Isotope Engineered Fluorinated Single and Bilayer Graphene: Insights into Fluorination Selectivity, Stability, and Defect Passivation.

Tailoring the physicochemical properties of graphene through functionalization remains a major interest for next-generation technological applications. However, defect formation due to functionalization greatly endangers the intrinsic properties of graphene, which remains a serious concern. Despite numerous attempts to address this issue, a comprehensive analysis has not been conducted. This work reports a two-step fluorination process to stabilize the fluorinated graphene and obtain control over the fluorination-induced defects in graphene layers. The structural, electronic and isotope-mass-sensitive spectroscopic characterization unveils several not-yet-resolved facts, such as fluorination sites and CF bond stability in partially-fluorinated graphene (F-SLG). The stability of fluorine has been correlated to fluorine co-shared between two graphene layers in fluorinated-bilayer-graphene (F-BLG). The desorption energy of co-shared fluorine is an order of magnitude higher than the CF bond energy in F-SLG due to the electrostatic interaction and the inhibition of defluorination in the F-BLG. Additionally, F-BLG exhibits enhanced light-matter interaction, which has been utilized to design a proof-of-concept field-effect phototransistor that produces high photocurrent response at a time <200 µs. Thus, the study paves a new avenue for the in-depth understanding and practical utilization of fluorinated graphenic carbon.

Two-Dimensional CVD-Graphene/Polyaniline Supercapacitors: Synthesis Strategy and Electrochemical Operation.

Nanocomposites of graphene materials and conducting polymers have been extensively studied as promising materials for electrodes of supercapacitors. Here, we present a graphene/polyaniline heterostructure consisting of a CVD-graphene and polyaniline monolayer and its electrochemical operation in a supercapacitor. The synthesis employs functionalization of graphene by p-phenylene sulfonic groups and oxidative polymerization of anilinium by ammonium persulfate under reaction conditions, providing no bulk polyaniline. Scanning electron microscopy, atomic force microscopy, and Raman spectroscopy showed the selective formation of polyaniline on the graphene. In situ Raman spectroelectrochemistry and cyclic voltammetry (both in a microdroplet setup) confirm the reversibility of polyaniline redox transitions and graphene electrochemical doping. After an increase within the initial 200 cycles due to the formation of benzoquinone-hydroquinone defects in polyaniline, the specific areal capacitance remained for 2400 cycles with ±1% retention at 21.2 µF cm-2, one order of magnitude higher than the capacitance of pristine graphene.

The use of sample positioning to control defect creation by oxygen plasma in isotopically labelled bilayer graphene membranes.

Monolayer and isotopically labelled bilayer graphene membranes were prepared on grids for transmission electron microscopy (TEM). In order to create defects in the graphene layers in a controlled way, we studied the sensitivity of the individual graphene layers to the oxygen plasma treatment. We tested samples with different configurations by varying the order of the transfer of layers and changing the orientation of the samples with respect to the plasma chamber. Using Raman spectroscopy, HRTEM and X-ray photoelectron spectroscopy, we demonstrated defect formation and determined the quantity and chemical composition of the defects. By keeping the sample structure and the setup of the experiment unchanged, the significant role of the sample orientation with respect to the chamber was demonstrated. The effect was accounted for by the variation of the accessibility of the sample surface for the reactive species. Therefore, this effect can be used to control the degree of damage in each layer, resulting in differing numbers of defects present on each side of the sample.

Towards Catalytically Active Porous Graphene Membranes with Pulsed Laser Deposited Ceria Nanoparticles.

Porous graphene with catalytically active ceria nanometre-size particles were prepared using pulsed laser deposition (PLD) on graphene produced through chemical vapour deposition (CVD). The reported process provided porous graphene containing ceria nanoparticles as confirmed by HR TEM and XPS. Isotopically labelled 13 C graphene was employed to study desorption of the species containing carbon. Methanol adsorption was utilised to probe the nature of the catalytic activity of prepared ceria decorated graphene. The important role of graphene support for the stabilization of reduced ceria nanoparticles was finally confirmed. Increased dehydrogenation activity of graphene with ceria nanoparticles leading to CO and H2 formation was demonstrated.

