The potential of graphene coatings as neural interfaces.

Recent advances in nanotechnology design and fabrication have shaped the landscape for the development of ideal cell interfaces based on biomaterials. A holistic evaluation of the requirements for a cell interface is a highly complex task. Biocompatibility is a crucial requirement which is affected by the interface's properties, including elemental composition, morphology, and surface chemistry. This review explores the current state-of-the-art on graphene coatings produced by chemical vapor deposition (CVD) and applied as neural interfaces, detailing the key properties required to design an interface capable of physiologically interacting with neural cells. The interfaces are classified into substrates and scaffolds to differentiate the planar and three-dimensional environments where the cells can adhere and proliferate. The role of specific features such as mechanical properties, porosity and wettability are investigated. We further report on the specific brain-interface applications where CVD graphene paved the way to revolutionary advances in biomedicine. Future studies on the long-term effects of graphene-based materials in vivo will unlock even more potentially disruptive neuro-applications.

Bipolar Resistive Switching in 2D MoSe2 Grown by Atmospheric Pressure Chemical Vapor Deposition.

Two-dimensional (2D) transition metal dichalcogenides (TMDCs) are highly promising nanomaterials for various electronic devices such as field-effect transistors, junction diodes, tunneling devices, and, more recently, memristors. 2D MoSe2 stands out for having high electrical conductivity, charge carrier mobility, and melting point. While these features make it particularly appropriate as a switching layer in memristive devices, reliable and scalable production of large-area 2D MoSe2 still represents a challenge. In this study, we manufacture 2D MoSe2 films by atmospheric-pressure chemical vapor deposition and investigate them on the atomic scale. We selected and transferred MoSe2 bilayer to serve as a switching layer between asymmetric Au-Cu electrodes in miniaturized crossbar vertical memristors. The electrochemical metallization devices showed forming-free, bipolar resistive switching at low voltages, with clearly identifiable nonvolatile states. Other than low-power neuromorphic computing, low switching voltages approaching the range of biological action potentials could unlock hybrid biological interfaces.

Frailty, psychological well-being, and social isolation in older adults with cognitive impairment during the SARS-CoV-2 pandemic: data from the GeroCovid initiative.

BACKGROUND: The containment measures linked to the COVID-19 pandemic negatively affected the phyco-physical well-being of the population, especially older adults with neurocognitive disorders (NCDs). This study aims to evaluate whether the frailty of NCD patients was associated with different changes in multiple health domains, in particular in relation to loneliness and social isolation, pre- and post-lockdown. MATERIALS AND METHODS: Patients were recruited from 10 Italian Centers for Cognitive Disorders and Dementia. Data were collected in the pre-pandemic period (T0), during the pandemic lockdown (T1), and 6-9 months post-lockdown (T2). The UCLA Loneliness Scale-3, Activities of Daily Living (ADL), Instrumental ADL (IADL), Mini-Mental State Examination, and Neuropsychiatric Inventory (NPI) were administered. Caregivers' burden was also tested. Patients were categorized as non-frail, pre-frail, and frail according to the Fatigue, Resistance, Ambulation, Illness, and Loss of Weight scale. RESULTS: The sample included 165 subjects (61.9% women, mean age 79.5 ± 4.9 years). In the whole sample, the ADL, IADL, and NPI scores significantly declined between T0 and T2. There were no significative variations in functional and cognitive domains between the frail groups. During lockdown we recorded higher Depression Anxiety Stress Scales and Perceived Stress Scale scores in frail people. In multivariable logistic regression, frailty was associated with an increase in social isolation, and a loss of IADL. CONCLUSIONS: We observed a global deterioration in functional and neuro-psychiatric domains irrespective of the degree of frailty. Frailty was associated with the worsening of social isolation during lockdown. Frail patients and their caregivers seemed to experience more anxiety and stress disorders during SARS-CoV-2 pandemic.

Material jetting of carbon nano onions for printed electronics.

