Mn 2p Spectra Research Articles

Multiplet XPS analysis of the Mn 2p for Mn3O4 thin films

In this work, we performed a detailed analysis of the x-ray photoemission spectroscopy (XPS) of the Mn 2ppeak for Mn3O4(001) thin films. This is a challenging task since Mn3O4is composed of two different cations, Mn2+at tetrahedral and Mn3+at octahedral sites, which both contribute to the XPS spectra. The oxide spectra consist of many multiplets arising from the angular momentum coupling of the open Mn 2pand 3dshells, thus increasing the spectrums' complexity. Moreover, the energy spacing and intensities of the different multiplets also reflect the covalent mixing between Mn 3dand O 2pshells. However, we show that a detailed analysis, which provides relevant information about the cations in the oxide structure, is possible. We prepared experimentally different Mn3O4films on Au(111), and their structure was monitored with the diffraction pattern obtained with low-energy electron diffraction. The Mn 2pspectra were fit, guided by cluster model theoretical predictions, and checked for films prepared at different oxygen partial pressures. Therefore, we could observe the Mn2+and Mn3+cations' relative concentration in the Mn 2pmains peaks.

Crystal structure, composition and valence state of cations in mixed-valence A1-xCdxMnO3 (A=Pr, La) ceramics

Abstract Complex manganites A1−xCdxMnO3 (A = Pr, La) are synthesized by solid state reaction method. X-ray diffraction, scanning electron microscopy and energy-dispersive analysis are applied to study their crystal structure, surface morphology, elemental and phase composition. X-ray photoelectron spectroscopy (XPS) methods are used to study the charge states of Pr and La cations, as well as to quantify the fractions of coexisting Mn3+ and Mn4+ ions. La3d-, La4d-, Pr4d- и Mn2p-spectra of La3+, Pr3+, Mn3+ and Mn4+ ions are calculated in the isolated–ion approximation with accounting for multiplet splitting and charge transfer effect. Good agreement with the experiment is obtained. The relative fractions of trivalent and tetravalent manganese ions in La0.45Cd0.78Mn0,9O2.86 and Pr0.50Cd0.76Mn0.86O2.88 samples are determined by fitting the Mn2p spectra by superposition of experimental spectra containing only Mn3+, and only Mn4+ ions; they were found to be 0.71Mn3+/0.29Mn4+ and 0.54Mn3+/0.46Mn4+, respectively.

Elements distribution and interfacial structure of CaO-SiO2-10mass% MnO under CO-CO2-SO2-Ar gas

In this work, the interfacial element distribution and structure of CaO-SiO2-10%mass MnO slag was explored using the gas-slag equilibrium experimental method and XPS detection method at the temperature of 1873 K. Based on the full spectrum, the relative content of sulfur gradually decreases, the manganese has the same trend, while the calcium content keeps increasing. According to the analysis of the Mn2p and S2p spectra, it indicated that Mn and S exist as positive divalent (Mn2+) and negative divalent (S2-), respectively. The O1s fitting result indicates that the proportion of non-bridged oxygen (O-) increased, while that of bridged oxygen (O0) decreased with the etching time increased. The structural units obtained by Raman spectroscopy are closer to the evaluation data of the CaO-SiO2 system, while the interfacial structure information tends to the MnO-SiO2 system. Although CaS is thermodynamically more stable than MnS, the reason for the sulfur accumulation in the gas-slag interface is due to the d electron supplement from Mn. Thus, the concept of interface sulfide capacity is proposed. As the etching depth increases, the interface sulfide capacity decreases continuously. Comparing XPS and Raman, the structure has a gradient change trend at the gas-slag interface, which confirms the presence of the boundary layer at the gas-slag interface.

Enhancing nitrate removal from wastewater by integrating heterotrophic and autotrophic denitrification coupled manganese oxidation process (IHAD-MnO): Internal carbon utilization performance

