Hybridized Radial and Edge Coupled 3D Plasmon Modes in Self-Assembled Graphene Nanocylinders.

Current graphene-based plasmonic devices are restricted to 2D patterns defined on planar substrates; thus, they suffer from spatially limited 2D plasmon fields. Here, 3D graphene forming freestanding nanocylinders realized by a plasma-triggered self-assembly process are introduced. The graphene-based nanocylinders induce hybridized edge (in-plane) and radial (out-of-plane) coupled 3D plasmon modes stemming from their curvature, resulting in a four orders of magnitude stronger field at the openings of the cylinders than in rectangular 2D graphene ribbons. For the characterization of the 3D plasmon modes, synchrotron nanospectroscopy measurements are performed, which provides the evidence of preservation of the hybridized 3D graphene plasmons in the high precision curved nanocylinders. The distinct 3D modes introduced in this paper, provide an insight into geometry-dependent 3D coupled plasmon modes and their ability to achieve non-surface-limited (volumetric) field enhancements.

Growth of black arsenic phosphorus thin films and its application for field-effect transistors.

Black arsenic phosphorus single crystals were grown using a short-way transport technique resulting in crystals up to 12 × 110µmand ranging from 200 nm to 2µmthick. The reaction conditions require tin, tin (IV) iodide, gray arsenic, and red phosphorus placed in an evacuated quartz ampule and ramped up to a maximum temperature of 630 °C. The crystal structure and elemental composition were characterized using Raman spectroscopy, x-ray diffraction, and x-ray photoelectron spectroscopy, cross-sectional transmission microscopy, and electron backscatter diffraction. The data provides valuable insight into the growth mechanism. A previously developed b-P thin film growth technique can be adapted to b-AsP film growth with slight modifications to the reaction duration and reactant mass ratios. Devices fabricated from exfoliated bulk-b-AsP grown in the same reaction condition as the thin film growth process are characterized, showing an on-off current ratio of 102, a threshold voltage of -60 V, and a peak field-effect hole mobility of 23 cm2V-1s-1atVd= -0.9 V andVg= -60 V.

Ambipolar transport in van der Waals black arsenic field effect transistors.

Black arsenic (BAs) is an elemental van der Waals semiconductor that is promising for a wide range of electronic and photonic applications. The narrow bandgap and symmetric band structure suggest that ambipolar (both n- and p-type) transport should be observable, however, only p-type transport has been experimentally studied to date. Here, we demonstrate and characterize ambipolar transport in exfoliated BAs field effect transistors. In the thickest flakes (∼ 80 nm), maximum currents, I max, up to 60 µA µm-1 and 90 µA µm-1are achieved for hole and electron conduction, respectively. Room-temperature hole (electron) mobilities up to 150 cm2 V-1 s-1 (175 cm2 V-1 s-1) were obtained, with temperature-dependence consistent with a phonon-scattering mechanism. The Schottky barrier height for Ni contacts to BAs was also extracted from the temperature-dependent measurements. I max for both n- and p-type conductivity was found to decrease with reduced thickness, while the ratio of I max to the minimum current, I min, increased. In the thinnest flakes (∼ 1.5 nm), only p-type conductivity was observed with the lowest value of I min = 400 fA µm-1. I max/I min ratios as high as 5 × 105 (5 × 102) were obtained, for p- (n-channel) devices. Finally, the ambipolarity was used to demonstrate a complementary logic inverter and a frequency doubling circuit.

Self-Assembled Three-Dimensional Graphene-Based Polyhedrons Inducing Volumetric Light Confinement.

The ability to transform two-dimensional (2D) materials into a three-dimensional (3D) structure while preserving their unique inherent properties might offer great enticing opportunities in the development of diverse applications for next generation micro/nanodevices. Here, a self-assembly process is introduced for building free-standing 3D, micro/nanoscale, hollow, polyhedral structures configured with a few layers of graphene-based materials: graphene and graphene oxide. The 3D structures have been further modified with surface patterning, realized through the inclusion of metal patterns on their 3D surfaces. The 3D geometry leads to a nontrivial spatial distribution of strong electric fields (volumetric light confinement) induced by 3D plasmon hybridization on the surface of the graphene forming the 3D structures. Due to coupling in all directions, resulting in 3D plasmon hybridization, the 3D closed box graphene generates a highly confined electric field within as well as outside of the cubes. Moreover, since the uniform coupling reduces the decay of the field enhancement away from the surface, the confined electric field inside of the 3D structure shows two orders of magnitude higher than that of 2D graphene before transformation into the 3D structure. Therefore, these structures might be used for detection of target substances (not limited to only the graphene surfaces, but using the entire volume formed by the 3D graphene-based structure) in sensor applications.

