Development of Morphologically engineered Flower-like Hafnium-Doped ZnO with Experimental and DFT Validation for Low-Temperature and Ultrasensitive Detection of NOX Gas.

Substitutional doping and different nanostructures of ZnO have rendered it an effective sensor for the detection of volatile organic compounds in real-time atmosphere. However, the low selectivity of ZnO sensors limits their applications. Herein, hafnium (Hf)-doped ZnO (Hf-ZnO) nanostructures are developed by the hydrothermal method for high selectivity of hazardous NOX gas in the atmosphere, substantially portraying the role of doping concentration on the enhancement of structural, optical, and sensing behavior. ZnO microspheres with 5% Hf doping showed excellent sensing and detected 22 parts per billion (ppb) NOX gas in the atmosphere, within 24 s, which is much faster than ZnO (90 s), and rendered superior sensing ability (S = 67) at a low temperature (100 °C) compared to ZnO (S = 40). The sensor revealed exceptional stability under humid air (S = 55 at 70% RH), suggesting a potential of 5% Hf-ZnO as a new stable sensing material. Density functional theory (DFT) and other characterization analyses revealed that the high sensing activity of 5% Hf-ZnO is attributed to the accessibility of more adsorption sites arising due to charge distortion, increased oxygen vacancies concentration, Lewis acid base, porous morphology, small particle size (5 nm), and strong bond interaction amidst NO2 molecule with ZnO-Hf-Ovacancy sites, resulting from the substitution of the host cation (Zn2+) with doping cation (Hf4+).

RF Sputtered Nb-Doped MoS2 Thin Film for Effective Detection of NO2 Gas Molecules: Theoretical and Experimental Studies.

Doping plays a significant role in affecting the physical and chemical properties of two-dimensional (2D) dichalcogenide materials. Controllable doping is one of the major factors in the modification of the electronic and mechanical properties of 2D materials. MoS2 2D materials have gained significant attention in gas sensing owing to their high surface-to-volume ratio. However, low response and recovery time hinder their application in practical gas sensors. Herein, we report the enhanced gas response and recovery of Nb-doped MoS2 gas sensor synthesized through physical vapor deposition (PVD) toward NO2 at different temperatures. The electronic states of MoS2 and Nb-doped MOS2 monolayers grown by PVD were analyzed based on their work functions. Doping with Nb increases the work function of MoS2 and its electronic properties. The Nb-doped MoS2 showed an ultrafast response and recovery time of t rec = 30/85 s toward 5 ppm of NO2 at their optimal operating temperature (100 °C). The experimental results complement the electron difference density functional theory calculation, showing both physisorption and chemisorption of NO2 gas molecules on niobium substitution doping in MoS2.

Topological phase transition associated with structural phase transition in ternary half Heusler compound LiAuBi.

In this article, we report detailed theoretical investigations of topological phases in non-centrosymmetric half Heusler compound LiAuBi up to a pressure of 30 GPa. It is found that the compound forms into a dynamically stable face-centered cubic (FCC) lattice structure of space groupF4¯3m(216) at ambient pressure. The compound is topologically non-trivial at ambient pressure, but undergoes a quantum phase transition to trivial topological phase at 23.4 GPa. However, the detailed investigations show a structural phase transition from FCC lattice (space group 216) to a honeycomb lattice (space group 194) at 13 GPa, which is also associated with a non-trivial to trivial topological phase transition. Further investigations show that the compound also carries appreciable thermoelectric properties at ambient pressure. The figure of merit (ZT) increases from 0.21 at room temperature to a maximum value of 0.22 at 500 K. The theoretical findings show its potential for practical applications in spintronics as well as thermoelectricity, therefore LiAuBi needs to be synthesized and investigated experimentally for its applications.

Revisiting the Mechanism of Electric Field Sensing in Graphene Devices.

Electric field sensing has various real-life applications, such as early prediction of lightning. In this study, we effectively used graphene as an electric field sensor that can detect both positive and negative electric fields. The response of the sensor is recorded as the change in drain current under the application of an electric field. In addition, by systematic analysis, we established the mechanism of the graphene electric field sensor, and it is found to be different from the previously proposed one. The mechanism relies on the transfer of electrons between graphene and the traps at the SiO2/graphene interface. While the direction of charge transfer depends on the polarity of the applied electric field, the amount of charge transferred depends on the magnitude of the electric field. Such a charge transfer changes the carrier concentration in the graphene channel, which is reflected as the change in drain current.

