Woody plant material represents a vast renewable resource that has the potential to produce biofuels and other bio-based products with favorable net CO2 emissions.1,2 Its potential has been demonstrated in a recent study that generated novel structural materials from flexible moldable wood.3 Apple rubbery wood (ARW) disease is the result of a viral infection that causes woody stems to exhibit increased flexibility.4 Although ARW disease is associated with the presence of an RNA virus5 known as apple rubbery wood virus (ARWV), how the unique symptoms develop is unknown. We demonstrate that the symptoms of ARWV infections arise from reduced lignification within the secondary cell wall of xylem fibers and result in increased wood digestibility. In contrast, the mid-lamellae region and xylem ray cells are largely unaffected by the infection. Gene expression and proteomic data from symptomatic xylem clearly show the downregulation of phenylalanine ammonia lyase (PAL), the enzyme catalyzing the first committed step in the phenylpropanoid pathway leading to lignin biosynthesis. A large increase in soluble phenolics in symptomatic xylem, including the lignin precursor phenylalanine, is also consistent with PAL downregulation. ARWV infection results in the accumulation of many host-derived virus-activated small interfering RNAs (vasiRNAs). PAL-derived vasiRNAs are among the most abundant vasiRNAs in symptomatic xylem and are likely the cause of reduced PAL activity. Apparently, the mechanism used by the virus to alter lignin exhibits similarities to the RNAi strategy used to alter lignin in genetically modified trees to generate comparable improvements in wood properties.6-8.

Partially fluorinated graphene samples were studied by conductive AFM. The conductivity is found to be strongly non-uniform with low conductivity patches of about 10 nm. We interpret this observation as formation of low conducting clusters of fluorinated graphene separated by areas of pristine material. This is the first direct observation of clustering of covalently bonded impurities on graphene surface.

We report the gate-modulated Raman spectrum of defective graphene. We show that the intensity of the D peak can be reversibly tuned by applying a gate voltage. This effect is attributed to chemical functionalization of the graphene crystal lattice, generated by an electrochemical reaction involving the water layer trapped at the interface between silicon and graphene.

When a crystal is subjected to a periodic potential, under certain circumstances it can adjust itself to follow the periodicity of the potential, resulting in a commensurate state. Of particular interest are topological defects between the two commensurate phases, such as solitons and domain walls. Here we report a commensurate–incommensurate transition for graphene on top of hexagonal boron nitride (hBN). Depending on the rotation angle between the lattices of the two crystals, graphene can either stretch to adapt to a slightly different hBN periodicity (for small angles, resulting in a commensurate state) or exhibit little adjustment (the incommensurate state). In the commensurate state, areas with matching lattice constants are separated by domain walls that accumulate the generated strain. Such soliton-like objects are not only of significant fundamental interest, but their presence could also explain recent experiments where electronic and optical properties of graphene-hBN heterostructures were observed to be considerably altered. A single layer of graphene on top of a hexagonal boron-nitride sheet can stretch to form a commensurate structure, or not — depending on the rotation angle between the two layers. In the case of commensurability, strain gets concentrated in domain walls, resulting in soliton-like structures.

The new paradigm of heterostructures based on two-dimensional (2D) atomic crystals has already led to the observation of exciting physical phenomena and creation of novel devices. The possibility of combining layers of different 2D materials in one stack allows unprecedented control over the electronic and optical properties of the resulting material. Still, the current method of mechanical transfer of individual 2D crystals, though allowing exceptional control over the quality of such structures and interfaces, is not scalable. Here we show that such heterostructures can be assembled from chemically exfoliated 2D crystals, allowing for low-cost and scalable methods to be used in device fabrication.

In this work, covalent modification of mono- and bilayer graphene is achieved using tetrafluoromethane (CF4), oxygen and hydrogen RF plasma. Controlled modification of graphene is usually difficult to achieve, in particular with oxygen plasma, which is rather aggressive and usually leads to etching of graphene. Here we use x-ray photoelectron spectroscopy and Raman spectroscopy to show that mild plasma conditions and fine tuning of the number of functional groups can be obtained in all plasmas by varying parameters such as exposure time and sample position inside the chamber. We found that even for the usual harsh oxygen treatment the defect density could be lowered, down to one defect for 3.5 × 104 carbon atoms. Furthermore, we show that CF4 plasma leads to functionalization without etching and that graphene becomes an insulator at saturation coverage. In addition, the reactivity of mono- and bilayer graphene was studied revealing faster modification of monolayer in oxygen and CF4 plasma, in agreement with previous works. In contrast, similar modification rates were observed for both mono- and bilayer during hydrogenation. We attribute this discrepancy to the presence of more energetic species in the hydrogen plasma such as positive ions that could play a role in the functionalization process.

