The ability to tailor oxide heterointerfaces has led to novel properties in low-dimensional oxide systems. A fundamental understanding of these properties is based on the concept of electronic charge transfer. However, the electronic properties of oxide heterointerfaces crucially depend on their ionic constitution and defect structure: ionic charges contribute to charge transfer and screening at oxide interfaces, triggering a thermodynamic balance of ionic and electronic structures. Quantitative understanding of the electronic and ionic roles regarding charge-transfer phenomena poses a central challenge. Here, the electronic and ionic structure is simultaneously investigated at the prototypical charge-transfer heterointerface, LaAlO3 /SrTiO3 . Applying in situ photoemission spectroscopy under oxygen ambient, ionic and electronic charge transfer is deconvoluted in response to the oxygen atmosphere at elevated temperatures. In this way, both the rich and variable chemistry of complex oxides and the associated electronic properties are equally embraced. The interfacial electron gas is depleted through an ionic rearrangement in the strontium cation sublattice when oxygen is applied, resulting in an inverse and reversible balance between cation vacancies and electrons, while the mobility of ionic species is found to be considerably enhanced as compared to the bulk. Triggered by these ionic phenomena, the electronic transport and magnetic signature of the heterointerface are significantly altered.

Chemical Sciences Division Lawrence Berkeley National Lab Berkeley CA 94720 USA

Department of Inorganic Chemistry Fritz Haber Institute of the Max Planck Society 14195 Berlin Germany

Department of Surface and Plasma Science Faculty of Mathematics and Physics Charles University Prague 180 00 Czech Republic

Institute for Electronic Materials RWTH Aachen University 52074 Aachen Germany

Peter Grünberg Institute 1 and Institute for Advanced Simulation Forschungszentrum Jülich GmbH and JARA FIT 52425 Jülich Germany

Peter Grünberg Institute 6 and JARA FIT Forschungszentrum Jülich GmbH 52425 Jülich Germany

Peter Grünberg Institute 7 Forschungszentrum Jülich GmbH and JARA FIT 52425 Jülich Germany

Physical and Computational Sciences Directorate Pacific Northwest National Laboratory Richland WA 99354 USA

Zobrazit více v PubMed

Mannhart J., Schlom D. G., Science 2010, 327, 607. PubMed

Hwang H. Y., Iwasa Y., Kawasaki M., Keimer B., Nagaosa N., Tokura Y., Nat. Mater. 2012, 11, 103. PubMed

Smyth D. M., The Defect Chemistry of Metal Oxides, Oxford University Press, Oxford, UK: 2000.

Moos R., Härdtl K. H., J. Am. Ceram. Soc. 1997, 80, 2549.

Meyer R., Zurhelle A. F., De Souza R. A., Waser R., Gunkel F., Phys. Rev. B 2016, 94, 115408.

Merkle R., Maier J., Angew. Chem., Int. Ed. 2008, 47, 3874. PubMed

Waser R., Hagenbeck R., Acta Mater. 2000, 48, 797.

Zubko P., Gariglio S., Gabay M., Ghosez P., Triscone J., Annu. Rev. Condens. Matter Phys. 2011, 2, 141.

Verma A., Raghavan S., Stemmer S., Jena D., Appl. Phys. Lett. 2015, 107, 192908.

Ohtomo A., Hwang H. Y., Appl. Phys. Lett. 2004, 84, 1716.

Gunkel F., Waser R., Ramadan A. H. H., De Souza R. A., Hoffmann‐Eifert S., Dittmann R., Phys. Rev. B 2016, 93, 245431.

Bagdzevicius S., Maas K., Boudard M., Burriel M., J. Electroceram. 2017, 39, 157.

Sanna S., Esposito V., Andreason J. W., Hjelm J., Zhang W., Kasama T., Simonsen S. B., Christensen M., Linderoth S., Pryds N., Nat. Mater. 2015, 14, 500. PubMed

Bibes M., Villegas J. E., Barthelemy A., Adv. Phys. 2011, 60, 5.

Mannhart J., Blank D. H. A., Hwang H. Y., Millis A. J., Triscone J.‐M., MRS Bull. 2008, 33, 1027.

Pentcheva R., Pickett W. E., Phys. Rev. B 2006, 74, 35112.

Pentcheva R., Pickett W. E., Phys. Rev. B 2008, 78, 205106.

Gloter A., Tieri G., Li D., Caputo M., Strocov V., Stéphan O., Triscone J., Gariglio S., APL Mater. 2020, 8, 041103.

