Substrate Coverage Research Articles

Reconstruction of Hole Transport Layer via Co‐Self‐Assembled Molecules for High‐Performance Inverted Perovskite Solar Cells

AbstractAdjusting the hole transport layer (HTL) to optimize its interface with perovskite is crucial for minimizing interface recombination, enhancing carrier extraction, and achieving efficient and stable inverted perovskite solar cells (PSCs). However, as a commonly used HTL, the self‐assemble layer (SAM) of [2‐(3,6‐dimethoxy‐9H‐carbazol‐9‐yl)ethyl] phosphonic acid (MeO‐2PACz) tends to form clusters and micelles during the deposition process, leading to inadequate coverage of the ITO substrate. Here, a Co‐SAM strategy is employed by incorporating 4‐mercaptobenzoic acid (SBA) and 4‐trifluoromethyl benzoic acid (TBA) as additives into MeO‐2PACz to fabricate a Co‐SAM‐based HTL. The introduced additive can interact with MeO‐2PACz, facilitating cluster dispersion and thereby enabling better deposition on ITO for improved HTL coverage. Moreover, Co‐SAM exhibits superior energy level alignment with perovskite to enhance interfacial contact and improve carrier extraction efficiency as well as promote growth of bottom perovskite grains. As a result, an impressive increase of the power conversion efficiency (PCE) from 21.34% to 23.31% is achieved in the inverted device based on the Co‐SAM HTL of MeO‐2PACz+TBA while maintaining ≈90% of its initial efficiency under continuous operation at 1‐sun.

Thin Film Formation Based on a Nanoporous Metal-Organic Framework by Layer-By-Layer Deposition.

Understanding the structure of thin films is essential for successful applications of metal-organic frameworks (MOFs), such as low k-dielectrics in electronic devices. This study focuses on the thin film formation of the 3D nanoporous MOF Cu2(bdc)2(dabco). The thin films are prepared by a layer-by-layer technique with varying deposition cycles (1 to 50). Thin film morphologies and crystallographic properties were investigated using atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, and grazing-incidence X-ray diffraction (GIXD). AFM revealed an island growth (Volmer-Weber) with plate-like shaped islands. FTIR and GIXD revealed that Cu2(bdc)2(dabco) crystals form already during the first preparation cycle. The heights of the islands do not increase linearly with the number of deposition cycles, suggesting multiple growth stages. X-ray diffraction pole figures uncover a uniplanar texture of the Cu2(bdc)2(dabco) crystals, together with randomly oriented crystallites. The fraction of uniplanar oriented crystals increases with each deposition cycle, reaching a maximum of 75% at ten deposition cycles, simultaneously achieving complete substrate coverage. However, already at five cycles, an additional phase of randomly oriented copper-terephthalate (Cu2(bdc)) crystals appeared; this phase reaches a fraction of 22% at the largest film thickness (50 cycles). In summary, a detailed understanding of the thin film formation of an archetypal layer-pillar MOF is presented, elucidating how films grow in terms of their morphology and crystalline properties. Samples prepared by ten cycles show complete coverage of the substrate together with the highest degree of preferred crystal orientation. These results establish a deepened understanding of critical parameters for MOF thin film applications, such as complete substrate coverage and definition of the nanopores relative to the substrate surface.

Epitaxial growth of single unit-cell superconducting β-Bi2Pd

Bismuth-based binary alloy β-Bi2Pd has recently been suggested as a connate topological superconductor with immense promise for Majorana zero modes. However, the epitaxial thin films down to the ultimate level of single unit-cell have been challenging. Here, we employed the state-of-the-art molecular beam epitaxy to prepare single unit-cell superconducting β-Bi2Pd films with lateral dimensions of hundreds of nanometers. Utilizing in situ scanning tunneling microscopy/spectroscopy, we uncover evidence of anisotropic superconductivity whose spectra are well fit by anisotropic s-wave gap functions and demonstrate that the epitaxial growth of β-Bi2Pd films relies substantially on the substrate temperature, flux ratio, growth rate, and coverage. The high-quality epitaxial films provide a promising platform to investigate the topological superconductivity at the two-dimensional limit.

Large-Scale Formation of a Close-Packed Monolayer of Spheres Using Different Colloidal Lithography Techniques.

