnO the IBs form in head-to-head configuration, where ZnO4 tetrahedra in both ZnO domains point towards the IB plane composed of a close packed layer of octahedrally coordinated Sn and Zn atoms. The in-plane composition is driven by the local charge balance, following Pauling's principle of electroneutrality for ionic crystals, according to which the average oxidation state of cations is 3+. To satisfy this condition, the cation ratio in the IB-layer is Sn4+ : Zn2+ =1:1. This was confirmed by concentric electron probe analysis employing energy dispersive spectroscopy (EDS) showing that Sn atoms occupy 0.504 +/- 0.039 of the IB layer, while the rest of the octahedral sites are occupied by Zn. IBs in SnO2-doped Zn...O occur in the lowest energy, IB3 translation state with the cation sublattice expansion of Delta IB(zn-zn) of +91 pm with corresponding O-sublattice contraction Delta IB(O-O) of -46 pm. Based on quantitative HRTEM and HAADF-STEM analysis of in-plane ordering of Sn and Zn atoms, we identified two types of short-range distributions, (i) zigzag and (ii) stripe. Our density functional theory (DFT) calculations showed that the energy difference between the two arrangements is small (similar to 6 meV) giving rise to their alternation within the octahedral IB layer. As a result, cation ordering intermittently changes its type and the direction to maximize intrinsic entropy of the IB layer driven by the in-plane electroneutrality and 6-fold symmetry restrictions. A long-range in-plane disorder, as shown by our work would enhance quantum well effect to phonon scattering, while Zn2+ located in the IB octahedral sites, would modify the the bandgap, and enhance the in-plane conductivity and concentration of carriers.
Кључне речи:
Thermoelectrics / Sn-doped ZnO / Polarity engineering / Optoelectronics / Inversion domain boundary (IDB)Извор:
Science of Sintering, 2021, 53, 2, 237-252Издавач:
- Međunarodni Institut za nauku o sinterovanju, Beograd
Финансирање / пројекти:
- NSC cluster at IJS (Ljubljana)
- Министарство науке, технолошког развоја и иновација Републике Србије, институционално финансирање - 200053 (Универзитет у Београду, Институт за мултидисциплинарна истраживања) (RS-MESTD-inst-2020-200053)
- Slovenian Research AgencySlovenian Research Agency - Slovenia [P2-0084, J1-9177]
- SlovenianSerbian bilateral Projects [BI-RS/16-17-053, BI-RS/18-19-026]
- European UnionEuropean Commission [823717 ESTEEM3]
DOI: 10.2298/SOS2102237R
ISSN: 0350-820X
WoS: 000691836600008
Scopus: 2-s2.0-85110488912
Институција/група
Institut za multidisciplinarna istraživanjaTY - JOUR AU - Ribić, Vesna AU - Recnik, Aleksander AU - Drazic, Goran AU - Podlogar, Matejka AU - Branković, Zorica AU - Branković, Goran PY - 2021 UR - http://rimsi.imsi.bg.ac.rs/handle/123456789/1471 AB - In our recent study (Ribie et al. 2020) we reported the structure of inversion boundaries (IBs) in Sb2O3 -doped ZnO. Here, we focus on IBs that form in SnO2-doped ZnO. Using atomic resolution scanning transmission electron microscopy (STEM) methods we confirm that in SnO2-doped ZnO the IBs form in head-to-head configuration, where ZnO4 tetrahedra in both ZnO domains point towards the IB plane composed of a close packed layer of octahedrally coordinated Sn and Zn atoms. The in-plane composition is driven by the local charge balance, following Pauling's principle of electroneutrality for ionic crystals, according to which the average oxidation state of cations is 3+. To satisfy this condition, the cation ratio in the IB-layer is Sn4+ : Zn2+ =1:1. This was confirmed by concentric electron probe analysis employing energy dispersive spectroscopy (EDS) showing that Sn atoms occupy 0.504 +/- 0.039 of the IB layer, while the rest of the octahedral sites are occupied by Zn. IBs in SnO2-doped ZnO occur in the lowest energy, IB3 translation state with the cation sublattice expansion of Delta IB(zn-zn) of +91 pm with corresponding O-sublattice contraction Delta IB(O-O) of -46 pm. Based on quantitative HRTEM and HAADF-STEM analysis of in-plane ordering of Sn and Zn atoms, we identified two types of short-range distributions, (i) zigzag