Forming Stable van der Waals Contacts between Metals and 2D Semiconductors.

High-performing 2D electrical and optical devices can be realized by forming an ideal van der Waals (vdW) metal contact with weak interactions and stable interface states. However, the methods for applying metal contacts while avoiding damage from metal deposition present challenges in realizing a uniform, stable vdW interface. To overcome this problem, this study develops a method for forming vdW contacts using a sacrificial Se buffer layer. This study explores this method by investigating the difference in the Schottky barrier height between the vdW metal contact deposited using a buffer layer, a transferred metal contact, and a conventional directly deposited metal contact using rectification and photovoltaic characteristics of a Schottky diode structure with graphite. Evidently, the Se buffer layer method forms the most stable and ideal vdW contact while preventing Fermi-level pinning. A tungsten diselenide Schottky diode fabricated using these vdW contacts with Au and graphite as the top and bottom electrodes, respectively, exhibits excellent operation with an ideality factor of ≈1, an on/off ratio of > 107 , and coherent properties. Additionally, when using only the vdW Au contact, the electrical and optical properties of the device can be minutely modulated by changing the structure of the Schottky diode.

Funnel Devices Based on Asymmetrically Strained Transition Metal Dichalcogenides.

The strain applied to transition metal dichalcogenides (TMDs) reduces their energy bandgap, and local strains result in a funnel-like band structure in which funneled excitons move toward the most strained region. Herein, a funnel device based on asymmetrically strained WS2 and MoS2 is reported. Asymmetric strains are induced by transferring the TMD flakes onto a fork-shaped SU-8 microstructure. Raman and photoluminescence spectra peaks are shifted according to the morphology of the SU-8 microstructure, indicating the application of asymmetric strains to the TMDs. To investigate whether funneled excitons can be converted to electrical currents, various devices are constructed by depositing symmetric and asymmetric electrodes onto the strained TMDs. The scanning photocurrent mapping images follow a fork-shaped pattern, indicating probable conversion of the funneled excitons into electrical currents. In the case of the funnel devices with asymmetric Au and Al electrodes, short-circuit current (ISC ) of WS2 is enhanced by the strains, whereas ISC of MoS2 is suppressed because the Schottky barrier lowers with increasing strain for the MoS2 . These results demonstrate that the funnel devices can be implemented using asymmetrically strained TMDs and the effect of strains on the Schottky barrier is dependent on the TMD used.

Enhancement of triboelectricity based on fully organic composite films with a conducting polymer.

Triboelectric nanogenerators (TENGs) based on ferroelectric organic materials have advantages of high flexibility, biocompatibility, controllable ferroelectric properties, etc. However, this has limited the electrical output performance due to their lower ferroelectric characteristics than those of inorganic ferroelectric materials. A lot of effort has been made to improve the organic ferroelectric characteristics through composites, surface modifications, structures, etc. Herein, we report TENGs made of ferroelectric composite materials consisting of poly(vinylidene fluoride-co-trifluoroethylene) (PVDF-TrFE) and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). The composite was prepared by simply blending PVDF-TrFE and PEDOT:PSS with a weight ratio from 0% to 60%. When the ratio was 20%, the ferroelectric-crystalline phase was enhanced and the highest dielectric constant was observed. Accordingly, the TENGs consisting of 20% composite film and polyimide exhibited the best output performance: the maximum open circuit voltage and short circuit current were ∼15 V and ∼2.3 µA at 1 Hz oscillation, respectively. These results indicate that the ferroelectric characteristics of PVDF-TrFE can be enhanced by adding PEDOT:PSS as a nanofiller.

Ferroelastic-Ferroelectric Multiferroicity in van der Waals Rhenium Dichalcogenides.

2D multiferroics with combined ferroic orders have gained attention owing to their novel functionality and underlying science. Intrinsic ferroelastic-ferroelectric multiferroicity in single-crystalline van der Waals rhenium dichalcogenides, whose symmetries are broken by the Peierls distortion and layer-stacking order, is demonstrated. Ferroelastic switching of the domain orientation and accompanying anisotropic properties is achieved with 1% uniaxial strain using the polymer encapsulation method. Based on the electron localization function and bond dissociation energy of the Re-Re bonds, the change in bond configuration during the evolution of the domain wall and the preferred switching between the two specific orientation states are explained. Furthermore, the ferroelastic switching of ferroelectric polarization is confirmed using the photovoltaic effect. The study provides insights into the reversible bond-switching process and potential applications based on 2D multiferroicity.

Photothermal inactivation of universal viral particles by localized surface plasmon resonance mediated heating filter membrane.

