Plasma polymerization of cyclopropylamine in a low-pressure cylindrical magnetron reactor: A PIC-MC study of the roles of ions and radicals

Mathioudaki, Stella; Vandenabeele, Cédric; Tonneau, Romain; Pflug, Andreas; Tennyson, Jonathan; Lucas, Stéphane

doi:10.1116/1.5142913

Cited by 3 publications

(4 citation statements)

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“…The high contact angle for cyclopropylamine thermal reaction was as expected and in trend of agreement with our previous work [47] pertaining to grafting cyclopropylamine with thermal reaction. However, the sessile droplet contact angle registering at 44.71 • for the sonochemical reaction sample may be indicative of a different reaction profile that may suggest either polymerization [47,49] or non-reactivity, but at this stage of analysis there was not enough details to make a definitive conclusion. Nevertheless, XPS experiments were needed to make further deductions or to support some early hypothesis.…”

Section: Resultsmentioning

confidence: 97%

Sonochemical Reaction of Bifunctional Molecules on Silicon (111) Hydride Surface

2021

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While the sonochemical grafting of molecules on silicon hydride surface to form stable Si–C bond via hydrosilylation has been previously described, the susceptibility towards nucleophilic functional groups during the sonochemical reaction process remains unclear. In this work, a competitive study between a well-established thermal reaction and sonochemical reaction of nucleophilic molecules (cyclopropylamine and 3-Butyn-1-ol) was performed on p-type silicon hydride (111) surfaces. The nature of surface grafting from these reactions was examined through contact angle measurements, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Cyclopropylamine, being a sensitive radical clock, did not experience any ring-opening events. This suggested that either the Si–H may not have undergone homolysis as reported previously under sonochemical reaction or that the interaction to the surface hydride via a lone-pair electron coordination bond was reversible during the process. On the other hand, silicon back-bond breakage and subsequent surface roughening were observed for 3-Butyn-1-ol at high-temperature grafting (≈150 °C). Interestingly, the sonochemical reaction did not produce appreciable topographical changes to surfaces at the nano scale and the further XPS analysis may suggest Si–C formation. This indicated that while a sonochemical reaction may be indifferent towards nucleophilic groups, the surface was more reactive towards unsaturated carbons. To the best of the author’s knowledge, this is the first attempt at elucidating the underlying reactivity mechanisms of nucleophilic groups and unsaturated carbon bonds during sonochemical reaction of silicon hydride surfaces.

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Section: Resultsmentioning

confidence: 97%

Sonochemical Reaction of Bifunctional Molecules on Silicon (111) Hydride Surface

2021

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“…Other theoretical tools (i.e. molecular dynamics, particle-in-cell Monte Carlo) have also been employed for simulating the film growth [124][125][126][127][128][129]. These methods were mainly applied to a-C:H layers likely because of 'simpler' plasma chemistry rather than for functionalized PPF (containing a hetero-element).…”

Section: Into the Intimacy Of Ppmentioning

confidence: 99%

“…These methods were mainly applied to a-C:H layers likely because of 'simpler' plasma chemistry rather than for functionalized PPF (containing a hetero-element). To the best of our knowledge, only two studies have addressed the simulation of the growth of functionalized PPF, both from the cyclopropylamine precursor [124,130]. Compared with experimental data, these studies shed light on the role of ions and radicals in the global surface reaction scheme, the ultimate goal being to predict the film properties.…”

Section: Into the Intimacy Of Ppmentioning

confidence: 99%

Foundations of plasma enhanced chemical vapor deposition of functional coatings

Snyders

Hegemann

Thiry

et al. 2023

Plasma Sources Sci. Technol.

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Since decades, the PECVD (“Plasma Enhanced Chemical Vapor Deposition”) processes have emerged as one of the most convenient and versatile approaches to synthesizing either organic or inorganic thin films on many types of substrates, including complex shapes. As a consequence, PECVD is today utilized in many fields of application such as microelectronic circuit fabrication, optics/photonics, biotechnology, energy, smart textiles, and many others. Nevertheless, owing to the complexity of the process including numerous gas phase and surface reactions, the fabrication of tailor-made materials for a given application is still a major challenge in the field making it obvious that the mastery of the technique can only be achieved through the fundamental understanding of the chemical and physical phenomena involved in the film formation.In this context, the aim of this foundation paper is to share with the readers our perception and understanding of the basic principles behind the formation of PECVD layers considering the co-existence of different reaction pathways that can be tailored by controlling the energy dissipated in the gas phase and/or at the growing surface. We demonstrate that the key parameters controlling the functional properties of the PECVD films are similar whether they are inorganic or organic-like (plasma polymers) in nature, thus supporting a unified description of the PECVD process. Several concrete examples of the gas phase processes and the film behavior illustrate our vision.To complete the document, we also discuss the present and future trends in the development of the PECVD processes and provide examples of important industrial applications using this powerful and versatile technology.

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“…Owing to its easy operation, low-energy consumption, moderate working conditions and highly reactive characteristics, plasma surface treatment has been developed as an effective tool to modify, activate and functionalize materials. The energetic electrons (>1 eV) in non-thermal plasmas can induce molecule excitation, ionization and dissociation, resulting in the breaking and restructuring of chemical bonds [134]. Additionally, since the plasma species only typically have a small penetration depth on the order of 10~100 nm, they are capable of modifying materials surface without changing their bulk properties [135].…”

Section: Surface Modificationmentioning

confidence: 99%