Raman Fingerprints of Graphene Produced by Anodic Electrochemical Exfoliation.

Electrochemical exfoliation is one of the most promising methods for scalable production of graphene. However, limited understanding of its Raman spectrum as well as lack of measurement standards for graphene strongly limit its industrial applications. In this work, we show a systematic study of the Raman spectrum of electrochemically exfoliated graphene, produced using different electrolytes and types of solvents in varying amounts. We demonstrate that no information on the thickness can be extracted from the shape of the 2D peak as this type of graphene is defective. Furthermore, the number of defects and the uniformity of the samples strongly depend on the experimental conditions, including postprocessing. Under specific conditions, the formation of short conductive trans-polyacetylene chains has been observed. Our Raman analysis provides guidance for the community on how to get information on defects coming from electrolyte, temperature, and other experimental conditions, by making Raman spectroscopy a powerful metrology tool.

Anomalous Cyclotron Motion in Graphene Superlattice Cavities.

We consider graphene superlattice miniband fermions probed by electronic interferometry in magnetotransport experiments. By decoding the observed Fabry-Pérot interference patterns together with our corresponding quantum transport simulations, we find that the Dirac quasiparticles originating from the superlattice minibands do not undergo conventional cyclotron motion but follow more subtle trajectories. In particular, dynamics at low magnetic fields is characterized by peculiar, straight trajectory segments. Our results provide new insights into superlattice miniband fermions and open up novel possibilities to use periodic potentials in electron optics experiments.

Measuring in Situ Length Distributions of Polymer-Wrapped Monochiral Single-Walled Carbon Nanotubes Dispersed in Toluene with Analytical Ultracentrifugation.

The length of a carbon nanotube is an important dimension that has to be adjusted to the requirements of an experiment or application, e.g., through sorting methods. So far, atomic force microscopy (AFM) has been the method of choice for measuring length distributions, despite being an ex situ method with apparent shortcomings. In this work, we explore analytical ultracentrifugation (AUC) as an in situ method for measuring the length distribution of polymer-wrapped (7, 5) single-walled carbon nanotubes dispersed in toluene. This is an AUC study of nanotubes in nonaqueous media, the preferred media for nanotubes used in device fabrication. In AUC, the temporally and spatially dependent change in optical absorption of a sample is measured under centrifugation. The resulting sedimentation curves can be deconvoluted with a standard data processing procedure (SEDFIT), to yield the sedimentation coefficient distribution. However, the conversion of the sedimentation coefficient distribution into a length distribution is nontrivial and requires finding a suitable model for the nanotube friction coefficient. Also, since AUC is based on optical absorption, it yields a volume distribution and not a number distribution as obtained from AFM reference data. By meeting these challenges and finding a surprisingly simple empirical flexible-chain-like model to describe the sedimentation behavior of one specific chiral structure, we suggest AUC as a viable method for measuring in situ nanotube length distributions of nonaqueous dispersions.

Tuning Anti-Klein to Klein Tunneling in Bilayer Graphene.

We show that in gapped bilayer graphene, quasiparticle tunneling and the corresponding Berry phase can be controlled such that they exhibit features of single-layer graphene such as Klein tunneling. The Berry phase is detected by a high-quality Fabry-Pérot interferometer based on bilayer graphene. By raising the Fermi energy of the charge carriers, we find that the Berry phase can be continuously tuned from 2π down to 0.68π in gapped bilayer graphene, in contrast to the constant Berry phase of 2π in pristine bilayer graphene. Particularly, we observe a Berry phase of π, the standard value for single-layer graphene. As the Berry phase decreases, the corresponding transmission probability of charge carriers at normal incidence clearly demonstrates a transition from anti-Klein tunneling to nearly perfect Klein tunneling.

Directional couplers with integrated carbon nanotube incandescent light emitters.

We combine on-chip single-walled carbon nanotubes (SWNTs) emitters with directional coupling devices as fundamental building blocks for carbon photonic systems. These devices are essential for studying the emission properties of SWNTs in the few photon regime for future applications in on-chip quantum photonics. The combination of SWNTs with on-chip beam splitters herein provides the basis for correlation measurements as necessary for nanoscale source characterization. The employed fabrication methods are fully scalable and thus allow for implementing a multitude of functional and active circuits in a single fabrication run. Our metallic SWNT emitters are broadband and cover both visible and near-infrared wavelengths, thus holding promise for emerging hybrid optoelectronic devices with fast reconfiguration times.

