An in operando study of chemical expansion and oxygen surface exchange rates in epitaxial GdBaCo2O5.5 electrodes in a solid-state electrochemical cell by time-resolved X-ray diffraction

This report explores the fundamental characteristics of epitaxial thin films of a mixed ionic electronic conducting GdBaCoO (GBCO) material with a layered perovskite structure, relevant for use as an active electrode for the oxygen reduction and evolution reactions in electrochemical devices. Time-resolved X-ray diffraction in combination with voltage step chrono-amperometric measurements in a solid state electrochemical cell provides a deeper insight into the chemical expansion mechanism in the GBCO electrode. The chemical expansion coefficient along the c-axis, α, shows a negative value upon the compound oxidation contrary to standard perovskite materials with disordered oxygen vacancies. Chemical expansion also shows a remarkable asymmetry from α = -0.037 to -0.014 at δ 0, respectively. This change in chemical expansion is an indication of a different mechanism of the structural changes associated with the variable Co cation oxidation state from Co → Co → Co. Since redox reactions are dominated by oxygen surface exchange between the GBCO electrode and gas atmosphere, monitoring the time response of the structural changes allows for direct determination of oxygen reduction and evolution reaction kinetics. The reaction kinetics are progressively slowed down upon reduction in the δ 0 region, in agreement with the structural changes and the electronic carrier delocalization when crossing δ = 0. This work validates the time-resolved XRD technique for fast and reversible measurements of electrode activity in a wide range of oxygen non-stoichiometry in a solid-state electrochemical cell operating under realistic working conditions

Tunable Molecular Electrodes for Bistable Polarization Screening

The polar discontinuity at any ferroelectric surface creates a depolarizing field that must be screened for the polarization to be stable. In capacitors, screening is done by the electrodes, while in bare ferroelectric surfaces it is typically accomplished by atmospheric adsorbates. Although chemisorbed species can have even better screening efficiency than conventional electrodes, they are subject to unpredictable environmental fluctuations and, moreover, dominant charged species favor one polarity over the opposite. This paper proposes a new screening concept, namely surface functionalization with resonance-hybrid molecules, which combines the predictability and bipolarity of conventional electrodes with the screening efficiency of adsorbates. Thin films of barium titanate (BaTiO) coated with resonant para-aminobenzoic acid (pABA) display increased coercivity for both signs of ferroelectric polarization irrespective of the molecular layer thickness, thanks to the ability of these molecules to swap between different electronic configurations and adapt their surface charge density to the screening needs of the ferroelectric underneath. Because electron delocalization is only in the vertical direction, unlike conventional metals, chemical electrodes allow writing localized domains of different polarity underneath the same electrode. In addition, hybrid capacitors composed of graphene/pABA/ferroelectric have been made with enhanced coercivity compared to pure graphene-electode capacitors

Role of pO2 and film microstructure on the memristive properties of La2NiO4+δ/LaNiO3−δ bilayers

Altres ajuts: ICN2 is funded by the CERCA programme/Generalitat de Catalunya.LaNiO/LaNiO bilayers deposited at varying pO conditions resulted in remarkable differences in film microstructure and cell parameters, directly affecting the electrical behaviour of Pt/LaNiO/LaNiO/Pt devices. The devices deposited at low pO showed the largest memristance. We propose this is due to the formation of a p-type Schottky contact between LaNiO and LaNiO, where the extent of its carrier depletion width can be modulated by the electric-field induced drift of interstitial oxygen ions acting as mobile acceptor dopants in LaNiO

Bipolar "table with legs" resistive switching in epitaxial perovskite heterostructures

We report the experimental investigation of bipolar resistive switching with "table with legs" shaped hysteresis switching loops in epitaxial perovskite GdBaCo O /LaNiO bilayers deposited by pulsed laser deposition. The possibility of varying the resistivity of GdBaCo O by changing its oxygen content allowed engineering this perovskite heterostructure with controlled interfaces creating two symmetric junctions. It has been proved that the resistance state of the device can be reproducibly varied by both continuous voltage sweeps and by electrical pulses. The symmetric devices show slightly non-symmetric resistance profiles, which can be explained by a valence change resistive switching model, and presented promising multilevel properties required for novel memories and neuromorphic computing

Control of lateral composition distribution in graded films of soluble solid systems A1-xBx by partitioned dual-beam pulsed laser deposition

Altres ajuts: AGAUR agency (project 2017SGR)Lateral compositionally-graded thin films are powerful media for the observation of phase boundaries aswell as for high-throughputmaterials exploration.We herein propose amethod to prepare epitaxial lateral compositionally-graded films using a dual-beampulsed laser deposition (PLD)method with two targets separated by a partition. Tuning the ambient pressure and the partition-substrate gap makes it possible to control of the gradient length of the deposits at the small sizes (≤ 10 mm) suitable for commercial oxide single crystal substrates. A simple Monte Carlo simulation qualitatively reproduced the characteristic features of the lateral thickness distribution. To demonstrate this method, we prepared (1-x)PbTiO-xPbZrO and (1-x)LaMnOLaSrMnO films with lateral composition gradient widths of 10 and 1 mm, respectively, with the partitioned dual PLD

Carbon incorporation in MOCVD of MoS2 thin films grown from an organosulfide precursor