Interfacial Ammonia Selectivity, Atmospheric Passivation, and Molecular Identification in Graphene-Nanopored Activated Carbon Molecular-Sieve Gas Sensors.

Graphene's inherent nonselectivity and strong atmospheric doping render most graphene-based sensors unsuitable for atmospheric applications in environmental monitoring of pollutants and breath detection of biomarkers for noninvasive medical diagnosis. Hence, demonstrations of graphene's gas sensitivity are often in inert environments such as nitrogen, consequently of little practical relevance. Herein, target gas sensing at the graphene-activated carbon interface of a graphene-nanopored activated carbon molecular-sieve sensor obtained via the postlithographic pyrolysis of Novolac resin residues on graphene nanoribbons is shown to simultaneously induce ammonia selectivity and atmospheric passivation of graphene. Consequently, 500 parts per trillion (ppt) ammonia sensitivity in atmospheric air is achieved with a response time of ∼3 s. The similar graphene and a-C workfunctions ensure that the ambipolar and gas-adsorption-induced charge transfer characteristics of pristine graphene are retained. Harnessing the van der Waals bonding memory and electrically tunable charge-transfer characteristics of the adsorbed molecules on the graphene channel, a molecular identification technique (charge neutrality point disparity) is developed and demonstrated to be suitable even at parts per billion (ppb) gas concentrations. The selectivity and atmospheric passivation induced by the graphene-activated carbon interface enable atmospheric applications of graphene sensors in environmental monitoring and noninvasive medical diagnosis.

Strain effect on topological and thermoelectric properties of half Heusler compoundsXPtS (X=Sr, Ba).

In this article, we report theoretical investigations of topological and thermoelectric (TE) properties of non-centrosymmetric half Heusler compoundsXPtS (X= Sr, Ba) using first principles calculations. In addition, we also investigated the effect of static strain (up to 10%) on its topological and TE properties. Our detailed investigations show that the XPtS compounds are topological insulators (TIs) and continue as TIs up to a strain of 10%. However, the band gap becomes a maximum of 0.213 eV under a strain of 3% for SrPtS and 0.164 eV at a strain of 5% for BaPtS. TE investigations show that the figure of merit (a measure of TE performance) ZT becomes maximum (0.222) at room temperature for BaPtS under a strain of 1%. The detailed theoretical investigations ofXPtS with and without strain provide a theoretical platform for experiments and its possible applications in spintronics and thermoelectricity.

In-situ electrical conductance measurement of suspended ultra-narrow graphene nanoribbons observed via transmission electron microscopy.

Graphene nanoribbon is an attractive material for nano-electronic devices, as their electrical transport performance can be controlled by their edge structures. However, in most cases, the electrical transport has been investigated only for graphene nanoribbons fabricated on a substrate, which hinders the appearance of intrinsic electrical transport due to screening effects. In this study, we developed special devices based on silicon chips for transmission electron microscopy to observe a monolayer graphene nanoribbon suspended between two gold electrodes. Moreover, with the development of an in-situ transmission electron microscopy holder, the current-voltage characteristics were achieved simultaneously with observing and modifying the structure. We found that the current-voltage characteristics differed between 1.5 nm-wide graphene nanoribbons with armchair and zigzag edge structures. The energy gap of the zigzag edge was more than two-fold larger than that of the armchair edge and exhibited an abrupt jump above a critical bias voltage in the differential conductance curve. Thus, our in-situ transmission electron microscopy method is promising for elucidating the structural dependence of electrical conduction in two-dimensional materials.

Design of Graphene Phononic Crystals for Heat Phonon Engineering.

Controlling the heat transport and thermal conductivity through a material is of prime importance for thermoelectric applications. Phononic crystals, which are a nanostructured array of specially designed pores, can suppress heat transportation owing to the phonon wave interference, resulting in bandgap formation in their band structure. To control heat phonon propagation in thermoelectric devices, phononic crystals with a bandgap in the THz regime are desirable. In this study, we carried out simulation on snowflake shaped phononic crystal and obtained several phononic bandgaps in the THz regime, with the highest being at ≈2 THz. The phononic bandgap position and the width of the bandgap were found to be tunable by varying the neck-length of the snowflake structure. A unique bandgap map computed by varying the neck-length continuously provides enormous amounts of information as to the size and position of the phononic bandgap for various pore dimensions. We have also carried out transmission spectrum analysis and found good agreement with the band structure calculations. The pressure map visualized at various frequencies validates the effectiveness of snowflake shaped nano-pores in suppressing the phonons partially or completely, depending on the transmission probabilities.

