Atomic Spalling of a van der Waals Nanomembrane.

ConspectusThe vertical integration of van der Waals nanomembranes (vdW NMs), composed of two-dimensional (2D) layered materials and three-dimensional (3D) freestanding films with vdW surfaces, opens new avenues for exploring novel physical phenomena and offers a promising pathway for prototyping ultrathin, superior-performance electronic and optoelectronic applications with unique functionalities. Achieving the desired functionality through vdW integration necessitates the production of high-quality individual vdW NMs, which is a fundamental prerequisite. A profound understanding of the synthetic strategies for vdW NMs, along with their fundamental working principles, is crucial in guiding the experimental design toward 3D integrated heterostructures. The foremost synthetic challenges in fabricating high-quality vdW NMs are achieving exact control over thickness and ensuring surface planarity on the atomic scale. Despite the development of numerous chemical and mechanical approaches to tackle these issues, an all-encompassing solution has yet to be realized. To address these challenges, we have developed advanced spalling techniques, specifically known as atomic spalling or 2D material-based layer transfer, which emerge as a promising technology for achieving both atomically precise thickness-engineered and atomically smooth vdW NMs. These techniques involve engineering the interfacial fracture toughness and strain energy in the vdW system, allowing for precise control over the initiation and the propagation of cracks within the vdW material based on controlled spalling theory.In this Account, we summarize our recent advancements in the atomic precision spalling technique for the preparation of vdW NMs and their applications. We begin by introducing the fundamentals of advanced spalling techniques, which are based on spalling mode fracture in bilayer systems. Following this, we succinctly describe the preparation methods for source materials for vdW NMs, with a primary focus on chemical synthesis approaches. We then delve into the working principles underlying our recent contributions to advanced spalling techniques, providing insights into how this method attains unprecedented atomic-precision control compared to other fabrication methods with a particular emphasis on tuning the interface between the stressor and the vdW system. Subsequently, we highlight cutting-edge applications based on vdW heterostructures, which combine our spalled vdW NMs. Finally, we discuss the current challenges and future directions for advanced spalling techniques, underscoring their potential to be established as a robust methodology for the preparation of high-quality vdW NMs. Our advanced spalling strategy not only ensures the reliable production of vdW NMs with exceptional control over thickness and atomic-level flatness but also provides a robust theoretical framework essential for producing high-quality vdW NMs.

Perovskite nanocomposites: synthesis, properties, and applications from renewable energy to optoelectronics.

The oxide and halide perovskite materials with a ABX3 structure exhibit a number of excellent properties, including a high dielectric constant, electrochemical properties, a wide band gap, and a large absorption coefficient. These properties have led to a range of applications, including renewable energy and optoelectronics, where high-performance catalysts are needed. However, it is difficult for a single structure of perovskite alone to simultaneously fulfill the diverse needs of multiple applications, such as high performance and good stability at the same time. Consequently, perovskite nanocomposites have been developed to address the current limitations and enhance their functionality by combining perovskite with two or more materials to create complementary materials. This review paper categorizes perovskite nanocomposites according to their structural composition and outlines their synthesis methodologies, as well as their applications in various fields. These include fuel cells, electrochemical water splitting, CO2 mitigation, supercapacitors, and optoelectronic devices. Additionally, the review presents a summary of their research status, practical challenges, and future prospects in the fields of renewable energy and electronics.

Topological van der Waals Contact for Two-Dimensional Semiconductors.

The relentless miniaturization inherent in complementary metal-oxide semiconductor technology has created challenges at the interface of two-dimensional (2D) materials and metal electrodes. These challenges, predominantly stemming from metal-induced gap states (MIGS) and Schottky barrier heights (SBHs), critically impede device performance. This work introduces an innovative implementation of damage-free Sb2Te3 topological van der Waals (T-vdW) contacts, representing an ultimate contact electrode for 2D materials. We successfully fabricate p-type and n-type transistors using monolayer and multilayer WSe2, achieving ultralow SBH (∼24 meV) and contact resistance (∼0.71 kΩ·µm). Simulations highlight the role of topological surface states in Sb2Te3, which effectively mitigate the MIGS effect, thereby significantly elevating device efficiency. Our experimental insights revealed the semiohmic behavior of Sb2Te3 T-vdW contacts, with an exceptional photoresponsivity of 716 A/W and rapid response times of approximately 60 µs. The findings presented herein herald topological contacts as a superior alternative to traditional metal contacts, potentially revolutionizing the performance of miniaturized electronic and optoelectronic devices.

The processed C-terminus of AvrRps4 effector suppresses plant immunity via targeting multiple WRKYs.