Altres ajuts: CERCA Programme/Generalitat de CatalunyaWith the rise of two-dimensional (2D) transition-metal dichalcogenide (TMD) semiconductors and their prospective use in commercial (opto)electronic applications, it has become key to develop scalable and reliable TMD synthesis methods with well-monitored and controlled levels of impurities. While metal-organic chemical vapor deposition (MOCVD) has emerged as the method of choice for large-scale TMD fabrication, carbon (C) incorporation arising during MOCVD growth of TMDs has been a persistent concern-especially in instances where organic chalcogen precursors are desired as a less hazardous alternative to more toxic chalcogen hydrides. However, the underlying mechanisms of such unintentional C incorporation and the effects on film growth and properties are still elusive. Here, we report on the role of C-containing side products of organosulfur precursor pyrolysis in MoS2 thin films grown from molybdenum hexacarbonyl Mo(CO)6 and diethyl sulfide (CH3CH2)2S (DES). By combining in situ gas-phase monitoring with ex situ microscopy and spectroscopy analyses, we systematically investigate the effect of temperature and Mo(CO)6/DES/H2 gas mixture ratios on film morphology, chemical composition, and stoichiometry. Aiming at high-quality TMD growth that typically requires elevated growth temperatures and high DES/Mo(CO)6 precursor ratios, we observed that temperatures above DES pyrolysis onset (â 600 °C) and excessive DES flow result in the formation of nanographitic carbon, competing with MoS2 growth. We found that by introducing H2 gas to the process, DES pyrolysis is significantly hindered, which reduces carbon incorporation. The C content in the MoS2 films is shown to quench the MoS2 photoluminescence and influence the trion-To-exciton ratio via charge transfer. This finding is fundamental for understanding process-induced C impurity doping in MOCVD-grown 2D semiconductors and might have important implications for the functionality and performance of (opto)electronic devices

Antisite Defects and Chemical Expansion in Low-damping, High-magnetization Yttrium Iron Garnet Films

Yttrium iron garnet is widely investigated for its suitability in applications ranging from magneto-optical and microwave devices to magnonics. However, in the few-nanometer thickness range, epitaxial films exhibit a strong variability in magnetic behavior that hinders their implementation in technological devices. Here, direct visualization and spectroscopy of the atomic structure of a nominally stoichiometric thin film, exhibiting a small damping factor of 3.0 ⋅ 10, reveals the occurrence of Y-excess octahedral antisite defects. The two-magnon strength is very small, Γ≈10 Oe, indicating a very low occurrence of scattering centers. Notably, the saturation magnetization, 4πM=2.10 (±0.01) kOe, is higher than the bulk value, in consistency with the suppression of magnetic moment in the minority octahedral sublattice by the observed antisite defects. Analysis of elemental concentration profiles across the substrate-film interface suggests that the Y-excess is originated from unbalanced cationic interdiffusion during the early growth stages

Revealing Strain Effects on the Chemical Composition of Perovskite Oxide Thin Films Surface, Bulk, and Interfaces

Understanding the effects of lattice strain on oxygen surface and diffusion kinetics in oxides is a controversial subject that is critical for developing efficient energy storage and conversion materials. In this work, high-quality epitaxial thin films of the model perovskite LaSrMnCoO (LSMC), under compressive or tensile strain, are characterized with a combination of in situ and ex situ bulk and surface-sensitive techniques. The results demonstrate a nonlinear correlation of mechanical and chemical properties as a function of the operation conditions. It is observed that the effect of strain on reducibility is dependent on the "effective strain" induced on the chemical bonds. In-plain strain, and in particular the relative BO length bond, is the key factor controlling which of the B-site cation can be reduced preferentially. Furthermore, the need to use a set of complimentary techniques to isolate different chemically induced strain effects is proven. With this, it is confirmed that tensile strain favors the stabilization of a more reduced lattice, accompanied by greater segregation of strontium secondary phases and a decrease of oxygen exchange kinetics on LSMC thin films

Native defect association in beta-Ga2O3 enables room-temperature p-type conductivity

The room temperature hole conductivity of the ultra wide bandgap semiconductor beta Ga2O3 is a pre-requisite for developing the next-generation electronic and optoelectronic devices based on this oxide. In this work, high-quality p-type beta-Ga2O3 thin films grown on r-plane sapphire substrate by metalorganic chemical vapor deposition (MOCVD) exhibit Rho = 50000Ohm.cm resistivity at room temperature. A low activation energy of conductivity as Ea2=170 meV was determined, associated to the oxygen - gallium native acceptor defect complex. Further, taking advantage of cation (Zn) doping, the conductivity of Ga2O3:Zn film was remarkably increased by three orders of magnitude, showing a long-time stable room-temperature hole conductivity with the conductivity activation energy of around 86 meV.Comment: 21pages; 9figure

The impact of Mn nonstoichiometry on the oxygen mass transport properties of La0.8Sr0.2MnyO3±δ thin films

Oxygen mass transport in perovskite oxides is relevant for a variety of energy and information technologies. In oxide thin films, cation nonstoichiometry is often found but its impact on the oxygen transport properties is not well understood. Here, we used oxygen isotope exchange depth profile technique coupled with secondary ion mass spectrometry to study oxygen mass transport and the defect compensation mechanism of Mn-deficient La0.8Sr0.2Mn (y) O-3 +/-delta epitaxial thin films. Oxygen diffusivity and surface exchange coefficients were observed to be consistent with literature measurements and to be independent on the degree of Mn deficiency in the layers. Defect chemistry modeling, together with a collection of different experimental techniques, suggests that the Mn-deficiency is mainly compensated by the formation of La-x(Mn) antisite defects. The results highlight the importance of antisite defects in perovskite thin films for mitigating cationic nonstoichiometry effects on oxygen mass transport properties