Defect Concentration Research Articles

Interfacial Proton Precompensation: Suppressing Deprotonation-Driven Lattice Collapse for Enhanced Efficiency and Stability in Perovskite Solar Cells.

The chemical property of the buried interface plays a crucial role in improving the performance and stability of perovskite solar cells (PSCs). The SnO2/perovskite interface prepared from SnO2 alkaline hydrogel with high proton affinity triggers directional migration and irreversible reactions of protons, exacerbating the disintegration of perovskite crystal. In this study, we proposed proton precompensation strategy to suppress the deprotonation effect of the buried interface and improve the durability of the devices. By modulating the chemical environment and surface energy state of the buried interface, the domain-limiting and spontaneous compensation of protons in formamidinium (FA+) under Coulomb force were achieved, thereby stabilizing the perovskite crystal structure. The stability of target perovskite films under UV illumination and heating at 85 °C was significantly enhanced. As a result, the devices can retain around 90% of their initial power conversion efficiency (PCE) after 1000 h of continuous irradiation at the maximum power point (MPP). Moreover, due to the reduction of defect content at the buried interface and the improvement of conductivity and carrier mobility by the precompensation treatment, the interfacial energy loss and non-radiative recombination were substantially diminished. The target PSC devices exhibited much higher PCE of 25.55% than the control devices (23.03%).

Interfacial Proton Precompensation: Suppressing Deprotonation‐Driven Lattice Collapse for Enhanced Efficiency and Stability in Perovskite Solar Cells

The chemical property of the buried interface plays a crucial role in improving the performance and stability of perovskite solar cells (PSCs). The SnO2/perovskite interface prepared from SnO2 alkaline hydrogel with high proton affinity triggers directional migration and irreversible reactions of protons, exacerbating the disintegration of perovskite crystal. In this study, we proposed proton precompensation strategy to suppress the deprotonation effect of the buried interface and improve the durability of the devices. By modulating the chemical environment and surface energy state of the buried interface, the domain‐limiting and spontaneous compensation of protons in formamidinium (FA+) under Coulomb force were achieved, thereby stabilizing the perovskite crystal structure. The stability of target perovskite films under UV illumination and heating at 85 °C was significantly enhanced. As a result, the devices can retain around 90% of their initial power conversion efficiency (PCE) after 1000 h of continuous irradiation at the maximum power point (MPP). Moreover, due to the reduction of defect content at the buried interface and the improvement of conductivity and carrier mobility by the precompensation treatment, the interfacial energy loss and non‐radiative recombination were substantially diminished. The target PSC devices exhibited much higher PCE of 25.55% than the control devices (23.03%).

Optimisation of laser surface ablation of alumina/GO coating on AZ31D magnesium alloy using Cuckoo Search Algorithm method

ABSTRACT Graphene oxide (GO) and alumina (Al2O3) work in concert to give magnesium alloys advantageous surface qualities and protection from adverse environments. This paper aims to investigate the effect of laser surface treatment on plasma sprayed alumina-graphene oxide (GO) coating on AZ31D magnesium alloy. Key ablation quality responses; HAZ width, surface roughness and ablation rate were correlated with laser parameters using the Response Surface Methodology and optimised using the metaheuristic Cuckoo Search Algorithm Method. Laser power significantly influenced all ablation characteristics of the composite coating. The addition of 1.5 wt% GO in the alumina coating caused a significant reduction in HAZ width (43.32%), surface roughness (25.11%) and ablation rate (76.58%) when treated with optimal combinations of laser power (8 W), scanning speed (950 mm/s) and frequency (78.2 kHz). The surface quality was characterised by smooth textures, and resolidified splats along with deep pits when ablated with lower and intermediate power whereas surfaces ablated with higher power showed debonded splats with peripheral surface destruction. While a prominent 2D peak at 16 W confirmed the presence of GO layers during high-power laser contacts, the ID/IG ratio below unity across all specimens indicated minimal defect concentrations.

Highly Selective, Room-Temperature Triethylamine Sensor Using Humidity-Resistant Novel TiZn Alloy Nanoparticles-Decorated MoS₂ Nanosheets.

