Unusual Dzyaloshinskii-Moriya Interaction in Graphene/Fe3GeTe2 Van der Waals Heterostructure.

Dzyaloshinskii-Moriya interaction (DMI) is shown to induce a topologically protected chiral spin texture in magnetic/nonmagnetic heterostructures. In the context of van der Waals spintronic devices, graphene emerges as an excellent candidate material. However, due to its negligible spin-orbit interaction, inducing DMI to stabilize topological spins when coupled to 3d-ferromagnets remains challenging. Here, it is demonstrated that, despite these challenges, a sizeable Rashba-type spin splitting followed by significant DMI is induced in graphene/Fe3GeTe2. This is made possible due to an interfacial electric field driven by charge asymmetry together with the broken inversion symmetry of the heterostructure. These findings reveal that the enhanced DMI energy parameter, resulting from a large effective electron mass in Fe3GeTe2, remarkably contributes to stabilizing non-collinear spins below the Curie temperature, overcoming the magnetic anisotropy energy. These results are supported by the topological Hall effect, which coexists with the non-trivial breakdown of Fermi liquid behavior, confirming the interplay between spins and non-trivial topology. This work paves the way toward the design and control of interface-driven skyrmion-based devices.

Pulsed-Mode Metalorganic Vapor-Phase Epitaxy of GaN on Graphene-Coated c-Sapphire for Freestanding GaN Thin Films.

We report the growth of high-quality GaN epitaxial thin films on graphene-coated c-sapphire substrates using pulsed-mode metalorganic vapor-phase epitaxy, together with the fabrication of freestanding GaN films by simple mechanical exfoliation for transferable light-emitting diodes (LEDs). High-quality GaN films grown on the graphene-coated sapphire substrates were easily lifted off by using thermal release tape and transferred onto foreign substrates. Furthermore, we revealed that the pulsed operation of ammonia flow during GaN growth was a critical factor for the fabrication of high-quality freestanding GaN films. These films, exhibiting excellent single crystallinity, were utilized to fabricate transferable GaN LEDs by heteroepitaxially growing InxGa1-xN/GaN multiple quantum wells and a p-GaN layer on the GaN films, showing their potential application in advanced optoelectronic devices.

Wafer-Scale Epitaxial Growth of an Atomically Thin Single-Crystal Insulator as a Substrate of Two-Dimensional Material Field-Effect Transistors.

As the electron mobility of two-dimensional (2D) materials is dependent on an insulating substrate, the nonuniform surface charge and morphology of silicon dioxide (SiO2) layers degrade the electron mobility of 2D materials. Here, we demonstrate that an atomically thin single-crystal insulating layer of silicon oxynitride (SiON) can be grown epitaxially on a SiC wafer at a wafer scale and find that the electron mobility of graphene field-effect transistors on the SiON layer is 1.5 times higher than that of graphene field-effect transistors on typical SiO2 films. Microscale and nanoscale void defects caused by heterostructure growth were eliminated for the wafer-scale growth of the single-crystal SiON layer. The single-crystal SiON layer can be grown on a SiC wafer with a single thermal process. This simple fabrication process, compatible with commercial semiconductor fabrication processes, makes the layer an excellent replacement for the SiO2/Si wafer.

Algae development in rivers with artificially constructed weirs: Dominant influence of discharge over temperature.

Algal blooms contribute to water quality degradation, unpleasant odors, taste issues, and the presence of harmful substances in artificially constructed weirs. Mitigating these adverse effects through effective algal bloom management requires identifying the contributing factors and predicting algal concentrations. This study focused on the upstream region of the Seungchon Weir in Korea, which is characterized by elevated levels of total nitrogen and phosphorus due to a significant influx of water from a sewage treatment plant. We employed four distinct machine learning models to predict chlorophyll-a (Chl-a) concentrations and identified the influential variables linked to local algal bloom events. The gradient boosting model enabled an in-depth exploration of the intricate relationships between algal occurrence and water quality parameters, enabling accurate identification of the causal factors. The models identified the discharge flow rate (D-Flow) and water temperature as the primary determinants of Chl-a levels, with feature importance values of 0.236 and 0.212, respectively. Enhanced model precision was achieved by utilizing daily average D-Flow values, with model accuracy and significance of the D-Flow amplifying as the temporal span of daily averaging increased. Elevated Chl-a concentrations correlated with diminished D-Flow and temperature, highlighting the pivotal role of D-Flow in regulating Chl-a concentration. This trend can be attributed to the constrained discharge of the Seungchon Weir during winter. Calculating the requisite D-Flow to maintain a desirable Chl-a concentration of up to 20 mg/m3 across varying temperatures revealed an escalating demand for D-Flow with rising temperatures. Specific D-Flow ranges, corresponding to each season and temperature condition, were identified as particularly influential on Chl-a concentration. Thus, optimizing Chl-a reduction can be achieved by strategically increasing D-Flow within these specified ranges for each season and temperature variation. This study highlights the importance of maintaining sufficient D-Flow levels to mitigate algal proliferation within river systems featuring weirs.

