Photo-Assisted Ferroelectric Domain Control for α-In2Se3 Artificial Synapses Inspired by Spontaneous Internal Electric Fields.

α-In2Se3 semiconductor crystals realize artificial synapses by tuning in-plane and out-of-plane ferroelectricity with diverse avenues of electrical and optical pulses. While the electrically induced ferroelectricity of α-In2Se3 shows synaptic memory operation, the optically assisted synaptic plasticity in α-In2Se3 has also been preferred for polarization flipping enhancement. Here, the synaptic memory behavior of α-In2Se3 is demonstrated by applying electrical gate voltages under white light. As a result, the induced internal electric field is identified at a polarization flipped conductance channel in α-In2Se3/hexagonal boron nitride (hBN) heterostructure ferroelectric field effect transistors (FeFETs) under white light and discuss the contribution of this built-in electric field on synapse characterization. The biased dipoles in α-In2Se3 toward potentiation polarization direction by an enhanced internal built-in electric field under illumination of white light lead to improvement of linearity for long-term depression curves with proper electric spikes. Consequently, upon applying appropriate electric spikes to α-In2Se3/hBN FeFETs with illuminating white light, the recognition accuracy values significantly through the artificial learning simulation is elevated for discriminating hand-written digit number images.

Epitaxial Growth of Thin Ferroelectric Polymer Films on Graphene Layer for Fully Transparent and Flexible Nonvolatile Memory.

Enhancing the device performance of organic memory devices while providing high optical transparency and mechanical flexibility requires an optimized combination of functional materials and smart device architecture design. However, it remains a great challenge to realize fully functional transparent and mechanically durable nonvolatile memory because of the limitations of conventional rigid, opaque metal electrodes. Here, we demonstrate ferroelectric nonvolatile memory devices that use graphene electrodes as the epitaxial growth substrate for crystalline poly(vinylidene fluoride-trifluoroethylene) (PVDF-TrFE) polymer. The strong crystallographic interaction between PVDF-TrFE and graphene results in the orientation of the crystals with distinct symmetry, which is favorable for polarization switching upon the electric field. The epitaxial growth of PVDF-TrFE on a graphene layer thus provides excellent ferroelectric performance with high remnant polarization in metal/ferroelectric polymer/metal devices. Furthermore, a fully transparent and flexible array of ferroelectric field effect transistors was successfully realized by adopting transparent poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] semiconducting polymer.

Tunable Electrical and Optical Characteristics in Monolayer Graphene and Few-Layer MoS2 Heterostructure Devices.

Lateral and vertical two-dimensional heterostructure devices, in particular graphene-MoS2, have attracted profound interest as they offer additional functionalities over normal two-dimensional devices. Here, we have carried out electrical and optical characterization of graphene-MoS2 heterostructure. The few-layer MoS2 devices with metal electrode at one end and monolayer graphene electrode at the other end show nonlinearity in drain current with drain voltage sweep due to asymmetrical Schottky barrier height at the contacts and can be modulated with an external gate field. The doping effect of MoS2 on graphene was observed as double Dirac points in the transfer characteristics of the graphene field-effect transistor (FET) with a few-layer MoS2 overlapping the middle part of the channel, whereas the underlapping of graphene have negligible effect on MoS2 FET characteristics, which showed typical n-type behavior. The heterostructure also exhibits a strongest optical response for 520 nm wavelength, which decreases with higher wavelengths. Another distinct feature observed in the heterostructure is the peak in the photocurrent around zero gate voltage. This peak is distinguished from conventional MoS2 FETs, which show a continuous increase in photocurrent with back-gate voltage. These results offer significant insight and further enhance the understanding of the graphene-MoS2 heterostructure.

Temperature-dependent resonance energy transfer from semiconductor quantum wells to graphene.