Moetakef P., Zhang J. Y., Kozhanov A., Jalan B., Sehadri R., Allen S. J., Stemmer S., Appl. Phys. Lett. 2011, 98, 112110.

Moetakef P., Cain T. A., Ouellette D. G., Zhang J. Y., Klenov D. O., Janotti A., Van de Walle C. G., Rajan S., Allen S. J., Stemmer S., Appl. Phys. Lett. 2011, 99, 232116.

Ohtomo A., Hwang H. Y., Nature 2004, 427, 423. PubMed

Nakagawa N., Hwang H. Y., Muller D. A., Nat. Mater. 2006, 5, 204.

Huijben M., Brinkman A., Koster G., Rijnders G., Hilgenkamp H., Blank D. H. A., Adv. Mater. 2009, 21, 1665.

Chen Y. Z., Trier F., Wijnands T., Green R. J., Gauquelin N., Egoavil R., Christensen D. V., Koster G., Huijben M., Bovet N., Macke S., He F., Sutarto R., Andersen N. H., Sulpizio J. A., Honig M., Prawiroatmodjo G. E. D. K., Jespersen T. S., Linderoth S., Ilani S., Verbeeck J., Van Tendeloo G., Rijnders G., Sawatzky G. A., Pryds N., Nat. Mater. 2015, 14, 801. PubMed

Son J., Moetakef P., Jalan B., Bierwagen O., Wright N. J., Engel‐Herbert R., Stemmer S., Nat. Mater. 2010, 9, 482. PubMed

Gariglio S., Fête A., Triscone J., J. Phys.: Condens. Matter 2015, 27, 283201. PubMed

Reyren N., Thiel S., Caviglia A. D., Kourkoutis L. F., Hammerl G., Richter C., Schneider C. W., Kopp T., Ruetschi A.‐S., Jaccard D., Gabay M., Muller D. A., Triscone J. ‐M., Mannhart J., Science 2007, 317, 1196. PubMed

Brinkman A., Huijben M., Van Zalk M., Huijben J., Zeitler U., Maan J. C., Van der Wiel W. G., Rijnders G., Blank D. H. A., Hilgenkamp H., Nat. Mater. 2007, 6, 493. PubMed

Li L., Richter C., Mannhart J., Ashoori R. C., Nat. Phys. 2011, 7, 762.

Dikin D. A., Mehta M., Bark C. W., Folkman C. M., Eom C. B., Chandrasekhar V., Phys. Rev. Lett. 2011, 107, 056802. PubMed

Breckenfeld E., Bronn N., Karthik J., Damodaran A. R., Lee S., Mason N., Martin L. W., Phys. Rev. Lett. 2013, 110, 196804. PubMed

Gunkel F., Skaja K., Shkabko A., Dittmann R., Hoffmann‐Eifert S., Waser R., Appl. Phys. Lett. 2013, 102, 71601.

Kalabukhov A., Gunnarsson R., Borjesson J., Olsson E., Claeson T., Winkler D., Phys. Rev. B 2007, 75, 121404. PubMed

Xu C., Baeumer C., Heinen R. A., Hoffmann‐Eifert S., Gunkel F., Dittmann R., Sci. Rep. 2016, 6, 22410. PubMed PMC

Basletic M., Maurice J., Carretero C., Herranz G., Copie O., Bibes M., Jacquet E., Bouzehouane K., Fusil S., Barthelemy A., Nat. Mater. 2008, 7, 621. PubMed

Thiel S., Hammerl G., Schmehl A., Schneider C. W., Mannhart J., Science 2006, 313, 1942. PubMed

Hensling F. V. E., Keeble D. J., Zhu J., Brose S., Xu C., Gunkel F., Danylyuk S., Nonnenmann S. S., Egger W., Dittmann R., Sci. Rep. 2018, 8, 8846. PubMed PMC

Gunkel F., Hoffmann‐Eifert S., Dittmann R., Mi S. B., Jia C. L., Meuffels P., Waser R., Appl. Phys. Lett. 2010, 97, 12103.

Hagemann H.‐J., Ihrig H., Phys. Rev. B 1979, 20, 3871.

Hagenbeck R., Simulation der elektrischen Korngrenzeneigenschaften akzeptordotierter SrTiO3‐Keramiken, RWTH Publications, Aachen, Germany: 1999.

Tanaka T., Matsunaga K., Ikuhara Y., Yamamoto T., Phys. Rev. B 2003, 68, 205213.

Waser R., J. Am. Ceram. Soc. 1991, 74, 1934.

