Graphene Thin Films Research Articles

Polyaniline doped graphene thin film to enhance the electrical conductivity in carbon fiber-reinforced composites for lightning strike mitigation

Multifunctional carbon fiber-reinforced polymer (CFRP) composites are promising structural materials for lightweight applications. However, the low conductivity in the through-thickness direction of the composites limits its applications in the fields that require the high stability of composite against lightning strikes. This work presents the study on the synergetic effect of conducting polymer, polyaniline (PANI), and graphene nanoplatelets (GNP) for increasing the electrical conductivity of CFRP composites. PANI doped GNP flexible film is fabricated with the aid of compatible polymer polyvinylpyrrolidone (PVP), and its effect on the electrical conductivity of CFRP composites has been studied. About 250% in through-thickness conductivity has improved with 11 wt% GNP as a function of the composite. The incorporation of conductive film not only increases the conductivity of the CFRP laminates but also enhances the resistance against lightning strikes. Scanning Electron Microscopy (SEM), Thermogravimetric Analysis (TGA), three-point bending tests were used to analyze the morphology, thermal stability, and mechanical strengths of the composites. Finally, the observation of post-strike damage confirms the importance of through-thickness conductivity for mitigating the lightning strike damage.

Functionalized Masks: Powerful Materials against COVID-19 and Future Pandemics.

The outbreak of COVID‐19 revealed the vulnerability of commercially available face masks. Without having antibacterial/antiviral activities, the current masks act only as filtering materials of the aerosols containing microorganisms. Meanwhile, in surgical masks, the viral and bacterial filtration highly depends on the electrostatic charges of masks. These electrostatic charges disappear after 8 h, which leads to a significant decline in filtration efficiency. Therefore, to enhance the masks’ protection performance, fabrication of innovative masks with more advanced functions is in urgent demand. This review summarizes the various functionalizing agents which can endow four important functions in the masks including i) boosting the antimicrobial and self‐disinfectant characteristics via incorporating metal nanoparticles or photosensitizers, ii) increasing the self‐cleaning by inserting superhydrophobic materials such as graphenes and alkyl silanes, iii) creating photo/electrothermal properties by forming graphene and metal thin films within the masks, and iv) incorporating triboelectric nanogenerators among the friction layers of masks to stabilize the electrostatic charges and facilitating the recharging of masks. The strategies for creating these properties toward the functionalized masks are discussed in detail. The effectiveness and limitation of each method in generating the desired properties are well‐explained along with addressing the prospects for the future development of masks.

Controlled Fabrication of Quality ZnO NWs/CNTs and ZnO NWs/Gr Heterostructures via Direct Two-Step CVD Method.

A novel and advanced approach of growing zinc oxide nanowires (ZnO NWs) directly on single-walled carbon nanotubes (SWCNTs) and graphene (Gr) surfaces has been demonstrated through the successful formation of 1D–1D and 1D–2D heterostructure interfaces. The direct two-step chemical vapor deposition (CVD) method was utilized to ensure high-quality materials’ synthesis and scalable production of different architectures. Iron-based universal compound molecular ink was used as a catalyst in both processes (a) to form a monolayer of horizontally defined networks of SWCNTs interfaced with vertically oriented ZnO NWs and (b) to grow densely packed ZnO NWs directly on a graphene surface. We show here that our universal compound molecular ink is efficient and selective in the direct synthesis of ZnO NWs/CNTs and ZnO NWs/Gr heterostructures. Heterostructures were also selectively patterned through different fabrication techniques and grown in predefined locations, demonstrating an ability to control materials’ placement and morphology. Several characterization tools were employed to interrogate the prepared heterostructures. ZnO NWs were shown to grow uniformly over the network of SWCNTs, and much denser packed vertically oriented ZnO NWs were produced on graphene thin films. Such heterostructures can be used widely in many potential applications, such as photocatalysts, supercapacitors, solar cells, piezoelectric or thermal actuators, as well as chemical or biological sensors.

