Bulk Resistivity Research Articles

A rational study of transduction mechanisms of different materials for all solid contact-ISEs

The new era of solid contact ion selective electrodes (SC-ISEs) miniaturized design has received an extensive amount of concern. Because it eliminated the requirement for ongoing internal solution composition optimization and created a two-phase system with stronger detection limitations. Herein, the determination of venlafaxine HCl is based on a comparison study between different ion- to electron transduction materials (such as; multiwalled carbon nanotubes (MWCNTs), polyaniline (PANi), and ferrocene) and illustrating their mechanisms in their applied sensors. Their different electrochemical features (such as bulk resistance (Rb**), double-layer capacitance (Cdl), geometric capacitance (Cg), and specific capacitance (Cp)) were evaluated and discussed by using the Electrochemical Impedance Spectroscopy (EIS), Chronopotentiometry (CP), and Cyclic Voltammetry (CV) experiments. The results indicated that each transducer's influence on the proposed sensor's electrochemical characteristics is determined by their unique chemical and physical properties. The electrochemical features vary for different solid contact materials used in transduction mechanisms. The results confirm that the MWCNT sensor revealed the best electrochemical behavior with the potentiometric response of a near-Nernestian slope of 56.1 ± 0.8 mV/decade with detection limits of 3.8 × 10−6 mol/L (r2 = 0.999) and a low potential drift (∆E/∆t) of 34.6 µV/s. Also, the selectivity study was performed in the presence of different interfering species either in single or complex matrices. This demonstrates excellent selectivity, stability, conductivity, and reliability as a VEN-TPB ion pair sensor for accurately measuring VEN in its various formulations. The proposed method was compared to HPLC reported technique and confirmed no significant difference between them. So, the proposed sensors fulfill their solutions' demand features for VEN appraisal.

Structural and dielectric characterization of Potassium diphosphate/Hydroxyapatite ceramic biocomposite

We study the KH2PO4 (KDP) /Ca10(PO4)6(OH)2 (HA) biocomposite to evaluate its electrical conductivity. It was prepared by manual grinding on a 1:3 molar ratio. Studies by X-ray powder diffraction and Raman spectroscopy show a variation in the volume of the unit cell between KDP and HA and the disappearance of bands associated with KDP. Impedance spectroscopy was studied over a range of temperatures (25-80 ºC) and frequencies from 10 Hz to 1 MHz. It was found that the bulk resistance of the composite is higher in pure KDP. Using the Jonscher empirical expression suggest that the ionic hopping conduction mechanism is responsible for the conductivity behavior with hopping frequency of 1.21 x104 Rad at 80ºC.

Effect of the Seed Layer on the Growth and Charge Transfer Behavior of Zn2SnO4 Nanorods in Photoelectrochemical Water Splitting.

The growth of Zn2SnO4 nanorods on two differently prepared ZnO seed layers is demonstrated using a hydrothermal approach. The ZnO seed layers are prepared using dip-coating and electrodeposition techniques. The grown Zn2SnO4 nanorods are in the cubic phase. However, the different seed layers result in alternation in the diameter of grown Zn2SnO4 nanorods. The photocurrent of Zn2SnO4 nanorods grown on an electrodeposited ZnO seed layer is ∼4.5 times larger than that of Zn2SnO4 grown on a dip-coated ZnO seed layer. The Nyquist plots of Zn2SnO4 nanorods on the electrodeposited ZnO seed layer result in a lower charge transfer resistance (Rct = 37.7 Ω) and a lower bulk resistance (Rbulk = 64 kΩ), improving the charge transport properties. The change in diameter of Zn2SnO4 nanorods significantly alters the charge transfer behavior. The calculated charge injection efficiency did not exhibit a significant change. However, there was a 1.6-fold enhancement observed in the charge separation efficiency for Zn2SnO4 when grown on an electrodeposited seed layer.

