Transformative Dynamics: Self-Assembly of Iron Oxide Hydroxide Nanorods into Iron Oxide Microcubes for Enhanced Perfluoroalkyl Substance Remediation.

We report the controlled synthesis of iron oxide microcubes (IOMCs) through the self-assembly arrays of ferric oxide hydroxide nanorods (NRs). The formation of IOMCs involves a complex interplay of nucleation, self-assembly, and growth mechanisms influenced by time, thermal treatment, and surfactant dynamics. The self-assembly of vertically aligned NRs into IOMCs is controlled by dynamic magnetism properties and capping agents like cetyltrimethylammonium bromide (CTAB), whose concentration and temperature modulation dictate growth kinetics and structural uniformity. These controlled structural growths were obtained via a hydrothermal process at 120 °C at various intervals of 8, 16, 24, and 32 h in the presence of CTAB as the capping agent. In this hydrothermal method, the formation of vertically oriented NR arrays was observed without the presence of ligands, binders, harsh drying techniques, and solvent evaporation. The formation of the self-assembly of NRs to IOMCs is obtained with an increase in saturated magnetization to attain the most stable state. The synthesized IOMCs have a uniform size, quasi-shape, and excellent dispersion. Due to its excellent magnetic and catalytic properties, IOMCs were employed to remove the various emerging pollutants known as per- and polyfluorinated substances (PFAS). Various microscopic and spectroscopic techniques were employed for the characterization and interaction studies of IOMCs with various PFAS. The interaction between IOMCs and perfluoroalkyl substances (PFAS) was investigated, revealing strong adsorption tendencies facilitated by electrostatic interactions, as evidenced by UV-vis and FT-IR spectroscopic studies. Furthermore, the higher magnetic and positive surface charge of IOMCs is responsible for an effective remediation eliminating any secondary pollution with ease of recovery after the sorption interaction studies, thereby making it practically worthwhile.

Ultrahigh Capacitive Energy Density in Stratified 2D Nanofiller-Based Polymer Dielectric Films.

Dielectric capacitors are critical components in electronics and energy storage devices. The polymer-based dielectric capacitors have the advantages of device flexibility, fast charge-discharge rates, low loss, and graceful failure. Elevating the use of polymeric dielectric capacitors for advanced energy applications such as electric vehicles (EVs), however, requires significant enhancement of their energy densities. Here, we report a polymer thin film heterostructure-based capacitor of poly(vinylidene fluoride)/poly(methyl methacrylate) with stratified 2D nanofillers (Mica or h-BN nanosheets) (PVDF/PMMA-2D fillers/PVDF), that shows enhanced permittivity, high dielectric strength, and an ultrahigh energy density of ≈75 J/cm3 with efficiency over 79%. Density functional theory calculations verify the observed permittivity enhancement. This approach of using oriented 2D nanofillers-based polymer heterostructure composites is expected to be versatile for designing high energy density thin film polymeric dielectric capacitors for myriads of applications.

Insulator-to-metal phase transition in a few-layered MoSe2 field effect transistor.

The metal-to-insulator phase transition (MIT) in low-dimensional materials and particularly two-dimensional layered semiconductors is exciting to explore due to the fact that it challenges the prediction that a two-dimensional system must be insulating at low temperatures. Thus, the exploration of MITs in 2D layered semiconductors expands the understanding of the underlying physics. Here we report the MIT of a few-layered MoSe2 field effect transistor under a gate bias (electric field) applied perpendicular to the MoSe2 layers. With low applied gate voltage, the conductivity as a function of temperature from 150 K to 4 K shows typical semiconducting to insulating character. Above a critical applied gate voltage, Vc, the conductivity becomes metallic (i.e., the conductivity increases continuously as a function of decreasing temperature). Evidence of a metallic state was observed using an applied gate voltage or, equivalently, increasing the density of charge carriers within the 2D channel. We analyzed the nature of the phase transition using percolation theory, where conductivity scales with the density of charge carriers as σ ∝ (n - nc)δ. The critical exponent for a percolative phase transition, δ(T), has values ranging from 1.34 (at T = 150 K) to 2 (T = 20 K), which is close to the theoretical value of 1.33 for percolation to occur. Thus we conclude that the MIT in few-layered MoSe2 is driven by charge carrier percolation. Furthermore, the conductivity does not scale with temperature, which is a hallmark of a quantum critical phase transition.

