Chemical vapour deposition (CVD) enables nanoscale control for the synthesis of high-purity polymer thin films. Ultrathin (<20 nm) and ultrasmooth (<1 nm r.m.s. roughness) layers of CVD polymers can conform to the geometry of the growth surface. This Review focuses on CVD polymerization methods adapted from solution chemistry for selectively forming different classes of macromolecules. The mechanistically based CVD approaches provide full retention of the monomer’s organic functional groups and thus provide a rational basis for designing and optimizing film characteristics for a diverse array of applications. These include conjugated polymers for energy storage, thin dielectrics for low-power, flexible devices and responsive hydrogels for controlled drug release. Systematic variation in the CVD process parameters provides remarkable control of π–π stacking in conducting polymers, mesh sizes in hydrogels, crystallographic texture, surface energy, permeation rates of molecules and ions, optoelectronic properties and switchable smart behaviour. The initial research focus on process fundamentals, including adsorption, reaction kinetics, mass transport and conformality, formed a strong basis for the recent rapid expansion of materials, applications and scale-up activities in multiple laboratories. The materials and approaches used in CVD polymerization are also extending into hybrid inorganic/organic materials and devices.

化学气相沉积（CVD）可以实现纳米级控制，以合成高纯度聚合物薄膜。CVD聚合物的超薄（<20 nm）和超光滑（<1 nm rms粗糙度）层可以符合生长表面的几何形状。这篇综述着重于从溶液化学中选择选择性地形成不同种类的大分子的CVD聚合方法。基于机械的CVD方法可完全保留单体的有机官能团，从而为设计和优化各种应用的薄膜特性提供了合理的基础。这些包括用于能量存储的共轭聚合物，用于低功率，柔性设备的薄电介质以及用于控制药物释放的响应水凝胶。导电聚合物中的π – π堆积，水凝胶的筛孔大小，晶体结构，表面能，分子和离子的渗透率，光电特性和可切换的智能行为。最初的研究侧重于过程基础，包括吸附，反应动力学，传质和保形性，为近期在多个实验室快速扩展材料，应用和扩大规模的活动奠定了坚实的基础。CVD聚合中使用的材料和方法也扩展到无机/有机混合材料和设备中。