Chiral-index resolved length mapping of carbon nanotubes in solution using electric-field induced differential absorption spectroscopy.

The length of single-walled carbon nanotubes (SWCNTs) is an important metric for the integration of SWCNTs into devices and for the performance of SWCNT-based electronic or optoelectronic applications. In this work we propose a rather simple method based on electric-field induced differential absorption spectroscopy to measure the chiral-index-resolved average length of SWCNTs in dispersions. The method takes advantage of the electric-field induced length-dependent dipole moment of nanotubes and has been verified and calibrated by atomic force microscopy. This method not only provides a low cost, in situ approach for length measurements of SWCNTs in dispersion, but due to the sensitivity of the method to the SWCNT chiral index, the chiral index dependent average length of fractions obtained by chromatographic sorting can also be derived. Also, the determination of the chiral-index resolved length distribution seems to be possible using this method.

Light emission, light detection and strain sensing with nanocrystalline graphene.

Graphene is of increasing interest for optoelectronic applications exploiting light detection, light emission and light modulation. Intrinsically, the light-matter interaction in graphene is of a broadband type. However, by integrating graphene into optical micro-cavities narrow-band light emitters and detectors have also been demonstrated. These devices benefit from the transparency, conductivity and processability of the atomically thin material. To this end, we explore in this work the feasibility of replacing graphene with nanocrystalline graphene, a material which can be grown on dielectric surfaces without catalyst by graphitization of polymeric films. We have studied the formation of nanocrystalline graphene on various substrates and under different graphitization conditions. The samples were characterized by resistance, optical transmission, Raman and x-ray photoelectron spectroscopy, atomic force microscopy and electron microscopy measurements. The conducting and transparent wafer-scale material with nanometer grain size was also patterned and integrated into devices for studying light-matter interaction. The measurements show that nanocrystalline graphene can be exploited as an incandescent emitter and bolometric detector similar to crystalline graphene. Moreover the material exhibits piezoresistive behavior which makes nanocrystalline graphene interesting for transparent strain sensors.

On the mechanism of piezoresistance in nanocrystalline graphite.

Strain sensors are sensitive to mechanical deformations and enable the detection of strain also within integrated electronics. For flexible displays, the use of a seamlessly integrated strain sensor would be beneficial, and graphene is already in use as a transparent and flexible conductor. However, graphene intrinsically lacks a strong response, and only by engineering defects, such as grain boundaries, one can induce piezoresistivity. Nanocrystalline graphene (NCG), a derivative form of graphene, exhibits a high density of defects in the form of grain boundaries. It holds an advantage over graphene in easily achieving wafer-scale growth with controlled thickness. In this study, we explore the piezoresistivity in thin films of nanocrystalline graphite. Simultaneous measurements of sheet resistance and externally applied strain on NCG placed on polyethylene terephthalate (PET) substrates provide intriguing insights into the underlying mechanism. Raman measurements, in conjunction with strain applied to NCG grown on flexible glass, indicate that the strain is concentrated at the grain boundaries for smaller strain values. For larger strains, mechanisms such as grain rotation and the formation of nanocracks might contribute to the piezoresistive behavior in nanocrystalline graphene.

Correlation Measurements for Carbon Nanotubes with Quantum Defects.

Single-photon sources are essential building blocks for the development of photonic quantum technology. Regarding potential practical application, an on-demand electrically driven quantum-light emitter on a chip is notably crucial for photonic integrated circuits. Here, we propose functionalized single-walled carbon nanotube field-effect transistors as a promising solid-state quantum-light source by demonstrating photon antibunching behavior via electrical excitation. The sp3 quantum defects were formed on the surface of (7, 5) carbon nanotubes by 3,5-dichlorophenyl functionalization, and individual carbon nanotubes were wired to graphene electrode pairs. Filtered electroluminescent defect-state emission at 77 K was coupled into a Hanbury Brown and Twiss experiment setup, and single-photon emission was observed by performing second-order correlation function measurements. We discuss the dependence of the intensity correlation measurement on electrical power and emission wavelength, highlighting the challenges of performing such measurements while simultaneously analyzing acquired data. Our results indicate a route toward room-temperature electrically triggered single-photon emission.

Single- and double-sided chemical functionalization of bilayer 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).

Enhancing Raman signals with an interferometrically controlled AFM tip.