Due to cause the deterioration of water quality and can produce toxic nitrite, the nitrate constituted of great threatens to human health and eco-systematic safety. Among most well-known biotechnology to remove nitrate, the integrated heterotrophic and autotrophic denitrification (IHAD) process is promising, especially for the organic-limited polluted water. In this work, the IHAD coupled manganese oxidation (IHAD-MnO) process was developed by using Pseudomonas sp. SZF15 (Gram negative strain, and rod-shaped morphology with 2.3 μm in length) in the glass serum bottles. It was found that limited organic content could accelerate nitrate removal rate, and manganese oxidation efficiency can reach up to 60.08%. To further explain carbon conversion characteristics of the process, pure heterotrophic condition assays were conducted, the results confirmed that inorganic carbon will be generated by organic carbon metabolism in heterotrophic condition, the maximum accumulation content of inorganic carbon was 142.21 mg/L (when the initial organic carbon level was 293 mg-C/L). Subsequently, since the consumption of organic carbon, biogenic inorganic carbon can be further utilized by microorganisms to support autotrophic denitrification (AuDN). Besides, X-ray photoelectron spectroscopy (XPS) was employed to analyze precipitation products produced from the process. The magnified Mn 2p spectra results showed that a typical characteristic peak of manganese dioxide was observed with the intense peak at 641.8 eV and a satellite peak at 653.7 eV, respectively. This showed that Mn(II) was oxidized to manganese dioxide by the process, which may be a functional material with adsorption properties. The process posed a highly efficient and cost effective solution with less carbon consumption and less greenhouse gas emission for sustainable water treatment technologies.

Simultaneous quantitative recognition of all purines including N6-methyladenine via the host-guest interactions on a Mn-MOF

Simultaneous quantitative recognition of all purines including N6-methyladenine via the host-guest interactions on a Mn-MOF

Cathode-Electrolyte Interphase in Lithium Batteries Revealed by Cryogenic Electron Microscopy

Summary Cathode electrolyte interphase (CEI), the intimate coating layer formed on the positive electrode, has been thought to be critical. However, many aspects of CEI remain unclear. This originates from the lack of effective tools to characterize structural and chemical properties of these sensitive interphases at nanoscale. Here, we develop a protocol to preserve the native state and directly visualize the interface on the positive electrode using cryogenic electron microscopy. We find that under normal operation conditions, there does not exist an intimate coating layer at the single-particle level in carbonate-based electrolyte. However, upon brief external electrical shorting, a solid-electrolyte interphase, which usually forms on anodes, could form on cathodes and be electrochemically converted into a stable, conformal CEI in situ. The conformal CEI helps improve Coulombic efficiency and overall capacity retention of the battery. This generates a different perspective of CEI in commercial carbonate-based electrolytes than previously understood.

Structural, morphological and magnetic properties of GaSbMn/Si(111) thin films prepared by radio frequency magnetron sputtering

The structural, chemical and magnetic properties of GaSbMn thin films grown by Radio Frequency magnetron sputtering on Si (111) substrates, varying the growth temperature, were studied. X-ray diffraction analysis shows that the samples are polycrystalline with multiple phases, and their crystalline quality improves as the substrate temperature increases. A morphological study was carried out using transmission electron microscopy and scanning electron microscopy, revealing the formation of magnetic nanoparticles and precipitates, which depends on the growth temperature. The electronic structure of the films, studied by X-Ray Photoelectron Spectroscopy, exhibits a closely spaced doublet that arises from the spin-orbital coupling into Ga 2p, Sb 3d, and Mn 2p spectra. Measurements of Magnetization as function of temperature, performed in a low external magnetic field (0.05 T), revealed a ferromagnetic ordering from low temperatures to above room temperature, due to the existence of the multiphases GaSbMn, MnSb and GaMn. The magnetization loops taken at 5 K, 150 K, 298 K and 350 K, show that saturation magnetization depends on the sample preparation temperature. For the sample grown at 573.15 K, saturation magnetization decreases with increasing temperature from 5 to 350 K, while for the sample grown at 773.15 K, it is almost independent of temperature, due to the formation of MnSb and GaMn precipitates embedded into GaSb semiconductor matrix.

Arsenic remediation onto redox and photo-catalytic/electrocatalytic Mn-Al-Fe impregnated rGO: Sustainable aspects of sludge as supercapacitor

