A study of impedance spectroscopy was done for the electrical characterization of pyrochlore materials. The experiment consisted of measurements of the dependence of the impedance of such systems with the temperature during heating (25 to 110 °C) and cooling (110 to 25 °C). The goal was to try to avoid the effect of humidity in the impedance spectrum. However, for the sample with x = 0.20, we get an anomalous response of the conductivity during the cooling process. To explain this result, we performed micro-structure characterization in this sample and in the samples with x = 0.80 and 0.67. The result is that the sample with x = 0.20 is well characterized by the model "easy-path" because it has high porosity while the other two must have phase precipitate structure type Suzuki. These results served to explain why the anomaly on the Arrhenius plot occurred only in the 0.20 concentration sample: microstructure difference. In this study we can also note that the doped samples had a dependence of activation energies related to the rates of concentration. Except for the sample with concentration rate of 0.20, the activation energies during cooling are among the values of 0.60 and 0.23 eV of their pure counterparts which are registered in the literature.
Electromechanical activity, remanent polarization states, and hysteresis loops in paraelectric TiO2 and SrTiO3 are observed. The coupling between the ionic dynamics and incipient ferroelectricity in these materials is analyzed using extended Ginsburg Landau Devonshire (GLD) theory. The possible origins of electromechanical coupling including ionic dynamics, surface-charge induced electrostriction, and ionically-induced ferroelectricity are identified. For the latter, the ionic contribution can change the sign of first order GLD expansion coefficient, rendering material effectively ferroelectri…
New emerging disciplines such as Nanoionics and Iontronics are dealing with the exploitation of mesoscopic size effects in materials, which become visible (if not predominant) when downsizing the system to the nanoscale. Driven by the worldwide standardisation of thin film deposition techniques, the access to radically different properties than those found in the bulk macroscopic systems can be accomplished. This opens up promising approaches for the development of advanced microdevices, by taking advantage of the nanostructural deviations found in nanometre sized, interface dominated material…
The ability to pattern the location of pillars in epitaxial matrix-pillar nanocomposites is a key challenge to develop future technologies using these intriguing materials. One such model system employs a ferrimagnetic CoFe$_{2}$O$_{4}$ (CFO) pillar embedded in a ferroelectric BiFeO$_{3}$ (BFO) matrix, which has been proposed as a possible memory or logic system. These composites self-assemble spontaneously with pillars forming through nucleation at a random location when grown via physical vapor deposition. Recent results have shown that if an island of the pillar material is pre-patterned on…
Blend solid polymer electrolyte based on PEO, PVP complexed with lithium LiBOB were synthesized by solution cast technique and impact of LiBOB on the morphology, structure, and electrochemical properties is examined. The XRD and FESEM analysis reveals the enhancement of amorphous content on salt addition. The FTIR spectroscopy evidences the complex formation. The ionic conductivity for optimized system was two order higher than salt free system, i.e. ~0.5x10-5 S cm-1 (@RT) and increases to ~0.65 mS cm-1 (@100 oC) for O/Li=16 and temperature dependent conductivity follows Arrhenius nature. The …
Atom probe tomography is routinely used for the characterisation of materials microstructures usually assuming that the microstructure is unaltered by the analysis. When analysing ionic conductors, however, gradients in the chemical potential and the electric field penetrating dielectric atom probe specimens can cause significant ionic mobility. While ionic mobility is undesired when aiming for materials characterisation it offers a strategy to manipulate materials directly in-situ in the atom probe. Here, we present experimental results on the analysis of the ionic conductor Lithium-Manganese…
The structural, optical and electrical properties of spray deposited antimony (Sb) doped tin oxide (SnO2) thin films, prepared from SnCl4 precursor, have been studied as a function of antimony doping concentration. The doping concentration was varied from 0 to 1.5 wt.% of Sb. The analysis of x-ray diffraction patterns revealed that the as deposited doped and undoped tin oxide thin films are pure crystalline tetragonal rutile phase of tin oxide which belongs to the space group P42/mnm (number 136). The surface morphological examination with field emission scanning electron microscopy (FESEM) re…
