MnO3 Films Research Articles

Layered Manganese Dioxide Intercalated with Copper Ions for Electrochemical Reduction of Nitrate to Ammonia

Electrochemical nitrate reduction reaction (NO3RR) offers a new pathway for low-temperature green ammonia synthesis. Here, we prepared a thin film of layered MnO2, the interlayer of which accommodates Cu2+ ions coordinated with water molecules. The process consisted of electrodeposition of layered MnO2 intercalated with tetrabutylammonium cations (TBA+) by anodic oxidation of aqueous Mn2+ ions in the presence of TBA+, followed by ion exchange of the initially incorporated bulkier TBA+ with the Cu2+ ions in solution. The resulting layered MnO2 intercalated with Cu2+ ions (Cu2+/MnO2) supported on a FTO substrate was applied to electrochemical NO3RR. In the potentiostatic reduction at –0.7 V vs RHE in NaOH electrolyte, the Cu2+/MnO2 electrode catalyzed NO3RR with higher faradic efficiency for ammonia formation than Cu plating electrode. X-ray diffraction spectroscopy indicated that the structure of layered MnO2 was maintained during NO3RR. In addition, linear sweep voltammogram and X-ray photoelectron spectroscopy suggested the electrochemical reduction of the Cu2+ ions between MnO2 layers and in situ generation of metallic Cu particles prior to NO3RR. Figure 1

Magnetic Circular Dichroism of Oxide Films: Study of Electronic, Magnetic and Charge States

Semiconductor materials based on ZnO and RE3+MnO3 oxides are considered as potential candidates for spintronics. This article presents the methodology and results of studying the effect of magnetic circular dichroism for Zn1-xCoxO, Zn1-x-yCoxAlyO and RE1-x 3+Ax 2+MnO3 film structures in the visible radiation range. It has been shown that the magnetic circular dichroism behavior of the manganite films reflects not only the magnetic, but also the charge component of the material. This indicates the possibility of studying the magnetic and transport characteristics of the films using the magnetic circular dichroism spectroscopy. Since the magnetic circular dichroism effect also directly probes the ground and excited electronic states of the film, it has been obtained data that update calculated parameters for describing the manganites band structure. In the case of the Zn1-xCoxO and Zn1-x-yCoxAlyO films, the magnetic circular dichroism spectroscopy acts as a tool for detecting Co nanoparticles in the solid solution matrix of ZnO:Co and ZnO:(Co+Al).

Exploration of electrical conduction mechanisms via modulating sintering period of La0.67Ca0.33MnO3 films in various phase regions

Perovskite manganese oxide films have garnered significant attention due to their unique and diverse physical properties. In this work, La0.67Ca0.33MnO3 (LCMO) films are prepared on LaAlO3 (00l) substrates using the sol−gel spin coating method with varying sintering period (Ps). By optimizing Ps, improvements were observed in the films’ structure, morphology, ionic valence, and temperature−dependent resistivity. The reduction in Mn−O bond length and the increase in Mn−O−Mn bond angle change the degree of MnO6 distortion, resulting in an increased eg bandwidth. As Ps increased, the LCMO films exhibited better crystalline quality. The improved Mn4+/Mn3+ ratio strengthened the double exchange effect, facilitating the carrier hopping of the eg electrons. Analyses of various electrical conduction mechanisms showed that optimized electron scattering behavior, reduced hopping distance, energy and theoretical Curie temperature collectively enhance the temperature coefficient of resistivity (TCR) of LCMO films under optimal Ps. The TCR of the LCMO films reached a maximum value (31.64 % K−1) at Ps = 18 min. These findings offer valuable insights into the main electrical conduction mechanisms in both metallic and semiconducting phases, providing a deeper understanding of the underlying physical processes and offering experimental guidance for optimizing the electrical transport properties of perovskite films.