and (ii) stripe. Our density functional theory (DFT) calculations showed that the energy difference between the two arrangements is small (similar to 6 meV) giving rise to their alternation within the octahedral IB layer. As a result, cation ordering intermittently changes its type and the direction to maximize intrinsic entropy of the IB layer driven by the in-plane electroneutrality and 6-fold symmetry restrictions. A long-range in-plane disorder, as shown by our work would enhance quantum well effect to phonon scattering, while Zn2+ located in the IB octahedral sites, would modify the the bandgap, and enhance the in-plane conductivity and concentration of carriers. PB - Međunarodni Institut za nauku o sinterovanju, Beograd T2 - Science of Sintering T1 - TEM and DFT Study of Basal-plane Inversion Boundaries in SnO2-doped ZnO EP - 252 IS - 2 SP - 237 VL - 53 DO - 10.2298/SOS2102237R ER -
@article{ author = "Ribić, Vesna and Recnik, Aleksander and Drazic, Goran and Podlogar, Matejka and Branković, Zorica and Branković, Goran", year = "2021", abstract = "In our recent study (Ribie et al. 2020) we reported the structure of inversion boundaries (IBs) in Sb2O3 -doped ZnO. Here, we focus on IBs that form in SnO2-doped ZnO. Using atomic resolution scanning transmission electron microscopy (STEM) methods we confirm that in SnO2-doped ZnO the IBs form in head-to-head configuration, where ZnO4 tetrahedra in both ZnO domains point towards the IB plane composed of a close packed layer of octahedrally coordinated Sn and Zn atoms. The in-plane composition is driven by the local charge balance, following Pauling's principle of electroneutrality for ionic crystals, according to which the average oxidation state of cations is 3+. To satisfy this condition, the cation ratio in the IB-layer is Sn4+ : Zn2+ =1:1. This was confirmed by concentric electron probe analysis employing energy dispersive spectroscopy (EDS) showing that Sn atoms occupy 0.504 +/- 0.039 of the IB layer, while the rest of the octahedral sites are occupied by Zn. IBs in SnO2-doped ZnO occur in the lowest energy, IB3 translation state with the cation sublattice expansion of Delta IB(zn-zn) of +91 pm with corresponding O-sublattice contraction Delta IB(O-O) of -46 pm. Based on quantitative HRTEM and HAADF-STEM analysis of in-plane ordering of Sn and Zn atoms, we identified two types of short-range distributions, (i) zigzag and (ii) stripe. Our density functional theory (DFT) calculations showed that the energy difference between the two arrangements is small (similar to 6 meV) giving rise to their alternation within the octahedral IB layer. As a result, cation ordering intermittently changes its type and the direction to maximize intrinsic entropy of the IB layer driven by the in-plane electroneutrality and 6-fold symmetry restrictions. A long-range in-plane disorder, as shown by our work would enhance quantum well effect to phonon scattering, while Zn2+ located in the IB octahedral sites, would modify the the bandgap, and enhance the in-plane conductivity and concentration of carriers.", publisher = "Međunarodni Institut za nauku o sinterovanju, Beograd", journal = "Science of Sintering", title = "TEM and DFT Study of Basal-plane Inversion Boundaries in SnO2-doped ZnO", pages = "252-237", number = "2", volume = "53", doi = "10.2298/SOS2102237R" }
Ribić, V., Recnik, A., Drazic, G., Podlogar, M., Branković, Z.,& Branković, G.. (2021). TEM and DFT Study of Basal-plane Inversion Boundaries in SnO2-doped ZnO. in Science of Sintering Međunarodni Institut za nauku o sinterovanju, Beograd., 53(2), 237-252. https://doi.org/10.2298/SOS2102237R
Ribić V, Recnik A, Drazic G, Podlogar M, Branković Z, Branković G. TEM and DFT Study of Basal-plane Inversion Boundaries in SnO2-doped ZnO. in Science of Sintering. 2021;53(2):237-252. doi:10.2298/SOS2102237R .
Ribić, Vesna, Recnik, Aleksander, Drazic, Goran, Podlogar, Matejka, Branković, Zorica, Branković, Goran, "TEM and DFT Study of Basal-plane Inversion Boundaries in SnO2-doped ZnO" in Science of Sintering, 53, no. 2 (2021):237-252, https://doi.org/10.2298/SOS2102237R . .