Quantum Graphene Asymmetric Devices for Harvesting Electromagnetic Energy.

We present here the fabrication at the wafer level and the electrical performance of two types of graphene diodes: ballistic trapezoidal-shaped graphene diodes and lateral tunneling graphene diodes. In the case of the ballistic trapezoidal-shaped graphene diode, we observe a large DC current of 200 µA at a DC bias voltage of ±2 V and a large voltage responsivity of 2000 v/w, while in the case of the lateral tunneling graphene diodes, we obtain a DC current of 1.5 mA at a DC bias voltage of ±2 V, with a voltage responsivity of 3000 v/w. An extended analysis of the defects produced during the fabrication process and their influences on the graphene diode performance is also presented.

Subthreshold slope below 60 mV/decade in graphene transistors induced by channel geometry at the wafer-scale.

In this paper, we demonstrate experimentally that field-effect transistors with nanoconstricted graphene monolayer channels have a subthreshold swing (SS) below 60 mV/dec, which is slightly dependent on temperature. Two shapes of nanoconstricted graphene monolayers are considered: (i) a bow-tie shape, representative for a symmetric channel, and (ii) a trapezoidal shape, which illustrates an asymmetric channel. While both types of nonuniform channels are opening a bandgap in graphene, thus showing an on/off ratio of 105, the SS in the graphene bow-tie channel is below 60 mV/dec in the temperature range 25 °C-44 °C.

Synthesis and Mechanical Performances of Polyurethane Bio-Based Adhesives Resulted from the Depolymerization of Lignocellulose Biomass.

The purpose of this study is to valorize biomass waste into products with added value for indoor applications. Thus, broadleaf sawdust was chemically processed by the solvolysis reaction in acid catalysis in the presence of diethylene glycol at 160 °C for 4 h. After filtration and removal of the unreacted biomass, the glycolysis product was used in 6 different polyurethane adhesive formulations for wood bonding. The adhesive films were characterized by FT-IR, TGA, and DMA, while the mechanical performances were investigated by tensile and three-point bending tests. An innovative method for the determination of the working time was proposed. After the displacement of the wood substrates by the tensile test, the bonded area was investigated by SEM analysis. To confirm a correlation between the mechanical performances of the adhesives and their structure/formulation, two-dimensional (2D) simulations were performed based on the tensile tests.

Tuning the infrared resonance of thermal emission from metasurfaces working in near-infrared.

We simulated numerically and demonstrated experimentally that the thermal emittance of a metasurface consisting of an array of rectangular metallic meta-atoms patterned on a layered periodic dielectric structure grown on top of a metallic layer can be tuned by changing several parameters. The resonance frequency, designed to be in the near-infrared spectral region, can be tuned by modifying the number of dielectric periods, and the polarization and incidence angle of the incoming radiation. In addition, the absorbance/emittance value at the resonant wavelength can be tuned by modifying the orientation of meta-atoms with respect to the illumination direction.

Surface Modification Using MAPLE Technique for Improving the Mechanical Performance of Adhesive Joints.

The adhesive bonds that ensure the appropriate mechanical properties for metal joining imply the surface chemical and wetting modification characteristics of the substrates. In this work, matrix-assisted pulsed laser evaporation (MAPLE) was used for the surface modification of Al via the deposition of two chemical compounds, polyvinyl alcohol (PVA) and triethanolamine (TEA), from frozen aqueous solutions. The deposition of the TEA and PVA layers was evidenced by FT-IR, SEM, and AFM analysis. The contact angle measurements evidenced the change in the hydrophilicity of the surface and surface free energies. The performance of the commercial silyl-based polymer adhesive Bison Max Repair Extreme Adhesive® was evaluated by tensile strength measurements. This method led to a change in tensile strength of 54.22% in the case of Al-TEA and 36.34% for Al-PVA compared with the control. This study gives preliminary insights into using MAPLE, for the first time in adhesive applications, as a pretreatment method for Al plates for adhesive bonding reinforcement.

UV-Nanoimprint and Deep Reactive Ion Etching of High Efficiency Silicon Metalenses: High Throughput at Low Cost with Excellent Resolution and Repeatability.

As metasurfaces begin to find industrial applications there is a need to develop scalable and cost-effective fabrication techniques which offer sub-100 nm resolution while providing high throughput and large area patterning. Here we demonstrate the use of UV-Nanoimprint Lithography and Deep Reactive Ion Etching (Bosch and Cryogenic) towards this goal. Robust processes are described for the fabrication of silicon rectangular pillars of high pattern fidelity. To demonstrate the quality of the structures, metasurface lenses, which demonstrate diffraction limited focusing and close to theoretical efficiency for NIR wavelengths λ ∈ (1.3 µm, 1.6 µm), are fabricated. We demonstrate a process which removes the characteristic sidewall surface roughness of the Bosch process, allowing for smooth 90-degree vertical sidewalls. We also demonstrate that the optical performance of the metasurface lenses is not affected adversely in the case of Bosch sidewall surface roughness with 45 nm indentations (or scallops). Next steps of development are defined for achieving full wafer coverage.