The future of environmental monitoring, medical diagnostics, and industrial safety depends on developing room-temperature, long-term operable, stable, miniaturized, ultrahigh-performance sensors integrated into the Internet of Things (IoT). While noble metals and high-entropy alloys (HEAs) lead in addressing the limitations of conventional transition-metal dichalcogenides (TMDs) like MoS₂, they face challenges such as high-cost, limited availability, and fabrication complexity. To address this, multifunctional, cost-effective, humidity-insensitive novel phase Ti₀.₅Zn₀.₅ (TiZn) alloy nanoparticle-decorated MoS₂ nanosheets (MoS₂_NP) is developed for ultra-selective and highly sensitive triethylamine (TEA) vapor detection at room temperature (RT). This exhibited a 24-fold increase in response compared to MoS₂, with a high signal-to-noise ratio, negligible humidity interference, sensitivity of 9.92×10⁻⁵ ppm⁻¹ at RT, and a detection limit of 48ppm. The enhanced catalytic activity and defect concentration, the reduction of the edge oxidation resulting in strong Fermi-level pinning, and the relatively high adsorption energy lead to a target gas-specific carrier-type response, demonstrating the potential of binary alloy nanoparticles (NPs) as decorative materials for enhanced sensing applications. The superior performance of the sensor led to the development of a TEA detection prototype interfaced with a mobile device via IoT for continuous monitoring, enhancing practicality and usability by offering immediate access to critical information.

First Principles Study of Bismuth Vacancy Formation in (111)-Strained BiFeO3

Epitaxial strain is known to significantly influence the structural and functional properties of oxide thin films. However, its impact on point defect concentration has been less explored. Due to the challenges in experimentally measuring thin-film stoichiometry, computational studies become crucial. In this work, we use first-principles calculations based on density functional theory to investigate the formation and stability of Bi vacancies and Bi-O vacancy pairs in BiFeO3 (BFO) under (111) epitaxial strain. Our results demonstrate that compressive strain (−4%) decreases the formation enthalpy of Bi vacancies by 0.88 eV, whereas tensile strain (4%) increases it by 0.39 eV. Out-of-plane (OP) Bi-O vacancy pairs exhibit enhanced stability under both compressive and tensile strain, with formation enthalpy reductions of 1.49 eV and 1.05 eV, respectively. In contrast, in-plane (IP) vacancy pairs are stabilized under compressive strain but are insensitive to tensile strain. Finally, we discuss how these findings influence Bi stoichiometry during thin-film growth and the role of local strain fields in the formation of conducting domain walls.

Energetics of Point Defects in D0a Ag3Sn: First‐Principles Calculations

The Ag3Sn intermetallic compound is commonly found and acts as a strengthening factor in the key lead‐free solders based on Sn‐Ag‐Cu. The Ag3Sn phase exhibits also an asymmetric off‐stoichiometry, which necessitates the existence of constitutional point defects. The presence of point defects can, in general, sensitively affect the plastic deformation of materials and the strengthening role of Ag3Sn in particular. To understand the nature of the point defects and the compositional stability of Ag3Sn, the relaxed structures and the energies of single point defects (vacancies and antisite defects) in all three sublattices of Ag3Sn are calculated at 0 K using ab initio density functional theory (DFT) and the supercell method. The first‐principles‐based calculations predict that the AgSn antisite defect (Ag substitution for Sn) has the smallest enthalpy of formation, thus indicating that the AgSn antisite defect is the dominant point defect in Ag3Sn. The point defect concentrations as a function of Sn content are estimated using the DFT defect energies and the Wagner–Schottky model. The compositional dependence of the point defect concentrations gives new insights on the atomistic mechanisms of formation of nonstoichiometric Ag3Sn.

Carbon defect induced electron transfer promotes electrocatalytic activation of molecular oxygen to selectively generate singlet oxygen for pollutants removal

This study explored the design of heterojunctions incorporating defective graphene and boron nitride (BN) to activate molecular oxygen (O₂) and degrade sulfamethoxazole (SMX) by establishing efficient electron transport channels. These heterojunction catalysts, designed using theoretical predictions, were synthesized by controlling carbon defect concentration and pyrolysis temperature. The optimized GBN cathode achieved a maximum SMX degradation rate of 0.0252min⁻¹, with a total organic carbon (TOC) removal efficiency of 47.31%. Singlet oxygen (¹O₂) was identified as the primary reactive oxygen species, exhibiting a generation rate of 18.66μMmin⁻¹ and contributing 93.5% to SMX degradation. Results demonstrated that an optimal defect concentration enhances electron transfer, promoting the 2-electron reduction of O₂ to H₂O₂ and facilitating further H₂O₂ activation, thereby accelerating SMX degradation. This work advances the development of non-metallic cathodic catalysts and provides valuable insights into electrochemical degradation mechanisms for organic pollutants.

