Biosensor Based on Graphene Directly Grown by MW-PECVD for Detection of COVID-19 Spike (S) Protein and Its Entry Receptor ACE2.

Biosensors based on graphene field-effect transistors (G-FET) for detecting COVID-19 spike S protein and its receptor ACE2 were reported. The graphene, directly synthesized on SiO2/Si substrate by microwave plasma-enhanced chemical vapor deposition (MW-PECVD), was used for FET biosensor fabrication. The commercial graphene, CVD-grown on a copper substrate and subsequently transferred onto a glass substrate, was applied for comparison purposes. The graphene structure and surface morphology were studied by Raman scattering spectroscopy and atomic force microscope. Graphene surfaces were functionalized by an aromatic molecule PBASE (1-pyrenebutanoic acid succinimidyl ester), and subsequent immobilization of the receptor angiotensin-converting enzyme 2 (ACE2) was performed. A microfluidic system was developed, and transfer curves of liquid-gated FET were measured after each graphene surface modification procedure to investigate ACE2 immobilization by varying its concentration and subsequent spike S protein detection. The directly synthesized graphene FET sensitivity to the receptor ACE2, evaluated in terms of the Dirac voltage shift, exceeded the sensitivity of the transferred commercial graphene-based FET. The concentration of the spike S protein was detected in the range of 10 ag/mL up to 10 µg/mL by using a developed microfluidic system and measuring the transfer characteristics of the liquid-gated G-FETs. It was found that the shift of the Dirac voltage depends on the spike S concentration and was 27 mV with saturation at 10 pg/mL for directly synthesized G-FET biosensor, while for transferred G-FET, the maximal shift of 70 mV was obtained at 10 µg/mL with a tendency of saturation at 10 ng/mL. The detection limit as low as 10 ag/mL was achieved for both G-FETs. The sensitivity of the biosensors at spike S concentration of 10 pg/mL measured as relative current change at a constant gate voltage corresponding to the highest transconductance of the G-FETs was found at 5.6% and 8.8% for directly synthesized and transferred graphene biosensors, respectively. Thus, MW-PECVD-synthesized graphene-based biosensor demonstrating high sensitivity and low detection limit has excellent potential for applications in COVID-19 diagnostics.

Hydrophilic Surface Modification of Amorphous Hydrogenated Carbon Nanocomposite Films via Atmospheric Oxygen Plasma Treatment.

Herein we investigated hydrophilic surface modification of SiOx containing amorphous hydrogenated carbon nanocomposite films (DLC:SiOx) via the use of atmospheric oxygen plasma treatment. The modified films exhibited effective hydrophilic properties with complete surface wetting. More detailed water droplet contact angle (CA) measurements revealed that oxygen plasma treated DLC:SiOx films maintained good wetting properties with CA of up to 28 ± 1° after 20 days of aging in ambient air at room temperature. This treatment process also increased surface root mean square roughness from 0.27 nm to 1.26 nm. Analysis of the surface chemical states suggested that the hydrophilic behavior of DLC:SiOx treated with oxygen plasma is attributed to surface enrichment with C-O-C, SiO2, and Si-Si chemical bonds as well as significant removal of hydrophobic Si-CHx functional groups. The latter functional groups are prone to restoration and are mainly responsible for the increase in CA with aging. Possible applications of the modified DLC:SiOx nanocomposite films could include biocompatible coatings for biomedical applications, antifogging coatings for optical components, and protective coatings to prevent against corrosion and wear.

The Graphene Structure's Effects on the Current-Voltage and Photovoltaic Characteristics of Directly Synthesized Graphene/n-Si(100) Diodes.

Graphene was synthesized directly on Si(100) substrates by microwave plasma-enhanced chemical vapor deposition (MW-PECVD). The effects of the graphene structure on the electrical and photovoltaic properties of graphene/n-Si(100) were studied. The samples were investigated using Raman spectroscopy, atomic force microscopy, and by measuring current-voltage (I-V) graphs. The temperature of the hydrogen plasma annealing prior to graphene synthesis was an essential parameter regarding the graphene/Si contact I-V characteristics and photovoltaic parameters. Graphene n-type self-doping was found to occur due to the native SiO2 interlayer at the graphene/Si junction. It was the prevalent cause of the significant decrease in the reverse current and short-circuit current. No photovoltaic effect dependence on the graphene roughness and work function could be observed.