Adsorbed Molecules as Interchangeable Dopants and Scatterers with a Van der Waals Bonding Memory in Graphene Sensors.

Molecular adsorption-induced doping and scattering play a central role in the detection mechanism of graphene gas sensors. However, while the doping contributions in electric field-enhanced gas sensing is well studied, an understanding of the effects of scattering is still lacking. In this work, the scattering contribution of the graphene-molecule van der Waals (vdW) complex is studied under various electric fields and the associated vdW bonding retention in the complex is investigated. We show that contrary to the generally opined view, doping does not always dominate the graphene-molecule vdW complex interaction and consequently the conductivity response in graphene sensors, rather the vdW complex interaction only shows doping-dominated interaction at zero electric fields while scattering increases with electric field modulation. The experimentally observed electric field-dependent scattering response agrees with electron difference density analysis from density functional theory (DFT) calculations, which shows that scattering is directly dependent on the electric field-induced molecular reorientation as well as the redistribution and delocalization of charge in the graphene-gas molecule vdW complex. Furthermore, "vdW bonding memory", i.e., retention of electric field-induced vdW bonding states after turning off the electric field, is observed and shown to result from the high binding energies of the vdW complexes, which are an order of magnitude higher than the sensing measurement thermal energy. This vdW bonding memory in the graphene-molecule complexes is important for the molecular identification of adsorbed gases based on their tunable charge transfer characteristics.

Conductance Tunable Suspended Graphene Nanomesh by Helium Ion Beam Milling.

This paper demonstrates that the electrical properties of suspended graphene nanomesh (GNM) can be tuned by systematically changing the porosity with helium ion beam milling (HIBM). The porosity of the GNM is well-controlled by defining the pitch of the periodic nanopores. The defective region surrounding the individual nanopores after HIBM, which limits the minimum pitch achievable between nanopores for a certain dose, is investigated and reported. The exponential relationship between the thermal activation energy (EA) and the porosity is found in the GNM devices. Good EA tuneability observed from the GNMs provides a new approach to the transport gap engineering beyond the conventional nanoribbon method.

Dielectric-Screening Reduction-Induced Large Transport Gap in Suspended Sub-10 nm Graphene Nanoribbon Functional Devices.

The predicted quasiparticle energy gap of more than 1 eV in sub-6 nm graphene nanoribbons (GNRs) is elusive, as it is strongly suppressed by the substrate dielectric screening. The number of techniques that can produce suspended high-quality and electrically contacted GNRs is small. The helium ion beam milling technique is capable of achieving sub-5 nm patterning; however, the functional device fabrication and the electrical characteristics are not yet reported. Here, the electrical transport measurement of suspended ≈6 nm wide mono- and bilayer GNR functional devices is reported, which are obtained through sub-nanometer resolution helium ion beam milling with controlled total helium ion budget. The transport gap opening of 0.16-0.8 eV is observed at room temperature. The measured transport gap of the different edge orientated GNRs is in good agreement with first-principles simulation results. The enhanced electron-electron interaction and reduced dielectric screening in the suspended quasi-1D GNRs and anti-ferromagnetic coupling between opposite edges in the zigzag GNRs substantiate the observed large transport gap.

Electrically controlled valley states in bilayer graphene.

Valley current, a stable, dissipationless current, originates due to the emergence of Berry curvature in inversion symmetry broken systems. Several theoretical predictions and experimental observations have explored layer symmetry breaking in AB-stacked bilayer graphene due to long-range Coulomb interactions between the electrons. However, none of the experimental studies conducted so far have observed valley current in unbiased bilayer graphene, which makes it vital to study the Berry curvature in unbiased bilayer graphene. In this study, we observed a non-zero Berry curvature with opposite values at K and K' valleys, validating the argumentation of the asymmetry persistent in unbiased bilayer graphene. The magnitude, as well as the polarity of the Berry curvature, is tunable with the application of an out-of-plane electric field. These results are especially important because they can lead to the realization of a valley valve, in which the carriers from the K and K' valleys can be regulated with a gate at the centre of a bilayer graphene nanoribbon.

Quantum Dot Formation in Controllably Doped Graphene Nanoribbon.

We introduce the controllable doping from hydrogen silsesquioxane (HSQ) to graphene by changing its electron-beam exposure dose. Using HSQ as the dopant, a fine-resolution electron-beam resist allows us to selectively dope graphene with an extremely high spatial resolution of a few nanometers. Therefore, we can design and demonstrate the single quantum dot (QD)-like transport in the graphene nanoribbon (GNR) with the opening of the energy gap. Moreover, we suggest a rough geometric design rule in which a relatively short and wide GNR is required for observing the single QD-like transport. We envisage that this method can be utilized for other materials and for other applications, such as p-n junctions and tunnel field-effect transistors.