The possibility of using colloidal lithography at the industrial level depends on the ability to form defect-free coatings over large areas. The spin-coating method has not yet shown acceptable results, but a more detailed studying of the regularities of this process may improve the quality of masks. The Langmuir-Blodgett method is expected to be the most preferable for forming high-quality large-scale monolayers. Real-time controlling the surface pressure of the monolayer can allow to obtain close-packed arrays with long-range order. In this work, to develop the spin-coating technology, the influence of technological parameters (spin-coating speed and time, concentrations of components in suspension) on the substrate coverage area with a monolayer of polystyrene spheres (1.25 μm) was studied. An original automated Langmuir-Blodgett system was developed to study the influence of the monolayer surface pressure on its quality using polystyrene spheres (1.25, 1.8, 2.1 μm). The developed spin-coating technology resulted in a record coverage area (90%) of Si substrate (76 mm) and a defect-free hexagonally ordered domain area of 500 μm2. As a result of the developed Langmuir-Blodgett technique, a close-packed monolayer coating was obtained over the entire substrate area (coverage area 99.5%, defect-free domain area 3000 μm2) without the use of any surfactants.

The interaction of microplastic and heavy metal in bioretention cell: Contributions of water-soil-plant system

The effectiveness of bioretention cells for heavy metals (HMs) and microplastics (MPs) removal from stormwater runoff has been demonstrated. Knowledge of the mechanisms that dictate the interactions between MPs and HMs would be helpful in pollution control. In this study, the performances of different water-soil-plant bioretention cells for HMs removal through the interception of polyethylene MPs (PE-MPs) were investigated. The results showed that PE-MPs bound to HMs and preferentially tended to bind to Pb (32%–44%) in the complex HMs (Cu, Zn, Cd, and Pb). This could be the reason that the concentration of Pb significantly increased in the effluent under low-intensity simulated rainfall events over a long duration. The accumulation of 1.49 g/kg PE-MPs caused a significant soil pH value decrease and a notable soil zeta potential increase in the bioretention cell, while the low sand/silt ratio media buffered this process. The retention of PE-MPs increased 138.5% in the 0–10 cm soil surface layer when the sand/silt ratio reduced from 2:1 to 1:1 and planted with Canna indica. Meanwhile, PE-MPs amplified the instability of Zn removal in bioretention cells under low-intensity rainfall events in long-duration, high silt percentage substrate and vegetation coverage. The study would contribute to developing a long-term management program for PE-MPs and HMs trapped in bioretention cells to reduce the risk of pollution transport.

Screen-Assisted Self-Spreading of TiO2 Precursor Solution on FTO Substrates for High-Quality Electron Transport Layers in Perovskite Solar Cells.

The electron transport layer (ETL) plays a critical role in efficient and stable perovskite solar cells (PSCs). The current effective method for the large-scale preparation of metal oxide ETLs is mainly based on expensive sputtering processes. Here, a screen-assisted self-spreading method is proposed as a novel approach to prepare uniformly thin and conformal TiO2 films on a rough fluorine-doped tin oxide (FTO) substrate as an ETL in planar PSCs. The TiO2 ETL deposited by this method exhibited good coverage and homogeneity on the rough FTO substrate, thereby minimizing interfacial recombination. The photovoltaic performance of the PSCs fabricated by this method is superior to that of the cells fabricated by spin coating, especially in terms of the fill factor. The performance enhancement can be attributed to the complete coverage of the FTO substrate by the conformal TiO2 film, confirming the effectiveness and reliability of the proposed method for the preparation of the TiO2 ETL. The advantages of this method lie in its scalability to prepare oxide films with a large area, eliminating the requirement of complex equipment, such as spinners, sputters, or physical vapor deposition equipment.

Binding energies of CD4 and fragment species to Pt(111): Implications for measurements of anion electron stimulated desorption.

We consider the electron stimulated desorption, via dissociative electron attachment, of anionic species from thin condensed CD4 films deposited on a Pt substrate and compare experimentally observed desorption yields with density functional theory calculations of the binding energies of various anionic and neutral moieties to Pt(111). Certain species (which can be considered chemisorbed) exhibit very high binding energies and large charge transfer with the substrate. Other "physisorbed" species have much lower binding energies. Species that chemisorb have lower desorption yields than those that physisorb, especially at 1-2 monolayer coverage of the Pt substrate. The binding energy of D- to Pt is the weakest, and experimentally, the desorption yield is the highest regardless of the thickness of CD4. The calculations show that the formation and desorption of anionic species at a distance of 16Å from the substrate, which is equivalent to the thickness of CD4 films of four monolayers, are not influenced by the short-range interactions between the substrate and the molecule and DEA products.