Pathogens generate and secrete effector proteins to the host plant cells during pathogenesis to promote virulence and colonization. If the plant carries resistance (R) proteins that recognize pathogen effectors, effector-triggered immunity (ETI) is activated, resulting in a robust immune response and hypersensitive response (HR). The bipartite effector AvrRps4 from Pseudomonas syringae pv. pisi has been well studied in terms of avirulence function. In planta, AvrRps4 is processed into two parts. The C-terminal fragment of AvrRps4 (AvrRps4C) induces HR in turnip and is recognized by the paired resistance proteins AtRRS1/AtRPS4 in Arabidopsis. Here, we show that AvrRps4C targets a group of Arabidopsis WRKY, including WRKY46, WRKY53, WRKY54, and WRKY70, to induce its virulence function. Indeed, AvrRps4C suppresses the general binding and transcriptional activities of immune-positive regulator WRKY54 and WRKY54-mediated resistance. AvrRps4C interferes with WRKY54's binding activity to target gene SARD1 in vitro, suggesting WRKY54 is sequestered from the SARD1 promoter by AvrRps4C. Through the interaction of AvrRps4C with four WRKYs, AvrRps4 enhances the formation of homo-/heterotypic complexes of four WRKYs and sequesters them in the cytoplasm, thus inhibiting their function in plant immunity. Together, our results provide a detailed virulence mechanism of AvrRps4 through its C-terminus.

C-Type LECTIN receptor-like kinase 1 and ACTIN DEPOLYMERIZING FACTOR 3 are key components of plasmodesmata callose modulation.

Plasmodesmata (PDs) are intercellular organelles carrying multiple membranous nanochannels that allow the trafficking of cellular signalling molecules. The channel regulation of PDs occurs dynamically and is required in various developmental and physiological processes. It is well known that callose is a critical component in regulating PD permeability or symplasmic connectivity, but the understanding of the signalling pathways and mechanisms of its regulation is limited. Here, we used the reverse genetic approach to investigate the role of C-type lectin receptor-like kinase 1 (CLRLK1) in the aspect of PD callose-modulated symplasmic continuity. Here, we found that loss-of-function mutations in CLRLK1 resulted in excessive PD callose deposits and reduced symplasmic continuity, resulting in an accelerated gravitropic response. The protein interactome study also found that CLRLK1 interacted with actin depolymerizing factor 3 (ADF3) in vitro and in plants. Moreover, mutations in ADF3 result in elevated PD callose deposits and faster gravitropic response. Our results indicate that CLRLK1 and ADF3 negatively regulate PD callose accumulation, contributing to fine-tuning symplasmic opening apertures. Overall, our studies identified two key components involved in the deposits of PD callose and provided new insights into how symplasmic connectivity is maintained by the control of PD callose homoeostasis.

Nondestructive Single-Atom-Thick Crystallographic Scanner via Sticky-Note-Like van der Waals Assembling-Disassembling.

Crystallographic characteristics, including grain boundaries and crystallographic orientation of each grain, are crucial in defining the properties of two-dimensional materials (2DMs). To date, local microstructure analysis of 2DMs, which requires destructive and complex processes, is primarily used to identify unknown 2DM specimens, hindering the subsequent use of characterized samples. Here, a nondestructive large-area 2D crystallographic analytical method through sticky-note-like van der Waals (vdW) assembling-disassembling is presented. By the vdW assembling of veiled polycrystalline graphene (PCG) with a single-atom-thick single-crystalline graphene filter (SCG-filter), detailed crystallographic information of each grain in PCGs is visualized through a 2D Raman signal scan, which relies on the interlayer twist angle. The scanned PCGs are seamlessly separated from the SCG-filter using vdW disassembling, preserving their original condition. The remaining SCG-filter is then reused for additional crystallographic scans of other PCGs. It is believed that the methods can pave the way for advances in the crystallographic analysis of single-atom-thick materials, offering huge implications for the applications of 2DMs.

High energy density in artificial heterostructures through relaxation time modulation.

Electrostatic capacitors are foundational components of advanced electronics and high-power electrical systems owing to their ultrafast charging-discharging capability. Ferroelectric materials offer high maximum polarization, but high remnant polarization has hindered their effective deployment in energy storage applications. Previous methodologies have encountered problems because of the deteriorated crystallinity of the ferroelectric materials. We introduce an approach to control the relaxation time using two-dimensional (2D) materials while minimizing energy loss by using 2D/3D/2D heterostructures and preserving the crystallinity of ferroelectric 3D materials. Using this approach, we were able to achieve an energy density of 191.7 joules per cubic centimeter with an efficiency greater than 90%. This precise control over relaxation time holds promise for a wide array of applications and has the potential to accelerate the development of highly efficient energy storage systems.

