Reinforcing Synaptic Plasticity of Defect-Tolerant States in Alloyed 2D Artificial Transistors.

While two-dimensional (2D) materials possess the desirable future of neuromorphic computing platforms, unstable charging and de-trapping processes, which are inherited from uncontrollable states, such as the interface trap between nanocrystals and dielectric layers, can deteriorate the synaptic plasticity in field-effect transistors. Here, we report a facile and effective strategy to promote artificial synaptic devices by providing physical doping in 2D transition-metal dichalcogenide nanomaterials. Our experiments demonstrate that the introduction of niobium (Nb) into 2D WSe2 nanomaterials produces charge trap levels in the band gap and retards the decay of the trapped charges, thereby accelerating the artificial synaptic plasticity by encouraging improved short-/long-term plasticity, increased multilevel states, lower power consumption, and better symmetry and asymmetry ratios. Density functional theory calculations also proved that the addition of Nb to 2D WSe2 generates defect tolerance levels, thereby governing the charging and de-trapping mechanisms of the synaptic devices. Physically doped electronic synapses are expected to be a promising strategy for the development of bioinspired artificial electronic devices.

Drug classification with a spectral barcode obtained with a smartphone Raman spectrometer.

Measuring, recording and analyzing spectral information of materials as its unique finger print using a ubiquitous smartphone has been desired by scientists and consumers. We demonstrated it as drug classification by chemical components with smartphone Raman spectrometer. The Raman spectrometer is based on the CMOS image sensor of the smartphone with a periodic array of band pass filters, capturing 2D Raman spectral intensity map, newly defined as spectral barcode in this work. Here we show 11 major components of drugs are classified with high accuracy, 99.0%, with the aid of convolutional neural network (CNN). The beneficial of spectral barcodes is that even brand name of drug is distinguishable and major component of unknown drugs can be identified. Combining spectral barcode with information obtained by red, green and blue (RGB) imaging system or applying image recognition techniques, this inherent property based labeling system will facilitate fundamental research and business opportunities.

Glasswing-Butterfly-Inspired Multifunctional Scleral Lens and Smartphone Raman Spectrometer for Point-of-Care Tear Biomarker Analysis.

Augmenting contact lenses with sensing capabilities requires incorporating multiple functionalities within a diminutive device. Inspired by multifunctional biophotonic nanostructures of glasswing butterflies, a nanostructured scleral lens with enhanced optical, bactericidal, and sensing capabilities is reported. When used in conjunction with a smartphone-integrated Raman spectrometer, the feasibility of point-of-care applications is demonstrated. The bioinspired nanostructures made on parylene films are mounted on the anterior and posterior side of a scleral lens to create a nanostructured lens. Compared to unstructured parylene, nanostructured parylene minimizes glare by 4.3-fold at large viewing angles up to 80o . When mounted on a scleral lens, the nanostructures block 2.8-fold more ultraviolet (UVA) light while offering 1.1-fold improved transmission in the visible regime. Furthermore, the nanostructures exhibit potent bactericidal activity against Escherichia coli, killing 89% of tested bacteria within 4 h. The same nanostructures, when gold-coated, are used to perform rapid label-free multiplex detection of lysozyme and lactoferrin, the protein biomarkers of the chronic dry eye disease, in whole human tears using drop-coating deposition Raman spectroscopy. The detection of both proteins in whole human tear samples from different subjects using the nanostructured lens produced excellent correlation with commercial enzyme-based assays while simultaneously displaying a 1.5-fold lower standard deviation.

Two-dimensional Dirac plasmon-polaritons in graphene, 3D topological insulator and hybrid systems.

