Layout pattern analysis and coverage evaluation in computational lithography.

In advanced semiconductor technology nodes, the model accuracy of optical proximity correction (OPC) is the key for integrated circuit (IC) chip mask tape out, yield ramp up, and product time-to-market. An accurate model means a small prediction error for the full chip layout. As the full chip layout usually has large pattern variety, an optimal pattern set with good coverage is desired during the model calibration process. Currently, no existing solutions can provide the effective metrics to evaluate the coverage sufficiency of the selected pattern set before a real mask tape out, which may potentially cause higher re-tape out cost and product time-to-market delay due to the multiple rounds of model calibration. In this paper, we construct the metrics to evaluate the pattern coverage before any metrology data is obtained. The metrics are based on either the pattern's intrinsic, numerical feature representation, or its potential model simulation behavior. Experimental results show a positive correlation between these metrics and lithographic model accuracy. An incremental selection method is also proposed based on the pattern simulation error. It reduces up to 53% of the model's verification error range. These pattern coverage evaluation methods can improve the efficiency of OPC model building, and are, in turn, beneficial to the whole OPC recipe development process.

Selective Gas Permeation in Defect-Engineered Bilayer Graphene.

Defective graphene holds great potential to enable the permeation of gas molecules at high rates with high selectivity due to its one-atom thickness and resultant atomically small pores at the defect sites. However, precise control and tuning of the size and density of the defects remain challenging. In this work, we introduce atomic-scale defects into bilayer graphene via a decoupled strategy of defect nucleation using helium ion irradiation followed by defect expansion using hydrogen plasma treatment. The cotreated membranes exhibit high permeability and simultaneously high selectivity compared to those singly treated by ion irradiation or hydrogen plasma only. High permeation selectivity values for H2/N2 and H2/CH4 of 495 and 877, respectively, are achieved for optimally cotreated membranes. The method presented can also be scaled up to prepare large-area membranes for gas separation, e.g., for hydrogen purification and recovery from H2/CH4 and H2/N2 mixtures.

Valonea Tannin: Tyrosinase Inhibition Activity, Structural Elucidation and Insights into the Inhibition Mechanism.

Valonea tannin is a natural product readily extracted from acorn shells that has been suggested to have potential skin whitening properties. This study investigated the tyrosinase inhibition activity of extracted valonea tannin and the associated structure-function activity. Nuclear magnetic resonance spectroscopy and molecular weight analysis with gel permeation chromatography revealed that valonea tannin could be characterized as a hydrolysable tannin with galloyl, hexahydroxydiphenoyl and open formed-glucose moieties and an average molecular weight of 3042 ± 15 Da. Tyrosinase inhibition assays demonstrated that valonea tannin was 334 times more effective than gallic acid and 3.4 times more effective than tannic acid, which may relate to the larger molecular size. Kinetic studies of the inhibition reactions indicated that valonea tannin provided tyrosinase inhibition through mixed competitive-uncompetitive way. Stern-Volmer fitted fluorescence quenching analysis, isothermal titration calorimetry analysis and in silico molecule docking showed valonea tannin non-selectively bound to the surface of tyrosinase via hydrogen bonds and hydrophobic interactions. Inductively coupled plasma-optical emission spectroscopy and free radical scavenging assays indicated the valonea tannin had copper ion chelating and antioxidant ability, which may also contribute to inhibition activity. These results demonstrated the structure-function activity of valonea tannin as a highly effective natural tyrosinase inhibitor that may have commercial application in dermatological medicines or cosmetic products.

Dual-Additive Assisted Chemical Vapor Deposition for the Growth of Mn-Doped 2D MoS2 with Tunable Electronic Properties.