Investigating the atomic structures and electronic properties of WS2 thin films with sulfur vacancies via a neural network potential-aided first-principles study

Transition metal dichalcogenides are promising materials for high-performance electronics, whereas the impact of defects on their electronic properties remains elusive. Here, we employ neural network potentials (NNPs) constructed from density functional theory (DFT) data to investigate defect-laden WS2 thin films. Molecular dynamics simulations reveal that at low defect concentrations (S/W ratio of 1.9), single sulfur vacancies are predominant. Conversely, at high defect concentrations (S/W ratio of 1.7), complex defects with short lifetimes appear. Additionally, DFT results indicate that the band gap persists at S/W = 1.9 but disappears at 1.7, aligning with observed device degradation at high defect concentrations.

The energy-storage density of Polymers/BNBT6 nanocomposites with high breakdown field

Ceramic/polymer dielectric composites show significant potential for energy storage devices in advanced microelectronic applications. However, an excessive quantity of inorganic nanofillers within the polymeric matrix can lead to a substantially unequal distribution of the electric field, which may impede the improvement of energy storage density. Herein, 0.94Bi0.5Na0.5TiO3-0.06BaTiO3 (BNBT6) nanoparticles were synthesized using a combined solid-phase method followed by sieving. The silane coupling agent KH560 was used to modify the nanoparticles. Additionally, polyphenylene oxide (PPO), polytetrafluoroethylene (PTFE), and perfluoroalkyl (PFA) were utilized as matrices. The surface modification enhanced the interfacial coupling interaction between BNBT6 and the polymers, resulting in a lower concentration of interfacial hole defects. The findings demonstrated that BNBT6@KH560/PPO nanocomposites attained a high Wrec (2.71 J cm−³) and an excellent of η ∼ 81.1 % with 50 wt% BNBT6@KH560 nanofiller at 1550 kV cm−1. Furthermore, the exceptional frequency and thermal stability of BNBT6@KH560/PPO nanocomposites made it a strong contender for future portable energy devices. This work presents a feasible solution for synthesizing high-performance dielectric nanocomposites using straightforward preparation techniques.

Simplified synthesis of Pt-MnOx supported on three dimensional Co3O4 for catalytic removal of toluene

In this study, a simplified method was developed for synthesizing Pt-(MnOx)/three-dimensional (3D)-Co3O4 catalysts. This approach represents a convenient alternative to the typical procedure of initially synthesizing nanoparticles (NPs) and subsequently depositing them onto supports. The Pt1-(MnOx)1/3D Co3O4 catalyst, with a molar ratio of Pt:Mn=1:1, demonstrated excellent catalytic efficacy at a comparatively low reaction temperature and displayed commendable thermal stability during prolonged operation in the deep oxidation of toluene. The T90 (temperature required for 90% conversion) of Pt1-(MnOx)1/3D Co3O4 was merely 163 °C. Characterization analysis revealed that the catalyst's remarkable catalytic efficiency is attributed to the elevated concentration of oxygen vacancy defects on Pt1-(MnOx)1/3D Co3O4 and its low-temperature reducibility. In situ DRIFTS analysis was conducted to investigate the possible reaction pathway of Pt1-(MnOx)1/3D Co3O4. The results indicated that the rapid dehydrogenation of methyl and the demethylation of toluene facilitate the cleavage of the benzene ring on the Pt1-(MnOx)1/3D Co3O4 catalyst, due to the abundant absorption of oxygen species. This process enhances the catalytic combustion of toluene

Oxygen 1s X-ray Photoelectron Spectra of Iridium Oxides as a Descriptor of the Amorphous-Rutile Character of the Surface.