This study introduces localized surface plasmon resonance (L-SPR) mediated heating filter membrane (HFM) for inactivating universal viral particles by using the photothermal effect of plasmonic metal nanoparticles (NPs). Plasmonic metal NPs were coated onto filter membrane via a conventional spray-coating method. The surface temperature of the HFM could be controlled to approximately 40-60 °C at room temperature, owing to the photothermal effect of the gold (Au) NPs coated on them, under irradiation by visible light-emitting diodes. Due to the photothermal effect of the HFMs, the virus titer of H1Npdm09 was reduced by > 99.9%, the full inactivation time being < 10 min, confirming the 50% tissue culture infective dose (TCID50) assay. Crystal violet staining showed that the infectious samples with photothermal inactivation lost their infectivity against Mardin-Darby Canine Kidney cells. Moreover, photothermal inactivation could also be applied to reduce the infectivity of SARS-CoV-2, showing reduction rate of 99%. We used quantitative reverse transcription polymerase chain reaction (qRT-PCR) techniques to confirm the existence of viral genes on the surface of the HFM. The results of the TCID50 assay, crystal violet staining method, and qRT-PCR showed that the effective and immediate reduction in viral infectivity possibly originated from the denaturation or deformation of membrane proteins and components. This study provides a new, simple, and effective method to inactivate viral infectivity, leading to its potential application in various fields of indoor air quality control and medical science.

Collective dynamics of neuronal activities in various modular networks.

Modularity is a key feature of structural and functional brain networks. However, the association between the structure and function of modular brain networks has not been revealed. We constructed three types of modular cortical networks in vitro and investigated their neuronal activities. The modular networks comprising 4, 3, or 2 modules were constructed using polydimethylsiloxane (PDMS) microstructures fabricated directly on a multi-electrode array (MEA) without transfer. The 4-module network had the strongest modular connectivity, followed by the 3-module and 2-module networks. To investigate how neuronal activities were affected by the modular network structure, spontaneous neuronal activities were recorded on different days in vitro and analyzed based on spike amplitudes, network bursts, and the propagation properties of individual spikes. Different characteristics were observed depending on the network topology and modular connectivity. Moreover, when an electrode was stimulated by biphasic voltage pulses, bursts were elicited for the 4-module network, whereas spikes were elicited for the 3-module and 2-module networks. Direct fabrication of the PDMS microstructures on the MEA without transfer allows microscale construction of modular networks and high-density functional recording; therefore, the technique utilizing the PDMS microstructures can be applied to the systematic study of the dynamics of modular neuronal networks in vitro.

Large field-of-view nanometer-sectioning microscopy by using metal-induced energy transfer and biexponential lifetime analysis.

Total internal reflection fluorescence (TIRF) microscopy, which has about 100-nm axial excitation depth, is the method of choice for nanometer-sectioning imaging for decades. Lately, several new imaging techniques, such as variable angle TIRF microscopy, supercritical-angle fluorescence microscopy, and metal-induced energy transfer imaging, have been proposed to enhance the axial resolution of TIRF. However, all of these methods use high numerical aperture (NA) objectives, and measured images inevitably have small field-of-views (FOVs). Small-FOV can be a serious limitation when multiple cells need to be observed. We propose large-FOV nanometer-sectioning microscopy, which breaks the complementary relations between the depth of focus and axial sectioning by using MIET. Large-FOV imaging is achieved with a low-magnification objective, while nanometer-sectioning is realized utilizing metal-induced energy transfer and biexponential fluorescence lifetime analysis. The feasibility of our proposed method was demonstrated by imaging nanometer-scale distances between the basal membrane of human aortic endothelial cells and a substrate.

Rectifying optoelectronic memory based on WSe2/graphene heterostructures.

van der Waals heterostructures composed of two-dimensional materials vertically stacked have been extensively studied to develop various multifunctional devices. Here, we report WSe2/graphene heterostructure devices with a top floating gate that can serve as multifunctional devices. They exhibit gate-controlled rectification inversion, rectified nonvolatile memory effects, and multilevel optoelectronic memory effects. Depending on the polarity of the gate voltage pulses (V Gp), electrons or holes can be trapped in the floating gate, resulting in rectified nonvolatile memory properties. Furthermore, upon repeated illumination with laser pulses, positive or negative staircase photoconductivity is observed depending on the history of V Gp, which is ascribed to the tunneling of electrons or holes between the WSe2 channel and the floating gate. These multifunctional devices can be used to emulate excitatory and inhibitory synapses that have different neurotransmitters. Various synaptic functions, such as potentiation/depression curves and spike-timing-dependent plasticity, have been also implemented using these devices. In particular, 128 optoelectronic memory states with nonlinearity less than 1 can be achieved by controlling applied laser pulses and V Gp, suggesting that the WSe2/graphene heterostructure devices with a top floating gate can be applied to optoelectronic synapse devices.