Doping of bulk silicon and III-V materials has paved the foundation of the current semiconductor industry. Controlled doping of 2D semiconductors, which can also be used to tune their bandgap and type of carrier thus changing their electronic, optical, and catalytic properties, remains challenging. Here the substitutional doping of nonlike element dopant (Mn) at the Mo sites of 2D MoS2 is reported to tune its electronic and catalytic properties. The key for the successful incorporation of Mn into the MoS2 lattice stems from the development of a new growth technology called dual-additive chemical vapor deposition. First, the addition of a MnO2 additive to the MoS2 growth process reshapes the morphology and increases lateral size of Mn-doped MoS2 . Second, a NaCl additive helps in promoting the substitutional doping and increases the concentration of Mn dopant to 1.7 at%. Because Mn has more valance electrons than Mo, its doping into MoS2 shifts the Fermi level toward the conduction band, resulting in improved electrical contact in field effect transistors. Mn doping also increases the hydrogen evolution activity of MoS2 electrocatalysts. This work provides a growth method for doping nonlike elements into 2D MoS2 and potentially many other 2D materials to modify their properties.

A High-Performance Food Package Material Prepared by the Synergistic Crosslinking of Gelatin with Polyphenol-Titanium Complexes.

This study aims to enhance gelatin film performance in the food industry by incorporating polyphenol-titanium complexes (PTCs) as crosslinkers. PTCs introduce multiple linkages with gelatin, including coordination and hydrogen bonds, resulting in synergistic crosslinking effects. This leads to an increased hydrodynamic volume, particle size, and thermal stability of the gelatin films. Compared to films crosslinked solely by polyphenols or titanium, PTC-crosslinked gelatin films exhibit significant improvements. They show enhanced mechanical properties with a tensile strength that is 1.7 to 2.6 times higher than neat gelatin films. Moreover, these films effectively shield UV light (from 82% to 99%), providing better protection for light-sensitive food ingredients and preserving lutein content (from 74.2% to 78.1%) under light exposure. The incorporation of PTCs also improves film hydrophobicity, as indicated by water contact angles ranging from 115.3° to 131.9° and a water solubility ranging from 31.5% to 33.6%. Additionally, PTC-enhanced films demonstrate a superior antioxidant ability, with a prolonged polyphenol release (up to 18 days in immersed water) and a higher free radical scavenging ability (from 22% to 25.2%). Overall, the improved characteristics of gelatin films enabled by PTCs enhance their performance, making them suitable for various food packaging applications.

Mechanism of the wine pomace tannin in hyperpigmentation inhibition: Impact on signaling pathways, cell proliferation, and tyrosinase activity.

After winemaking, tannins with high polymerization remain in the pomace. Utilizing these tannin fractions is a concern for the wine industry. While tannins show potential in treating hyperpigmentation, their mechanisms in vivo and at the cellular level are unclear. Herein, pomace tannin fractions (PTFs) were isolated post-winemaking. Nuclear magnetic resonance spectroscopy and mass spectrometry analysis showed PTFs were composed of (epi)catechin gallate and (epi)catechin as terminal and extensional units, with polymerization degrees of 10, 16, and 35. In vivo studies demonstrated that PTFs removed ∼76 % of skin melanin, comparable to hydroquinone. The inhibition by PTFs is due to: (1) Inhibition of the Wnt and melanogenesis pathways, downregulating key melanin synthesis proteins (TYR, TYRP1, TYRP2); (2) Inducing cell cycle arrest at the G1/S checkpoint, disrupting DNA, decreasing mitochondrial membrane potential and integrity, and slowing melanocyte proliferation; (3) Superior tyrosinase inhibitory activity by binding to tyrosinase, chelating copper ions, and demonstrating antioxidant properties. These findings suggest that PTFs inhibit melanin synthesis by the combination of the above mentioned ways, supporting the medical use of winemaking tannins.

Ecological experiential learning and tourists' pro-environmental behavior intentions: The mediating roles of awe and nature connection.

Due to the important role of tourists' behavior plays in marine protected areas (MPAs) and the increasing popularity of ecological experiential learning (EEL) journeys, this study aims to investigate whether and how EEL impact tourists' pro-environmental behavior (PEB) intentions through both emotional and cognitive pathways. To achieve this, four nature education trips with EEL content were organized, and PEB intentions of 228 tourists to MPAs were analyzed using surveys. The findings revealed that the low-effort PEB intentions of individuals under 24 years old were significantly lower compared to those of older tourists. Furthermore, EEL was positively associated with both low and high effort PEB intentions. The sense of awe acted as a mediator between EEL and low-effort PEB intentions, whereas nature connection was found to mediate the relationship between EEL and both low and high-effort PEB intentions. This study contributes to the growing body of research on the drivers of tourists PEB and provides a theoretical framework for promoting PEB intentions in MPAs.''''.