Synergistic Mn-Al-Fe impregnated rGO hybrid (MAF-rGO) is developed and verified for arsenic remediation. Preliminary adsorption studies are observed through vibrational spectroscopy and morphological tools. Adsorption isotherms are fitted by Freundlich model multilayer sorption with a loading of 402 mg g−1 [As(III)], and 339 mg g−1 [As(V)]. Adsorption kinetics study in competing ion environment [SO42−, PO43−, NO3−, CO32−] confirms the PSO model-controlled chemisorption as the rate-limiting step. The irradiation of white light (> 420 nm) in adsorption kinetics study shows a two-fold increase in the arsenic loading parameters (5–10 min). Multiplet peaks in As3d spectra (XPS) confirm the transformation of arsenic species in the near-surface region of hybrid [i.e., As(III), As(V)]. The occurrence of redox-active, ligand-exchange reactions are confirmed by individual Mn2p, Fe2p, Al2p, O1s, and C1s spectra. The dedicated electrochemical study confirms arsenic decontamination occurred through both reduction and sorption (i.e., electrosorption). An energy bandgap (Eg) of 2.17 eV resulted in the photocatalytic activity, which enhanced the arsenic remediation. Photo-electrocatalytic synergism resulted in high photocurrent densities (0.2–0.9 mA cm−2) with charge separation [e−–h+], and built-in potential abilities (Schottky-junction; Water-splitting). Arsenic-treated hybrid (i.e., sludge) is observed with an ultra-high stable charge–discharge cyclic performance for 100,000 cycles (~77 %) with improved specific-capacity of 125 F g−1 over pristine hybrid (92 F g−1). The better electrochemical parameters of sludge are due to the efficient lithiation/de-lithiation process supported by adsorbed arsenic. This work proposes sustainable approach towards environmental remediation and energy storage applications.

Electronic structure of CaMn1-xNbxO3 (x=0.02, 0.04, 0.06 and 0.08) perovskites. Self-organization of terminal layers

Electronic structure of niobium doped CaMn1-xNbxO3 (x = 0.02, 0.04, 0.06 and 0.08) powder and fresh chip manganites was studied by x-ray absorption near edge spectroscopy (XANES) at Mn K-edge, and by x-ray photoelectron spectroscopy (XPS) of Mn 3s -, Mn 2p -, O 1s -, Ca 2p- and Nb 3d-core levels. These XPS spectra for all the studied perovskites are very similar. The O 1s and Ca 2p spectra for powders differ from those for fresh chips because of the quick oxidation and carbonization of powder surface. The Mn 3s, Mn 2p and Nb 3d spectra for the powders and fresh chips are almost the same. According to Mn 3s spectra the formal valence of surface manganese ions is 3.82 for all studied oxides indicating the presence of oxygen vacancies in the samples. Niobium is in pentavalent state as evidenced by XPS measurements, but the negative chemical shift of the Nb 3d5/2 core level with respect to Nb2O5 oxide is observed. High similarity of the XPS spectra of the samples with different Nb doping is probably a result of the self-organization of terminal layers.

Transition mixed-metal molybdates (MnMoO4) as an electrode for energy storage applications

MnMoO4 nanoparticles were synthesized by employing solvothermal method at optimized experimental condition to explore their electrochemical properties. The fundamental characterization studies such as X-ray diffraction, Raman spectroscopy, and Fourier transform infrared spectra confirmed the formation of pure phase of monoclinic crystal structure with C2/m space group. X-ray photoelectron spectroscopy studies revealed that the core-level Mn-2p spectrum peaks observed at 641.2 eV can be attributed to Mn-2p3/2 and that at 654.1 eV can be indexed to the binding energy of Mn-2p5/2. Major infrared peaks observed at 725, 800, 867, and 946 cm−1 could be designated to the characteristics bands of tetrahedral MoO4 groups in MnMoO4 nanoparticles. Raman peaks observed at 351, 823, 886, and 932 cm−1 corresponded to characteristics bands for MnMoO4 nanoparticles. The cyclic voltammetry studies at different scan rates (i.e., 10, 20, 30, 50, 80, and 100 mV s−1) were performed for all three MnMoO4 nanoparticles and displayed similar redox peaks in the positive and negative current regions, reflecting the pseudocapacitive nature. From galvanostatic charge–discharge profiles, it was found that MnMoO4 nanorods (R2) show high- capacitance of 697.4 F g−1 at 0.5 A g−1 current density and 40% increment in specific capacitance than other nanoparticles and can be considered as suitable nanomaterials as electrode for energy storage applications.