Riva M., Franceschi G., Lu Q., Schmid M., Yildiz B., Diebold U., Phys. Rev. Mater. 2019, 3, 43802.

Andrä M., Dvorák F., Vorokhta M., Nemšák S., Matolín V., Schneider C. M., Dittmann R., Gunkel F., Mueller D. N., Waser R., APL Mater. 2017, 5, 56106.

Andrae M., Bluhm H., Schneider C. M., Dittmann R., Waser R., Mueller D. N., Gunkel F., Phys. Rev. Mater. 2019, 3, 44604/1.

Caviglia A. D., Gariglio S., Cancellieri C., Sacepe B., Fete A., Reyren N., Gabay M., Morpurgo A. F., Triscone J.‐M., Phys. Rev. Lett. 2010, 105, 236802. PubMed

Ben Shalom M., Ron A., Palevski A., Dagan Y., Phys. Rev. Lett. 2010, 105, 206401. PubMed

Gunkel F., Wicklein S., Brinks P., Hoffmann‐Eifert S., Huijben M., Rijnders G., Waser R., Dittmann R., Nanoscale 2015, 7, 1013. PubMed

Joshua A., Pecke S., Ruhman J., Altman E., Ilani S., Nat. Commun. 2012, 3, 1129. PubMed

Gunkel F., Bell C., Inoue H., Kim B., Swartz A. G., Merz T. A., Hikita Y., Harashima S., Sato H. K., Minohara M., Hoffmann‐Eifert S., Dittmann R., Hwang H. Y., Phys. Rev. X 2016, 6, 031035.

Stornaiuolo D., Cantoni C., De Luca G. M., Di Capua R., Di Gennaro E., Ghiringhelli G., Jouault B., Marre D., Massarotti D., Granozio F. M., Pallecchi I., Piamonteze C., Rusponi S., Tafuri F., Salluzzo M., Nat. Mater. 2016, 15, 278. PubMed

Doennig D., Pentcheva R., Sci. Rep. 2015, 5, 7909. PubMed PMC

Jiang W., Zhou X. Z., Williams G., Phys. Rev. B 2010, 82, 144424.

Zhang S. X., Yu W., Ogale S. B., Shinde S. R., Kundaliya D. C., Tse W., Young S. Y., Higgins J. S., Salamanca‐Riba L. G., Herrera M., Fu L. F., Browning N. D., Greene R. L., Venkatesan T., Phys. Rev. B 2007, 76, 085323.

Mathieu R., Asamitsu A., Yamada H., Takahashi K. S., Kawasaki M., Fang Z., Nagaosa N., Tokura Y., Phys. Rev. Lett. 2004, 93, 016602.

Christensen D. V., Frenkel Y., Schuetz P., Trier F., Wissberg S., Claessen R., Kalisky B., Smith A., Chen Y., Pryds N., Phys. Rev. Appl. 2018, 9, 054004.

Sarantopoulos A., Ferreiro‐Vila E., Pardo V., Magen C., Aguirre M. H., Rivadulla F., Phys. Rev. Lett. 2015, 115, 166801. PubMed

Copie O., Garcia V., Boedefeld C., Carretero C., Bibes M., Herranz G., Jacquet E., Maurice J., Vinter B., Fusil S., Bouzehouane K., Jaffres H., Barthelemy A., Phys. Rev. Lett. 2009, 102, 216804. PubMed

Pan J. M., Maschhoff B. L., Diebold U., Madey T. E., J. Vac. Sci. Technol. A 1992, 10, 2470.

Szot K., Speier W., Breuer U., Meyer R., Szade J., Waser R., Surf. Sci. 2000, 460, 112.

van der Heide P. A. W., Jiang Q. D., Kim Y. S., Rabalais J. W., Surf. Sci. 2001, 473, 59.

Treske U., Heming N., Knupfer M., Buechner B., Koitzsch A., Di Gennaro E., di Uccio U. S., Miletto Granozio F., Krause S., APL Mater. 2014, 2, 12108. PubMed PMC

Chambers S. A., Du Y., Zhu Z., Wang J., Wahila M. J., Piper L. F. J., Prakash A., Yue J., Jalan B., Spurgeon S. R., Kepaptsoglou D. M., Ramasse Q. M., Sushko P. V., Phys. Rev. B 2018, 97, 245204.

Wang L., Du Y., Chang L., Soerzinger K. A., Bowden M. E., Wang J., Chambers S. A., Appl. Phys. Lett. 2018, 112, 261601.

