Amorphous carbon (a-C) films have garnered significant attention over the past few decades, principally due to their remarkable thermophysical properties, strong adherence to various materials, and good chemical inertness. These intrinsic characteristics of a-C films have led to their use as protective overcoats in numerous applications, such as hard-disk drives, microelectromechanical systems, and biomedical implants. The significant thinning of a-C films to a few nanometers, dictated by rapid advances in device miniaturization and compactness, motivated the development of thin-film deposition methods that preserve important film attributes like uniformity, strength, and structural stability. This article provides a comprehensive assessment of the most effective deposition techniques for synthesizing ultrathin films, particularly a-C films due to their wide application range as protective overcoats in contemporary technologies, state-of-the-art microanalysis methods for ultrathin films, and the technology challenges that must be overcome for CVA to capture a bigger share of the thin-film technology marketplace.