Towards graphene-based asymmetric diodes: a density functional tight-binding study.

Self-consistent charge density functional tight-binding (DFTB) calculations have been performed to investigate the electrical properties and transport behavior of asymmetric graphene devices (AGDs). Three different nanodevices constructed of different necks of 8 nm, 6 nm and 4 nm, named Graphene-N8, Graphene-N6 and Graphene-N4, respectively, have been proposed. All devices have been tested under two conditions of zero gate voltage and an applied gate voltage of +20 V using a dielectric medium of 3.9 epsilon interposed between the graphene and the metallic gate. As expected, the results of AGD diodes exhibited strong asymmetric I(V) characteristic curves in good agreement with the available experimental data. Our predictions implied that Graphene-N4 would achieve great asymmetry (A) of 1.40 at |VDS| = 0.2 V with maximum transmittance (T) of 6.72 in the energy range 1.30 eV. More importantly, while the A of Graphene-N4 was slightly changed by applying the gate voltage, Graphene-N6/Graphene-N8 showed a significant effect with their A increased from 1.20/1.03 under no gate voltage (NGV) to 1.30/1.16 under gate voltage (WGV) conditions. Our results open up unprecedented numerical prospects for designing tailored geometric diodes.

Developing the next generation of renewable energy technologies: an overview of low-TRL EU-funded research projects.

A cluster of eleven research and innovation projects, funded under the same call of the EU's H2020 programme, are developing breakthrough and game-changing renewable energy technologies that will form the backbone of the energy system by 2030 and 2050 are, at present, at an early stage of development. These projects have joined forces at a collaborative workshop, entitled ' Low-TRL Renewable Energy Technologies', at the 10th Sustainable Places Conference (SP2022), to share their insights, present their projects' progress and achievements to date, and expose their approach for exploitation and market uptake of their solutions.

Analytical expressions for spreading resistance in lossy media and their application to the calibration of scanning microwave microscopy.

This paper presents the analytical derivation of spreading resistance expressions for diverse geometries of a conducting probe submerged in a lossy medium. Resulting equations can be used to calibrate scanning impedance/scanning microwave microscopes operating in liquid. The expressions are systematically validated through numerical and experimental methods for the calibration of an inverted Scanning Microwave Microscope (iSMM) when operating in a lossy saline medium, such as Dulbecco's Modified Eagle Medium (DMEM), a widely used medium for supporting the growth of biological cells. The calibration process within DMEM plays an important role in the quantitative local evaluation of electromagnetic properties of biological samples under physiological conditions. Additionally, measurements are performed in distilled water for comparative analysis.

First-principles investigation of interface phenomena in hafnium-based metal-insulator-metal diodes.

Metal-insulator-metal (MIM) diodes are very interesting in many different applications exploiting environment-friendly renewable energy solutions. Moreover, since the dimensions of such devices are at the nanoscale, the size and the characteristics of their constitutive elements can drastically influence their macroscale performance. As it could be difficult to describe in detail the physical phenomena occurring among materials in nanoscale systems, in this work first-principles calculations have been used to study the structural and electrical properties of three different hafnium oxide (HfO2)-MIM diodes. These devices have been simulated at the atomistic level by interposing 3 nm of HfO2 between drain and source electrodes made of gold and platinum, respectively. The monoclinic and orthorhombic polymorphs of HfO2 have been considered to model different types of MIM diodes, and the interface geometries have been optimized to compute the current-voltage characteristics, reflecting the tunneling mechanisms occurring in such devices. The calculation of the transmission pathways has also been carried out to investigate the effects of atomistic coordinates despite the use of the same material. The results demonstrate the role of the Miller indices of metals and the influence of the HfO2 polymorphs on the MIM properties. In this study, the importance of interface phenomena on the measurable properties of the proposed devices has been investigated in detail.

First-Principles Calculation of MoO2 and MoO3 Electronic and Optical Properties Compared with Experimental Data.