We determine the Raman scattering efficiency of the G and 2D peaks in graphene. Three substrates are used: silicon covered with 300 or 90 nm oxide, and calcium fluoride (CaF2). On Si/SiOx, the areas of the G and 2D peak show a strong dependence on the substrate due to interference effects, while on CaF2 no significant dependence is detected. Unintentional doping is reduced by placing graphene on CaF2. We determine the Raman scattering efficiency by comparison with the 322 cm(-1) peak area of CaF2. At 2.41 eV, the Raman efficiency of the G peak is similar to 200 x 10(-5) m(-1)Sr(-1), and changes with the excitation energy to the power of 4. The 2D Raman efficiency is at least one order of magnitude higher than that of the G peak, with a different excitation energy dependence.

We present a detailed Raman study of defective graphene samples containing specific types of defects. In particular, we compared sp(3) sites, vacancies, and substitutional Boron atoms. We find that the ratio between the D and G peak intensities, I(D)/I(G), does not depend on the geometry of the defect (within the Raman spectrometer resolution). In contrast, in the limit of low defect concentration, the ratio between the D' and G peak intensities is higher for vacancies than sp3 sites. By using the local activation model, we attribute this difference to the term C S, x, representing theRaman cross section of I(x)/I(G) associated with the distortion of the crystal lattice after defect introduction per unit of damaged area, where x = D or D'. We observed that CS, D = 0 for all the defects analyzed, while C-S,C-D' of vacancies is 2.5 times larger than C-S,C-D' of sp3 sites. This makes I(D)/I(D') strongly sensitive to the nature of the defect. We also show that the exact dependence of I(D)/I(D') on the excitation energy may be affected by the nature of the defect. These results can be used to obtain further insights into the Raman scattering process (in particular for the D' peak) in order to improve our understanding and modeling of defects in graphene.

In this work, covalent modification of mono-and bilayer graphene is achieved using tetrafluoromethane (CF4), oxygen and hydrogen RF plasma. Controlled modification of graphene is usually difficult to achieve, in particular with oxygen plasma, which is rather aggressive and usually leads to etching of graphene. Here we use x-ray photoelectron spectroscopy and Raman spectroscopy to show that mild plasma conditions and fine tuning of the number of functional groups can be obtained in all plasmas by varying parameters such as exposure time and sample position inside the chamber. We found that even for the usual harsh oxygen treatment the defect density could be lowered, down to one defect for 3.5 x 10(4) carbon atoms. Furthermore, we show that CF4 plasma leads to functionalization without etching and that graphene becomes an insulator at saturation coverage. In addition, the reactivity of mono-and bilayer graphene was studied revealing faster modification of monolayer in oxygen and CF4 plasma, in agreement with previous works. In contrast, similar modification rates were observed for both mono-and bilayer during hydrogenation. We attribute this discrepancy to the presence of more energetic species in the hydrogen plasma such as positive ions that could play a role in the functionalization process.

Graphene placed on hexagonal-boron nitride (h-BN) experiences a superlattice (Moiré) potential, which leads to a strong reconstruction of graphene's electronic spectrum with new Dirac points emerging at sub-eV energies. Here we study the effect of such superlattices on graphene's Raman spectrum. In particular, the 2D Raman peak is found to be exquisitely sensitive to the misalignment between graphene and h-BN lattices, probably due to the presence of a strain distribution with the same periodicity of the Moiré potential. This feature can be used to identify graphene superlattices with a misalignment angle smaller than 2°.

We present a joint theoretical and experimental investigation of charge doping and electronic potential landscapes in hybrid structures composed of graphene and semiconducting single layer molybdenum disulfide (MoS2). From first-principles simulations, we find electron doping of graphene due to the presence of rhenium impurities in MoS2. Furthermore, we show that MoS2 edges give rise to charge reordering and a potential shift in graphene, which can be controlled through external gate voltages. The interplay of edge and impurity effects allows the use of the graphene-MoS2 hybrid as a photodetector. Spatially resolved photocurrent signals can be used to resolve potential gradients and local doping levels in the sample.