Characterization of the surface of iridium oxide (IrOx) materials is of crucial importance to understand catalysts for the oxygen evolution reaction (OER) in low-temperature water electrolysis. While much of our current knowledge is based on well-defined single-crystal surfaces, surface-sensitive techniques like X-ray photoelectronic spectroscopy (XPS) are relevant to characterize the nanostructures considered. In this work, we describe a simple approach to use oxygen 1s spectra as an identifier of the amorphous/crystalline characteristics of iridium oxide structures from purely amorphous to purely crystalline. This conceptual approach was validated on seven commercially available materials. The presence of oxygen-associated defects in the surface moieties/species is shown even for purely crystalline materials with defect concentration increasing with greater amorphous character. This methodology provides us with an accessible ex situ descriptor of the catalyst surface as a baseline for further studies of the impact on catalytic properties.

The reduced graphene oxide conductive additives with a certain defect concentration enabling rate-capability of lithium-ion batteries

Graphene as conductive additives for enhancing the electrochemical performance of commercial cathode materials (e.g., LiFePO4, LiCoO2, and LiMn2O4) in advanced Li-ion batteries (LIBs) has attracted great attention in recent years. However, the LiFePO4 and LiCoO2 electrodes usually show a poor rate capability when using graphene as the conductive additive, since its planar structure hinders ion transmission. Herein, a variety of reduced graphene oxides (rGO-x) have been successfully prepared using the modified Hummer's method followed by calcination. The results show that due to a large specific area and moderate defect density, rGO-5 can ensure good enough interfacial contact between active material particles and collector, thus maintaining fast electron/ion transportation. It has been found that LiFePO4 and LiCoO2 electrodes exhibit good lithium storage properties of 160.95 and 139.41 mA h g-1 at a rate of 0.1 C when rGO-5 is utilized as a conductivity additive. Meanwhile, combined with the electrochemical impedance and kinetic exploration, it can be seen that the LiFePO4 and LiCoO2 electrodes demonstrate a high Li+ diffusion coefficient (DLi+) of 6.7 × 10-14 cm2 s-1 and 4.3 × 10-13 cm2 s-1, respectively. Therefore, this research sheds new light on the practical utilization of rGO additives in high-performance lithium-ion batteries.

Visible-light-operative photocatalyst based on Er-TiO2 Nanostructures Blended with Room temperature ferromagnetism, band-gap Increment, and high optical transparency

TiO2 thin films doped with Er+3 percentage (1-5wt.%) have been prepared using the sol-gel dip coating technique. Er influences the morphological, structural, magnetic, electrochemical, UV, dielectric, Photoluminescence, and photocatalytic properties of TiO2. FTIR was utilized to examine the different functional groups. The confirmation of the anatase phase formation was established through XRD spectra and FTIR spectra. When the concentration of dopant increased, the crystallite size was found to be decreased from 7.96 to 5.62 nm. A blue shift was noticed in transmission spectra as the dopant concentration increased leading to an increase in the bandgap of thin films. The dielectric properties of all thin films exhibited typical behavior. The barrier height, density of localized states at fermi levels, and hopping distance were examined using AC conductivity measurements. As dopant concentrations increased the dielectric constant increased while AC conductivity decreased. The outcomes of electrochemical charge-discharge tests provided the specific capacitance, power density, and Energy of Er-doped TiO2. Er-doped TiO2 especially at 5wt.% showed significant photocatalytic activity in decomposing indigo carmine under sunlight, suggesting its potential for water treatment, and mitigating environmental pollution. Furthermore, Er-doped TiO2 demonstrated efficient functionality as a CO gas sensor. Er-doped TiO2 exhibited violet photoluminescence, with emission intensity modulated by elevating the Er percentage attributed to heightened defect concentration. These properties find a utility in Optoelectronic device applications. Magnetic analysis indicated that incorporating a trivalent dopant (Er+3) into the Ti-O lattice enhanced ferromagnetic properties.

Black Jamun Fruit Peel Extract Modified Gum Acacia Biopolymer Suitable for Energy Device Applications via Charge Transfer Enhancement

The visible light absorption capabilities, along with its electrical characteristics, of a low-cost, plant-based, biopolymer, gum acacia, have been chemically modified by tailoring its defect concentrations via pH modification, where the acid solvent of fruit (peel) extracts of jamun was used to influence the chemical structure by reactive modification. Ultraviolet-visible and photoluminescence spectroscopy of the gum acacia biopolymer treated with the extracted anthocyanin from jamun peel showed a prominent, characteristic red shift in the visible spectrum range. Impedance spectroscopy analysis showed the occurrence of localized ionic conduction. The bulk conductivity of the modified specimens increased due to the profound release of conducting ions in the water-swollen network. The reactively modified biopolymer could be used in multiple fields of material science, specifically in energy device applications, viz., photovoltaics (PV), by utilizing its cost effectiveness and photolytic effectiveness. 2nd, as a polymer electrolyte and dye-sensitised solar cells (DSSCs) material by utilizing its capacity of gel formation. In our research described in this article, the underlying charge transfer mechanism for such responses was examined after crosslinking in the organic dyes extracted from the peel of jamun fruit with gum acacia.