Electron-lattice coupling and double exchange effects to improve TCR of La0.67-xNdxCa0.25Sr0.08MnO3 films grown on La0.3Sr0.7Al0.65Ta0.35O3 substrates

In this study, La0.67−xNdxCa0.25Sr0.08MnO3 (LNCSMO, x = 0.09, 0.10, 0.11, 0.12) films were prepared by sol-gel spin coating method. The results indicate that the LNCSMO film is oriented and grown on a La0.3Sr0.7Al0.65Ta0.35O3 (LSATO) (00l) substrate. In addition, with the increase of Nd3+ content, the Mn-O bond length (dMn-O) and Mn-O-Mn bond angle (θMn-O-Mn) decreases. The concentration ratio of Mn4+ increases firstly and then decreases, and resulting in an enhanced and then weakened double exchange (DE) effect. Measuring the variation of sample resistivity with temperature (ρ-T) using the standard four-probe method. As the content of Nd3+ increases, the metal-insulator transition temperature (Tp) gradually decreases, and the resistivity (ρ) gradually increases. The replacement of Nd3+ makes the peak temperature coefficient of resistivity value (TCRmax) of the material firstly increase and then decrease. At x = 0.11, the TCRmax reaches 34.28% K-1 at 254.72 K. This provides new insights into the impact of Nd doping on electrical transport properties.

Characterization of Mn3O4/(x)Nb2O5 thin films as a promising material for supercapacitors

The thin films of Mn3O4/(x)Nb2O5 oxides (x = 0, 2, 4, and 6 %) were prepared by the electron beam evaporation method and then annealed at 400 °C. The structural analysis showed a tetragonal phase of Mn3O4, according to X-ray diffraction results. The quantitative elemental analysis of films confirms the stoichiometry of the Mn3O4, while the Nb2O5 couldn’t be recognized using energy dispersive X-ray fluorescence. The chemical speciation of the films was investigated using X-ray photoelectron spectroscopy. Three oxidation states of Mn were recognized at average binding energies of 645.70±0.35, 642.99±0.40, and 641.58±0.48 eV that correlated to Mn4+, Mn3+, and Mn2+, respectively. As the Nb2O5 increases, a slight decrease in the binding energy of Mn4+ is recognized, whereas it is nearly constant for the deconvoluted Mn3+ and Mn2+. Two electronic transitions (Eg1 and Eg2) of the optical band gap showed an increase with increasing Nb2O5 dopant from 2 % to 6 %. The optical parameters such as Eosc, the single oscillator energy, Edis, the dispersion energy, both moments (M−1) and (M−3), the ratio of carrier concentration/effective mass (N/m*), and the lattice dielectric constant (εL) were determined. From electrochemical measurements of pure Mn3O4 films, it is found that the voltammetric current density is directly proportional to the scan rates of cyclic voltammetry CV, with good cyclic stability, and by increasing the scan rates, the values of specific capacitance decrease while the values of specific power increase. In doped thin films, no potential drop is observed in the discharging process, which indicates good interfacial contact between the active material and the substrate during the charge/discharge process. These results suggest that the obtained Mn3O4 nanoparticles are a better candidate for supercapacitor applications.

Robust resistance switching performance in a Ca3Ti2O7/La0.67Sr0.33MnO3 heterostructure induced by the interface

Ruddlesden–Popper phase oxides, such as Ca3Ti2O7, have been established as hybrid improper ferroelectrics. However, investigations into Ca3Ti2O7 have primarily concentrated on their structural and ferroelectric properties. In this study, we prepared epitaxial Ca3Ti2O7 thin films via magnetron sputtering. Conducting atomic force microscopy was employed to characterize local current variations under an applied bias voltage. Electron paramagnetic resonance measurements of the Ca3Ti2O7/La0.67Sr0.33MnO3 film were conducted to assess its defect characteristics. Interestingly, the Ca3Ti2O7/La0.67Sr0.33MnO3 stacks exhibited remarkable macroscopic resistance switching, with a resistance on/off ratio reaching 100, alongside robust retention (∼2500 s) and endurance (∼2000 cycles) features. Additionally, density functional theory calculations suggest that the resistance switching is attributable to the interface barrier of the Ca3Ti2O7/La0.67Sr0.33MnO3 interface and the efficacy of space charge limitation. This work proposes an avenue for the utilization of Ruddlesden–Popper phase Ca3Ti2O7 in various applications.