The effects of increasing filler loading on the contact resistivity of interconnects based on silver–epoxied conductive adhesives and silver metallization pastes

AbstractOur previous work highlighted how microscopic structural effects influence the sheet and contact resistance of electrically conductive adhesives (ECAs). Herein, we delve further by investigating how the contact and bulk resistivity of several ECAs that are based on the same formulation, but with different filler content, are correlated with the filler content. Additionally, two different filler geometries — high and low surface area (HSA and LSA) fillers — are combined in different ratios to maintain a similar viscosity and therefore processability. Hence, contact and bulk resistivities are also correlated with the different geometry ratios of these two fillers. As expected, it was found that the contact and bulk resistivities decreased when the filler content was increased. However, the magnitude of the decrease was found to depend strongly on the filler geometry ratio. At extreme filler geometry ratios, when the bulk is either mostly loaded with HSA‐fillers or mostly with LSA‐fillers, the impact of changes in the filler content on the bulk and contact resistivities is markedly different. The measured data is interpreted within the context of percolation theory and it is determined that the optimum ratio of the LSA and HSA Ag‐fillers investigated in this study is approximately 60:40 (for an epoxy‐based adhesive). This work has important ramifications for the design of ECAs, where cost considerations and the need to reduce silver resource usage demand the lowest (silver) filler content, but the demands of product performance point to higher filler content.

Achieving CoAl2O4@Li1.2Ni0.13Co0.13Mn0.54O2 with Long Cyclic and High-Rate Performance via Citric Acid Combustion Method

Lithium-rich manganese-based cathode materials (LNCM) have high specific capacities and operating voltages. However, they also have intractable deficiencies such as low capacity retention and unsatisfactory rate capability. Herein, CoAl2O4 with spinel structure and chemically stable is adopted to decorate the surface of LNCM to modify the cyclic and high-rate performance of final product. 3CoAl2O4@LNCM synthesized by self combustion of citric acid shows the best electrochemical properties such as lower voltage drop (4.7 mV per cycle) and higher capacity retention of 81.33% (1 C) after 100 cycles, which is exceed to bare LNCM (7.7 mV per cycle, 47.65%). Besides, the charge transfer resistance R ct of the modified sample is lower, and its lithium ion diffusion coefficient D Li + is higher. Consequently, 3CoAl2O4@LNCM is able to demonstrate high rate performance, whereby a capacity retention of 65.84% (5 C) is achieved after 100 cycles. The improved electrochemical properties of 3CoAl2O4@LNCM because of the 3D diffusion channel of CoAl2O4 benefits lithium ion diffusion; and the chemical stability of CoAl2O4 enhances the corrosion resistance of LNCM bulk to the electrolyte. As such, this results in the suppression of TM ion dissolution, and the enhancement of cyclic stability and initial coulomb efficiency.

Electrical resistance switching of YbFe2O4 single crystal bulk

We report the electrical resistance switching of YbFe2O4, which is one of the electronic ferroelectrics and shows multi-step polarization reversal. The electrical resistance of the single crystal bulk of YbFe2O4 was measured along the c-axis. Three kinds of resistance states were observed: high resistance state (HRS), low resistance state (LRS), and extra low resistance state (ELRS). The as-grown sample was in HRS. The resistance state switched from HRS to LRS under an electric field of ∼180 V/cm. HRS was reproduced under the same magnitude of the electric field in the opposite direction. The switching from LRS to ELRS was assisted by a current flow in the ab-plane, which is orthogonal to the measurement axis (c-axis). The switching from LRS to ELRS was observed under an electric field of ∼140 V/cm during the resistance measurement along the c-axis after a current flow in the ab-plane for a few seconds. The resistance ratio in HRS, LRS, and ELRS was ∼2:1.5:1, which is regarded as a large value considering that the sample size was sub-millimeter order. This multi-step resistive switching is likely due to the multi-step reversal of electric polarization, accompanied by a multi-step change in Schottky barrier height between the sample and electrodes. The currents in the ab-plane are considered to release some pinnings and assist in the polarization reversal.

Megaflood Erosion on Mars—How Lava‐Filled Craters Became Mesas (With Insights From Lava Physics, Stream Power, and Rock Mechanics)

