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At least 91 records · Page 5

Numerical electromagnetic frequency domain analysis with discrete exterior calculus

In this paper, we perform a numerical analysis in frequency domain for various electromagnetic problems based on discrete exterior calculus (DEC) with an arbitrary 2-D triangular or 3-D tetrahedral mesh. We formulate the governing equations in terms of DEC for 3-D and 2-D inhomogeneous structures, and also show that the charge continuity relation is naturally satisfied. Then we introduce a general construction for signed dual volume to incorporate material information and take into account the case when circumcenters fall outside triangles or tetrahedrons, which may lead to negative dual volume without Delaunay triangulation. Then we examine the boundary terms induced by the dual mesh and provide a systematical treatment of various boundary conditions, including perfect magnetic conductor (PMC), perfect electric conductor (PEC), Dirichlet, periodic, and absorbing boundary conditions (ABC) within this method. An excellent agreement is achieved through the numerical calculation of several problems, including homogeneous waveguides, microstructured fibers, photonic crystals, scattering by a 2-D PEC, and resonant cavities. - Highlights: • The formulation of 2D and 3D electromagnetic equations with DEC are presented. • Characteristic Hodge stars are constructed without well-centered triangulation or Delaunay triangulation. • Systematical treatment of various boundary conditions, including PMC, PEC, periodic, and absorbing boundary conditions. • Switching between E to H field can change PEC from essential boundary condition to natural boundary condition. • Quality factor of an open dielectric sphere is considered.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

All-vanadium photoelectrochemical storage cells using dye sensitized geometry-enhanced TiO{sub 2} nanobelts

Highlights: • Dye-sensitized photoelectrode using nanostructured anatase TiO{sub 2} nanobelts was studied in photoelectrochemical storage cells. • An intricate balance between a series of charge-transfer processes related to the dye sensitizer, redox species, and photoelectrode was discovered. • Under AM1.5 illumination rapid charge transfer in the 1D nanobelts enhances photocurrent. • Large specific surface area of the photoelectrode dominates the performance under visible light. - Abstract: Photoelectrochemical (PEC) devices, which use solar energy to drive charge transfer, have been considered as a low cost and effective approach to harvest energy from the sun. Dye sensitization designs are promising alternative to traditional semiconductor-based cells, as they can absorb a wide spectrum of light and provide free energy for PEC reactions. However, an intricate balance exists between a number of series charge-transfer processes related to the dye sensitizer, redox species, and photoelectrode. Here, we study a dye-sensitized photoelectrode using nanostructured anatase TiO{sub 2} nanobelts (TNBs) in the newly developed all-vanadium PEC storage cell (all-V PESC) to understand the performance dominating factor as well as to enhance photoexcitation and charge transfer, thus the solar energy storage efficiency. Preliminary results show enhanced photocurrent and reduced charge transfer resistance under AM1.5 illumination upon dye sensitization. Under visible light, however, large specific surface area of the photoelectrode seems to dominate the PEC performance.

36 MATERIALS SCIENCE↗

Employing overlayers to improve the performance of Cu 2 BaSnS 4 thin film based photoelectrochemical water reduction devices

Earth-abundant copper-barium-thiostannate Cu 2 BaSnS 4 (CBTS)-based thin films have recently been reported to exhibit the optoelectronic and defect properties suitable as absorbers for photoelectrochemical (PEC) water splitting and the top cell of tandem photovoltaic solar cells. However, the photocurrents of CBTS-based PEC devices are still much lower than the theoretical value, partially due to ineffective charge collection at CBTS/water interface and instability of CBTS in electrolytes. Here, we report on overcoming these issues by employing overlayer engineering. We find that CdS/ZnO/TiO 2 overlayers can significant-ly improve the PEC performance, achieving saturated cathodic photocurrents up to 7.8 mA cm -2 at the potential of -0.10 V versus reversible hydrogen electrode (RHE) in a neutral electrolyte solution, which is much higher than the best bare CBTS film attaining a photocurrent of 4.8 mA cm -2 at the potential of -0.2 V versus RHE. Finally, our results suggest a viable approach for improving the performance of CBTS-based PEC cells.