Influences of CO2 laser modification on the surface morphology and optical absorption of graphene thin films

Abnormal optical absorption phenomena were observed in as-modified few-layer graphene thin films by 10.6-μm CO2 laser under ambient conditions. Saturable absorption (SA) responses were measured using z-scan technology. The graphene samples showed SA before laser modification, whereas they exhibited reverse SA behavior after laser modification due to the effects of thinning and damage to samples. The shift of 2D peak and appearance of D peak from Raman scattering spectra further confirm the effects of laser irradiation on graphene.

Continuously and reversibly electro-tunable optical nanoantennas based on phase transition of vanadium dioxide

Optical nanoantennas have attracted significant attention over the past decades, owing to their exceptional capabilities in terms of light manipulation and versatile optical applications. Recently, active nanoantennas have been developed by introducing phase change materials, to achieve specific tunable electromagnetic responses. However, most of these attempts only function with ‘ON’/‘OFF’ states or switch in a few discrete states, significantly restricting the application in dynamic tunability. Thus far, the continuous and reversible modulation of optical nanoantennas has not been sufficiently explored. In this article, we experimentally demonstrate a continuously and reversibly electro-tunable optical nanoantenna, by integrating an asymmetric gold nanodisk dimer array with a vanadium dioxide (VO2) film and graphene thin film. By accurately controlling the applied electrical current, the Joule heat generated in the graphene film excites the metal-insulator phase transition of VO2, and the refractive index of VO2 exhibits a relatively large variation. When VO2 is in the insulating phase, we observe an apparent resonance dip in the reflection spectrum, which is attributed to a hybrid mode originating from the gap plasmon in the dimers and localized surface plasmon (LSP) resonance excited at the edge of the nanodisks. Meanwhile, owing to the coupling between two asymmetric LSP resonances in the neighboring nanodisks, the reflected peak based on the Fano effect is realized. However, once VO2 is in the metallic phase, the hybrid mode becomes weaker and red-shifted, and the Fano effect disappears. Thereafter, the continuous and reversible electro-modulation of the nanoantenna features, including the resonant wavelength, resonant intensity, and quality factors (Q), are experimentally verified in the optical communication region, by varying the applied electrical current in the hybrid structure. To further increase the modulation range of these properties, we scan the gap size and structural asymmetry parameter of the nanodisk dimer. The results show that, with a smaller gap size, the resonant intensity of the nanoantenna is stronger. When the structural asymmetry parameter increases, the resonant wavelength is redshifted. We expect that such continuously and reversibly electro-tunable nanoantennas will stimulate various applications in optical communication systems, tunable photoelectric sensors, and beyond.

Biocompatible Flexible Carbon Fabric for Joule Heaters With and Without Graphene Oxide Coating.

In this study, we demonstrate a carbon-based fabric Joule heater with and without a graphene oxide (GO) thin coating. The electrothermal performance of the carbon fabric used in the Joule heater was obtained using an infrared camera and by conducting electrical measurements. The outer GO could control the electrothermal efficiency and heating rate. In this research work, using the Joule heating of thin graphene films, we report adaptive thermal heating with electrical control covering temperatures ranging 30 to 50 °C (near infrared). This electrothermal GO materials can be potential nano-materials for various functional applications. Moreover, we demonstrate a general approach to achieve spin-coating of GO and confirm its biocompatibility Such biocompatibility indicates the non-toxic nature of GO, thereby extending its possible use in biomedical applications.

