摘要:The graphdiyne (GD), a carbon allotrope with a 2D structure comprising benzene rings and carbon–carbon triple bonds, can be synthesized through cross-coupling on the surface of copper foil. The key problem is in understanding the dependence of layers number and properties, however, the controlled growth of the layers numbers of GD film have not been demonstrated, its controlled growth into large-area and high ordered films with different numbers of layers is still an important challenge. Here, we show that a new strategy for synthesizing GD films with 2D nanostructures on ZnO nanorod arrays through a combination of reduction and a self-catalyzed vapor–liquid–solid growth process, using GD powder as the vapor source and ZnO nanorod arrays as the substrate. HRTEM shows the distance between pairs of streaks being approximately 0.365 nm by different thicknesses of GD films. The approach enables us to construct large-area ordered semiconductive films with high-quality surfaces showing high conductivity (up to 2800 S cm−1). FETs were fabricated based on the well ordered films; we prepared and measured over 100 devices. Devices incorporating these well-ordered and highly conductive GD films exhibited field-effect mobility as high as 100 cm2 V−1 s−1.