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High specific surface area of carbon nanowalls (CNWs) makes them an attractive catalyst support material or electrode material for energy storage devices (e.g. supercapacitors, Li-ion batteries). Secondary nucleation process (formation of secondary nanowalls on the surface of pre-grown primary structures) plays important role in CNWs growth. It can significantly increase CNW film surface area, but at the same time be a limiting step for producing films with open pore structure. Both of these factors may be important for applications mentioned above. In this work we discuss possible mechanisms of secondary nucleation during CNW growth in the plasma of direct current glow discharge. We also demonstrate novel multi-step synthesis process with controllable secondary nucleation rates at different stages, which is an effective way to modulate CNW film morphology and produce films with desirable surface area and porosity.