Synergistically achieving particulate matter reduction and production performance optimization for zinc electrolysis by ultrasonication coupling anode-coated MnO2

Abating particulate matter (PM) from electrolysis processes is significant because this PM poses occupational threats to workers and has a negative impact on air quality. However, it remains a challenge to synergize the reduction of PM production and the improvement of electrolysis performance. This study developed a green method, termed as the coupling of ultrasonication and pre-coating MnO2 anode treatment (UMT). The effects on PM generation rate and electrolysis performance indicators were estimated using the bench-scale zinc electrolysis device, and the synergistic mechanism of UMT was expanded from the perspective of electrochemical reactions and bubble characteristics using analysis of reaction products, camera technique, and PM generation prediction models. The results showed UMT not only overcame the degradation of deposited zinc quality caused by the ultrasonication treatment but also solved the increased PM generation by the pre-coating MnO2 film treatment. The UMT simultaneously reduced PM (33.9 %-57.5 %), decreased zinc impurity content by (11.2 %-54.3 %), improved current efficiency of zinc deposition (0.19 %-1.71 %), and conserved electrolysis energy (0.27 %-1.01 %). The optimal performance of UMT occurred at 80 kHz. The UMT suppressed the gas evolution reactions and prematurely bursting bubbles, in favor of reducing the number and size of bubbles, to reduce PM generation. Meanwhile, the UMT improved the electrolysis performance by inhibiting the corrosion of lead-based anodes, promoting the mass transfer rate of Zn2+, providing more active surfaces, and decreasing the overpotential of reactions. The findings may provide references for the green development of the metal electrolysis industry.

Efficient electrical control of magnetization switching and ferromagnetic resonance in flexible La0.7Sr0.3MnO3 films

Efficient electrical control of magnetization switching and ferromagnetic resonance in flexible La0.7Sr0.3MnO3 films

Effect of pH on the Selectivity of γ-MnO2 Electrocatalysts Towards Oxygen Evolution Reaction in the Presence of Chloride Ions in Alkaline Environment

This paper reports on progress in development of electrocatalysts intended for use in seawater, which optimize the balance of competing reactions between chlorine evolution and oxygen evolution. The oxygen evolution reaction (OER) from H2O is thermodynamically more favorable due to a lower equilibrium potential [1]. However, chlorine evolution successfully competes with the OER due to faster kinetics. One of a few catalysts that demonstrates high selectivity towards the OER in the presence of chloride ions in the alkaline environment (i.e. pH 12) is γ-MnO2 [2].In this presentation, we (1) compare activities and selectivities towards the OER of electrodeposited and chemically synthesized γ-MnO2 and (2) determine how pH affects selectivity in the pH range from 11 to 13.g-MnO2 powder was synthesized using hydrothermal method. The synthesis resulted in fabrication of material with a flower-like morphology, characterized by a crystallite size of 5-15 nm and BET surface area of 75 m2/g. In parallel, MnO2 films were prepared by electrodeposition on a Pt RDE substrate, following the procedure outlined by Tsagareli et al. [3]. The electrocatalytic activity of both γ-MnO2 powder and electrodeposited MnO2 was investigated by the thin-film RDE method. The thin films of γ-MnO2 powder were obtained by drop-casting MnO2/VC ink [1] on glassy carbon substrates.We found that the shape of polarization curves on MnO2/VC films is strongly dependent on the Nafionä loading. At low Nafion loadings, we observe diffusion-limited currents, which we attribute to OH- diffusion through the Nafion. At higher Nafion loadings, neither diffusion-limited currents, nor the currents’ dependence on the rotation rate are observed. Our data indicate that at low Nafion loadings, MnO2/VC films selectively produce O2 in 0.5M NaCl at pH 12 and 13 and current densities up to 15 mA/cm2. Because of the potential effect of Nafion on the permeability of Cl- ions to the catalyst’s active sites, a set of parallel experiments is being carried out on the electrolytically deposited MnO2 films. The results of the latter experiments will be compared to those obtained on MnO2/VC films in the presentation.

