Cyclododecane as support material for clean and facile transfer of large-area few-layer graphene

The transfer of chemical vapor deposited graphene is a crucial process, which can affect the quality of the transferred films and compromise their application in devices. Finding a robust and intrinsically clean material capable of easing the transfer of graphene without interfering with its properties remains a challenge. We here propose the use of an organic compound, cyclododecane, as a transfer material. This material can be easily spin coated on graphene and assist the transfer, leaving no residues and requiring no further removal processes. The effectiveness of this transfer method for few-layer graphene on a large area was evaluated and confirmed by microscopy, Raman spectroscopy, x-ray photoemission spectroscopy, and four-point probe measurements. Schottky-barrier solar cells with few-layer graphene were fabricated on silicon wafers by using the cyclododecane transfer method and outperformed reference cells made by standard methods.

Combined effect of double antireflection coating and reversible molecular doping on performance of few-layer graphene/n-silicon Schottky barrier solar cells

Few-layer graphene films were grown by chemical vapor deposition and transferred onto n-type crystalline silicon wafers to fabricate graphene/n-silicon Schottky barrier solar cells. In order to increase the power conversion efficiency of such cells the graphene films were doped with nitric acid vapor and an antireflection treatment was implemented to reduce the sunlight reflection on the top of the device. The doping process increased the work function of the graphene film and had a beneficial effect on its conductivity. The deposition of a double antireflection coating led to an external quantum efficiency up to 90% across the visible and near infrared region, the highest ever reported for this type of devices. The combined effect of graphene doping and antireflection treatment allowed to reach a power conversion efficiency of 8.5% exceeding the pristine (undoped and uncoated) device performance by a factor of 4. The optical properties of the antireflection coating were found to be not affected by the exposure to nitric acid vapor and to remain stable over time.

Hybrid graphene and graphitic carbon nitride nanocomposite : gap opening, electron–hole puddle, interfacial charge transfer, and enhanced visible light response

Opening up a band gap and finding a suitable substrate material are two big challenges for building graphene-based nanodevices. Using state-of-the-art hybrid density functional theory incorporating long range dispersion corrections, we investigate the interface between optically active graphitic carbon nitride (g-C3N4) and electronically active graphene. We find an inhomogeneous planar substrate (g-C3N4) promotes electronrich and hole-rich regions, i.e., forming a well-defined electron−hole puddle, on the supported graphene layer. The composite displays significant charge transfer from graphene to the g-C3N4 substrate, which alters the electronic properties of both components. In particular, the strong electronic coupling at the graphene/g-C3N4 interface opens a 70 meV gap in g-C3N4-supported graphene, a feature that can potentially allow overcoming the graphene’s band gap hurdle in constructing field effect transistors. Additionally, the 2-D planar structure of g-C3N4 is free of dangling bonds, providing an ideal substrate for graphene to sit on. Furthermore, when compared to a pure g-C3N4 monolayer, the hybrid graphene/g-C3N4 complex displays an enhanced optical absorption in the visible region, a promising feature for novel photovoltaic and photocatalytic applications.

Hybrid graphene/titania nanocomposite : interface charge transfer, hole doping, and sensitization for visible light response

We demonstrated for the first time by large-scale ab initio calculations that a graphene/titania interface in the ground electronic state forms a charge-transfer complex due to the large difference of work functions between graphene and titania, leading to substantial hole doping in graphene. Interestingly, electrons in the upper valence band can be directly excited from graphene to the conduction band, that is, the 3d orbitals of titania, under visible light irradiation. This should yield well-separated electron−hole pairs, with potentially high photocatalytic or photovoltaic performance in hybrid graphene and titania nanocomposites. Experimental wavelength-dependent photocurrent generation of the graphene/titania photoanode demonstrated noticeable visible light response and evidently verified our ab initio prediction.

Multifunctional three-dimensional T-junction graphene micro-wells: Energy-efficient, plasma-enabled growth and instant water-based transfer for flexible device applications

The “third-generation” 3D graphene structures, T-junction graphene micro-wells (T-GMWs) are produced on cheap polycrystalline Cu foils in a single-step, low-temperature (270 °C), energy-efficient, and environment-friendly dry plasma-enabled process. T-GMWs comprise vertical graphene (VG) petal-like sheets that seemlessly integrate with each other and the underlying horizontal graphene sheets by forming T-junctions. The microwells have the pico-to-femto-liter storage capacity and precipitate compartmentalized PBS crystals. The T-GMW films are transferred from the Cu substrates, without damage to the both, in de-ionized or tap water, at room temperature, and without commonly used sacrificial materials or hazardous chemicals. The Cu substrates are then re-used to produce similar-quality T-GMWs after a simple plasma conditioning. The isolated T-GMW films are transferred to diverse substrates and devices and show remarkable recovery of their electrical, optical, and hazardous NO2 gas sensing properties upon repeated bending (down to 1 mm radius) and release of flexible trasparent display plastic substrates. The plasma-enabled mechanism of T-GMW isolation in water is proposed and supported by the Cu plasma surface modification analysis. Our GMWs are suitable for various optoelectronic, sesning, energy, and biomedical applications while the growth approach is potentially scalable for future pilot-scale industrial production.