08 HYDROGEN↗

Wide Band Gap CuGa(S,Se) 2 Thin Films on Transparent Conductive Fluorinated Tin Oxide Substrates as Photocathode Candidates for Tandem Water Splitting Devices

Theaim of this report was to explore the potential of CuGa(S,Se)2 thin films as wide-E G top cell absorbers for photoelectrochemical (PEC) water splitting. A synthesis was developed on fluorinated tin oxide (FTO) photocathodes by converting copper-rich co-evaporated CuGaSe2 into CuGa(S,Se)2 via a post-deposition annealing. We found it necessary to first anneal CuGaSe2 at low-temperature in sulfur then at high-temperature in nitrogen to preserve the transparency and conductivity of the FTO. Using this two-step synthesis, we fabricated a 1.72eV CuGa(S,Se) 2 photocathode with a saturation current density and photocurrent onset potential of 10mA/cm 2 and -0.20V vs. RHE, respectively. Yet we found that the PEC performance and sub-E G transmittance, worsened with increasing copper content. Using flatband potential measurements and the Gerischer model, we show that divergences in PEC performance of CuGa(S,Se) 2 photocathodes can be explained by differences in conduction band minimums and Fermi levels. We also explain that sub-E G transmittance is likely hampered by a defect band 100-400 meV below E C . Additional external quantum efficiency measurements of a high-efficiency 1.1 eV Cu(In,Ga)Se 2 photovoltaic driver, while shaded by the CuGa(S,Se) 2 photocathode, yielded a short-circuit current density of 4.14 mA/cm 2 revealing that CuGa(S,Se) 2 reflects promise as a top cell for PEC water splitting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single Nanoflake Photoelectrochemistry Reveals Intrananoflake Doping Heterogeneity That Explains Ensemble-Level Photoelectrochemical Behavior

Transition metal dichalcogenide (TMD) nanoflake thin films are attractive electrode materials for photoelectrochemical (PEC) solar energy conversion and sensing applications, but their photocurrent quantum yields are generally lower than those of bulk TMD electrodes. The poor PEC performance has been primarily attributed to enhanced charge carrier recombination at exposed defect and edge sites introduced by the exfoliation process. Here, a single nanoflake PEC approach reveals how an alternative effect, doping heterogeneity, limits ensemble-level PEC performance. Photocurrent mapping and local photocurrent–potential (i–E) measurements of MoS 2 nanoflakes exfoliated from naturally occurring bulk crystals revealed the presence of n- and p-type domains within the same nanoflake. Interestingly, the n- and p-type domains in the natural MoS 2 nanoflakes were equally efficient for iodide oxidation and tri-iodide reduction (IQE values exceed 80%). At the single domain-level, the natural MoS 2 nanoflakes were nearly as efficient as nanoflakes exfoliated from synthetic n-type MoS 2 crystals. Single domain-level i–E measurements explain why natural MoS 2 nanoflakes exhibit an n-type to p-type photocurrent switching effect in ensemble-level measurements: the n- and p-type diode currents from individual domains oppose each other upon illuminating the entire nanoflake, resulting in zero photocurrent at the switching potential. Furthermore, the doping heterogeneity effect is likely due to nonideal stoichiometry, where p-type domains are S-rich according to XPS measurements. Although this doping heterogeneity effect limits photoanode or photocathode performance, these findings open the possibility to synthesize efficient TMD nanoflake photocatalysts with well-defined lateral p- and n-type domains for enhanced charge separation.

14 SOLAR ENERGY↗

Temperature Effect on Photoelectrochemical Water Splitting: A Model Study Based on BiVO 4 Photoanodes

Photoelectrochemical (PEC) water splitting is typically studied at room temperature. In this work, the temperature effect on PEC water splitting is studied using crystalline BiVO4 thin film photoanode as a model system. Systematic temperature-dependent electrochemical study demonstrates that the PEC activity is boosted at elevated electrolyte temperatures and indicates that thermal energy plays a main role in improving charge carrier transport in the bulk of BiVO 4 . Irreversible surface reconstruction is observed after PEC reactions at elevated temperature in the presence of hole scavengers, with regularly spaced stripes emerging on BiVO4 grains. The surface-reconstructed photoanode exhibits up to 40% improvement in photocurrent densities and ~0.25 V shift of photocurrent onset to favorable direction. Detailed investigation shows the formation of amorphous layer without stoichiometric change at the reconstructed surface. Furthermore, this work provides insights of temperature effect on photoelectrode in solar water splitting and reveals the non-negligible effect of hole scavengers in photoelectrochemical measurement.