High broadband photoconductivity of few-layered MoS2 field-effect transistors measured using multi-terminal methods: effects of contact resistance.

Among the layered two dimensional semiconductors, molybdenum disulfide (MoS2) is considered to be an excellent candidate for applications in optoelectronics and integrated circuits due to its layer-dependent tunable bandgap in the visible region, high ON/OFF current ratio in field-effect transistors (FET) and strong light-matter interaction properties. In this study, using multi-terminal measurements, we report high broadband photocurrent response (R) and external quantum efficiency (EQE) of few-atomic layered MoS2 phototransistors fabricated on a SiO2 dielectric substrate and encapsulated with a thin transparent polymer film of Cytop. The photocurrent response was measured using a white light source as well as a monochromatic light of wavelength λ = 400 nm-900 nm. We measured responsivity using a 2-terminal configuration as high as R = 1 × 103 A W-1 under white light illumination with an optical power Popt = 0.02 nW. The R value increased to 3.5 × 103 A W-1 when measured using a 4-terminal configuration. Using monochromatic light on the same device, the measured values of R were 103 and 6 × 103 A W-1 under illumination of λ = 400 nm when measured using 2- and 4-terminal methods, respectively. The highest EQE values obtained using λ = 400 nm were 105% and 106% measured using 2- and 4-terminal configurations, respectively. The wavelength dependent responsivity decreased from 400 nm to the near-IR region at 900 nm. The observed photoresponse, photocurrent-dark current ratio (PDCR), detectivity as a function of applied gate voltage, optical power, contact resistances and wavelength were measured and are discussed in detail. The observed responsivity is also thoroughly studied as a function of contact resistance of the device.

Suspended state heteroaggregation kinetics of kaolinite and fullerene (nC60) in the presence of tannic acid: Effect of π-π interactions.

The colloidal heteroassociation between natural mineral colloids and engineered nanoparticles (ENPs) can reduce the bioavailability and toxicity of the ENPs. However, the efficacy of this heteroassociation-based entrapment of ENPs depends on the intrinsic material properties of the particles and the physicochemical parameters of the aquatic environment. Natural organic matter (NOM)-induced surface modifications of clay colloids, functionalization of ENPs, and efficiency of counterions as effective coagulants profoundly affect the effectiveness of heteroaggregation-based attenuation of anthropogenic colloids. In this study, tannic acid (TA), a surrogate of NOM, prevented the edge-to-face self-association of sodium-saturated kaolinite (Na-kaolinite) at acidic pH, as evaluated from the transverse proton spin-spin relaxation data (T2). Likewise, fullerene water suspension (FWS) adhesion to Na-kaolinite prevented the self-association of Na-kaolinite and enhanced the colloidal stability. At pH 4 and diffusion-limited aggregation regime salt concentrations, the Na-kaolinite and FWS heteroaggregation rates were lower than the Na-kaolinite homoaggregation rates, and eventually reached a plateau. The higher colloidal stability of the Na-kaolinite and FWS binary mixture than that of Na-kaolinite, regardless of stronger charge screening by Ca2+, reflects steric stabilization. However, at pH 7, the increased electrostatic barrier reduces the feasibility of colloidal heteroassociation between Na-kaolinite and FWS; thus, higher salt concentrations are required to initiate aggregation. Weak adsorption of TA on Na-kaolinite at pH 7 facilitated stronger π-π interactions with FWS. All suspensions exhibited faster aggregate growth at pH 7 than pH 4, possibly due to the stronger cation response at pH 7. In situ atomic force microscopy imaging and line profile plots of Na-kaolinite, TA, and FWS mixture in CaCl2 further corroborated the difference in the heteroaggregation rates observed at the two different pH values. Thus, TA-induced surface functionalization of FWS and the consequent increased electrostatic barrier to heteroassociation with Na-kaolinite may facilitate the environmental mobility of FWS in aquatic media.

Raman and electrical transport properties of few-layered arsenic-doped black phosphorus.