Collective oscillations of massless particles in two-dimensional (2D) Dirac materials offer an innovative route toward implementing atomically thin devices based on low-energy quasiparticle interactions. Strong confinement of near-field distribution on the 2D surface is essential to demonstrate extraordinary optoelectronic functions, providing means to shape the spectral response at the mid-infrared (IR) wavelength. Although the dynamic polarization from the linear response theory has successfully accounted for a range of experimental observations, a unified perspective was still elusive, connecting the state-of-the-art developments based on the 2D Dirac plasmon-polaritons. Here, we review recent works on graphene and three-dimensional (3D) topological insulator (TI) plasmon-polariton, where the mid-IR and terahertz (THz) radiation experiences prominent confinement into a deep-subwavelength scale in a novel optoelectronic structure. After presenting general light-matter interactions between 2D Dirac plasmon and subwavelength quasiparticle excitations, we introduce various experimental techniques to couple the plasmon-polaritons with electromagnetic radiations. Electrical and optical controls over the plasmonic excitations reveal the hybridized plasmon modes in graphene and 3D TI, demonstrating an intense near-field interaction of 2D Dirac plasmon within the highly-compressed volume. These findings can further be applied to invent optoelectronic bio-molecular sensors, atomically thin photodetectors, and laser-driven light sources.

Visualizing Line Defects in non-van der Waals Bi2O2Se Using Raman Spectroscopy.

Atomic-layered materials, such as high-quality bismuth oxychalcogenides, which are composed of oppositely charged alternate layers grown using chemical vapor deposition, have attracted considerable attention. Their physical properties are well-suited for high-speed, low-power-consumption optoelectronic devices, and the rapid determination of their crystallographic characteristics is crucial for scalability and integration. In this study, we introduce how the crystallographic structure and quality of such materials can be projected through Raman spectroscopy analysis. Frequency modes at ∼55, ∼78, ∼360, and ∼434 cm-1 were detected, bearing out theoretical calculations from the literature. The low-frequency modes positioned at 55 and 78 cm-1 were activated by structural defects, such as grain boundaries and O-rich edges in the Bi2O2Se crystals, accompanied by sensitivity to the excitation energy. Furthermore, the line defects at ∼55 cm-1 exhibited a strong 2-fold polarization dependence, similar to graphene/graphite edges. Our results can help illuminate the mechanism for activating the Raman-active mode from the infrared active mode by defects, as well as the electronic structures of these two-dimensional layered materials. We also suggest that the nanoscale width line defects in Bi2O2Se can be visualized using Raman spectroscopy.

Gate-controlled gas sensor utilizing 1D-2D hybrid nanowires network.

Novel gas sensors that work at room temperature are attracting attention due to their low energy consumption and stability in the presence of toxic gases. However, the development of sensing characteristics at room temperature is still a primary challenge. Diverse reaction pathways and low adsorption energy for gas molecules are required to fabricate a gas sensor that works at room temperature with high sensitivity, selectivity, and efficiency. Therefore, we enhanced the gas sensing performance at room temperature by constructing hybridized nanostructure of 1D-2D hybrid of SnSe2 layers and SnO2 nanowire networks and by controlling the back-gate bias (Vg = 1.5 V). The response time was dramatically reduced by lowering the energy barrier for the adsorption on the reactive sites, which are controlled by the back gate. Consequently, we believe that this research could contribute to improving the performance of gas sensors that work at room temperature.

Bandgap Engineering in 2D Lateral Heterostructures of Transition Metal Dichalcogenides via Controlled Alloying.

2D heterostructures made of transition metal dichalcogenides (TMD) have emerged as potential building blocks for new-generation 2D electronics due to their interesting physical properties at the interfaces. The bandgap, work function, and optical constants are composition dependent, and the spectrum of applications can be expanded by producing alloy-based heterostructures. Herein, the successful synthesis of monolayer and bilayer lateral heterostructures, based on ternary alloys of MoS2(1- x ) Se2 x -WS2(1- x ) Se2 x , is reported by modifying the ratio of the source precursors; the bandgaps of both materials in the heterostructure are continuously tuned in the entire range of chalcogen compositions. Raman and photoluminescence (PL) spatial maps show good intradomain composition homogeneity. Kelvin probe measurements in different heterostructures reveal composition-dependent band alignments, which can further be affected by unintentional electronic doping during the growth. The fabrication of sequential multijunction lateral heterostructures with three layers of thickness, composed of quaternary and ternary alloys, is also reported. These results greatly expand the available tools kit for optoelectronic applications in the 2D realm.