36 MATERIALS SCIENCE↗

Integrated Strategies for Overcoming Resolution Limits in Electron Beam Lithography of Chemically Amplified Resists

Electron beam lithography (EBL) of chemically amplified resists (CARs) faces fundamental challenges, including stochastic electron scattering and acid diffusion, that limit resolution and reproducibility. Using SU-8 as a model CAR, this study systematically investigated complementary strategies to address these challenges, combining multipass exposure, proximity effect correction (PEC) with midrange correction factors, base quencher incorporation, and post-exposure bake (PEB) suppression. Monte Carlo simulations and calibrated PEC modeling revealed that extending the point spread function to include a midrange scattering component significantly improved critical dimension (CD) control across varying pattern densities, correcting deviations that conventional two-term PEC failed to capture. Multipass exposure, particularly 4-pass writing with a 25% offset, redistributed the dose to average stochastic beam and scattering fluctuations, reducing line-width roughness by more than 50% and yielding more uniform nanoscale features. Photoacid confinement was investigated by adding urea as a base quencher, which successfully reduced acid diffusion but introduced substantial sensitivity penalties without improving ultimate resolution or Z-factor performance, underscoring the trade-offs of chemical versus physical confinement. Suppressing PEB most directly minimized acid diffusion, resulting in improved Z-factors and reproducible 30 nm half-pitch dense line/space patterns. Overall, these results demonstrated that PEC with midrange correction, multipass strategies, quencher additives, and PEB-free processing addresses different aspects of the EBL process window and that their integration provides a comprehensive framework for managing stochastic scattering, diffusion, and chemical amplification effects. This framework advances dense nanoscale patterning in CARs and establishes guiding principles for optimizing resist design and process strategies in high-resolution EBL and potentially other advanced lithographies, such as extreme ultraviolet (EUV) lithography.

36 MATERIALS SCIENCE↗

3D Printing of Polyelectrolyte Complex-Integrated Photocurable Hydrogel Resins

In this study, we developed a photocurable hydrogel resin incorporating a polyelectrolyte complex (PEC) for 3D printing. Acrylamide-based monomers were formulated with varying PEC contents (0–15 wt %) in an aqueous KBr medium to fabricate patterned porous hydrogel structures. The morphology of printed hydrogels was characterized by field-emission scanning electron microscopy and energy-dispersive X-ray spectroscopy. Notably, the PEC5 and PEC10 formulations exhibited optimal thermal stability and compressive properties, attributed to the homogeneous distribution of PEC domains within the hydrogel matrix. Furthermore, dye adsorption experiments demonstrated excellent removal efficiency, highlighting the potential of PEC-containing hydrogels for environmental remediation applications, particularly in the treatment of dye-contaminated wastewater.

Yang, Jinchul [University of Tennesse Knoxville]↗

Hydrogen from Sunlight and Water: A Side-by-Side Comparison between Photoelectrochemical and Solar Thermochemical Water-Splitting

Photoelectrochemical (PEC) and solar thermochemical (STCH) water-splitting represent two promising pathways for direct solar hydrogen generation. PEC water-splitting integrates multiple functional materials and utilizes energetic electrons and holes generated from sunlight to produce hydrogen and oxygen in two half-reactions, while STCH water-splitting couples a series of consecutive chemical reactions and uses absorbed heat from sunlight to generate hydrogen and oxygen in two full reactions. In this Focus Review, the basic operating principles, sunlight utilization, device architecture, reactor design, instantaneous and annually averaged solar-to-hydrogen (STH) conversion efficiency, and the operating conditions and constraints of both pathways are compared. A side-by-side comparison addresses some common sources of confusion and misinterpretation, especially in the evaluation of STH conversion efficiencies, and reveals distinct features and challenges in both PEC and STCH technologies. Furthermore, this Focus Review also addresses materials and device challenges in PEC and STCH for cost-competitive hydrogen generation.