Single-crystalline GaN microdisk arrays grown on graphene for flexible micro-LED application.

We report the growth of single-crystalline GaN microdisk arrays on graphene and their application in flexible light-emitting diodes (LEDs). Graphene layers were directly grown onc-sapphire substrates using chemical vapor deposition and employed as substrates for GaN growth. Position-controlled GaN microdisks were laterally overgrown on the graphene layers with a micro-patterned SiO2mask using metal-organic vapor-phase epitaxy. The as-grown GaN microdisks exhibited excellent single crystallinity with a uniform in-plane orientation. Furthermore, we fabricated flexible micro-LEDs by achieving heteroepitaxial growth ofn-GaN, InxGa1-xN/GaN multiple quantum wells, andp-GaN layers on graphene-coated sapphire substrates. The GaN micro-LED arrays were successfully transferred onto bendable substrates and displayed strong blue light emission under room illumination, demonstrating their potential for integration into flexible optoelectronic devices.

Value-added application of cattle manure bottom ash for phosphorus recovery from water and replenishment in soil.

This study addresses ways to circulate the flow of phosphorus (P) from water to soil to improve water quality and provide a sustainable supply of P into soil. Here, bottom ash (BA_CCM), the byproduct of the combustion of cattle manure, which is performed for obtaining energy, was used to remove P in wastewater. Next, the P-captured BA_CCM was used as P fertilizer for rice growth. BA_CCM was primarily composed of Ca (49.4%), C (24.0%), and P (9.9%), and the crystalline phases of Ca were calcium carbonate (CaCO3) and hydroxyapatite (Ca5(PO4)3OH). The mechanism of P removal by BA_CCM involves the formation of hydroxyapatite by reacting Ca2+ with PO43-. A reaction time of 3 h was required to achieve P adsorption to BA_CCM, and the maximum P adsorption capacity of BA_CCM was 45.46 mg/g. The increase in solution pH reduced P adsorption. However, at pH > 5, the P adsorption amount was maintained regardless of the pH increase. The presence of 10 mM SO42- and CO32- reduced P adsorption by 28.4% and 21.5%, respectively, and the impact of the presence of Cl- and NO3- was less than 10%. The feasibility of BA_CCM was tested using real wastewater, and 3.33 g/L of BA_CCM dose achieved a P removal ratio of 99.8% and a residual concentration of <0.02 mg/L. The toxicity unit of BA_CCM determined for Daphnia magna (D. magna) was 5.1; however, the BA_CCM after P adsorption (P-BA_CCM) did not show any toxicity to D. magna. BA_CCM after P adsorption was used as an alternative to commercial P fertilizer. Rice fertilized with a medium level of P-BA_CCM showed better agronomic values for most agronomic traits, except root length, than that seen with the commercial P fertilizer. This study suggests that BA_CCM can be used as a value-added product to address environmental issues.

Spin Dynamics Slowdown near the Antiferromagnetic Critical Point in Atomically Thin FePS3.

