High resolution electron energy loss spectroscopy of manganese oxides: Application to Mn3O4 nanoparticles

Laffont, Lydia; Gibot, Pierre

doi:10.1016/j.matchar.2010.09.001

Cited by 106 publications

(99 citation statements)

References 15 publications

(20 reference statements)

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“…2(blue). A split of the Mn L 3 edge into peak 1 (639.8 eV) and peak 2 (641.5 eV) is observed, as reported for energy resolutions higher than 0.5 eV [28,36,37]. The high spatial resolution in these experiments, apparent from the simultaneously acquired HAADF-STEM image (Fig.…”

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confidence: 81%

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2D Atomic Mapping of Oxidation States in Transition Metal Oxides by Scanning Transmission Electron Microscopy and Electron Energy-Loss Spectroscopy

et al. 2011

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Using a combination of high-angle annular dark-field scanning transmission electron microscopy and atomically resolved electron energy-loss spectroscopy in an aberration-corrected transmission electron microscope we demonstrate the possibility of 2D atom by atom valence mapping in the mixed valence compound Mn 3 O 4 . The Mn L 2;3 energy-loss near-edge structures from Mn 2þ and Mn 3þ cation sites are similar to those of MnO and Mn 2 O 3 references. Comparison with simulations shows that even though a local interpretation is valid here, intermixing of the inelastic signal plays a significant role. This type of experiment should be applicable to challenging topics in materials science, such as the investigation of charge ordering or single atom column oxidation states in, e.g., dislocations. DOI: 10.1103/PhysRevLett.107.107602 PACS numbers: 79.20.Uv, 68.37.Ma, 75.25.Dk In transition metal oxides, the oxidation state of the transition metal cations is of fundamental importance as the physical properties of many oxides are determined by the occupancy of the cation d bands. Multiferroicity, for example, can be driven by charge ordering of these cations, as in Fe 3 O 4 and Pr 1Àx Ca x MnO 3 [1-3]. However, the exact mechanism of multiferroic behavior is not fully understood to date. A method allowing for direct mapping of cation valence states in these materials at atomic resolution should therefore provide further insight into the origin of multiferroicity.Recently, atomic resolution elemental mapping has become feasible by means of spatially resolved electron energy-loss spectroscopy and energy dispersive x-ray spectroscopy in a scanning transmission electron microscope (STEM-EELS and STEM-EDX) [4][5][6][7][8][9]. At the same time, tremendous effort is being invested into the identification of the oxidation states of cations using electron energy-loss spectroscopy (EELS). The shape of the L 2;3 edge [10], the chemical shift [11,12] and the L 3 =L 2 ratio [13] have all been used as a fingerprint for the transition metal valence. In fact, the correlation between the energy-loss near-edge structure (ELNES) and valence in different transition metal oxides was confirmed by several experiments in literature [10,[14][15][16][17][18][19][20][21]. The higher the energy resolution, the more convincing this link between valence and ELNES features becomes. Combining the atomic resolution capabilities of a STEM with bonding and valence information from EELS is a highly attractive prospect. While bonding information has been obtained at atomic resolution [7,17,22], 2D oxidation state mapping at the atomic level in, e.g., metaloxide materials has remained challenging due to poor EELS signal-to-noise ratio and the need for simultaneous high spatial and energy resolution of the instrument [10,17,23].Mn 3 O 4 is known to be a mixed valence compound, containing both Mn 2þ and Mn 3þ ions at room temperature [24]. It has a spinel structure with lattice parameters a ¼ 5:762 A and c ¼ 9:4696 A and space group I41=amd. Many interesting...

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“…2 [10,14], especially in the case of Mn [17,19,20,37,38]. Indeed the dominance of ELNES peak 1 or 2 can be attributed to Mn 2þ or Mn 3þ respectively as can be observed from the reference spectra.…”

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2D Atomic Mapping of Oxidation States in Transition Metal Oxides by Scanning Transmission Electron Microscopy and Electron Energy-Loss Spectroscopy

et al. 2011

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“…Then, the calculated intensity ratios of (Mn-L 2 /Mn-L 3 ) for Spectra 2 and 3 are found to be 0.6 and 0.4, respectively. From a previous paper, 23 The Ni-L EELS spectra of the passive film of 15 Mn steel Although more work is needed to identify precisely, the chemical state of each element in the passive film of 15 Mn steel has been examined in this study.…”

Section: Surface Analysis Of the Passive Film On 15 Mn Steelmentioning

confidence: 99%

Crevice Corrosion Resistance and Structure of Passive Film on Fe–Mn–Si–Cr–Ni Steel

Nishimura

2016

ISIJ Int.

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“…Laffont reported very similar EELS spectra for Mn oxides. 15) The EELS observation position of 7 (P7) is the result of the metallic alloy. S-L2 and S-L3 (eV) at each position are measured as compared to P7.…”

Section: Surface Analysis Of the Rust On 28 Mn Shape Memory Alloymentioning

confidence: 99%

Nano Structure of the Rust Formed on an Iron-based Shape Memory Alloy (Fe–Mn–Si–Cr) in a High Chloride Environment

Nishimura

2014

ISIJ Int.

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The corrosion resistance of an Iron-based shape memory alloy (28 Mn: Fe-Mn-Si-Cr) was estimated by using wet and dry corrosion test. The structure of the rust formed on the alloy was examined via EELS (Electron Energy Loss Spectroscopy) using TEM (Transmission Electron Microscopy) analysis. The electrochemical behavior of the 28 Mn alloy was investigated via EIS (Electrochemical Impedance Spectroscopy). The 28 Mn alloy showed a much higher corrosion resistance than SM (carbon steel) in wet and dry corrosion test. In EIS measurement following the corrosion tests, the 28 Mn alloy exhibited a much larger value of corrosion resistance (Z1mHz) as compared to SM, which can be attributed to rust formation. TEM analysis indicated that the inner rust was composed of Mn-rich, Cr-Si rich and interface layer. The corrosion resistance was primarily dependent on the Cr-Si rich layer, and further supported by the Mn rich layer. It was found that the 28 Mn alloy could maintain a protective rust layer composed of effective elements in the wet and dry environment.

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High resolution electron energy loss spectroscopy of manganese oxides: Application to Mn3O4 nanoparticles

Abstract: OATAO is an open access repository that collects the work of Toulouse researchers and makes it freely available over the web where possible.

Cited by 106 publications

References 15 publications

2D Atomic Mapping of Oxidation States in Transition Metal Oxides by Scanning Transmission Electron Microscopy and Electron Energy-Loss Spectroscopy

2D Atomic Mapping of Oxidation States in Transition Metal Oxides by Scanning Transmission Electron Microscopy and Electron Energy-Loss Spectroscopy

Crevice Corrosion Resistance and Structure of Passive Film on Fe–Mn–Si–Cr–Ni Steel

Nano Structure of the Rust Formed on an Iron-based Shape Memory Alloy (Fe–Mn–Si–Cr) in a High Chloride Environment

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