Resonance energy transfer (RET) has been employed for interpreting the energy interaction of graphene combined with semiconductor materials such as nanoparticles and quantum-well (QW) heterostructures. Especially, for the application of graphene as a transparent electrode for semiconductor light emitting diodes, the mechanism of exciton recombination processes such as RET in graphene-semiconductor QW heterojunctions should be understood clearly. Here, we characterized the temperature-dependent RET behaviors in graphene/semiconductor QW heterostructures. We then observed the tuning of the RET efficiency from 5% to 30% in graphene/QW heterostructures with ∼60 nm dipole-dipole coupled distance at temperatures of 300 to 10 K. This survey allows us to identify the roles of localized and free excitons in the RET process from the QWs to graphene as a function of temperature.

Flexible and transparent gas molecule sensor integrated with sensing and heating graphene layers.

Graphene leading to high surface-to-volume ratio and outstanding conductivity is applied for gas molecule sensing with fully utilizing its unique transparent and flexible functionalities which cannot be expected from solid-state gas sensors. In order to attain a fast response and rapid recovering time, the flexible sensors also require integrated flexible and transparent heaters. Here, large-scale flexible and transparent gas molecule sensor devices, integrated with a graphene sensing channel and a graphene transparent heater for fast recovering operation, are demonstrated. This combined all-graphene device structure enables an overall device optical transmittance that exceeds 90% and reliable sensing performance with a bending strain of less than 1.4%. In particular, it is possible to classify the fast (≈14 s) and slow (≈95 s) response due to sp(2) -carbon bonding and disorders on graphene and the self-integrated graphene heater leads to the rapid recovery (≈11 s) of a 2 cm × 2 cm sized sensor with reproducible sensing cycles, including full recovery steps without significant signal degradation under exposure to NO2 gas.

Graphene-based plasmonic photodetector for photonic integrated circuits.

We developed a planar-type graphene-based plasmonic photodetector (PD) for the development of all-graphene photonic-integrated-circuits (PICs). By configuring the graphene plasmonic waveguide and PD structure all-in-one, the proposed graphene PD detects horizontally incident light. The photocurrent profile with opposite polarity is the maximum at graphene-electrode interfaces due to a Schottky-like barrier effect at the interface. The photocurrent amplitude increases with an increase of the graphene-metal interface length. Obtaining time constants of less than 39.7 ms for the time response, we concluded that the proposed graphene PD could be exploited further for application in all graphene-based PICs.

Immunogenicity and safety of concomitant bivalent COVID-19 and quadrivalent influenza vaccination: implications of immune imprinting and interference.

OBJECTIVES: Concomitant COVID-19 and influenza vaccination would be an efficient strategy. Although the co-administration of monovalent COVID-19 and influenza vaccinations showed acceptable immunogenicity, it remains unknown whether the bivalent COVID-19 vaccine could intensify immune interference. We aimed to evaluate the immunogenicity and safety of concomitant BA.5-based bivalent COVID-19 and influenza vaccination. METHODS: An open-label, nonrandomized clinical trial was conducted for 154 age-matched and sex-matched healthy adults between October 2022 and December 2022. Participants received either a concomitant bivalent COVID-19 mRNA booster and quadrivalent influenza vaccination (group C) or separate vaccinations (group S) at least 4 weeks apart. Solicited and unsolicited adverse events were reported up to 6 months postvaccination. Immunogenicity was evaluated by anti-spike (S) IgG electrochemiluminescence immunoassay, focus reduction neutralization test, and hemagglutination inhibition assay. RESULTS: Group C did not meet the noninferiority criteria for the seroconversion rates of anti-S IgG and neutralizing antibodies against the wild-type SARS-CoV-2 strain compared with group S (44.2% vs. 46.8%, difference of -2.6% [95% CI, -18 to 13.4]; 44.2% vs. 57.1%, difference of -13.0% [95% CI to -28.9 to 2.9]). However, group C showed a stronger postvaccination neutralizing antibody response against Omicron BA.5 (72.7% vs. 64.9%). Postvaccination geometric mean titers for SARS-CoV-2 and influenza strains were similar between groups, except for influenza B/Victoria. Most adverse events were mild and comparable between the study groups. DISCUSSION: Concomitant administration of bivalent COVID-19 mRNA and quadrivalent influenza vaccines showed tolerable safety profiles and sufficient immunogenicity, particularly attenuating immune imprinting induced by previous ancestral vaccine strains.