Electrical antimicrobial susceptibility testing based on aptamer-functionalized capacitance sensor array for clinical isolates.

To prescribe effective antibiotics to patients with bacterial infections in a timely manner and to avoid the misuse of antibiotics, a rapid antimicrobial susceptibility test (AST) is essential. However, conventional AST methods require more than 16 h to provide results; thus, we developed an electrical AST (e-AST) system, which provides results within 6 h. The proposed e-AST is based on an array of 60 aptamer-functionalized capacitance sensors that are comparable to currently available AST panels and a pattern-matching algorithm. The performance of the e-AST was evaluated in comparison with that of broth microdilution as the reference test for clinical strains isolated from septic patients. A total of 4,554 tests using e-AST showed a categorical agreement of 97% with a minor error of 2.2%, major error of 0.38%, and very major error of 0.38%. We expect that the proposed e-AST could potentially aid antimicrobial stewardship efforts and lead to improved patient outcomes.

Methotrexate-loaded multifunctional nanoparticles with near-infrared irradiation for the treatment of rheumatoid arthritis.

BACKGROUNDS: Despite the advances of rheumatoid arthritis (RA) therapeutics, several patients do not receive adequate treatment due to the toxicity and/or insufficient response of drugs. The aim of this study is to design photothermally controlled drug release from multifunctional nanoparticles (MNPs) at a near-infrared (NIR) irradiated site to improve therapeutic efficacy for RA and reduce side effects. METHODS: Au film was deposited onto methotrexate (MTX)-loaded poly(ethylene glycol)-poly(lactic-co-glycolic acid) (PLGA) nanoparticles, resulting in MTX-loaded MNPs. The synergistic effects of MTX-loaded MNPs with NIR irradiation were investigated using RA fibroblast-like synoviocytes (FLSs) and collagen-induced arthritis (CIA) mice. RESULTS: Upon NIR irradiation, NIR resonance of the Au half-shell generated heat locally, accelerating MTX release from PLGA nanoparticles. In vivo NIR images of MTX-loaded MNPs indicated effective delivery of the MNPs to the inflamed joints. Moreover, in collagen-induced arthritis mice, MTX-loaded MNPs containing 1/1400 of MTX solution (repeated-dose administration) had therapeutic effects comparable to conventional treatment with MTX solution. In vitro experiments showed higher therapeutic efficacy of MTX-loaded MNPs with NIR irradiation than that of chemotherapy alone. CONCLUSIONS: A combination therapy of MTX-loaded MNP and NIR irradiation showed durable and good treatment efficacy for the suppression of arthritis in a single administration of small dose of MTX. Our results demonstrate that the treatment modality using drug-loaded MNP with NIR irradiation may be a promising therapeutic strategy for the treatment of RA and allow in vivo NIR optical imaging.

Tunable Wettability of Graphene through Nondestructive Hydrogenation and Wettability-Based Patterning for Bioapplications.

The wettability of graphene has been extensively studied and successfully modified by chemical functionalization. Nevertheless, the unavoidable introduction of undesired defects and the absence of systematic and local control over wettability by previous methods have limited the use of graphene in applications. In addition, microscale patterning, according to wettability, has not been attempted. Here, we demonstrate that the wettability of graphene can be systematically controlled and surface patterned into microscale sections based on wettability without creating significant defects, possible by nondestructive hydrogen plasma. Hydrophobic graphene is progressively converted to hydrophilic hydrogenated graphene (H-Gr) that reaches superhydrophilicity. The great contrast in wettability between graphene and H-Gr makes it possible to selectively position and isolate human breast cancer cells on arrays of micropatterns since strong hydrophilicity facilitates the adsorption of the cells. We believe that our method will provide an essential technique for enabling surface and biological applications requiring microscale patterns with different wettability.

Vertical capacitance aptasensors for real-time monitoring of bacterial growth and antibiotic susceptibility in blood.

