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  • Review Article
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Nanoscale control by chemically vapour-deposited polymers

Nature Reviews Physics volume 2, pages 347–364 (2020)Cite this article

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Abstract

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.

Key points

  • The purity, precision and pinhole-free nature of CVD expands the realm of utility for polymer films in applications including optoelectronics, energy and wearable devices; membranes for molecular separation; and biointerfaces.

  • Conformal CVD polymers are compatible with nanostructured substrates and 3D device architectures, while low growth temperatures and the absence of solvent allow CVD polymers to form directly on fragile substrates, even liquids, without the need for a complex transfer step.

  • Adapting the mechanisms developed for solution synthesis enables the growth of different families of CVD macromolecules, representing hundreds of organic homopolymers, copolymers, crosslinked networks and hybrid organic/inorganic materials.

  • The diverse library of compositions allows CVD polymers to span full ranges of properties, for instance, from electronic conductors to insulators, from superhydrophobic to superhydrophilic and from mass-transport barriers to semipermeable layers for molecular and ionic transport.

  • Preserving the organic functional groups present in monomers is essential for designing and rationally optimizing the properties of CVD polymers, such as the fine-tuning of surface energy, forming a high density of sites for further surface reaction, or achieving smart, responsive behaviour for applications including sensing and controlled drug release.

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Fig. 1: oCVD and iCVD polymerization.
Fig. 2: Morphology of oCVD PEDOT.
Fig. 3: Electrical transport in oCVD PEDOT.
Fig. 4: The chemical structure and electrochemical activity of PEDOT chains.
Fig. 5: Examples of iCVD films on devices.
Fig. 6: Influence of surface pretreatment on iCVD film morphology.
Fig. 7: Examples of iCVD hydrogels.

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Acknowledgements

The author thanks M. H. Gharahcheshmeh for help with the figures.

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    Karen K. Gleason

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K.K.G. is a co-founder of two companies that commercialize CVD polymer technologies: GVD Corporation and Dropwise Technology.

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Gleason, K.K. Nanoscale control by chemically vapour-deposited polymers. Nat Rev Phys 2, 347–364 (2020). https://doi.org/10.1038/s42254-020-0192-6

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