As an additive manufacturing process, material jetting techniques allow to selectively deposit droplets of materials in liquid or powder form through a small-diameter aperture, such as a nozzle of a print head. For the fabrication of printed electronics, a variety of inks and dispersions of functional materials can be deposited by drop-on-demand printing on rigid and flexible substrates. In this work, zero-dimensional multi-layer shell-structured fullerene material, also known as carbon nano-onion (CNO) or onion-like carbon, is printed on polyethylene terephthalate substrates using drop-on-demand inkjet printing. CNOs are produced using a low-cost flame synthesis technique and characterized by electron microscopy, Raman, x-ray photoelectron spectroscopy, and specific surface area and pore size measurements. The produced CNO material has an average diameter of ∼33 nm, pore diameter in the range ∼2-40 nm and a specific surface area of 160 m2.g-1. The CNO dispersions in ethanol have a reduced viscosity (∼1.2 mPa.s) and are compatible with commercial piezoelectric inkjet heads. The jetting parameters are optimized to avoid satellite drops and to obtain a reduced drop volume (52 pL), resulting in optimal resolution (220µm) and line continuity. A multi-step process is implemented without inter-layer curing and a fine control over the CNO layer thickness is achieved (∼180 nm thick layer after 10 printing passes). The printed CNO structures show an electrical resistivity of ∼600 Ω.m, a high negative temperature coefficient of resistance (-4.35 × 10-2°C-1) and a marked dependency on relative humidity (-1.29 × 10-2RH%-1). The high sensitivity to temperature and humidity, combined to the large specific area of the CNOs, make this material and the corresponding ink a viable prospect for inkjet-printed technologies, such as environmental and gas sensors.

Solution-Processed Functionalized Graphene Film Prepared by Vacuum Filtration for Flexible NO2 Sensors.

Large-scale production of graphene nanosheets (GNSs) has led to the availability of solution-processable GNSs on the commercial scale. The controlled vacuum filtration method is a scalable process for the preparation of wafer-scale films of GNSs, which can be used for gas sensing applications. Here, we demonstrate the use of this deposition method to produce functional gas sensors, using a chemiresistor structure from GNS solution-based techniques. The GNS suspension was prepared by liquid-phase exfoliation (LPE) and transferred to a polyvinylidene fluoride (PVDF) membrane. The effect of non-covalent functionalization with Co-porphyrin and Fe-phthalocyanines on the sensor properties was studied. The pristine and functionalized GNS films were characterized using different techniques such as Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), X-ray diffraction (XRD), and electrical characterizations. The morphological and spectroscopic analyses both confirm that the molecules (Co-porphyrin and Fe-phthalocyanine) were successfully adsorbed onto the GNSs surface through π-π interactions. The chemiresistive sensor response of functionalized GNSs toward the low concentrations of nitrogen dioxide (NO2) (0.5-2 ppm) was studied and compared with those of the film of pristine GNSs. The tests on the sensing performance clearly showed sensitivity to a low concentration of NO2 (5 ppm). Furthermore, the chemical modification of GNSs significantly improves NO2 sensing performance compared to the pristine GNSs. The sensor response can be modulated by the type of adsorbed molecules. Indeed, Co-Por exhibited negative responsiveness (the response of Co-Por-GNS sensors and pristine GNS devices was 13.1% and 15.6%, respectively, after exposure to 0.5 ppm of NO2). Meanwhile, Fe-Phc-GNSs induced the opposite behavior resulting in an increase in the sensor response (the sensitivity was 8.3% and 7.8% of Fe-Phc-GNSs and pristine GNSs, respectively, at 0.5 ppm NO2 gas).

Optimizing PMMA solutions to suppress contamination in the transfer of CVD graphene for batch production.

Mass production and commercial adoption of graphene-based devices are held back by a few crucial technical challenges related to quality control. In the case of graphene produced by chemical vapor deposition, the transfer process represents a delicate step that can compromise device performance and reliability, thus hindering industrial production. In this context, the impact of poly(methyl methacrylate) (PMMA), the most common support material for transferring graphene from the Cu substrate to any target surface, can be decisive in obtaining reproducible sample batches. Although effective in mechanically supporting graphene during the transfer, PMMA solutions needs to be efficiently designed, deposited, and post-treated to serve their purpose while minimizing potential contaminations. Here, we prepared and tested PMMA solutions with different average molecular weight (AMW) and weight concentration in anisole, to be deposited by spin coating. Optical microscopy and Raman spectroscopy showed that the amount of PMMA residues on transferred graphene is proportional to the AMW and concentration in the solvent. At the same time, the mechanical strength of the PMMA layer is proportional to the AMW. These tests served to design an optimized PMMA solution made of a mixture of 550,000 (550k) and 15,000 (15k) AMW PMMA in anisole at 3% concentration. In this design, PMMA-550k provided suitable mechanical strength against breakage during the transfer cycles, while PMMA-15k promoted depolymerization, which allowed for a complete removal of PMMA residues without the need for any post-treatment. An XPS analysis confirmed the cleanness of the optimized process. We validated the impact of the optimized PMMA solution on the mass fabrication of arrays of electrolyte-gated graphene field-effect transistors operating as biosensors. On average, the transistor channel resistance decreased from 1860 to 690 Ω when using the optimized PMMA. Even more importantly, the vast majority of these resistance values are distributed within a narrow range (only ca. 300 Ω wide), in evident contrast with the scattered values obtained in non-optimized devices (about 30% of which showed values above 1 MΩ). These results prove that the optimized PMMA solution unlock the production of reproducible electronic devices at the batch scale, which is the key to industrial production.