Base Metals Induced Oxygen Migration and Adjustable Performance in Multifunctional Oxide Heterojunction Devices

AbstractThe chemical and electronic interactions at metal/oxide heterojunctions is pivotal in determining the electronic properties of oxide devices utilized in microelectronics, catalysis, and photovoltaic systems. In this study, interfacial oxidation migrations within a model heterostructure system, consisting of a La0.7Sr0.3MnO3 film overlaid by various metallic (Ti, Al, Cu, Ag, and Au) ultrathin layers are systematically investigated. It is experimentally demonstrated that at elevated deposition temperature, the oxygen‐active ultrathin overlayers of base metals such as Ti and Al significantly derive oxygen from the underlying La0.7Sr0.3MnO3 film, inducing a perovskite to brownmillerite phase transition in the underlying functional oxide film. Conversely, no structural transitions are observed for La0.7Sr0.3MnO3 film when it is capped by noble metals (Au, Ag), which possess relative high oxidation formation energy. These observations are crucial for the development of novel crystalline and electronic architectures in metal/oxide heterostructures, offering a refined approach to modulate interfacial reactivity without compromising the functionality of oxide‐based heterojunction devices.

Sign reversal and symmetry change of anisotropic magnetoresistance in antiferromagnetic LSMO films

The study of anisotropic magnetoresistance (AMR) holds dual significance in both theoretical and applied contexts. The underlying mechanisms of AMR remain unclear, and the phenomenon of AMR sign reversal (positive and negative transitions in values) has garnered multiple interpretations, demanding experimental verification. In this work, the effect of epitaxial strain on magnetic and transport properties of perovskite manganese oxide La0.35Sr0.65MnO3 films is investigated. The AMR demonstrates sign reversal and symmetry change behaviors. The symmetry changes of AMR stem from the competition between Zeeman energy, exchange interaction energy, and magnetocrystalline anisotropy energy. The sign reversal of AMR is attributed to the change in the density of states of spin up and spin down of conduction electrons during the magnetic phase transition induced by epitaxial strain. Our work offers experimental evidence and a reasonable explanation for the origin of the sign reversal of AMR.

Manganite Heterostructures: SrIrO<sub>3</sub>/La<sub>0.7</sub>Sr<sub>0.3</sub>MnO<sub>3</sub> and Pt/La<sub>0.7</sub>Sr<sub>0.3</sub>MnO<sub>3</sub> for Generation and Registration of Spin Current

This paper presents the results of experimental studies of the cross section of the boundaries of the SrIrO3/La0.7Sr0.3MnO3 и Pt/La0.7Sr0.3MnO3, heterostructures, in which, upon excitation of ferromagnetic resonance in a La0.7Sr0.3MnO3 film, a spin current arises that flows through the boundary in structure. Epitaxial growth of thin films of strontium iridate SrIrO3 and manganite La0.7Sr0.3MnO3 on a (110) NdGaO3 single-crystal substrate was carried out using magnetron sputtering at high temperature in a mixture of argon and oxygen gases. The spin mixing conductance, which determines the amplitude of the spin current and generally has real Re g↑↓ and imaginary Im g↑↓ parts, was determined from the frequency dependence of the FMR spectrum of the LSMO film and heterostructures. It is shown that the Im g↑↓ quantity, can play an important role in determining the spin Hall angle (θSH) from the angular dependence of the spin magnetoresistance. For the SrIrO3/La0.7Sr0.3MnO3 heterostructures, θSH turned out to be significantly higher (almost an order of magnitude) than for the Pt/La0.7Sr0.3MnO3 heterostructure.

MnO2 with/without Ni doped films on carbon fibers by for enhancing compression and thermoelectric performances of cement

A microwave anodic deposition process was developed to prepare MnO2/Ni-doped MnO2 films on carbon fibersfor the fillers of cement composites (CFRC) to enhance both thermoelectric and compression performances simultaneously. The resulting CFRCs were designated as M-MnO2/CFRC and M-Ni-MnO2/CFRC, respectively. The results showed that the M-Ni-MnO2/CFRC exhibited the best thermoelectric performance at 313K, achieving a Seebeck coefficient of −873.9 μV/K, electrical and thermal conductivities of 3.42 S/m and 0.613 W/mK, respectively, and thus ZT and PF values of 1.69 × 10−3 and 3.42μW/(m·K2), respectively. The superior thermoelectric performance of the M-Ni-MnO2/CFRCs compared to that of the M-MnO2/CFRCs or the MnO2/CFRCs without microwave involvement in electrodeposition was attributed to the increased density of states at the Fermi level in MnO2 due to Ni doping, and the better interfacial scattering electron carrier effect. Surprisingly, the compression strength of the M-Ni-MnO2/CFRC reached 82.5 MPa, marking a 171.2 % increase, while the elongation reached 1.71 %, a 3.50 times increase compared to pure cement.

