Multiscale Model of CVD Growth of Graphene on Cu(111) Surface

Due to its outstanding properties, graphene has emerged as one of the most promising 2D materials in a large variety of research fields. Among the available fabrication protocols, chemical vapor deposition (CVD) enables the production of high quality single-layered large area graphene. To better understand the kinetics of CVD graphene growth, multiscale modeling approaches are sought after. Although a variety of models have been developed to study the growth mechanism, prior studies are either limited to very small systems, are forced to simplify the model to eliminate the fast process, or they simplify reactions. While it is possible to rationalize these approximations, it is important to note that they have non-trivial consequences on the overall growth of graphene. Therefore, a comprehensive understanding of the kinetics of graphene growth in CVD remains a challenge. Here, we introduce a kinetic Monte Carlo protocol that permits, for the first time, the representation of relevant reactions on the atomic scale, without additional approximations, while still reaching very long time and length scales of the simulation of graphene growth. The quantum-mechanics-based multiscale model, which links kinetic Monte Carlo growth processes with the rates of occurring chemical reactions, calculated from first principles makes it possible to investigate the contributions of the most important species in graphene growth. It permits the proper investigation of the role of carbon and its dimer in the growth process, thus indicating the carbon dimer to be the dominant species. The consideration of hydrogenation and dehydrogenation reactions enables us to correlate the quality of the material grown within the CVD control parameters and to demonstrate an important role of these reactions in the quality of the grown graphene in terms of its surface roughness, hydrogenation sites, and vacancy defects. The model developed is capable of providing additional insights to control the graphene growth mechanism on Cu(111), which may guide further experimental and theoretical developments

Kinetics of Graphene Growth on Liquid Copper by Chemical Vapor Deposition

We report a combined experimental and computational study of the kinetics of graphene growth during chemical vapor deposition on a liquid copper catalyst. The use of liquid metal catalysts offers bright perspectives for controllable large-scale, high-quality synthesis technologies of two-dimensional materials. We carried out a series of growth experiments varying CH4-to-H2 pressure ratios and deposition temperature. By monitoring the graphene flake morphology in real time during growth using in situ optical microscopy in radiation mode, we explored the morphology and kinetics of the growth within a wide range of experimental conditions. Following an analysis of the flakes' growth rates, we conclude that the growth mode was attachment-limited. The attachment and detachment activation energies of carbon species are derived as 1.9 +- 0.3 eV and 2.0 +- 0.1 eV, respectively. We also conducted free-energy calculations by a moment tensor potential trained to density functional theory data. Our simulations propose that carbon dimers are most likely the active carbon species during growth, with attachment and detachment barriers of 1.71 +- 0.15 eV and 2.09 +- 0.02 eV, respectively, being in good agreement with the experimental results

Chemical vapor deposition of Al, Fe and of the Al13Fe4 approximant intermetallic phase : experiments and multiscale simulations

Films containing intermetallic compounds exhibit properties and combination of properties which are only partially explored. They carry potential solutions to confer multifunctionality to advanced materials required by industrial sectors and to become a source of breakthrough and innovation.Metalorganic chemical vapor deposition (MOCVD) potentially allows conformal deposition on, and functionalization of complex surfaces, with high throughput and moderate cost. For this reason, it is necessary to control the complex chemical reactions and the transport mechanisms involved in a MOCVD process. In this perspective, computational modeling of the process, fed with experimental information from targeted deposition experiments, provides an integrated tool for the investigation and the understanding of the phenomena occurring at different length scales, from the macro- to the nanoscale. The MOCVD of Al-Fe intermetallic compounds is investigated in the present thesis as a paradigm of implementation of such a combined, experimental and theoretical approach. Processing of the approximant phase Al13Fe4 is particularly targeted, due to its potential interest as low-cost and environmentally benign alternative to noble metal catalysts in the chemical industry. The attainment of the targeted Al13Fe4 intermetallic phase passes through the investigation of the MOCVD of unary Al and Fe films. The MOCVD of Al from dimethylethylamine alane (DMEAA) in the range 139oC-241oC results in pure films. Increase of the deposition temperature yields higher film density and decreased roughness. The Aldeposition rate increases to a maximum of 15.5 nm/min at 185oC and then decreases. Macroscopic simulations of the process predictdeposition rates in sufficient agreement with experimental measurements, especially in the range 139oC-227oC. At higher temperatures, competitive gas phase and surface phenomena cannot be captured by the applied model. Multiscale modeling of the process predicts the RMS roughness of the films accurately, thus allowing the control of properties such as electrical resistivity which depend on the microstructure. The MOCVD of Fe from iron pentacarbonyl, Fe(CO)5, is investigated in the range 130oC-250oC for the possibility toobtain fairly pure Fe films with low Oand C contamination. The surface morphology depends strongly on the temperature and changes are observed above 200oC. The Fe deposition rate increases up to 200oC, to a maximum of 60 nm/min, and then decreases. Moreover, the deposition rate decreases sharply with increasing pressure. Computational predictions capture accurately the experimental behavior and they reveal that the decrease athigher temperatures and pressures is attributed to the high gas phase decomposition rate of the precursor and to inhibition of the surface fromCO. The multiscale model calculates RMS roughness in good agreement with experimental data, especially at higher temperatures. Upon investigation of the two processes, aseries of Al-Fe co-depositions performed at 200oC results in Al-rich films with a loose microstructure. They contain no intermetallic phases and they are O-contaminated due to the reaction of the Al with the carbonyl ligands. Sequential deposition of Al and Fe followed by in situ annealing at 575oC for 1 h is applied to bypass the Ocontamination. The process conditions of Fe are modified to 140oC, 40 Torr and 10 min resulting in O-free films with Al:Fe atomic ratio close to the targeted 13:4 one. Characterization techniques including X-ray diffraction, TEM an