Graphene transparent electrode for enhanced optical power and thermal stability in GaN light-emitting diodes.

We report an improvement of the optical power and thermal stability of GaN LEDs using a chemically doped graphene transparent conducting layer (TCL) and a low-resistance contact structure. In order to obtain low contact resistance between the TCL and p-GaN surface, a patterned graphene TCL with Cr/Au electrodes is suggested. A bi-layer patterning method of a graphene TCL was utilized to prevent the graphene from peeling off the p-GaN surface. To improve the work function and the sheet resistance of graphene, CVD (chemical vapor deposition) graphene was doped by a chemical treatment using a HNO(3) solution. The effect of the contact resistance on the power degradation of LEDs at a high injection current level was investigated. In addition, the enhancement of the optical power via an increase in the current spreading and a decrease in the potential barrier of the graphene TCL was investigated.

Water-gated charge doping of graphene induced by mica substrates.

We report on the existence of water-gated charge doping of graphene deposited on atomically flat mica substrates. Molecular films of water in units of ~0.4 nm thick bilayers were found to be present in regions of the interface of graphene/mica heterostacks prepared by micromechanical exfoliation of kish graphite. The spectral variation of the G and 2D bands, as visualized by Raman mapping, shows that mica substrates induce strong p-type doping in graphene with hole densities of (9 ± 2) × 10(12) cm(-2). The ultrathin water films, however, effectively block interfacial charge transfer, rendering graphene significantly less hole-doped. Scanning Kelvin probe microscopy independently confirmed a water-gated modulation of the Fermi level by 0.35 eV, which is in agreement with the optically determined hole density. The manipulation of the electronic properties of graphene demonstrated in this study should serve as a useful tool in realizing future graphene applications.

Gate-Tuned Gas Molecule Sensitivity of a Two-Dimensional Semiconductor.

In this work, we develop a gate-tunable gas sensor based on a MoS2/hBN heterostructure field effect transistor. Through experimental measurements and numerical simulations, we systematically reveal a principle that relates the concentration of the target gas and sensing signals (ΔI/I0) as a function of gate bias. Because a linear relationship between ΔI/I0 and the gas concentration guarantees reliable sensor operation, the optimal gate bias condition for linearity was investigated. Taking NO2 and NH3 as target molecules, it is clarified that the bias condition greatly depends on the electron accepting/donating nature of the gas. The effects of the bandgap and polarity of the transition metal dichalcogenides (TMDC) channel are also discussed. In order to achieve linearly increasing signals that are stable with respect to the gas concentration, a sufficiently large VBG within VBG > 0 is required. We expect this work will shed light on a way to precisely design reliable semiconducting gas sensors based on the characteristics of TMDC and target gas molecules.

Atmospheric oxygen binding and hole doping in deformed graphene on a SiO2 substrate.

Using micro-Raman spectroscopy and scanning tunneling microscopy, we study the relationship between structural distortion and electrical hole doping of graphene on a silicon dioxide substrate. The observed upshift of the Raman G band represents charge doping and not compressive strain. Two independent factors control the doping: (1) the degree of graphene coupling to the substrate and (2) exposure to oxygen and moisture. Thermal annealing induces a pronounced structural distortion due to close coupling to SiO2 and activates the ability of diatomic oxygen to accept charge from graphene. Gas flow experiments show that dry oxygen reversibly dopes graphene; doping becomes stronger and more irreversible in the presence of moisture and over long periods of time. We propose that oxygen molecular anions are stabilized by water solvation and electrostatic binding to the silicon dioxide surface.