Capacitance-Based Dosimetry of Co-60 Radiation using Fully-Depleted Silicon-on-Insulator Devices.

The capacitance based sensing of fully-depleted silicon-on-insulator (FDSOI) variable capacitors for Co-60 gamma radiation is investigated. Linear response of the capacitance is observed for radiation dose up to 64 Gy, while the percent capacitance change per unit dose is as high as 0.24 %/Gy. An analytical model is developed to study the operational principles of the varactors and the maximum sensitivity as a function of frequency is determined. The results show that FDSOI varactor dosimeters have potential for extremely-high sensitivity as well as the potential for high frequency operation in applications such as wireless radiation sensing.

Multifunctional graphene optical modulator and photodetector integrated on silicon waveguides.

Graphene's unique optoelectronic properties have been exploited for many photonic applications. Here, we demonstrate a single graphene-based device that simultaneously provides efficient optical modulation and photodetection. The graphene device is integrated on a silicon waveguide and is tunable with a graphene gate to achieve a near-infrared photodetection responsivity of 57 mA/W and modulation depth of 64% with GHz bandwidth. Simultaneous modulation of photocurrent and optical transmission has been achieved, which may lead to unprecedented optoelectronic applications.

Using Machine Learning to Overcome Interfering Oxygen Effects in a Graphene Volatile Organic Compound Sensor.

Discriminating between volatile organic compounds (VOCs) for applications including disease diagnosis and environmental monitoring, is often complicated by the presence of interfering compounds such as oxygen. Graphene sensors are effective at detecting VOCs; however, they are also known to be highly sensitive to oxygen. Therefore, the combined effects of each of these gases on graphene sensors must be understood. In this work, we use graphene variable capacitor (varactor) sensors to examine the cross-selectivity of oxygen at 3 concentrations and 3 VOCs (ethanol, methanol, and methyl ethyl ketone) at 5 concentrations each. The sensor responses exhibit distinct shapes dependent on the relative concentrations in mixtures of oxygen and VOCs. Because the entire response shape is therefore informative for distinguishing between each gas mixture, a classification algorithm that utilizes entire sequences of data is needed. Accordingly, a long short-term memory (LSTM) network is used to classify the mixtures and VOC concentrations. The model achieves 100% accurate classification of the VOC type, even in the presence of varying levels of oxygen. When the VOC type and VOC concentration are classified, we show that the sensors can provide VOC concentration resolution within approximately 200 ppm. Throughout this work, we also demonstrate that an effective gas mixture classification can be achieved, even while the sensors exhibit varied drift patterns typical of graphene sensors. This is made possible due to the data analysis and machine learning methods employed.

Hybrid Molecular Beam Epitaxy for Single-Crystalline Oxide Membranes with Binary Oxide Sacrificial Layers.

The advancement in thin-film exfoliation for synthesizing oxide membranes has led to possibilities for creating artificially assembled heterostructures with structurally and chemically incompatible materials. The sacrificial layer method is a promising approach to exfoliate as-grown films from a compatible material system, allowing for their integration with dissimilar materials. Nonetheless, the conventional sacrificial layers often possess an intricate stoichiometry, thereby constraining their practicality and adaptability, particularly when considering techniques such as molecular beam epitaxy (MBE). This is where easy-to-grow binary alkaline-earth-metal oxides with a rock salt crystal structure are useful. These oxides, which include (Mg, Ca, Sr, Ba)O, can be used as a sacrificial layer covering a much broader range of lattice parameters compared to conventional sacrificial layers and are easily dissolvable in deionized water. In this study, we show the epitaxial growth of the single-crystalline perovskite SrTiO3 (STO) on sacrificial layers consisting of crystalline SrO, BaO, and Ba1-xCaxO films, employing a hybrid MBE method. Our results highlight the rapid (≤5 min) dissolution of the sacrificial layer when immersed in deionized water, facilitating the fabrication of millimeter-sized STO membranes. Using high-resolution X-ray diffraction, atomic-force microscopy, scanning transmission electron microscopy, impedance spectroscopy, and scattering-type near-field optical microscopy (SNOM), we demonstrate single-crystalline STO membranes with bulk-like intrinsic dielectric properties. The employment of alkaline earth metal oxides as sacrificial layers is likely to simplify membrane synthesis, particularly with MBE, thus expanding the research and application possibilities.

