Graphene has attracted extensive attention due to its outstanding electrical, thermal, and mechanical properties, showing broad application prospects in flexible electronic devices, transparent conductive films, sensors, energy storage, and functional composites. To address the controllable synthesis of graphene, Ni₃C_x thin films were deposited by plasma-enhanced atomic layer deposition (PEALD) using Ni(^tBu2amd)₂ as the precursor. Combined with subsequent Ni overlayer deposition and thermal annealing, the annealing-induced structural evolution of the Ni₃C_x-containing system and the associated graphene-formation behavior were systematically investigated. The results show that under deposition conditions of a precursor pulse time of 5 s, purge time of 10 s, H₂ plasma exposure time of 10 s, plasma power of 60 W, and deposition temperature of 95 °C, Ni₃C_x thin films prepared by 400 PEALD cycles and subsequently coated with a 71.5 nm Ni layer by magnetron sputtering exhibited particle size and elemental distribution more favorable for graphene growth after annealing at 900 °C, which was more conducive to the formation of high-quality graphene with Raman characteristics consistent with a bilayer/few-layer structure. Raman mapping over a 50 × 50 μm² area showed relatively continuous and consistent spatial distributions of I_2D/I_G and I_D/I_G within the examined region, supporting local spatial uniformity. These results provide a controllable route toward substrate-supported graphene formation based on PEALD Ni₃C_x films and indicate potential for direct integration on insulating substrates after further optimization of metal removal and device processing.

PEALD; Ni3Cx thin films; graphene; annealing; Raman spectroscopy