Tuning humidity sensing properties via grafting fluorine and nitrogen-containing species on single-walled carbon nanotubes.

The effect of humidity on the electrical conductivity of single-walled carbon nanotube (SWCNT) films depends on both the conductivity of individual nanotubes and the electrical contacts between them. Here, we study these factors by comparing the sensor response of nanotubes with fluorine- and nitrogen-containing groups attached to the sidewalls. Experiments carried out in a wide range of relative humidity (RH) at room and elevated temperatures showed that the conductivity of non-functionalized SWCNTs and contacts between them decreases upon the adsorption of water molecules. Covalent fluorination reduces the conductivity of SWCNTs and significantly increases the sensitivity of the film to low concentrations of water vapor. The response at high RH decreases due to the large number of water molecules adsorbed on the conductive regions of the nanotubes. As a result of substitutional reactions of fluorinated SWCNTs with dimethylformamide and ethylenediamine, nitrogen-containing groups are added, the amount of which, however, is much less than the amount of fluorine. This modification of the SWCNTs improves intertube contacts in the film and increases the surface area for water adsorption. Our results show that an increase in the number of functional groups on the SWCNT surface enhances the sensitivity of the sensor to low water concentrations and worsens the response at high RH. SWCNTs modified with ethylenediamine have the highest sensitivity over the entire range of RH.

Fluorinated graphene grating metasurface for terahertz dark state excitation.

We propose an original technique for the grating metasurfaces fabrication by low-power ultraviolet laser treatment of fluorinated graphene (FG) films with the focus on terahertz applications. The laser treatment reduces dielectric FG to its conductive counterparts, increasing DC conductivity to 170 S·m-1for treated areas. The electromagnetic response of the grating metasurfaces studied by THz time-domain spectroscopy in the 100 GHz-1 THz frequency range demonstrates enhanced resonant transmittance through metasurfaces. The intensity and position of transmittance peak could be tuned by changing the metasurface geometry, i.e. the period of the structure and width of the reduced and unreduced areas. In particular, the decrease of the reduced FG area width from 400 to 170µm leads to the shift of the resonance peak from 0.45 THz to the higher frequencies, 0.85 THz. Theoretical description based on the multipole theory supported by finite element numerical calculations confirms the excitation of the dark state in the metasurface unit cells comprising reduced and unreduced FG areas at resonance frequency determined by the structure geometrical features. Fabricated metasurfaces have been proved to be efficient narrowband polarizers being rotated by 50° about the incident THz field vector.

Adsorption kinetics of NO2 gas on oxyfluorinated graphene film.

We report the fabrication of high-performance NO2 gas sensors based on oxyfluorinated graphene (OFG) layers. At room temperature, the times of adsorption/desorption of NO2 on/from the surface of thin OFG films are less than 1200 s and can be reduced by increasing the operation temperature. The sensors are capable of detecting NO2 molecules at sub-ppm level with a sensitivity of 0.15 ppm-1 at 348 K. The temperature dependence of the rate constants shows that the simultaneous presence of a large number of fluorine- and oxygen-containing groups on the graphene surface provides the formation of low-energy sites (ΔHa < 0.1 eV) for NO2 adsorption. The combination of the high sensitivity of the sensor and a reasonable adsorption/desorption time of the analyte is promising for on-line monitoring.

Enhancement of Volumetric Capacitance of Binder-Free Single-Walled Carbon Nanotube Film via Fluorination.

Robust electrode materials without the addition of binders allow increasing efficiency of electrical storage devices. We demonstrate the fabrication of binder-free electrodes from modified single-walled carbon nanotubes (SWCNTs) for electrochemical double-layer capacitors (EDLCs). Modification of SWCNTs included a sonication in 1,2-dichlorobenzene and/or fluorination with gaseous BrF3 at room temperature. The sonication caused the shortening of SWCNTs and the splitting of their bundles. As a result, the film prepared from such SWCNTs had a higher density and attached a larger amount of fluorine as compared to the film from non-sonicated SWCNTs. In EDLCs with 1M H2SO4 electrolyte, the fluorinated films were gradually defluorinated, which lead to an increase of the specific capacitance by 2.5-4 times in comparison with the initial values. Although the highest gravimetric capacitance (29 F g-1 at 100 mV s-1) was observed for the binder-free film from non-modified SWCNT, the fluorinated film from the sonicated SWCNTs had an enhanced volumetric capacitance (44 F cm-3 at 100 mV s-1). Initial SWCNT films and defluorinated films showed stable work in EDLCs during several thousand cycles.

Chemiresistive Properties of Imprinted Fluorinated Graphene Films.

The electrical conductivity of graphene materials is strongly sensitive to the surface adsorbates, which makes them an excellent platform for the development of gas sensor devices. Functionalization of the surface of graphene opens up the possibility of adjusting the sensor to a target molecule. Here, we investigated the sensor properties of fluorinated graphene films towards exposure to low concentrations of nitrogen dioxide NO2. The films were produced by liquid-phase exfoliation of fluorinated graphite samples with a composition of CF0.08, CF0.23, and CF0.33. Fluorination of graphite using a BrF3/Br2 mixture at room temperature resulted in the covalent attachment of fluorine to basal carbon atoms, which was confirmed by X-ray photoelectron and Raman spectroscopies. Depending on the fluorination degree, the graphite powders had a different dispersion ability in toluene, which affected an average lateral size and thickness of the flakes. The films obtained from fluorinated graphite CF0.33 showed the highest relative response ca. 43% towards 100 ppm NO2 and the best recovery ca. 37% at room temperature.