Unusual Mn Oxidation State Distribution in the Vicinity of the Tensile-Strained Interface between Camno3 and La0.7ca0.3mno3 Layers

Oxide perovskite materials with heterointerfaces are important structures with applications such as electronic devices. The functionality of these materials depends on many factors, such as the charge, structure, and presence of defects at the interface. Thus, understanding the properties of interfaces and their effects on material function is important in the design and optimization of functional materials. In this study, the interplay among the Mn oxidation state distribution, the presence of oxygen vacancies (VOs), and the structure of the interface is investigated in the heterointerface between CaMnO3−δ and La0.7Ca0.3MnO3 layers by using electron energy loss spectroscopy combined with scanning transmission electron microscopy. Unlike the expectation that the Mn oxidation state distribution is controlled by the distribution of cations intermixing at the interface, it is dominantly influenced by the presence of VOs when the substrate gives tensile stress to it. As a result, the tensile-strained heterointerface shows an anomalously sharp reduction in the Mn oxidation state at the interface. This result suggests that VOs and strain are two essential ingredients to consider for the understanding of oxidation state distribution at interfaces. This study provides insights into the nature of various oxide heterointerfaces.

[1]  Van Hien-Hoang,et al.  Electrical transport properties and Kondo effect in La1−xPrxNiO3−δthin films , 2021, Scientific reports.

[2]  R. Dittmann,et al.  Identifying Ionic and Electronic Charge Transfer at Oxide Heterointerfaces , 2020, Advances in Materials.

[3]  R. Stark,et al.  Probing Charge Accumulation at SrMnO3/SrTiO3 Heterointerfaces via Advanced Electron Microscopy and Spectroscopy , 2020, ACS nano.

[4]  Joonhyuk Lee,et al.  Effect of Ceramic-Target Crystallinity on Metal-to-Insulator Transition of Epitaxial Rare-Earth Nickelate Films Grown by Pulsed Laser Deposition , 2019, ACS Applied Electronic Materials.

[5]  R. Dittmann,et al.  Nanospectroscopy of Infrared Phonon Resonance Enables Local Quantification of Electronic Properties in Doped SrTiO3 Ceramics , 2018, Advanced Functional Materials.

[6]  T. Ma,et al.  Multi-functional Ultrasonic Micro-elastography Imaging System , 2017, Scientific Reports.

[7]  W. Sigle,et al.  Oxygen octahedra picker: A software tool to extract quantitative information from STEM images. , 2016, Ultramicroscopy.

[8]  P. Vullum,et al.  Structural phases driven by oxygen vacancies at the La0.7Sr0.3MnO3/SrTiO3 hetero-interface , 2015 .

[9]  Jin-Cheng Zheng,et al.  Kondo scattering in δ -doped LaTiO 3 / SrTiO 3 interfaces: Renormalization by spin-orbit interactions , 2014 .

[10]  M. P. Paranthaman,et al.  Orienting Oxygen Vacancies for Fast Catalytic Reaction , 2013, Advanced materials.

[11]  Yan Chen,et al.  Electronic Activation of Cathode Superlattices at Elevated Temperatures – Source of Markedly Accelerated Oxygen Reduction Kinetics , 2013 .

[12]  T. Grande,et al.  Strain-controlled oxygen vacancy formation and ordering in CaMnO3 , 2013, 1303.4749.

[13]  He Tian,et al.  Artificial Construction of the Layered Ruddlesden–Popper Manganite La2Sr2Mn3O10 by Reflection High Energy Electron Diffraction Monitored Pulsed Laser Deposition , 2012, Journal of the American Chemical Society.

[14]  J. Hosson,et al.  Influence of strain on the electronic structure of the TbMnO3/SrTiO3 epitaxial interface , 2011 .

[15]  J. Mannhart,et al.  Coexistence of magnetic order and two-dimensional superconductivity at LaAlO3/SrTiO3 interfaces , 2011, 1105.0235.

[16]  L. Qiao,et al.  Direct observation of Ni3+ and Ni2+ in correlated LaNiO3−δ films , 2011 .

[17]  Y. Sato,et al.  Quantitative analyses of oxidation states for cubic SrMnO(3) and orthorhombic SrMnO(2.5) with electron energy loss spectroscopy. , 2010, Journal of applied physics.