Correlating Voltage Profile to Molecular Transformations in Ramsdellite MnO2 and Its Implication for Polymorph Engineering of Lithium Ion Battery Cathodes

Transition metal oxides are the primary choice for cathode materials in lithium ion batteries. These oxides occur as different polymorphs that have varied structures, stabilities, and affinities for Li+, and consequently, it is desirable to develop heuristics for the choice of the optimal polymorph. MnO2 is the most extensively used cathode material for lithium ion battery, and it exists in more than ten polymorphic forms. Among them, ϒ-MnO2, the most electrochemically active polymorph, is a mixture of pyrolusite and ramsdellite polymorphs. Here we have focused on the less explored ramsdellite MnO2 (R-MnO2). Highly crystalline R-MnO2 has been synthesized, and the experimentally obtained discharge features are compared with the calculations based on density functional theory followed by cluster expansion to obtain molecular insights into the intercalation process. R-MnO2 shows voltage fading beyond x = 0.5 (in LixMnO2). Computational results suggest that change in Li environment from tetrahedral to octahedral beyond x = 0.5 (in LixMnO2) causes the voltage fading. This change in Li environment is also correlated with experimentally obtained Mn 2p, O 1s, and valence band XPS spectra. The shift in the d-band center, plotted for valence band spectra at different lithium concentrations, is adduced for the migration of lithium ion from the tetrahedral site to the less favorable octahedral site beyond x = 0.5. Volume expansion of about 20% at full lithiation is accompanied by Jahn–Teller distortion of MnO6. Further, computations reveal the diffusional energy barrier to be 200 meV in the limit of dilute Li concentration (x = 0.125) and 481 meV in the limit of dilute vacancy concentration (x = 0.875). A structural rationale for the energy barrier is developed. The experimental and computational studies provide insight into the lithiation mechanism in R-MnO2 and are relevant to rationalize the high performance of the intergrowth structure of ϒ-MnO2. We discuss a wider implication of the study by correlating the voltage profile with structural changes in MnO2 polymorphs, which gives general design principles to make better cathodes through polymorphic engineering.

Valence state of cations in manganites Pr1-xCaxMnO3 (0.3 ≤ x ≤ 0.5) from X-ray diffraction and X-ray photoelectron spectroscopy

Polycrystalline Pr1-xCaxMnO3 (х = 0.3, 0.35, 04, 0.45, and 0.5) samples are synthesized by solid-state reaction method. Crystal structure of the samples is studied by X-ray diffraction method with Rietveld refinement. Diffraction patterns from all the samples are well indexed within the Pnma space group. It is shown that lattice parameters and unit cell volume decrease monotonically and O−Mn−O angles become closer to the ideal 180⁰ value upon the growth of x. Mn2p, Mn3s, Ca2p, Pr3d, Pr4d, and O1s X-ray photoelectron spectra are measured. Pr3d and Pr4d spectra are calculated in isolated ion approximation with approximate accounting for the charge transfer effect. Elemental compositions of samples are measured by the XPS method; they differ noticeably from the nominal ones. Charge compensation upon heterovalent Pr3+ → Ca2+ substitution is shown to realize via two mechanisms: creation of oxygen vacancies and formation of Mn4+ ions coexisting with Mn3+. Relative Mn4+/Mn3+ abundances are determined via decomposition of Mn2p and Mn3s XPS into contributions from the spectra of tri- and quadrivalent Mn ions. The amount of Mn4+ ions is shown to increase with Ca content x.

Systematic study on surface and magnetostructural changes in Mn-substituted dysprosium ferrite by hydrothermal method

Dysprosium iron garnets are of scientific importance because of the wide range of magnetic properties that can be obtained in substituting dysprosium by a rare earth metal. In the present work, the effect of Mn substitution on magnetostructural changes in dysprosium ferrite nanoparticles is studied. Highly crystalline pure and Mn doped dysprosium ferrite nanoparticles were synthesized by hydrothermal method. The samples were calcined at 1100°C for 2h in air atmosphere which is followed by characterization using XRD, FT-IR analysis, SEM, XPS and VSM. The average crystallite size of synthesized samples were calculated by X-ray diffraction falls in the range of 88.4–86.8nm and was found to be in cubic garnet structure. For further investigation of the structure and corresponding changes in the tetrahedral and octahedral stretching vibrational bonds, FT-IR was used. The synthesized samples consist of multiple oxidation (Fe3+ and Fe2+) states for Fe ions and (Mn3+ and Mn2+) Mn ions analyzed in three ways of Fe 2p and Mn 2p spectra from the XPS analysis. With respect to Mn dopant in Dy3Fe5O12, the cationic distributions of elements were discussed from high resolution XPS spectra by peak position and shift, area, width. To find out the porous/void surface morphology of the sample, scanning electron microscopy was used. From XPS analysis, the presence of elements (Dy, Mn, Fe and O) and their composition in the prepared samples were confirmed. Further, the role of dopant on the magnetic properties of the dysprosium ferrite nanoparticles was also observed from VSM which shows the ferromagnetic behavior. It was concluded that the magnetic properties of synthesized nanoparticles mainly depended on the oxidation state of elements, cationic distribution and crystallinity.

