New inversion boundary structure in Sb-doped ZnO predicted by DFT calculations and confirmed by experimental HRTEM

Ribić, Vesna; Rečnik, Aleksander; Komelj, Matej; Kokalj, Anton; Branković, Zorica; Zlatović, Mario; Branković, Goran

doi:10.1016/j.actamat.2020.08.035

Cited by 19 publications

(21 citation statements)

References 61 publications

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“…The d IB(Zn-Zn) distance, 1 measured from several STEM images, normalized to bulk ZnO, amounts to 6.12 ± 0.10 Å. This value is slightly larger than the d IB(Zn-Zn) distance of the Sb-rich IB 3 reported by Ribić et al [69] based on quantitative HRTEM (5.99 ± 0.05 Å), but we must keep in mind that the variations in the reported IB expansions measured from STEM images may be considerable. Park et al [56] reported the d IB(Zn-Zn) distance of 6.02 Å for the SnO 2 -doped ZnO nanobelts, which is similar to that of the Sb-doped nanorods [77].…”

Section: Translation Of the Sn-rich Ibsmentioning

confidence: 64%

“…For initial supercells, unit-cell parameters of ZnO were used according to Kisi & Elcombe [68]: a = 3.2501 Å, c = 5.2071 Å, u = 0.3817. Structural modeling was performed following the methodology described by Ribić et al [69]. Briefly, the models were generated by CrystalMaker ® software [70] in such a manner that IB-plane is placed at the center of the supercell at the middle of its longer A-axis running parallel with the polar c-axis of ZnO.…”

Section: Structural Modelingmentioning

confidence: 99%

“…The methodology of ab-initio calculations adhered to the methodology described by Ribić et al [69]. Structural relaxations were based on the density functional theory (DFT) as implemented in the Quantum-Espresso code [71].…”

Section: Dft Calculationsmentioning

confidence: 99%

“…1b show that IBs lie in basal planes. No streaks normal to {000l} reflections can be seen in the diffraction patterns in either [21 -1 -0] or [011 -0] view, that would reflect ordering in the IB plane, such as in Sb-doped ZnO [69]. This indicates that we either have no long-range ordering, or the distribution of Sn-atoms is random in the IB-plane.…”

Section: General Characteristics Of the Sn-doped Zno Ceramicsmentioning

confidence: 99%

“…

In our recent study (Ribić et al 2020) we reported the structure of inversion boundaries (IBs) in Sb 2 O 3 -doped ZnO. Here, we focus on IBs that form in SnO 2 -doped ZnO.

…”

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confidence: 99%

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TEM and DFT study of basal-plane inversion boundaries in SnO2-doped ZnO

et al. 2021

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In our recent study (Ribic 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 ?IB(Zn-Zn) of +91 pm with corresponding O-sublattice contraction ?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 (~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 bandgap, and enhance the in-plane conductivity and concentration of carriers. Keywords

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Section: Translation Of the Sn-rich Ibsmentioning

confidence: 64%

Section: Structural Modelingmentioning

confidence: 99%

Section: Dft Calculationsmentioning

confidence: 99%

Section: General Characteristics Of the Sn-doped Zno Ceramicsmentioning

confidence: 99%

“…

In our recent study (Ribić et al 2020) we reported the structure of inversion boundaries (IBs) in Sb 2 O 3 -doped ZnO. Here, we focus on IBs that form in SnO 2 -doped ZnO.

…”

mentioning

confidence: 99%

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TEM and DFT study of basal-plane inversion boundaries in SnO2-doped ZnO

et al. 2021

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Mnemonic Rutile–Rutile Interfaces Triggering Spontaneous Dissociation of Water

Ribić,

Jordan,

Drev

et al. 2023

Advanced Materials

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Water interaction with mineral surfaces is a complex living system decisive for any photocatalytic process. Resolving the atomistic structure of mineral–water interfaces is thus crucial for understanding these processes. Fibrous rutile TiO2, grown hydrothermally on twinned rutile seeds under acidic conditions, is studied in terms of interface translation, atomic structure, and surface chemistry in the presence of water, by means of advanced microscopy and spectroscopy methods combined with structure modeling and density functional theory calculations. It is shown that fibers while staying in stable separation during their growth, adopt a special crystallographic registry that is controlled by repulsion forces between fully hydroxylated and protonated (110) surfaces. During relaxation, a turbulent proton transfer and cracking of O─H bonds is observed, generating a strong acidic character via proton jump from bridge ─OHb to terminal ─OHt groups, and spontaneous dissociation of interfacial water via a transient protonation of the ─OHt groups. It is shown, that this specific interface structure can be implemented to induce acidic response in an initially neutral medium when re‐immersed. This is thought to be the first demonstration of quantum‐confined mineral–water interface, capable of memorizing its past and conveying its structurally encoded properties into a new environment.

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The presence of superoxide ions and related dioxygen species in zinc oxide—A structural characterization by in situ Raman spectroscopy

Fischer

Zagorac

Schön

2022

J Raman Spectroscopy

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Zinc oxide exhibits unique properties that are reflected in a wide variety of applications, particularly in the field of transparent, conductive films. However, less attention has been paid to their color. Here, we present the synthesis of yellow-gray ZnO films at room temperature by femtosecond pulsed laser deposition. In situ Raman investigations of these polycrystalline ZnO films reveal the existence of superoxide ions, O 2 À , in zinc oxide, which are responsible for the yellow color, and are also detected in ZnO powder and single crystals. In addition, further dioxygen species are identified in the samples, including the O 2 -molecule. The negative charge excess caused by the dioxygen species creates metallic zinc as a byproduct. Structural analysis reveals an unforced realization of the dioxygen species in the ZnO lattice. Density functional theory (DFT) calculations support the assumed structural displacements as well as the observed, unexpected Raman bands. These results open up completely new insights into the behavior of ZnO.

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New inversion boundary structure in Sb-doped ZnO predicted by DFT calculations and confirmed by experimental HRTEM

Cited by 19 publications

References 61 publications

TEM and DFT study of basal-plane inversion boundaries in SnO2-doped ZnO

TEM and DFT study of basal-plane inversion boundaries in SnO2-doped ZnO

Mnemonic Rutile–Rutile Interfaces Triggering Spontaneous Dissociation of Water

The presence of superoxide ions and related dioxygen species in zinc oxide—A structural characterization by in situ Raman spectroscopy

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