Pitsiri Sukkaew

Effects of surface charge and Gibbs surface energy on the settlement behaviour of barnacle cyprids (Balanus amphitrite)

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) (CH3-, OH-, COOH-, N(CH3)3 +-, NH2-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 CH3- 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.

Simulation of Gas-Phase Chemistry for Selected Carbon Precursors in Epitaxial Growth of SiC

Numerical simulations are one way to obtain a better and more detailed understanding of the chemical vapor deposition process of silicon carbide. Although several attempts have been made in this area during the past ten years, there is still no general model valid for any range of process parameters and choice of precursors, that can be used to control the growth process, and to optimize growth equipment design. In this paper a first step towards such a model is taken. Here, mainly the hydrocarbon chemistry is studied by a detailed gas-phase reaction model, and comparison is made between C3H8 and CH4 as carbon precursor. The results indicate that experimental differences, which previous models have been unable to predict, may be explained by the new model.

Matching precursor kinetics to afford a more robust CVD chemistry: a case study of the C chemistry for silicon carbide using SiF4 as Si precursor

Chemical Vapor Deposition (CVD) is one of the technology platforms forming the backbone of the semiconductor industry and is vital in the production of electronic devices. To upscale a CVD process from the lab to the fab, large area uniformity and high run-to-run reproducibility are needed. We show by a combination of experiments and gas phase kinetics modeling that the combinations of Si and C precursors with the most well-matched gas phase chemistry kinetics gives the largest area of of homoepitaxial growth of SiC. Comparing CH4, C2H4 and C3H8 as carbon precursors to the SiF4 silicon precursor, CH4 with the slowest kinetics renders the most robust CVD chemistry with large area epitaxial growth and low temperature sensitivity. We further show by quantum chemical modeling how the surface chemistry is impeded by the presence of F in the system which limits the amount of available surface sites for the C to adsorb.

Revisiting the Thermochemical Database of Si-C-H System Related to SiC CVD Modeling

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/H2 system 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.

Growth Mechanism of SiC CVD: Surface Etching by H2, H Atoms, and HCl

Silicon carbide is a wide bandgap semiconductor with unique characteristics suitable for high temperature and high power applications. Fabrication of SiC epitaxial layers is usually performed using chemical vapor deposition (CVD). In this work, we use quantum chemical density functional theory (B3LYP and M06-2X) and transition state theory to study etching reactions occurring on the surface of SiC during CVD in order to combine etching effects to the surface kinetic model for SiC CVD. H2, H atoms and HCl gases are chosen in the study as the most likely etchants responsible for surface etching. We consider etchings of four surface sites, namely CH3(ads), SiH3CH2(ads), SiH2(CH2)2(ads), and SiH(CH2)3(ads), which represent four subsequent snapshots of the surface as the growth proceeds. We find that H atoms are the most effective etchant on CH3(ads) and SiH3CH2(ads), which represent the first and second steps of the growth. HCl and H2 are shown to be much less effective than H atoms and produce the etching rate constants which are ∼104 and ∼107 times slower. In comparison to CH3(ads), SiH3CH2(ads) is shown to be less stable and more susceptible to etchings. Unlike the first and second steps of the growth, the third and fourth steps (i.e., SiH2(CH2)2(ads) and SiH(CH2)3(ads)) are stable and much less susceptible to any of the three etchants considered. This implies that the growth species become more stable via forming Si-C bonds with another surface species. The formation of a larger surface cluster thus helps stabilizing the growth against etchings.