Selective epitaxial growth of graphene on SiC

We present an innovative method of selective epitaxial growth of few layers graphene (FLG) on a pre-patterned SiC substrate. The methods involves, successively, the sputtering of a thin AlN layer on top of a mono-crystalline SiC substrate and, then, patterning it with e-beam lithography (EBL) and wet etching. The sublimation of few atomic layers of Si from the SiC substrate occurs only through the selectively etched AlN layer. The presence of the Raman G-band at ~1582 cm-1 in the AlN-free areas is used to validate the concept, it gives absolute evidence of the selective FLG growth.Comment: comments: 3 pages, reference 3 replace

Early stage formation of graphene on the C-face of 6H-SiC

An investigation of the early stage formation of graphene on the C-face of 6H-SiC is presented. We show that the sublimation of few atomic layers of Si out of the SiC substrate is not homogeneous. In good agreement with the results of theoretical calculations it starts from defective sites, mainly dislocations that define nearly circular flakes, which have a pyramidal, volcano-like, shape with a center chimney where the original defect was located. At higher temperatures, complete conversion occurs but, again, it is not homogeneous. Within the sample surface the intensity of the Raman G and 2D bands, evidences non-homogeneous thickness.Comment: 12 pages, 3 figure

Investigation of Long Monolayer Graphene Ribbons grown on Graphite Capped 6H-SiC (000-1)

We present an investigation of large, isolated, graphene ribbons grown on the C-face of on-axis semi-insulating 6H-SiC wafers. Using a graphite cap to cover the SiC sample, we modify the desorption of the Si species during the Si sublimation process. This results in a better control of the growth kinetics, yielding very long (about 300 microns long, 5 microns wide), homogeneous monolayer graphene ribbons. These ribbons fully occupy unusually large terraces on the step bunched SiC surface, as shown by AFM, optical microscopy and SEM. Raman spectrometry indicates that the thermal stress has been partially relaxed by wrinkles formation, visible in AFM images. In addition, we show that despite the low optical absorption of graphene, optical differential transmission can be successfully used to prove the monolayer character of the ribbons

Sub-harmonic resonant excitation of confined acoustic modes at GHz frequencies with a high-repetition-rate femtosecond laser

We propose sub-harmonic resonant optical excitation with femtosecond lasers as a new method for the characterization of phononic and nanomechanical systems in the gigahertz to terahertz frequency range. This method is applied for the investigation of confined acoustic modes in a free-standing semiconductor membrane. By tuning the repetition rate of a femtosecond laser through a sub-harmonic of a mechanical resonance we amplify the mechanical amplitude, directly measure the linewidth with megahertz resolution, infer the lifetime of the coherently excited vibrational states, accurately determine the system's quality factor, and determine the amplitude of the mechanical motion with femtometer resolution

Sources of uncertainty in modeled land carbon storage within and across three MIPs: Diagnosis with three new techniques

This is the final version. Available from the American Meteorological Society via the DOI in this recordTerrestrial carbon cycle models have incorporated increasingly more processes as a means to achieve more-realistic representations of ecosystem carbon cycling. Despite this, there are large across-model variations in the simulation and projection of carbon cycling. Several model intercomparison projects (MIPs), for example, the fifth phase of the Coupled Model Intercomparison Project (CMIP5) (historical simulations), Trends in Net Land-Atmosphere Carbon Exchange (TRENDY), and Multiscale Synthesis and Terrestrial Model Intercomparison Project (MsTMIP), have sought to understand intermodel differences. In this study, the authors developed a suite of new techniques to conduct post-MIP analysis to gain insights into uncertainty sources across 25 models in the three MIPs. First, terrestrial carbon storage dynamics were characterized by a three-dimensional (3D) model output space with coordinates of carbon residence time, net primary productivity (NPP), and carbon storage potential. The latter represents the potential of an ecosystem to lose or gain carbon. This space can be used to measure how and why model output differs. Models with a nitrogen cycle generally exhibit lower annual NPP in comparison with other models, and mostly negative carbon storage potential. Second, a transient traceability framework was used to decompose any given carbon cycle model into traceable components and identify the sources of model differences. The carbon residence time (or NPP) was traced to baseline carbon residence time (or baseline NPP related to the maximum carbon input), environmental scalars, and climate forcing. Third, by applying a variance decomposition method, the authors show that the intermodel differences in carbon storage can be mainly attributed to the baseline carbon residence time and baseline NPP (>90% in the three MIPs). The three techniques developed in this study offer a novel approach to gain more insight from existing MIPs and can point out directions for future MIPs. Since this study is conducted at the global scale for an overview on intermodel differences, future studies should focus more on regional analysis to identify the sources of uncertainties and improve models at the specified mechanism level.This paper is financially supported by the Research and Development Special Fund for Public Welfare Industry of the Ministry of Water Research in China (201501028). JBF and CRS were supported in part by NASA’s Carbon Cycle Science program. JBF was also supported in part by NASA’s Terrestrial Ecology and Carbon Monitoring System programs. JT acknowledges RCN funded project EVA (229771) and BCCR-BIGCHANGE