Two-dimensional (2D) magnetic materials have attracted much recent interest with unique properties emerging at the few-layer limit. Beyond the reported impacts on the static magnetic properties, the effects of reducing the dimensionality on the magnetization dynamics are also of fundamental interest and importance for 2D device development. In this report, we investigate the spin dynamics in atomically thin antiferromagnetic FePS3 of varying layer numbers using ultrafast pump-probe spectroscopy. Following the absorption of an optical pump pulse, the time evolution of the antiferromagnetic order parameter is probed by magnetic linear birefringence. We observe a strong divergence in the demagnetization time near the Néel temperature. The divergence can be characterized by a power-law dependence on the reduced temperature, with an exponent decreasing with sample thickness. We compare our results to expectations from critical slowing down and a two-temperature model involving spins and phonons and discuss the possible relevance of spin-substrate phonon interactions.

Contamination of typical phthalate acid esters in surface water and sediment of the Pearl River, South China: Occurrence, distribution, and health risk assessment.

The occurrence and distribution of six phthalate acid esters (PAEs) in surface water and sediment of the Pearl River were investigated, including Xijiang River (XR), Beijiang River (BR), Lingdingyang Estuary (LE), and Guangzhou River (GR) in South China. Six target PAEs were identified in surface water and sediment at almost all sites in the Pearl River, with di(2-ethyl-ethyl) phthalate (DEHP) and dibutyl phthalate (DBP) as dominant PAEs. Total 6 PAEs (ΣPAEs) in surface water and sediment ranged from 1,797.5 to 4,968.5 ng L-1 and 95.24 to 3,677.26 ng g-1 dw, respectively. In addition, the contamination levels of PAEs in the Pearl River are in the following order: XR > BR > GR > LE for surface water and BR > XR > GR for sediment. Local agricultural activities, industrial production, water confluence, and seawater intrusion are the probable sources of PAEs in the Pearl River. Based on correlation analysis, the possible collocation patterns of different PAEs were revealed. The risk assessment indicates that residual PAEs in the Pearl River pose a serious threat to the ecological environment. According to risk characterization of fish living in the Pearl River, the decreasing order of health risks was: GR > LE > XR > BR.

Synthesis of 2D semiconducting single crystalline Bi2S3 for high performance electronics.

2-Dimensional (2D) semiconducting materials are attractive candidates for future electronic device applications due to the tunable bandgap, transparency, flexibility, and downscaling to the atomic level in material size and thickness. However, 2D materials have critical issues regarding van der Waals contact, interface instability and power consumption. In particular, the development of semiconducting electronics based on 2D materials is significantly hindered by a low charge-carrier mobility. In order to improve the critical shortcoming, diverse efforts have been made in synthesis and device engineering. Here, we propose a synthesis method of single crystalline 2D Bi2S3 by chemical vapor deposition for high performance electronic device applications. The ion-gel gated field effect transistor with the as-grown Bi2S3 on the SiO2 substrate exhibits a high mobility of 100.4 cm2 V-1 S-1 and an on-off current ratio of 104 under a low gate voltage below 4 V at room temperature without chemical doping and surface engineering. The superior performance is attributed to the high crystal quality of Bi2S3 that shows low sulfur vacancies and atomic ratio close to the ideal value (2 : 3) under a rich sulfur growth process using H2S gas instead of sulfur powder. The synthesis method will provide a platform to realize high performance electronics and optoelectronics based on 2D semiconductors.

Asymmetric carrier transport and weak localization in few layer graphene grown directly on a dielectric substrate.

Temperature-dependent electrical and magneto-transport measurements have been performed on devices composed of few layer (4L) graphene grown directly on SiO2/Si substrates using the CVD method. An intrinsic energy band-gap of 4.6 meV in 4L graphene is observed, which primarily dictates the current transport at T <50 K. Unusual temperature dependent electron-hole conduction asymmetry is observed at T >50 K, which can be explained in the framework of the defect scattering of relativistic charge carriers. Magneto-transport measurements reveal a weak localization effect sustainable till T >200 K. The coexistence of phonon mediated carrier mobility and defect induced weak localization effects in measuring devices suggests low disorder and impurity scattering.

Exchange Bias Effect in Ferro-/Antiferromagnetic van der Waals Heterostructures.