Black phosphorus (b-P) is an allotrope of phosphorus whose properties have attracted great attention. In contrast to other 2D compounds, or pristine b-P, the properties of b-P alloys have yet to be explored. In this report, we present a detailed study on the Raman spectra and on the temperature dependence of the electrical transport properties of As-doped black phosphorus (b-AsP) for an As fraction x = 0.25. The observed complex Raman spectra were interpreted with the support of Density Functional Theory (DFT) calculations since each original mode splits in three due to P-P, P-As, and As-As bonds. Field-effect transistors (FET) fabricated from few-layered b-AsP exfoliated onto Si/SiO2 substrates exhibit hole-doped like conduction with a room temperature ON/OFF current ratio of ∼103 and an intrinsic field-effect mobility approaching ∼300 cm2 V-1 s-1 at 300 K which increases up to 600 cm2 V-1 s-1 at 100 K when measured via a 4-terminal method. Remarkably, these values are comparable to, or higher, than those initially reported for pristine b-P, indicating that this level of As doping is not detrimental to its transport properties. The ON to OFF current ratio is observed to increase up to 105 at 4 K. At high gate voltages b-AsP displays metallic behavior with the resistivity decreasing with decreasing temperature and saturating below T ∼100 K, indicating a gate-induced insulator to metal transition. Similarly to pristine b-P, its transport properties reveal a high anisotropy between armchair (AC) and zig-zag (ZZ) directions. Electronic band structure computed through periodic dispersion-corrected hybrid Density Functional Theory (DFT) indicate close proximity between the Fermi level and the top of the valence band(s) thus explaining its hole doped character. Our study shows that b-AsP has potential for optoelectronics applications that benefit from its anisotropic character and the ability to tune its band gap as a function of the number of layers and As content.

Tannic acid- and cation-mediated interfacial self-assembly and epitaxial growth of fullerene (nC60) and kaolinite binary graphitic aggregates.

In this study, we investigated the tannic acid (TA)-, Ca2+-, and mica-enabled interfacial assembly of nC60 fullerene (FWS) and Na-saturated kaolinite (Na-Kl) with in and ex situ atomic force microscopy (AFM). The epitaxial growth of herringbone motif, two dimensional (2D) chiral clusters and 3D mounds were detected. π-π electron donor-acceptor (EDA) interactions drove the transformation of the FWS, and the symmetry of the muscovite substrate directed the epitaxial ordering of self-assembled herringbone motifs. A ternary mixture of Na-Kl/FWS/TA in the presence of Ca2+ produced double-stranded (ds) helices and 2D platelets of chiral clusters with a nano-porous monolayer on K+-treated muscovite surfaces. The weak hydration of exchangeable K+ and stronger electric fields possibly contributed to the 1D and 2D propagation of aggregates. However, the local increment in carbon content due to the nucleation of functionalized FWS on mica diminished the K+-induced electric field effect and facilitated the 3D growth of helical mounds. The diffusion limited mass-transfer of particulates across the Ehrlich-Schwoebel barrier (ESB) and screw dislocation assisted motion of particulates specifically at higher steps aided mound growth. Thus, the structural incorporation of FWS can substantially impede its interfacial transport and produce hierarchical hybrid mineral-enriched graphitic aggregates.

Low temperature photoconductivity of few layer p-type tungsten diselenide (WSe2) field-effect transistors (FETs).

We report on the low-temperature photoconductive properties of few layer p-type tungsten diselenide (WSe2) field-effect transistors (FETs) synthesized using the chemical vapor transport method. Photoconductivity measurements show that these FETs display room temperature photo-responsivities of ∼7 mAW-1 when illuminated with a laser of wavelength λ = 658 nm with a power of 38 nW. The photo-responsivities of these FETs showed orders of magnitude improvement (up to ∼1.1 AW-1 with external quantum efficiencies reaching as high as ∼188%) upon application of a gate voltage (V G = -60 V). A temperature dependent (100 K < T < 300 K) photoconductivity study reveals a weak temperature dependence of responsivity for these WSe2 phototransistors. We demonstrate that it is possible to obtain stable photo-responsivities of ∼0.76 ± 0.2 AW-1 (with applied V G = -60 V), at low temperatures in these FETs. These findings indicate the possibility of developing WSe2-based FETs for highly robust, efficient, and swift photodetectors with a potential for optoelectronic applications over a broad range of temperatures.