[18]  K. Livi,et al.  Determination of manganese valence states in (Mn3+, Mn4+) minerals by electron energy-loss spectroscopy , 2010 .

[19]  Masashi Watanabe,et al.  Atomic-resolution imaging of oxidation states in manganites , 2009 .

[20]  N. Sakai,et al.  Enhancement of Oxygen Surface Exchange at the Hetero-interface of ( La , Sr ) CoO3 / ( La , Sr ) 2CoO4 with PLD-Layered Films , 2008 .

[21]  N. Reyren,et al.  Superconducting Interfaces Between Insulating Oxides , 2007, Science.

[22]  S. Pennycook,et al.  Orbital-occupancy versus charge ordering and the strength of electron correlations in electron-doped CaMnO3. , 2007, Physical review letters.

[23]  A. Fert,et al.  High mobility in LaAlO3/SrTiO3 heterostructures: origin, dimensionality, and perspectives. , 2007, Physical review letters.

[24]  T. Gemming,et al.  Determination of manganese valency in La1-xSrxMnO3 using ELNES in the (S)TEM. , 2007, Micron.

[25]  W. G. van der Wiel,et al.  Magnetic effects at the interface between non-magnetic oxides. , 2007, Nature materials.

[26]  T. Al,et al.  Manganese valence imaging in Mn minerals at the nanoscale using STEM-EELS , 2007 .

[27]  J. Mannhart,et al.  Tunable Quasi-Two-Dimensional Electron Gases in Oxide Heterostructures , 2006, Science.

[28]  B. Vilquin,et al.  Transport and magnetic properties of Ce-doped LaMnO3 thin films , 2005 .

[29]  Akira Ohtomo,et al.  A high-mobility electron gas at the LaAlO3/SrTiO3 heterointerface , 2004, Nature.

[30]  G. Kothleitner,et al.  Electron energy-loss near-edge structures of 3d transition metal oxides recorded at high-energy resolution. , 2003, Ultramicroscopy.

[31]  P. V. van Aken,et al.  Quantification of ferrous/ferric ratios in minerals: new evaluation schemes of Fe L23 electron energy-loss near-edge spectra , 2002 .

[32]  K. Lee,et al.  Colossal Magnetoresistance in La0.7Ca0.3MnO3-δ: Comparative Study of Single-Crystal and Polycrystalline Material , 2000 .

[33]  Jiang,et al.  EELS analysis of cation valence states and oxygen vacancies in magnetic oxides , 2000, Micron.

[34]  J. Goodenough,et al.  Paramagnetic phase in single-crystal LaMnO 3 , 1999 .

[35]  Cheong,et al.  Low temperature magnetoresistance and the magnetic phase diagram of La1-xCaxMnO3. , 1995, Physical review letters.

[36]  Colliex,et al.  Electron-energy-loss core-edge structures in manganese oxides. , 1993, Physical review. B, Condensed matter.

[37]  C. Colliex,et al.  Curve fitting methods for quantitative analysis in electron energy loss spectroscopy , 1990 .

[38]  Thole,et al.  Branching ratio in x-ray absorption spectroscopy. , 1988, Physical review. B, Condensed matter.

[39]  Peter R. Buseck,et al.  Determination of manganese oxidation states in solids by electron energy-loss spectroscopy , 1987 .

[40]  Humphreys,et al.  White lines in the L2,3 electron-energy-loss and x-ray absorption spectra of 3d transition metals. , 1986, Physical review. B, Condensed matter.

[41]  C. Rao,et al.  L3/L2 white-line intensity ratios in the electron energy-loss spectra of 3d transition-metal oxides , 1984 .

[42]  Richard D. Leapman,et al.  Study of the L 23 edges in the 3 d transition metals and their oxides by electron-energy-loss spectroscopy with comparisons to theory , 1982 .

[43]  Richard D. Leapman,et al.  Oxygen K near-edge fine structure: An electron-energy-loss investigation with comparisons to new theory for selected 3 d Transition-metal oxides , 1982 .

[44]  P. de Gennes,et al.  Effects of Double Exchange in Magnetic Crystals , 1960 .

[45]  G. H. Jonker,et al.  Magnetic compounds wtth perovskite structure III. ferromagnetic compounds of cobalt , 1953 .