The recent discovery of magnetic van der Waals (vdW) materials provides a platform to answer fundamental questions on the two-dimensional (2D) limit of magnetic phenomena and applications. An important question in magnetism is the ultimate limit of the antiferromagnetic layer thickness in ferromagnetic (FM)/antiferromagnetic (AFM) heterostructures to observe the exchange bias (EB) effect, of which origin has been subject to a long-standing debate. Here, we report that the EB effect is maintained down to the atomic bilayer of AFM in the FM (Fe3GeTe2)/AFM (CrPS4) vdW heterostructure, but it vanishes at the single-layer limit. Given that CrPS4 is of A-type AFM and, thus, the bilayer is the smallest unit to form an AFM, this result clearly demonstrates the 2D limit of EB; only one unit of AFM ordering is sufficient for a finite EB effect. Moreover, the semiconducting property of AFM CrPS4 allows us to electrically control the exchange bias, providing an energy-efficient knob for spintronic devices.

As(III) adsorption onto Fe-impregnated food waste biochar: experimental investigation, modeling, and optimization using response surface methodology.

Biochar derived from food waste was modified with Fe to enhance its adsorption capacity for As(III), which is the most toxic form of As. The synthesis of Fe-impregnated food waste biochar (Fe-FWB) was optimized using response surface methodology (RSM), and the pyrolysis time (1.0, 2.5, and 4.0 h), temperature (300, 450, and 600 °C), and Fe concentration (0.1, 0.3, and 0.5 M) were set as independent variables. The pyrolysis temperature and Fe concentration significantly influenced the As(III) removal, but the effect of pyrolysis time was insignificant. The optimum conditions for the synthesis of Fe-FWB were 1 h and 300 °C with a 0.42-M Fe concentration. Both physical and chemical properties of the optimized Fe-FWB were studied. They were also used for kinetic, equilibrium, thermodynamic, pH, and competing anion studies. Kinetic adsorption experiments demonstrated that the pseudo-second-order model had a superior fit for As(III) adsorption than the pseudo-first-order model. The maximum adsorption capacity derived from the Langmuir model was 119.5 mg/g, which surpassed that of other adsorbents published in the literature. Maximum As(III) adsorption occurred at an elevated pH in the range from 3 to 11 owing to the presence of As(III) as H2AsO3- above a pH of 9.2. A slight reduction in As(III) adsorption was observed in the existence of bicarbonate, hydrogen phosphate, nitrate, and sulfate even at a high concentration of 10 mM. This study demonstrates that aqueous solutions can be treated using Fe-FWB, which is an affordable and readily available resource for As(III) removal.

Crossover between Photochemical and Photothermal Oxidations of Atomically Thin Magnetic Semiconductor CrPS4.

Many two-dimensional (2D) semiconductors represented by transition metal dichalcogenides have tunable optical bandgaps in the visible or near IR-range standing as a promising candidate for optoelectronic devices. Despite this potential, however, their photoreactions are not well understood or controversial in the mechanistic details. In this work, we report a unique thickness-dependent photoreaction sensitivity and a switchover between two competing reaction mechanisms in atomically thin chromium thiophosphate (CrPS4), a two-dimensional antiferromagnetic semiconductor. CrPS4 showed a threshold power density 2 orders of magnitude smaller than that for MoS2 obeying a photothermal reaction route. In addition, reaction cross section quantified with Raman spectroscopy revealed distinctive power dependences in the low and high power regimes. On the basis of optical in situ thermometric measurements and control experiments against O2, water, and photon energy, we proposed a photochemical oxidation mechanism involving singlet O2 in the low power regime with a photothermal route for the other. We also demonstrated a highly effective encapsulation with Al2O3 as a protection against the destructive photoinduced and ambient oxidations.

Use of calcined sepiolite in removing phosphate from water and returning phosphate to soil as phosphorus fertilizer.