Tuning the graphene work function by electric field effect.

We report variation of the work function for single and bilayer graphene devices measured by scanning Kelvin probe microscopy (SKPM). By use of the electric field effect, the work function of graphene can be adjusted as the gate voltage tunes the Fermi level across the charge neutrality point. Upon biasing the device, the surface potential map obtained by SKPM provides a reliable way to measure the contact resistance of individual electrodes contacting graphene.

Direct Mapping of the Gate Response of a Multilayer WSe2/MoS2 Heterostructure with Locally Different Degrees of Charge Depletion.

Understanding the interlayer charge coupling mechanism in a two-dimensional van der Waals (vdW) heterojunction is crucial for optimizing the performance of heterostructure-based (opto)electronic devices. Here, we report mapping the gate response of a multilayer WSe2/MoS2 heterostructure with locally different degrees of charge depletion through mobile carrier measurements based on electrostatic force microscopy. We observed ambipolar or unipolar behavior depending on the degree of charge depletion in the heterojunction under tip gating. Interestingly, the WSe2 on MoS2 shows gating behavior that is more efficient than that on the SiO2/Si substrate, which can be explained by the high dielectric environment and screening of impurities on the SiO2 surface by the MoS2. Furthermore, we found that the gate-induced majority carriers in the heterojunction reduce the carrier lifetime, leading to the enhanced interlayer recombination of the photogenerated carriers under illumination. Our work provides a comprehensive understanding of the interfacial phenomena at the vdW heterointerface with charge depletion.

Gate-tuned conductance of graphene-ribbon junctions with nanoscale width variations.

To utilize graphene as interconnection electrodes in high-density nanoelectronic structures, the electrical stability of graphene should be guaranteed under nanometer-scale deviations. Graphene-ribbon (GR) junctions with accessible dimensions (i.e., sub-micrometer widths) are used in diverse interconnection electrode applications and should be characterized properly if they are to be applied in high-density nanoelectronics. Analyzing the effects of nanoscale GR width variations on the conductance of the entire graphene electrode is necessary for their proper characterization. Here, we diagnose the conductance and thermal effect of graphene electrode junctions constructed from GRs of various widths and directions under gate-tuned voltages. On applying partial gate voltages, we identify the effect of local potential variance on the entire graphene electrode junction. As a result, we were able to perceive precise and minute conductance variations for the entire graphene electrode, arising mainly from different sub-micrometer-scale widths of the GRs, which could not be distinguished using conventional global gating methods.

High Efficiency and Long Lifetime of a Fluorescent Blue-Light Emitter Made of a Pyrene Core and Optimized Side Groups.

In this study, four emitters of blue light are synthesized by selecting pyrene with its high photoluminescence quantum yield (PLQY) as the core group and variants of the electron-donating diphenylamine (DPA) as side groups. The four compounds have different numbers, sizes, and substitution positions of alkyl groups on the DPA. Each of the four compounds when doped in OLED devices shows a high current efficiency (CE) of over 7 cd A-1 and a high external quantum efficiency (EQE) of over 7.5%. In addition, the compounds yield electroluminescence (EL) spectra showing peaks with narrow full width at half-maximum (fwhm) values of 37-40 nm and hence indicative of high color purity. Moreover, one compound N1,N6-bis(5-( tert-butyl)-2-methylphenyl)-N1,N6-bis(2,4-dimethylphenyl)pyrene-1,6-diamine (3Me-1Bu-TPPDA), shows a very high EQE of 9.25% and a very long lifetime with an LT95 of 471 h.

Layer number identification of CVD-grown multilayer graphene using Si peak analysis.