08 HYDROGEN↗

Establishing the Role of Operating Potential and Mass Transfer in Multicarbon Product Generation for Photoelectrochemical CO 2 Reduction Cells Using a Cu Catalyst

There is increasing interest in the possibility of photoelectrochemical (PEC) reduction of CO 2 to C 2+ products; however, the criteria for maximizing PEC solar-to-C 2+ (STC 2+ ) rates are not well understood. We report here a continuum-scale model of PEC CO 2 reduction (CO 2 R) on Cu in 0.1 M CsHCO 3 and use it to optimize the design and operating conditions for generating C 2+ products. Furthermore, we demonstrate that the potential-dependent product distribution of CO 2 R on Cu requires operating near the potential that maximizes C 2+ generation rates ($V$ id ), unlike PEC water splitting, which desires operation at the maximum photocurrent density. Because of this requirement, the criterion for a high STC 2+ rate includes high-photocurrent semiconductors with photovoltages near $V$ id and low series resistance. The STC 2+ rate in these systems is enhanced by optimal CO 2 transport and exhibits low sensitivity to dirunal solar irradiance variations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Interparticle Interactions in Dilute Solutions of Polyelectrolyte Complex Micelles.

The application of dilute solutions of poly electrolyte complex (PEC) micelles for delivering therapeutic nucleic acids into disease sites has gained momentum. This Letter reports a detailed characterization of PEC micelles in dilute solutions including their internal structures and the determination of the interparticle interactions. The polymer concentration ranges from 0.1 to 0.5 wt %, a regime where micelle-micelle interactions are infrequent. We employ synchrotron small-angle X-ray scattering (SAXS) to simultaneously probe the morphology, internal structure, and radius of gyration (R-g) of the self-assemblies formed by charged diblock polyelectrolytes and homopolyelectrolytes. The emerging appearance of the structure factor in SAXS profiles with the increasing polymer concentration demonstrates the presence of the repulsive intermicellar correlations, which is further confirmed by the differences between the "reciprocal R-g" estimated by Guinier approximation and the "real space R-g" determined by pair distribution functions. We find that the soft corona chains tethered on the surface of phase-separated complex domains are compressed when micelles come close to the point where a hard-sphere interaction takes over. These findings contribute to the fundamental understanding of the structure and space-filling constraints in the complexation-driven self-assemblies and advance the rational design of cationic polymer-based nonviral gene delivery vectors.

Wu, Hao↗

Perovskite-driven solar C 2 hydrocarbon synthesis from CO 2

Photoelectrochemistry (PEC) presents a direct pathway to solar fuel synthesis by integrating light absorption and catalysis into compact electrodes. Yet, PEC hydrocarbon production remains elusive due to high catalytic overpotentials and insufficient semiconductor photovoltage. Here we demonstrate ethane and ethylene synthesis by interfacing lead halide perovskite photoabsorbers with suitable copper nanoflower electrocatalysts. The resulting perovskite photocathodes attain a 9.8% Faradaic yield towards C 2 hydrocarbon production at 0 V against the reversible hydrogen electrode. The catalyst and perovskite geometric surface areas strongly influence C 2 photocathode selectivity, which indicates a role of local current density in product distribution. The thermodynamic limitations of water oxidation are overcome by coupling the photocathodes to Si nanowire photoanodes for glycerol oxidation. These unassisted perovskite–silicon PEC devices attain partial C 2 hydrocarbon photocurrent densities of 155 µA cm -2 , 200-fold higher than conventional perovskite–BiVO 4 artificial leaves for water and CO 2 splitting. These insights establish perovskite semiconductors as a versatile platform towards PEC multicarbon synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The role of the domain size and titanium dopant in nanocrystalline hematite thin films for water photolysis

