The well-known effect of the local interaction between graphene and photoresist (LIGF) during the creation of biosensors is shown to lead to non-uniform distribution of compressive stresses, which deteriorates the adsorption properties of graphene, parameter reproducibility, and detecting ability of influenza B and SARS-Cov-2 biosensors. It is also shown that controlling the occurrence of LIGF areas on a graphene surface by atomic force microscopy or introducing a protective layer between graphene and photoresist can minimize the non-persistent effect of LIGF. The results of influenza B and SARS-CoV-2 imaging on the graphene surface in biosensor chips in a scanning electron microscope are presented.
The quality of graphene intended for use in biosensors was assessed on manufactured chips using a set of methods including atomic force microscopy (AFM), Raman spectroscopy, and low-frequency noise investigation. It is shown that local areas of residues on the graphene surface, formed as a result of the interaction of graphene with a photoresist at the initial stage of chip development, led to a spread of chip resistance (R) in the range of 1–10 kOhm and to an increase in the root mean square (RMS) roughness up to 10 times, which can significantly worsen the reproducibility of the parameters of graphene chips for biosensor applications. It was observed that the control of the photoresist residues after photolithography (PLG) using AFM and subsequent additional cleaning reduced the spread of R values in chips to 1–1.6 kOhm and obtained an RMS roughness similar to the roughness in the graphene film before PLG. Monitoring of the spectral density of low-frequency voltage fluctuation (SU), which provides integral information about the system of defects and quality of the material, makes it possible to identify chips with low graphene quality and with inhomogeneously distributed areas of compressive stresses by the type of frequency dependence SU(f).
To analyze the modification of the functionalized surface of graphene by protein molecules, a chemiluminescent enzyme-linked immunosorbent assay based method was proposed. Using the example of functionalized graphene (FG) purification, the possibilities of chemiluminescent control of the state of its surface are shown. Methods for purifying FG from protein molecules with the restoration of the ability to resorb protein molecules are discussed. It has been shown that the FG surface can be cleaned from sorbed proteins, and a biosensor can be designed again based on such purified graphene, including with a different specificity. Therefore, the graphene sensor can be used repeatedly. Keywords: functionalized graphene, 1-pyrenemethylamine hydrochloride, cyclic voltammetry, chemiluminescence, monoclonal antibodies, biosensors
The well-known effect of the local interaction between graphene and photoresist (LIGF) during the creation of biosensors is shown to lead to non-uniform distribution of compressive stresses, which deteriorates the adsorption properties of graphene, parameter reproducibility, and detecting ability of influenza B and SARS-Cov-2 biosensors. It is also shown that controlling the occurrence of LIGF areas on a graphene surface by atomic force microscopy or introducing a protective layer between graphene and photoresist can minimize the non-persistent effect of LIGF. The results of influenza B and SARS-CoV-2 imaging on the graphene surface in biosensor chips in a scanning electron microscope are presented.
To analyze the modification of the functionalized surface of graphene by protein molecules, a chemiluminescent enzyme immunoassay method was proposed. Using the example of functionalized graphene (FG) purification, the possibilities of chemiluminescent control of the state of its surface are shown. Methods for purifying FG from protein molecules with the restoration of the ability to resorb protein molecules are discussed. It has been shown that the FG surface can be cleaned from sorbed proteins, and a biosensor can be designed again based on such purified graphene, including with a different specificity. Therefore, the graphene sensor can be used repeatedly.
In this study, we discuss the mechanisms behind changes in the conductivity, low-frequency noise, and surface morphology of biosensor chips based on graphene films on SiC substrates during the main stages of the creation of biosensors for detecting influenza viruses. The formation of phenylamine groups and a change in graphene nano-arrangement during functionalization causes an increase in defectiveness and conductivity. Functionalization leads to the formation of large hexagonal honeycomb-like defects up to 500 nm, the concentration of which is affected by the number of bilayer or multilayer inclusions in graphene. The chips fabricated allowed us to detect the influenza viruses in a concentration range of 10−16 g/mL to 10−10 g/mL in PBS (phosphate buffered saline). Atomic force microscopy (AFM) and scanning electron microscopy (SEM) revealed that these defects are responsible for the inhomogeneous aggregation of antibodies and influenza viruses over the functionalized graphene surface. Non-uniform aggregation is responsible for a weak non-linear logarithmic dependence of the biosensor response versus the virus concentration in PBS. This feature of graphene nano-arrangement affects the reliability of detection of extremely low virus concentrations at the early stages of disease.