Catalyst-Less and Transfer-Less Synthesis of Graphene on Si(100) Using Direct Microwave Plasma Enhanced Chemical Vapor Deposition and Protective Enclosures.

In this study, graphene was synthesized on the Si(100) substrates via the use of direct microwave plasma-enhanced chemical vapor deposition (PECVD). Protective enclosures were applied to prevent excessive plasma etching of the growing graphene. The properties of synthesized graphene were investigated using Raman scattering spectroscopy and atomic force microscopy. Synthesis time, methane and hydrogen gas flow ratio, temperature, and plasma power effects were considered. The synthesized graphene exhibited n-type self-doping due to the charge transfer from Si(100). The presence of compressive stress was revealed in the synthesized graphene. It was presumed that induction of thermal stress took place during the synthesis process due to the large lattice mismatch between the growing graphene and the substrate. Importantly, it was demonstrated that continuous horizontal graphene layers can be directly grown on the Si(100) substrates if appropriate configuration of the protective enclosure is used in the microwave PECVD process.

Diamond Like Carbon Films Containing Si: Structure and Nonlinear Optical Properties.

In the present research diamond-like carbon (DLC) films containing 4-29 at.% of silicon were deposited by reactive magnetron sputtering of carbon target. Study by X-ray photoelectron spectroscopy revealed the presence of Si-C bonds in the films. Nevertheless, a significant amount of Si-O-C and Si-Ox bonds was present too. The shape of the Raman scattering spectra of all studied diamond-like carbon containing silicon (DLC:Si) films was typical for diamond-like carbon. However, some peculiarities related to silicon doping were found. Studies on the dependence of DLC:Si of the optical transmittance spectra on the Si atomic concentration have shown that doping by silicon affects linear, as well as nonlinear, optical properties of the films. It is shown that the normalized reflectance of DLC:Si films decreased with the increased exciting light fluence. No clear relation between the normalized reflectance and photoexcited charge carrier relaxation time was found. It was suggested that that the normalized reflectance decrease with fluence can be related to nonlinear optical properties of the hydrogenated diamond-like carbon phase in DLC:Si film.

Hydrogen-Free Diamond Like Carbon Films with Embedded Cu Nanoparticles: Structure, Composition and Reverse Saturable Absorption Effect.

In the present research, hydrogen-free diamond like carbon films with embedded copper nanoparticles (DLC:Cu) were grown by simultaneous DC magnetron sputtering of the graphite and copper targets. X-ray photoelectron spectroscopy was used to define the composition of the samples. Atomic force microscopy studies of diamond, like carbon films containing different amount of copper, revealed wide range of the surface morphologies as well as sizes and shapes of the embedded copper nanoclusters. Raman scattering spectra of all the DLC:Cu films investigated were typical for diamond-like carbon (including samples containing more than 60 at.% of copper). sp3/sp2 carbon bond ratio in the films decreased with the increase of the Cu amount in the films. According to the optical absorbance measurements, the surface plasmon resonance related absorption peak of DLC:Cu films was only detected in the films containing 28.45 at.% Cu. For the diamond like carbon films containing more than 40 at.% Cu, a further increase of Cu amount in the nanocomposite resulted in minor changes of the absorbance spectra. Some correlation between the changes of the samples surface morphology as well as phase structure and optical absorbance spectra of the films was found. In all cases, reverse-saturable absorption of the DLC:Cu films was observed. For some DLC:Cu films damage of the sample occurred at higher light fluences that can be related to the heating that is caused by the surface plasmon resonance effect.

Diamond like carbon nanocomposites with embedded metallic nanoparticles.

In this work we present an overview on structure formation, optical and electrical properties of diamond like carbon (DLC) based metal nanocomposites deposited by reactive magnetron sputtering and treated by plasma and laser ablation methods. The influence of deposition mode and other technological conditions on the properties of the nanosized filler, matrix components and composition were studied systematically in relation to the final properties of the nanocomposites. Applications of the nanocomposites in the development of novel biosensors combining resonance response of wave guiding structures in DLC based nanocomposites as well as plasmonic effects are also presented.

Photovoltaic Properties and Ultrafast Plasmon Relaxation Dynamics of Diamond-Like Carbon Nanocomposite Films with Embedded Ag Nanoparticles.