AbstractRound mesas up to 500 m high occur in Martian outflow channels. Mesas in Ravi and Elaver Valles occur in deepest parts of the channels where the most intense megaflood erosion occurred. I theorize that Noachian basalts poured into craters which acted as lava traps, similar to Kilauean lava lakes. Subsequent flood basalts buried the infilled craters. Hesperian megafloods stripped away hundreds of meters of basalts, exhuming erosion‐resistant strata. Lava solidification theory is explored to assess the role of cooling in governing the structure and strength of the Martian basalts. The postulated lava lakes that formed the Ravi Vallis mesas would have needed millennia to cool. The larger Elaver Vallis mesa may have needed up to 20,000 years to solidify. Long cooling times led to coarse, doleritic mineral textures and reduced numbers of cooling joints, greatly increasing bulk rock strength and resistance to hydrodynamic erosion. Using rock mechanics theory, cores of exhumed lava‐filled craters would have bulk rock strengths at least 5 to 30 times greater than more highly fractured basalts. Discharge hydrographs for the Morella Crater breach flood that carved Elaver Vallis peak at ∼2.1 × 107 m3 s−1. Stream power per unit streambed area ranged up to >150,000 W m−2 as the breach grew in size. The calculations provide an envelope of power sufficient to erode hundreds of meters of basalts, but not great enough to remove the large mesa. Thus the legacy of an ancient, lava‐filled crater is a high mesa on the floor of Elaver Vallis.

Cryogenic RPWELL: a novel charge-readout element for dual-phase argon TPCs

The first operation of a cryogenic Resistive Plate WELL (RPWELL) detector in the saturated vapor of liquid argon is reported. The RPWELL detector was composed of a Thick Gas Electron Multiplier (THGEM) electrode coupled to a metallic anode via Fe2O3/YSZ ceramics (Fe2O3 in weight equal to 75%), with tunable bulk resistivity in the range 109–1012 Ω·cm. The detector was operated at liquid argon temperature in saturated argon vapor (90 K, 1.2 bar) and characterized in terms of its effective charge gain and stability against discharges. Maximum stable gain of G≈17 was obtained, without discharges. In addition, preliminary results from novel 3D-printed thermoplastic plates doped with carbon nanotubes are presented.

Advanced multilayer model electrode for binder distribution within composite electrodes of lithium batteries

The loading levels of composite electrodes are increasing continuously to satisfy the energy density requirements of lithium-ion batteries (LIBs) in electric vehicles (EVs). Furthermore, a faster coating and drying process in the mass-production line yields a nonuniform binder distribution. Thus, it is necessary to understand its distribution within the composite electrode and control it for a better and more reliable electrochemical performance. Therefore, we propose the utilization of an advanced multilayer electrode model consisting of several electrode layers with different binder contents. Using these controlled electrode models, the adhesive strength within each layer was examined using a surface and interfacial cutting analysis system (SAICAS). This was followed by a composition analysis using EDX on each surface. Subsequently, the electronic conductivities of the model electrodes were measured using an electrode resistance meter to determine the bulk and interfacial electrode resistances. Furthermore, the electrochemical properties of each model electrode were evaluated to correlate their relationships and design the optimum binder distribution. Thus, this multilayer model provides a highly effective platform for determining the optimum binder distribution in highly loaded composite electrodes for high-energy–density and long-lasting LIBs.

Effect of localization–delocalization transition on thermoelectric properties of Bi2Te2Se topological insulator

The thermal transport properties of Bi2Te2Se topological insulators show a range of complex features. Large bulk resistivities coexisting with prominent Shubnikov–de Haas quantum oscillations and proximity to metallic states mark this p-band system as an unconventional topological quantum material. Here, using the density functional plus dynamical mean-field theory method, we show how localization–delocalization transition underpins the T-dependence of thermoelectric responses from room down to low temperatures. We present the implications of our many-particle analysis to resistivity, Seebeck coefficient, thermal conductivity, and Lorenz number and propose that related broadband systems close to electronic transitions could be of use in thermoelectrics.

Grain-size adjustment in Hf0.5Zr0.5O2 ferroelectric film to improve the switching time in Hf0.5Zr0.5O2-based ferroelectric capacitor

By adjusting the rising time in annealing ferroelectric HfO2-based films, the grain size of the film can be controlled. In this study, we found that increasing the rising time from 10 to 30 s at an annealing temperature of 700 °C in N2 atmosphere resulted in improved ferroelectric switching speed. This is because the larger grain size reduces the internal resistance components, such as the grain bulk resistance and grain boundary resistance, of the HZO film. This in turn lowers the overall equivalent resistance. By minimizing the RC time constants, increasing the grain size plays a key role in improving the polarization switching speed of ferroelectric films.