Green Solvents for the Liquid Phase Exfoliation Production of Graphene: The Promising Case of Cyrene.

The liquid phase exfoliation (LPE) of graphite has allowed to produce graphene materials on a large scale and at a reasonable cost. By this method, stable dispersions, inks and liquid suspensions containing atomic-thick graphene flakes with tailored concentrations can be produced, opening up applications in a wide range of cutting-edge technologies such as functional coatings, printed and flexible electronics, and composites. However, currently established LPE techniques raise several health and environmental risks, since unsafe and toxic solvents (such as NMP, DMF, and DMSO) are often regarded as the most effective liquid media for the process. Therefore, it appears necessary to unlock eco-friendly and sustainable methods for the production of graphene at an industrial scale. This review focuses on the latest developments in terms of green solvents for LPE production of graphene. We highlight the use of a new green solvent, Cyrene, and its performance when compared to conventional solvents.

Tuning the Electronic Properties of Graphane via Hydroxylation: An Ab Initio Study.

The thermodynamic stability of hydroxylated graphane, that is, fully sp3 graphene derivatives coordinated with -H and -OH groups, has been recently demonstrated by ab initio calculations. Within the density functional theory approach, we investigate the electronic property modifications of graphane by progressive hydroxylation, that is, by progressively substituting -H with -OH groups. When 50% of graphane is hydroxylated, the energy bandgap reaches its largest value of 6.68 eV. The electronic affinity of 0.8 eV for graphane can widely change in the 0.28-1.60 eV range depending on the geometric configuration. Hydroxylated graphane has two interfaces with vacuum, hence its electron affinity can be different on each interface with the formation of an intrinsic dipole perpendicular to the monolayer. We envisage the possibility of using hydroxylated graphane allotropes with tunable electronic affinity to serve as interfacial layers in 2D material-based heterojunctions.

Efficient ReSe2 Photodetectors with CVD Single-Crystal Graphene Contacts.

Rhenium-based 2D transition metal dichalcogenides such as ReSe2 are suitable candidates as photoactive materials for optoelectronic devices. Here, photodetectors based on mechanically exfoliated ReSe2 crystals were fabricated using chemical vapor deposited (CVD) graphene single-crystal (GSC) as lateral contacts. A "pick & place" method was adopted to transfer the desired crystals to the intended position, easing the device fabrication while reducing potential contaminations. A similar device with Au was fabricated to compare contacts' performance. Lastly, a CVD hexagonal boron nitride (hBN) substrate passivation layer was designed and introduced in the device architecture. Raman spectroscopy was carried out to evaluate the device materials' structural and electronic properties. Kelvin probe force measurements were done to calculate the materials' work function, measuring a minimal Schottky barrier height for the GSC/ReSe2 contact (0.06 eV). Regarding the electrical performance, I-V curves showed sizable currents in the GSC/ReSe2 devices in the dark and under illumination. The devices presented high photocurrent and responsivity, along with an external quantum efficiency greatly exceeding 100%, confirming the non-blocking nature of the GSC contacts at high bias voltage (above 2 V). When introducing the hBN passivation layer, the device under white light reached a photo-to-dark current ratio up to 106.

Hydrogenated Graphene Improves Neuronal Network Maturation and Excitatory Transmission.

Graphene is regarded as a viable bio-interface for neuroscience due to its biocompatibility and electrical conductivity, which would contribute to efficient neuronal network signaling. Here, monolayer graphene grown via chemical vapor deposition is treated with remote hydrogen plasma to demonstrate that hydrogenated graphene (HGr) fosters improved cell-to-cell communication with respect to pristine graphene in primary cortical neurons. When transferred to polyethylene terephthalate, HGr exhibits higher wettability than graphene (water contact angle of 83.7° vs 40.7°), while preserving electrical conductivity (≈3 kΩ â–¡-1 ). A rich and mature network is observed to develop onto HGr. The intrinsic excitability and firing properties of neurons plated onto HGr appears unaltered, while the basic passive and active membrane properties are fully preserved. The formation of excitatory synaptic connections increases in HGr with respect to pristine graphene, leading to a doubled miniature excitatory postsynaptic current frequency. This study supports the use of hydrogenation for tailoring graphene into an improved neuronal interface, indicating that wettability, more than electrical conductivity, is the key parameter to be controlled. The use of HGr can bring about a deeper understanding of neuronal behavior on artificial bio-interfaces and provide new insight for graphene-based biomedical applications.