MoO3 and MoO2 systems have attracted particular attention for many widespread applications thanks to their electronic and optical peculiarities; from the crystallographic point of view, MoO3 adopts a thermodynamically stable orthorhombic phase (α-MoO3) belonging to the space group Pbmn, while MoO2 assumes a monoclinic arrangement characterized by space group P21/c. In the present paper, we investigated the electronic and optical properties of both MoO3 and MoO2 by using Density Functional Theory calculations, in particular, the Meta Generalized Gradient Approximation (MGGA) SCAN functional together with the PseudoDojo pseudopotential, which were used for the first time to obtain a deeper insight into the nature of different Mo-O bonds in these materials. The calculated density of states, the band gap, and the band structure were confirmed and validated by comparison with already available experimental results, while the optical properties were validated by recording optical spectra. Furthermore, the calculated band-gap energy value for the orthorhombic MoO3 showed the best match to the experimental value reported in the literature. All these findings suggest that the newly proposed theoretical techniques reproduce the experimental evidence of both MoO2 and MoO3 systems with high accuracy.

SARS-CoV-2 multi-variant rapid detector based on graphene transistor functionalized with an engineered dimeric ACE2 receptor.

Reliable point-of-care (POC) rapid tests are crucial to detect infection and contain the spread of Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2). The emergence of several variants of concern (VOC) can reduce binding affinity to diagnostic antibodies, limiting the efficacy of the currently adopted tests, while showing unaltered or increased affinity for the host receptor, angiotensin converting enzyme 2 (ACE2). We present a graphene field-effect transistor (gFET) biosensor design, which exploits the Spike-ACE2 interaction, the crucial step for SARS-CoV-2 infection. Extensive computational analyses show that a chimeric ACE2-Fragment crystallizable (ACE2-Fc) construct mimics the native receptor dimeric conformation. ACE2-Fc functionalized gFET allows in vitro detection of the trimeric Spike protein, outperforming functionalization with a diagnostic antibody or with the soluble ACE2 portion, resulting in a sensitivity of 20 pg/mL. Our miniaturized POC biosensor successfully detects B.1.610 (pre-VOC), Alpha, Beta, Gamma, Delta, Omicron (i.e., BA.1, BA.2, BA.4, BA.5, BA.2.75 and BQ.1) variants in isolated viruses and patient's clinical nasopharyngeal swabs. The biosensor reached a Limit Of Detection (LOD) of 65 cps/mL in swab specimens of Omicron BA.5. Our approach paves the way for a new and reusable class of highly sensitive, rapid and variant-robust SARS-CoV-2 detection systems.

Nanoscale Characterization of Graphene Oxide-Based Epoxy Nanocomposite Using Inverted Scanning Microwave Microscopy.

Scanning microwave microscopy (SMM) is a novel metrological tool that advances the quantitative, nanometric, high-frequency, electrical characterization of a broad range of materials of technological importance. In this work, we report an inverted near-field scanning microwave microscopy (iSMM) investigation of a graphene oxide-based epoxy nanocomposite material at a nanoscopic level. The high-resolution spatial mapping of local conductance provides a quantitative analysis of the sample's electrical properties. In particular, the electrical conductivity in the order of ∼10-1 S/m as well as the mapping of the dielectric constant with a value of ∼4.7 ± 0.2 are reported and validated by the full-wave electromagnetic modeling of the tip-sample interaction.

The Effect of Y Doping on Monoclinic, Orthorhombic, and Cubic Polymorphs of HfO2: A First Principles Study.