In this study, we develop a novel technique for preparing high quality Ti-doped hematite thin films for photoelectrochemical (PEC) water splitting, through sputtering deposition of metallic iron films from an iron target embedded with titanium (dopants) pellets, followed by a thermal oxidation step that turns the metal films into doped hematite. It is found that the hematite domain size can be tuned from ~10 nm to over 100 nm by adjusting the sputtering atmosphere from more oxidative to mostly inert. The better crystallinity at a larger domain size ensures excellent PEC water splitting performance, leading to record high photocurrent from pure planar hematite thin films on FTO substrates. Titanium doping further enhances the PEC performance of hematite photoanodes. The photocurrent is improved by 50%, with a titanium dopant concentration as low as 0.5 atom%. It is also found that the role of the titanium dopant in improving the PEC performance is not apparently related to the films’ electrical conductivity which had been widely believed, but is more likely due to the passivation of surface defects by the titanium dopants.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Progress on ternary oxide-based photoanodes for use in photoelectrochemical cells for solar water splitting

Solar water splitting using photoelectrochemical cells (PECs) has emerged as one of the most promising routes to produce hydrogen as a clean and renewable fuel source. Among various semiconductors that have been considered as photoelectrodes for use in PECs, oxide-based photoanodes are particularly attractive because of their stability in aqueous media in addition to inexpensive and facile processing compared to other types of semiconductors. However, they typically suffer from poor charge carrier separation and transport. In the past few years, there has been tremendous progress in developing ternary oxide-based photoelectrodes, specifically, photoanodes. The use of ternary oxides provides more opportunities to tune the composition and electronic structure of the photoelectrode compared to binary oxides, thus providing more freedom to tune the photoelectrochemical properties. In this article, we outline the important characteristics to analyze when evaluating photoanodes and review the major recent progress made on the development of ternary oxide-based photoanodes. For each system, we highlight the favorable and unfavorable features and summarize the strategies utilized to address the challenges associated with each material. Finally, by combining our analyses of all the photoanodes surveyed in this review, we provide possible future research directions for each compound and an outlook for constructing more efficient oxide-based PECs. Overall, this review will provide a critical overview of current ternary oxide-based photoanodes and will serve as a platform for the design of future oxide-based PECs.

25 ENERGY STORAGE↗

Unassisted solar water splitting with 9.8% efficiency and over 100 h stability based on Si solar cells and photoelectrodes catalyzed by bifunctional Ni–Mo/Ni

Designing a highly efficient and stable photoelectrochemical (PEC) tandem cell for unassisted solar water splitting is considered a promising approach for large-scale solar energy storage. To date, various tandem device configurations have been reported. However, the achievement of a solar-to-hydrogen conversion efficiency (η STH ) of 10% is still full of challenges, due to the incompatibility between the two photoelectrode materials. Here, we report a highly efficient and stable photovoltaic (PV)–PEC tandem device composed of a dual Si photoelectrode and two series-connected ordinary Si PV cells. The dual-photoelectrode device consists of an n + np + -Si photocathode and p + pn + -Si photoanode, which allow back illumination from the Si substrate, spatially and functionally decoupling the optical absorption and the catalytic activity. By further employing a Ni protective layer together with a bifunctional Ni–Mo catalyst for both the Si photocathode and photoanode, the PV–PEC tandem cell can perform spontaneous water splitting without any applied bias. A high η STH of 9.8% with a stability of over 100 h was achieved in alkaline solution under parallel AM 1.5G 1 sun illumination. Furthermore, this work essentially allows a modular independent optimization of each component which can enhance the efficiency and stability of the PV–PEC cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Harnessing emergent multiple scattering resonances in a photonic glass structure for photoelectrochemical energy conversion

Light trapping nanostructures are often necessary to improve carrier collection yields in semiconductor photoelectrodes with intrinsically poor electron transport. Photonic crystal templates can generate tailorable light trapping via periodic and precise nanostructure, though this is not a scalable strategy for photoelectrochemical (PEC) applications. It is therefore critical to identify alternative mechanisms for light trapping that tolerate disorder. Light trapping in disordered media is generated by the diffusive transport caused by multiple scattering. In some cases, multiple scattering can generate resonances that resemble those observed in photonic crystals. While resonant multiple scattering is a disorder tolerant light trapping mechanism, it is unclear if the effect is sufficiently adaptable, or even useful, for PEC applications. Here, we describe a photonic omission glass, a nanostructure that can controllably induce resonances in multiple scattering transport. We characterized the emergence of these resonances after coating a disordered SiO 2 colloidal structure with a layer of TiO 2 , which functions both as dielectric contrast and as a light absorbing semiconductor. We show in finite element simulations and spectroscopic characterization that the resonant multiple scattering effect improves light trapping near the interface between the structure and the bulk electrolyte. This effect, coupled with the increased electrochemically active surface area, results in a hierarchically structured TiO 2 photoanode with orders of magnitude higher photocurrents compared to an equivalent planar photoanode for PEC reactions such as alkaline water oxidation. We show that controlling this resonant multiple scattering effect can be advantageous for improving PEC energy conversion in disordered photoelectrodes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