Host-Guest Interactions in Metal-Organic Frameworks Doped with Acceptor Molecules as Revealed by Resonance Raman Spectroscopy.

Metal-organic frameworks (MOFs) represent a class of porous materials whose properties can be altered by doping with redox-active molecules. Despite advanced properties such as enhanced electrical conduction that doped MOFs exhibit, understanding physical mechanisms remains challenging because of their heterogeneous nature hindering experimental observations of host-guest interactions. Here, we show a study of charge transfer between Mn-MOF-74 and electron acceptors, 7,7,8,8-tetracyanoquinodimethane (TCNQ) and XeF2, employing selective enhancement of Raman scattering of different moieties under various optical-resonance conditions. We identify Raman modes of molecular components and elucidate that TCNQ gets oxidized into dicyano-p-toluoyl cyanide (DCTC-) while XeF2 fluorinates the MOF upon infiltration. The framework's linker in both cases acts as an electron donor as deduced from blue shifts of the C-O stretching mode accompanied by the emergence of a quinone-like mode. This work demonstrates a generally applicable methodology for investigating charge transfer in various donor-acceptor systems by means of resonance Raman spectroscopy.

Graphene-enhanced Raman scattering on single layer and bilayers of pristine and hydrogenated graphene.

Graphene-enhanced Raman scattering (GERS) on isotopically labelled bilayer and a single layer of pristine and partially hydrogenated graphene has been studied. The hydrogenated graphene sample showed a change in relative intensities of Raman bands of Rhodamine 6 G (R6G) with different vibrational energies deposited on a single layer and bilayer graphene. The change corresponds qualitatively to different doping of graphene in both areas. Pristine graphene sample exhibited no difference in doping nor relative intensities of R6G Raman peaks in the single layer and bilayer areas. Therefore, it was concluded that strain and strain inhomogeneities do not affect the GERS. Because of analyzing relative intensities of selected peaks of the R6G probe molecules, it is possible to obtain these results without determining the enhancement factor and without assuming homogeneous coverage of the molecules. Furthermore, we tested the approach on copper phtalocyanine molecules.

Strong and efficient doping of monolayer MoS2 by a graphene electrode.

The efficient manipulation of the optoelectronic properties of layered semiconductors is essential for future applications of these unique materials. Here, we demonstrate that single-layer, large-area graphene can serve as a conductive spacer between an electrolyte solution and single-layer MoS2. In situ Raman and photoluminescence (PL) spectroscopies were employed to monitor the charge transfer from graphene to MoS2. The Raman G and 2D bands were used to quantify the carrier concentration in graphene. The high efficiency of the charge transfer via graphene in a broad carrier concentration range of ±2.1 × 1013 cm-2 was documented by the extreme sensitivity of the MoS2 Raman mode to the electron-doping (shift rate of ∼2.5 cm-1/1 × 1013 cm-2 electron concentration) and the high sensitivity of the PL yield, which drops by more than one and two orders of magnitude in the hole and electron doping regimes, respectively. The easy implementation, and the lithography-free effectiveness of the setup, in terms of the achievable carrier concentration range and the charge-transfer efficiency, could be an asset in near-future research and in the development of optoelectronic devices.

Spatially Resolved Covalent Functionalization Patterns on Graphene.

Spatially resolved functionalization of 2D materials is highly demanded but very challenging to achieve. The chemical patterning is typically tackled by preventing contact between the reagent and material, which brings various accompanying challenges. Photochemical transformation on the other hand inherently provides remote high spatiotemporal resolution using the cleanest reagent-a photon. Herein, we combine two competing reactions on a graphene substrate to create functionalization patterns on a micrometer scale via the Mitsunobu reaction. The mild reaction conditions allow introduction of covalently dynamic linkages, which can serve as reversible labels for surface- or graphene-enhanced Raman spectroscopy characterization of the patterns prepared. The proposed methodology thus provides a pathway for local introduction of arbitrary functional groups on graphene.