Electrical Transport Properties and Hopping Mechanism of ZrCuSiAs Type Compound GdFeAsO

Abstract Iron-based ceramic GdFeAsO has been prepared using the solid-state reaction method. This material exhibits unique properties, showing superconductivity at extremely low temperatures and behaving as a semiconductor at high temperatures. Raman spectroscopy revealed various Raman active modes in the sample. UV-visible spectroscopy was employed to study the optical properties of the material in the wavelength range of 200-800 nm. Using Tauc's plot, the optical band energy values of the sample were estimated to be approximately 2.78 eV. The electrical characterizations have been performed through an impedance analyzer. Additionally, the sample displayed negative temperature coefficient of resistance behavior and positive temperature coefficient resistance. The thermistor parameters are evaluated using the bulk resistance at various temperatures. This opens up potential uses for thermistors in devices like fuses and temperature sensors. The ac conductivity spectrum of the sample followed both Jonscher's universal power law and the Arrhenius equation. The activation energy was calculated for different temperature regions. The correlated barrier hopping model is used to analyze the electrical conduction mechanism in the sample. This study provides insights into the unique electrical and optical properties of the GdFeAsO ceramic and sheds light on its potential applications in various fields.

Piezoresistive relaxation and creep model of porous polymer nanocomposite supported by experimental data

Porous piezoresistive nanocomposites (PPNs), a blend of conductive nanomaterials and a porous polymer matrix, have garnered significant attention in the realm of flexible pressure sensors. The porous microstructure offers exceptional sensitivity and lightweight characteristics of these sensors, but it also introduces challenges such as relaxation and creep behaviors. Grounded in viscoelastic theory, this paper introduces a mathematical model that provides a quantitative analysis of the resistance-strain relationship of PPN-based piezoresistive sensors, considering both bulk resistance and contact resistance. To elucidate the relaxation and creep behaviors, the model incorporates the conformational change and the slip motion of the polymer macromolecules during the deformation. Utilizing the Adam optimization algorithm, the model can accurately depict the piezoresistive behavior of various PPNs (with different porosities and conductive nanomaterial contents) with a fitting accuracy exceeding 99%. Furthermore, we explored some atypical characteristics of the PPN-based sensor, such as the negative resistance-strain behavior and the overshooting of bulk resistance. This study sets a theoretical basis for the development of sensitive and stable PPN-based sensors.

Carboxylate ester-based electrolytes for Na-ion batteries.

Sodium-ion batteries (SIBs) is a promising technology for next-generation energy storage. However, their performance is limited at low temperatures due to the inferior bulk and interfacial resistance of current electrolytes. Here we present a systematic study to evaluate carboxylate ester-based electrolytes for SIB applications, due to their favorable properties (i.e., low melting point, low viscosity and high dielectric constant). The effects of salt, concentration and solvent molecular structure were systematically examined and compared with those of carbonate-based electrolytes. By combining electrochemical tests with spectroscopic characterization, the performance of selective carboxylate ester-based electrolytes in hard carbon/Na and Na3V2(PO4)3/Na half-cells was evaluated. We found carboxylates enable high electrolyte conductivities, especially at low temperatures. However, carboxylates alone are inadequate to form a stable interphase due to their high reactivity, which can be addressed by choosing a suitable anion and facilitating anion-rich Na+ solvation by increasing salt concentration. Fundamental knowledge on the chemistry-property-performance correlation of this new family of electrolytes was obtained, and their benefits and pitfalls were thoroughly discussed. These discoveries and knowledge will shed light on the potential of carboxylate ester-based electrolytes and provide the foundation for further electrolyte engineering.

An approach to substitute costly-commercial capattery electrodes by activated carbon@Co with advanced retention: Detailed device study supported by DFT investigation

Modern technological development requires researchers to develop cost-effective materials for energy storage/conversion device. The activated carbon, its composite with oxyhydroxide opens new areas for making low-cost commercial sustainable devices synthesized by hydrothermal method. Here, we have broadly compared the different types (Al, Co, Ni) of oxyhydroxide carbon composite for energy storage with detailed theoretical investigations. The detailed DFT simulation is done to see the electronic properties by evaluating the total density of the state and the orbital contribution of the density of the state along with the band structure. The band structure and orbital contribution of DOS show the metallic nature of the CoOOH and the quantum capacitance(QC) obtained for pure CoOOH is 3000 μF. The crucial finding of the research is broad comparative electrochemical performance, with surface area variation for all electrode materials AlOOH@activated carbon, CoOOH@activated carbon, and NiOOH@activated carbon, respectively. The specific capacitance value for otimized CoOOH@activated carbon, from cyclic voltammetry, is 230 F g−1 at 10 mV/s. The bulk and charge transfer resistance calculated for CoOOH@activated carbon (Co@AC) is, respectively 0.82 Ω and 1.18 Ω. The energy, and power density values for CoOOH@AC are 37.34 W h kg−1 and 4200 W kg−1 at a current density of 2 A g−1. The capacitance retention and Columbic efficiency for Co@AC are 72, and 96 % for Co@AC till the last 20,000 segments of GCD. Overall, out of all electrode, the devices with Co@AC electrode shows very promising performance. The fabricated device can glow 26 LED panels for 5 min.