For the treatment of bacteremia, early diagnosis and rapid antibiotic susceptibility tests (ASTs) are necessary because survival chances decrease significantly if the proper antibiotic administration is delayed. However, conventional methods require several days from blood collection to AST as it requires three overnight cultures, including blood culture, subculture, and AST culture. Herein, we report a more rapid method of sensing bacterial growth and AST in blood based on a vertical capacitance sensor functionalized with aptamers. Owing to their vertical structure, the influence of blood cells sunk by gravity on capacitance measurements were minimized. Thus, bacterial growth in blood at 100-103 CFU/mL was monitored in real-time by measuring changes in capacitance at f = 10 kHz. Moreover, real-time capacitance measurements at f = 0.5 kHz provided information on biofilm formation induced during blood cultures. Bacterial growth and biofilm formation are inhibited above the minimal inhibitory concentration of antibiotics; therefore, we also demonstrated that vertical capacitance aptasensors could be applied to rapid AST from positive blood cultures without a need for the subculture process.

Multilevel MoS2 Optical Memory with Photoresponsive Top Floating Gates.

Optoelectronic memory devices, whose states can be controlled using electrical optical signals, are receiving much attention for their potential applications in image sensing and parallel data transmission and processes. Here, we report MoS2-based devices with top floating gates of Au, graphene, and MoS2. Unlike conventional floating gate memory devices, our devices have the photoresponsive floating gate at the top, acting as a charge trapping layer. Stable and reliable switching with an on/off ratio of ∼106 and a retention time of >104 s is achieved by illumination with 405 nm light pulses as well as application of gate voltage pulses. However, upon illumination with 532 or 635 nm light pulses, multilevel optical memory effects are observed, which are dependent on the wavelength and the optical exposure dosage. In addition, compared to the device employing a graphene floating gate, the device with an MoS2 floating gate is more sensitive to light, suggesting that the multilevel optical memory properties originate from photoexcited carriers in the top floating gate and can be modulated by adjusting the top floating gate materials. The structure of the top floating gate may open up a new way to novel optoelectronic memory devices.

Enhanced output performance on LbL multilayer PVDF-TrFE piezoelectric films for charging supercapacitor.

The piezoelectric nanogenerator (PENG) has the potential to become a promising power supply for monitoring and sensors in Internet of Things (IoT) systems through wireless networks. In order to further increase the utilization of energy harvesters in an IoT system, we introduce a novel approach that greatly enhances the piezoelectric output performances by employing the layer-by-layer (LbL) method. Poly(vinylidenefluoride-co-trifluoroethylene) (PVDF-TrFE) polymer film, which has piezoelectric properties and mechanical flexibility, was used for the active layer in PENG. The maximum open-circuit voltage and closed-circuit current of the LbL multilayer PENG reached 34 V and 100 nA, respectively. In particular, the closed-circuit current of the LbL multilayer PENG was dramatically improved to be five times higher than that of the single-layer PENG. Furthermore, a supercapacitor was employed to investigate the energy storage capability of PENGs using different methods. The proposed LbL multilayer PENG is expected to be a candidate for a promising power supply for self-powered systems in the IoT system.

Artificial Synaptic Emulators Based on MoS2 Flash Memory Devices with Double Floating Gates.

We fabricated MoS2-based flash memory devices by stacking MoS2 and hexagonal boron nitride (hBN) layers on an hBN/Au substrate and demonstrated that these devices can emulate various biological synaptic functions, including potentiation and depression processes, spike-rate-dependent plasticity, and spike-timing dependent plasticity. In particular, compared to a flash memory device prepared on an hBN substrate, the device fabricated on the hBN/Au exhibited considerably more symmetric and linear bidirectional gradual conductance change curves, which may be attributed to the device structure incorporating double floating gate. For the device on the hBN/Au, electron transfers may occur between the floating gate MoS2 and Au, as well as between the floating gate MoS2 and the channel MoS2, allowing for more control over electron tunneling and injection. To test our hypothesis, we also fabricated a MoS2-based flash memory device on an hBN/Pd substrate and found behavior similar to the device fabricated on hBN/Au. Our results demonstrate that flexible synaptic electronics may be implemented using MoS2-based flash memory devices with double floating gates.

Label-free and real-time monitoring of human mesenchymal stem cell differentiation in 2D and 3D cell culture systems using impedance cell sensors.

Three dimensional (3D) stem cell culture has recently received considerable attention because it may enable the development of in vitro 3D tissue models. In particular, label-free and real-time monitoring of stem cell differentiation is of importance for tissue engineering applications; however, only a few non-invasive monitoring methods are available, especially for 3D cell culture. Here, we describe impedance cell sensors that allowed the monitoring of cellular behaviors in 2D and 3D cell cultures in real-time. Specifically, apparent capacitance peaks appeared in both 2D and 3D cell culture systems when human mesenchymal stem cells (hMSCs) were cultured in osteogenic induction medium. In contrast, when hMSCs were cultured in adipogenic induction medium, the capacitance increased monotonically. In addition, distinct characteristics were noted in the plots of capacitance versus conductance for the cells cultured in osteogenic and adipocyte induction media. These results demonstrated that the differentiation of hMSCs toward osteoblasts and adipocytes in 2D and 3D cell culture systems could be discriminated non-invasively by measuring the real-time capacitance and conductance. Furthermore, the vertical distribution of cellular activities in 3D cell cultures could be monitored in real-time using the 3D impedance cell sensors. Thus, these sensors may be suitable for monitoring the differentiation of various stem cells into different types of cells with distinct dielectric properties for tissue engineering applications.