Preparation and Electrochromic Properties of MnO2/PPy Composite Films with Coral-like Structures.

MnO2/polypyrrole (PPy) composite films were deposited on fluorine-doped tin oxide (FTO) conductive glasses by a two-step wet-chemical method, including electrochemical deposition and chemical bath deposition (CBD). The porous MnO2 films were first grown on FTO glasses by an electrodeposition method. Second, polypyrrole nanoparticles were polymerized by the oxidation-reduction reaction between MnO2 and pyrrole, using the presynthesized MnO2 as the skeleton. Then, MnO2/PPy composite films with coral-like structures were obtained. The electrochemical and electrochromic (EC) properties of the prepared films were investigated. The results show that, compared to the single MnO2 or PPy film, the MnO2/PPy composite film has a larger optical modulation (67.3% at a wavelength of 900 nm), faster response times (4 s for coloration and 3 s for bleaching), and a higher coloration efficiency (218.16 cm2·C-1). The high coloration efficiency attests to the exceptional performance of the composite film in converting electrical signals into vivid color changes. The electrochemical stability test results show that the composite film maintains a stable EC performance after 200 coloration/bleaching cycles. The coral-like structures of the composite film are responsible for the better EC properties.

Nuclear and magnetic structure of an epitaxial La0.67Sr0.33MnO3 film using diffraction methods

We use a combination of transmission electron microscopy, X-ray and neutron diffraction, Superconducting Quantum Interference Device (SQUID) magnetometry and symmetry analysis to determine the nuclear and magnetic structure of an epitaxial La0.67Sr0.33MnO3 film, deposited on a Si substrate. The film undergoes a magnetic ordering transition at 260 K. At 300 K, in the paramagnetic phase, the manganite film has a I4/m space group. In the magnetic phase, SQUID and neutron diffraction results lead us to assign a ferromagnetic spin-order to the film, associated to magnetic moments with a slightly out-of-plane component, namely (3.5,0,0.3)μB. Symmetry analysis further shows that only the P1̄′ group is compatible with such a magnetic ordering.

Improving electrical transport properties of LaxCa0.89-xSr0.11MnO3 films via optimized La content

Optimized LaxCa0.89-xSr0.11MnO3 (x = 0.65, 0.68, 0.71 and 0.74) films were fabricated using spin-coating method. According to double exchange (DE) mechanism and Jahn-Teller effect, the enhancement of peak temperature coefficient of resistivity (TCR) was attributed to low residual resistivity and weak various electron scatterings, including electron–electron, electron–phonon and electron-magnon. Also, peak TCR temperature is not only influenced mainly by the DE mechanism, but also by the Mott transition. Moreover, optimized sintering improved film crystallinity, increasing peak TCR value. The resulting La0.71Ca0.18Sr0.11MnO3 film displayed a peak TCR of 10.74 %/K at 294.11 K. Appropriate chemical composition and sintering promoted the enhancement of electrical transport properties.

Effect of Annealing Process on the Morphological, Optical and Electrical Properties of Cu:MnO Films Prepared by PLD Technique

In this study, Nd:YAG laser pulses with a wavelength of 1064 nm, a power of 500 mJ, a pulse width of 9 ns, and a repetition frequency of 6 Hz were used to hit a manganese oxide (MnO) target surface 300 times. Pure MnO and copper Cu-doped MnO (Cu:MnO) with different amounts of Cu (0.03, 0.05, 0.07, and 0.09 wt%) produced by PLD were studied. Cu:MnO thin films were annealed at 473 K, and their morphological, optical, and electrical characteristics were studied. The results of the atomic force microscopic (AFM) investigation of morphological properties showed that Cu dopant impacted the creation of roughness and particle size in MnO2 films. The optical transmission was examined using a UV-Vis spectrophotometer. The highest optical absorption was noted at 0.09 dopant content. The dielectric constants' real (εr) and imaginary (εi) components, as well as the extinction coefficient (k), refractive index (n), and other optical constants, were studied. At an annealing temperature of (473 K), Hall effect studies demonstrate that all produced films exhibit a P-type conductivity.