Correction to Nb Doping and Alloying of 2D WS2 by Atomic Layer Deposition for 2D Transition Metal Dichalcogenide Transistors and HER Electrocatalysts.

[This corrects the article DOI: 10.1021/acsanm.4c00094.].

Nb Doping and Alloying of 2D WS2 by Atomic Layer Deposition for 2D Transition Metal Dichalcogenide Transistors and HER Electrocatalysts.

We utilize plasma-enhanced atomic layer deposition to synthesize two-dimensional Nb-doped WS2 and NbxW1-xSy alloys to expand the range of properties and improve the performance of 2D transition metal dichalcogenides for electronics and catalysis. Using a supercycle deposition process, films are prepared with compositions spanning the range from WS2 to NbS3. While the W-rich films form crystalline disulfides, the Nb-rich films form amorphous trisulfides. Through tuning the composition of the films, the electrical resistivity is reduced by 4 orders of magnitude compared to pure ALD-grown WS2. To produce Nb-doped WS2 films, we developed a separate ABC-type supercycle process in which a W precursor pulse precedes the Nb precursor pulse, thereby reducing the minimum Nb content of the film by a factor of 3 while maintaining a uniform distribution of the Nb dopant. Initial results are presented on the electrical and electrocatalytic performances of the films. Promisingly, the NbxW1-xSy films of 10 nm thickness and composition x ≈ 0.08 are p-type semiconductors and have a low contact resistivity of (8 ± 1) × 102 Ω cm to Pd/Au contacts, demonstrating their potential use in contact engineering of 2D TMD transistors.

Doping the Undopable: Hybrid Molecular Beam Epitaxy Growth, n-Type Doping, and Field-Effect Transistor Using CaSnO3.

The alkaline earth stannates are touted for their wide band gaps and the highest room-temperature electron mobilities among all of the perovskite oxides. CaSnO3 has the highest measured band gap in this family and is thus a particularly promising ultrawide band gap semiconductor. However, discouraging results from previous theoretical studies and failed doping attempts had described this material as "undopable". Here we redeem CaSnO3 using hybrid molecular beam epitaxy, which provides an adsorption-controlled growth for the phase-pure, epitaxial, and stoichiometric CaSnO3 films. By introducing lanthanum (La) as an n-type dopant, we demonstrate the robust and predictable doping of CaSnO3 with free electron concentrations, n3D, from 3.3 × 1019 cm-3 to 1.6 × 1020 cm-3. The films exhibit a maximum room-temperature mobility of 42 cm2 V-1 s-1 at n3D = 3.3 × 1019 cm-3. Despite having a comparable radius as the host ion, La expands the lattice parameter. Using density functional calculations, this effect is attributed to the energy gain by lowering the conduction band upon volume expansion. Finally, we exploit robust doping by fabricating CaSnO3-based field-effect transistors. The transistors show promise for CaSnO3's high-voltage capabilities by exhibiting low off-state leakage below 2 × 10-5 mA/mm at a drain-source voltage of 100 V and on-off ratios exceeding 106. This work serves as a starting point for future studies on the semiconducting properties of CaSnO3 and many devices that could benefit from CaSnO3's exceptionally wide band gap.

Achieving near-perfect light absorption in atomically thin transition metal dichalcogenides through band nesting.

Near-perfect light absorbers (NPLAs), with absorbance, [Formula: see text], of at least 99%, have a wide range of applications ranging from energy and sensing devices to stealth technologies and secure communications. Previous work on NPLAs has mainly relied upon plasmonic structures or patterned metasurfaces, which require complex nanolithography, limiting their practical applications, particularly for large-area platforms. Here, we use the exceptional band nesting effect in TMDs, combined with a Salisbury screen geometry, to demonstrate NPLAs using only two or three uniform atomic layers of transition metal dichalcogenides (TMDs). The key innovation in our design, verified using theoretical calculations, is to stack monolayer TMDs in such a way as to minimize their interlayer coupling, thus preserving their strong band nesting properties. We experimentally demonstrate two feasible routes to controlling the interlayer coupling: twisted TMD bi-layers and TMD/buffer layer/TMD tri-layer heterostructures. Using these approaches, we demonstrate room-temperature values of [Formula: see text]=95% at λ=2.8 eV with theoretically predicted values as high as 99%. Moreover, the chemical variety of TMDs allows us to design NPLAs covering the entire visible range, paving the way for efficient atomically-thin optoelectronics.

Switching energy limits of waveguide-coupled graphene-on-graphene optical modulators.