HfO2 can assume different crystalline structures, such as monoclinic, orthorhombic, and cubic polymorphs, each one characterized by unical properties. The peculiarities of this material are also strongly related to the presence of doping elements in the unit cell. Thus, the present paper has the main purpose of studying and comparing twelve different systems characterized by diverse polymorphs and doping percentages. In particular, three different crystalline structures were considered: the monoclinic P21/c, the orthorhombic Pca21, and the cubic Fm3¯m phases of HfO2. Each one has been studied by using Y as a doping agent with three different contents: 0% Y:HfO2, 8% Y:HfO2, 12% Y:HfO2, and 16% Y:HfO2. For all the systems, density functional theory (DFT) methods based on PBE/GGA, and on the HSE hybrid functionals were used to optimize the geometry as well as to study their optical properties. Depending on the polymorphs, Y affects the formation energy in different ways and causes changes in the optical properties. When the percentage of Y did not exceed 12%, a stabilization of the cubic phase fraction and an increase of the dielectric constant was observed. Additionally, the calculated optical bandgap energies and the refractive index are examined to provide an overview of the systems and are compared with experimental data. The bandgaps obtained are in perfect agreement with the experimental values and show a slight increase as the doping percentage grows, while only minor differences are found between the three polymorphs in terms of both refractive index and optical band gap. The adopted first principles study generates a reasonable prediction of the physical-chemical properties of all the systems, thus identifying the effects of doping phenomena.

PBEsol/HSE functional: a promising candidate for vanadium dioxide (B) characterization.

A VO2(B) polymorph has been thoroughly investigated by means of density functional theory (DFT) calculations to evaluate the structure, Raman spectrum, cohesive energy, phonon band structure, an delectronic and optical properties. Among the computed Raman modes, eight of them have been assigned to the VO2(B) structure in full agreement with the corresponding experimental spectra. The minimized structure of the VO2(B) polymorph indicated the presence of negative frequencies in its phonon dispersion curves, confirming the dynamic instability of this material. Herein, the combination of generalized gradient approximation (GGA)/PBEsol with a hybrid HSE functional has been employed to perform ab initio calculations on VO2(B), since the conventional semi-local DFT calculations are believed to underestimate the band gap of materials. By considering the electronic structure calculations, for the first time, we found that the calibration of the PBEsol functional can efficiently model the metallic-like properties of VO2(B) with a band gap of 0.26 eV, while the corresponding electronic bandgap of VO2(B) based on the HSE functional possesses a larger band gap of 0.67 eV. The prediction of optical characteristics of VO2(B) indicated that the optical conductivity of VO2(B) lies in the infrared region of light. This work strongly suggests the combination of GGA/PBEsol with HSE hybrid functionals to carefully describe the physical properties of smart materials exploitable in electronics and optoelectronics applications. The nanostructure of VO2(B) looks promising for IR photodetectors and smart windows applications as a semiconductor material with excellent optical features. It is predicted that in the future VO2(B) will continue to expand the envelope of its capabilities because of its remarkable properties.

Insights into first-principles characterization of the monoclinic VO2(B) polymorph via DFT + U calculation: electronic, magnetic and optical properties.

We have studied the structural, electronic, magnetic, and optical properties of the VO2(B) polymorph using first-principles calculations based on density functional theory (DFT). This polymorph was found to display four optimized structures namely VO2(B)PP, VO2(B)LP, VO2(B)PPD, and VO2(B)LPD using the generalized gradient approximation (GGA) PBE exchange-correlation functional by including/excluding van der Waals interaction. Our derivation provides a theoretical justification for adding an on-site Coulomb U value in the conventional DFT calculations to allow a direct comparison of the two methods. We predicted a zero bandgap of the VO2(B) structure based on GGA/PBE. However, by GGA/PBE + U, we found accurate bandgap values of 0.76, 0.66, and 0.70 eV for VO2(B)PP, VO2(B)LP, and VO2(B)PPD, respectively. The results obtained from DFT + U were accompanied by a structural transition from the metallic to semiconductor property. Here, we verified the non-magnetic characteristic of the monoclinic VO2(B) phase with some available experimental and theoretical data. However, the debate on the magnetic property of this polymorph remains unresolved. Imaginary and real parts of the dielectric function, as computed with the GGA/PBE functional and the GGA/PBE + U functional, were also reported. The first absorption peaks of all considered geometries in the imaginary part of the dielectric constants indicated that the VO2(B) structure could perfectly absorb infrared light. The computed static dielectric constants with positive values, as derived from the optical properties, confirmed the conductivity of this material. Among the four proposed geometries of VO2(B) in this study, the outcomes obtained by VO2(B)PPD reveal good results owing to the excellent consistency of its bandgap, magnetic and optical properties with other experimental and theoretical observations. The theoretical framework in our study will provide useful insight for future practical applications of the VO2(B) polymorph in electronics and optoelectronics.

