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.

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.

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.

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.

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.

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.

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.

Low-Temperature Electroluminescence Excitation Mapping of Excitons and Trions in Short-Channel Monochiral Carbon Nanotube Devices.

Single-walled carbon nanotubes as emerging quantum-light sources may fill a technological gap in silicon photonics due to their potential use as near-infrared, electrically driven, classical or nonclassical emitters. Unlike in photoluminescence, where nanotubes are excited with light, electrical excitation of single tubes is challenging and heavily influenced by device fabrication, architecture, and biasing conditions. Here we present electroluminescence spectroscopy data of ultra-short-channel devices made from (9,8) carbon nanotubes emitting in the telecom band. Emissions are stable under current biasing, and no enhanced suppression is observed down to 10 nm gap size. Low-temperature electroluminescence spectroscopy data also reported exhibit cold emission and line widths down to 2 meV at 4 K. Electroluminescence excitation maps give evidence that carrier recombination is the mechanism for light generation in short channels. Excitonic and trionic emissions can be switched on and off by gate voltage, and corresponding emission efficiency maps were compiled. Insights are gained into the influence of acoustic phonons on the line width, absence of intensity saturation and exciton-exciton annihilation, environmental effects such as dielectric screening and strain on the emission wavelength, and conditions to suppress hysteresis and establish optimum operation conditions.

Separation of Specific Single-Enantiomer Single-Wall Carbon Nanotubes in the Large-Diameter Regime.

The enantiomer-level isolation of single-walled carbon nanotubes (SWCNTs) in high concentration and with high purity for nanotubes greater than 1.1 nm in diameter is demonstrated using a two-stage aqueous two-phase extraction (ATPE) technique. In total, five different nanotube species of ∼1.41 nm diameter are isolated, including both metallics and semiconductors. We characterize these populations by absorbance spectroscopy, circular dichroism spectroscopy, resonance Raman spectroscopy, and photoluminescence mapping, revealing and substantiating mod-dependent optical dependencies. Using knowledge of the competitive adsorption of surfactants to the SWCNTs that controls partitioning within the ATPE separation, we describe an advanced acid addition methodology that enables the fine control of the separation of these select nanotubes. Furthermore, we show that endohedral filling is a previously unrecognized but important factor to ensure a homogeneous starting material and further enhance the separation yield, with the best results for alkane-filled SWCNTs, followed by empty SWCNTs, with the intrinsic inhomogeneity of water-filled SWCNTs causing them to be worse for separations. Lastly, we demonstrate the potential use of these nanotubes in field-effect transistors.

Graphene Field-Effect Transistors Employing Different Thin Oxide Films: A Comparative Study.

In this work, we report on a comparison among graphene field-effect transistors (GFETs) employing different dielectrics as gate layers to evaluate their microwave response. In particular, aluminum oxide (Al2O3), titanium oxide (TiO2), and hafnium oxide (HfO2) have been tested. GFETs have been fabricated on a single chip and a statistical analysis has been performed on a set of 24 devices for each type of oxide. Direct current and microwave measurements have been carried out on such GFETs and short circuit current gain and maximum available gain have been chosen as quality factors to evaluate their microwave performance. Our results show that all of the devices belonging to a specific group (i.e., with the same oxide) have a well-defined performance curve and that the choice of hafnium oxide represents the best trade-off in terms of dielectric properties. Graphene transistors employing HfO2 as the dielectric layer, in fact, exhibit the best performance in terms of both the cutoff frequency and the maximum frequency of oscillation.

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.

Nanocrystalline graphene at high temperatures: insight into nanoscale processes.

During high temperature pyrolysis of polymer thin films, nanocrystalline graphene with a high defect density, active edges and various nanostructures is formed. The catalyst-free synthesis is based on the temperature assisted transformation of a polymer precursor. The processing conditions have a strong influence on the final thin film properties. However, the precise elemental processes that govern the polymer pyrolysis at high temperatures are unknown. By means of time resolved in situ transmission electron microscopy investigations we reveal that the reactivity of defects and unsaturated edges plays an integral role in the structural dynamics. Both mobile and stationary structures with varying size, shape and dynamics have been observed. During high temperature experiments, small graphene fragments (nanoflakes) are highly unstable and tend to lose atoms or small groups of atoms, while adjacent larger domains grow by addition of atoms, indicating an Ostwald-like ripening in these 2D materials, besides the mechanism of lateral merging of nanoflakes with edges. These processes are also observed in low-dose experiments with negligible electron beam influence. Based on energy barrier calculations, we propose several inherent temperature-driven mechanisms of atom rearrangement, partially involving catalyzing unsaturated sites. Our results show that the fundamentally different high temperature behavior and stability of nanocrystalline graphene in contrast to pristine graphene is caused by its reactive nature. The detailed analysis of the observed dynamics provides a pioneering overview of the relevant processes during ncg heating.

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.

Graphene-enabled and directed nanomaterial placement from solution for large-scale device integration.

Directed placement of solution-based nanomaterials at predefined locations with nanoscale precision limits bottom-up integration in semiconductor process technology. We report a method for electric-field-assisted placement of nanomaterials from solution by means of large-scale graphene layers featuring nanoscale deposition sites. The structured graphene layers are prepared via either transfer or synthesis on standard substrates, and then are removed once nanomaterial deposition is completed, yielding material assemblies with nanoscale resolution that cover surface areas >1 mm2. In order to demonstrate the broad applicability, we have assembled representative zero-dimensional, one-dimensional, and two-dimensional semiconductors at predefined substrate locations and integrated them into nanoelectronic devices. Ultimately, this method opens a route to bottom-up integration of nanomaterials for industry-scale applications.