Tribological manufacturing of ZDDP tribofilms functionalised by graphene nanoplatelets

Abstract 3D Tribo-Nanoprinting (3D TNP), which uses a highly controllable tribological contact to deposit tribofilms, has been proposed as a manufacturing method for nanoscale structures. Inspired by this, we show for the first time, as a proof of concept, the ability to electrically functionalise tribofilms for potential use in the manufacture of structures with nanoscale thickness. Zinc dialkyldithiophosphate (ZDDP) tribofilms have been generated to include varying concentrations of graphene nanoplatelets (GNPs) resulting in them becoming electrically conductive when tested using conductive atomic force microscopy. In its highest GNP concentration, approximately 55% of the surface of the tribofilm was able to sustain current up to a threshold of 245 pA. The higher graphene content led to a suppression in film formation and decreased substrate coverage. Transmission electron microscopy revealed a dual-layered tribofilm with a carbon-rich layer above a pure layer of ZDDP tribofilm. Within the carbon-rich layer, the GNPs formed into scrolls which created an internal network through which current could flow, being limited by the insulating pure ZDDP layer at the film-substrate interface, and the presence of surface graphene sheets. A modified lateral force microscopy procedure supported the presence of surface graphene sheets. Despite limited deposition precision in terms of homogeneity and distribution of the tribofilms, this work provides a step towards the use of 3D TNP for the manufacture of electronic structures on the nanoscale by proving that tribofilms can be functionalised by the addition of particle additives.

Reversibly photochromic wood constructed by electric field-assisted self-assembled chitosan and tungsten trioxide coatings

ABSTRACT The photochromic properties are highly desirable for advanced wood applications, but they have not been extensively studied. To incorporate photochromic capabilities into wood materials, composite coatings were developed on the wood surface using an electric field-assisted layer-by-layer (LBL) self-assembly technique. The composite coatings consist of cationic chitosan and anionic tungsten trioxide (WO3) nanoparticles. By applying a direct current voltage during the deposition process, a well-organized distribution of WO3 nanoparticles was achieved, resulting in a uniform coverage of the wood substrate. This assembly process facilitated the creation of structured photochromic coatings with minimal nanoparticle fillers, a straightforward and rapid procedure, and potential for large-scale production. Lab colorimetric results demonstrated that the wooden substrate changed color from its natural state to blue when exposed to UV light. UV-vis spectroscopy further confirmed the efficient absorption of WO3 and photochromic properties of the modified wood.

Comparing rapid assessment methodologies in response to widespread epibiosis by Haliclona sp. (Porifera) on coral reef pinnacles in the Gulf of Thailand

Increasing documentation of coral-competing sponges have been made across the Indo-Pacific in recent years, utilising a variety of in-situ survey methods to quantify and classify the competitive capacity of these sponges. Estimating the abundance and comparative abundances of sponges in marine environments is made challenging due to the number of variables that can be assessed and the cost/benefit analysis of differing survey methods that may be used. Regular monitoring surveys at two adjacent submerged pinnacle sites in the Gulf of Thailand revealed colonisation and rapid proliferation of a previously undocumented coral-competing sponge at one pinnacle but not the other. To investigate the influence of survey methodology on the abundance and substrate specificity of the sponge, tentatively identified as Haliclona sp., we conducted point-intercept (PIT) and quadrat surveys along transect lines, alongside roving diver assessments. Qualitative assessments unsurprisingly found roving-diver surveys as documenting the greatest diversity of Anthozoa colonised by the sponge, with quadrat surveys generally classifying a similar or greater diversity colonised than PIT surveys. Quantitative analyses however revealed that, despite broadly similar substrate compositions, PIT surveys tended to find higher substrate coverage of certain biotic substrates than quadrat surveys. We discuss the merits and flaws of different survey methodologies, and possible applications of each, in the context of our findings.

