Graphene-based multifunctional humidity sensors with an ultrahigh current response.

Prospective composites, based on graphene (G) and hexagonal boron nitride (h-BN) nanoparticles, synthesized using a plasma jet and conducting polymer PEDOT:PSS, were used to create and study a set of sensors in the current study. The composites used were G:PEDOT:PSS (GPP) and G:h-BN:PEDOT:PSS (GBNPP). The PEDOT:PSS content in the composites was 10-3 wt%, and the ratio of G : h-BN was 1 : 1 in GBNPP. The development of these new highly conductive graphene-based composites makes it possible to create an active sensor layer with an ultra-low thickness of several nanometers. The ultra-high sensitivity of the current response, S, was ((2.0-3.3) × 106)% for GPP and GBNPP (2-3 printing layers) for a humidity range of 20-80%. The sensor response in the form of current pulses associated with human breathing has a range of ∼2-3 orders of magnitude. Two different processes are assumed to determine the form of the current pulse: the first is a fast process with a rise time of less than 1-4 seconds; the second is a relatively slow process with a front time of several tens of seconds. When touching with a finger (useful, for instance, for a flexible touchpad), a current response was observed as pulses of ∼2-3 orders of magnitude. We hypothesize that skin sweat is likely to play a critical role in the sensory response. Thus, this work presents an effective approach to creating a highly sensitive humidity sensor based on composite 2D materials. Moreover, the ultra-high sensitivity of the studied sensors is accompanied by their low cost and ease of manufacturing by 2D-printing.

Thin V2O5 films synthesized by plasma-enhanced atomic layer deposition for memristive applications.

In the present study, the V2O5 films synthesized by plasma-enhanced atomic layer deposition on p-Si and fluorinated graphene on Si (or FG/Si) substrates were analyzed for memristive applications. A number of samples were grown with V2O5 films with an average thickness of 1.0-10.0 nm, as determined by ellipsometric measurements. The study of surface morphology by atomic force microscopy showed that an island growth occurs in the initial stages of the film growth. The Raman spectra of the synthesized V2O5 films with an average thickness of more than 2.0 nm on the SiO2/Si substrates exhibit six distinct modes typical of the orthorhombic V2O5 phase. A large hysteresis was found in the C-V characteristics of the V2O5 films with a thickness of 1.0-4.2 nm. In general, the built-in charge in the V2O5 layers with an average thickness of 1.0-4.0 nm is positive and has a value of about ∼(2-8) × 1011 cm-2 at the 1 MHz frequency. Increasing the V2O5 film thickness leads to the accumulation of negative built-in charge up to -(1.7 to 2.3) × 1011 cm-2 at the 1 MHz frequency. The temperature dependence of the conductivity exhibits different electrically active states in V2O5/Si and V2O5/FG/Si structures. Thus, the FG layer can modify these states. V2O5 layers with an average film thickness of 1.0-3.6 nm demonstrate the memristive switching with an ON/OFF ratio of ∼1-4 orders of magnitude. At film thicknesses above 5.0 nm, the memristive switching practically vanishes. V2O5 films with an average thickness of 3.6 nm were found to be particularly stable and promising for memristive switching applications.

Visualization of Swift Ion Tracks in Suspended Local Diamondized Few-Layer Graphene.

In the present study we investigated the nanostructuring processes in locally suspended few-layer graphene (FLG) films by irradiation with high energy ions (Xe, 26-167 MeV). For such an energy range, the main channel of energy transfer to FLG is local, short-term excitation of the electronic subsystem. The irradiation doses used in this study are 1 × 1011-5 × 1012 ion/cm2. The structural transformations in the films were identified by Raman spectroscopy and transmission electron microscopy. Two types of nanostructures formed in the FLG films as a result of irradiation were revealed. At low irradiation doses the nanostructures were formed preferably at a certain distance from the ion track and had the form of 15-35 nm "bunches". We assumed that the internal mechanical stress that arises due to the excited atoms ejection from the central track part creates conditions for the nanodiamond formation near the track periphery. Depending on the energy of the irradiating ions, the local restructuring of films at the periphery of the ion tracks can lead either to the formation of nanodiamonds (ND) or to the formation of AA' (or ABC) stacking. The compressive strain value and pressure at the periphery of the ion track were estimated as ~0.15-0.22% and ~0.8-1.2 GPa, respectively. The main novel results are the first visualization of ion tracks in graphene in the form of diamond or diamond-like rings, the determination of the main condition for the diamond formation (the absence of a substrate in combination with high ion energy), and estimates of the local strain at the track periphery. Generally, we have developed a novel material and have found how to control the film properties by introducing regions similar to quantum dots with the diamond interface in FLG films.