Long range resonance energy transfer from a dye molecule to graphene has (distance)-4 dependence

In our previous report on resonance energy transfer from a dye molecule to graphene [J. Chem. Phys.129, 054703 (2008)], we had derived an expression for the rate of energy transfer from a dye to graphene. An integral in the expression for the rate was evaluated approximately. We found a Yuwaka-type dependence of the rate on the distance. We now present an exact evaluation of the integral involved, leading to very interesting results. For short distances (z < 20 A), the present rate and the previous rate are in good agreement. For larger distances, the rate is found to have a z(-4) dependence on the distance, exactly. Thus we predict that for the case of pyrene on graphene, it is possible to observe fluorescence quenching up to a distance of 300 A. This is in sharp contrast to the traditional fluorescence resonance energy transfer where the quenching is observable only up to 100 A.

Single layer graphene film by ethanol chemical vapor deposition: Highly efficient growth and clean transfer method

The choice of ethanol (C2H5OH) as carbon source in the Chemical Vapor Deposition (CVD) of graphene on copper foils can be considered as an attractive alternative among the commonly used hydrocarbons, such as methane (CH4) [1]. Ethanol, a safe, low cost and easy handling liquid precursor, offers fast and efficient growth kinetics with the synthesis of fullyformed graphene films in just few seconds [2]. In previous studies of graphene growth from ethanol, various research groups explored temperature ranges lower than 1000 °C, usually reported for methane-assisted CVD. In particular, the 650–850 °C and 900 °C ranges were investigated, respectively for 5 and 30 min growth time [3, 4]. Recently, our group reported the growth of highly-crystalline, few-layer graphene by ethanol-CVD in hydrogen flow (1– 100 sccm) at high temperatures (1000–1070 °C) using growth times typical of CH4-assisted synthesis (10–30 min) [5]. Furthermore, a synthesis time between 20 and 60 s in the same conditions was explored too. In such fast growth we demonstrated that fully-formed graphene films can be grown by exposing copper foils to a low partial pressure of ethanol (up to 2 Pa) in just 20 s [6] and we proposed that the rapid growth is related to an increase of the Cu catalyst efficiency due weak oxidizing nature of ethanol. Thus, the employment of such liquid precursor, in small concentrations, together with a reduced time of growth and very low pressure leads to highly efficient graphene synthesis. By this way, the complete coverage of a copper catalyst surface with high spatial uniformity can be obtained in a considerably lower time than when using methane.

XPS evidence for molecular charge-transfer doping of graphene

By employing X-ray photoelectron spectroscopy (XPS), we have been able to establish the occurrence of charge-transfer doping in few-layer graphene covered with electron acceptor (TCNE) and donor (TTF) molecules. We have performed quantitative estimates of the extent of charge transfer in these complexes and elucidated the origin of unusual shifts of their Raman G-bands and explained the differences in the dependence of conductivity on n- and p-doping. The study unravels the cause of the apparent difference between the charge-transfer doping and electrochemical doping. (C) 2010 Elsevier B.V. All rights reserved.

Molecular charge-transfer interaction with single-layer graphene

While the effect of electrochemical doping on single-layer graphene (SG) with holes and electrons has been investigated, the effect of charge-transfer doping on SG has not been examined hitherto. Effects of varying the concentration of electron donor and acceptor molecules such as tetrathiafulvalene (TTF) and tetracyanoethylene (TCNE) on SG produced by mechanical exfoliation as well as by the reduction of single-layer graphene oxide have been investigated. TTF softens the G-band in the Raman spectrum, whereas TCNE stiffens the G-band. The full-width-at-half-maximum of the G-band increases on interaction with both TTF and TCNE. These effects are similar to those found with few-layer graphene, but in contrast to those found with electrochemical doping. A common feature between the two types of doping is found in the case of the 2-D band, which shows softening and stiffening on electron and hole doping, respectively. The experimental results are explained on the basis of the frequency shifts, electron-phonon coupling and structural inhomogeneities that are relevant to molecule-graphene interaction.

Excitation energy transfer from dye molecules to doped graphene

Recently, we have reported theoretical studies on the rate of energy transfer from an electronically excited molecule to graphene. It was found that graphene is a very efficient quencher of the electronically excited states and that the rate infinity z(-4). The process was found to be effective up to 30 nm which is well beyond the traditional FRET limit. In this report, we study the transfer of an amount of energy (h) over bar Omega from a dye molecule to doped graphene. We find a crossover of the distance dependence of the rate from z(-4) to exponential as the Fermi level is increasingly shifted into the conduction band, with the crossover occurring at a shift of the Fermi level by an amount (h) over bar Omega/2.