Nanomaterials and Devices for Harvesting Ambient Electromagnetic Waves.

This manuscript presents an overview of the implications of nanomaterials in harvesting ambient electromagnetic waves. We show that the most advanced electromagnetic harvesting devices are based on oxides with a thickness of few nanometers, carbon nanotubes, graphene, and molybdenum disulfide thanks to their unique physical properties. These tiny objects can produce in the years to come a revolution in the harvesting of energy originating from the Sun, heat, or the Earth itself.

Harvesting microwave energy using pyroelectricity of nanostructured graphene/zirconium-doped hafnium oxide ferroelectric heterostructures.

In this work, we present the design, atomistic/circuit/electromagnetic simulations, and the experimental results for graphene monolayer/zirconium-doped hafnium oxide (HfZrO) ultra-thin ferroelectric-based field effect transistors fabricated at the wafer scale, regarding the pyroelectricity generation directly from microwave signals, at room temperature and below it, namely at 218 K and at 100 K. The transistors work like energy harvesters, i.e. they collect low-power microwave energy and transform it into DC voltages with a maximum amplitude between 20 and 30 mV. The same devices function as microwave detectors in the band 1-10.4 GHz and at very low input power levels not exceeding 80µW when they are biased by using a drain voltage, with average responsivity values in the range 200-400 mV mW-1.

Ultralow voltage (1µV) electrical switching of SnS thin films driven by a vertical electric field.

In this paper, we show in a series of experiments on 10 nm thick SnS thin film-based back-gate transistors that in the absence of the gate voltage, the drain current versus drain voltage (ID-VD) dependence is characterized by a weak drain current and by an ambipolar transport mechanism. When we apply a gate voltage as low as 1µV, the current increases by several orders of magnitude and theID-VDdependence changes drastically, with the SnS behaving as ap-type semiconductor. This happens because the current flows from the source (S) to the drain (D) electrode through a discontinuous superficial region of the SnS film when no gate voltage is applied. On the contrary, when minute gate voltages are applied, the vertical electric field applied to the multilayer SnS induces a change in the flow path of the charge carriers, involving the inner and continuous SnS layer in the electrical conduction. Moreover, we show that high gate voltages can tune significantly the SnS bandgap.

Synthesis and characterization of polyurethane flexible foams provided from PET derivatives, fly ash, and glass wastes.

The aim of this study involved the synthesis and characterization of polyurethane (PUR) foams obtained from poly(ethylene terephthalate) (PET) depolymerization products and two types of filling agents, namely fly ash and glass waste. The depolymerized PET-based products were obtained by zinc acetate-catalyzed glycolysis process in diethylene glycol (DEG) as a co-reactant. The resulting glycolysis products were contacted with methylene diphenyl diisocyanate, castor oil, and reinforcing agents. The resulting PUR specimens were characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), EDX mapping, mechanical tests, and thermal analysis. The analysis confirmed that the best mechanical performances were registered by the specimens with the lowest concentration of filling agent, while the highest thermal resistance was achieved by the PUR foams with the highest concentration of reinforcing agent.

Ultrathin tin sulfide field-effect transistors with subthreshold slope below 60 mV/decade.

In this paper, we present for the first time a field-effect-transistor (FET) having a 10 nm thick tin sulfide (SnS) channel fabricated at the wafer scale with high reproducibility. SnS-based FETs are in on-state for increasing positive back-gate voltages up to 6 V, whereas the off-state is attained for negative back-gate voltages not exceeding -6 V, the on/off ratio being in the range 102-103depending on FET dimensions. The SnS FETs show a subthreshold slope (SS) below 60 mV/decade thanks to the in-plane ferroelectricity of SnS and attaining a minimum value SS = 21 mV/decade. Moreover, the low SS values can be explained by the existence of a negative value of the capacitance of the SnS thin film up to 10 GHz (for any DC bias voltage between 1 and 5 V), with the minimum value being -12.87 pF at 0.1 GHz.

Epoxy Coatings Containing Modified Graphene for Electromagnetic Shielding.