Aptamer-functionalized capacitance sensors for real-time monitoring of bacterial growth and antibiotic susceptibility.

To prevent spread of infection and antibiotic resistance, fast and accurate diagnosis of bacterial infection and subsequent administration of antimicrobial agents are important. However, conventional methods for bacterial detection and antibiotic susceptibility testing (AST) require more than two days, leading to delays that have contributed to an increase in antibiotic-resistant bacteria. Here, we report an aptamer-functionalized capacitance sensor array that can monitor bacterial growth and antibiotic susceptibility in real-time. While E. coli and S. aureus were cultured, the capacitance increased over time, and apparent bacterial growth curves were observed even when 10 CFU/mL bacteria was inoculated. Furthermore, because of the selectivity of aptamers, bacteria could be identified within 1h using the capacitance sensor array functionalized with aptamers. In addition to bacterial growth, antibiotic susceptibility could be monitored in real-time. When bacteria were treated with antibiotics above the minimum inhibitory concentration (MIC), the capacitance decreased because the bacterial growth was inhibited. These results demonstrate that the aptamer-functionalized capacitance sensor array might be applied for rapid ASTs.

Dielectric imaging for differentiation between cancer and inflammation in vivo.

In this study, we develop an in vivo dielectric imaging technique that measures capacitance using pin-type electrode arrays. Compared to normal tissues, cancer tissues exhibit higher capacitance values, allowing us to image the cancer region and monitor the chemotherapeutic effects of cancer in real-time. A comparison with the histopathological results shows that the in vivo dielectric imaging technique is able to detect small tumors (<3 mm) and tumor-associated changes. In addition, we demonstrate that cancer and inflammation may be distinguished by measuring the capacitance images at different frequencies. In contrast, the positron emission tomography using 2-[18F]-fluoro-2-deoxy-D-glucose was not capable of discriminating between cancer and inflammation.

Analysis of Tertiary Interactions between SART3 and U6 Small Nuclear RNA Using Modified Nanocapillaries.

We employed modified glass nanocapillaries to investigate interactions between the RNA-binding protein, known as cell carcinoma antigen recognized by T cells-3 (SART3), and the noncoding spliceosome component, U6 small nuclear RNA (snRNA), at the single-molecule level. We functionalized the nanocapillaries with U6 snRNA fragments, which were hybridized to DNA molecules and then covalently attached to the nanocapillary surface. When transported through the modified nanocapillaries, two different SART3-derived constructs, HAT-RRM1-RRM2 and RRM1-RRM2, exhibited resistive ionic current pulses with different dwell times, which represented their different binding affinities to tethered U6 snRNAs. The dissociation constants (KD), estimated from the bias voltage dependence of translocation events, were approximately 1.9 µM and 201 µM for HAT-RRM1-RRM2 and RRM1-RRM2, respectively. These values were comparable to corresponding values obtained with isothermal titration calorimetry, demonstrating that the modified glass nanocapillaries are applicable to analyses of protein-ligand interactions at the single-molecule level.

Mo1-xWxSe2-Based Schottky Junction Photovoltaic Cells.

We developed Schottky junction photovoltaic cells based on multilayer Mo1-xWxSe2 with x = 0, 0.5, and 1. To generate built-in potentials, Pd and Al were used as the source and drain electrodes in a lateral structure, and Pd and graphene were used as the bottom and top electrodes in a vertical structure. These devices exhibited gate-tunable diode-like current rectification and photovoltaic responses. Mo0.5W0.5Se2 Schottky diodes with Pd and Al electrodes exhibited higher photovoltaic efficiency than MoSe2 and WSe2 devices with Pd and Al electrodes, likely because of the greater adjusted band alignment in Mo0.5W0.5Se2 devices. Furthermore, we showed that Mo0.5W0.5Se2-based vertical Schottky diodes yield a power conversion efficiency of ∼16% under 532 nm light and ∼13% under a standard air mass 1.5 spectrum, demonstrating their remarkable potential for photovoltaic applications.