Hop Tannins as Multifunctional Tyrosinase Inhibitor: Structure Characterization, Inhibition Activity, and Mechanism.

The application of hops could be extended to obtain higher commercial values. Tannins from hops were assessed for their tyrosinase inhibition ability, and the associated mechanisms were explored. Nuclear magnetic resonance (NMR) and high-performance liquid chromatography-electrospray ionization-tandem mass spectrometry (HPLC-ESI-MS/MS) revealed that the hop tannins were characterized as condensed tannins with (epi)catechin and (epi)gallocatechin as subunits and an average polymerization degree of 10.32. Tyrosinase inhibition assay indicated that hop tannins had an IC50 = 76.52 ± 6.56 µM. Kinetic studies of the inhibition processes indicated the tannins provided inhibition through competitive-uncompetitive mixed reactions. In silico molecule docking showed that tannins were bound to the active site of tyrosinase via hydrogen and electrovalent bonds. Circular dichroism (CD) observed the structural variation in the tyrosinase after reacting with the tannins. Fluorescence quenching analysis and free radical scavenging assays indicated that the tannins had copper ion chelating and antioxidant activities, which may also contribute to inhibition. The intracellular inhibition assay revealed that the melanin was reduced by 34.50% in B16F10 cells. These results indicate that these tannins can be applied as whitening agents in the cosmetics industry.

TKF, a mexicanolide-type limonoid derivative, suppressed hepatic stellate cells activation and liver fibrosis through inhibition of the YAP/Notch3 pathway.

BACKGROUND: Liver fibrosis is a common scarring response and may ultimately lead to liver cancer, unfortunately, there is currently no effective antifibrotic drug approved for human use. Limonoids exhibit a broad spectrum of biological activities; however, the potential role of limonoids against fibrosis is largely unknown. PURPOSE: This study investigates the antifibrotic activities and potential mechanisms of TKF (3-tigloyl-khasenegasin F), a natural mexicanolide-type limonoid derivative. STUDY DESIGN/METHODS: Two well-established mouse models (CCl4 challenge and bile duct ligation) were used to assess anti-fibrotic effects of TKF in vivo. Human hepatic stellate cell (HSC) line LX-2 and mouse primary hepatic stellate cells (pHSCs) also served as in vitro liver fibrosis models. RESULT: TKF administration significantly attenuated hepatic histopathological injury and collagen accumulation and suppressed fibrogenesis-associated gene expression including Col1a1, Acta2, and Timp1. In LX-2 cells and mouse pHSCs, TKF dose-dependently suppressed HSC activation and the expression levels of fibrogenic markers. Mechanistic studies showed that TKF inhibited Notch3-Hes1 and YAP signalings in vivo and in vitro. Furthermore, YAP inhibition or knockdown downregulated the Notch3 expression; however, Notch3 inhibition or knockdown did not affect the level of YAP in activated HSC. We revealed that TKF inhibited Notch3-Hes1 activation and downregulated hepatic fibrogenic gene expression via inhibiting YAP. CONCLUSION: The therapeutic benefit of TKF against liver fibrosis results from inhibition of YAP and Notch3-Hes1 pathways, indicating that TKF may be a novel therapeutic candidate for liver fibrosis.

Anthocyanins from purple passion fruit (Passiflora edulia Sims) rind-An innovative source for nonbleachable pigment production.