We investigated the application of cheap but efficient sepiolite for the removal of phosphate and the use of phosphate-adsorbed sepiolite for rice cultivation. Sepiolite was calcined under different temperatures to improve its phosphate adsorption capacity; the sepiolite calcined at 950 °C (950-SPL) was found to have highest adsorption capacity. As the calcination temperature increased, the amount of Ca eluted from sepiolite also increased, resulting in the formation of Ca-P precipitates. Phosphate adsorption on 950-SPL reached equilibrium within 12 h. Both the Langmuir and Freudlich models were not well-fitted to the equilibrium adsorption model because phosphate at initial concentration was fully removed by 950-SPL. The maximum adsorption capacity of 950-SPL with respect to phosphate was 172.34 mg/g. The phosphate adsorption of 950-SPL was endothermic and spontaneous. Phosphate adsorption at pH 3 was two times higher than at pH 11. The presence of bicarbonate significantly influenced the decrease of phosphate by 950-SPL. A breakthrough of column packed with 950-SPL/sand was not observed during >200 h. The phosphate fraction in 950-SPL was mainly composed of apatite-P and residual fraction. A toxicity test using Daphnia magna showed that the toxic units of 950-SPL corresponded to no acute toxicity. Tiller number, shoot height, shoot dry weight and total dry weight were significantly higher in P-adsorbed 950-SPL application than control. It can be concluded that calcined sepiolite can be effective in the removal of phosphate and that the sepiolite after phosphate adsorption can be used as a P fertilizer in soil.

Multifunctional van der Waals Broken-Gap Heterojunction.

The finite energy band-offset that appears between band structures of employed materials in a broken-gap heterojunction exhibits several interesting phenomena. Here, by employing a black phosphorus (BP)/rhenium disulfide (ReS2 ) heterojunction, the tunability of the BP work function (Φ BP ) with variation in flake thickness is exploited in order to demonstrate that a BP-based broken-gap heterojunction can manifest diverse current-transport characteristics such as gate tunable rectifying p-n junction diodes, Esaki diodes, backward-rectifying diodes, and nonrectifying devices as a consequence of diverse band-bending at the heterojunction. Diversity in band-bending near heterojunction is attributed to change in the Fermi level difference (Δ) between BP and ReS2 sides as a consequence of Φ BP modulation. No change in the current transport characteristics in several devices with fixed Δ also provides further evidence that current-transport is substantially impacted by band-bending at the heterojunction. Optoelectronic experiments on the Esaki diode and the p-n junction diode provide experimental evidence of band-bending diversity. Additionally, the p+ -n-p junction comprising BP (38 nm)/ReS2 /BP(5.8 nm) demonstrates multifunctionality of binary and ternary inverters as well as exhibiting the behavior of a bipolar junction transistor with common-emitter current gain up to 50.

Antiferromagnetic coupling of van der Waals ferromagnetic Fe3GeTe2.

Among two-dimensional (2D) layered van der Waals materials, ferromagnetic 2D materials can be useful for compact low-power spintronic applications. One promising candidate material is Fe3GeTe2 (FGT), which has a strong perpendicular magnetic anisotropy and relatively high Curie temperature. In this study, we confirmed that an oxide layer (O-FGT) naturally forms on top of exfoliated FGT and that an antiferromagnetic coupling (AFC) exists between FGT and O-FGT layers. From a first-principles calculation, oxide formation at the interface of each layer induces an AFC between the layers. An AFC causes a tailed hysteresis loop, where two-magnetization reversal curves are included, and a negative remanence magnetization at a certain temperature range.

Topological Insulator-Based van der Waals Heterostructures for Effective Control of Massless and Massive Dirac Fermions.

Three dimensional (3D) topological insulators (TIs) are an important class of materials with applications in electronics, spintronics and quantum computing. With the recent development of truly bulk insulating 3D TIs, it has become possible to realize surface dominated phenomena in electrical transport measurements e.g. the quantum Hall (QH) effect of massless Dirac fermions in topological surface states (TSS). However, to realize more advanced devices and phenomena, there is a need for a platform to tune the TSS or modify them e.g. gap them by proximity with magnetic insulators, in a clean manner. Here we introduce van der Waals (vdW) heterostructures in the form of topological insulator/insulator/graphite to effectively control chemical potential of the TSS. Two types of gate dielectrics, normal insulator hexagonal boron nitride (hBN) and ferromagnetic insulator Cr2Ge2Te6 (CGT) are utilized to tune charge density of TSS in the quaternary TI BiSbTeSe2. hBN/graphite gating in the QH regime shows improved quantization of TSS by suppression of magnetoconductivity of massless Dirac fermions. CGT/graphite gating of massive Dirac fermions in the QH regime yields half-quantized Hall conductance steps and a measure of the Dirac gap. Our work shows the promise of the vdW platform in creating advanced high-quality TI-based devices.

Ultrahigh Photoresponsive Device Based on ReS2 /Graphene Heterostructure.