Enhanced Sodium Ion Storage in Interlayer Expanded Multiwall Carbon Nanotubes.

We report an effective approach of utilizing multiwalled carbon nanotubes (MWCNTs) as an active anode material in sodium ion batteries by expanding the interlayer distance in a few outer layers of multiwalled carbon nanotubes. The performance enhancement was investigated using a density functional tight binding (DFTB) molecular dynamics simulation. It is found that a sodium atom forms a stable bonding with the partially expanded MWCNT (PECNT) with the binding energy of -1.50 eV based on the density functional theory calculation with van der Waals correction, where a sodium atom is caged between the two carbon hexagons in the two consecutive MWCNTs. Wave function and charge density analyses show that this binding is physisorption in nature. This larger exothermic nature of binding energy favors the stable bonding between the PECNT and a sodium atom, and thereby, it helps to enhance the electrochemical performance. In the experimental works, partial opening of the MWCNT with the expanded interlayer has been designed by the well-known Hummer's method. It has been found that the introduction of functional groups causes a partial opening of the outer few layers of a MWCNT, with the inner core remaining undisturbed. The enhanced performance is due to an expanded interlayer of carbon nanotubes, which provide sufficient active sites for the sodium ions to adsorb as well as to intercalate into the carbon structure. The PECNT shows a high specific capacity of 510 mAh g-1 at a current density of 20 mA g-1, which is about 2.3 times the specific capacity obtained for a pristine MWCNT at the same current density. This specific capacity is higher when compared to other carbon-based materials. The PECNT also shows a satisfactory cyclic stability at a current density of 200 mA g-1 for 100 cycles. Based on our experimental and theoretical results, an alternative perspective for the storage of sodium ions in MWCNTs is proposed.

Fabrication of a three-terminal graphene nanoelectromechanical switch using two-dimensional materials.

An alternative three-terminal (3T) subthermal subthreshold slope (SS) switch is required to overcome the exponential increase in leakage current with an increase in the drive current of CMOS devices. In this study, we present a 3T graphene nanoelectromechanical (3T-GNEM) switch with a physically isolated channel in the off-state by using heterogeneously stacked two-dimensional (2D) materials. Hexagonal boron nitride (h-BN) was used as a dielectric layer, and graphene was used as a the top double-clamped beam drain, gate and source electrode material; the drain, gate, and source layers were stacked vertically to achieve a small footprint. The drain to source contact is normally open with an air gap in the off-state, and the gate voltage is applied to mechanically deflect the drain terminal of the doubly clamped graphene beam to make electric contact with the source terminal for the on-state. This 3T-GNEM switch exhibits an SS as small as 10.4 mV dec-1 at room temperature, a pull-in voltage less than 6 V, and a switching voltage window of under 2 V. Since the source and drain terminals are not connected physically in the off-state, this 3T-GNEM switch is a promising candidate for future high-performance low-power logic circuits and all-2D flexible electronics.

Controlled fabrication of electrically contacted carbon nanoscrolls.

Carbon nanoscrolls (CNS) with their open ended morphology have recently attracted interest due to the potential application in gas capture, biosensors and interconnects. However, CNS currently suffer from the same issue that have hindered widespread integration of CNTs in sensors and devices: formation is done ex situ, and the tubes have to be placed with precision and reliability-a difficult task with low yield. Here, we demonstrate controlled in situ formation of electrically contacted CNS from suspended graphene nanoribbons with slight tensile stress. Formation probability depends on the length to width aspect ratio. Van der Waals interaction between the overlapping layers fixes the nanoscroll once formed. The stability of these CNSs is investigated by helium nano ion beam assisted in situ cutting. The loose stubs remain rolled and mostly suspended unless subject to a moderate helium dose corresponding to a damage rate of 4%-20%. One CNS stub remaining perfectly straight even after touching the SiO2 substrate allows estimation of the bending moment due to van der Waals force between the CNS and the substrate. The bending moment of 5400 eV is comparable to previous theoretical studies. The cut CNSs show long-term stability when not touching the substrate.

Structurally Controlled Large-Area 10 nm Pitch Graphene Nanomesh by Focused Helium Ion Beam Milling.