The fundamental switching energy limitations for waveguide coupled graphene-on-graphene optical modulators are described. The minimum energy is calculated under the constraints of fixed insertion loss and extinction ratio. Analytical relations for the switching energy both for realistic structures and in the quantum capacitance limit are derived and compared with numerical simulations. The results show that sub-femtojoule per bit switching energies and peak-to-peak voltages less than 0.1 V are achievable in graphene-on-graphene optical modulators using the constraint of 3 dB extinction ratio and 3 dB insertion loss. The quantum-capacitance limited switching energy for a single TE-mode modulator geometry is found to be < 0.5 fJ/bit at λ = 1.55 µm, and the dependences of the minimum energy on the waveguide geometry, wavelength, and graphene location are investigated. The low switching energy is a result of the very strong optical absorption in graphene, and the extremely-small operating voltages needed as the device approaches the quantum capacitance regime.

Machine Learning-Based Rapid Detection of Volatile Organic Compounds in a Graphene Electronic Nose.

Rapid detection of volatile organic compounds (VOCs) is growing in importance in many sectors. Noninvasive medical diagnoses may be based upon particular combinations of VOCs in human breath; detecting VOCs emitted from environmental hazards such as fungal growth could prevent illness; and waste could be reduced through monitoring of gases produced during food storage. Electronic noses have been applied to such problems, however, a common limitation is in improving selectivity. Graphene is an adaptable material that can be functionalized with many chemical receptors. Here, we use this versatility to demonstrate selective and rapid detection of multiple VOCs at varying concentrations with graphene-based variable capacitor (varactor) arrays. Each array contains 108 sensors functionalized with 36 chemical receptors for cross-selectivity. Multiplexer data acquisition from 108 sensors is accomplished in tens of seconds. While this rapid measurement reduces the signal magnitude, classification using supervised machine learning (Bootstrap Aggregated Random Forest) shows excellent results of 98% accuracy between 5 analytes (ethanol, hexanal, methyl ethyl ketone, toluene, and octane) at 4 concentrations each. With the addition of 1-octene, an analyte highly similar in structure to octane, an accuracy of 89% is achieved. These results demonstrate the important role of the choice of analysis method, particularly in the presence of noisy data. This is an important step toward fully utilizing graphene-based sensor arrays for rapid gas sensing applications from environmental monitoring to disease detection in human breath.

Freestanding epitaxial SrTiO3 nanomembranes via remote epitaxy using hybrid molecular beam epitaxy.

The epitaxial growth of functional oxides using a substrate with a graphene layer is a highly desirable method for improving structural quality and obtaining freestanding epitaxial nanomembranes for scientific study, applications, and economical reuse of substrates. However, the aggressive oxidizing conditions typically used in growing epitaxial oxides can damage graphene. Here, we demonstrate the successful use of hybrid molecular beam epitaxy for SrTiO3 growth that does not require an independent oxygen source, thus avoiding graphene damage. This approach produces epitaxial films with self-regulating cation stoichiometry. Furthermore, the film (46-nm-thick SrTiO3) can be exfoliated and transferred to foreign substrates. These results open the door to future studies of previously unattainable freestanding oxide nanomembranes grown in an adsorption-controlled manner by hybrid molecular beam epitaxy. This approach has potentially important implications for the commercial application of perovskite oxides in flexible electronics and as a dielectric in van der Waals thin-film electronics.

Ultraflat Sub-10 Nanometer Gap Electrodes for Two-Dimensional Optoelectronic Devices.

Two-dimensional (2D) materials are promising candidates for building ultrashort-channel devices because their thickness can be reduced down to a single atomic layer. Here, we demonstrate an ultraflat nanogap platform based on atomic layer deposition (ALD) and utilize the structure to fabricate 2D material-based optical and electronic devices. In our method, ultraflat metal surfaces, template-stripped from a Si wafer mold, are separated by an Al2O3 ALD layer down to a gap width of 10 nm. Surfaces of both electrodes are vertically aligned without a height difference, and each electrode is ultraflat with a measured root-mean-square roughness as low as 0.315 nm, smaller than the thickness of monolayer graphene. Simply by placing 2D material flakes on top of the platform, short-channel field-effect transistors based on black phosphorus and MoS2 are fabricated, exhibiting their typical transistor characteristics. Furthermore, we use the same platform to demonstrate photodetectors with a nanoscale photosensitive channel, exhibiting higher photosensitivity compared to microscale gap channels. Our wafer-scale atomic layer lithography method can benefit a diverse range of 2D optical and electronic applications.