The isolation of various two-dimensional (2D) materials, and the possibility to combine them in vertical stacks, has created a new paradigm in materials science: heterostructures based on 2D crystals. Such a concept has already proven fruitful for a number of electronic applications in the area of ultrathin and flexible devices. Here, we expand the range of such structures to photoactive ones by using semiconducting transition metal dichalcogenides (TMDCs)/graphene stacks. Van Hove singularities in the electronic density of states of TMDC guarantees enhanced light-matter interactions, leading to enhanced photon absorption and electron-hole creation (which are collected in transparent graphene electrodes). This allows development of extremely efficient flexible photovoltaic devices with photoresponsivity above 0.1 ampere per watt (corresponding to an external quantum efficiency of above 30%).

In less than a decade of research, graphene has earned a long list of superlatives to its name and is expected to have applications in various fields such as electronics, photonics, optoelectronics, materials, biology and chemistry. Graphene has also attracted a lot of attention because its properties can be engineered either via intrinsic changes or by modification of its environment. Raman spectroscopy has become an ideal characterization method to obtain qualitative and quantitative information on these changes. This thesis investigates the possibility to change, supplement and monitor the electonic and optical properties as well as the chemical reactivity of graphene. It is achieved by i) substrate effect, ii) introduction of defects in the structure of graphene and iii) the combination of graphene with other two- dimensional crystals such as hexagonal boron nitride (h-BN) and transition metal dichacolgenides.In particular, the experimental work presented here describes:I - The influence of the type of substrate on the Raman intensity of graphene. This work leads to the calculation of the Raman scattering efficiency of graphene after CaF2 is found to be a suitable substrate for this kind of study in contrast to Si/SiOx that strongly modulates the Raman intensities. The G peak scattering efficiency is found to be about 200 x 10-5 m-1 Sr-1 at 2.4 eV while that of the 2D peak is one order of magnitude higher, confirming the resonant nature of the 2D peak Raman scattering process.II - An attractive method to produce large (up to several hundreds of microns across) and high quality graphene by anodic bonding. This cheap, fast and solvent-free method also allows introduction of vacancy like defects in the samples in a relatively controllable way. III - The Raman signatures of several types of defect such as sp3 sites, vacancies and substitutional atoms. For low defect concentration (stage 1) the intensitiy ratio I(D)/I(D') is constant and is 13 for sp3 sites, 9 for substitutional atoms and 7 for vacancies. This signature is explained using the local activation model recently proposed to model the amorphization trajectory of graphene with containing vacancy-like defects.IV - Controlled modification of graphene through mild oxygen plasma. The influence of sp3 sites on monolayer and bilayer graphene's electrical properties are discussed. In the case of bilayer under controlled conditions, it is possible to modify only the top layer. This may lead to decoupling between the two layers, which could explain the good mobility measured for this system. The possiblity to use such system as a sensor is discussed. V - The characteristic Raman signature of aligned graphene/h-BN superlattices. The Raman spectrum shows strong changes in perfectly aligned superlattices, which could be attributed to the reconstruction of the Dirac spectrum.VI - A prototype photovoltaic cell made of a graphene and tungsten disulphide (WS2) heterostructure with an external quantum efficiency of about 30%. The beneficial combination of an excellent absorption in WS2 atomically thin films due to the presence of van Hove singularities and graphene used as a transparent, flexible and conductive electrode is demonstrated.

Graphene based devices fabrication is currently impeded by its metallic behavior and its lack of reactivity making it hard to create graphene based transistors or sensors. In order to overcome this problem, various approaches to tune and control the electronic properties of graphene have been considered. In this work, we investigate the controlled modification of graphene using mild oxygen (O2) plasma treatment [1]. The treatments were performed on monolayer and bilayer graphene and graphite. The comparison between these three samples allows us to study the difference of reactivity when increasing the number of layers. X-ray photoelectron spectroscopy (XPS) using a micro beam probe is then performed on pristine and plasma modified graphene and graphite. This technique is able to give chemical bonding information on single exfoliated graphene flakes. We studied the carbon 1s peak evolution with different plasma parameters such as treatment time, power or sample position inside the chamber. The functionalized graphene layers present a shoulder at high binding energy (286-289 eV) which corresponds to carbon-oxygen bonds such as hydroxyl, carbonyl and carboxyl. We show that changing plasma parameters allows tuning of the functionalization. In addition, the amount and type of functional groups are found to vary with the number of graphene layers.