Selective self-assembly and light emission tuning of layered hybrid perovskites on patterned graphene.

The emission of light in two-dimensional (2-D) layered hybrid organic lead halide perovskites, namely (R-NH3)2PbX4, can be effectively tuned using specific building blocks for the perovskite formation. Herein this behaviour is combined with a non-covalent graphene functionalization allowing excellent selectivity and spatial resolution of the perovskite film growth, promoting the formation of hybrid 2-D perovskite : graphene heterostructures with uniform coverage of up to centimeter scale graphene sheets and arbitrary shapes down to 5 µm. Using cryo-Raman microspectroscopy, highly resolved spectra of the perovskite phases were obtained and the Raman mapping served as a convenient spatially resolved technique for monitoring the distribution of the perovskite and graphene constituents on the substrate. In addition, the stability of the perovskite phase with respect to the thermal variation was inspected in situ by X-ray diffraction. Finally, time-resolved photoluminescence characterization demonstrated that the optical properties of the perovskite films grown on graphene are not hampered. Our study thus opens the door to smart fabrication routes for (opto)-electronic devices based on 2-D perovskites in contact with graphene with complex architectures.

Electronic and mechanical response of graphene on BaTiO3 at martensitic phase transitions.

Graphene is extremely sensitive to optical, electrical and mechanical stimuli, which cause a significant variation of the band structure, thus the physiochemical properties. In our work, we report on changes of strain and doping in graphene grown by chemical vapor deposition on copper and transferred onto a BaTiO3(1 0 0) (BTO) single-crystal. The BTO is known as a ferroelectric material, which undergoes several thermoelastic martensitic phase transitions when it is cooled from 300 K to 10 K. In order to enhance the very weak Raman signal of the graphene monolayer (ML) on the BTO, a 15 nm thin gold layer was deposited on top of the graphene ML to benefit from the surface enhanced Raman scattering. Using temperature dependent Raman spectral mapping, the principal Raman modes (D, G and 2D) of the graphene ML were followed in situ. From a careful analysis of these Raman modes, we conclude that the induced strain and doping of the graphene ML follows the martensitic phase transitions of the BTO crystal. Our study suggests potential exploitation of the graphene as a highly sensitive opto-mechanical sensor or transducer.

Tuning the Reactivity of Graphene by Surface Phase Orientation.

Tuning the local reactivity of graphene is a subject of paramount importance. Among the available strategies, the activation/passivation of graphene by copper substrate is very promising because it enables the properties of graphene to be influenced without any transfer procedure, since graphene can be grown directly on copper. Herein, it is demonstrated that the reactivity of graphene towards fluorination is strongly influenced by the face of the surface of the copper substrate. Graphene on the copper foil was probed and grain orientations were identified. The results of the reactivity were evaluated by means of X-ray photo electron and Raman spectroscopy. Graphene on the grains with a surface orientation close to the (111) face is the most reactive, whereas graphene on the grains close to the (110) surface is least reactive. The long-term stability test showed that the decomposition of fluorinated graphene was slowest on the grains with a surface orientation close to the (111) face. The results are consistent with the variation of the mechanical strain of graphene on different faces of copper. In contrast, no clear correlation of the graphene reactivity with doping induced by different facets was found.

Decomposition of Fluorinated Graphene under Heat Treatment.

Fluorination modifies the electronic properties of graphene, and thus it can be used to provide material with on-demand properties. However, the thermal stability of fluorinated graphene is crucial for any application in electronic devices. Herein, X-ray photoelectron spectroscopy (XPS), temperature-programmed desorption (TPD), and Raman spectroscopy were used to address the impact of the thermal treatment on fluorinated graphene. The annealing, at up to 700 K, caused gradual loss of fluorine and carbon, as was demonstrated by XPS. This loss was associated with broad desorption of CO and HF species, as monitored by TPD. The minor single desorption peak of CF species at 670 K is suggested to rationalize defect formation in the fluorinated graphene layer during the heating. However, fluorine removal from graphene was not complete, as some fraction of strongly bonded fluorine can persist despite heating to 1000 K. The role of intercalated H2 O and OH species in the defluorination process is emphasised.