Graphene nanomesh (GNM) is formed by patterning graphene with nanometer-scale pores separated by narrow necks. GNMs are of interest due to their potential semiconducting characteristics when quantum confinement in the necks leads to an energy gap opening. GNMs also have potential for use in phonon control and water filtration. Furthermore, physical phenomena, such as spin qubit, are predicted at pitches below 10 nm fabricated with precise structural control. Current GNM patterning techniques suffer from either large dimensions or a lack of structural control. This work establishes reliable GNM patterning with a sub-10 nm pitch and an < 4 nm pore diameter by the direct helium ion beam milling of suspended monolayer graphene. Due to the simplicity of the method, no postpatterning processing is required. Electrical transport measurements reveal an effective energy gap opening of up to ∼450 meV. The reported technique combines the highest resolution with structural control and opens a path toward GNM-based, room-temperature semiconducting applications.

Chemical Simultaneous Synthesis Strategy of Two Nitrogen-Rich Carbon Nanomaterials for All-Solid-State Symmetric Supercapacitor.

Present work demonstrates a single step process for simultaneous synthesis of metal-nanoparticle-encapsulated nitrogen-doped bamboo-shaped carbon nanotubes (M/N-BCNTs) and graphitic carbon nitride (G-C3N3). The synthesis of two different carbon nanostructures in a single step is recognized for the first time. This process involves the use of inexpensive and nontoxic precursors such as melamine as carbon and nitrogen sources for the growth of G-C3N3 and M/N-BCNTs. In this technique, the utilization of unwanted gases such as ammonia and hydrocarbons released during the decomposition of melamine is the key to grow M/N-BCNTs over the catalyst along with the formation of G-C3N4. The implementation of M/N-BCNTs as the electrode material for all-solid-state symmetric supercapacitor results in a maximum specific capacitance of ∼368 F g-1 with excellent electrochemical stability with 97% capacity retention after 10 000 cycles. Furthermore, fabricated symmetric supercapacitor shows maximum high energy and power density up to 10.88 W h kg-1 and 2.06 kW kg-1, respectively. The superior electrochemical activity of M/N-BCNTs can be attributed to its high surface to area volume ratio, unique structural characteristics, ultrahigh electrical conductivity, and carrier mobility.

Partial hydrogenation induced interaction in a graphene-SiO2 interface: irreversible modulation of device characteristics.

The transformation of systematic vacuum and hydrogen annealing effects in graphene devices on the SiO2 surface is reported based on experimental and van der Waals interaction corrected density functional theory (DFT) simulation results. Vacuum annealing removes p-type dopants and reduces charged impurity scattering in graphene. Moreover, it induces n-type doping into graphene, leading to the improvement of the electron mobility and conductivity in the electron transport regime, which are reversed by exposing to atmospheric environment. On the other hand, annealing in hydrogen/argon gas results in smaller n-type doping along with a decrease in the overall conductivity and carrier mobility. This degradation of the conductivity is irreversible even the graphene devices are exposed to ambience. This was clarified by DFT simulations: initially, silicon dangling bonds were partially terminated by hydrogen, subsequently, the remaining dangling bonds became active and the distance between the graphene and SiO2 surface decreased. Moreover, both annealing methods affect the graphene channel including the vicinity of the metal contacts, which plays an important role in asymmetric carrier transport.

Three-Dimensional Finite Element Method Simulation of Perforated Graphene Nano-Electro-Mechanical (NEM) Switches.

The miniaturization trend leads to the development of a graphene based nanoelectromechanical (NEM) switch to fulfill the high demand in low power device applications. In this article, we highlight the finite element (FEM) simulation of the graphene-based NEM switches of fixed-fixed ends design with beam structures which are perforated and intact. Pull-in and pull-out characteristics are analyzed by using the FEM approach provided by IntelliSuite software, version 8.8.5.1. The FEM results are consistent with the published experimental data. This analysis shows the possibility of achieving a low pull-in voltage that is below 2 V for a ratio below 15:0.03:0.7 value for the graphene beam length, thickness, and air gap thickness, respectively. The introduction of perforation in the graphene beam-based NEM switch further achieved the pull-in voltage as low as 1.5 V for a 250 nm hole length, 100 nm distance between each hole, and 12-number of hole column. Then, a von Mises stress analysis is conducted to investigate the mechanical stability of the intact and perforated graphene-based NEM switch. This analysis shows that a longer and thinner graphene beam reduced the von Mises stress. The introduction of perforation concept further reduced the von Mises stress at the graphene beam end and the beam center by approximately ~20⁻35% and ~10⁻20%, respectively. These theoretical results, performed by FEM simulation, are expected to expedite improvements in the working parameter and dimension for low voltage and better mechanical stability operation of graphene-based NEM switch device fabrication.