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This work presents results from in situ conductance measurements at thicknesses from sub-nm to around 250\u2009nm with parallel X-ray photoelectron spectroscopy. An enhanced conductivity at low thickness is explained by the occurrence of Cu(II), which is segregated in the grain boundary and locally causes a conductivity similar to CuO, although the surface of the thick film has Cu2O stoichiometry. Since grains grow with an increasing film thickness, the effect of an apparent oxygen excess is most pronounced in vicinity to the substrate interface. Electrical properties of Cu2O grains are at least partially short-circuited by this effect. The study focuses on properties inherent to copper oxide, although interface effects cannot be ruled out. This non-destructive, bottom-up analysis reveals phenomena which are commonly not observable after device fabrication, but clearly dominate electrical properties of polycrystalline thin films.<\/jats:p>","DOI":"10.1063\/1.4954002","type":"journal-article","created":{"date-parts":[[2016,6,16]],"date-time":"2016-06-16T18:07:24Z","timestamp":1466100444000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":27,"title":["Highly conductive grain boundaries in copper oxide thin films"],"prefix":"10.1063","volume":"119","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-2764-3124","authenticated-orcid":false,"given":"Jonas","family":"Deuermeier","sequence":"first","affiliation":[{"name":"Universidade NOVA de Lisboa and CEMOP\/UNINOVA 1 Department of Materials Science, Faculty of Science and Technology, i3N\/CENIMAT, , Campus de Caparica, 2829-516 Caparica, Portugal"},{"name":"Technische Universit\u00e4t Darmstadt 2 Department of Materials and Earth Sciences, , Jovanka-Bontschits-Stra\u00dfe 2, D-64287 Darmstadt, Germany"}]},{"given":"Hans F.","family":"Wardenga","sequence":"additional","affiliation":[{"name":"Technische Universit\u00e4t Darmstadt 2 Department of Materials and Earth Sciences, , Jovanka-Bontschits-Stra\u00dfe 2, D-64287 Darmstadt, Germany"}]},{"given":"Jan","family":"Morasch","sequence":"additional","affiliation":[{"name":"Technische Universit\u00e4t Darmstadt 2 Department of Materials and Earth Sciences, , Jovanka-Bontschits-Stra\u00dfe 2, D-64287 Darmstadt, Germany"}]},{"given":"Sebastian","family":"Siol","sequence":"additional","affiliation":[{"name":"Technische Universit\u00e4t Darmstadt 2 Department of Materials and Earth Sciences, , Jovanka-Bontschits-Stra\u00dfe 2, D-64287 Darmstadt, Germany"}]},{"given":"Suman","family":"Nandy","sequence":"additional","affiliation":[{"name":"Universidade NOVA de Lisboa and CEMOP\/UNINOVA 1 Department of Materials Science, Faculty of Science and Technology, i3N\/CENIMAT, , Campus de Caparica, 2829-516 Caparica, Portugal"}]},{"given":"Tom\u00e1s","family":"Calmeiro","sequence":"additional","affiliation":[{"name":"Universidade NOVA de Lisboa and CEMOP\/UNINOVA 1 Department of Materials Science, Faculty of Science and Technology, i3N\/CENIMAT, , Campus de Caparica, 2829-516 Caparica, Portugal"}]},{"given":"Rodrigo","family":"Martins","sequence":"additional","affiliation":[{"name":"Universidade NOVA de Lisboa and CEMOP\/UNINOVA 1 Department of Materials Science, Faculty of Science and Technology, i3N\/CENIMAT, , Campus de Caparica, 2829-516 Caparica, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7463-1495","authenticated-orcid":false,"given":"Andreas","family":"Klein","sequence":"additional","affiliation":[{"name":"Technische Universit\u00e4t Darmstadt 2 Department of Materials and Earth Sciences, , Jovanka-Bontschits-Stra\u00dfe 2, D-64287 Darmstadt, Germany"}]},{"given":"Elvira","family":"Fortunato","sequence":"additional","affiliation":[{"name":"Universidade NOVA de Lisboa and CEMOP\/UNINOVA 1 Department of Materials Science, Faculty of Science and Technology, i3N\/CENIMAT, , Campus de Caparica, 2829-516 Caparica, Portugal"}]}],"member":"317","published-online":{"date-parts":[[2016,6,16]]},"reference":[{"key":"2023062402580638300_c1","doi-asserted-by":"publisher","first-page":"2945","DOI":"10.1002\/adma.201103228","volume":"24","year":"2012","journal-title":"Adv. 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