Accelerated Learning in Wide-Band-Gap AlN Artificial Photonic Synaptic Devices: Impact on Suppressed Shallow Trap Level.

Artificial synaptic platforms are promising for next-generation semiconductor computing devices; however, state-of-the-art optoelectronic approaches remain challenging, owing to their unstable charge trap states and limited integration. We demonstrate wide-band-gap (WBG) III-V materials for photoelectronic neural networks. Our experimental analysis shows that the enhanced crystallinity of WBG synapses promotes better synaptic characteristics, such as effective multilevel states, a wider dynamic range, and linearity, allowing the better power consumption, training, and recognition accuracy of artificial neural networks. Furthermore, light-frequency-dependent memory characteristics suggest that artificial optoelectronic synapses with improved crystallinity support the transition from short-term potentiation to long-term potentiation, implying a clear emulation of the psychological multistorage model. This is attributed to the charge trapping in deep-level states and suppresses fast decay and nonradiative recombination in shallow traps. We believe that the fingerprints of these WBG synaptic characteristics provide an effective strategy for establishing an artificial optoelectronic synaptic architecture for innovative neuromorphic computing.

Facile Morphological Qualification of Transferred Graphene by Phase-Shifting Interferometry.

Post-growth graphene transfer to a variety of host substrates for circuitry fabrication has been among the most popular subjects since its successful development via chemical vapor deposition in the past decade. Fast and reliable evaluation tools for its morphological characteristics are essential for the development of defect-free transfer protocols. The implementation of conventional techniques, such as Raman spectroscopy, atomic force microscopy (AFM), and transmission electron microscopy in production quality control at an industrial scale is difficult because they are limited to local areas, are time consuming, and their operation is complex. However, through a one-shot measurement within a few seconds, phase-shifting interferometry (PSI) successfully scans ≈1 mm2 of transferred graphene with a vertical resolution of ≈0.1 nm. This provides crucial morphological information, such as the surface roughness derived from polymer residues, the thickness of the graphene, and its adhesive strength with respect to the target substrates. Graphene samples transferred via four different methods are evaluated using PSI, Raman spectroscopy, and AFM. Although the thickness of the nanomaterials measured by PSI can be highly sensitive to their refractive indices, PSI is successfully demonstrated to be a powerful tool for investigating the morphological characteristics of the transferred graphene for industrial and research purposes.

Time Evolution Studies on Strain and Doping of Graphene Grown on a Copper Substrate Using Raman Spectroscopy.

The enhanced growth of Cu oxides underneath graphene grown on a Cu substrate has been of great interest to many groups. In this work, the strain and doping status of graphene, based on the gradual growth of Cu oxides from underneath, were systematically studied using time evolution Raman spectroscopy. The compressive strain to graphene, due to the thermal expansion coefficient difference between graphene and the Cu substrate, was almost released by the nonuniform Cu2O growth; however, slight tensile strain was exerted. This induced p-doping in the graphene with a carrier density up to 1.7 × 1013 cm-2 when it was exposed to air for up to 30 days. With longer exposure to ambient conditions (>1 year), we observed that graphene/Cu2O hybrid structures significantly slow down the oxidation compared to that using a bare Cu substrate. The thickness of the CuO layer on the bare Cu substrate was increased to approximately 270 nm. These findings were confirmed through white light interference measurements and scanning electron microscopy.

Anomalous K-Point Phonons in Noble Metal/Graphene Heterostructure Activated by Localized Surface Plasmon Resonance.

