Process-specific mechanisms of vertically oriented graphene growth in plasmas

Applications of plasma-produced vertically oriented graphene nanosheets (VGNs) rely on their unique structure and morphology, which can be tuned by the process parameters to understand the growth mechanism. Here, we report on the effect of the key process parameters such as deposition temperature, discharge power and distance from plasma source to substrate on the catalyst-free growth of VGNs in microwave plasmas. A direct evidence for the initiation of vertical growth through nanoscale graphitic islands is obtained from the temperature-dependent growth rates where the activation energy is found to be as low as 0.57 eV. It is shown that the growth rate and the structural quality of the films could be enhanced by (a) increasing the substrate temperature, (b) decreasing the distance between the microwave plasma source and the substrate, and (c) increasing the discharge power. The correlation between the wetting characteristics, morphology and structural quality is established. It is also demonstrated that morphology, crystallinity, wettability and sheet resistance of the VGNs can be varied while maintaining the same sp3 content in the film. The effects of the substrate temperature and the electric field in vertical alignment of the graphene sheets are reported. These findings help to develop and optimize the process conditions to produce VGNs tailored for applications including sensing, field emission, catalysis and energy storage.