Unraveling the Effects of Carbon Corrosion on Oxygen Transport Resistance in Low Pt Loading Proton Exchange Membrane Fuel Cells.

Cost and durability have become crucial hurdles for the commercialization of proton exchange membrane fuel cells (PEMFCs). Although a continuous reduction of Pt loading within the cathode catalyst layers (CCLs) can lead to cost savings, it also increases the oxygen transport resistance, which is further compounded by key material degradation. Hence, a further understanding of the mechanism of significant performance loss due to oxygen transport limitations at the triple phase boundaries (TPBs) during the degradation process is critical to the development of low Pt loading PEMFCs. The present study systematically investigates the impact of carbon corrosion in CCLs on the performance and oxygen transport process of low Pt loading PEMFCs through accelerated stress tests (ASTs) that simulate start-up/shutdown cycling. A decline in peak power density from 484.3 to 251.6 mW cm-2 after 1500 AST cycles demonstrates an apparent performance loss, especially at high current densities. The bulk and local oxygen transport resistances (rbulk and Rlocal) of the pristine cell and after 200, 600, 1000, and 1500 AST cycles are quantified by combining the limiting current method with a dual-layer CCL design. The results show that rbulk increased from 1527 to 1679 s cm-2, Rlocal increased from 0.38 to 0.99 s cm-1, and the local oxygen transport resistance with the normalized Pt surface area (rlocal) exhibited an increase from 18.5 to 32.0 s cm-1, indicating a crucial impact on the structure collapse and changes in the chemical properties of the carbon supports in the CCLs. Further, the interaction between the ionomer and carbon supports during the carbon corrosion process is deeply studied via electrochemical quartz crystal microbalance and molecular dynamics simulations. It is concluded that the oxygen-containing functional groups on the carbon surface could impede the adsorption of ionomers on carbon supports by creating an excessively water-rich layer, which in turn aggravates the formation of ionomer agglomerations within the CCLs. This process ultimately leads to the destruction of the TPBs and hinders the transport of oxygen through the ionomer.

Modifying electric and multiferroic properties of lead-free 0.7BFO-0.3BTO ceramics via Sm and Ga co-doping

Polycrystalline lead-free composite ceramics composed of 0.7Bi1-xSmxFe0.95Ga0.05O3−0.3BaTiO3 (BSxFG-BT) with varying doping concentration of x (0.025, 0.05, 0.10, 0.15, and 0.20) were synthesized. This study comprehensively explores the influence of co-doping Samarium (Sm) and Gallium (Ga) on the microstructures, spectral properties, electrical characteristics, and multiferroic behaviour within the 0.7BiFeO3−0.3BaTiO3 system. These composite ceramics exhibited coexistence of R (rhombohedral) and T (tetragonal) phases, characterized by the space groups R3c and P4mm, respectively. The XRD and AFM results show that the Sm and Ga co-doping influenced the crystal structure as well as grain size of BSxFG-BT ceramics. Raman spectroscopy was used to analyze the positions of the phonon modes. High dielectric constant with high Curie temperature of 550 °C were obtained. The impact of grain and grain boundary on the capacitance and resistance in the ceramics was investigated utilizing Z-view software and high magnitude of bulk resistance was obtained for dopant value x = 0.20 at 300 °C. Enhanced multiferroic properties, remanent magnetisation Mr = 0.051 emu g−1 with coercive field (Hc) = 6450 Oe and remanent polarization Pr = 10.98 μC cm−2 with coercive filed Ec = 14.73 kV cm−1 were obtained for x = 0.20.