Since the successful exfoliation of graphene, various methodologies have been developed to identify the number of layers of exfoliated graphene. The optical contrast, Raman G-peak intensity, and 2D-peak line-shape are currently widely used as the first level of inspection for graphene samples. Although the combination analysis of G- and 2D-peaks is powerful for exfoliated graphene samples, its use is limited in chemical vapor deposition (CVD)-grown graphene because CVD-grown graphene consists of various domains with randomly rotated crystallographic axes between layers, which makes the G- and 2D-peaks analysis difficult for use in number identification. We report herein that the Raman Si-peak intensity can be a universal measure for the number identification of multilayered graphene. We synthesized a few-layered graphene via the CVD method and performed Raman spectroscopy. Moreover, we measured the Si-peak intensities from various individual graphene domains and correlated them with the corresponding layer numbers. We then compared the normalized Si-peak intensity of the CVD-grown multilayer graphene with the exfoliated multilayer graphene as a reference and successfully identified the layer number of the CVD-grown graphene. We believe that this Si-peak analysis can be further applied to various 2-dimensional (2D) materials prepared by both exfoliation and chemical growth.

Thickness-dependent Schottky barrier height of MoS2 field-effect transistors.

2D semiconductors, including transition metal dichalcogenides (TMDs), have been widely studied recently. However, the device performance is deteriorated due to the significant contact resistance. The contact resistance of MoS2-metal contacts decreases with the thickness of MoS2. We obtained a Schottky barrier height as low as about 70 meV when MoS2 is trilayer-thick. It is important to find the optimal choice of contact metal and layer thickness of MoS2.

Epitaxially Self-Assembled Alkane Layers for Graphene Electronics.

The epitaxially grown alkane layers on graphene are prepared by a simple drop-casting method and greatly reduce the environmentally driven doping and charge impurities in graphene. Multiscale simulation studies show that this enhancement of charge homogeneity in graphene originates from the lifting of graphene from the SiO2 surface toward the well-ordered and rigid alkane self-assembled layers.

Gas molecule sensing of van der Waals tunnel field effect transistors.

van der Waals (vdW) heterostructures with two-dimensional (2D) crystals such as graphene, hexagonal boron nitride (hBN) and transition metal dichalcogenides (TMDCs) allow us to demonstrate atomically thin field-effect transistors (FETs), photodetectors (PDs) and photovoltaic devices capable of higher performance and greater stability levels than conventional devices. Although there have been studies of gas molecule sensing with 2D crystal channels, vdW heterostructures based on 2D crystals have not been employed thus far. Here, utilizing graphene/WS2/graphene (G/WS2/G) vdW heterostructure tunnel FETs, we demonstrate the rectification behavior of the sensitivity signal by tuning the WS2 potential barriers as a function of the gas molecule concentration and devise a fingerprint map of the sensitivity variation corresponding to an individual ratio of two different molecules in a gas mixture. Because the separation of different gas molecule concentrations from gas mixtures is in high demand in the gas-sensing research field, this result will greatly assist in the progress on selective gas sensing.

Hardening by cooling rate control and post-firing heat treatment in Pd-Ag-Sn alloy for bonding porcelain.

The aim of this study was to determine the hardening effect by controlling the cooling rate during the porcelain firing process and performing an additional post-firing heat treatment in a Pd-Ag-Sn alloy. The most effective cooling rate for alloy hardening was determined by cooling the specimens at various cooling rates after oxidation treatment. A subsequent porcelain firing simulation followed by cooling at the selected cooling rate was performed. A post-firing heat treatment was then done at 600°C in a porcelain furnace. The hardening mechanism was characterized by a hardness test, X-ray diffraction, field emission scanning electron microscopy and energy dispersive X-ray spectroscopy. Alloy softening occurred during the porcelain firing process followed by cooling at a controlled cooling rate. A post-firing heat treatment allowed apparent precipitation hardening. It is advisable to perform a postfiring heat treatment at 600°C in a porcelain furnace by annealing metal substructure after porcelain fusing.