Kinetics of electromigration mass transfer in micro- and nanoelectronics interface elements depending on the strength of thin-film junctions

The theoretical model proposed earlier by the authors, which describes the interrelation of strength and electromigration (diffusion) properties of interfaces formed by joined materials, has been perfected and extended. Within the framework of the developed model, a linear relationship between the values of the work of reversible interface separation Wa and the activation energy of electromigration in the interface HEM was established. The coefficients of the obtained relation are estimated and compared with experimental data on the study of electromigration in a copper conductors covered with protective dielectrics. Using also the model developed earlier by the authors, which describes the dependence of the value on the concentrations of non-equilibrium lattice defects in the volumes of joined materials, a number of effects due to the influence of such defects on the processes caused by electromigration have been predicted and investigated. In the paper we obtained that by introducing non-equilibrium lattice defects in the volumes of bonded materials in the form of atomic impurities of interstition or substitution it is possible to effectively influence the characteristics of electromigration instability of the shape of the interlayer interface. For the introduction impurities, quantitative analytical estimates of the impurity concentration necessary for a significant change (both increase and decrease) in the characteristic rise time of the instability of the shape of the initially flat interface have been obtained.

Mixed Conduction in A-Site Double-Perovskite Na1+xLa1-xZr2O6-δ Proton Conductors.

Perovskite-type proton conductors exist in two structural forms, ABO3 and A2B'B″O6. In this study, novel A-site double-perovskite proton conductors (A'A″B2O6) were proposed. Na1+xLa1-xZr2O6-δ (x = 0, 0.1, 0.2) perovskites were prepared by a solid-state reaction at 1200 °C. However, raising the sintering temperature to 1300 °C resulted in the Na to volatilize, converting the Na1.1La0.9Zr2O6-δ into La0.9Zr2O6-δ. The conductivities of these materials in a humid atmosphere were tested using electrochemical impedance spectroscopy, and their carrier transport numbers were measured using the defect equilibria model and concentration cell method. Na1.1La0.9Zr2O6-δ and Na1.2La0.8Zr2O6-δ are predominantly proton conductors, with Na1.1La0.9Zr2O6-δ exhibiting the highest proton transport number of 0.52 at 800 °C. In contrast, NaLaZr2O6 is predominantly an electronic conductor, while La0.9Zr2O6-δ functions as an oxide ion conductor. Due to their high protonic transport numbers, these Na1+xLa1-xZr2O6-δ A-site double-perovskite oxides present a promising avenue for the development of proton conductors.

Regulation of the Built‐In Electric Fields of MIL‐125(Ti)@Ti‐Ce‐MOF Yolk‐Shell Z‐Scheme Heterojunctions via Ligand Defects Toward Optimized Photocatalytic Performances

AbstractThe controllable formation of a built‐in electric field (IEF) can effectively separate photogenerated electrons and holes and optimize the band structure of a material, thus improving its photocatalytic performance. Here, a novel type of defective metal‐organic framework (MOF), i.e., an MIL‐125(Ti)@Ti‐Ce‐MOF yolk‐shell Z‐scheme heterojunction, is synthesized using a simple ion‐etching‐coupled reconstruction method. By controlling the concentration of ligand defects within the MOF heterojunction, the strength of the IEF within the heterojunction can be effectively regulated. Moreover, the experimental and theoretical results demonstrated that ligand defects within the Z‐scheme heterojunction structure can enhance the efficiency of photogenerated carrier separation and improve the transport capacity by regulating the IEF. The photocatalytic tetracycline (TC) degradation performance of the resultant MIL‐125(Ti)@Ti‐Ce‐MOF yolk‐shell heterojunction is ≈52.5‐ and 5.5‐fold higher than those of Ti‐Ce‐MOF and MIL‐125(Ti), respectively, indicating the efficient spatial charge separation due to the enhanced IEF. This study reveals the precise control of the IEF over the MIL‐125(Ti)@Ti‐Ce‐MOF yolk‐shell Z‐scheme heterojunction, elucidating the relationship between the IEF and ligand defect concentration and promoting the photocatalytic performances of MOF@MOF‐based catalysts via density functional theory and related experiments.