ISTransbase: an online database for inhibitor and substrate of drug transporters

Abstract Drug transporters, integral membrane proteins found throughout the human body, play critical roles in physiological and biochemical processes through interactions with ligands, such as substrates and inhibitors. The extensive and disparate data on drug transporters complicate understanding their complex relationships with ligands. To address this challenge, it is essential to gather and summarize information on drug transporters, inhibitors and substrates, and simultaneously develop a comprehensive and user-friendly database. Current online resources often provide fragmented information and have limited coverage of drug transporter substrates and inhibitors, highlighting the need for a specialized, comprehensive and openly accessible database. ISTransbase addresses this gap by amassing a substantial amount of data from literature, government documents and open databases. It includes 16 528 inhibitors and 4465 substrates of 163 drug transporters from 18 different species, resulting in a total of 93 841 inhibitor records and 51 053 substrate records. ISTransbase provides detailed insights into drug transporters and their inhibitors/substrates, encompassing transporter and molecule structure, transporter function and distribution, as well as experimental methods and results from transport or inhibition experiments. Furthermore, ISTransbase offers three search strategies that allow users to retrieve drugs and transporters based on multiple selectable constraints, as well as perform checks for drug–drug interactions. Users can also browse and download data. In summary, ISTransbase (https://istransbase.scbdd.com/) serves as a valuable resource for accurately and efficiently accessing information on drug transporter inhibitors and substrates, aiding researchers in exploring drug transporter mechanisms and assisting clinicians in mitigating adverse drug reactions Database URL: https://istransbase.scbdd.com/

Synthesis of Silver Nanostructures on Different Supports: From Nanoparticle Decoration to a Complete Shell Growth

AbstractIn this work, we investigate a complete strategy to obtain supported silver nanostructures (AgNSs) which can be used for different applications such as catalysis, optoelectronics, and biomedical devices. Given the poor wetting of silver on many support materials, the anchorage of silver nanoparticles (AgNPs) to the substrate (decoration) is achieved by employing an oxide precipitation‐decomposition method. This protocol is optimized to obtain rapid and homogeneous decoration of AgNPs on different substrates such as silica, titania, and hydroxyapatite with a negligible production of free‐standing silver nanoparticles. Going a step further, we have also studied the growth of AgNPs attached to silica spheres (SiO2NPs) using a seed‐mediated growth strategy. The interplay of different processes like growth, corrosion, coalescence, and sintering determines the morphological features of the grown nanoparticles. Therefore, the substrate coverage and nanoparticle morphology can be qualitatively modified by varying the composition of the growth bath. The observed growth is consistent with a radial growth mechanism which, in most experimental conditions, allows for the production of anisotropic AgNSs onto silica surface. In addition, if the corrosion effects are minimized, the coalescence process of neighboring particles can lead to high surface coverages.

Effect of the Growth Conditions on Organic Crystals with Rare Earth Ions and 1,10-Phenanthroline.

Using a simple solution growth technique, we grow crystals with phenanthroline as a ligand and various rare earth ions: thulium (Tm), ytterbium (Yb), gadolinium (Gd), lanthanum (La), neodymium (Nd), europium (Eu), and erbium (Er). We then selected the composition that forms thin plates with well-defined shapes, Er(NO3)Phen2, and explored the effects of various conditions on crystal formation and growth, including temperature regime, light illumination, and substrates where the crystals are formed and grown. The composition and local environment strongly affect the size and shape of microcrystals and substrate coverage. The use of gold substrates significantly enhances the crystal growing process. Elevated temperatures negatively affect the crystal growth.

Full utilization of poplar sawdust with chemical-mechanical pretreatment for coproduction of xylooligosaccharides, fermentable sugars and porous carbon materials