Heterostructures that combine graphene and transition metal dichalcogenides, such as MoS2 , MoTe2 , and WS2 , have attracted attention due to their high performances in optoelectronic devices compared to homogeneous systems. Here, a photodevice based on a hybrid van der Waals heterostructure of rhenium disulfide (ReS2 ) and graphene is fabricated using the stacking method. The device presents a remarkable ultrahigh photoresponsivity of 7 × 105 A W-1 and a detectivity of 1.9 × 1013 Jones, along with a fast response time of less than 30 ms. Tremendous photocurrents are generated in the heterostructure due to the direct bandgap, high quantum efficiency, and strong light absorption by the multilayer ReS2 and the high carrier mobility of graphene. The ReS2 /graphene heterostructured device displays a high photocurrent under the applied gate voltages due to the photogating effect induced by the junction between graphene and ReS2 . The ReS2 /graphene heterostructure may find promising applications in future optoelectronic devices, providing a high sensitivity, flexibility, and transparency.

Easily Recoverable, Micrometer-Sized TiO2 Hierarchical Spheres Decorated with Cyclodextrin for Enhanced Photocatalytic Degradation of Organic Micropollutants.

Micrometer-sized titanium dioxide hierarchical spheres (TiO2-HS) were assembled from nanosheets to address two common limitations of photocatalytic water treatment: (1) inefficiency associated with scavenging of oxidation capacity by nontarget water constituents and (2) energy-intensive separation and recovery of the photocatalyst slurry. These micrometer-sized spheres are amenable to low-energy separation, and over 99% were recaptured from both batch and continuous flow reactors using microfiltration. Using nanosheets as building blocks resulted in a large specific surface area-3 times larger than that of commercially available TiO2 powder (Evonik P25). Anchoring food-grade cyclodextrin onto TiO2-HS (i.e., CD-TiO2-HS) provided hydrophobic cavities to entrap organic contaminants for more effective utilization of photocatalytically generated reactive oxygen species. CD-TiO2-HS removed over 99% of various contaminants with dissimilar hydrophobicity (i.e., bisphenol A, bisphenol S, 2-naphthol, and 2,4-dichlorophenol) within 2 h under a low-intensity UVA input (3.64 × 10-6 einstein/L/s). As with other catalyst (including TiO2 slurry), periodic replacement or replenishment would be needed to maintain high treatment efficiency (e.g., we demonstrate full reactivation through simple reanchoring of CD). Nevertheless, this task would be offset by significant savings in photocatalyst separation. Thus, CD-TiO2-HS is an attractive candidate for photocatalytic water and wastewater treatment of recalcitrant organic pollutants.

Porous Electrospun Fibers Embedding TiO2 for Adsorption and Photocatalytic Degradation of Water Pollutants.

Using a bipolymer system consisting of polyvinylpyrrolidone (PVP) and poly(vinylidene fluoride) (PVDF), P25-TiO2 was immobilized into thin film mats of porous electrospun fibers. Pores were introduced by dissolving sacrificial PVP to increase surface area and enhance access to TiO2. The highest photocatalytic activity was achieved using a PVDF:PVP weight ratio of 2:1. Methylene blue (MB) was used to visualize contaminant removal, assess the sorption capacity (5.93 ± 0.23 mg/g) and demonstrate stable removal kinetics ( kMB > 0.045 min-1) under UVA irradiation (3.64 × 10-9 einstein/cm2/s) over 10 cycles. Treatment was also accomplished via sequential MB sorption in the dark and subsequent photocatalytic degradation under UVA irradiation, to illustrate that these processes could be uncoupled to overcome limited light penetration. The photocatalytic mat degraded bisphenol A and 17α-ethynylestradiol in secondary wastewater effluent (17 mg TOC/L), and (relative to TiO2 slurry) immobilization of TiO2 in the mat mitigated performance inhibition by co-occurring organics that scavenge oxidation capacity. This significantly lowered the electrical energy-per-order of reaction (EEO) needed to remove such endocrine disruptors in the presence of oxidant scavenging/inhibitory organics. Thus, effective TiO2 immobilization into polymers with affinity toward specific priority pollutants could both increase the efficiency and reduce energy requirements of photocatalytic water treatment.