dc.contributor.author | SCANLON, DAVID | en |
dc.contributor.author | KEHOE, AOIFE | en |
dc.contributor.author | WATSON, GRAEME | en |
dc.date.accessioned | 2012-01-04T12:42:35Z | |
dc.date.available | 2012-01-04T12:42:35Z | |
dc.date.issued | 2011 | en |
dc.date.submitted | 2011 | en |
dc.identifier.citation | David 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, 5 | en |
dc.identifier.other | Y | en |
dc.description | PUBLISHED | en |
dc.description.abstract | Lead 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.sponsorship | This 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.extent | 5 | en |
dc.language.iso | en | en |
dc.relation.ispartofseries | Physical Review Letters | en |
dc.relation.ispartofseries | 107 | en |
dc.relation.ispartofseries | 246402 | en |
dc.rights | Y | en |
dc.subject | Chemistry | en |
dc.subject | Lead dioxide | en |
dc.title | Nature of the Band Gap and Origin of the Conductivity of PbO2 Revealed by Theory and Experiment | en |
dc.type | Journal Article | en |
dc.type.supercollection | scholarly_publications | en |
dc.type.supercollection | refereed_publications | en |
dc.identifier.peoplefinderurl | http://people.tcd.ie/watsong | en |
dc.identifier.rssinternalid | 76528 | en |
dc.identifier.doi | http://dx.doi.org/10.1103/PhysRevLett.107.246402 | en |
dc.subject.TCDTheme | Nanoscience & Materials | en |
dc.identifier.rssuri | http://link.aps.org/doi/10.1103/PhysRevLett.107.246402 | en |
dc.contributor.sponsor | Science Foundation Ireland (SFI) | en |
dc.contributor.sponsorGrantNumber | 06/IN.1/I92/EC07 | en |
dc.contributor.sponsor | Science Foundation Ireland (SFI) | en |
dc.contributor.sponsorGrantNumber | 06/IN.1/I92 | en |
dc.identifier.uri | http://hdl.handle.net/2262/61490 | |