The Role of Zr on Monoclinic and Orthorhombic HfxZryO2 Systems: A First-Principles Study.

HfO2 shows different polymorphs, including monoclinic and orthorhombic ones, that exhibit singular properties. Moreover, the character of HfO2 is also influenced by the Zr atoms as a doping agent. Here, an extensive study of the monoclinic P21/c and the orthorhombic Pca21 polymorphs of HfO2, Hf0.75Zr0.25O2, and Hf0.5Zr0.5O2 is reported. For all six systems, density functional theory (DFT) methods based on generalized gradient approximations (GGAs) were first used; then the GGA + U method was settled and calibrated to describe the electrical and optical properties of polymorphs and the responses to the oxygen vacancies. Zr had different effects in relation to the polymorph; moreover, the amount of Zr led to important differences in the optical properties of the Pca21 polymorph. Finally, oxygen vacancies were investigated, showing an important modulation of the properties of HfxZryO2 nanostructures. The combined GGA and GGA + U methods adopted in this work generate a reasonable prediction of the physicochemical properties of o- and m-HfxZryO2, identifying the effects of doping phenomena.

Gain enhancement of BiCMOS on-chip sub-THz antennas by mean of meta-cells.

A MM-loaded sub-THz on-chip antenna with a narrow beamwidth, 9 dB gain and a simulated peak efficiency of 76% at the center frequency of 300 GHz is presented. By surrounding the antenna with a single MM-cell ring defined solely on the top metal of the back-end of line, an efficient suppression of the surface waves is obtained. The on-chip antenna has been designed using IHPs 130 nm SiGe BiCMOS technology with a 7-layer metallization stack, combined with the local backside etching process aimed to creating an air cavity which is then terminated by a reflective plane. By comparing the measured MM-loaded antenna performances to its non-MM-loaded counterpart, an enhanced integrity of the main lobe due to the MM-cells shielding effect can be observed. An excellent agreement between the simulated and measured performances has been found, which makes the MM-loaded antennas a valid alternative for the upcoming next-generation sub-THz transceivers.

Nano-antenna array for high efficiency sunlight harvesting.

Solar rectennas are promising devices for energy harvesting. Capability of rectennas to convert incident light into useful energy depends on the antenna efficiency, that is the ratio between the power transferred to the load vs the incoming power. In this work, we first emphasize that for the efficiency to be calculated accurately, antennas need to be treated as receiving devices, not as transmitting ones. Then, we propose an arrangement of antennas that differs from those published so far in three respects: (1) the proposed arrangement is formed by an array of nano-antennas with sub-wavelength inter-element spacing, (2) it comprises a reflecting mirror, and (3) it allows for dual polarization operation. Through numerical simulations, we show that the small lattice pitch we use is responsible for frequency flattening of the lattice impedance over the whole solar spectrum, eventually allowing for excellent matching with the antennas' loads. Also, the small pitch allows for a smooth dependence of the receiving efficiency on the angle of incidence of sunlight. Finally, we show numerically that the reflecting mirror also allows for an almost complete cancellation of light scattered by the receiving antennas. The final result is a polarization insensitive receiving theoretical efficiency larger than 70% over the whole 300-3000 nm spectral range, with a less than 10% energy wasting due to back-scattering of sunlight.