Valence state of manganese and iron ions in La1−xAxMnO3 (A = Ca, Sr) and Bi1−xSrxFeO3 systems from Mn2p, Mn3s, Fe2p and Fe3s X-ray photoelectron spectra. Effect of delocalization on Fe3s spectra splitting

La1−xCaxMnO3 (x = 0.5, 0.7, 0.85, 0.95) ceramic samples are synthesized by solid state reaction method. Mn3s and Mn2p X-ray photoelectron spectra (XPS) of La1−xCaxMnO3, and Fe3s-spectra of Bi1−xSrxFeO3 (0 ≤ x ≤ 1) are measured at room temperature. Both Mn3+ and Mn4+ ions are discovered in La1−xCaxMnO3 similarly to the case of Fe3+ and Fe4+ found earlier in Bi1−xSrxFeO3 ceramics. Relative Mn3+/Mn4+ contents are determined by fitting measured Mn2p spectra with combinations of Mn2p spectra of compounds containing tri- and quadrivalent Mn ions. Relative portion of Mn4+ is shown to increase with the increase of x. Fe3s spectrum splitting in Bi1−xSrxFeO3 increases with x in contrast to the Mn3s-spectrum splitting in La1−xCaxMnO3 and La1−xSrxMnO3. Anomalous behavior of Fe3s splitting is explained in the frame of the model of partly itinerant 3d-electrons by strong effect of 3d electron delocalization on electron correlation interaction in final state of 3s photoabsorption.

Thallium and manganese complexes involved in the luminescence emission of potassium-bearing aluminosilicates

The luminescence emission at 285nm in natural K-feldspar has been studied by Russian groups and associated with thallium ions in structural positions of K+ sites as artificially thallium-doped feldspars display the same emission band. Here attention is focussed on spectra of CL emission bands centered near 285 and 560nm from paragenetic adularia, moscovite and quartz micro-inclusions. With accesorial thallium they show clear resemblances to each other. Associated sedimentary and hydrothermal aluminosilicate samples collected from Guadalix (Madrid, Spain) were analyzed with a wide range of experimental techniques including Environmental Scanning Electron Microscopy (ESEM) with an attached X-Ray Energy-Dispersive Spectrometer (EDS) and a cathodoluminescence probe (CL) and Electron Probe Microanalysis (EPMA), X-Ray Fluorescence Spectrometry (XRF), Inductively Coupled Plasma-Optical Emission Spectrometry (ICP-OES), Differential and Thermogravimetric Analyses (DTA-TG), radioluminescence (RL), Mössbauer spectroscopy and X-Ray Photoelectron Spectrometry (XPS). The luminescence emission bands at 285 and 560nm seem to be associated with hydrous thallium–manganese complexes bonded to potassium-bearing aluminosilicates since various minerals such as K-feldspar, moscovite and quartz micro-inclusions display similar CL spectra, accesorial thallium and hydroxyl groups. The presence of iron introduces a brown color which is attributed to submicroscopic iron oxides detectable in the optical and chemical microanalysis, but this does not contribute to the luminescence emission. The XPS Mn 2p spectrum of the adularia sample at room temperature is composed of a spin–orbit doublet plus clear shake-up satellite structure ~4eV above the main photoemision lines and is consistent with Mn2+ in good agreement with the observed luminescence emission at 560nm for aluminosilicates produced by a 4T1(4G)→6A1(6S) transition in tetrahedrally coordinated Mn2+. Moscovite samples display spectral CL bands at 285 and 560nm but only when the electron-beam is directed along the (010) orientation and not along the (001) orientation. The Tl+ versus K+ cation isomorphism anchors the luminogenous hydrous thallium–manganese complexes to the potassium-bearing aluminosilicate surfaces under analyses. The CL emission bands at 285 and 560nm of these complexes together with the EDS detection of thallium are a fast analytical measurement detecting the presence of thallium in further studies involving this toxic element.