Microcrystalline Cellulose as Graphite Exfoliation Agent and its Effect on Electrical Conductivity

Graphene has drawn a lot of attention as a promising material for a conductive ink due to its high electrical conductivity and abundant source. Selection of solvent for ink formulation is crucial to obtain the desired result. In this work, microcrystal cellulose solution is investigated as alternative solvent for conductive ink formulation. Although the viability of the microcrystal cellulose solution was already presented in other works, further thorough and systematic study is highly required. Cellulose solution was prepared using microcrystalline cellulose and sodium hydroxide aqueous solution. Dispersions with different graphite-to-cellulose ratio were prepared. The exfoliation process was for sonication times of 8, 16, 24 and 32 hours. For Raman spectroscopy and 4-point probe measurement, graphene thin film was formed by drop-casting 20μl dispersion on glossy paper. Sample with low graphite-to-cellulose ratio exhibited more significant reduction in unexfoliated graphite content over the sonication time. The sufficient amount of cellulose in the dispersion leads to more effective exfoliation process. According to analysis on the Raman spectra, the exfoliated graphite could be classified as few-layer graphene with low defect content. The drop-casted thin film from dispersion with ratio of 20:1 showed sheet resistance lesser than 100 Ω/sq. The obtained results confirmed the effectiveness of microcrystal cellulose as the agent for exfoliation process.

Optimising the fabrication of 3D binder-free graphene electrode for electrochemical energy storage application

Herein, a one-step fabrication of three-dimensional (3D) binder-free graphene-nickel foam (G-Ni) electrode via atmospheric pressure chemical vapour deposition (APCVD) is reported. Graphene thin films were deposited on nickel foam under isobaric conditions in an inert environment. The process parameters such as temperature, time, and the gas flow rate were statistically optimised using design of experiment (DOE) to maximise the yield of graphene. The structural and morphological properties of the fabricated graphene electrode were investigated through X-ray diffraction (XRD), Raman spectroscopy, field emission scanning electron microscopy (FESEM), and energy dispersive X-ray spectroscopy (EDS). The electrochemical investigations were conducted through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements. The results confirmed few-layered graphene with good surface morphology, high purity, and crystallinity of a binder-free electrode. The statistical analysis revealed that the optimal graphene electrode fabrication conditions were 900 °C, 10 min, and 100 sccm, respectively. Moreover, the regressed model and experimental results for the graphene growth were determined to be 3.93 mg/cm2, and 4.01 mg/cm2, respectively. Electrochemically, a specific capacitance value of 62.07 F/g was recorded at a scan rate of 3 mV/s showing an excellent performance of the fabricated 3D graphene electrode for energy storage applications.

All-parylene flexible wafer-scale graphene thin film transistor

Graphene is an ideal candidate as a component of flexible/wearable electronics due to its two-dimensional nature and low gate bias requirements for high quality devices. However, the proven methods for fabrication of graphene thin film transistors (TFTs) on fixed substrates involve using a sacrificial polymer layer to transfer graphene to a desired surface have led to mixed results for flexible devices. Here, by using the same polymer layer (parylene C) for both graphene transfer and the flexible substrate itself, we produced graphene TFTs on the wafer-scale requiring less than |2 V| gate bias and with high mechanical resilience of 30,000 bending cycles.

Graphene-enabled block copolymer lithography transfer to arbitrary substrates

We describe a method for phase separating and transferring block copolymer (BCP) nanoscale patterns to arbitrary substrates for surface-independent nanolithography. The enabling technology is a hydrogenated or oxidized graphene thin film that only weakly adheres to its substrate. BCPs are applied to these graphene-based materials and solvent annealed to effect nanoscale phase separation. Then, taking advantage of the weak interaction of the graphene film and its substrate, the BCP/graphene stack is delaminated easily in water. A target substrate is then used to retrieve the stack, which can then serve as a lithographic mask. The use of water as a lift-off agent allows for chemically mild retrieval of the phase-separated BCP, extending the BCP lithography technique to essentially arbitrary substrates. We demonstrate this graphene-enabled BCP lithography on silicon nitride and polyethylene. We also show that using reduced graphene oxide (RGO) as a thin film enables the transfer of wafer-scale BCP films and lithography on SiOx and Si. We use an RGO support to produce phase-separated BCP solvent-annealed patterns on polystyrene, a result which is not possible using standard BCP solvent annealing and which shows the utility of this technique. Finally, we demonstrate the ability to create nanopatterns of higher complexity by stacking multiple BCP masks, a capability that is not possible using conventional BCP lithography. This technique may have applications in fabricating nanoporous membranes and photonically active coatings.