MacGyvered Multiproperty Materials Using Nanocarbon and Jam: A Spectroscopic, Electromagnetic, and Rheological Investigation.

As part of a biopolymer matrix, pectin was investigated to obtain an engineered jam, due to its biodegradability. Only a few examples of pectin-based nanocomposites are present in the literature, and even fewer such bionanocomposites utilize nanocarbon as a filler-mostly for use in food packaging. In the present paper, ecofriendly nanocomposites made from household reagents and displaying multiple properties are presented. In particular, the electrical behavior and viscoelastic properties of a commercial jam were modulated by loading the jam with carbon nanotubes and graphene nanoplates. A new nanocomposite class based on commercial jam was studied, estimating the percolation threshold for each filler. The electrical characterization and the rheological measurements suggest that the behavior above the percolation threshold is influenced by the different morphology-i.e., one-dimensional or two-dimensional-of the fillers. These outcomes encourage further studies on the use of household materials in producing advanced and innovative materials, in order to reduce the environmental impact of new technologies, without giving up advanced devices endowed with different physical properties.

Reversing the Humidity Response of MoS2- and WS2-Based Sensors Using Transition-Metal Salts.

Two-dimensional materials, such as transition-metal dichalcogenides (TMDs), are attractive candidates for sensing applications due to their high surface-to-volume ratio, chemically active edges, and good electrical properties. However, their electrical response to humidity is still under debate and experimental reports remain inconclusive. For instance, in different studies, the impedance of MoS2-based sensors has been found to either decrease or increase with increasing humidity, compromising the use of MoS2 for humidity sensing. In this work, we focus on understanding the interaction between water and TMDs. We fabricated and studied humidity sensors based on MoS2 and WS2 coated with copper chloride and silver nitrate. The devices exhibited high chemical stability and excellent humidity sensing performance in relative humidity between 4 and 80%, with response and recovery times of 2 and 40 s, respectively. We have systematically investigated the humidity response of the materials as a function of the type and amount of induced metal salt and observed the reverse action of sensing mechanisms. This phenomenon is explained based on a detailed structural analysis of the samples considering the Grotthuss mechanism in the presence of charge trapping, which was represented by an appropriate lumped-element model. Our findings open up a possibility to tune the electrical response in a facile manner and without compromising the high performance of the sensor. They offer an insight into the time-dependent performance and aging of the TMD-based sensing devices.

Heterodyne phase shifting method in scanning probe microscopy.

The present paper describes a novel implementation of the continuous phase shifting method (PSM), named heterodyne holography, in a scanning probe microscope configuration, able to retrieve the complex scattered field in on-axis configuration. This can be achieved by acquiring a continuous sequence of holograms at different wavelengths in just a single scan through the combination of scanning interference microscopy and a low-coherent signal acquired in the frequency domain. This method exploits the main advantages of the phase shifting technique and avoids some limits relative to off-axis holography in providing quantitative phase imaging.

Fabrication of ring oscillators using organic molecules of phenacene and perylenedicarboximide.