The introduction of foreign atoms, such as nitrogen, into the hexagonal network of an sp(2)-hybridized carbon atom monolayer has been demonstrated and constitutes an effective tool for tailoring the intrinsic properties of graphene. Here, we report that boron atoms can be efficiently substituted for carbon in graphene. Single-layer graphene substitutionally doped with boron was prepared by the mechanical exfoliation of boron-doped graphite. X-ray photoelectron spectroscopy demonstrated that the amount of substitutional boron in graphite was ~0.22 atom %. Raman spectroscopy demonstrated that the boron atoms were spaced 4.76 nm apart in single-layer graphene. The 7-fold higher intensity of the D-band when compared to the G-band was explained by the elastically scattered photoexcited electrons by boron atoms before emitting a phonon. The frequency of the G-band in single-layer substitutionally boron-doped graphene was unchanged, which could be explained by the p-type boron doping (stiffening) counteracting the tensile strain effect of the larger carbon-boron bond length (softening). Boron-doped graphene appears to be a useful tool for engineering the physical and chemical properties of graphene.

An experimental study on the interaction between the top and bottom layer of a chemically functionalized graphene bilayer by mild oxygen plasma is reported. Structural, chemical, and electrical properties are monitored using Raman spectroscopy, transport measurements, conductive atomic force microscopy and X-ray photoelectron spectroscopy. Single- and double-sided chemical functionalization are found to give very different results: single-sided modified bilayers show relatively high mobility (200-600 cm(2) V(-1) s(-1) at room temperature) and a stable structure with a limited amount of defects, even after long plasma treatment (>60 s). This is attributed to preferential modification and limited coverage of the top layer during plasma exposure, while the bottom layer remains almost unperturbed. This could eventually lead to decoupling between top and bottom layers. Double-sided chemical functionalization leads to a structure containing a high concentration of defects, very similar to graphene oxide. This opens the possibility to use plasma treatment not only for etching and patterning of graphene, but also to make heterostructures (through single-sided modification of bilayers) for sensors and transistors and new graphene-derivatives materials (through double-sided modification).

Raman spectroscopy is able to probe disorder in graphene through defect-activated peaks. It is of great interest to link these features to the nature of disorder. Here we present a detailed analysis of the Raman spectra of graphene containing different type of defects. We found that the intensity ratio of the D and D' peak is maximum (∼13) for sp(3)-defects, it decreases for vacancy-like defects (∼7), and it reaches a minimum for boundaries in graphite (∼3.5). This makes Raman Spectroscopy a powerful tool to fully characterize graphene.

In this work we use a chemical approach based on supra-molecular and non-covalent interactions between graphene and 1-pyrenesulfonic acid sodium salt (Py–1SO3) to obtain a stable dispersion of graphene by using only water as solvent. The material has been characterized by a combination of spectroscopic and microscopic techniques. In particular, an extensive Raman analysis shows that we have ∼70% few-graphene layers (<7). We also show that the exfoliation efficiency strongly depends on the number of functional groups by comparing suspensions obtained by Py–1SO3 and 1,3,6,8-pyrenetetrasulfonic acid (Py–4SO3). A strong decrease in the exfoliation yield has been observed by using pyrene with 4 sulphonic groups (Py–4SO3), as compared to one sulphonic group (Py–1SO3). Being completely water-based, these suspensions can be used as inks for printable tattoo-based electro-chemical sensors.

Results of a study on the electrochemical properties of exfoliated single and multilayer graphene flakes are presented. Graphene flakes were deposited on silicon/silicon oxide wafers to enable fast and accurate characterization by optical microscopy and Raman spectroscopy. Conductive silver paint and silver wires were used to fabricate contacts; epoxy resin was employed as a masking coating in order to expose a stable, well-defined area of graphene. Both multilayer and monolayer graphene microelectrodes showed quasi-reversible behavior during voltammetric measurements in potassium ferricyanide. However, the standard heterogeneous charge transfer rate constant, k°, was estimated to be higher for monolayer graphene flakes.