Float-stacked graphene-PMMA laminate.

Semi-infinite single-atom-thick graphene is an ideal reinforcing material that can simultaneously improve the mechanical, electrical, and thermal properties of matrix. Here, we present a float-stacking strategy to accurately align the monolayer graphene reinforcement in polymer matrix. We float graphene-poly(methylmethacrylate) (PMMA) membrane (GPM) at the water-air interface, and wind-up layer-by-layer by roller. During the stacking process, the inherent water meniscus continuously induces web tension of the GPM, suppressing wrinkle and folding generation. Moreover, rolling-up and hot-rolling mill process above the glass transition temperature of PMMA induces conformal contact between each layer. This allows for pre-tension of the composite, maximizing its reinforcing efficiency. The number and spacing of the embedded graphene fillers are precisely controlled. Notably, we accurately align 100 layers of monolayer graphene in a PMMA matrix with the same intervals to achieve a specific strength of about 118.5 MPa g-1 cm3, which is higher than that of lightweight Al alloy, and a thermal conductivity of about 4.00 W m-1 K-1, which is increased by about 2,000 %, compared to the PMMA film.

Uniform Synthesis of Bilayer Hydrogen Substituted Graphdiyne for Flexible Piezoresistive Applications.

Graphdiyne (GDY) has garnered significant attention as a cutting-edge 2D material owing to its distinctive electronic, optoelectronic, and mechanical properties, including high mobility, direct bandgap, and remarkable flexibility. One of the key challenges hindering the implementation of this material in flexible applications is its large area and uniform synthesis. The facile growth of centimeter-scale bilayer hydrogen substituted graphdiyne (Bi-HsGDY) on germanium (Ge) substrate is achieved using a low-temperature chemical vapor deposition (CVD) method. This material's field effect transistors (FET) showcase a high carrier mobility of 52.6 cm2 V-1 s-1 and an exceptionally low contact resistance of 10 Ω µm. By transferring the as-grown Bi-HsGDY onto a flexible substrate, a long-distance piezoresistive strain sensor is demonstrated, which exhibits a remarkable gauge factor of 43.34 with a fast response time of ≈275 ms. As a proof of concept, communication by means of Morse code is implemented using a Bi-HsGDY strain sensor. It is believed that these results are anticipated to open new horizons in realizing Bi-HsGDY for innovative flexible device applications.

Protocol for preparing layer-engineered van der Waals materials through atomic spalling.

Here, we present a protocol for preparing layer-engineered van der Waals (vdW) materials via an atomic spalling process. We describe steps for fixing bulk crystals and introduce the appropriate stressor materials. We then detail a deposition technique for internal stress regulation of stressor film, followed by layer-engineered atomic-scale spalling to exfoliate vdW materials with a controlled number of layers from bulk crystals. Lastly, we outline a procedure for polymer/stressor film removal. For complete details on the use and execution of this protocol, please refer to Moon et al.1.

Engineering plant immune circuit: walking to the bright future with a novel toolbox.

Plant pathogens destroy crops and cause severe yield losses, leading to an insufficient food supply to sustain the human population. Apart from relying on natural plant immune systems to combat biological agents or waiting for the appropriate evolutionary steps to occur over time, researchers are currently seeking new breakthrough methods to boost disease resistance in plants through genetic engineering. Here, we summarize the past two decades of research in disease resistance engineering against an assortment of pathogens through modifying the plant immune components (internal and external) with several biotechnological techniques. We also discuss potential strategies and provide perspectives on engineering plant immune systems for enhanced pathogen resistance and plant fitness.

Conserved Opposite Functions in Plant Resistance to Biotrophic and Necrotrophic Pathogens of the Immune Regulator SRFR1.

Plant immunity is mediated in large part by specific interactions between a host resistance protein and a pathogen effector protein, named effector-triggered immunity (ETI). ETI needs to be tightly controlled both positively and negatively to enable normal plant growth because constitutively activated defense responses are detrimental to the host. In previous work, we reported that mutations in SUPPRESSOR OF rps4-RLD1 (SRFR1), identified in a suppressor screen, reactivated EDS1-dependent ETI to Pseudomonas syringae pv. tomato (Pto) DC3000. Besides, mutations in SRFR1 boosted defense responses to the generalist chewing insect Spodoptera exigua and the sugar beet cyst nematode Heterodera schachtii. Here, we show that mutations in SRFR1 enhance susceptibility to the fungal necrotrophs Fusarium oxysporum f. sp. lycopersici (FOL) and Botrytis cinerea in Arabidopsis. To translate knowledge obtained in AtSRFR1 research to crops, we generated SlSRFR1 alleles in tomato using a CRISPR/Cas9 system. Interestingly, slsrfr1 mutants increased expression of SA-pathway defense genes and enhanced resistance to Pto DC3000. In contrast, slsrfr1 mutants elevated susceptibility to FOL. Together, these data suggest that SRFR1 is functionally conserved in both Arabidopsis and tomato and functions antagonistically as a negative regulator to (hemi-) biotrophic pathogens and a positive regulator to necrotrophic pathogens.