Interactions Between 2D Materials and Living Matter: A Review on Graphene and Hexagonal Boron Nitride Coatings.

Two-dimensional material (2DM) coatings exhibit complex and controversial interactions with biological matter, having shown in different contexts to induce bacterial cell death and contribute to mammalian cell growth and proliferation in vitro and tissue differentiation in vivo. Although several reports indicate that the morphologic and electronic properties of the coating, as well as its surface features (e.g., crystallinity, wettability, and chemistry), play a key role in the biological interaction, these kinds of interactions have not been fully understood yet. In this review, we report and classify the cellular interaction mechanisms observed in graphene and hexagonal boron nitride (hBN) coatings. Graphene and hBN were chosen as study materials to gauge the effect of two atomic-thick coatings with analogous lattice structure yet dissimilar electrical properties upon contact with living matter, allowing to discern among the observed effects and link them to specific material properties. In our analysis, we also considered the influence of crystallinity and surface roughness, detailing the mechanisms of interaction that make specific coatings of these 2DMs either hostile toward bacterial cells or innocuous for mammalian cells. In doing this, we discriminate among the material and surface properties, which are often strictly connected to the 2DM production technique, coating deposition and post-processing method. Building on this knowledge, the selection of 2DM coatings based on their specific characteristics will allow to engineer desired functionalities and devices. Antibacterial coatings to prevent biofouling, biocompatible platforms suitable for biomedical applications (e.g., wound healing, tissue repairing and regeneration, and novel biosensing devices) could be realized in the next future. Overall, a clear understanding on how the 2DM coating's properties may modulate a specific bacterial or cellular response is crucial for any future innovation in the field.

Rational Design of Photo-Electrochemical Hybrid Devices Based on Graphene and Chlamydomonas reinhardtii Light-Harvesting Proteins.

Dye-sensitized solar cells (DSSCs) have been highlighted as the promising alternative to generate clean energy based on low pay-back time materials. These devices have been designed to mimic solar energy conversion processes from photosynthetic organisms (the most efficient energy transduction phenomenon observed in nature) with the aid of low-cost materials. Recently, light-harvesting complexes (LHC) have been proposed as potential dyes in DSSCs based on their higher light-absorption efficiencies as compared to synthetic dyes. In this work, photo-electrochemical hybrid devices were rationally designed by adding for the first time Leu and Lys tags to heterologously expressed light-harvesting proteins from Chlamydomonas reinhardtii, thus allowing their proper orientation and immobilization on graphene electrodes. The light-harvesting complex 4 from C. reinhardtii (LHC4) was initially expressed in Escherichia coli, purified via affinity chromatography and subsequently immobilized on plasma-treated thin-film graphene electrodes. A photocurrent density of 40.30 ± 9.26 µA/cm2 was measured on devices using liquid electrolytes supplemented with a phosphonated viologen to facilitate charge transfer. Our results suggest that a new family of graphene-based thin-film photovoltaic devices can be manufactured from rationally tagged LHC proteins and opens the possibility to further explore fundamental processes of energy transfer for biological components interfaced with synthetic materials.

Electrically Conducting and Mechanically Strong Graphene-Polylactic Acid Composites for 3D Printing.

The advent of 3D printing has had a disruptive impact in manufacturing and can potentially revolutionize industrial fields. Thermoplastic materials printable into complex structures are widely employed for 3D printing. Polylactic acid (PLA) is among the most promising polymers used for 3D printing, owing to its low cost, biodegradability, and nontoxicity. However, PLA is electrically insulating and mechanically weak; this limits its use in a variety of 3D printing applications. This study demonstrates a straightforward and environment-friendly method to fabricate conductive and mechanically reinforced PLA composites by incorporating graphene nanoplatelets (GNPs). To fully utilize the superior electrical and mechanical properties of graphene, liquid-exfoliated GNPs are dispersed in isopropyl alcohol without the addition of any surfactant and combined with PLA dissolved in chloroform. The GNP-PLA composites exhibit improved mechanical properties (improvement in tensile strength by 44% and maximum strain by 57%) even at a low GNP threshold concentration of 2 wt %. The GNP-PLA composites also exhibit an electrical conductivity of over 1 mS/cm at >1.2 wt %. The GNP-PLA composites can be 3D-printed into various features with electrical conductivity and mechanical flexibility. This work presents a new direction toward advanced 3D printing technology by providing higher flexibility in designing multifunctional 3D printed features.

An ab initio study of hydroxylated graphane.