Organic field-effect transistors (FETs) can be applied to radio-frequency identification tags (RFIDs) and active-matrix flat-panel displays. For RFID application, a cardinal functional block is a ring oscillator using an odd number of inverters to convert DC voltage to AC. Herein, we report the properties of two ring oscillators, one formed with [6]phenacene for a p-channel FET and N,N'-dioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C8) for an n-channel FET, and one formed with 3,10-ditetradecylpicene ((C14H29)2-picene) for a p-channel FET and PTCDI-C8 for an n-channel FET. The former ring oscillator provided a maximum oscillation frequency, f osc of 26 Hz, and the latter a maximum f osc of 21 Hz. The drain-drain voltage, V DD, applied to these ring oscillators was 100 V. This may be the first step towards a future practical ring oscillator using phenacene molecules. The values of field-effect mobility, µ in the p-channel [6]phenacene FET and n-channel PTCDI-C8 FET, which form the building blocks in the ring oscillator with an f osc value of 26 Hz, are 1.19 and 1.50 × 10-1 cm2 V-1 s-1, respectively, while the values in the p-channel (C14H29)2-picene FET and n-channel PTCDI-C8 FET, which form the ring oscillator with an f osc of 21 Hz, are 1.85 and 1.54 × 10-1 cm2 V-1 s-1, respectively. The µ values in the p-channel FETs are higher by one order of magnitude than those of the n-channel FET, which must be addressed to increase the value of f osc. Finally, we fabricated a ring oscillator with ZrO2 instead of parylene for the gate dielectric, which provided the low-voltage operation of the ring oscillator, in which [6]phenacene and PTCDI-C8 thin-film FETs were employed. The value of f osc obtained in the ring oscillator was 24 Hz. In this ring oscillator, the V DD value applied was limited to 20 V. The durability of the ring oscillators was also investigated, and the bias stress effect on the f osc and the amplitude of the output voltage, V out are discussed. This successful operation of ring oscillators represents an important step towards the realization of future practical integrated logic gate circuits using phenacene molecules.

Modeling and Electrochemical Characterization of Electrodes Based on Epoxy Composite with Functionalized Nanocarbon Fillers at High Concentration.

This paper deals with the electrochemical characterization and the equivalent circuit modeling of screen-printed electrodes, modified by an epoxy composite and loaded with carbon nanotubes (CNTs), pristine and functionalized NH2, and graphene nanoplates (GNPs). The fabrication method is optimized in order to obtain a good dispersion even at high concentration, up to 10%, to increase the range of investigation. Due to the rising presence of filler on the surface, the cyclic voltammetric analysis shows an increasing of (i) electrochemical response and (ii) filler concentration as observed by the scanning electron microscopy (SEM). Epoxy/CNTs-NH2 and epoxy/GNPs, at 10% of concentration, show the best electrochemical behavior. Furthermore, epoxy/CNTs-NH2 show a lower percolation threshold than epoxy/CNT, probably due to the direct bond created by amino groups. Furthermore, the electrochemical impedance spectroscopy (EIS) is used to obtain an electrical equivalent circuit (EEC). The EEC model is a remarkable evolution of previous circuits present in the literature, by inserting an accurate description of the capacitive/inductive/resistive characteristics, thus leading to an enhanced knowledge of phenomena that occur during electrochemical processes.

Advanced numerical investigation of the heat flux in an array of microbolometers.

The investigation of the thermal properties of an array of microbolometers has been carried out by mean of two independent numerical analysis, respectively the Direct-Simulation Monte Carlo (DSMC) and the classic diffusive approach of the Fourier's equation. In particular, the thermal dissipation of a hot membrane placed in a low-pressure cavity has been studied for different values of the temperature of the hot body and for different values of the pressure of the environment. The results for the heat flux derived from the two approaches have then been compared and discussed.

Blisters on graphite surface: a scanning microwave microscopy investigation.

Scanning microwave microscopy (SMM) is based on the interaction between a sample and an electromagnetic evanescent field, in the microwave frequency range. SMM is usually coupled with a scanning probe microscopy (SPM) technique such as in our case, a scanning tunneling microscope (STM). In this way, the STM tip is used to control the distance between the probe and the sample while acting as an antenna for the microwave field. Thanks to the peculiarity of our home-made setup, the SMM is a suitable method to study blisters formed on HOPG surface as consequence of an electrochemical treatment. Our system has a "broad-band" approach that opens the way to perform local microwave spectroscopy over a broad frequency range. Moreover, microwaves have the ability to penetrate into the sample allowing the sub-surface characterization of materials. The application of the SMM to characterize blisters formed on the HOPG surface provides information on the sub-layer structures.