Engineering of graphene flakes in the process of synthesis in DC plasma jets.

During the pyrolysis of hydrocarbons in helium plasma jets in a plasma-chemical reactor, graphene flakes of a different structure and resistance were obtained. The presence of hydrogen in these structures was established by physicochemical methods, and its content depends on the pressure in the plasma-chemical reactor and the composition of a plasma-forming system. In addition to hydrogen, a relatively low concentration of oxygen atoms is present in the graphene flakes. Hydrogen is involved in the graphene nucleation, whereas oxygen is absorbed on graphene flakes from the air at low temperatures. It was found that a pressure increase in the reactor (up to 710 Torr) leads to the formation of flakes with a low resistivity (0.12-0.20 kOhm sq-1) and low defect density. In the case of synthesis at a low pressure (350-500 Torr), the resistance of graphene flakes is increased by three orders of magnitude (100-400 kOhm sq-1) with a more complicated defect structure and built-in hydrogen. Moreover, hydrogen is difficult to remove from these flakes, and annealing at relatively high temperatures (up to 300 °C) leads to a weak decrease in the resistance due to flake deformation. Additionally, the functionalization of the graphene flakes synthesized at a low pressure with fluorine atoms is suppressed due to their structural features. In general, the selection of growth parameters (gas pressure in a camera, flow rate and content of impurity atoms) allows one to control the defects in graphene, and its structure and conductivity.

Graphene: Hexagonal Boron Nitride Composite Films with Low-Resistance for Flexible Electronics.

The structure and electric properties of hexagonal boron nitride (h-BN):graphene composite with additives of the conductive polymer PEDOT:PSS and ethylene glycol were examined. The graphene and h-BN flakes synthesized in plasma with nanometer sizes were used for experiments. It was found that the addition of more than 10-3 mass% of PEDOT:PSS to the graphene suspension or h-BN:graphene composite in combination with ethylene glycol leads to a strong decrease (4-5 orders of magnitude, in our case) in the resistance of the films created from these suspensions. This is caused by an increase in the conductivity of PEDOT:PSS due to the interaction with ethylene glycol and synergetic effect on the composite properties of h-BN:graphene films. The addition of PEDOT:PSS to the h-BN:graphene composite leads to the correction of the bonds between nanoparticles and a weak change in the resistance under the tensile strain caused by the sample bending. A more pronounced flexibility of the composite films with tree components is demonstrated. The self-organization effects for graphene flakes and polar h-BN flakes lead to the formation of micrometer sized plates in drops and uniform-in-size nanoparticles in inks. The ratio of the components in the composite was found for the observed strong hysteresis and a negative differential resistance. Generally, PEDOT:PSS and ethylene glycol composite films are promising for their application as electrodes or active elements for logic and signal processing.

Memristive FG-PVA Structures Fabricated with the Use of High Energy Xe Ion Irradiation.

A new approach based on the irradiation by heavy high energy ions (Xe ions with 26 and 167 MeV) was used for the creation of graphene quantum dots in the fluorinated matrix and the formation of the memristors in double-layer structures consisting of fluorinated graphene (FG) on polyvinyl alcohol (PVA). As a result, memristive switchings with an ON/OFF current relation ~2-4 orders of magnitude were observed in 2D printed crossbar structures with the active layer consisting of dielectric FG films on PVA after ion irradiation. All used ion energies and fluences (3 × 1010 and 3 × 1011 cm-2) led to the appearance of memristive switchings. Pockets with 103 pulses through each sample were passed for testing, and any changes in the ON/OFF current ratio were not observed. Pulse measurements allowed us to determine the time of crossbar structures opening of about 30-40 ns for the opening voltage of 2.5 V. Thus, the graphene quantum dots created in the fluorinated matrix by the high energy ions are a perspective approach for the development of flexible memristors and signal processing.

Fluorinated graphene nanoparticles with 1-3 nm electrically active graphene quantum dots.