Graphene-based derivatives with covalent functionalization and well-defined stoichiometry are highly desirable in view of their application as functional surfaces. Here, we have evaluated by ab initio calculations the energy of formation and the phase diagram of hydroxylated graphane structures, i.e., fully functionalized graphene derivatives coordinated with -H and -OH groups. We compared these structures to different hydrogenated and non-hydrogenated graphene oxide derivatives, with high level of epoxide and hydroxyl groups functionalization. Based on our calculations, stable phases of hydroxylated graphane with low and high contents of hydrogen are demonstrated for high oxygen and hydrogen partial pressure, respectively. Stable phases of graphene oxide with a mixed carbon hybridization are also found. Notably, the synthesis of hydroxylated graphane has been recently reported in the literature.

Contamination-free graphene by chemical vapor deposition in quartz furnaces.

Although the growth of graphene by chemical vapor deposition is a production technique that guarantees high crystallinity and superior electronic properties on large areas, it is still a challenge for manufacturers to efficiently scale up the production to the industrial scale. In this context, issues related to the purity and reproducibility of the graphene batches exist and need to be tackled. When graphene is grown in quartz furnaces, in particular, it is common to end up with samples contaminated by heterogeneous particles, which alter the growth mechanism and affect graphene's properties. In this paper, we fully unveil the source of such contaminations and explain how they create during the growth process. We further propose a modification of the widely used quartz furnace configuration to fully suppress the sample contamination and obtain identical and clean graphene batches on large areas.

Chemical Vapor Deposited Graphene-Based Derivative As High-Performance Hole Transport Material for Organic Photovoltaics.

The development of efficient charge transport layers is a key requirement for the fabrication of efficient and stable organic solar cells. A graphene-based derivative with planar resistivity exceeding 10(5) Ω/□ and work function of 4.9 eV is here produced by finely tuning the parameters of the chemical vapor deposition process on copper. After the growth, the film is transferred to glass/indium tin oxide and used as hole transport layer in organic solar cells based on a PBDTTT-C-T:[70]PCBM blend. The cells attained a maximum power conversion efficiency of 5%, matching reference cells made with state-of-the-art PEDOT: PSS as the hole transport layer. Our results indicate that functionalized graphene could represent an effective alternative to PEDOT: PSS as hole transport/electron blocking layer in solution-processed organic photovoltaics.

Nitrogen-doped graphene films from chemical vapor deposition of pyridine: influence of process parameters on the electrical and optical properties.

Graphene films were produced by chemical vapor deposition (CVD) of pyridine on copper substrates. Pyridine-CVD is expected to lead to doped graphene by the insertion of nitrogen atoms in the growing sp(2) carbon lattice, possibly improving the properties of graphene as a transparent conductive film. We here report on the influence that the CVD parameters (i.e., temperature and gas flow) have on the morphology, transmittance, and electrical conductivity of the graphene films grown with pyridine. A temperature range between 930 and 1070 °C was explored and the results were compared to those of pristine graphene grown by ethanol-CVD under the same process conditions. The films were characterized by atomic force microscopy, Raman and X-ray photoemission spectroscopy. The optical transmittance and electrical conductivity of the films were measured to evaluate their performance as transparent conductive electrodes. Graphene films grown by pyridine reached an electrical conductivity of 14.3 × 10(5) S/m. Such a high conductivity seems to be associated with the electronic doping induced by substitutional nitrogen atoms. In particular, at 930 °C the nitrogen/carbon ratio of pyridine-grown graphene reaches 3%, and its electrical conductivity is 40% higher than that of pristine graphene grown from ethanol-CVD.

Low-temperature synthesis of carbon nanotubes on indium tin oxide electrodes for organic solar cells.

The electrical performance of indium tin oxide (ITO) coated glass was improved by including a controlled layer of carbon nanotubes directly on top of the ITO film. Multiwall carbon nanotubes (MWCNTs) were synthesized by chemical vapor deposition, using ultrathin Fe layers as catalyst. The process parameters (temperature, gas flow and duration) were carefully refined to obtain the appropriate size and density of MWCNTs with a minimum decrease of the light harvesting in the cell. When used as anodes for organic solar cells based on poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM), the MWCNT-enhanced electrodes are found to improve the charge-carrier extraction from the photoactive blend, thanks to the additional percolation paths provided by the CNTs. The work function of as-modified ITO surfaces was measured by the Kelvin probe method to be 4.95 eV, resulting in an improved matching to the highest occupied molecular orbital level of the P3HT. This is in turn expected to increase the hole transport and collection at the anode, contributing to the significant increase of current density and open-circuit voltage observed in test cells created with such MWCNT-enhanced electrodes.