A Comprehensive Multiphysics, Multiscale Modeling Framework for Carbon Nanotube Fabrication Process by Chemical Vapor Deposition

Carbon nanotubes (CNTs) are among the most promising nanosize materials as evidenced by the attention they have received since their discovery in 1991 and a wide range of scientific and industrial applications. Each of these applications requires unique CNTs with specific length, diameter and chirality. However, control of these parameters is considered as one of the main challenges for large scale production of CNTs. Furthermore, these processes are not well designed so as to limit the number of CNT defect sites or the production of unwanted byproducts such as amorphous carbon. Therefore, it is crucial to develop a controlled CNTs fabrication process that is capable of producing pure CNTs with uniform properties. Along this line of reasoning, a time-dependent multiphysics, multiscale modeling framework is proposed to describe CNTs fabrication using chemical vapor deposition (CVD). The fully integrated model accounts for multiphase chemical reactions as well as fluid, heat and mass transport phenomena. Moreover, the fabrication process is divided into three physical scales. As the first modeling scale, a control volume is placed around the CVD reactor chamber to investigate the effects of physical phenomena on fabrication process effective parameters such as gas phase reaction sets. The obtained information from this scale are then utilized in the substrate scale modeling to investigate these physical effects as well as the effects of substrate dislocation and orientation, on the produced carbon species. Finally, by utilizing molecular dynamics (MD) simulation technique, the diffusivity of carbon species into the deposited nanoparticles and the effects of fabrication temperature on diameter and chirality of CNTs are investigated. The developed model is ultimately utilized to investigate the effect of temperature; total flow rate and feed gases mixture ratio on CNTs growth rate and amorphous carbon formation. As representative outcomes of current research and developed model, CNTs with especial configurations such as Y-shaped, spring-shaped and CNT with variable diameter have been experimentally produced. The outcomes from this study could provide a fundamental understanding and basis for the design of an efficient CNT fabrication process that is capable of producing high yield CNTs and with a minimum amount of amorphous carbon. Moreover, this work can be utilized to introduce a pathway for optimization of a controllable CVD-based CNTs fabrication process when accompanying by some in-situ measurement and diagnosis systems. The optimization process can be selectively tuned depending on the expectation cost and application of CNTs final product criteria

Performance and degradation of Proton Exchange Membrane Fuel Cells: State of the art in modeling from atomistic to system scale

Jahnke, T. et al.Proton Exchange Membrane Fuel Cells (PEMFC) are energy efficient and environmentally friendly alternatives to conventional energy conversion systems in many yet emerging applications. In order to enable prediction of their performance and durability, it is crucial to gain a deeper understanding of the relevant operation phenomena, e.g., electrochemistry, transport phenomena, thermodynamics as well as the mechanisms leading to the degradation of cell components. Achieving the goal of providing predictive tools to model PEMFC performance, durability and degradation is a challenging task requiring the development of detailed and realistic models reaching from the atomic/molecular scale over the meso scale of structures and materials up to components, stack and system level. In addition an appropriate way of coupling the different scales is required. This review provides a comprehensive overview of the state of the art in modeling of PEMFC, covering all relevant scales from atomistic up to system level as well as the coupling between these scales. Furthermore, it focuses on the modeling of PEMFC degradation mechanisms and on the coupling between performance and degradation models.The research leading to this review has been partially supported by the European Union's Seventh Framework Program for the Fuel Cells and Hydrogen Joint Technology Initiative under the project PUMA MIND (grant agreement no 303419).Peer Reviewe

WRF-CMAQ two-way coupled system with aerosol feedback: software development and preliminary results

Air quality models such as the EPA Community Multiscale Air Quality (CMAQ) require meteorological data as part of the input to drive the chemistry and transport simulation. The Meteorology-Chemistry Interface Processor (MCIP) is used to convert meteorological data into CMAQ-ready input. Key shortcoming of such one-way coupling include: excessive temporal interpolation of coarsely saved meteorological input and lack of feedback of atmospheric pollutant loading on simulated dynamics. We have developed a two-way coupled system to address these issues. A single source code principle was used to construct this two-way coupling system so that CMAQ can be consistently executed as a stand-alone model or part of the coupled system without any code changes; this approach eliminates maintenance of separate code versions for the coupled and uncoupled systems. The design also provides the flexibility to permit users: (1) to adjust the call frequency of WRF and CMAQ to balance the accuracy of the simulation versus computational intensity of the system, and (2) to execute the two-way coupling system with feedbacks to study the effect of gases and aerosols on short wave radiation and subsequent simulated dynamics. Details on the development and implementation of this two-way coupled system are provided. When the coupled system is executed without radiative feedback, computational time is virtually identical when using the Community Atmospheric Model (CAM) radiation option and a slightly increased (~8.5 %) when using the Rapid Radiative Transfer Model for GCMs (RRTMG) radiation option in the coupled system compared to the offline WRF-CMAQ system. Once the feedback mechanism is turned on, the execution time increases only slightly with CAM but increases about 60 % with RRTMG due to the use of a more detailed Mie calculation in this implementation of feedback mechanism. This two-way model with radiative feedback shows noticeably reduced bias in simulated surface shortwave radiation and 2 m temperatures as well improved correlation of simulated ambient ozone and PM<sub>2.5</sub> relative to observed values for a test case with significant tropospheric aerosol loading from California wildfires