Passion fruit rind is a waste product from the beverage industry that is rich in anthocyanins that can be potentially applied as a natural colorant. However, the inherent instability of anthocyanins causes rapid discoloration. In this study, the cyanidin-3-glucoside (C-3-G) in passion fruit rind was extracted using 50% ethanol and converted into nonbleachable pigments by reaction with Oolong tea extracts and acetaldehyde. Reactions over 70 days formed high concentrations of stable nonbleachable pigments (3.07-6.68 absorbance unit [A.U.], in total) such as pyranoanthocyanins, as well as oligomeric and polymeric pigments with ethyl-linked bridges. In C-3-G and acetaldehyde reaction, positive relations were found among acetaldehyde concentration, color density, and nonbleachable pigment concentrations. As for reactions with C-3-G and Oolong tea extract combined with acetaldehyde, greater color density and greater concentrations of nonbleachable pigments (10.80-12.34, 4.25-4.40 A.U., respectively) were formed compared with acetaldehyde alone. In addition, the antioxidant capabilities of the extracts were enhanced after reaction with Oolong tea extracts. The results of this study show a useful method to enhance the stability of anthocyanins from passion fruit rind and also provide greater economic value to this waste product. PRACTICAL APPLICATION: Ripened passion fruits contain a high concentration of anthocyanins in their rind. These anthocyanins can be optimally extracted by ultrasonic assisted solvent extraction to provide stable pigments by inducing acetaldehyde (a volatile compound often found in foods and beverages) into the anthocyanins. These stable pigments have a greater reddish hue in solution than the anthocyanin extracted from the rind and are more stable over a greater pH range. In addition, these stable pigments can be potentially used as colorant throughout the food and cosmetic industry to provide high economical values.

Laminar Metal Foam: A Soft and Highly Thermally Conductive Thermal Interface Material with a Reliable Joint for Semiconductor Packaging.

Future electronic packaging technology requires semiconductor chips having a larger size and higher power for advanced applications, e.g., new energy conversion systems, electric vehicles, and data center servers, yet traditional thermal interface materials (TIMs) with a high thermal conductivity are generally stiff materials with weak joints, which cause the accumulated thermal stress to concentrate at the chip corners, leading to cracking and popcorn problems. To address such a critical challenge, herein for the first time we report a low-cost and high-performance porous copper (Cu)-indium (In) laminar structure as TIM, which can provide a superior thermal conductivity (50 W m-1 K-1) comparable to indium, yet the Young's modulus (1.0 GPa) is an order of magnitude lower than indium, which is a state-of-the-art value. Additionally, the In-based intermetallic compound (IMC) joints enable more robust mechanical interconnection above the melting point of pure indium, providing better high-temperature performance. The discontinuous IMCs spread the global interfacial thermal stress into numerous isolated local areas, ensuring a reliable joint to resist thermal-mechanical fatigue. In the silicon-TIM-copper package testing vehicles with a large die size (1 × 1 square inch), this structure shows excellent thermal management ability and superior reliability, compared with classical indium and classic commercial silver pastes.

Author Correction: Chemical trends of deep levels in van der Waals semiconductors.

A Correction to this paper has been published: https://doi.org/10.1038/s41467-020-20151-x.

Chemical trends of deep levels in van der Waals semiconductors.

Properties of semiconductors are largely defined by crystal imperfections including native defects. Van der Waals (vdW) semiconductors, a newly emerged class of materials, are no exception: defects exist even in the purest materials and strongly affect their electrical, optical, magnetic, catalytic and sensing properties. However, unlike conventional semiconductors where energy levels of defects are well documented, they are experimentally unknown in even the best studied vdW semiconductors, impeding the understanding and utilization of these materials. Here, we directly evaluate deep levels and their chemical trends in the bandgap of MoS2, WS2 and their alloys by transient spectroscopic study. One of the deep levels is found to follow the conduction band minimum of each host, attributed to the native sulfur vacancy. A switchable, DX center - like deep level has also been identified, whose energy lines up instead on a fixed level across different hosts, explaining a persistent photoconductivity above 400 K.

Sandwiching h-BN Monolayer Films between Sulfonated Poly(ether ether ketone) and Nafion for Proton Exchange Membranes with Improved Ion Selectivity.