A new approach to creating a new and locally nanostructured graphene-based material is reported. We studied the electric and structural properties of partially fluorinated graphene (FG) films obtained from an FG-suspension and nanostructured by high-energy Xe ions. Local shock heating in ion tracks is suggested to be the main force driving the changes. It was found that ion irradiation leads to the formation of locally thermally expanded FG and its cracking into nanoparticles with small (∼1.5-3 nm) graphene quantum dots (GQD), embedded in them. The bandgap of GQD was estimated as 1 -1.5 eV. A further developed approach was applied to correct the functional properties of printed FG-based crossbar memristors. Dielectric FG films with small quantum dots may offer prospects in graphene-based electronics due to their stability and promising properties.

Flexibility of Fluorinated Graphene-Based Materials.

The resistivity of different films and structures containing fluorinated graphene (FG) flakes and chemical vapor deposition (CVD)-grown graphene of various fluorination degrees under tensile and compressive strains due to bending deformations was studied. Graphene and multilayer graphene films grown by means of the chemical vapor deposition (CVD) method were transferred onto the flexible substrate by laminating and were subjected to fluorination. They demonstrated a weak fluorination degree (F/C lower 20%). Compressive strains led to a strong (one-two orders of magnitude) decrease in the resistivity in both cases, which was most likely connected with the formation of additional conductive paths through fluorinated graphene. Tensile strain up to 3% caused by the bending of both types of CVD-grown FG led to a constant value of the resistivity or to an irreversible increase in the resistivity under repeated strain cycles. FG films created from the suspension of the fluorinated graphene with a fluorination degree of 20-25%, after the exclusion of design details of the used structures, demonstrated a stable resistivity at least up to 2-3% of tensile and compressive strain. The scale of resistance changes R/R0 was found to be in the range of 14-28% with a different sign at the 10% tensile strain (bending radius 1 mm). In the case of the structures with the FG thin film printed on polyvinyl alcohol, a stable bipolar resistive switching was observed up to 6.5% of the tensile strain (bending radius was 2 mm). A further increase in strain (6.5-8%) leads to a decrease in ON/OFF current ratio from 5 down to 2 orders of magnitude. The current ratio decrease is connected with an increase under the tensile strain in distances between conductive agents (graphene islands and traps at the interface with polyvinyl alcohol) and thickness of fluorinated barriers within the active layer. The excellent performance of the crossbar memristor structures under tensile strain shows that the FG films and structures created from suspension are especially promising for flexible electronics.

Recognition of Spatial Distribution of CNT and Graphene in Hybrid Structure by Mapping with Coherent Anti-Stokes Raman Microscopy.

The shape of coherent anti-Stokes Raman scattering (CARS) spectral line depends on the ratio of the vibrational and electronic contributions to the third-order susceptibility of the material. The G-mode (1590 cm-1) of graphene and carbon nanotubes (CNTs) exhibits opposite features in the CARS spectrum, showing "dip" and "peak," respectively. Here, we consider the CARS spectra of graphene and carbon nanotubes in terms of Fano formalism describing the line shapes of CARS resonances. We show that imaging at only 1590 cm-1 is not sufficient to separate the constituents of a composite material consisting of both graphene and CNTs. We propose an algorithm to map the graphene and CNTs in a composite material.

Graphene-PEDOT: PSS Humidity Sensors for High Sensitive, Low-Cost, Highly-Reliable, Flexible, and Printed Electronics.

A comparison of the structure and sensitivity of humidity sensors prepared from graphene (G)-PEDOT: PSS (poly (3,4-ethylenedioxythiophene)) composite material on flexible and solid substrates is performed. Upon an increase in humidity, the G: PEDOT: PSS composite films ensure a response (a linear increase in resistance versus humidity) up to 220% without restrictions typical of sensors fabricated from PEDOT: PSS. It was found that the response of the examined sensors depends not only on the composition of the layer and on its thickness but, also, on the substrate used. The capability of flexible substrates to absorb the liquid component of the ink used to print the sensors markedly alters the structure of the film, making it more porous; as a result, the response to moisture increases. However, in the case of using paper, a hysteresis of resistance occurs during an increase or decrease of humidity; that hysteresis is associated with the capability of such substrates to absorb moisture and transfer it to the sensing layer of the sensor. A study of the properties of G: PEDOT: PSS films and test device structures under deformation showed that when the G: PEDOT: PSS films or structures are bent to a bending radius of 3 mm (1.5% strain), the properties of those films and structures remain unchanged. This result makes the composite humidity sensors based on G: PEDOT: PSS films promising devices for use in flexible and printed electronics.

Resistive switching effects in fluorinated graphene films with graphene quantum dots enhanced by polyvinyl alcohol.