The metal/graphene interface has been one of the most important research topics with regard to charge screening, charge transfer, contact resistance, and solar cells. Chemical bond formation of metal and graphene can be deduced from the defect induced D-band and its second-order mode, 2D band, measured by Raman spectroscopy, as a simple and nondestructive method. However, a phonon mode located at ∼1350 cm-1, which is normally known as the defect-induced D-band, is intriguing for graphene deposited with noble metals (Ag, Au, and Cu). We observe anomalous K-point phonons in nonreactive noble metal/graphene heterostructures. The intensity ratio of the midfrequency mode at ∼1350 cm-1 over G-band (∼1590 cm-1) exhibits nonlinear but resonant behavior with the excitation laser wavelength, and more importantly, the phonon frequency-laser energy dispersion is ∼10-17 cm-1 eV-1, which is much less than the conventional range. These phonon modes of graphene at nonzero phonon wave vector (q ≠ 0) around K points are activated by localized surface plasmon resonance and not by the defects due to chemical bond formation of metal/graphene. This hypothesis is supported by density functional theory (DFT) calculations for noble metals and Cr along with the measured contact resistances.

Misorientation-Angle-Dependent Phase Transformation in van der Waals Multilayers via Electron-Beam Irradiation.

Misorientation-angle dependence on layer thickness is an intriguing feature of van der Waals materials, which causes stark optical gain and electrical transport modulation. However, the influence of misorientation angle on phase transformation is not determined yet. Herein, this phenomenon in a MoS2 multilayer via in situ electron-beam irradiation is reported. An AA'-stacked MoS2 bilayer undergoes structural transformation from the 2H semiconducting phase to the 1T' metallic phase, similar to a MoS2 monolayer, which is confirmed via in situ transmission electron microscopy. Moreover, non-AA' stacking, which has no local AA' stacking order in the Moiré pattern, does not reveal such a phase transformation. While a collective sliding motion of chalcogen atoms easily occurs during the transformation in AA' stacking, in non-AA' stacking it is suppressed by the weak van der Waals strength and by the chalcogen atoms interlocked at different orientations, which disfavor their kinetics by the increased entropy of mixing.

Metasurface electrode light emitting diodes with planar light control.

The ability of metasurfaces to manipulate light at the subwavelength scale offers unprecedented functionalities for passive and active lasing devices. However, applications of metasurfaces to optical devices are rare due to fabrication difficulties. Here, we present quantum dot light emitting diodes (QDLEDs) with a metasurface-integrated metal electrode and demonstrate microscopically controlled LED emission. By incorporating slot-groove antennas into the metal electrode, we show that LED emission from randomly polarized QD sources can be polarized and directed at will. Utilizing the relation between polarization and emission direction, we also demonstrate microscopic LED beam splitting through the selective choice of polarization.

Realization of continuous Zachariasen carbon monolayer.

Rapid progress in two-dimensional (2D) crystalline materials has recently enabled a range of device possibilities. These possibilities may be further expanded through the development of advanced 2D glass materials. Zachariasen carbon monolayer, a novel amorphous 2D carbon allotrope, was successfully synthesized on germanium surface. The one-atom-thick continuous amorphous layer, in which the in-plane carbon network was fully sp2-hybridized, was achieved at high temperatures (>900°C) and a controlled growth rate. We verified that the charge carriers within the Zachariasen carbon monolayer are strongly localized to display Anderson insulating behavior and a large negative magnetoresistance. This new 2D glass also exhibited a unique ability as an atom-thick interface layer, allowing the deposition of an atomically flat dielectric film. It can be adopted in conventional semiconductor and display processing or used in the fabrication of flexible devices consisting of thin inorganic layers.

Optical Gain in MoS2 via Coupling with Nanostructured Substrate: Fabry-Perot Interference and Plasmonic Excitation.

Despite the direct band gap of monolayer transition metal dichalcogenides (TMDs), their optical gain remains limited because of the poor light absorption in atomically thin, layered materials. Most approaches to improve the optical gain of TMDs mainly involve modulation of the active materials or multilayer stacking. Here, we report a method to enhance the optical absorption and emission in MoS2 simply through the design of a nanostructured substrate. The substrate consisted of a dielectric nanofilm spacer (TiO2) and metal film. The overall photoluminescence intensity from monolayer MoS2 on the nanostructured substrate was engineered based on the TiO2 thickness and amplified by Fabry-Perot interference. In addition, the neutral exciton emission was selectively amplified by plasmonic excitations from the local field originating from the surface roughness of the metal film with spacer thicknesses of less than 10 nm. We further demonstrate that the quality factor of the device can also be engineered by selecting a spacer material with a different refractive index.