Among the most significant challenges presented to modern medicine is the problem of cognitive disorders. The relevance of her research is determined by the wide spread of disorders of the higher cortical functions, their significant negative impact on the quality of life of patients, as well as high economic costs on the part of the state and the patient's relatives aimed at organizing medical, diagnostic and rehabilitation processes. The main cause of cognitive impairment in the elderly is Alzheimer's disease. Currently, the criteria for the diagnosis of this nosological form have been developed and are widely used in practice. However, it should be noted that their use is most effective if the patient has a detailed clinical picture, at the stage of dementia. In addition, they provide for the study of biomarkers in a number of cases in the cerebrospinal fluid or using positron emission tomography, which presents certain technical difficulties. Especially significant problems arise in the pre-dement stages. This situation dictates the need to search for new promising diagnostic methods that will have high sensitivity and specificity, as well as the possibility of application in the early stages of Alzheimer's disease, including in outpatient settings. The article provides information about modern methods of computer neuroimaging, discusses the research directions of individual biomarkers, and also shows the prospects for using diagnostic test panels developed on the basis of graphene biosensors, taking into account the latest achievements of nanotechnology and their integration into medical science.
This work is devoted to the development and optimization of the parameters of graphene-based sensors. The graphene films used in the present study were grown on semi-insulating 6H-SiC substrates by thermal decomposition of SiC at the temperature of ~1700 °C. The results of measurements by Auger and Raman spectroscopies confirmed the presence of single-layer graphene on the silicon carbide surface. Model approach to the theory of adsorption on epitaxial graphene is presented. It is demonstrated that the Green-function method in conjunction with the simple substrate models permit one to obtain analytical results for the charge transfer between adsorbed molecules and substrate. The sensor structure was formed on the graphene film by laser. Initially, a simpler gas sensor was made. The sensors developed in this study demonstrated sensitivity to the NO2 concentration at the level of 1–0.01 ppb. The results obtained in the course of development and the results of testing of the graphene-based sensor for detection of protein molecules are also presented. The biosensor was fabricated by the technology previously developed for the gas sensor. The working capacity of the biosensor was tested with an immunochemical system constituted by fluorescein and monoclonal antibodies (mAbs) binding this dye.
In this work, the modification of the surface parameters of graphene chips after electrolysis treatment in a NaClO 4 aqueous solution has been studied. Two electrolysis modes have been analysed. In the first one, a negative potential (-0.2 V) is applied to the graphene chips, while in the second one the potential is positive (0.8 V). Investigation using a number of techniques including atomic force microscopy, Kelvin probe force microscopy, Raman spectroscopy, measurements of current-voltage characteristics and low-frequency noise has shown that the electrolysis mode with application of a positive potential on graphene chips decreases the 1/ f noise and allows one to obtain a uniform surface potential distribution while leaving the graphene structure undamaged. The results of this study help to understand the efficiency and reproducibility of the procedure for electrolysis treatment of graphene chips.
Indium nitride epilayers were grown by metalorganic chemical vapour deposition (MOCVD) on graphene/SiC substrates with different terrace widths. Photoluminescence (PL) properties in the epilayers of different thickness and along the epilayer growth direction were studied with spatial resolution using confocal microscopy. The PL properties have been linked with the structure of the epilayers studied by X-ray diffraction, transmission electron microscopy, atomic force microscopy and Raman scattering. It is revealed that InN on graphene/SiC layers with a thickness of up to similar to 2 mu m consists of chaotically oriented nanocrystals of 20 nm in diameter but tends to transform into a more homogeneous multicrystalline layer at longer deposition durations. The PL band in the top part of thick layers is peaked at 0.687 eV, closer to the band gap than in any InN epilayer grown by MOCVD before. This evidences a low density of equilibrium electrons usually deteriorating performance of InN epilayers. The PL band in thin samples or in the lower part of thick samples is shifted by 60 meV predominantly to quantum confinement in the nanocrystals.
Deep levels studies on a set of n-GaN films grown by MOCVD and HVPE reveal the presence of electron traps with levels near Ec−0.25 eV, Ec−0.55 eV, Ec−0.8 eV, Ec−1 eV, hole traps with levels near Ev+0.9 eV and a band of relatively shallow states in the lower half of the bandgap. The total density of these latter states was estimated to be some 1016 cm−3 and they were tentatively associated with dislocations in GaN based on their high concentration and band-like character. None of the electron or hole traps could be unambiguously related with strong changes of diffusion lengths of minority carriers in various samples. It is proposed that such changes occur due to different surface recombination velocities. An important role of Ec−0.55 eV traps in persistent photoconductivity phenomena in n-GaN has been demonstrated.
Abstract. The response of the chips based on graphene films on SiC substrates (the relative change of the chip resistance) on fluorescein (C20H12O5) in a wide range of its concentrations in phosphate-buffered solution from 1 • 10-3 ng/ml, to 1 • 10+4 ng/ml (7 orders of magnitude) is studied. Detection of fluorescein seems to be a simple and cheap model experiment to study a sensing capability of the graphene in the production of biosensors. It was shown that graphene chips with wide terraces on the surface (1000-nm width and 5-nm height) made it possible to plot calibration dependences of the response of the chips on the concentration of fluorescein.
Graphene is considered as a promising candidate for manufacturing of sensors due to its extreme sensitivity to molecule absorption. In this work, we show the connection between the electrical and optical properties of epitaxial graphene chips grown on 4 H -SiC and intended for the production of protein-based sensors. Using of a complex of techniques, including Raman spectroscopy, atomic force microscopy, Kelvin probe microscopy, study of I-V characteristics and low-frequency noise, it is shown that the character of frequency dependence of the spectral density of voltage fluctuations and its value at a frequency of 1 Hz can be used for classification and selection of graphene chips for their application as sensors. Classification of the graphene chips will allow more efficient development of graphene-based biosensors.