Realization of Wafer-Scale 1T-MoS2 Film for Efficient Hydrogen Evolution Reaction.

The octahedral structure of 2D molybdenum disulfide (1T-MoS2 ) has attracted attention as a high-efficiency and low-cost electrocatalyst for hydrogen production. However, the large-scale synthesis of 1T-MoS2 films has not been realized because of higher formation energy compared to that of the trigonal prismatic phase (2H)-MoS2 . In this study, a uniform wafer-scale synthesis of the metastable 1T-MoS2 film is performed by sulfidation of the Mo metal layer using a plasma-enhanced chemical vapor deposition (PE-CVD) system. Thus, plasma-containing highly reactive ions and radicals of the sulfurization precursor enable the synthesis of 1T-MoS2 at 150 °C. Electrochemical analysis of 1T-MoS2 shows enhanced catalytic activity for the hydrogen evolution reaction (HER) compared to that of previously reported MoS2 electrocatalysts 1T-MoS2 does not transform into stable 2H-MoS2 even after 1000 cycles of HER. The proposed low-temperature synthesis approach may offer a promising solution for the facile production of various metastable-phase 2D materials.

Enhanced third-harmonic generation by manipulating the twist angle of bilayer graphene.

Twisted bilayer graphene (tBLG) has received substantial attention in various research fields due to its unconventional physical properties originating from Moiré superlattices. The electronic band structure in tBLG modified by interlayer interactions enables the emergence of low-energy van Hove singularities in the density of states, allowing the observation of intriguing features such as increased optical conductivity and photocurrent at visible or near-infrared wavelengths. Here, we show that the third-order optical nonlinearity can be considerably modified depending on the stacking angle in tBLG. The third-harmonic generation (THG) efficiency is found to significantly increase when the energy gap at the van Hove singularity matches the three-photon resonance of incident light. Further study on electrically tuneable optical nonlinearity reveals that the gate-controlled THG enhancement varies with the twist angle in tBLG, resulting in a THG enhanced up to 60 times compared to neutral monolayer graphene. Our results prove that the twist angle opens up a new way to control and increase the optical nonlinearity of tBLG, suggesting rotation-induced tuneable nonlinear optics in stacked two-dimensional material systems.

Layer-engineered large-area exfoliation of graphene.

The competition between quality and productivity has been a major issue for large-scale applications of two-dimensional materials (2DMs). Until now, the top-down mechanical cleavage method has guaranteed pure perfect 2DMs, but it has been considered a poor option in terms of manufacturing. Here, we present a layer-engineered exfoliation technique for graphene that not only allows us to obtain large-size graphene, up to a millimeter size, but also allows selective thickness control. A thin metal film evaporated on graphite induces tensile stress such that spalling occurs, resulting in exfoliation of graphene, where the number of exfoliated layers is adjusted by using different metal films. Detailed spectroscopy and electron transport measurement analysis greatly support our proposed spalling mechanism and fine quality of exfoliated graphene. Our layer-engineered exfoliation technique can pave the way for the development of a manufacturing-scale process for graphene and other 2DMs in electronics and optoelectronics.

One-Dimensional Poisson Calculation for Electrically Controlled Band Bending in GaAs/AlGaAs Heterostructure.

Here, we describe the band-bending situation for introducing electrons in an undoped GaAs and AlGaAs quantum well. Our calculation has shown that an externally applied electric field can modulate two-dimensional electron gas (2DEG) without standard modulation doping. The topic of electrically modulated 2DEG has only background impurities, no intentional dopants, so scattering or dephasing by background potential fluctuations should be much reduced. Using our calculation, it is straightforward to confine carriers (in the range of 1010~1011 cm-2), when the external electric field is more than threshold voltage, 4 V to the surface metal gate.

The Impact of Natural Selection on the Evolution and Function of Placentally Expressed Galectins.

