Raman spectroscopy as a versatile tool for studying the properties of graphene.

Raman spectroscopy is an integral part of graphene research. It is used to determine the number and orientation of layers, the quality and types of edge, and the effects of perturbations, such as electric and magnetic fields, strain, doping, disorder and functional groups. This, in turn, provides insight into all sp(2)-bonded carbon allotropes, because graphene is their fundamental building block. Here we review the state of the art, future directions and open questions in Raman spectroscopy of graphene. We describe essential physical processes whose importance has only recently been recognized, such as the various types of resonance at play, and the role of quantum interference. We update all basic concepts and notations, and propose a terminology that is able to describe any result in literature. We finally highlight the potential of Raman spectroscopy for layered materials other than graphene.

Raman spectroscopy of shear and layer breathing modes in multilayer MoS2

We study by Raman scattering the shear and layer breathing modes in multilayer MoS2. These are identified by polarization measurements and symmetry analysis. Their positions change significantly with the number of layers, with different scaling for odd and even layers. A chain model can explain the results, with general applicability to any layered material, allowing a reliable diagnostic of their thickness. © 2013 American Physical Society.

Probing the electronic structure of multi-walled carbon nanotubes by transient optical transmittivity

High-resolution time resolved transmittivity measurements on horizontally aligned free-standing multi-walled carbon nanotubes reveal a different electronic transient behavior from that of graphite. This difference is ascribed to the presence of discrete energy states in the multishell carbon nanotube electronic structure. Probe polarization dependence suggests that the optical transitions involve definite selection rules. The origin of these states is discussed and a rate equation model is proposed to rationalize our findings. © 2013 Elsevier Ltd. All rights reserved.

Study of steady state and transient EGR behaviour of a medium duty diesel engine

It is well known that accurate EGR control is paramount to controlling engine out emissions during steady state and transient operation of a diesel engine. The direct measurement of EGR is however non-trivial and especially difficult in engines with no external EGR control where the intake manifold CO2 levels can be measured more readily. This work studies the EGR behaviour in a medium duty diesel engine with a passive EGR rebreathing strategy for steady state and transient operation. High speed (response time ∼1ms) in-cylinder sampling using modified GDI valves is coupled with high frequency response analysers to measure the cyclic in-cylinder CO2, from which the EGR rate is deduced. It was found that controlling the EGR using the passive rebreathing strategy during certain combined speed and load transients is challenging, causing high smoke and NO emissions. The in-cylinder sampling method coupled with fast CO2 measurement (time constant ∼8ms) in the exhaust port gave insights about the EGR rate during these transients. The complex interaction of the manifold pressures, turbo-charger operation and trapped charge composition from the previous cycle simply can cause high dilution and therefore high smoke levels. The steady state variation of NO emissions with respect to EGR is also studied using a fast NO analyzer (time constant ∼2ms) in the exhaust port. Cyclic variation was found to be up to ±5% at some load conditions. © 2008 SAE International.

A simple diesel engine air-path model to predict the cylinder charge during transients: Strategies for reducing transient emissions spikes

Simple air-path models for modern (VGT/EGR equipped) diesel engines are in common use, and have been reported in the literature. This paper addresses some of the shortcomings of control-oriented models to allow better prediction of the cylinder charge properties. A fast response CO2 analyzer is used to validate the model by comparing the recorded and predicted CO2 concentrations in both the intake port and exhaust manifold of one of the cylinders. Data showing the recorded NOx emissions and exhaust gas opacity during a step change in engine load illustrate the spikes in both NOx and smoke seen during transient conditions. The predicted cylinder charge properties from the model are examined and compared with the measured NOx and opacity. Together, the emissions data and charge properties paint a consistent picture of the phenomena occurring during the transient. Alternative strategies for the fueling and cylinder charge during these load transients are investigated and discussed. Experimental results are presented showing that spikes in both NOx and smoke can be avoided at the expense of some loss in torque response. Even if the torque response must be maintained, it is demonstrated that it is still possible to eliminate spikes in NOx emissions for the transient situation being examined. Copyright © 2006 SAE International.

Diesel smoke transient control using a real-time smoke sensor

A novel real time smoke sensor is described, which is mounted in the exhaust manifold and detects the smoke by virtue of the natural electrical charge which is carried on the smoke. The somewhat obscure origin of the charge on the smoke is briefly considered, as well as the operation of the sensor itself. The use of the sensor as part of a feedback control shows that it can be very effective in reducing smoke puffs. Copyright © 1987 Society of Automotive Engineers, Inc.