Hydrogen Crossover in Anion Exchange Membrane Fuel Cells

In recent years anion exchange membrane fuel cells (AEMFC) have started to draw more attention by potentially allowing catalysts based on more abundant materials, and by showing high performance [1]. One often overlooked parameter in these systems is membrane permeability of hydrogen, often referred to as hydrogen crossover, which directly affects fuel cell stability and efficiency. This undesirable effect creates mixed potential due to the permeated hydrogen reacting with oxygen on the cathode, and not generating useful electric energy, only water and heat [2]. The generated heat creates hotspots of temperatures enough to cause membrane defects or even destruction which further accelerates the degrading process [3].During fuel cell operation relative humidity (RH) and temperature varies in the system, therefore in this study hydrogen crossover is measured at different temperatures (between 50 and 70 ⁰C) and RH (between 30 and 100 %), on Aemion anion exchange membranes (AEMs) with and without reinforcement and with a variety of membrane thicknesses (25 and 50 μm in Figure 1. a). The hydrogen crossover is measured using a mass spectrometer (MS) at the inert gas exhaust. To avoid effects of other components pure membranes and gas diffusion layers (GDLs) were utilized without electrodes.It is shown that AEMs increase in permeability with temperature for all tested while the effect of RH depends on if they are reinforced or not (Figure 1. a). The non-reinforced membranes show a constant decrease in hydrogen crossover with increasing RH, while the reinforced show constant hydrogen crossover until full humidification where it sharply decreases. While the observed trends are different, the quantitative values between reinforced and non-reinforced membranes were relatively similar: at dry conditions, RHs lower than 50 %, crossover is 10 to 30 % lower for reinforced membranes, around 10 % higher at 70 % RH, and at full humidification a non-significant difference compared with non-reinforced (Figure 1. a). It is shown that an increase in the membrane thickness is not proportional to the decrease in hydrogen crossover, suggesting that interface resistance is not negligible. The calculated interface resistance is higher than the bulk resistance for both reinforced and non-reinforced membranes at all RHs (Figure 1. b). However, the bulk resistance is higher for reinforced membranes than for non-reinforced, while interface resistances are relatively similar. Interestingly, the ratio between the interface and the bulk resistance remains constant at all RHs. However, for the membranes without reinforcement the bulk resistance is 20 % of total crossover resistance, while for reinforced it is two times higher, 40 %. Scanning electron microscope (SEM) cross-section analysis shows that the reinforcement is a relatively thin layer of a different polymer in the membrane, which suggests that even a very thin reinforcement could affect membrane permeability properties. Understanding the effects of the reinforcement and their influence on fuel cells will allow for more durable and safer AEMFCs.Figure 1. H2 crossover measured using a MS at the inert gas side. a) At different temperatures, relative humidities and membrane thicknesses. b) H2 crossover resistance at the interface and in the bulk for membranes with and without reinforcement. Measurements are done at 70 °C and at flows 20 ml/min of both hydrogen and the inert gas (Ar).[1] D. R. Dekel, “Review of cell performance in anion exchange membrane fuel cells,” J. Power Sources, vol. 375, pp. 158–169, 2018, doi: 10.1016/j.jpowsour.2017.07.117.[2] S. S. Kocha, J. D. Yang, and J. S. Yi, “Characterization of Gas Crossover and Its Implications in PEM Fuel Cells,” 2006, doi: 10.1002/aic.10780.[3] Q. Tang, B. Li, D. Yang, P. Ming, C. Zhang, and Y. Wang, “Review of hydrogen crossover through the polymer electrolyte membrane,” Int. J. Hydrogen Energy, vol. 46, no. 42, pp. 22040–22061, 2021, doi: 10.1016/j.ijhydene.2021.04.050. Figure 1

Nucleation Behavior and Growth Characteristics of Atomic-Layer Deposited Iridium Thin Films with Ticp and Oxygen