Two-dimensional (2D) hexagonal boron nitride (h-BN) has attracted great interest due to its excellent chemical and thermal stability, electrical insulating property, high proton conductivity, and good flexibility. Integration of 2D h-BN into commercial proton exchange membranes (PEMs) has the potential to improve ion selectivity while maintaining the proton conductivity of PEMs simultaneously, which has been a longstanding challenge in membrane separation technology. Until now, such attempts are only limited in mechanically exfoliated small area h-BN and in proof-of-concept devices, due to the difficulty of growing and transferring large area uniform h-BN monolayers. Here, we develop a space-confined chemical vapor deposition approach and achieve the growth of wafer-scale uniform h-BN monolayer films on Cu rolls. We further develop a Nafion functional layer assisted transfer method which effectively transfers as-grown h-BN monolayer films from the Cu roll to sulfonated poly(ether ether ketone) (SPEEK) membrane. The as-fabricated Nafion/h-BN/SPEEK sandwich structure is used as the membrane and compared with the pure SPEEK membrane for flow batteries. Results show that the sandwich membrane exhibits ion selectivity 3-fold greater than that of a pure SPEEK membrane ( i.e., 32.1 × 104 vs 9.7 × 104 S min cm-3). In addition, we fabricate vanadium flow batteries using the Nafion/h-BN/SPEEK sandwich membrane and find that the sandwich structure does not affect the proton transport but inhibits vanadium crossover at low current density (<120 mA cm-2) due to the selective blocking of vanadium ions by 2D h-BN. As a result, the sandwich membrane exhibits a significantly improved Coulombic efficiency and energy efficiency, ∼95% and ∼91%, respectively. Our results suggest that a functional layer/2D film/target substrate-based sandwich structure shows clear potential for future 2D material-based membranes in separation technologies.

Simultaneous Production and Functionalization of Boron Nitride Nanosheets by Sugar-Assisted Mechanochemical Exfoliation.

Due to their extraordinary properties, boron nitride nanosheets (BNNSs) have great promise for many applications. However, the difficulty of their efficient preparation and their poor dispersibility in liquids are the current factors that limit this. A simple yet efficient sugar-assisted mechanochemical exfoliation (SAMCE) method is developed here to simultaneously achieve their exfoliation and functionalization. This method has a high actual exfoliation yield of 87.3%, and the resultant BNNSs are covalently grafted with sugar (sucrose) molecules, and are well dispersed in both water and organic liquids. A new mechanical force-induced exfoliation and chemical grafting mechanism is proposed based on experimental and density functional theory investigations. Thanks to the good dispersibility of the nanosheets, flexible and transparent BNNS/poly(vinyl alcohol) (PVA) composite films with multifunctionality is fabricated. Compared to pure PVA films, the composite films have a remarkably improved tensile strength and thermal dissipation capability. Noteworthy, they are flame retardant and can effectively block light from the deep blue to the UV region. This SAMCE production method has proven to be highly efficient, green, low cost, and scalable, and is extended to the exfoliation and functionalization of other two-dimensional (2D) materials including MoS2 , WS2 , and graphite.

Tuning the Hydrogen Evolution Performance of Metallic 2D Tantalum Disulfide by Interfacial Engineering.

Metallic transition metal dichalcogenides, such as tantalum disulfide (TaS2), have recently emerged as promising electrocatalysts for the hydrogen evolution reaction. This work reports an effective strategy to further tune their performance through interfacial engineering, including lattice mismatch and electron injection between electrocatalysts and the underlying substrates. A unique two-zone chemical vapor deposition technique has been developed, and 2D TaS2 has been successfully grown on four different substrates, including glassy carbon, carbon fibers, Mo foil, and Au foil, providing excellent platforms to study catalyst-substrate interactions. Among them, TaS2 on Au foil offers the best performance with lowest overpotential and smallest charge transfer resistance, due to a suitable lattice mismatch and charge injection between TaS2 and Au, as revealed by theoretical calculations and experimental measurements. This work highlights the key roles the substrate plays in the catalysis and demonstrates the validity of interfacial engineering in catalyst design.