The current–voltage (I–V) characteristics of N-doped A-plane-oriented ZnO pre- and post-annealing at specific temperatures exhibit distinct electrical behaviors. Pre-annealing, N-doped A-plane-oriented ZnO displays moderate electrical performance, with I–V curves reflecting modest conductivity. However, after annealing, a substantial enhancement in electric properties is observed. The annealing process at elevated temperatures induces structural modifications and optimizes the doping distribution within the material. This alteration leads to a remarkable improvement in conductivity and carrier mobility, evidenced by a notable shift in I–V characteristics toward higher conductivity, lower resistance, and improved electron transport efficiency. The high-performance post-annealing underscores the crucial role of thermal treatment in tailoring the electrical behavior of N-doped A-plane-oriented ZnO for advanced electronic applications. Otherwise, graphene, known for its high electronic mobility, is in various components of photovoltaic cells, including electrodes and charge transport layers, which exhibit unique electronic properties crucial for solar energy conversion. By analyzing the density of states (DOS) and band structures, insights into their charge carrier behavior, carrier mobility, a photovoltaic efficiency is expected based on the A-plane-oriented ZnO as an active photolayer.