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Role of Oxygen in PECVD Carbon Nanotubes Growth: Experiments and Modeling

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Abstract

We investigate by modeling supported by experiments the role of oxygen in carbon nanotubes (CNT) growth by plasma enhanced chemical vapor deposition (PECVD) process. We found that a suitable content of molecular oxygen in a H2/CH4 mixture can significantly increase the vertical CNT growth rate. We take the advantage of such system in order to better understand the mechanisms responsible for nanotube growth in a chemical environment represented by a ternary C–H–O system. In our approach, gas phase and surface chemistries are considered through two quantitative modeling approaches. As a first approximation, the plasma is described by spatially averaged bulk properties, and the species molar fractions are determined using transient zero-dimensional (0D) thermo-chemical model. Then two-dimensional model (2D) is proposed with reducing gas chemistry and considering surface reactions through site fraction and surface molar concentrations. The nanotube growth rate is then obtained by compiling the effects of gas and surface reactions at the gas/substrate interface via surface CHEMKIN software. To get an accurate estimation of the density of sites for bulk CNT growth, SEM and HRTEM analysis were used. The influence of the oxygen content, substrate temperature and microwave power on CNT growth rate are obtained from the model and compared to the experiments. There was good agreement between experimental and the modeling results, providing an insight into optimizing PECVD CNT growth. The specific role of generated oxygenated species such as H2O, OH, CO and O is found to be decisive.

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Acknowledgements

We thank Dr Carl D. Scott from Johnson Space Center, Houston TX for his valuable help during models development. ANR (Agence Nationale de la Recherche), and CGI (Commissariat à l’Investissement d’Avenir) are gratefully acknowledged for their financial support of this work through Labex SEAM (Science and Engineering for Advanced Materials and devices) ANR 11 LABX 086, ANR 11 IDEX 05 02, and ANR14CE08-0018. L’Agence Universitaire de la Francophonie (AUF) and the Fund “Scientific Research”, Bulgaria are gratefully acknowledged for their financial support of this work via bilateral project TherMoVapCar. Embassy of France in Nouakchott, Mauritania and University of Nouakchott are gratefully acknowledged for funding through international mobility fellowship.

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Authors and Affiliations

  1. Laboratoire des Sciences des Procédés et des Matériaux, Université Sorbonne Paris Nord, CNRS, LSPM-UPR 3407, 93430, Villetaneuse, France

    A. Andalouci, O. Brinza, S. M. Chérif & S. Farhat

  2. Department of Chemical Engineering, University of Chemical Technology and Metallurgy, 8 Boulevard St. Kliment Ohridski, 1756, Sofia, Bulgaria

    I. Hinkov

  3. Département of Chemistry, Faculté des Sciences et Techniques de L’Université de Nouakchott, Nouakchott, Mauritania

    A. Kane & A. H. Barry

  4. Plasma and Radiation Physics, National Institute for Laser, NILPRP, 077125, Bucharest, Romania

    C. Porosnicu

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  1. A. Andalouci
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Andalouci, A., Hinkov, I., Brinza, O. et al. Role of Oxygen in PECVD Carbon Nanotubes Growth: Experiments and Modeling. Plasma Chem Plasma Process 43, 757–786 (2023). https://doi.org/10.1007/s11090-023-10317-y

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