We have studied the response of graphene-film-based chips on SiC substrates (the relative change in the chip resistance) to coming into contact with fluorescein (C 20 H 12 O 5 ) in a wide range of its concentrations in a phosphate-buffered saline solution: from 1 × 10 –3 to 1 × 10 4 ng/mL (seven orders of magnitude). Fluorescein detection seems to be a simple and cheap model experiment to study the sensory ability of graphene in the way of biochips manufacturing. It has been shown that chips with wide terraces on a surface with a step width of about 1000 nm and heights of up to 5 nm made it possible to construct the calibration dependences of chip response on fluorescein concentration.
Treatment of graphene/SiC dies in inorganic electrolytes (KOH, KCl and Na 2 SO 4 ) is discussed. An electrochemical method based on the cyclic voltammetry in a conventional three-electrode cell with Ag/AgCl reference electrode, a platinum counter electrode, and the graphene/SiC dies as working electrode (anode) is used for the treatment. It was observed either partial oxidation of graphene or its complete dissolution with the formation of CO 2 . The treatment performed resulted in the deterioration of the graphene films and change of the graphene-die resistivity depending on the range of the scanning potential applied to the graphene/SiC dies.
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We discuss graphene-on-SiC dies for blood-type sensing. For the sensor application, chemical species to be detected adsorb on the graphene surface and act as electron donors or acceptors resulting in resistance changes of the graphene channel. In this work, graphene films were formed on 4H-SiC substrates by thermal decomposition of the (0001) silicon surface in Ar ambient at a high temperature of 1800-2000 degrees C. The graphene functionalization was performed by the covalent bonding of a nitrophenyl group (C6H5NO2) followed by its reduction to a phenylamine group (C6H5NH2) by using a cyclic voltammetry process. There was a clear and prompt response (current change) of the antibody-coated graphene/SiC dies when the blood antigen matched the antibody. No response occurred when the antibody on the graphene surface mismatched the blood antigen. The experiments demonstrated that a functionalized graphene-on-SiC die has capability in blood sensing, opening a way to manufacture biosensors for detecting blood types and for other applications.
The investigation and identification of point defects in GaN is crucial for improving the reliability of light-emitting and high-power electronic devices. The RY3 defect with a characteristic emission band at about 1.8 eV is often observed in photoluminescence (PL) spectra of n-type GaN grown by hydride vapor phase epitaxy, and it exhibits unusual properties. Its emission band consists of two components: a fast (10-ns lifetime) RL3 with a maximum at 1.8 eV and a slow (100-300 mu s lifetime) YL3 with a maximum at 2.1 eV and zero-phonon line at 2.36 eV. In steady-state PL measurements, the YL3 component emerges with increasing temperature from 90 to 180 K, concurrently with a decrease in the RL3 intensity. The activation energy of both processes is about 0.06 eV. In time-resolved PL, the YL3 intensity abruptly rises when the RL3 intensity begins to saturate. These and other phenomena can be explained using a model of an acceptor with two excited states. A delocalized, effective-mass state at about 0.2 eV above the valence band captures photogenerated holes. These holes transition to the ground state, which produces the RL3 component with a lifetime of similar to 10 ns. Alternatively, they may nonradiatively transition over a 0.06 eV-high barrier to a localized excited state with a level at 1.13 eV above the valence band. Recombination of free electrons or electrons at shallow donors with the holes at this localized excited state is responsible for the YL3 component. The relative intensities of the RL3 and YL3 components are dictated by the probabilities of holes at the shallow excited state to transition to the ground or to the localized excited states. Transition metals and complex defects are considered as the main candidates for the RY3 center.
Functionalization of graphene/SiC dies by nitro-phenyl and its reduction to phenyl-amine is discussed. The graphene films were formed on a SiC substrate by the substrate surface thermal decomposition at 1800-2000°C. The functionalizing procedure included a two-step electrochemical process monitored by cyclic voltammetry and the die resistance. Functionalized graphene/SiC dies with applied antibody were blood sensitive and can be potentially applied to identify promptly types of the blood.
AbstractA fractal-percolation system that includes extended defects and random fluctuations in the alloy composition is formed during the growth of device structures based on Group-III nitrides. It is established that the specific features of this system are determined not only by the growth conditions. It is shown that the diversity of the electrical and optical properties of InGaN/GaN LEDs (light-emitting diodes) emitting at wavelengths of 450–460 and 519–530 nm, as well as that of the electrical properties of AlGaN/GaN HEMT (high-electron-mobility transistor) structures, is due to modification of the properties of the fractal-percolation system both during the growth process and under the action of the injection current and irradiation. The influence exerted by these specific features on the service life of light-emitting devices and on the reliability of AlGaN/GaN HEMT structures is discussed.