Gibbs surface energy has long been considered to be an important parameter in the design of fouling-resistant surfaces for marine applications. Rigorous testing of the hypothesis that settlement is related to Gibbs surface energy however has never been accomplished, due mainly to practical limitations imposed by the necessary combination of surface engineering and biological evaluation methods. In this article, the effects of surface charge and Gibbs surface energy on the settlement of cyprids of an important fouling barnacle, Balanus amphitrite, were evaluated. Settlement assays were conducted on a range of self-assembled monolayers (SAMs) (CH(3)-, OH-, COOH-, N(CH(3))(3) (+)-, NH(2)-terminated), presented in gold-coated polystyrene well plates, varying in terms of their surface charge and Gibbs surface energy. Contrary to contemporary theory, settlement was not increased by high-energy surfaces, rather the opposite was found to be the case with cyprids settling in greater numbers on a low-energy CH(3)- SAM compared to a high-energy OH- SAM. Settlement was also greater on negatively-charged SAMs, compared to neutral and positively-charged SAMs. These findings are discussed in the context of data drawn from surfaces that varied in multiple characteristics simultaneously, as have been used previously for such experiments. The finding that surface charge, rather than total surface energy, may be responsible for surface selection by cyprids, will have significant implications for the design of future fouling-resistant materials.
Silicon carbide is a semiconductor material with ideal properties for high temperature and high power applications. The epitaxial layer fabrication is usually performed using CVD under a hydrogen rich atmosphere and high temperature. At such conditions the surface of the growing layer is expected to be passivated by the abundantly present hydrogen. In this work, we use quantum chemical density functional theory (B3LYP and M06-2X) and transition state theory to study surface reactions related to the deposition of carbon on the (0001) surface of 4H−SiC. We show that it is unlikely for an adsorption to occur on a passivated site unless the hydrogen termination is removed. We propose that unterminated sites can be effectively created during the CVD by an abstraction process. We provide details of the adsorption process of active carbon species, namely CH3, CH4, C2H2 and C2H4 gases, and their subsequent surface reactions such as desorption, abstraction of neighboring surface hydrogens 2 and dimer formation. The reaction rates and sticking coefficients are provided for the temperature range of 298−2500 K. Finally, entire reaction paths from adsorptions to stable surface products are presented and discussed.
Silicon carbide is a wide bandgap semiconductor ideally suitable for high temperature and high power applications. An active SiC layer is usually fabricated using halide-assisted chemical vapor deposition (CVD). In this work, we use quantum chemical density functional theory (B3LYP and M06-2X) and transition state theory to study adsorptions of active Si species in the CVD process on both the Si face and the C face of 4H-SiC. We show that adsorptions of SiCl, SiCl2, SiHCl, SiH and SiH2 on the Si face likely occurs on a methylene site, CH2(ads), but the processes are thermodynamically less favorable than their reverse or desorptions. Nevertheless, the adsorbed products become stabilized with help of subsequent surface reactions to form a larger cluster.These cluster formation reactions happen with rates that are fast enough to compete with the desorption processes. On the C face, the adsorptions likely occur on a surface site terminated by a dangling bond, *(ads), and produce the products which are thermodynamically stable. Lastly, we present the Gibbs free energies of adsorptions of Si atoms, SiX, SiX2, SiHX, for X being F and Br. Adsorptions of Si atoms are shown to be the most thermodynamically favorable among all the species in the study. Among the halide-containing species, the Gibbs free energies (∆°) from smallest to largest are observed in the adsorptions of SiX, SiHX and SiX2, for X being the halides.The results in this study suggest that the major Si contributors in SiC-CVD process are Si atoms, SiX (for X being the halide) and SiH.
Chlorinated chemical vapor deposition (CVD) chemistry for growth of homoepitaxial layers of silicon carbide (SiC) has paved the way for very thick epitaxial layers in short deposition time as well as novel crystal growth processes for SiC. Here, we explore the possibility to use a brominated chemistry for SiC CVD by using HBr as additive to the standard SiC CVD precursors. We find that brominated chemistry leads to the same high material quality and control of material properties during deposition as chlorinated chemistry and that the growth rate is on average 10% higher for a brominated chemistry compared to chlorinated chemistry. Brominated and chlorinated SiC CVD also show very similar gas-phase chemistries in thermochemical modeling. This study thus argues that brominated chemistry is a strong alternative for SiC CVD because the deposition rate can be increased with preserved material quality. The thermochemical modeling also suggest that the currently used chemical mechanism for halogenated SiC CVD might need to be revised.
A comprehensive systematic method for chemical vapor deposition modeling consisting of seven well-defined steps is presented. The method is general in the sense that it is not adapted to a certain type of chemistry or reactor configuration. The method is demonstrated using silicon carbide (SiC) as a model system, with accurate matching to measured data without tuning of the model. We investigate the cause of several experimental observations for which previous research reports only have had speculative explanations. In contrast to previous assumptions, we can show that SiCl2 does not contribute to SiC deposition. We can confirm the presence of larger molecules at both low and high C/Si ratios, which have been thought to cause so-called step-bunching. We can also show that high concentrations of Si lead to other Si molecules other than the ones contributing to growth, which also explains why the C/Si ratio needs to be lower at these conditions to maintain high material quality as well as the observed saturation in deposition rates. Due to its independence of a chemical system and reactor configuration, the method paves the way for a general predictive CVD modeling tool.
Chemical vapor deposition of silicon carbide (SiC-CVD) is a complex process involving a Si-C-H system wherein a large number of reaction steps occur. To simulate such a system requires knowledge of thermochemical and transport properties of all the species involved in the process. The accuracy of this information consequently becomes a crucial factor toward the correctness of the outcome prediction. The database on thermochemical properties of well-known species such as small hydrocarbons has been established over decades and it is accurate and easily accessible. On the other hand, the database for less frequently used species such as organosilicons is still under development. Apart from the accuracy issue, a consistency in acquiring procedures, whether theoretical or experimental, is another factor controlling the final error of the simulated outcome. In this work, the thermochemical data for several important growth species for SiC CVD using the SiH4/CxHy/H2system has been calculated. For the most part an excellent agreement is seen with previously reported data, however for the organosilicons a larger deviation is detected and in particular for the CH3SiH2SiH species which shows a stark deviation from the CHEMKIN database.
The use of chlorinated chemical vapor deposition (CVD) chemistry for growth of homoepitaxial layers of silicon carbide (SiC) has diminished the problem of homogenous gas phase nucleation, mainly the formation of Si droplets, in CVD of SiC by replacing Si-Si bonds with stronger Si-Cl bonds. Employing the even stronger Si-F bond could potentially lead to an even more efficient CVD chemistry, however, fluorinated chemistry is very poorly understood for SiC CVD. Here, we present studies of the poorly understood fluorinated CVD chemistry for homoepitaxial SiC layers using SiF4 as Si precursor. We use a combination of experimental growth studies, thermal equilibrium calculations of gas phase composition and quantum chemical computations (i.e. hybrid density functional theory) of the surface chemistry to probe the silicon chemistry in the CVD process. We show that while growth rates on the order of 35 µm/h can be achieved with a fluorinated chemistry, the deposition chemistry is very sensitive to the mass flows of the precursors and not as robust as the chlorinated CVD chemistry which routinely yields 100 µm/h over wide conditions. By using the position for the onset of epitaxial growth along the gas flow direction as a measurable, together with modeling, we conclude that SiF is the main Si growth species with SiHF as a minor Si species contributing to growth.
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