Immunity genes have repeatedly experienced natural selection during mammalian evolution. Galectins are carbohydrate-binding proteins that regulate diverse immune responses, including maternal-fetal immune tolerance in placental pregnancy. Seven human galectins, four conserved across vertebrates and three specific to primates, are involved in placental development. To comprehensively study the molecular evolution of these galectins, both across mammals and within humans, we conducted a series of between- and within-species evolutionary analyses. By examining patterns of sequence evolution between species, we found that primate-specific galectins showed uniformly high substitution rates, whereas two of the four other galectins experienced accelerated evolution in primates. By examining human population genomic variation, we found that galectin genes and variants, including variants previously linked to immune diseases, showed signatures of recent positive selection in specific human populations. By examining one nonsynonymous variant in Galectin-8 previously associated with autoimmune diseases, we further discovered that it is tightly linked to three other nonsynonymous variants; surprisingly, the global frequency of this four-variant haplotype is ∼50%. To begin understanding the impact of this major haplotype on Galectin-8 protein structure, we modeled its 3D protein structure and found that it differed substantially from the reference protein structure. These results suggest that placentally expressed galectins experienced both ancient and more recent selection in a lineage- and population-specific manner. Furthermore, our discovery that the major Galectin-8 haplotype is structurally distinct from and more commonly found than the reference haplotype illustrates the significance of understanding the evolutionary processes that sculpted variants associated with human genetic disease.

Immune Regulation in Eutherian Pregnancy: Live Birth Coevolved with Novel Immune Genes and Gene Regulation.

Novel regulatory elements that enabled expression of pre-existing immune genes in reproductive tissues and novel immune genes with pregnancy-specific roles in eutherians have shaped the evolution of mammalian pregnancy by facilitating the emergence of novel mechanisms for immune regulation over its course. Trade-offs arising from conflicting fitness effects on reproduction and host defenses have further influenced the patterns of genetic variation of these genes. These three mechanisms (novel regulatory elements, novel immune genes, and trade-offs) played a pivotal role in refining the regulation of maternal immune systems during pregnancy in eutherians, likely facilitating the establishment of prolonged direct maternal-fetal contact in eutherians without causing immunological rejection of the genetically distinct fetus.

Signatures of Recent Positive Selection in Enhancers Across 41 Human Tissues.

Evolutionary changes in enhancers are widely associated with variation in human traits and diseases. However, studies comprehensively quantifying levels of selection on enhancers at multiple evolutionary periods during recent human evolution and how enhancer evolution varies across human tissues are lacking. To address these questions, we integrated a dataset of 41,561 transcribed enhancers active in 41 different human tissues (FANTOM Consortium) with whole genome sequences of 1,668 individuals from the African, Asian, and European populations (1000 Genomes Project). Our analyses based on four different metrics (Tajima's D, FST, H12, nSL) showed that ∼5.90% of enhancers showed evidence of recent positive selection and that genes associated with enhancers under very recent positive selection are enriched for diverse immune-related functions. The distributions of these metrics for brain and testis enhancers were often statistically significantly different and in the direction suggestive of less positive selection compared to those of other tissues; the same was true for brain and testis enhancers that are tissue-specific compared to those that are tissue-broad and for testis enhancers associated with tissue-enriched and non-tissue-enriched genes. These differences varied considerably across metrics and tissues and were generally in the form of changes in distributions' shapes rather than shifts in their values. Collectively, these results suggest that many human enhancers experienced recent positive selection throughout multiple time periods in human evolutionary history, that this selection occurred in a tissue-dependent and immune-related functional context, and that much like the evolution of their protein-coding gene counterparts, the evolution of brain and testis enhancers has been markedly different from that of enhancers in other tissues.

Graphene on Group-IV Elementary Semiconductors: The Direct Growth Approach and Its Applications.

Since the first development of large-area graphene synthesis by the chemical vapor deposition (CVD) method in 2009, CVD-graphene has been considered to be a key material in the future electronics, energy, and display industries, which require transparent, flexible, and stretchable characteristics. Although many graphene-based prototype applications have been demonstrated, several important issues must be addressed in order for them to be compatible with current complementary metal-oxide-semiconductor (CMOS)-based manufacturing processes. In particular, metal contamination and mechanical damage, caused by the metal catalyst for graphene growth, are known to cause severe and irreversible deterioration in the performance of devices. The most effective way to solve the problems is to grow the graphene directly on the semiconductor substrate. Herein, recent advances in the direct growth of graphene on group-IV semiconductors are reviewed, focusing mainly on the growth mechanism and initial growth behavior when graphene is synthesized on Si and Ge. Furthermore, recent progress in the device applications of graphene with Si and Ge are presented. Finally, perspectives for future research in graphene with a semiconductor are discussed.