X-ray photoelectron study of temperature effect on the valence state of Mn in single crystal YMnO3

Temperature effect on the valence state of Mn in single crystal YMnO3 is studied using Y3d-, Mn2p-, and O1s-spectra. Mn2p- spectra of Mn3+ and Mn4+ ions at various temperatures are calculated in an isolated ion approximation. Original crystal at room temperature was found to contain only Mn3+ ions, whereas after the temperature treatment (heating in vacuum up to 593K, cooling down back to room temperature and consecutive heating to a given temperature), Mn4+ ions were detected in the crystal. Relative Mn4+/Mn3+ abundances at various final temperatures are determined by fitting the experimental Mn2p spectra with the superposition of theoretical spectra from Mn3+ and Mn4+ ions, and from relative intensities of O1s-spectrum components. Concentration of Mn4+ ions correlates with the distortion of the crystal structure reflected in overstoichiometry of manganese and understoichiometry of oxygen.

X-ray photoelectron spectroscopy studies the cation valencies and distributions in crednerite-Cu1.1Mn0.9O2 thin films

In this study, the cation valencies and distributions in crednerite-Cu1.1Mn0.9O2 thin films are studied. The lattice parameters of the sol–gel-derived crednerite-Cu1.1Mn0.9O2 thin films were a=0.55759nm, b=0.28754nm, c=0.58847nm, and β=104.18°. The binding energies of the Cu-2p spectrum were 932.3±0.2eV (2p3/2) and 952.3±0.2eV (2p1/2), which represent the Cu+ in the thin films. Moreover, three binding energies at 639.8±0.2eV, 641.1±0.2eV, and 643.4±0.2eV were found in the Mn-2p spectrum. The binding energies of the Mn-3p spectrum were 47.3±0.2eV, 48.0±0.2eV, and 49.9±0.2eV for the crednerite-Cu1.1Mn0.9O2 thin films, which reveal that the thin films have Mn2+, Mn3+, and Mn4+ cations. Additionally, the cation distributions in the thin films were Cu1.1+[Mn0.24–0.272+Mn0.53–0.543+Mn0.20–0.224+]0.9O2 from the X-ray photoelectron spectroscopy.

Valence state of manganese ions in the La1−α BiLaβMnLa1−δ OLa3±γ ceramics

The valence state of the Mn ions in ceramic samples of the La1−α BiLaβMnLa1−δ OLa3±γ composition (LBMO) has been studied using the X-ray photoelectron spectroscopy. The presence of Mn3+ and Mn4+ ions in these compounds has been shown. The relative content Mn3+/Mn4+ has been determined by means of fitting the experimental Mn 2p spectra by the superposition of theoretical spectra of Mn3+ and Mn4+ ions. The elemental composition of the samples has been determined by the X-ray photoelectron spectroscopy and electron probe microanalysis. It has been established that the relative content of Mn4+ ions correlates with parameter δ, which characterizes the deviation of the actual elemental composition of the La1−α BiLaβMnLa1−δ OLa3±γ ceramics from stoichiometry La1 − xBixMnO3.

XPS analysis of manganese in stainless steel passive films on 1.4432 and the lean duplex 1.4162

Passive films were compared on two stainless steels: the recent lean duplex EN 1.4162 and EN 1.4432 (316L). For alloys with significant amount of manganese and nickel, the Mn 2p 3/2 peak will overlap with the Ni-LMM. To resolve this overlap, Ni 2p 3/2 to Ni-LMM intensity ratios were recorded on 1.4432, compensated for overlayer thickness, and then used to fix the Ni-LMM intensities in the Mn 2p spectra on the duplex material. Manganese was found in oxidation states II and V/VI; its film content was not dependent on the bulk composition.

Electronic structures and Hall effect in low-doped La0.9Hf0.1MnO3 epitaxial films

The electronic structures of low-doped epitaxial La0.9Hf0.1MnO3 (LHMO) thin films are investigated by x-ray photoemission spectroscopy (XPS) for the first time. XPS spectra of core levels (La 3d, Hf 4f, O 1s, Mn 2p, and Mn 3s) are taken from the cleaned LHMO film surface. Hf 4f spectrum exhibits a typical binding energy (BE=2 eV) of Hf4+. The splitting energy of La 3d core-lever spectrum agrees with the previous reports of other doped LaMnO3 and suggests a trivalent state in the LHMO film. The calculated result of LHMO nominal composition, the shape of Mn 2p spectrum, the separated BE (111.1 eV) between O 1s and Mn 2p2/3 peaks and the splitting energy (6.0 eV) of Mn 3s all reveal that the LHMO compound is in a mixed valence state of Mn2+ and Mn3+, implying an electron-doped conduction mechanism. The magnetic-field dependence of Hall resistivity further confirmed that the carriers in LHMO are electrons.