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The investigations reported here describe the synthesis of carbon nanowalls (CNWs) by microwave electron-cyclotron resonance (ECR) plasma-assisted chemical vapour deposition (PACVD) process without an application of external bias to the substrate during growth. CNWs were grown on silicon (Si) substrates using hydrogen (H2)/methane (CH4) plasma at 650°C substrate temperature. Nickel (Ni) was used as a catalyst for the synthesis of CNWs. To the best of our knowledge, this is the first report that describes the bias-independent growth of CNWs using the ECR PACVD process. Formation of CNWs is confirmed by scanning electron microscopy and Raman spectroscopy. The discussion part also includes a possible growth mechanism for CNWs in terms of the role of surface plasmons. [ABSTRACT FROM PUBLISHER]