The free standing solid polymer nanocomposite films has been prepared through standard solution cast technique. The improvement in structural, microstructural and electrochemical properties has been observed on the dispersion of nanofiller in polymer salt complex. X Ray diffraction studies clearly reflect the formation of complex formation as no corresponding salt peak appeared in the diffractograms. The FTIR analysis suggested a clear and convincing evidence of polymer ion, ion ion and polymer ion nanofiller interaction. The highest ionic conductivity of the prepared solid polymer electrolyte…
Tantalum, tantalum oxide and their hetero-interfaces are of tremendous technological interest in several applications spanning electronics, thermal management, catalysis and biochemistry. For example, local oxygen stoichiometry variation in TaOx memristors comprising of metallic (Ta) and insulating oxide (Ta2O5) have been shown to result in fast switching on the sub-nanosecond timescale over a billion cycles, relevant to neuromorphic computation. Despite its broad importance, an atomistic scale understanding of oxygen stoichiometry variation across Ta/TaOx hetero-interfaces, such as during ear…
Ionic liquid gating can markedly modulate the materials' carrier density so as to induce metallization, superconductivity, and quantum phase transitions. One of the main issues is whether the mechanism of ionic liquid gating is an electrostatic field effect or an electrochemical effect, especially for oxide materials. Recent observation of the suppression of the ionic liquid gate-induced metallization in the presence of oxygen for oxide materials suggests the electrochemical effect. However, in more general scenarios, the role of oxygen in ionic liquid gating effect is still unclear. Here, we …
Bulk samples of $(Sn_{1-x}Sb_{x}O_{2-δ})$ with x = 0.00, 0.10, 0.20, 0.30 are synthesized by solid-state reaction route. Samples were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and UV-Vis spectroscopy. The x-ray diffraction patterns indicate that the gross structure/phase of $(Sn_{1-x}$ $Sb_{x}O_{2-δ})$ do not change with the substitution of antimony (Sb) up to x = 0.30. The surface morphological examination with SEM revealed the fact that the grain size in the antimony doped sample is larger than that of undoped …
A commercially available membrane filter paper composed of mixed cellulose esters bearing typically an interconnected pore structure was transformed into a stimuli-responsive bilayer actuator by depositing a thin film of poly(ionic liquid)-modified graphene oxide sheets (GO-PIL) onto the filter paper. In acetone vapor, the as-synthesized bilayer actuator bent readily into multiple loops at a fast speed with the GO-PIL top film inwards. Upon pulling back into air the actuator recovered their original shape. The asymmetric swelling of the top GO-PIL film and the bottom porous filter paper toward…
Unraveling impacts of polycrystalline microstructures on ionic conductivity of ceramic electrolytes by computational homogenization and machine learning
The ground state electronic structures of the actinide oxides AO, A2O3 and AO2 (A=U, Np, Pu, Am, Cm, Bk, Cf) are determined from first-principles calculations, using the self-interaction corrected local spin-density (SIC-LSD) approximation. Emphasis is put on the degree of f-electron localization, which for AO2 and A2O3 is found to follow the stoichiometry, namely corresponding to A(4+) ions in the dioxide and A(3+) ions in the sesquioxides. In contrast, the A(2+) ionic configuration is not favorable in the monoxides, which therefore become metallic. The energetics of the oxidation and reducti…
The properties of AMO3 perovskite oxides, where M is a 3d transition metal, depend strongly on the level of covalency between the metal d and oxygen p orbitals. With their complex spin orders and metal-insulator transition, rare-earth nickelates verge between dominantly ionic and covalent characters. Accordingly, the nature of their ground state is highly debated. Here, we reconcile the ionic and covalent visions of the insulating state of nickelates. Through first-principles calculations, we show that it is reminiscent of the ionic charge disproportionation picture (with strictly low-spin 4+ …