Slooten E., Ph.D. Thesis, University of Amsterdam, Amsterdam, The Netherlands 2013.

Treske U., Heming N., Knupfer M., Büchner B., Di Gennaro E., Khare A., Di Uccio U. S., Granozio F. M., Krause S., Koitzsch A., Sci. Rep. 2015, 5, 14506. PubMed PMC

Segal Y., Ngai J. H., Reiner J. W., Walker F. J., Ahn C. H., Phys. Rev. B 2009, 80, 241107.

Chambers S. A., Engelhard M. H., Shutthanandan V., Zhu Z., Droubay T. C., Qiao L., Sushko P. V., Feng T., Lee H. D., Gustafsson T., Garfunkel E., Shah A. B., Zuo J.‐M., Ramasse Q. M., Surf. Sci. 2010, 65, 317.

Slooten E., Zhong Z., Molegraaf H. J. A., Eerkes P. D., de Jong S., Massee F., van Heumen E., Kruize M. K., Wenderich S., Kleibeuker J. E., Gorgoi M., Hilgenkamp H., Brinkman A., Huijben M., Rijnders G., Blank D. H. A., Koster G., Kelly P. J., Golden M. S., Phys. Rev. B 2013, 87, 85128.

Drera G., Salvinelli G., Brinkman A., Huijben M., Koster G., Hilgenkamp H., Rijnders G., Visentin D., Sangaletti L., Phys. Rev. B 2013, 87, 75435.

Yu L., Zunger A., Nat. Commun. 2014, 5, 5118. PubMed

Lenser C., Koehl A., Slipukhina I., Du H., Patt M., Feyer V., Schneider C. M., Lezaic M., Waser R., Dittmann R., Adv. Funct. Mater. 2015, 25, 6360.

Gunkel F., Brinks P., Hoffmann‐Eifert S., Dittmann R., Huijben M., Kleibeuker J. E., Koster G., Rijnders G., Waser R., Appl. Phys. Lett. 2012, 100, 52103.

Strocov V. N., Chikina A., Caputo M., Husanu M.‐A., Bisti F., Bracher D., Schmitt T., Miletto Granozio F., Vaz C. A. F., Lechermann F., Phys. Rev. Mater. 2019, 3, 106001.

Mohanta N., Taraphder A., J. Phys.: Condens. Matter 2014, 26, 025705. PubMed

Keeble D. J., Wicklein S., Jin L., Jia C. L., Egger W., Dittmann R., Phys. Rev. B 2013, 87, 11.

Warusawithana M. P., Richter C., Mundy J. A., Roy P., Ludwig J., Paetel S., Heeg T., Pawlicki A. A., Kourkoutis L. F., Zheng M., Lee M., Mulcahy B., Zander W., Zhu Y., Schubert J., Eckstein J. N., Muller D. A., Hellberg C. S., Mannhart J., Schlom D. G., Nat. Commun. 2013, 4, 2351. PubMed

Gunkel F., Hoffmann‐Eifert S., Heinen R. A., Christensen D. V., Chen Y. Z., Pryds N., Waser R., Dittmann R., ACS Appl. Mater. Interfaces 2017, 9, 1086. PubMed

Sato H. K., Bell C., Hikita Y., Hwang H. Y., Appl. Phys. Lett. 2013, 102, 251602.

Meyer T. L., Jeen H., Gao X., Petrie J. R., Chisholm M. F., Lee H. N., Adv. Electron. Mater. 2016, 2, 1500201/1.

Ogletree D. F., Bluhm H., Hebenstreit E. D., Salmeron M., Nucl. Instrum. Methods Phys. Res. Sect. A 2009, 601, 151.

Moos R., Menesklou W., Hardtl K. H., Appl. Phys. A 1995, 61, 389.

Kresse G., Furthmüller J., Comput. Mater. Sci. 1996, 6, 15.

Kresse G., Furthmüller J., Phys. Rev. B 1996, 54, 11169. PubMed

Kresse G., Hafner J., Phys. Rev. B 1993, 47, 558. PubMed

Perdew J. P., Burke K., Ernzerhof M., Phys. Rev. Lett. 1996, 77, 3865. PubMed

Blöchl P. E., Phys. Rev. B 1994, 50, 17953. PubMed

Dudarev S., Botton G., Savrasov S., Humphreys C., Sutton A., Phys. Rev. B 1998, 57, 1505.

Krause D., Thörnig P., J. Large‐Scale Res. Facil. 2018, 4, A132.

Space charge governs the kinetics of metal exsolution