ZnGa 2 Te 4 thin-film absorbers for photoelectrochemical CO 2 reduction

Photoelectrochemical (PEC) carbon dioxide reduction reaction (CO 2 RR) has been considered as a promising route to convert and store solar energy into chemical fuels. It is crucial to find suitable photoelectrode materials that are photo-catalytically active and exhibit excellent photochemical stability. One of the promising contenders is ZnTe with the ∼2.26 eV band gap and prolonged stability under CO 2 RR PEC conditions. Herein, a new telluride based thin-film ZnGa 2 Te 4 photocathode with lower band gap and stronger visible light absorption compared to ZnTe is synthesized and characterized using a combinatorial sputtering technique. A two-step annealing method with excess Te supply is implemented to synthesize nearly stoichiometric ZnGa 2 Te 4 absorber material with a zincblende-derived tetragonal crystal structure confirmed by synchrotron X-ray and electron diffraction. Theoretical calculations show that ZnGa 2 Te 4 has suitable direct bandgap (∼1.86 eV) and high absorption coefficient ∼10 5 cm −1 , in agreement with experimentally prepared films. Transient absorption spectroscopy reveals the biexponential decay dynamics, with time constants, τ 1 ∼ 0.04, and τ 2 ∼ 0.65 μs in microsecond time scales and provides the optical transition pathways for this semiconductor thin film. PEC measurements show that the ZnGa 2 Te 4 photocurrent densities are comparable to the widely investigated ZnTe photocathodes or even surpass it under simulated sunlight condition. ZnGa 2 Te 4 samples demonstrate promising photoelectrochemical stability, maintaining consistent performance under illumination. The inclusion of diaryliodonium additive substantially increases its CO 2 RR selectivity to ∼60%. These findings open a new avenue for the synthesis of telluride-based thin-film photocathodes for further exploration and will motivate future research to integrate this potential photocathode material into PEC devices.

36 MATERIALS SCIENCE↗

Photocatalytic and photoelectrochemical performance of Ta{sub 3}N{sub 5} microcolumn films fabricated using facile reactive sputtering

This paper presents the photocatalytic and photoelectrochemical (PEC) properties of Ta{sub 3}N{sub 5} microcolumn films. The highlights include (1) overcoming the fundamental barrier of standard reactive sputtering for fabricating microcolumns; (2) preventing unnecessary complexity from complicating facile sputtering; (3) an alternative but effective approach for fabricating Ta{sub 3}N{sub 5} without using caustic NH{sub 3} gases; (4) investigating morphology tuning for favorable photocatalysis and PEC reactions; and (5) elucidating the relationships of the structures, morphologies, and properties of Ta{sub 3}N{sub 5} microcolumns. High-resolution transmission electron microscopy and selective-area electron diffraction verified the polycrystallinity of Ta{sub 3}N{sub 5} microcolumns, of which the elemental compositions and stoichiometry were measured using electron-probe energy dispersive spectroscopy, Auger electron spectroscopy, and X-ray photoelectron spectroscopy. The corresponding band gap was determined to be approximately 2.1 eV. The sample exhibited a superior photodegradation capability; the photodegradation rate constant k was determined to be approximately 1.4 times higher than that of P25 under UV irradiation. A photocatalytic and PEC cycling test indicated the photodegradation reusability and photostability of the Ta{sub 3}N{sub 5} microcolumns. The incident photon-to-current efficiency performance reached 6%, suggesting that these microcolumns hold potential for application in PEC devices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