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dc.contributor.authorSCANLON, DAVIDen
dc.contributor.authorKEHOE, AOIFEen
dc.contributor.authorWATSON, GRAEMEen
dc.date.accessioned2012-01-04T12:42:35Z
dc.date.available2012-01-04T12:42:35Z
dc.date.issued2011en
dc.date.submitted2011en
dc.identifier.citationDavid O. Scanlon, Aoife B. Kehoe, Graeme W. Watson, Martin O. Jones, William I. F. David, David J. Payne, Russell G. Egdell, Peter P. Edwards, Aron Walsh , Nature of the Band Gap and Origin of the Conductivity of PbO2 Revealed by Theory and Experiment, Physical Review Letters, 107, 246402, 2011, 5en
dc.identifier.otherYen
dc.identifier.urihttp://hdl.handle.net/2262/61490
dc.descriptionPUBLISHEDen
dc.description.abstractLead dioxide has been used for over a century in the lead-acid battery. Many fundamental questions concerning PbO2 remain unanswered, principally: (i) is the bulk material a metal or a semiconductor, and (ii) what is the source of the high levels of conductivity? We calculate the electronic structure and defect physics of PbO2, using a hybrid density functional, and show that it is an n-type semiconductor with a small indirect band gap of ~0.2??eV. The origin of electron carriers in the undoped material is found to be oxygen vacancies, which forms a donor state resonant in the conduction band. A dipole-forbidden band gap combined with a large carrier induced Moss-Burstein shift results in a large effective optical band gap. The model is supported by neutron diffraction, which reveals that the oxygen sublattice is only 98.4% occupied, thus confirming oxygen substoichiometry as the electron source.en
dc.description.sponsorshipThis work was supported by SFI through the PI program (Grant No. 06/IN.1/I92 and No. 06/IN.1/I92/EC07). Calculations were performed on the TCHPC computing clusters, the Stokes cluster as maintained by ICHEC, and the University of Bath?s High Performance Computing Facility. A. W. acknowledges support from the U.K.?s HPC Materials Chemistry Consortium, which is funded by EPSRC Grant No. EP/F067496, and the EPSRC solar fuel Grant No. EP/I01330X.en
dc.format.extent5en
dc.language.isoenen
dc.relation.ispartofseriesPhysical Review Lettersen
dc.relation.ispartofseries107en
dc.relation.ispartofseries246402en
dc.rightsYen
dc.subjectChemistryen
dc.subjectLead dioxideen
dc.titleNature of the Band Gap and Origin of the Conductivity of PbO2 Revealed by Theory and Experimenten
dc.typeJournal Articleen
dc.contributor.sponsorScience Foundation Ireland (SFI)en
dc.contributor.sponsorScience Foundation Ireland (SFI)en
dc.type.supercollectionscholarly_publicationsen
dc.type.supercollectionrefereed_publicationsen
dc.identifier.peoplefinderurlhttp://people.tcd.ie/watsongen
dc.identifier.rssinternalid76528en
dc.identifier.doihttp://dx.doi.org/10.1103/PhysRevLett.107.246402en
dc.contributor.sponsorGrantNumber06/IN.1/I92/EC07en
dc.contributor.sponsorGrantNumber06/IN.1/I92en
dc.subject.TCDThemeNanoscience & Materialsen
dc.identifier.rssurihttp://link.aps.org/doi/10.1103/PhysRevLett.107.246402en


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