Electronic structure calculations are carried out to estimate the heats of formation of rare-earth orthophosphates from their oxides. The calculated heats of formation are systematically about 40 kJ/mol less exothermic than the measured values. Based on estimated corrections for zero-point energies and H(298.15)-H(0), the discrepancy is almost entirely electronic in origin. The decreasingly exothermic ΔHfox with decreasing ionic radius (i.e. LaPO4 more exothermic than ScPO4) results from the higher charge localization on the oxide anion (O2-) relative to the phosphate anion (PO43-). The lattic…
Voltage control of interfacial magnetism has been greatly highlighted in spintronics research for many years, as it might enable ultra-low power technologies. Among few suggested approaches, magneto-ionic control of magnetism has demonstrated large modulation of magnetic anisotropy. Moreover, the recent demonstration of magneto-ionic devices using hydrogen ions presented relatively fast magnetization toggle switching, tsw ~ 100 ms, at room temperature. However, the operation speed may need to be significantly improved to be used for modern electronic devices. Here, we demonstrate that the spee…
Due to the coexistence of many emergent phenomena, including 2D superconductivity and a large Rashba spin-orbit coupling, 5d transition metal oxides based two-dimensional electron systems (2DESs) have been prospected as one of the potential intrants for modern electronics. However, despite the lighter electron mass, the mobility of carriers, a key requisite for high-performance devices, in 5d-oxides devices remains far behind their 3d-oxides analogs. The carriers mobility in these oxides is significantly hampered by the inevitable presence of defects generated during the growth process. Here, …
Cerium oxide (ceria, CeO2) is one of the most promising mixed ionic and electronic conducting materials. Previous atomistic analysis has covered widely the effects of substitution on oxygen vacancy migration. However, an in-depth analysis of the role of cation substitution beyond trivalent cations has rarely been explored. Here, we investigate soluble monovalent, divalent, trivalent and tetravalent cation substituents. By combining classical simulations and quantum mechanical calculations, we provide an insight into defect association energies between substituent cations and oxygen vacancies a…
Uncovering microstructure evolution mechanisms that accompany the long-term operation of solid oxide fuel cells is a fundamental challenge in designing a more durable energy system for the future. To date, the study of fuel cell stack degradation has focused mainly on electrochemical performance and, more rarely, on averaged microstructural parameters. Here we show an alternative approach in which an evolution of three-dimensional microstructural features is studied using electron tomography coupled with topological data analysis. The latter produces persistent images of microstructure before …
There is a growing interest in the development of functional metal oxides with mixed ionic electronic conduction for their application in different strategic fields. In particular, ionic transport-related phenomena are of primary importance in energy transformation and storage devices, such as solid oxides fuel cells (SOFC) or batteries. Traditionally, the main issue that hindered a wide spread of solid state electrochemical devices is the slow ionic conduction and the reduced number of families of materials with pure ionic conductivity able to play the role of the electrolyte. This is due to …
We report the temperature variation of the $^{119}$Sn-Mössbauer spectra of the antiperovskite (inverse perovskite) oxide superconductor Sr$_{3-x}$SnO. Both superconductive (Sr-deficient) and non-superconductive (nearly stoichiometric) samples exhibit major $γ$-ray absorption with isomer shift similar to that of Mg$_2$Sn. This fact shows that Sr$_{3-x}$SnO contains the metallic anion Sn$^{4-}$, which is rare especially among oxides. In both samples, we observed another $γ$-ray absorption with a larger isomer shift, indicating that there is another ionic state of Sn with a higher oxidation numbe…
Compositionally complex ceramics (CCCs), including high-entropy ceramics (HECs) as a subclass, offer new opportunities of materials discovery beyond the traditional methodology of searching new stoichiometric compounds. Herein, we establish new strategies of tailoring CCCs via a seamless combination of (1) non-equimolar compositional designs and (2) controlling microstructures and interfaces. Using oxide solid electrolytes for all-solid-state batteries as an exemplar, we validate these new strategies via discovering a new class of compositionally complex perovskite oxides (CCPOs) to show the p…