Particulate matter emission during start-up and transient operation of a spark-ignition engine

In order to understand why emissions of Particulate Matter (PM) from Spark-Ignition (SI) automobiles peak during periods of transient operation such as rapid accelerations, a study of controlled, repeatable transients was performed. Time-resolved engine-out PM emissions from a modern four-cylinder engine during transient load and air/fuel ratio operation were examined, and the results could be fit in most cases to a first order time response. The time constants for the transient response are similar to those measured for changes in intake valve temperature, reflecting the strong dependence of PM emissions on the amount of liquid fuel in the combustion chamber. In only one unrepeatable case did the time response differ from a first order function: showing an overshoot in PM emissions during transition from the initial to the final steady state PM emission level. PM emissions during controlled, motored start-up experiments show a peak at start-up followed by a period during which emissions are either relatively constant or drift somewhat. When the fuel injection and ignition are shut off, PM emissions also peak briefly, but rapidly decay to low levels. Qualitative implications on the study and modeling of PM emissions during transient engine operation are discussed. Copyright © 1999 Society of Automotive Engineers, Inc.

Thermodynamic formulation of flowing soft matter with transient forces

The Responsive Particle Dynamics model is a very efficient method to account for the transient forces present in complex fluids, such as solutions of entangled polymers. This coarse-grained model considers a solution of particles that are made of a core and a corona. The cores typically interact through conservative interactions, while the coronae transiently penetrate each other to form short-lived temporary interactions, typically of entropic origin. In this study, we reformulate the resulting rheological model within the general framework of nonequilibrium thermodynamics called General Equation for the Nonequilibrium Reversible-Irreversible Coupling. This allows us to determine the consistency of the model, from a mechanistic and thermodynamic point of view, and to isolate the reversible and irreversible contributions to the dynamics of the model system. © 2012 Springer-Verlag Berlin Heidelberg.

Measurement of filling-factor-dependent magnetophonon resonances in graphene using Raman spectroscopy

We perform polarization-resolved Raman spectroscopy on graphene in magnetic fields up to 45 T. This reveals a filling-factor-dependent, multicomponent anticrossing structure of the Raman G peak, resulting from magnetophonon resonances between magnetoexcitons and E2g phonons. This is explained with a model of Raman scattering taking into account the effects of spatially inhomogeneous carrier densities and strain. Random fluctuations of strain-induced pseudomagnetic fields lead to increased scattering intensity inside the anticrossing gap, consistent with the experiments. © 2013 American Physical Society.

Electronic properties of GaAs, InAs and InP nanowires studied by terahertz spectroscopy.

We have performed a comparative study of ultrafast charge carrier dynamics in a range of III-V nanowires using optical pump-terahertz probe spectroscopy. This versatile technique allows measurement of important parameters for device applications, including carrier lifetimes, surface recombination velocities, carrier mobilities and donor doping levels. GaAs, InAs and InP nanowires of varying diameters were measured. For all samples, the electronic response was dominated by a pronounced surface plasmon mode. Of the three nanowire materials, InAs nanowires exhibited the highest electron mobilities of 6000 cm² V⁻¹ s⁻¹, which highlights their potential for high mobility applications, such as field effect transistors. InP nanowires exhibited the longest carrier lifetimes and the lowest surface recombination velocity of 170 cm s⁻¹. This very low surface recombination velocity makes InP nanowires suitable for applications where carrier lifetime is crucial, such as in photovoltaics. In contrast, the carrier lifetimes in GaAs nanowires were extremely short, of the order of picoseconds, due to the high surface recombination velocity, which was measured as 5.4 × 10⁵ cm s⁻¹. These findings will assist in the choice of nanowires for different applications, and identify the challenges in producing nanowires suitable for future electronic and optoelectronic devices.

Ultrafast dynamics of exciton formation in semiconductor nanowires.

The dynamics of free electron-hole pairs and excitons in GaAs-AlGaAs-GaAs core-shell-skin nanowires is investigated using femtosecond transient photoluminescence spectroscopy at 10 K. Following nonresonant excitation, a bimolecular interconversion of the initially generated electron-hole plasma into an exciton population is observed. This conducting-to-insulating transition appears to occur gradually over electron-hole charge pair densities of 2-4 × 10(16) cm(-3) . The smoothness of the Mott transition is attributed to the slow carrier-cooling during the bimolecular interconversion of free charge carriers into excitons and to the presence of chemical-potential fluctuations leading to inhomogeneous spectral characteristics. These results demonstrate that high-quality nanowires are model systems for investigating fundamental scientific effects in 1D heterostructures.

Environment induced variation in the photoconductivity of graphene observed by terahertz spectroscopy

Chemical vapour deposition (CVD) grown graphene sheets were investigated using optical-pump terahertz-probe spectroscopy, revealing a dramatic variation in the photoinduced terahertz conductivity of graphene in different atmospheres. © 2012 IEEE.

Characterisation of nanostructures via terahertz spectroscopy

We have used terahertz spectroscopy to measure the conductivity and time-resolved photoconductivity of a range of semiconducting nanostructures. This article focuses on our recent terahertz conductivity studies on semiconductor nanowires and single walled carbon nanotubes. © 2010 IEEE.