Nanophotonic biosensors harnessing van der Waals materials.

Low-dimensional van der Waals (vdW) materials can harness tightly confined polaritonic waves to deliver unique advantages for nanophotonic biosensing. The reduced dimensionality of vdW materials, as in the case of two-dimensional graphene, can greatly enhance plasmonic field confinement, boosting sensitivity and efficiency compared to conventional nanophotonic devices that rely on surface plasmon resonance in metallic films. Furthermore, the reduction of dielectric screening in vdW materials enables electrostatic tunability of different polariton modes, including plasmons, excitons, and phonons. One-dimensional vdW materials, particularly single-walled carbon nanotubes, possess unique form factors with confined excitons to enable single-molecule detection as well as in vivo biosensing. We discuss basic sensing principles based on vdW materials, followed by technological challenges such as surface chemistry, integration, and toxicity. Finally, we highlight progress in harnessing vdW materials to demonstrate new sensing functionalities that are difficult to perform with conventional metal/dielectric sensors.

Layer Dependence of Dielectric Response and Water-Enhanced Ambient Degradation of Highly Anisotropic Black As.

Black arsenic (BAs) is a van der Waals layered material with a puckered honeycomb structure and has received increased interest due to its anisotropic properties and promising performance in devices. Here, crystalline structure, thickness-dependent dielectric responses, and ambient stability of BAs nanosheets are investigated using scanning transmission electron microscopy (STEM) imaging and spectroscopy. Atomic-resolution high-angle annular dark-field (HAADF)-STEM images directly visualize the three-dimensional structure and evaluate the degree of anisotropy. STEM-electron energy loss spectroscopy is used to measure the dielectric response of BAs as a function of the number of layers. Finally, BAs degradation under different ambient environments is studied, highlighting high sensitivity to moisture in the air.

3D printed self-supporting elastomeric structures for multifunctional microfluidics.

Microfluidic devices fabricated via soft lithography have demonstrated compelling applications such as lab-on-a-chip diagnostics, DNA microarrays, and cell-based assays. These technologies could be further developed by directly integrating microfluidics with electronic sensors and curvilinear substrates as well as improved automation for higher throughput. Current additive manufacturing methods, such as stereolithography and multi-jet printing, tend to contaminate substrates with uncured resins or supporting materials during printing. Here, we present a printing methodology based on precisely extruding viscoelastic inks into self-supporting microchannels and chambers without requiring sacrificial materials. We demonstrate that, in the submillimeter regime, the yield strength of the as-extruded silicone ink is sufficient to prevent creep within a certain angular range. Printing toolpaths are specifically designed to realize leakage-free connections between channels and chambers, T-shaped intersections, and overlapping channels. The self-supporting microfluidic structures enable the automatable fabrication of multifunctional devices, including multimaterial mixers, microfluidic-integrated sensors, automation components, and 3D microfluidics.

MoTe2 Lateral Homojunction Field-Effect Transistors Fabricated using Flux-Controlled Phase Engineering.

The coexistence of metallic and semiconducting polymorphs in transition-metal dichalcogenides (TMDCs) can be utilized to solve the large contact resistance issue in TMDC-based field effect transistors (FETs). A semiconducting hexagonal (2H) molybdenum ditelluride (MoTe2) phase, metallic monoclinic (1T') MoTe2 phase, and their lateral homojunctions can be selectively synthesized in situ by chemical vapor deposition due to the small free energy difference between the two phases. Here, we have investigated, in detail, the structural and electrical properties of in situ-grown lateral 2H/1T' MoTe2 homojunctions grown using flux-controlled phase engineering. Using atomic-resolution plan-view and cross-sectional transmission electron microscopy analyses, we show that the round regions of near-single-crystalline 2H-MoTe2 grow out of a polycrystalline 1T'-MoTe2 matrix. We further demonstrate the operation of MoTe2 FETs made on these in situ-grown lateral homojunctions with 1T' contacts. The use of a 1T' phase as electrodes in MoTe2 FETs effectively improves the device performance by substantially decreasing the contact resistance. The contact resistance of 1T' electrodes extracted from transfer length method measurements is 470 ± 30 Ω·µm. Temperature- and gate-voltage-dependent transport characteristics reveal a flat-band barrier height of ∼30 ± 10 meV at the lateral 2H/1T' interface that is several times smaller and shows a stronger gate modulation, compared to the metal/2H Schottky barrier height. The information learned from this analysis will be critical to understanding the properties of MoTe2 homojunction FETs for use in memory and logic circuity applications.