Two-layer films of partially fluorinated graphene (PFG) with graphene quantum dots and polyvinyl alcohol (PVA) were prepared by means of 2D printing technology. A stable resistive switching effect with the ON/OFF current ratio amounting from one to 4-5 orders of magnitude is found. The decrease in the PVA thickness leads to a change of the unipolar threshold switchings to the bipolar resistive switchings. The crossbar Ag/PFG/PVA/Ag structures retain their performance up to 6.5% deformation. The switching phenomenon is observed for a period about a year. The traps with characteristic activation energies ∼0.05 eV are suggested to be responsible for resistive switching. The time of charge-carrier emission from the localized states was found to be ∼5 µs. A quality model to describe the resistive switching effect in two-layer films implying the conduction over quantum dots proceeding with the participation of active traps at the PFG/PVA interface is proposed. The structures with the design demonstrated threshold resistive switching have their high potential for development of selector devices integrated to sensor or memristors circuits, for information storage and data processing, for flexible and wearable electronics. The structures with lower PVA thickness and the bipolar threshold switching are perspective for non-volatile memory cells for printed and flexible electronics.

Synthesis, Crystal Structure, and Liquid Exfoliation of Layered Lanthanide Sulfides KLn2CuS6 (Ln = La, Ce, Pr, Nd, Sm).

Among the great amount of known lanthanide nanoparticles, reports devoted to chalcogenide ones are deficient. The properties of such nanoparticles remain almost unknown due to the lack of simple and proper synthetic methods avoiding hydrolysis and allowing preparation of oxygen-free lanthanide nanoparticles. A liquid exfoliation method was used to select the optimum strategy for the preparation of quaternary lanthanide sulfide nanoparticles. Bulk KLn2CuS6 (Ln = La-Sm) materials were obtained via a reactive flux method. The crystal structures of three new members of the KLn2CuS6 series were determined for Pr, Nd, and Sm as well as for known KLa2CuS6. KLn2CuS6 (Ln = La, Pr, Nd) compounds crystallize in the monoclinic C2 /c space group, whereas KSm2CuS6 crystallizes in the orthorhombic Fddd space group. The analysis of their electronic structures confirms that the main bonding interactions occur within the anionic {Ln2CuS6}- layers. Due to their layered structure, exfoliation of these compounds is possible using ultrasonic treatment in appropriate solvents with the formation of colloidal solutions. Colloidal particles show a plate-like morphology with a lateral size of 100-200 nm and a thickness of 2-10 nm. Highly negative or positive charges found in isopropanol and acetonitrile dispersions, respectively, are associated with high stability and concentration of the dispersions.

Films fabricated from partially fluorinated graphene suspension: structural, electronic properties and negative differential resistance.

The band structure and electric properties of films created from a partially fluorinated graphene suspension are analyzed in this paper. As may be inferred from the structural study, graphene islands (quantum dots) are formed in these films. Various types of negative differential resistance (NDR) and a step-like increase in the current are found for films created from the fluorinated graphene suspension. NDR resulting from the formation of the potential barrier system in the film and corresponding to the theoretical prediction is observed for a relatively low fluorination degree. The origin of the NDR varies with an increase in the fluorination degree of the suspension. The observation of NDR in the fluorinated films widens the range of application of such films, including as active device layers fabricated using 2D printed technologies on rigid and flexible substrates.

Synthesis, crystal structure, and colloidal dispersions of vanadium tetrasulfide (VS4).

Although many of the layered metal chalcogenides, such as MoS2, are well-studied, some other chalcogenides have received less attention by comparison. In particular, there has been an emerging interest in vanadium tetrasulfide (VS4), which displays useful properties as a component of hybrids. However, the synthetic methods and characteristics of individual VS4 are not yet well defined, and there is no report on its solution processability. Here we have synthesized VS4 by a simple and fast direct reaction between elements. Reinvestigation of the VS4 crystal structure yielded more precise atomic coordinates and interatomic distances, thereby confirming the crystallization of VS4 in the monoclinic C2/c group and its quasi-1D chainlike structure. As the chains in VS4 are only bonded by weak van der Waals forces, we further demonstrate that bulk VS4 may be ultrasonically dispersed in appropriate solvents to form colloids, similarly to the layered chalcogenides. VS4 particles in colloids retain their phase identity and rod-shaped morphology with lengths in the range of hundreds of nanometers. Isopropanol dispersion exhibited the highest concentration and stability, which was achieved owing to the repulsion caused by high negative charges on the edges of the particles.