In recent decades, one of the major challenges of biorefinery is the full utilization of lignocellulosic components for coproduction of value-added materials. In this context, we proposed an integrated process of acetic acid (AC) pretreatment, Papir Forsknings Institutet (PFI) refining and enzymatic hydrolysis to coproduce xylooligosaccharides, fermentable sugars and lignin-based porous carbon materials. Results showed AC pretreatment (170 ºC, 60 min, 5 w/v % acetic acid and 5% 2-naphthol addition based on dry mass of biomass) resulted in maximum xylooligosaccharids (XOS) yield of 51.08%. The integrated process of AC pretreatment assisted by 2-naphthol-7-sulfonate addition and PFI post-refining led to cellulose hydrolysis yield of 98.20% and lignin-based porous carbon materials with methylene blue adsorption capacity of up to 749.17 mg/g. Moreover, it was found lignin repolymerization inhibitors (i.e. 2-naphthol, 2-naphthol-7-sulfonate) in acid pretreatment helped increase the specific surface area of substrate and decrease surface lignin coverage, which enhanced cellulose accessibility to cellulase enzymes. Moreover, they enhanced lignin detaching during enzymatic hydrolysis, which reduced cellulase aggregation and promoted the ease of cellulose hydrolysis. Results demonstrated an efficient pretreatment strategy to maximize coproduction of xylooligosaccharids, fermentable sugars and lignin materials from lignocellulosic biomass for full utilization.

On-Demand Bioactivation of Inert Materials With Plasma-Polymerized Nanoparticles.

Conventional gas plasma treatments are crucial for functionalizing materials in biomedical applications, but have limitations hindering their broader use. These methods require exposure to reactive media under vacuum conditions, rendering them unsuitable for substrates that demand aqueous environments, such as proteins and hydrogels. In addition, complex geometries are difficult to treat, necessitating extensive customization for each material and shape. To address these constraints, an innovative approach employing plasma polymer nanoparticles (PPN) as a versatile functionalization tool is proposed. PPN share similarities with traditional plasma polymer coatings (PPC) but offer unique advantages: compatibility with aqueous systems, the ability to modify complex geometries, and availability as off-the-shelf products. Robust immobilization of PPN on various substrates, including synthetic polymers, proteins, and complex hydrogel structures is demonstrated in this study. This results in substantial improvements in surface hydrophilicity. Materials functionalization with arginylglycylaspartic acid (RGD)-loaded PPN significantly enhances cell attachment, spreading, and substrate coverage on inert scaffolds compared to passive RGD coatings. Improved adhesion to complex geometries and subsequent differentiation following growth factor exposure is also demonstrated. This research introduces a novel substrate functionalization approach that mimics the outcomes of plasma coating technology but vastly expands its applicability, promising advancements in biomedical materials and devices.

Assess the level of damage to the coral reef ecosystem based on substrate coverage on Bira Island, Kepulauan Seribu, Indonesia

Abstract. Komala R, Noer MI, Miarsyah M, Widyartini DS, Handayani. 2024. Assess the level of damage to the coral reef ecosystem based on substrate coverage on Bira Island, Kepulauan Seribu, Indonesia. Biodiversitas 25: 971-977. Coral reefs are coastal ecosystems that have an important ecological and economic role. Environmental pressures cause damage to ecosystems and decrease coral biodiversity. This study aims to analyze the level of damage to coral reef ecosystems based on substrate cover and obtain the latest information on coral reef ecosystem resources. The study employs a descriptive method with a survey design, utilizing Underwater Photo Transect (UPT) sampling at various depths along the coastline. The data is analyzed using Coral Point Count with Excel extension (CPCe) for substrate cover percentage and the Shannon-Wienner index for coral diversity. The findings reveal nine categories of basic substrate cover, with living hard corals constituting 32.51%, indicating a fairly damaged state. Coral resources are identified across 53 genera and 15 families, exhibiting medium diversity across stations and depths. The study highlights the need to monitor environmental threats that could further damage coral reefs and decrease diversity. The coral reef ecosystem in Bira Island is in a relatively damaged condition, with a decline in coral biodiversity, indicating an imbalance in the ecosystem. Several recommended steps include implementing coral restoration programs, monitoring coral growth, establishing critical coral habitat protection zones, and conducting conservation efforts.

Influence of Flexible and Textile Substrates on Frequency-Selective Surfaces (FSS).

Frequency-selective surfaces (FSS) are two-dimensional geometric structures made of conductive materials that selectively transmit or reflect electromagnetic waves. In this paper, flexible FSS made on textile and film substrates is presented and compared to show the effect of the texture associated with the type of substrate on the shielding properties. Three geometries of patterns of squares in the border, inversion of squares in the border, and circles with a border were used, and the patterns were made by the silver paste screen printing technique. Microscopic analysis (SEM and optical) was performed to determine the degree of substrate coverage and the actual geometry of the pattern. The resistance per square of the obtained patterns was about 50 mΩ/□. The shielding properties of FSS were simulated in Comsol Multiphysics 6.2 software and then measured by the antenna method. Selective textile filters were obtained, depending on the pattern used, with one or two modals with a transmission attenuation of about 15 dB. The paper analyzes the effect of the substrate and the screen printing technique used on the shielding properties of the flexible FSS.