This study presents the functionalization and characterization of graphene and electromagnetic interference (EMI) attenuation capacity in epoxy-nanocomposites. The modification of graphene involved both small molecules and polymers for compatibilization with epoxy resin components to provide EMI shielding. The TGA and RAMAN analyses confirmed the synthesis of graphene with a different layer thickness of the graphene sheets. Graphene samples with different layer thicknesses (monolayer, few layers, and multilayer) were selected and further employed for epoxy coating formulation. The obtained nanocomposites were characterized in terms of EMI shielding effectiveness, SEM, micro-CT, magnetic properties, and stress-strain resistance. The EMI shielding effectiveness results indicated that the unmodified graphene and hexamethylene diamine (HMDA) modified graphene displayed the best EMI shielding properties at 11 GHz. However, the epoxy nanocomposites based on HMDA modified graphene displayed better flexibility with an identical EMI shielding effectiveness compared to the unmodified graphene despite the formation of aggregates. The improved flexibility of the epoxy nanocomposites and EMI shielding characteristics of HMDA functionalized graphene offers a practical solution for textile coatings with microwave absorbing (MA) capacity.

The microwave properties of tin sulfide thin films prepared by RF magnetron sputtering techniques.

In this paper we present the microwave properties of tin sulfide (SnS) thin films with the thickness of just 10 nm, grown by RF magnetron sputtering techniques on a 4 inch silicon dioxide/high-resistivity silicon wafer. In this respect, interdigitated capacitors in coplanar waveguide technology were fabricated directly on the SnS film to be used as both phase shifters and detectors, depending on the ferroelectric or semiconductor behaviour of the SnS material. The ferroelectricity of the semiconducting thin layer manifests itself in a strong dependence of the electrical permittivity on the applied DC bias voltage, which induces a phase shift of 30 degrees mm-1at 1 GHz and of 8 degrees mm-1at 10 GHz, whereas the transmission losses are less than 2 dB in the frequency range 2-20 GHz. We have also investigated the microwave detection properties of SnS, obtaining at 1 GHz a voltage responsivity of about 30 mV mW-1in the unbiased case and with an input power level of only 16µW.

Influence of Random Plasmonic Metasurfaces on Fluorescence Enhancement.

One of the strategies employed to increase the sensitivity of the fluorescence-based biosensors is to deposit chromophores on plasmonic metasurfaces which are periodic arrays of resonating nano-antennas that allow the control of the electromagnetic field leading to fluorescence enhancement. While artificially engineered metasurfaces realized by micro/nano-fabrication techniques lead to a precise tailoring of the excitation field and resonant cavity properties, the technological overhead, small areas, and high manufacturing cost renders them unsuitable for mass production. A method to circumvent these challenges is to use random distribution of metallic nanoparticles sustaining plasmonic resonances, which present the properties required to significantly enhance the fluorescence. We investigate metasurfaces composed of random aggregates of metal nanoparticles deposited on a silicon and glass substrates. The finite difference time domain simulations of the interaction of the incident electromagnetic wave with the structures reveals a significant enhancement of the excitation field, which is due to the resonant plasmonic modes sustained by the nanoparticles aggregates. We experimentally investigated the role of these structures in the fluorescent behaviour of Rhodamine 6G dispersed in polymethylmethacrylate finding an enhancement that is 423-fold. This suggests that nanoparticle aggregates have the potential to constitute a suitable platform for low-cost, mass-produced fluorescent biosensors.

Graphene/Ferroelectric (Ge-Doped HfO2) Adaptable Transistors Acting as Reconfigurable Logic Gates.

We present an array of 225 field-effect transistors (FETs), where each of them has a graphene monolayer channel grown on a 3-layer deposited stack of 22 nm control HfO2/5 nm Ge-HfO2 intermediate layer/8 nm tunnel HfO2/p-Si substrate. The intermediate layer is ferroelectric and acts as a floating gate. All transistors have two top gates, while the p-Si substrate is acting as a back gate. We show that these FETs are acting memtransistors, working as two-input reconfigurable logic gates with memory, the type of the logic gate depending only on the values of the applied gate voltages and the choice of a threshold current.

Silicon Metalens Fabrication from Electron Beam to UV-Nanoimprint Lithography.

This study presents the design and manufacture of metasurface lenses optimized for focusing light with 1.55 µm wavelength. The lenses are fabricated on silicon substrates using electron beam lithography, ultraviolet-nanoimprint lithography and cryogenic deep reactive-ion etching techniques. The designed metasurface makes use of the geometrical phase principle and consists of rectangular pillars with target dimensions of height h = 1200 nm, width w = 230 nm, length l = 354 nm and periodicity p = 835 nm. The simulated efficiency of the lens is 60%, while the master lenses obtained by using electron beam lithography are found to have an efficiency of 45%. The lenses subsequently fabricated via nanoimprint are characterized by an efficiency of 6%; the low efficiency is mainly attributed to the rounding of the rectangular nanostructures during the pattern transfer processes from the resist to silicon due to the presence of a thicker residual layer.