Electronic interactions between graphene and cobaltite thin film La0.7Sr0.3CoO3 and its magnetic consequences

We have successfully synthesized and transferred graphene (Gr) monolayers on top of epitaxial mixed valence La0.7Sr0.3CoO3 (LSCO) thin films. Raman spectroscopy reveals that Jahn-Teller (JT) modes associated with the oxygen octahedral distortions usually unobserved for bare LSCO are activated by the deposited graphene. The appearance of these JT modes in the Gr/LSCO heterostructure is attributed to the electronic interactions at the interface between the graphene and the LSCO thin film promoting intermediate spin states of the Co ions. As a result, the magnetic properties of LSCO are affected. Indeed, magnetization measurements show a phase transition at ~135 K which is due to the presence of the graphene while the ferromagnetic transition of bare LSCO films is observed at~200 K. This magnetic phase is confirmed by Raman spectroscopy measurements as a function of temperature revealing a vibrational transition around the same temperature.

Direct Synthesis of Graphene on Silicon at Low Temperature for Schottky Junction Solar Cells

Graphene thin films synthesized directly at low temperature (550˚C) on silicon substrate by microwave (MW) surface wave plasma (SWP) chemical vapor deposition (CVD) using the cover on substrates for avoiding plasma emission ultraviolet ray’s effect during film deposition. Analytical methods such as Raman spectroscopy, Transmission electron microscopy (TEM) and Scanning electron microscopy (SEM), four-point probe method, and JASCO V-570 UV/VIS/NIR spectrophotometer were employed to characterize the properties of the graphene films. Here, we report that it is possible to grow graphene directly on the silicon substrate (without using catalyst) due to the high radical density of MW SWP CVD. Furthermore, we fabricated graphene/silicon Schottky junction solar cells with an efficiency of up to 6.39%. Compared to conventional silicon solar cells, the fabrication process is greatly simplified; just graphene is synthesized directly on n-type crystalline Si substrate at low temperate.

A heat-pulse method for detecting ice formation on surfaces

Early detection of ice formation on surfaces is a crucial requirement in many applications such as wind turbines, aeroplane’s wings, and radar domes. This paper presents the concept of a heat-pulse ice detection system. Its principle consists of recording the temperature evolution and assessing the relaxation time after the surfaces are subject to a heat excitation generated by an electrical pulse. The sensor comprises thin graphene films embedded in pre-preg layers of aeronautical grade as well as thermocouples to record the temperatures profiles at given locations. The criterion of ice detection exploits the high thermal capacity of ice compared to the air to capture the formation of icy spots. Numerical simulations and comparison with experimental investigations have been carried out to validate the principle and criteria of the ice detection system.

Photovoltaic performance of non-covalent functionalized single-layer graphene in dye-sensitized solar cells (DSSCs)

In this study, it was aimed to fabricate new effective alternative counter electrodes (CEs) in dye-sensitized solar cells (DSSCs). For this purpose, firstly, single-layer graphene (SLG) thin films were grown by chemical vapor deposition (CVD) method. Then, these films were separately functionalized with 1,8-cineole (ppCin/SLG), D-Limonene (ppLim/SLG) and Thiophene (ppTh/SLG) by plasma polymerization. Number of layers in CVD-grown graphene determined by Raman, transmission electron microscope (TEM) and ultraviolet–visible (UV–Vis) spectroscopy. Chemical structures of plasma polymerised (pp) thin films were investigated by Fourier transform infrared (FTIR) spectroscopy. Photovoltaic parameters of DSSCs were calculated, and electrocatalytic properties of CEs were investigated by electrochemical impedance spectroscopy (EIS). Polymer functionalization greatly enhanced the electrical conductivity and electrocatalytic activity properties of graphene compared to that of SLG. The efficiencies of DSSCs with ppCin/SLG and ppLim/SLG CEs were 1.10% and 1.02%, respectively. As a result, the cell efficiencies of ppCin/SLG and ppLim/SLG could be as alternative materials to platinum (Pt) counter electrode.