Ab initio wavefunction based methods are applied to the study of electron correlation effects on the band structure of oxide systems. We choose MgO as a prototype closed-shell ionic oxide. Our analysis is based on a local Hamiltonian approach and performed on finite fragments cut from the infinite solid. Localized Wannier functions and embedding potentials are obtained from prior periodic Hartree-Fock (HF) calculations. We investigate the role of various electron correlation effects in reducing the HF band gap and modifying the band widths. On-site and nearest-neighbor charge relaxation as wel…
Layered LiMnO$_2$ and Li$_2$MnO$_3$ are of great interest for lithium-ion battery cathodes because of their high theoretical capacities. The practical application of these materials is, however, limited due to poor electrochemical performance. We herein report a comprehensive first-principles study of defect physics in LiMnO$_2$ and Li$_2$MnO$_3$ using hybrid-density functional calculations. We find that manganese antisites have low formation energies in LiMnO$_2$ and may act as nucleation sites for the formation of impurity phases. The antisites can also occur with high concentrations in Li$_…
Normal operations of electrochemical devices such as solid oxide fuel cells (SOFC), solid oxide electrolyzer cells (SOEC) and lithium ion batteries (LIB) sometimes fail because of unexpected formation of internal phases. These phases include oxygen bubbles at grain boundaries inside the zirconia electrolyte of SOEC, isolated Li metal islands inside the (garnet type) Li7La3Zr2O12 electrolyte of all-solid-state LIB, and similar Na metal islands inside the Na-beta-alumina and NASICON electrolytes of Na-S batteries. Remarkably, although the devices can operate in both polarities, the propensity fo…
We performed a systematic study of soft X-ray absorption spectroscopy in various manganese oxides and fluorides. Both Mn L-edges and ligand (O and F) K-edges are presented and compared with each other. Despite the distinct crystal structure and covalent/ionic nature in different systems, the Mn-L spectra fingerprint the Mn valence and spin states through spectral lineshape and energy position consistently and evidently. The clear O- and F- K pre-edge features in our high resolution spectra enable a quantitative definition of the molecular orbital diagram with different Mn valence. In addition,…
First-principles FLAPW-GGA band structure calculations were employed to examine the structural, electronic properties and the chemical bonding picture for four ZrCuSiAs-like Th-based quaternary pnictide oxides ThCuPO, ThCuAsO, ThAgPO, and ThAgAsO. These compounds were found to be semimetals and may be viewed as "intermediate" systems between two main isostructural groups of superconducting and semiconducting 1111 phases. The Th 5f states participate actively in the formation of valence bands and the Th 5f states for ThMPnO phases are itinerant and partially occupied. We found also that the bon…
We report on a novel approach to synthesize cubic-phase fast ionic conducting garnet-type solid state electrolytes based on Bi doped Li7La3Zr2O12 (LLZO). Bi aliovalent substitution into LLZO utilizing the Pechini processing method is successfully employed to synthesize Li7-xLa3Zr2-xBixO12 compounds. Ionic conductivities up to 2.0 x 10-4 S/cm are achieved in structures not fully densified. Cubic phase Li6La3ZrBiO12 powders are generated in the temperature range from 650 °C to 900 °C in air. In contrast, in the absence of Bi and under identical synthesis conditions, the cubic garnet phase of Li7…
The world is at the cusp of a new era where pivotal importance is being attached to the development of sustainable and high-performance energy storage systems. Potassium-ion batteries are deemed not only as cheap battery candidates, but also as the penultimate high-voltage energy storage systems within the monovalent-cation chemistries. However, their performance and sustainability are undermined by the lack of suitable electrolytes for high-voltage operation particularly due to the limited availability of cathode materials. Here, the potential of ionic liquids based on potassium bis(trifluoro…
The atomic and electronic structures of the (001)-Si/(001)-gamma-Al2O3 heterointerface are investigated by first principles total energy calculations combined with a newly developed "modified basin-hopping" method. It is found that all interface Si atoms are fourfold coordinated due to the formation of Si-O and unexpected covalent Si-Al bonds in the new abrupt interface model. And the interface has perfect electronic properties in that the unpassivated interface has a large LDA band gap and no gap levels. These results show that it is possible to have clean semiconductor-oxide interfaces.