Phase Modulators Based on High Mobility Ambipolar ReSe2 Field-Effect Transistors.

We fabricated ambipolar field-effect transistors (FETs) from multi-layered triclinic ReSe2, mechanically exfoliated onto a SiO2 layer grown on p-doped Si. In contrast to previous reports on thin layers (~2 to 3 layers), we extract field-effect carrier mobilities in excess of 102 cm2/Vs at room temperature in crystals with nearly ~10 atomic layers. These thicker FETs also show nearly zero threshold gate voltage for conduction and high ON to OFF current ratios when compared to the FETs built from thinner layers. We also demonstrate that it is possible to utilize this ambipolarity to fabricate logical elements or digital synthesizers. For instance, we demonstrate that one can produce simple, gate-voltage tunable phase modulators with the ability to shift the phase of the input signal by either 90° or nearly 180°. Given that it is possible to engineer these same elements with improved architectures, for example on h-BN in order to decrease the threshold gate voltage and increase the carrier mobilities, it is possible to improve their characteristics in order to engineer ultra-thin layered logic elements based on ReSe2.

Colloidal aggregation and structural assembly of aspect ratio variant goethite (α-FeOOH) with nC60 fullerene in environmental media.

Environmental mobility of C60 fullerene can be significantly affected in the presence of naturally abundant α-FeOOH. However, α-FeOOH vary significantly in sizes, shapes and associated properties that can greatly influence the fate and transport of C60 fullerene in environmental media. Therefore, colloidal hetero-association between well crystallized low aspect (LAsp) α-FeOOH and nC60 fullerene may differ substantially to weakly crystallized high-aspect (HAsp) counterpart. In contrast to LAsp α-FeOOH, inherent crystal defects and surface charge generation in HAsp α-FeOOH facilitated strong Coulombic attraction and aggregation with fullerene in acidic pH. However, LAsp α-FeOOH demonstrated subtle entropic depletion mediated interaction with fullerene prevalent in hard rods. Humic acid (HA) encapsulation of HAsp α-FeOOH substantially blocked fullerene attachment. Minute enhancement in colloidal stability was detected for HA-coated HAsp α-FeOOH and fullerene mixture to HA-coated HAsp α-FeOOH alone. To investigate the interfacial assembly of α-FeOOH with fullerene "in situ" differential interference contrast (DIC) microscopic investigations were employed. This study showed significantly different interface behavior of the binary mixtures of fullerene and HAsp α-FeOOH NPs, and LAsp particles. On air-water interface, bare HAsp α-FeOOH displayed liquid crystalline packing. However, addition of fullerene to HAsp α-FeOOH suspension at pH5 produced closed-loop polygonal and circular ring structures. Head-to-tail alignment of magnetic dipoles as well as fullerene hydrophobicity facilitated such assembly formation. "Ex situ" AFM investigation revealed further the presence of magnetically derived ring structure which asserts that the formed "in situ" ensembles were not transient, hence, may abate fullerene transport through environmental interfaces. Barring hydrophobicity assisted attachment of fullerene to LAsp α-FeOOHs, the absence of any close-packed structures may unlikely abate fullerene transport as envisaged in case of HAsp α-FeOOH. Thus, aspect ratio variation and associated material properties of naturally abundant α-FeOOH may significantly impact fullerene transport through environmental media.

Metal to Insulator Quantum-Phase Transition in Few-Layered ReS2.