Inkjet-Printed Graphene-Based 1 × 2 Phased Array Antenna.

Low-cost and conformal phased array antennas (PAAs) on flexible substrates are of particular interest in many applications. The major deterrents to developing flexible PAA systems are the difficulty in integrating antenna and electronics circuits on the flexible surface, as well as the bendability and oxidation rate of radiating elements and electronics circuits. In this research, graphene ink was developed from graphene flakes and used to inkjet print the radiating element and the active channel of field effect transistors (FETs). Bending and oxidation tests were carried out to validate the application of printed flexible graphene thin films in flexible electronics. An inkjet-printed graphene-based 1 × 2 element phased array antenna was designed and fabricated. Graphene-based field effect transistors were used as switches in the true-time delay line of the phased array antenna. The graphene phased array antenna was 100% inkjet printed on top of a 5 mil flexible Kapton® substrate, at room temperature. Four possible azimuth steering angles were designed for −26.7°, 0°, 13°, and 42.4°. Measured far-field patterns show good agreement with simulation results.

Dual-functional graphene/carbon nanotubes thick film: Bidirectional thermal dissipation and electromagnetic shielding

Spacecraft materials are a key limiting factor for the rapid development of the aerospace exploration field. In an advanced spacecraft, superior multi-functional material with thermal management and electromagnetic shielding can ensure the normal operation of its equipment in space. Currently, graphene thin film can’t satisfy a high heat flux and excellent through-plane thermal conduction. In this contribution, a full-carbon dual-functional graphene/carbon nanotubes (CNTs) thick film with high heat flux was successfully prepared, and the structure and composition evolution was investigated after hot-pressing carbonization and graphitization of 2800 °C, which indicates the existence of a compact defects-free and high crystalline carbon structure. Molecular dynamics simulations further confirm the formation of C–C covalent bonds between graphene sheets and CNTs after 2800 °C graphitization, enhancing the phonons transfer in through-plane. Simultaneously, the axially adjacent graphene sheets are connected by the CNTs, which endow excellent thermal conductive properties. The in-plane and through-plane thermal diffusivity are as high as 1188.2 mm2/s and 8.0 mm2/s, respectively. Moreover, the electrical conductivity up to 1819.17 S/cm and EMI SE reach 75 dB in Ku-band. The results provide a bright prospect for spacecraft materials preparation and application.

Highly efficient sers performance from the silver nanoparticles/graphene nanoribbons/ cellulose paper

Introduction: Metal/graphene heterojunction structure has been one of the most crucial tools in the growth of high-performance Surface-enhanced Raman spectroscopy (SERS) platform, which is appropriate for sensing applications. In this research, we developed a SERS platform, graphene nanoribbons (GNRs) decorated silver nanoparticles (AgNPs) on cellulose paper substrate, in which GNRs was synthesized by wet chemical based on unzipping process of Multi-walled carbon nanotubes (MWCNTs), then GNRs hybridized with AgNPs through magnetron sputtering method.
 Methods: The morphology of graphene nanoribbons coated-Ag (AgNPs@GNRs) was analyzed by field emission scanning electronic microscopy (FESEM) and transmission electron microscopy (TEM). The quality and thermal stability of GNRs were characterized using thermogravimetric analysis. Besides, its structure and quality were also characterized by Raman spectroscope.
 Results: The results show that the unzipping process of MWCNTs to form GNRs was strongly affected by dispersing time and stirring temperature. The suitable condition creating the Graphene Nanoribbons using MWCNTs was the dispersing time of 10 mins in an acid environment, stirring in 30 mins at room temperature and in 45 min at 100°C. Moreover, SERS platform of AgNPs@GNRs exhibit the outstanding SERS signal enhancement with rhodamine 6G (R6G) low concentration of 10-5 M compared with pristine graphene and silver thin film. This could be attributed to the synergistic effect between AgNPs, GNRs and analyze molecules based on the enhancement of electromagnetic mechanism (EM) and chemical mechanism (CM), which plays a vital role in promoting the improvement SERS behavior.
 Conclusion: Ag NPs assembled onto graphene nanoribbons/ cellulose paper substrate could also serve as SERS active substrates for practical applications in various fields at trace levels.