Significantly reduced lattice defects and improved dielectric properties of MgTiO3 based microwave ceramics via supercritical-fluid assisted oxidation technology

Lattice defects play a crucial role in determining the microwave dielectric properties of ceramics. We herein report a simple way to significantly improve the dielectric properties of MgTiO3 based microwave ceramics by restoring the oxygen vacancy via supercritical assisted oxidation (SAO) technology. The high penetrability of SCCO2 fluid makes the OH− groups easy to approach oxygen vacancy, which react with the dangling bonds to form A-O-A (A=Ti/Mg) covalent coordinate bonds. The oxygen vacancy concentration in MgTiO3-CaTiO3 ceramics significantly decreases from 26.7 % to 18.5 % and the Ti-O bond strength is strengthened after SAO treatment. Furthermore, the activation energy Ea increases to 0.60 eV from 0.52 eV, indicating a lower defects density as well. Consequently, MgTiO3-CaTiO3 ceramics treated by SAO exhibit better high-temperature stability in dielectric properties and the Q×f values of MgTiO3-CaTiO3 ceramics increase by 11.3∼19.0 % due to the decreased defects concentration, thereby demonstrating the potential of supercritical fluid technology in achieving performance optimization of microwave dielectric ceramics.

Anisotropy of radiation-induced defects in Yb-implanted β-Ga2O3

RE-doped β-Ga2O3 seems attractive for future high-power LEDs operating in high irradiation environments. In this work, we pay special attention to the issue of radiation-induced defect anisotropy in β-Ga2O3, which is crucial for device manufacturing. Using the RBS/c technique, we have carefully studied the structural changes caused by implantation and post-implantation annealing in two of the most commonly used crystallographic orientations of β-Ga2O3, namely the (-201) and (010). The analysis was supported by advanced computer simulations using the McChasy code. Our studies reveal a strong dependence of the structural damage induced by Yb-ion implantation on the crystal orientation, with a significantly higher level of extended defects observed in the (-201) direction than for the (010). In contrast, the concentration and behavior of simple defects seem similar for both oriented crystals, although their evolution suggests the co-existence of two different types of defects in the implanted zone with their different sensitivity to both, radiation and annealing. It has also been found that Yb ions mostly occupy the interstitial positions in β-Ga2O3 crystals that remain unchanged after annealing. The location is independent of the crystal orientations. We believe that these studies noticeably extend the knowledge of the radiation-induced defect structure, because they dispel doubts about the differences in the damage level depending on crystal orientation, and are important for further practical applications.

High‐Performance Na‐Storage and Sodiation Behavior Identification in Cellulose‐Derived Hard Carbon by High‐Resolution Element Mapping Microscopy

Nowadays, hard carbon is one of the most promising anode materials for sodium‐ion batteries. However, the Na‐storage performance of hard carbon varies for different precursors and synthetic processes due to disparities in the dopant content, dimensions, and categories of defects, graphitic domains, which lead to controversial explanations for the energy storage mechanism. Herein, self‐freestanding membrane of cellulose‐derived carbon fibers is presented, delivering a reversible Na‐storage capacity of 330 mAh g−1 at 50 mA g−1 due to abundant ordered graphitic zones with enlarged interlayer spacings around 0.39 ± 0.03 nm. Benefiting from a robust solid electrolyte interphase layer rich in NaF nanocrystals, the membrane also holds a superior rate capability of 100 mAh g−1 at 2 A g−1 and long‐term cycling stability with capacity retention of 82.6% at 1.5 A g−1 for 4000 cycles. A clear sodiation behavior of Na+ intercalation into enlarged carbon graphitic layers at the slope step above 0.10 V and Na cluster evolution in the micropores at the plateau step around 0.01–0.10 V is disclosed by high‐resolution element mapping microscopy, different from the accepted mechanism of Na+ intercalation into graphitic layers at the plateau step.