Polaron formation in Bi-deficient ${\mathrm{BaBiO}}_{3}$

Polaron formation in Bi-deficient ${BaBiO}_{3}$

W. Román Acevedo, S. Di Napoli, F. Romano, G. Rodríguez Ruiz, P. Nukala, C. Quinteros, J. Lecourt, U. Lüders, V. Vildosola, and D. Rubi

Phys. Rev. B 104, 125307 – Published 23 September 2021

Abstract

$Ba Bi O_{3}$ is a charged ordered Peierls-like perovskite well known for its superconducting properties upon K or Pb doping. We present a study on the transport and electronic properties of $Ba Bi O_{3}$ perovskite with strong Bi deficiency. We show that it is possible to synthesize $Ba Bi O_{3}$ thin layers with Bi vacancies above 8–10% by depositing an yttrium-stabilized zirconia capping layer. By combining transport measurements with ab initio calculations we propose a scenario where the Bi vacancies give rise to the formation of polarons and suggest that the electrical transport is dominated by the migration of these polarons trapped at ${Bi}^{3 +}$ sites. Our paper shows that cation vacancies engineering, hardly explored to date, appears as a promising pathway to tune the electronic and functional properties of perovskites.

Received 10 April 2021
Revised 8 July 2021
Accepted 13 September 2021

DOI:https://doi.org/10.1103/PhysRevB.104.125307

Physics Subject Headings (PhySH)

Defects Density of states Electrical conductivity Electronic structure Growth Polarons Surface & interfacial phenomena Vacancies

Density functional calculations

Condensed Matter, Materials & Applied Physics

Authors & Affiliations

W. Román Acevedo^1,2, S. Di Napoli ^1,2, F. Romano^1,2,3, G. Rodríguez Ruiz ^1,2,3, P. Nukala ^4,5, C. Quinteros⁵, J. Lecourt⁶, U. Lüders⁶, V. Vildosola ^1,2, and D. Rubi^1,2

¹Departamento de Física de la Materia Condensada, GIyA-CNEA, Av. General Paz 1499, (1650) San Martín, Pcia. de Buenos Aires, Argentina
²Instituto de Nanociencia y Nanotecnología (INN CNEA-CONICET), 1650 San Martín, Argentina
³Depto. de Física, FCEyN, Universidad de Buenos Aires, Pab I, Ciudad Universitaria, Buenos Aires (1428), Argentina
⁴Center for Nanoscience and Engineering, Indian Institute of Science, Bangalore 560012, India
⁵Zernike Institute for Advanced Materials, University of Groningen, 9747AG The Netherlands
⁶CRISMAT, CNRS UMR 6508, ENSICAEN, 6 Boulevard Maréchal Juin, F-14050 Caen Cedex 4, France

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Vol. 104, Iss. 12 — 15 September 2021

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Figure 1
(a) X-ray diffraction spectra corresponding to both bare and capped BBO. Peaks indexes correspond to the pseudo-cubic (PC) perovskite BBO lattice. Peaks marked with * correspond to the sample holder used for the measurement of the capped BBO sample [35]. Zero-shift corrections were made from the position of Si peaks. (b) Blow-up of the spectra displayed in (a), evidencing the shift of diffraction peaks to lower angles for capped BBO. Maxima are shifted by 0.24º. Also, capped BBO displayed broader diffraction peaks (FWHM of $\approx 0.5$ º and $\approx 0.7$ º for BBO and capped BBO, respectively) with a slight asymmetry. (c) TEM HAADF image corrresponding to a BBO/YSZ bilayer on $Si / Si O_{2}$ , with the YSZ grown at an oxygen pressure of 0.1 mbar. The Pt layer on top of the YSZ layer was deposited for the lamella preparation.
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Figure 2
Sketches showing (a) the $Si O_{2}$ /BBO/Bi-def. BBO/YSZ stack and (b) a top view of the contacted device. Small parts of $Si O_{2}$ (top layer of the substrate, blue) were left exposed in order to access the BBO and Bi-deficient BBO layers for 4-points transport measurements. Same colors are used for (a) and (b). (c) 4-points resistance as a function of the temperature recorded for a bare BBO film and a YSZ-capped heterostructure.The red line shows a fitting assuming a polaronic conduction model for the Bi-deficient BBO layer (see text for details).
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Figure 3
Spin-polarized band structure of (a) perfect $Ba Bi O_{3}$ and Bi-deficient $Ba Bi O_{3}$ with (b) 25%, (c) 12.5%, and (d) 18.75% of Bi-vacancies. Solid lines correspond to spin-up projection and dashed lines to spin-down. In (a) and (c) spin-up and spin-down bands are degenerate. Red bands correspond to ${Bi}^{+ 3}$ , dark-green ones to original ${Bi}^{+ 5}$ atoms, and blue to created bipolarons. The orange band in (b) represents the hole trapped at the oxygen cloud centered at the Bi-vacancy sketched in Fig. 4 (a) and the violet bands in (d) correspond to the charge/hole polaron originated around ${Bi}_{12}$ [see text and Fig. 6].
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Figure 4
Charge density plots of Bi-deficient $Ba Bi O_{3}$ with a 25% of Bi vacancies. Panel (a) shows the hole trapped at the oxygen cloud around the vacancy, corresponding to the orange band depicted in Fig. 3. The charge density shown in (b) corresponds to the bipolaron at the remaining ${Bi}^{+ 3}$ site [blue band in Fig. 3].
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Figure 5
Activation barrier of the hole polaron trapped at the oxygen $p$ -bands that surround the Bi vacancy in the highly doped case, i.e., the $25 %$ concentration of Bi vacancies. The barrier is calculated using NEB taking into account two different migration pathways (see text for details).
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Figure 6
[(a) Top panel] PDOS projected onto the $s$ orbitals of two selected Bi atoms, the one with the polaron, i.e., ${Bi}_{12}$ and one of its nearest Bi neighbors, i.e., ${Bi}_{5}$ . [(a) Bottom panel] PDOS projected onto the same Bi atoms for the intermediate situation where the polaronic charge is half-transferred between neighboring sites. (b) Charge-density plot corresponding to the localized state close to $E_{F}$ shown in the top panel of (a), i.e.. the polaron centered at ${Bi}_{12}$ . (c) Idem (b) after the static perturbation where the polaronic charge is shared with ${Bi}_{5}$ .
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Physical Review B

covering condensed matter and materials physics

Polaron formation in Bi-deficient ${BaBiO}_{3}$

W. Román Acevedo, S. Di Napoli, F. Romano, G. Rodríguez Ruiz, P. Nukala, C. Quinteros, J. Lecourt, U. Lüders, V. Vildosola, and D. Rubi

Phys. Rev. B 104, 125307 – Published 23 September 2021

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Physical Review B

covering condensed matter and materials physics

Polaron formation in Bi-deficient BaBiO3

W. Román Acevedo, S. Di Napoli, F. Romano, G. Rodríguez Ruiz, P. Nukala, C. Quinteros, J. Lecourt, U. Lüders, V. Vildosola, and D. Rubi

Phys. Rev. B 104, 125307 – Published 23 September 2021

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Polaron formation in Bi-deficient ${BaBiO}_{3}$