In ReS2, a layer-independent direct band gap of 1.5 eV implies a potential for its use in optoelectronic applications. ReS2 crystallizes in the 1T'-structure, which leads to anisotropic physical properties and whose concomitant electronic structure might host a nontrivial topology. Here, we report an overall evaluation of the anisotropic Raman response and the transport properties of few-layered ReS2 field-effect transistors. We find that ReS2 exfoliated on SiO2 behaves as an n-type semiconductor with an intrinsic carrier mobility surpassing µ(i) ∼ 30 cm(2)/(V s) at T = 300 K, which increases up to ∼350 cm(2)/(V s) at 2 K. Semiconducting behavior is observed at low electron densities n, but at high values of n the resistivity decreases by a factor of >7 upon cooling to 2 K and displays a metallic T(2)-dependence. This suggests that the band structure of 1T'-ReS2 is quite susceptible to an electric field applied perpendicularly to the layers. The electric-field induced metallic state observed in transition metal dichalcogenides was recently claimed to result from a percolation type of transition. Instead, through a scaling analysis of the conductivity as a function of T and n, we find that the metallic state of ReS2 results from a second-order metal-to-insulator transition driven by electronic correlations. This gate-induced metallic state offers an alternative to phase engineering for producing ohmic contacts and metallic interconnects in devices based on transition metal dichalcogenides.

Pronounced Photovoltaic Response from Multilayered Transition-Metal Dichalcogenides PN-Junctions.

Transition metal dichalcogenides (TMDs) are layered semiconductors with indirect band gaps comparable to Si. These compounds can be grown in large area, while their gap(s) can be tuned by changing their chemical composition or by applying a gate voltage. The experimental evidence collected so far points toward a strong interaction with light, which contrasts with the small photovoltaic efficiencies η ≤ 1% extracted from bulk crystals or exfoliated monolayers. Here, we evaluate the potential of these compounds by studying the photovoltaic response of electrostatically generated PN-junctions composed of approximately 10 atomic layers of MoSe2 stacked onto the dielectric h-BN. In addition to ideal diode-like response, we find that these junctions can yield, under AM-1.5 illumination, photovoltaic efficiencies η exceeding 14%, with fill factors of ~70%. Given the available strategies for increasing η such as gap tuning, improving the quality of the electrical contacts, or the fabrication of tandem cells, our study suggests a remarkable potential for photovoltaic applications based on TMDs.

High Photoresponsivity and Short Photoresponse Times in Few-Layered WSe2 Transistors.

Here, we report the photoconducting response of field-effect transistors based on three atomic layers of chemical vapor transport grown WSe2 crystals mechanically exfoliated onto SiO2. We find that trilayered WSe2 field-effect transistors, built with the simplest possible architecture, can display high hole mobilities ranging from 350 cm(2)/(V s) at room temperature (saturating at a value of ∼500 cm(2)/(V s) below 50 K) displaying a strong photocurrent response, which leads to exceptionally high photoresponsivities up to 7 A/W under white light illumination of the entire channel for power densities p < 10(2) W/m(2). Under a fixed wavelength of λ = 532 nm and a laser spot size smaller than the conducting channel area, we extract photoresponsitivities approaching 100 mA/W with concomitantly high external quantum efficiencies up to ∼40% at room temperature. These values surpass values recently reported from more complex architectures, such as graphene and transition metal dichalcogenides based heterostructures. Also, trilayered WSe2 phototransistors display photoresponse times on the order of 10 µs. Our results indicate that the addition of a few atomic layers considerably decreases the photoresponse times, probably by minimizing the interaction with the substrates, while maintaining a very high photoresponsivity.

Binary short-range colloidal assembly of magnetic iron oxides nanoparticles and fullerene (nC60) in environmental media.

Colloidal assembly of nC60 fullerene with naturally abundant magnetic iron oxide NPs will affect their fate and transformation in environmental media. In solution, fullerene association to aggregating iron oxide NPs/clusters greatly enhanced the overall colloidal stability. Development of depletion-mediated structured fullerene layers between pure and surface modified γFe2O3 NPs possibly resulted in such stabilization. Here, we also report that on air-water interface, association of fullerene to pure and humic acid (HA7) coated γFe2O3 NPs led to the formation of ordered assemblies, e.g., binary wires and closed-packed "crystalline" and "glassy" structures in the presence and absence of electrolytes suggesting immobilization of the former. The interaction of fullerene to Fe3O4 NPs and clusters also produced ordered assemblies along with amorphous aggregates. Fullerene interaction with Fe3O4 NPs in low concentration of HA1 and Na(+) at pH 6 formed dendritic growth and polycrystalline circular assemblies on air-water interface. HRTEM study further revealed that the monolayer circular assemblies were highly ordered but structural degeneracy was evident in multilayers. Therefore, interfacial assemblies of fullerene with iron oxide NPs resulted in short-range periodic structures with concomitant immobilization and reduction in availability of the former, especially in soils or sediments rich in the latter.

