eprintid: 10204978 rev_number: 7 eprint_status: archive userid: 699 dir: disk0/10/20/49/78 datestamp: 2025-02-19 09:56:09 lastmod: 2025-02-19 09:56:09 status_changed: 2025-02-19 09:56:09 type: article metadata_visibility: show sword_depositor: 699 creators_name: Liu, T creators_name: Zhang, X creators_name: Guan, J creators_name: Chen, X creators_name: Lu, Y creators_name: Keal, TW creators_name: Buckeridge, J creators_name: Catlow, CRA creators_name: Sokol, AA title: Origins of intrinsic p-type conductivity, p-n transition and substoichiometry in SrO ispublished: pub divisions: UCL divisions: B04 divisions: C06 divisions: F56 note: This article is licensed under a Creative Commons Attribution 3.0 Unported Licence abstract: To understand the complex electrical behaviour and deviations from ideal stoichiometry in strontium oxide we have investigated its defect chemistry using a hybrid quantum mechanical/molecular mechanical (QM/MM) embedded-cluster approach. Depending on the temperature and oxygen partial pressure, oxygen interstitials or strontium and oxygen vacancies are found to dominate, while strontium interstitials are rare. Notably, charge-neutral oxygen interstitials form a peroxy-like closed-shell configuration, which is the commonest native point defect in SrO under normal conditions explaining the Sr substoichiometry which is not electrically active. Formally charged double acceptors strontium vacancies prove to be the primary source of the hole excess over negative carriers supplied by donor species, contributing to the material's p-type conductivity. Based on our calculations, we predict that at ultralow oxygen partial pressure (P = 1.0 × 10−15 bar) and high temperatures (>1100 K) in SrO, the electron concentration surpasses the hole concentration, which has previously been reported in pure BaO (also at about 1100 K) and the double barium-strontium oxide (at 850 K) by D. W. Wright, (Nature, 1949, 4173, 714) with the oxygen split interstitial acting as a donor. On increasing the oxygen partial pressure, the hole concentration exceeds the electron concentration, resulting in effective p-type conductivity. Only under low oxygen pressures (e.g., 10−8 bar) and high extrinsic donor concentrations (>1017 cm−3) might SrO switch to n-type conductivity at high temperatures (>1250 K). This study provides essential insights into intrinsic defects and mechanisms of SrO's p-type conductivity, aiding in understanding and predicting other p-type materials. date: 2025-01-01 date_type: published publisher: Royal Society of Chemistry (RSC) official_url: https://doi.org/10.1039/d4ta07690g oa_status: green full_text_type: pub language: eng primo: open primo_central: open_green verified: verified_manual elements_id: 2361741 doi: 10.1039/d4ta07690g lyricists_name: Catlow, Charles lyricists_name: Sokols, Alekseys lyricists_name: Guan, Jingcheng lyricists_id: CRACA43 lyricists_id: AASOK81 lyricists_id: JGUAN43 actors_name: Catlow, Charles actors_id: CRACA43 actors_role: owner full_text_status: public publication: Journal of Materials Chemistry A issn: 2050-7488 citation: Liu, T; Zhang, X; Guan, J; Chen, X; Lu, Y; Keal, TW; Buckeridge, J; ... Sokol, AA; + view all <#> Liu, T; Zhang, X; Guan, J; Chen, X; Lu, Y; Keal, TW; Buckeridge, J; Catlow, CRA; Sokol, AA; - view fewer <#> (2025) Origins of intrinsic p-type conductivity, p-n transition and substoichiometry in SrO. Journal of Materials Chemistry A 10.1039/d4ta07690g <https://doi.org/10.1039/d4ta07690g>. Green open access document_url: https://discovery.ucl.ac.uk/id/eprint/10204978/1/d4ta07690g.pdf