Covalent Reactions on Chemical Vapor Deposition Grown Graphene Studied by Surface-Enhanced Raman Spectroscopy.

Graphene is a material of unmatched properties and eminent potential in disciplines ranging from physics, to chemistry, to biology. Its advancement to applications with a specific function requires rational design and fine tuning of its properties, and covalent introduction of various substituents answers this requirement. We challenged the obstacle of non-trivial and harsh procedures for covalent functionalization of pristine graphene and developed a protocol for mild nucleophilic introduction of organic groups in the gas phase. The painstaking analysis problem of monolayered materials was addressed by using surface-enhanced Raman spectroscopy, which allowed us to monitor and characterize in detail the surface composition. These deliverables provide a toolbox for reactivity of fluorinated graphene under mild reaction conditions, providing structural freedom of the species to-be-grafted to the single-layer graphene.

Graphene wrinkling induced by monodisperse nanoparticles: facile control and quantification.

Controlled wrinkling of single-layer graphene (1-LG) at nanometer scale was achieved by introducing monodisperse nanoparticles (NPs), with size comparable to the strain coherence length, underneath the 1-LG. Typical fingerprint of the delaminated fraction is identified as substantial contribution to the principal Raman modes of the 1-LG (G and G'). Correlation analysis of the Raman shift of the G and G' modes clearly resolved the 1-LG in contact and delaminated from the substrate, respectively. Intensity of Raman features of the delaminated 1-LG increases linearly with the amount of the wrinkles, as determined by advanced processing of atomic force microscopy data. Our study thus offers universal approach for both fine tuning and facile quantification of the graphene topography up to ~60% of wrinkling.

Selective and Scalable Chemical Removal of Thin Single-Walled Carbon Nanotubes from their Mixtures with Double-Walled Carbon Nanotubes.

Double-walled carbon nanotubes (DWCNTs) are materials in high demand due to their superior properties. However, it is very challenging to prepare DWCNTs samples of high purity. In particular, the removal of single-walled carbon nanotubes (SWCNTs) contaminants is a major problem. Here, a procedure for a selective removal of thin-diameter SWCNTs from their mixtures with DWCNTs by lithium vapor treatment is investigated. The results are evaluated by Raman spectroscopy and in situ Raman spectroelectrochemistry. It is shown that the amount of SWCNTs was reduced by about 35 % after lithium vapor treatment of the studied SWCNTs-DWCNTs mixture.

Doping of C70 fullerene peapods with lithium vapor: Raman spectroscopic and Raman spectroelectrochemical studies.

Raman spectroscopy and in situ Raman spectroelectrochemistry were applied to study the lithium vapor doping of C70@SWCNTs (peapods). A strong degree of doping was proved by the vanishing of the single walled carbon nanotubes (SWCNT's) radial breathing mode (RBM) and by the attenuation of the tangential (TG) band intensity. In contrast to potassium vapor doping, the strong downshift of the frequency of the TG band has not been observed for Li-doping. The Li vapor treated peapods remained partly doped even if they were exposed to humid air. This has been reflected by a reduced intensity of the nanotube and the fullerene modes and by the change of the shape of the RBM band as compared to that of the undoped sample. The modes of the intratubular fullerene were almost unresolved after the contact of the Li-doped sample with water. A lithium insertion into the interior of a peapod and its strong interaction with the intratubular fullerene is suggested to be responsible for the air-insensitive residual doping. This residual doping was studied by spectroelectrochemical measurements. The TG band of the Li doped peapods is partly upshifted during the anodic doping, which points to the different state of C70@SWCNTs and C60@SWCNTs studied previously.