Ultrafast relaxation dynamics of diamond-like carbon (DLC) films with embedded Ag nanoparticles (DLC:Ag) and photovoltaic properties of heterojunctions consisting of DLC:Ag and crystalline silicon (DLC:Ag/Si) were investigated by means of transient absorption (TAS) spectroscopy and photovoltaic measurements. The heterojunctions using both p type and n type silicon were studied. It was found that TAS spectra of DLC:Ag films were dependent on the used excitation wavelength. At wavelengths where Ag nanoparticles absorbed light most intensively, only DLC signal was registered. This result is in good accordance with an increase of the DLC:Ag/Si heterojunction short circuit current and open circuit voltage with the excitation wavelength in the photovoltaic measurements. The dependence of the TAS spectra of DLC:Ag films and photovoltaic properties of DLC:Ag/Si heterostructures on the excitation wavelength was explained as a result of trapping of the photoexcited hot charge carriers in DLC matrix. The negative photovoltaic effect was observed for DLC:Ag/p-Si heterostructures and positive ("conventional") for DLC:Ag/n-Si ones. It was explained by the excitation of hot plasmonic holes in the Ag nanoparticles embedded into DLC matrix. Some decrease of DLC:Ag/Si heterostructures photovoltage as well as photocurrent with DLC:Ag film thickness was observed, indicating role of the interface in the charge transfer process of photocarriers excited in Ag nanoparticles.

Nitrogen-doped twisted graphene grown on copper by atmospheric pressure CVD from a decane precursor.

We present Raman studies of graphene films grown on copper foil by atmospheric pressure CVD with n-decane as a precursor, a mixture of nitrogen and hydrogen as the carrier gas, under different hydrogen flow rates. A novel approach for the processing of the Raman spectroscopy data was employed. It was found that in particular cases, the various parameters of the Raman spectra can be assigned to fractions of the films with different thicknesses. In particular, such quantities as the full width at half maximum of the 2D peak and the position of the 2D graphene band were successfully applied for the elaborated approach. Both the G- and 2D-band positions of single layer fractions were blue-shifted, which could be associated with the nitrogen doping of studied films. The XPS study revealed the characteristics of incorporated nitrogen, which was found to have a binding energy around 402 eV. Moreover, based on the statistical analysis of spectral parameters and the observation of a G-resonance, the twisted nature of the double-layer fraction of graphene grown with a lower hydrogen feeding rate was demonstrated. The impact of the varied hydrogen flow rate on the structural properties of graphene and the nitrogen concentration is also discussed.

Annealing Effects on Structure and Optical Properties of Diamond-Like Carbon Films Containing Silver.

In the present study, diamond-like carbon films with embedded Ag nanoparticles (DLC:Ag) were deposited by reactive magnetron sputtering. Structure of the films was investigated by Raman scattering spectroscopy. Atomic force microscopy was used to define thickness of DLC:Ag films as well as to study the surface morphology and size distribution of Ag nanoparticles. Optical absorbance and reflectance spectra of the films were studied in the 180-1100-nm range. Air annealing effects on structure and optical properties of the DLC:Ag were investigated. Annealing temperatures were varied in the 180-400 °C range. Changes of size and shape of the Ag nanoclusters took place due to agglomeration. It was found that air annealing of DLC:Ag films can result in graphitization following destruction of the DLC matrix. Additional activation of surface-enhanced Raman scattering (SERS) effect in DLC:Ag films can be achieved by properly selecting annealing conditions. Annealing resulted in blueshift as well as significant narrowing of the plasmonic absorbance and reflectance peaks. Moreover, quadrupole surface plasmon resonance peaks appeared. Modeling of absorption spectra of the nanoclusters depending on the shape and surrounding media has been carried out.

Spectroellipsometric characterization and modeling of plasmonic diamond-like carbon nanocomposite films with embedded Ag nanoparticles.

Diamond-like carbon nanocomposite films with embedded silver nanoparticles are considered experimentally (spectroellipsometric characterization) and theoretically (modeling of optical properties). Metallic nanocomposite films were synthesized by reactive magnetron sputtering and were studied by transmission electron microscope (TEM) and atomic force microscope (AFM). The optical constants of the films were determined from spectroscopic ellipsometry measurements and were modeled using the Maxwell-Garnett approximations. Comparison between the extended and renormalized Maxwell-Garnett theory was conducted. Surface plasmon resonance peak have been found to be strongly dependent on the shape of nanoparticles and interaction between them.