Sources of uncertainty in modeled land carbon storage within and across three MIPs: Diagnosis with three new techniques

This is the final version. Available from the American Meteorological Society via the DOI in this recordTerrestrial carbon cycle models have incorporated increasingly more processes as a means to achieve more-realistic representations of ecosystem carbon cycling. Despite this, there are large across-model variations in the simulation and projection of carbon cycling. Several model intercomparison projects (MIPs), for example, the fifth phase of the Coupled Model Intercomparison Project (CMIP5) (historical simulations), Trends in Net Land-Atmosphere Carbon Exchange (TRENDY), and Multiscale Synthesis and Terrestrial Model Intercomparison Project (MsTMIP), have sought to understand intermodel differences. In this study, the authors developed a suite of new techniques to conduct post-MIP analysis to gain insights into uncertainty sources across 25 models in the three MIPs. First, terrestrial carbon storage dynamics were characterized by a three-dimensional (3D) model output space with coordinates of carbon residence time, net primary productivity (NPP), and carbon storage potential. The latter represents the potential of an ecosystem to lose or gain carbon. This space can be used to measure how and why model output differs. Models with a nitrogen cycle generally exhibit lower annual NPP in comparison with other models, and mostly negative carbon storage potential. Second, a transient traceability framework was used to decompose any given carbon cycle model into traceable components and identify the sources of model differences. The carbon residence time (or NPP) was traced to baseline carbon residence time (or baseline NPP related to the maximum carbon input), environmental scalars, and climate forcing. Third, by applying a variance decomposition method, the authors show that the intermodel differences in carbon storage can be mainly attributed to the baseline carbon residence time and baseline NPP (>90% in the three MIPs). The three techniques developed in this study offer a novel approach to gain more insight from existing MIPs and can point out directions for future MIPs. Since this study is conducted at the global scale for an overview on intermodel differences, future studies should focus more on regional analysis to identify the sources of uncertainties and improve models at the specified mechanism level.This paper is financially supported by the Research and Development Special Fund for Public Welfare Industry of the Ministry of Water Research in China (201501028). JBF and CRS were supported in part by NASA’s Carbon Cycle Science program. JBF was also supported in part by NASA’s Terrestrial Ecology and Carbon Monitoring System programs. JT acknowledges RCN funded project EVA (229771) and BCCR-BIGCHANGE

Chemical and Electrochemical Recycling of End-Use Poly(ethylene terephthalate) (PET) Plastics in Batch, Microwave and Electrochemical Reactors

This work describes new methods for the chemical recycling of end-use poly(ethylene terephthalate) (PET) in batch, microwave and electrochemical reactors. The reactions are based on basic hydrolysis of the ester moieties in the polymer framework and occur under mild reaction conditions with low-cost reagents. We report end-use PET depolymerization in refluxing methanol with added NaOH with 75% yield of terephthalic acid in batch after 12 h, while yields up to 65% can be observed after only 40 min under microwave irradiation at 85 &deg;C. Using basic conditions produced in the electrochemical reduction of protic solvents, electrolytic experiments have been shown to produce 17% terephthalic acid after 1 h of electrolysis at &minus;2.2 V vs. Ag/AgCl in 50% water/methanol mixtures with NaCl as a supporting electrolyte. The latter method avoids the use of caustic solutions containing high-concentration NaOH at the outset, thus proving the concept for a novel, environmentally benign method for the electrochemical recycling of end-use PET based on low-cost solvents (water and methanol) and reagents (NaCl and electricity).&nbsp;</div

Predictive energetic tuning of C-Nucleophiles for the electrochemical capture of carbon dioxide

This work maps the thermodynamics of electrochemically generated C-nucleophiles for reactive capture of CO2. We identify a linear relationship between the pKa, the reduction potential of a protonated nucleophile (Ered), and the nucleophile&rsquo;s free energy of CO2 binding (&Delta;Gbind). Through synergistic experiments and computations, this study establishes a three-parameter correlation described by the equation &Delta;Gbind=&minus;0.78pKa+4.28Ered+20.95 for a series of twelve imidazol(in)ium/N-heterocyclic carbene pairs with an R2 of 0.92. The correlation allows us to predict the &Delta;Gbind of C-nucleophiles to CO2 using reduction potentials or pKas of imidazol(in)ium cations. The carbenes in this study were found to exhibit a wide range CO2 binding strengths, from strongly CO2 binding to nonspontaneous. This observation suggests that the &Delta;Gbind of imidazol(in)ium-based carbenes is tunable to a desired strength by appropriate structural changes. This work sets the stage for systematic energetic tuning of electrochemically enabled reactive separations. &nbsp;</p