Formation of nanocrystalline graphene on germanium.

Graphitization of a polymer layer provides a convenient route to synthesize nanocrystalline graphene on dielectric surfaces. The transparent and conducting wafer scale material is of interest as a membrane and a coating, and for the generation and detection of light, or strain sensing. In this work, we study the formation of nanocrystalline graphene on germanium, a surface which promotes the CVD synthesis of monocrystalline graphene. The surprising result that we obtained through graphitization is the formation of cavities in germanium, over which nanocrystalline graphene is suspended. Depending on the crystallographic orientation of the germanium surface, either trenches in (110)-Ge or pits in (111)-Ge are formed, and their dimensions depend on the graphitization temperature. Using Raman spatial imaging, we can show that nanocrystalline graphene is formed across the entire wafer in spite of the cavity formation. Interestingly, the Raman intensity is suppressed when the material is supported by germanium and is enhanced when the material is suspended. Through simulations, we can show that these effects are induced by the high refractive index of germanium and by interferences of the light field depending on the spacing between graphene and germanium. Using atomic force and scanning electron microscopy, we determined that ripples in the suspended material are induced by the mismatch of thermal expansion coefficients. Our results provide a new route to lithography-free fabrication of suspended membranes.

Tailoring supercurrent confinement in graphene bilayer weak links.

The Josephson effect is one of the most studied macroscopic quantum phenomena in condensed matter physics and has been an essential part of the quantum technologies development over the last decades. It is already used in many applications such as magnetometry, metrology, quantum computing, detectors or electronic refrigeration. However, developing devices in which the induced superconductivity can be monitored, both spatially and in its magnitude, remains a serious challenge. In this work, we have used local gates to control confinement, amplitude and density profile of the supercurrent induced in one-dimensional nanoscale constrictions, defined in bilayer graphene-hexagonal boron nitride van der Waals heterostructures. The combination of resistance gate maps, out-of-equilibrium transport, magnetic interferometry measurements, analytical and numerical modelling enables us to explore highly tunable superconducting weak links. Our study opens the path way to design more complex superconducting circuits based on this principle, such as electronic interferometers or transition-edge sensors.

Inner- and outer-wall sorting of double-walled carbon nanotubes.

Double-walled carbon nanotubes (DWCNTs) consist of two coaxially aligned single-walled carbon nanotubes (SWCNTs), and previous sorting methods only achieved outer-wall electronic-type selectivity. Here, a separation technique capable of sorting DWCNTs by semiconducting (S) or metallic (M) inner- and outer-wall electronic type is presented. Electronic coupling between the inner and outer wall is used to alter the surfactant coating around each of the DWCNT types, and aqueous gel permeation is used to separate them. Aqueous methods are used to remove SWCNT species from the raw material and prepare enriched DWCNT fractions. The enriched DWCNT fractions are then transferred into either chlorobenzene or toluene using the copolymer PFO-BPy to yield the four inner@outer combinations of M@M, M@S, S@M and S@S. The high purity of the resulting fractions is verified by absorption measurements, transmission electron microscopy, atomic force microscopy, resonance Raman mapping and high-density field-effect transistor devices.

Exploring the upper limit of single-walled carbon nanotube purity by multiple-cycle aqueous two-phase separation.

Ultrahigh purity semiconducting single-walled carbon nanotubes (S-SWCNTs) are required for high-performance transistors. Aqueous two-phase (ATP) separation is an attractive method to obtain such SWCNTs due to its simplicity and scalability. This work targeted two questions; namely what is the upper limit of S-SWCNT purity that can be achieved by multiple cycles of ATP separation from the most commonly used polyethylene glycol and dextran system and how accurately can commonly used methods characterize the improvement in purity? SWCNT purity in nanotube dispersions obtained by multi-cycle ATP separation (2, 4, 6 and 8 cycles) was evaluated by three methods, including UV-vis-NIR absorption spectroscopy analysis, performance of thin-film field effect transistors (FETs) prepared by drop casting and short-channel FET devices prepared by dielectrophoresis deposition. Absorption spectroscopic analysis and the performance of the thin-film FET devices can hardly differentiate metallic SWCNT residues in the dispersions obtained after 4 cycles with the purity above 99.5%, and the short channel FET devices prepared by dielectrophoresis deposition are more sensitive towards tiny metallic SWCNT residues. A new method was also demonstrated to visualize the minor metallic content in the nanotube suspension using voltage contrast imaging in a scanning electron microscope, which enables rapid screening of many devices and the accurate obtainment of metallic content without performing a large number of individual transconductance measurements.

Understanding the graphitization and growth of free-standing nanocrystalline graphene using in situ transmission electron microscopy.

Graphitization of polymers is an effective way to synthesize nanocrystalline graphene on different substrates with tunable shape, thickness and properties. The catalyst free synthesis results in crystallite sizes on the order of a few nanometers, significantly smaller than commonly prepared polycrystalline graphene. Even though this method provides the flexibility of graphitizing polymer films on different substrates, substrate free graphitization of freestanding polymer layers has not been studied yet. We report for the first time the thermally induced graphitization and domain growth of free-standing nanocrystalline graphene thin films using in situ TEM techniques. High resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED) and electron energy loss spectroscopy (EELS) techniques were used to analyze the graphitization and the evolution of nanocrystalline domains at different temperatures by characterizing the crystallinity and domain size, further supported by ex situ Raman spectroscopy. The graphitization was comparable to the substrate supported heating and the temperature dependence of graphitization was analyzed. In addition, the in situ analysis of the graphitization enabled direct imaging of some of the growth processes taking place at different temperatures.