Platinum group elements (Pt, Ru, Pd, Rh, Ag, Au, and Ir) have excellent properties of high thermal and chemical stability, and low electrical resistivity. Due to the attractive characteristics, these materials are also expected for applications in the semiconductor industries. In particular, iridium (Ir) has attracted interests as a potential electrode for memory devices because of its high work function and low resistivity (bulk: 4.7 μΩ cm).Despite the advantages of Ir, the deposition of Ir thin films for the next-generation memory applications faces critical challenges. Since metal has a high surface energy, it is difficult to adsorb on a surface with a lower surface energy. So, formation of metal nuclei is delayed in the initial growth of atomic layer deposition (ALD), and island growth is preferred. During the ALD, sparsely grown nuclei cause an increase in surface roughness which deteriorates the leakage current properties of capacitors.In this study, we attempted ALD of Ir films from newly synthesized tricarbonyl (1,2,3-η)-1,2,3-tri(tert-butyl)-cyclopropenyl iridium and oxygen. The growth behavior and film properties of impurity contents and bulk resistivity were investigated in terms of the growth temperature. Also, we examined the changes in the surface morphology of the iridium film with the film thickness. Consequently, we achieved the growth of continuous and smooth Ir films even below 4 nm by forming nucleation-promoting layer at high temperature and followed by ALD of Ir at low temperature. In addition, the capacitor device characteristics were also investigated using Ir as a bottom electrode.

Mathematical Model Based on Staircase Structure for Impedance Analysis of Non-Ideal and Non-Uniform Processes in Porous Electrodes

Electrochemical impedance spectroscopy analysis for porous electrodes in energy conversion and storage, described as resistance and capacitance, is widely used to understand their electrochemical processes. These processes include: (i) electronic resistance inside the electrode (R e), (ii) ionic resistance in the electrolyte bulk and inside the porous electrode (R ion), (iii) electrical double layer formation (C dl) and charge transfer resistance at the electrode electrolyte interface (R ct) , and (iv) diffusion for charge compensation.As one of the mathematical models in electrochemical impedance spectroscopy for porous electrodes, a transmission line model is known, in which the pore structure is described as a cylinder geometry.1 We have proposed an analytical method that combines the transmission line model with electrochemical impedance spectroscopy using a symmetric cell,2 and have investigated resistance separation in lithium-ion batteries and its effect on battery performances.3-5 Due to mathematical constraints, the transmission line model is limited to a representation of an ideal, uniform process model. Here we propose a mathematical model based on a network model consisting of a staircase structure for electrochemical impedance spectroscopy at porous electrodes that can describe not only ideal and uniform processes but also non-ideal and non-uniform processes (Fig. 1), and aims to help elucidate their borderline behavior.6 The proposed staircase model (Z SCM) gives a series equivalent circuit consisting of Z 0, which is a series circuit of electrode/electrolyte interface impedance (Z int0) and electronic resistance (R e0), and electrolyte resistance (R ion0) as an initial step without pores (Z SCM0 = R ion(0) + Z 0). The one-step model (Z SCM1) is then given a series equivalent circuit consisting of the parallel circuit of Z SCM0 and Z 1 and the electrolyte resistance R ion(1) in series (Z SCM1 = R ion(1) + (Z SCM0 −1+Z1 −1)−1). The staircase model is calculated by incorporating the 1 prior step (Fig. 2). Thus, the model with n steps (Z SCM(n)) is composed of a series equivalent circuit of the parallel circuit of Z SCM(n−1) and Z n and the electrolyte resistance R ion(n) (Z SCM(n) = R ion(n) + (Z SCM(n−1) −1 +Z n −1)−1).Fig. 3 shows Nyquist plots computed for each input parameter at 50 steps for non-Faradic and Faradic processes in the staircase model. The results are in good agreement with the profiles calculated for the transmission electric model.2 The presentation will further show examples of the calculated results using the staircase model for non-ideal and inhomogeneous processes and discuss the analysis of impedance behavior using real electrodes reflecting non-uniform processes. References R. de Levie, Electrochim. Acta, 9, 1231-1245 (1964). N. Ogihara, S. Kawauchi, C. Okuda, Y. Itou, Y. Takeuchi and Y. Ukyo, J. Electrochem. Soc., 159, A1034-A1039 (2012). N. Ogihara, Y. Itou, T. Sasaki and Y. Takeuchi, J. Phys. Chem. C, 119, 4612-4619 (2015). N. Ogihara, Y. Itou and S. Kawauchi, J. Phys. Chem. Lett., 10, 5013-5018 (2019). Y. Itou, N. Ogihara and S. Kawauchi, J. Phys. Chem. C, 124, 5559-5564 (2020). N. Ogihara and Y. Itou, Phys. Chem. Chem. Phys., 24, 21863-21871 (2022). Figure 1