Charge-exchange-driven interfacial antiferromagnetic ground state in La0.8Sr0.2MnO3 ultrathin films

The evolution of the magnetic ground state of ultrathin 0–10 unit cells (uc) thick La0.8Sr0.2MnO3 films interfaced to an antiferromagnetic La0.45Sr0.55MnO3/SrTiO3(001) buffer layer was investigated with x-ray photoemission electron microscopy. For 0–3 uc La0.8Sr0.2MnO3, we observe antiferromagnetic domains but no ferromagnetic contrast, showing that nominally ferromagnetic La0.8Sr0.2MnO3 adopts the antiferromagnetic ground state of the buffer layer. For larger thicknesses, ferromagnetic domains emerge, confirming that the additional layers revert to the ferromagnetic ground state. We also observe a drastic increase in the complexity of the domain configuration between 3 and 5 uc, which we attribute to competing magnetic and electronic ground states in the system. We attribute the interfacial modified magnetic ground state to charge sharing at the interface due to the chemical potential mismatch, which leads to hole doping at the La0.8Sr0.2MnO3 interface. The present work sheds light on the impact of charge sharing at the interface of complex oxide materials, in particular on the magnetic and electronic states, and presents a strategy for modulating the electronic ground state properties at metallic interfaces.

Novel promising aqueous electrolytes for manganese dioxide/stainless steel pseudocapacitor electrode

Manganese dioxide (MnO2) films are developed by potentiostatic electrodeposition on a stainless steel sheet as a current collector using manganese acetate tetrahydrate solution at a concentration of 0.25 mol L−1. The deposited sample layer is found to be amorphous as confirmed by the scanning electron microscope (SEM) and X-ray diffraction (XRD) analyses. The capacitive property of the prepared electrodes is characterized by charging/discharging, cyclic voltammetry, and electrochemical impedance spectroscopy techniques in four different aqueous solutions; sodium sulfate, magnesium acetate, nickel acetate, and a mixture of sodium chloride + sodium bicarbonate + borax. Charge–discharge curves reveal higher specific capacitance (Cs) of 1580 F g−1 at 0.5 mA cm−2 for the investigated MnO2 film which is characterized in Ni acetate aqueous solution. The structural, morphological, and electrochemical properties of the electrodeposited manganese oxide films are also studied. The results indicate that the specific capacitance of the deposited samples showed a strong dependency on the electrolyte aqueous solutions, resulting in developing new electrolytes which is a top priority effort in comparison to seeking new electrode materials. It is found that the matching between the pore size structure of the electrode and the ion size of the electrolyte is of great importance for the improved capacity of prepared capacitors.

Long-range superconducting proximity effect in YBa2Cu3O7/La0.7Ca0.3MnO3 weak-link arrays

The interplay between ferromagnetism and superconductivity has attracted substantial interest due to its potential for exotic quantum phenomena and advanced electronic devices. Although ferromagnetism and superconductivity are antagonistic phenomena, ferromagnets (F) can host spin-triplet superconductivity induced via proximity with superconductors (S). To date, most of the experimental effort has been focused on single S/F/S junctions. Here, we have found the fingerprints of long-range superconducting proximity effect in micrometric weak-link arrays, formed by embedding YBa2Cu3O7 superconducting islands in a half-metallic ferromagnet La0.7Ca0.3MnO3 film. These arrays show magnetoresistance oscillations that appear at temperatures below the critical temperature of YBa2Cu3O7 for currents below a threshold, indicating their superconducting origin. This realization paves the way for device architectures displaying macroscopic quantum interference effects, which are of interest for field sensing applications, among others.