Ambipolar molybdenum diselenide field-effect transistors: field-effect and Hall mobilities.

We report a room temperature study on the electrical response of field-effect transistors (FETs) based on few-layered MoSe2, grown by a chemical vapor transport technique, mechanically exfoliated onto SiO2. In contrast to previous reports on MoSe2 FETs electrically contacted with Ni, MoSe2 FETs electrically contacted with Ti display ambipolar behavior with current on to off ratios up to 10(6) for both hole and electron channels when applying a small excitation voltage. A rather small hysteresis is observed when sweeping the back-gate voltage between positive and negative values, indicating the near absence of charge "puddles". For both channels the Hall effect indicates Hall mobilities µH ≃ 250 cm(2)/(V s), which are comparable to the corresponding field-effect mobilities, i.e., µFE ∼ 150 to 200 cm(2)/(V s) evaluated through the conventional two-terminal field-effect configuration. Therefore, our results suggest that MoSe2 could be a good candidate for p-n junctions composed of a single atomic layer and for low-power, complementary logic applications.

Field-effect transistors based on few-layered α-MoTe(2).

Here we report the properties of field-effect transistors based on a few layers of chemical vapor transport grown α-MoTe2 crystals mechanically exfoliated onto SiO2. We performed field-effect and Hall mobility measurements, as well as Raman scattering and transmission electron microscopy. In contrast to both MoS2 and MoSe2, our MoTe2 field-effect transistors are observed to be hole-doped, displaying on/off ratios surpassing 10(6) and typical subthreshold swings of ∼140 mV per decade. Both field-effect and Hall mobilities indicate maximum values approaching or surpassing 10 cm(2)/(V s), which are comparable to figures previously reported for single or bilayered MoS2 and/or for MoSe2 exfoliated onto SiO2 at room temperature and without the use of dielectric engineering. Raman scattering reveals sharp modes in agreement with previous reports, whose frequencies are found to display little or no dependence on the number of layers. Given that MoS2 is electron-doped, the stacking of MoTe2 onto MoS2 could produce ambipolar field-effect transistors and a gap modulation. Although the overall electronic performance of MoTe2 is comparable to those of MoS2 and MoSe2, the heavier element Te leads to a stronger spin-orbit coupling and possibly to concomitantly longer decoherence times for exciton valley and spin indexes.

Controlled synthesis and transfer of large-area WS2 sheets: from single layer to few layers.

The isolation of few-layered transition metal dichalcogenides has mainly been performed by mechanical and chemical exfoliation with very low yields. In this account, a controlled thermal reduction-sulfurization method is used to synthesize large-area (~1 cm(2)) WS2 sheets with thicknesses ranging from monolayers to a few layers. During synthesis, WOx thin films are first deposited on Si/SiO2 substrates, which are then sulfurized (under vacuum) at high temperatures (750-950 °C). An efficient route to transfer the synthesized WS2 films onto different substrates such as quartz and transmission electron microscopy (TEM) grids has been satisfactorily developed using concentrated HF. Samples with different thicknesses have been analyzed by Raman spectroscopy and TEM, and their photoluminescence properties have been evaluated. We demonstrated the presence of single-, bi-, and few-layered WS2 on as-grown samples. It is well known that the electronic structure of these materials is very sensitive to the number of layers, ranging from indirect band gap semiconductor in the bulk phase to direct band gap semiconductor in monolayers. This method has also proved successful in the synthesis of heterogeneous systems of MoS2 and WS2 layers, thus shedding light on the controlled production of heterolayered devices from transition metal chalcogenides.

Adult idiopathic ileosigmoid intussusception prolapsing per rectum.

Ileosigmoid intussusception can lead to ischemia and necrosis of either the ileum or sigmoid colon. Ileosigmoid intussusception as a mass prolapsing per rectum in an adult has not been previously reported. We report a 50-year-old man with such a presentation. He recovered uneventfully after subtotal colectomy.