Ecological ramifications of marine debris in mangrove ecosystems: Estimation of substrate coverage and physical effects of marine debris on mangrove ecosystem in Negombo Lagoon, Sri Lanka

The adverse environmental impacts on mangrove ecosystems due to anthropogenic marine debris contamination have attracted public attention not only in Sri Lanka but worldwide. Therefore, quantification of marine debris in sensitive ecosystems like mangroves is critical to assess the impacts on ecosystem vitality and services. We conducted this study to assess the abundance and density of marine debris in Negombo lagoon, Western Province, Sri Lanka. We selected two sites (n = 2) using the purposive sampling technique. Marine debris cover and concentration were calculated to explore the extent of pollution from marine debris. The findings revealed that 9.83 ± 1.05 % of the substrate of the mangrove ecosystem is covered by debris. Nine types of marine debris were recorded, and a higher abundance belonged to single-use plastic items. A significantly higher debris cover was found in Kadolkele (18.80 ± 1.74 %, n = 120) than in Molekadolwetiya (0.85 ± 0.03 %, n = 120) (One-way ANOVA, p < 0.05). The study indicated that the mangroves in lagoon are highly polluted with marine debris and act as “litter catchers.” Correlation coefficient analysis was used to find the impact of debris cover on physical damage to roots, seedlings, and undergrowth vegetation. Correlation analysis revealed that physical damage to seedlings and branches/barks have a positive correlation with debris cover. To conserve these valuable coastal habitats in Negombo lagoon, it is recommended to take remedial measures to reduce arriving debris loads and to remove the debris present in mangroves.

Enhanced Particle‐to‐Particle Interaction of Tin Oxide Electron Transporter Layer for Scalable Flexible Perovskite Solar Cells

Perovskite solar cells (PSCs) have exceeded 26% efficiency. One attribute of PSCs is their printability at relatively low temperatures, particularly advantageous for flexible solar cells. However, developing efficient, fully printable flexible PSCs on rough and soft plastic substrates remains a challenge. Herein, efficient flexible PSCs fabricated by only scalable methods in ambient conditions are reported. First, the source of the issue in fabricating flexible PSCs—the presence of charge carrier shorting pathways within electron‐transport layer (ETL) due to incomplete coverage of surface of flexible substrates—is identified. To address this challenge, the ETL deposition ink is modified with a phase‐transfer catalyst, often used in synthetic organic chemistry. Dynamic light scattering and nuclear‐magnetic resonance studies show that the catalyst enhances ETL particle‐to‐particle interaction in the ink, eventually leading to conformal coverage of rough flexible substrates. As a result, a power conversion efficiency of 17.6% for all‐scalable flexible n–i–p‐structured PSCs based on methylammonium lead iodide (MAPbI3) is demonstrated, among the highest reported to date for fully scalable flexible PSCs, all fabricated in ambient air.

X-ray photoelectron spectroscopy of high-throughput mechanically exfoliated van der Waals materials.

X-ray photoelectron spectroscopy (XPS) is a widely used and easy accessible characterisation technique for investigating the chemical composition of materials. However, investigating the composition of van der Waals (vdW) flakes by XPS is challenging due to the typical spot size of XPS setups compared to the dimensions of the flakes, which are usually one thousand times smaller than the spot size. In this work, we demonstrate the feasibility of quantitative elemental analysis of vdW materials by using high-throughput mechanical exfoliations, which favour the coverage of arbitrary substrates with flakes of areas of the order of the cm2 using minimal quantities of materials (about 10 μg). We have analysed the chemical composition of MoS2, graphite, WSe2 and FePS3. The high-resolution measurement of their main core levels through XPS demonstrates the absence of significant contamination during the transfer method. In the case of air-sensitive FePS3, the glove box fabrication and its degradation in air are discussed. Overall, this research opens the possibility of evaluating the purity of commercial or lab-synthesized flakes and paves the way towards a more systematic comparison between the composition of vdW materials produced and used among different laboratories.