Understanding the interactions of graphene and chemical additives is crucial to achieve control over chemically modified graphene materials. Here, density functional theory and experiments are used to elucidate the chemical bonding of partially fluorinated graphene. This material includes F−C bonds whose ionicity varies depending upon local concentration and structure. Three bonding states dominate. Single fluorine on graphene forms a semi-ionic bond with a C atom in an sp 2 configuration. Fluorine in highly stable domains of poly(carbon fluoride) consists of covalent F−C bonds alternating in ortho position one to another on both sides of graphene. Fluorine in regions of poly(tetracarbon fluoride) has F species on one side of graphene in para position one to another, and F−C bonds with a character intermediate between the semi-ionic and covalent. Such variability in chemical bonding could be exploited to tailor fluorinated graphene materials to achieve a variety of properties.
Atomic layer etching (ALE) is a promising technique that can solve the challenges associated with continuous or pulsed plasma processes—trade-offs between selectivity, profile, and aspect ratio dependent etching. Compared to silicon, oxide, and other materials, atomic layer etching of silicon nitride has not been extensively reported. In this paper, the authors demonstrate the self-limited etching of silicon nitride in a commercial plasma etch chamber. The process discussed in this paper consists of two sequential steps—surface modification in hydrogen plasma followed by the removal of modified layers in fluorinated plasma. In addition to the ALE characteristics, the authors also demonstrate that the process is anisotropic and the selectivity to oxide is >100. Although the saturated etch rate of one monolayer per cycle could not be attained, self-limited etching of silicon nitride still enables us to incorporate the benefits of atomic layer etching such as an absence of isodense bias and an extremely high selectivity to oxide into practical etch applications.
Work function engineering of graphene facilitates its application as a transparent electrode material in organic electronic devices. Toward this end, we demonstrate the dependence of the work function of plasma-fluorinated epitaxial graphene on the polarity of carbon-fluorine bonds which is controlled by the nature of chemical bonding (ionic, semi-ionic, or covalent) between fluorine and carbon atoms. The work function of fluorinated graphene was measured using ultraviolet photoelectron spectroscopy and the polarity of carbon-fluorine bonds was established using x-ray photoelectron spectroscopy.
Fluorination of graphene has emerged as an attractive approach toward manipulating its physical, chemical, and electronic properties. To this end, we have demonstrated the viability of sulfur hexafluoride plasmas to fluorinate graphene as a safer alternative to the commonly reported techniques of fluorination that include exposures to fluorine and xenon difluoride gas. Incorporation of fluorine moieties on graphene after SF 6 plasma-treatment was confirmed by x-ray photoelectron spectroscopy. Modifications in the valence band states of graphene after plasmatreatment were characterized by ultraviolet photoelectron spectroscopy. Increase in work function of plasma-treated graphene demonstrates the ability of plasma-assisted fluorination to modify the electron emission characteristics of graphene. Raman spectroscopy reveals that the majority of carbon atoms in graphene retain their sp 2 hybridization after the plasma-treatment.
Atomic or layer by layer etching of silicon exploits temporally segregated self-limiting adsorption and material removal steps to mitigate the problems associated with continuous or quasicontinuous (pulsed) plasma processes: selectivity loss, damage, and profile control. Successful implementation of atomic layer etching requires careful choice of the plasma parameters for adsorption and desorption steps. This paper illustrates how process parameters can be arrived at through basic scaling exercises, modeling and simulation, and fundamental experimental tests of their predictions. Using chlorine and argon plasma in a radial line slot antenna plasma source as a platform, the authors illustrate how cycle time, ion energy, and radical to ion ratio can be manipulated to manage the deviation from ideality when cycle times are shortened or purges are incomplete. Cell based Monte Carlo feature scale modeling is used to illustrate profile outcomes. Experimental results of atomic layer etching processes are illustrated on silicon line and space structures such that iso-dense bias and aspect ratio dependent free profiles are produced. Experimental results also illustrate the profile control margin as processes move from atomic layer to multilayer by layer etching. The consequence of not controlling contamination (e.g., oxygen) is shown to result in deposition and roughness generation.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.