Design novel solid oxide electrolyte with enhanced ionic conductivity forms one of the Holy Grails in the field of materials science due to its great potential for wide range of energy applications. Conventional solid oxide electrolyte typically requires elevated temperature to activate the ionic transportation, while it has been increasing research interests to reduce the operating temperature due to the associated scientific and technological importance. Here, we report a conceptually new solid oxide electrolyte, HSrCoO2.5, which shows an exceptional enhanced proton conductivity at low tempe…
Depth Profiling of Oxygen Migration in Ta/HfO2 Stacks During Ionic Liquid Gating
Institute of Physics, Johannes Gutenberg University Mainz（美因茨约翰内斯·古腾堡大学物理研究所）；Faculty of Physics, Bielefeld University（比勒费尔德大学物理学院）；Faculty of Physics, Osnabrück University（奥斯纳布吕克大学物理学院）
Cation disorder is an important design criterion for technologically relevant transition-metal (TM) oxides, such as radiation-tolerant ceramics and Li-ion battery electrodes. In this letter, we use a combination of first-principles calculations, normal mode analysis, and band-structure arguments to pinpoint a specific electronic-structure effect that influences the stability of disordered phases. We find that the electronic configuration of a TM ion determines to which extent the structural energy is affected by site distortions. This mechanism explains the stability of disordered phases with …
Non-monotonic hydration dependence of ionic transport in atomically-thin MnO2 sheets
Institute of Materials Science and Nanotechnology, Bilkent University（比尔肯特大学材料科学与纳米技术研究所）；Bilkent National Nanotechnology Research Center - UNAM（比尔肯特国家纳米技术研究中心）；Department of Physics, Middle East Technical University（中东理工大学物理系）
We present a theoretical study of the impact of oxygen diffusion in oxide crystals on metal dopants ionic state and the conduction type under thermal equilibrium. Oxygen vacancy formation acting as a shallow, double-electronic donor is assumed to result from the crystal exposure to a low ambient oxygen pressure. It is shown, that critical transitions from n- to a p-type at an oxygen partial pressure Pi, and in ionization state of the metal dopant at an oxygen partial pressure PM, are usually not simultaneous, and depend on the different reaction constants. Experimental study of the different s…
Nitrogen oxides are textbook class of molecular compounds, with extensive industrial applications. Nitrogen and oxygen are also among the most abundant elements in the universe. We explore the N-O system at 0 K and up to 500 GPa though ab initio evolutionary simulations. Results show that two phase transformations of stable molecular NO2 exist at 7 and 64 GPa, and followed by decomposition of NO2 at 91 GPa. All of the NO+NO3- structures are found to be metastable at T=0 K, so experimentally reported ionic NO+NO3- is either metastable or stabilized by temperature. Upon increasing pressure, N2O5…
Solid state ionic approaches for modifying ion distributions in getter/oxide heterostructures offer exciting potentials to control material properties. Here we report a simple, scalable approach allowing for total control of the superconducting transition in optimally doped YBa$_{2}$Cu$_{3}$O$_{7-δ}$ (YBCO) films via a chemically-driven ionic migration mechanism. Using a thin Gd capping layer of up to 20 nm deposited onto 100 nm thick epitaxial YBCO films, oxygen is found to leach from deep within the YBCO. Progressive reduction of the superconducting transition is observed, with complete supp…
Lithium titanium oxide Li$_4$Ti$_5$O$_{12}$ (LTO) is an intriguing anode material promising particularly long lived batteries, due to its remarkable phase stability during (dis)charging of the cell. However, its usage is limited by its low intrinsic electronic conductivity. Introducing oxygen vacancies can be one method to overcome this drawback, possibly by altering the charge carrier transport mechanism. We use Hubbard corrected density-functional theory (DFT+U) to show that polaronic states in combination with a possible hopping mechanism can play a crucial role in the experimentally observ…