We demonstrate the upgrade of a commercial confocal Raman microscope into a tip-enhanced Raman microscope/spectroscopy system (TERS) by integrating an interferometrically controlled atomic force microscope into the base of an existing upright microscope to provide near-field detection and thus signal enhancement. The feasibility of the system is demonstrated by measuring the Raman near-field enhancement on thin PEDOT:PSS films and on carbon nanotubes within a device geometry. An enhancement factor of 2-3 and of 5-6 is observed, respectively. Moreover, on a nanotube device we show local conductivity measurement and its correlation to Raman and topography recordings. Upgrading an existing upright confocal Raman microscope in the demonstrated way is significantly cheaper than purchasing a complete commercial TERS system.

Probing the nature of defects in graphene by Raman spectroscopy.

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.

An electroluminescent and tunable cavity-enhanced carbon-nanotube-emitter in the telecom band.

Emerging photonic information processing systems require chip-level integration of controllable nanoscale light sources at telecommunication wavelengths. Currently, substantial challenges remain in the dynamic control of the sources, the low-loss integration into a photonic environment, and in the site-selective placement at desired positions on a chip. Here, we overcome these challenges using heterogeneous integration of electroluminescent (EL), semiconducting carbon nanotubes (sCNTs) into hybrid two dimensional - three dimensional (2D-3D) photonic circuits. We demonstrate enhanced spectral line shaping of the EL sCNT emission. By back-gating the sCNT-nanoemitter we achieve full electrical dynamic control of the EL sCNT emission with high on-off ratio and strong enhancement in the telecommunication band. Using nanographene as a low-loss material to electrically contact sCNT emitters directly within a photonic crystal cavity enables highly efficient EL coupling without compromising the optical quality of the cavity. Our versatile approach paves the way for controllable integrated photonic circuits.

Anisotropic organization and microscopic manipulation of self-assembling synthetic porphyrin microrods that mimic chlorosomes: bacterial light-harvesting systems.

Being able to control in time and space the positioning, orientation, movement, and sense of rotation of nano- to microscale objects is currently an active research area in nanoscience, having diverse nanotechnological applications. In this paper, we demonstrate unprecedented control and maneuvering of rod-shaped or tubular nanostructures with high aspect ratios which are formed by self-assembling synthetic porphyrins. The self-assembly algorithm, encoded by appended chemical-recognition groups on the periphery of these porphyrins, is the same as the one operating for chlorosomal bacteriochlorophylls (BChl's). Chlorosomes, rod-shaped organelles with relatively long-range molecular order, are the most efficient naturally occurring light-harvesting systems. They are used by green photosynthetic bacteria to trap visible and infrared light of minute intensities even at great depths, e.g., 100 m below water surface or in volcanic vents in the absence of solar radiation. In contrast to most other natural light-harvesting systems, the chlorosomal antennae are devoid of a protein scaffold to orient the BChl's; thus, they are an attractive goal for mimicry by synthetic chemists, who are able to engineer more robust chromophores to self-assemble. Functional devices with environmentally friendly chromophores-which should be able to act as photosensitizers within hybrid solar cells, leading to high photon-to-current conversion efficiencies even under low illumination conditions-have yet to be fabricated. The orderly manner in which the BChl's and their synthetic counterparts self-assemble imparts strong diamagnetic and optical anisotropies and flow/shear characteristics to their nanostructured assemblies, allowing them to be manipulated by electrical, magnetic, or tribomechanical forces.

The graphene-gold interface and its implications for nanoelectronics.

We combine optical microspectroscopy and electronic measurements to study how gold deposition affects the physical properties of graphene. We find that the electronic structure, the electron-phonon coupling, and the doping level in gold-plated graphene are largely preserved. The transfer lengths for electrons and holes at the graphene-gold contact have values as high as 1.6 µm. However, the interfacial coupling of graphene and gold causes local temperature drops of up to 500 K in operating electronic devices.

Tailoring Spectrally Flat Infrared Photodetection with Thickness-Controlled Nanocrystalline Graphite.

Graphene, a zero-gap semiconductor, absorbs 2.3% of incident photons in a wide wavelength range as a free-standing monolayer, whereas 50% is expected for ∼90 layers. Adjusting the layer number allows the tailoring of the photoresponse; however, controlling the thickness of multilayer graphene remains challenging on the wafer scale. Nanocrystalline graphene or graphite (NCG) can instead be grown with controlled thickness. We have fabricated photodetectors from NCG that are spectrally flat in the near-infrared to short-wavelength infrared region by tailoring the layer thicknesses. Transfer matrix simulations were used to determine the NCG thickness for maximum light absorption in the NCG layer on a silicon substrate. The extrinsic and intrinsic photoresponse was determined from 1100 to 2100 nm using chromatic aberration-corrected photocurrent spectroscopy. Diffraction-limited hyperspectral photocurrent imaging shows that the biased photoresponse is unipolar and homogeneous across the device area, whereas the short-circuit photoresponse gives rise to positive and negative photocurrents at the electrodes. The intrinsic photoresponses are wavelength-independent, indicative of bolometric and electrothermal photodetection.