High Response Photodetection by Applying the Optimized Photoreceptor Protein Modification on Graphene Based Field Effect Transistors

In this work, we combined photoreceptor protein with graphene based field effect transistors to achieve a high responsivity photodetector. Three different aromatic hydrocarbons were used to functionalize graphene with carboxyl groups via π-π stacking interactions, and 1-pyrenebutyric acid exhibited the best result for photoreceptor protein immobilization. Besides, the modification procedure of photoreceptor protein was also optimized by using a novel protein stack way on the device. Unlike conventional self-assembly method, photoreceptor proteins were cross-linked before immobilized on graphene thin film and yielded a higher modification density. Finally, the photocurrent response was significantly enhanced from -1% to -9.62%. These results bring key opportunity for graphene field effect transistor based photodetection, and the surface functionalization method are expected to help achieve high sensing performance on protein-based biosensors.

Enhanced electrochemical property of SILAR-deposited Mn3O4 thin films decorated on graphene

Manganese oxide and manganese oxide decorated on graphene thin films were successfully synthesized and decorated on graphene via successive ionic layer adsorption and reaction (SILAR) method. The morphological, elemental, structural, optical and electrochemical properties of the deposited films were respectively studied using scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX, or EDS), X-ray diffractometry (XRD), UV–vis spectrophotometry and a 3-electrode potentiostat. Decorating the manganese oxide film on graphene improved the morphological, structural, optical, and electrochemical features of the deposited films. SEM image revealed irregularly fused capsule-like nanoparticles, EDX spectra confirmed the elemental composition of the films while the structure of the film improved from amorphous to crystalline after decorating on graphene. Optical results showed improved the transmittance and optical band gap values of the films upon decoration on the graphene. Electrochemical studies showed good cyclic voltammograms and a recorded maximum specific capacitance value of 194Fg−1. The films find potential application in electrochemical storage devices and optical devices.

Synthesis of CuO–graphene nanocomposite material and the effect of gamma radiation on CuO–graphene/p-Si junction diode

Here, we introduce high-quality CuO–Graphene nanocomposite synthesis by hydrothermal method and used it as the interfacial layer to investigate radiation resistance in metal/interlayer/semiconductor (MIS) junction diode structure. In order to determine the effect of the nanocomposite layer on the electrical characteristics of Al/CuO–Graphene/p-Si/Al MIS junction diode, the current–voltage (I–V) measurements were performed at room temperature. The main electrical parameters of the junctions such as ideality factor (n), barrier height (Φb) were calculated using the thermionic emission (TE) theory and the results were compared with reference Schottky Diode (SD). The Φb and n values were calculated as 0.70 eV, 1.93 and 0.72 eV, 1.75 for reference SD and CuO–Graphene/p-Si MIS junction, respectively. The n value of the device reduced in the presence of the nanocomposite layer between the metal and the semiconductor. In addition, the Φb and series resistance (Rs) parameters were calculated from I–V measurements using Norde functions and the results were compared with the TE method. Furthermore, to determine the radiation tolerance property of the devices, gamma radiation was applied and the electrical parameters were evaluated for unirradiated and irradiated cases. The results showed that the fabricated devices may have various applications; thanks to radiation tolerance property. To the best of our knowledge, there is no research available regarding the exposure of CuO–Graphene thin films to gamma-ray irradiation studied using the I–V technique. Therefore, we believe that this study can make an important contribution to the literature.