Spectral Migration of Fluorescence in Graphene Oxide Aqueous Dispersions: Evidence for Excited-State Proton Transfer

Aqueous dispersions of graphene oxide (GO) exhibit strong pH-dependent fluorescence in the visible that originates, in part, from the oxygenated functionalities present. Here we examine the spectral migration on nanosecond time-scales of the pH dependent features in the fluorescence spectra. We show, from time-resolved emission spectra (TRES) constructed from the wavelength dependent fluorescence decay curves, that the migration is associated with excited state proton transfer. Both `intramolecular' and `intermolecular' transfer involving the quasi-molecular oxygenated aromatic fragments are observed. As a prerequisite to the time-resolved measurements, we have correlated the changes in the steady state fluorescence spectra with the sequence of dissociation events that occur in GO dispersions at different values of pH.

Transfer free suspended graphene devices on silicon using electrodeposited copper

Transfer free processes using Cu films greatly simplify the fabrication of reliable suspended graphene devices. In this paper, the authors report on the use of electrodeposited Cu films on Si for transfer free fabrication of suspended graphene devices. The quality of graphene layers on optimized electrodeposited Cu and Cu foil are found to be the same. By selectively etching the underlying Cu, the authors have realized by a transfer free process metal contacted, suspended graphene beams up to 50 mu m in length directly on Si. The suspended graphene beams do not show any increase in defect levels over the as grown state indicating the efficiency of the transfer free process. Measured room temperature electronic mobilities of up to 5200 cm(2)/V.s show that this simpler and CMOS compatible route has the potential to replace the foil based route for such suspended nano and micro electromechanical device arrays. (C) 2014 American Vacuum Society.

Frame assisted H2O electrolysis induced H2 bubbling transfer of large area graphene grown by chemical vapor deposition on Cu

An improved technique for transferring large area graphene grown by chemical vapor deposition on copper is presented. It is based on mechanical separation of the graphene/copper by H2 bubbles during H2O electrolysis, which only takes a few tens of seconds while leaving the copper cathode intact. A semi-rigid plastic frame in combination with thin polymer layer span on graphene gives a convenient way of handling- and avoiding wrinkles and holes in graphene. Optical and electrical characterizations prove the graphene quality is better than that obtained by traditional wet etching transfer. This technique appears to be highly reproducible and cost efficient. © 2013 American Institute of Physics.

Optical Properties and Charge-Transfer Excitations in Edge-Functionalized All-Graphene Nanojunctions

We investigate the optical properties of edge-fiinctionalized graphene nanosystems, focusing on the formation of junctions and charge-transfer excitons. We consider a class of graphene structures that combine the main electronic features of graphene with the wide tunability of large polycyclic aromatic hydrocarbons. By investigating prototypical ribbon-like systems, we show that, upon convenient choice of functional groups, low-energy excitations with remarkable charge-transfer character and large oscillator strength are obtained. These properties can be further modulated through an appropriate width variation, thus spanning a wide range in the low-energy region of the UV-vis spectra. Our results are relevant in view of designing all-graphene optoelectronic nanodevices, which take advantage of the versatility of molecular functionalization, together with the stability and the electronic properties of graphene nanostructures.

Controllable graphene oxide mediated efficient electron transfer pathways across self-assembly monolayers: a new class of graphene based electrodes

In this paper, the influence of chemically reduced graphene oxide sheets (CRGOs) on the electrochemical performance through methyl or carboxylic acid terminated self-assembled monolayers (SAMs) is reported. The gold electrode was initially modified with methyl or carboxylic acid terminated alkanethiols with various carbon chain lengths (n = 4, 6, 8 and 11) and subsequently immobilization of the CRGOs on a SAM surface was achieved via a hydrophobic and electrostatic interaction. By using the potassium ferricyanide as a redox probe, it was observed that CRGOs could effectively enhance the heterogeneous electron transfer (ET) of the SAM due to a tunneling effect. The assemblies based on thiol end groups with methyl head groups were observed to afford more hydrophobic interaction binding with CRGOs with a higher reduction time than the assemblies developed with thiol end groups and a -COOH group which were shown to bind more electrostatically with CRGOs, a lowering reduction time. The Nyquist plots developed show a gradual decrease of the charge transfer resistance (Rct) of [Fe(CN)6]3-/4- redox couple at the CRGOs-SAMs electrode with the controllable adsorption of different CRGO's onto the SAM. Depending on the chain length and terminal functional group the electron transfer rate kinetics were observed to differ considerably.