Electroluminescence from Single-Walled Carbon Nanotubes with Quantum Defects.

Individual single-walled carbon nanotubes with covalent sidewall defects have emerged as a class of photon sources whose photoluminescence spectra can be tailored by the carbon nanotube chirality and the attached functional group/molecule. Here we present electroluminescence spectroscopy data from single-tube devices based on (7, 5) carbon nanotubes, functionalized with dichlorobenzene molecules, and wired to graphene electrodes. We observe electrically generated, defect-induced emissions that are controllable by electrostatic gating and strongly red-shifted compared to emissions from pristine nanotubes. The defect-induced emissions are assigned to excitonic and trionic recombination processes by correlating electroluminescence excitation maps with electrical transport and photoluminescence data. At cryogenic conditions, additional gate-dependent emission lines appear, which are assigned to phonon-assisted hot-exciton electroluminescence from quasi-levels. Similar results were obtained with functionalized (6, 5) nanotubes. We also compare functionalized (7, 5) electroluminescence data with photoluminescence of pristine and functionalized (7, 5) nanotubes redox-doped using gold(III) chloride solution. This work shows that electroluminescence excitation is selective toward neutral defect-state configurations with the lowest transition energy, which in combination with gate-control over neutral versus charged defect-state emission leads to high spectral purity.

Electroluminescence from chirality-sorted (9,7)-semiconducting carbon nanotube devices.

We have measured the electroluminescence and photoluminescence of (9,7)-semiconducting carbon nanotube devices and demonstrate that the electroluminescence wavelength is determined by the nanotube's chiral index (n,m). The devices were fabricated on Si3N4-membranes by dielectrophoretic assembly of tubes from monochiral dispersion. Electrically driven (9,7)-devices exhibit a single Lorentzian-shaped emission peak at 825 nm in the visible part of the spectrum. The emission could be assigned to the excitonic E22 interband-transition by comparison of the electroluminescence spectra with corresponding photoluminescence excitation maps. We show a linear dependence of the EL peak width on the electrical current, and provide evidence for the inertness of Si3N4 surfaces with respect to the nanotubes optical properties.

Imaging conduction pathways in carbon nanotube network transistors by voltage-contrast scanning electron microscopy.

The performance of field-effect transistors based on single-walled carbon nanotube (SWCNT) networks depends on the electrical percolation of semiconducting and metallic nanotube pathways within the network. We present voltage-contrast scanning electron microscopy (VC-SEM) as a new tool for imaging percolation in a SWCNT network with nano-scale resolution. Under external bias, the secondary-electron contrast of SWCNTs depends on their conductivity, and therefore it is possible to image the preferred conduction pathways within a network by following the contrast evolution under bias in a scanning electron microscope. The experimental VC-SEM results are correlated to percolation models of SWCNT-bundle networks.

Sensing Molecules with Metal-Organic Framework Functionalized Graphene Transistors.

Graphene is inherently sensitive to vicinal dielectrics and local charge distributions, a property that can be probed by the position of the Dirac point in graphene field-effect transistors. Exploiting this as a useful sensing principle requires selectivity; however, graphene itself exhibits no molecule-specific interaction. Complementarily, metal-organic frameworks can be tailored to selective adsorption of specific molecular species. Here, a selective ethanol sensor is demonstrated by growing a surface-mounted metal-organic framework (SURMOF) directly onto graphene field-effect transistors (GFETs). Unprecedented shifts of the Dirac point, as large as 15 V, are observed when the SURMOF/GFET is exposed to ethanol, while a vanishingly small response is observed for isopropanol, methanol, and other constituents of the air, including water. The synthesis and conditioning of the hybrid materials sensor with its functional characteristics are described and a model is proposed to explain the origin, magnitude, and direction of the Dirac point voltage shift. Tailoring multiple SURMOFs to adsorb specific gases on an array of such devices thus generates a versatile, selective, and highly sensitive platform for sensing applications.