Electric Characteristics of the Carbon Nanotube Network Transistor with Directly Grown ZnO Nanoparticles.

We report on the electrical characteristics of field effect transistors fabricated with random networks of single-walled carbon nanotubes with surfaces modified by ZnO nanoparticles. ZnO nanoparticles are directly grown on single-walled carbon nanotubes by atomic layer deposition using diethylzinc (DEZ) and water. Electrical observations show that ZnO nanoparticles act as charge transfer sources that provide electrons to the nanotube channel. The valley position in ambipolar transport of nanotube transistors is negatively shifted for 3V due to the electronic n-typed property of ZnO nanoparticles. However, the Raman resonance remains invariant despite the charge transfer effect produced by ZnO nanoparticles.

Conductive network formation of carbon nanotubes in elastic polymer microfibers and its effect on the electrical conductance: Experiment and simulation.

We investigate how the electrical conductance of microfibers (made of polymers and conductive nanofillers) decreases upon uniaxial deformation by performing both experiments and simulations. Even though various elastic conductors have been developed due to promising applications for deformable electronic devices, the mechanism at a molecular level for electrical conductance change has remained elusive. Previous studies proposed that the decrease in electrical conductance would result from changes in either distances or contact numbers between conductive fillers. In this work, we prepare microfibers of single walled carbon nanotubes (SWCNTs)/polyvinyl alcohol composites and investigate the electrical conductance and the orientation of SWCNTs upon uniaxial deformation. We also perform extensive Monte Carlo simulations, which reproduce experimental results for the relative decrease in conductance and the SWCNTs orientation. We investigate the electrical networks of SWCNTs in microfibers and find that the decrease in the electrical conductance upon uniaxial deformation should be attributed to a subtle change in the topological structure of the electrical network.

Large Work Function Modulation of Monolayer MoS2 by Ambient Gases.

Although two-dimensional monolayer transition-metal dichalcogenides reveal numerous unique features that are inaccessible in bulk materials, their intrinsic properties are often obscured by environmental effects. Among them, work function, which is the energy required to extract an electron from a material to vacuum, is one critical parameter in electronic/optoelectronic devices. Here, we report a large work function modulation in MoS2 via ambient gases. The work function was measured by an in situ Kelvin probe technique and further confirmed by ultraviolet photoemission spectroscopy and theoretical calculations. A measured work function of 4.04 eV in vacuum was converted to 4.47 eV with O2 exposure, which is comparable with a large variation in graphene. The homojunction diode by partially passivating a transistor reveals an ideal junction with an ideality factor of almost one and perfect electrical reversibility. The estimated depletion width obtained from photocurrent mapping was ∼200 nm, which is much narrower than bulk semiconductors.

Visualizing Point Defects in Transition-Metal Dichalcogenides Using Optical Microscopy.

While transmission electron microscopy and scanning tunneling microscopy reveal atomic structures of point defect and grain boundary in monolayer transition-metal dichalcogenides (TMDs), information on point defect distribution in macroscale is still not available. Herein, we visualize the point defect distribution of monolayer TMDs using dark-field optical microscopy. This was realized by anchoring silver nanoparticles on defect sites of MoS2 under light illumination. The optical images clearly revealed that the point defect distribution varies with light power and exposure time. The number of silver nanoparticles increased initially and reached a plateau in response to light power or exposure time. The size of silver nanoparticles was a few hundred nanometers in the plateau region as observed using optical microscopy. The measured defect density in macroscale was ∼2 × 10(10) cm(-2), slightly lower than the observed value (4 × 10(11) cm(-2)) from scanning tunneling microscopy.