Magnetic silica particles functionalized with guanidine derivatives for microwave-assisted transesterification of waste oil.

This study aimed to develop a facile synthesis procedure for heterogeneous catalysts based on organic guanidine derivatives superbases chemically grafted on silica-coated Fe3O4 magnetic nanoparticles. Thus, the three organosilanes that were obtained by reacting the selected carbodiimides (N,N'-dicyclohexylcarbodiimide (DCC), N,N'-diisopropylcarbodiimide (DIC), respectively 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) with 3-aminopropyltriethoxysilane (APTES) were used in a one-pot synthesis stage for the generation of a catalytic active protective shell through the simultaneous hydrolysis/condensation reaction with tetraethyl orthosilicate (TEOS). The catalysts were characterized by FTIR, TGA, SEM, BET and XRD analysis confirming the successful covalent attachment of the organic derivatives in the silica shell. The second aim was to highlight the capacity of microwaves (MW) to intensify the transesterification process and to evaluate the activity, stability, and reusability characteristics of the catalysts. Thus, in MW-assisted transesterification reactions, all catalysts displayed FAME yields of over 80% even after 5 reactions/activation cycles. Additionally, the influence of FFA content on the catalytic activity was investigated. As a result, in the case of Fe3O4@SiO2-EDG, a higher tolerance towards the FFA content can be noticed with a FAME yield of over 90% (for a 5% (weight) vs oil catalyst content) and 5% weight FFA content.

Metasurface Fabrication by Cryogenic and Bosch Deep Reactive Ion Etching.

The research field of metasurfaces has attracted considerable attention in recent years due to its high potential to achieve flat, ultrathin optical devices of high performance. Metasurfaces, consisting of artificial patterns of subwavelength dimensions, often require fabrication techniques with high aspect ratios (HARs). Bosch and Cryogenic methods are the best etching candidates of industrial relevance towards the fabrication of these nanostructures. In this paper, we present the fabrication of Silicon (Si) metalenses by the UV-Nanoimprint Lithography method and cryogenic Deep Reactive Ion Etching (DRIE) process and compare the results with the same structures manufactured by Bosch DRIE both in terms of technological achievements and lens efficiencies. The Cryo- and Bosch-etched lenses attain efficiencies of around 39% at wavelength λ = 1.50 µm and λ = 1.45 µm against a theoretical level of around 61% (for Si pillars on a Si substrate), respectively, and process modifications are suggested towards raising the efficiencies further. Our results indicate that some sidewall surface roughness of the Bosch DRIE is acceptable in metalense fabrication, as even significant sidewall surface roughness in a non-optimized Bosch process yields reasonable efficiency levels.

Bisphenol A Adsorption on Silica Particles Modified with Beta-Cyclodextrins.

This study presents the synthesis of silica particles bearing two beta-cyclodextrin (BCD) (beta-cyclodextrin-BCD-OH and diamino butane monosubstituted beta-cyclodextrin-BCD-NH2). The successful synthesis of the BCD-modified silica was confirmed by FT-IR and TGA. Using contact angle measurements, BET analysis and SEM characterization, a possible formation mechanism for the generation of silica particles bearing BCD derivatives on their surface was highlighted. The obtained modified silica displayed the capacity to remove bisphenol A (BPA) from wastewater due to the presence of the BCD moieties on the surface of the silica. The kinetic analysis showed that the adsorption reached equilibrium after 180 min for both materials with qe values of 107 mg BPA/g for SiO2-BCD-OH and 112 mg BPA/g for SiO2-BCD-NH2. The process followed Ho's pseudo-second-order adsorption model sustaining the presence of adsorption sites with different activities. The fitting of the Freundlich isotherm model on the experimental results was also evaluated, confirming the BCD influence on the materials' adsorption properties.

The Behavior of Gold Metallized AlN/Si- and AlN/Glass-Based SAW Structures as Temperature Sensors.

Thin AlN piezoelectric layers have been deposited on high resistivity Si and glass substrates by reactive RF magnetron sputtering, in order to manufacture one-port gigahertz operating surface acoustic wave (SAW)-type resonators to be used as temperature sensors. The growth morphology surface topography, crystallographic structure, and crystalline quality of the AlN layers have been analyzed. Advanced nanolithographic techniques have been used to manufacture structures having interdigitated transducers with fingers and finger interdigit spacing width in the range of 250-170 nm. High resonance frequency ensures the increase of the sensitivity, but also of its normalized value, the temperature coefficient of frequency (TCF). The resonance frequency shift versus temperature has been measured in the -267°C-+150°C temperature range, using a cryostat setup adapted for on wafer microwave measurements up to 50 GHz. The sensitivity and the TCF were determined in the 25 °C-150 °C temperature range.