Recent progress in non-photolithographic patterning of polymer thin films

Qiu, Mingjun; Du, Weibin; Zhou, Shangyu; Cai, Pengzhe; Luo, Yingwu; Wang, Xiaoxue; Yang, Rong; Zha, Junjie

doi:10.1016/j.progpolymsci.2023.101688

Cited by 12 publications

(5 citation statements)

References 407 publications

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“…It is particularly suitable for polymers with limited solubility, such as cross-linked polymers, or when the solvent is incompatible with the application due to their toxicity or damage to the substrate. 1,2 CVD produces pinhole-free and conformal coverage, as the undesirable surface tension effects, which can cause dewetting, liquid bridging, liquid thinning, and meniscus formation during solution coating processes, 3 are absent in CVD.…”

Section: ■ Introductionmentioning

confidence: 99%

“…While polymer thin films/coatings are predominantly synthesized and subsequently processed using solution-based methods, such as spin-coating or inkjet printing, CVD polymerization synthesizes polymers and forms a thin film in a single step. It is particularly suitable for polymers with limited solubility, such as cross-linked polymers, or when the solvent is incompatible with the application due to their toxicity or damage to the substrate. , CVD produces pinhole-free and conformal coverage, as the undesirable surface tension effects, which can cause dewetting, liquid bridging, liquid thinning, and meniscus formation during solution coating processes, are absent in CVD.…”

Section: Introductionmentioning

confidence: 99%

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Curbing Chain Transfer in Initiated Chemical Vapor Deposition (iCVD) via Molecular Vapor Complexation

Chen,

Zhang,

Park

et al. 2024

Chem. Mater.

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Initiated chemical vapor deposition (iCVD) has revolutionized the preparation of high-quality conformal polymer films with excellent control over composition and properties at the nanoscale. It is compatible with over 70 functional monomers. Despite that chemical versatility, side reactions during iCVD are not well understood. For example, chain transfer could happen during the propagation of an important class of monomers that contain nitrogen (N), arresting the polymerization and limiting the molecular weight. Here, we use 1vinylimidazole (1VI) to demonstrate the chain transfer reaction to the imidazole group during iCVD, which leads to unpredictable deposition kinetics, low molecular weight, and undesirable products. We further introduce a strategy that utilizes a vapor solvent to engineer monomer reactivity and suppress side reactions. By replacing the traditional patch flow, Ar, with acetic acid (AcOH), which forms hydrogen bonding with 1VI, chain transfer is suppressed, and the deposition rate is increased by as much as 280% while restoring its linear dependence on the monomer partial pressure. That linear dependence has not been achieved previously for 1VI. The tunable deposition kinetics, in turn, leads to a broader range of attainable material properties, including nearly doubling the maximum attainable molecular weight (from 8 kDa to 16 kDa) and increasing the elastic modulus (from 3.5 to 4.7 GPa). The vapor solvent is also effective at suppressing chain transfer in other N-containing monomers, like (2-dimethylamine) ethyl methacrylate (DMAEMA), leading to a considerable increase in the molecular weight (from 16 kDa to 38 kDa). The vapor solvent selectively increases the reactivity of N-containing monomers during copolymerization, demonstrated using 1VI and divinylbenzene (DVB) or 1,3,5,7-tetravinyl tetramethylcyclotetrasiloxane (V4D4), increasing the reactivity ratio of 1VI by an order of magnitude according to the Fineman−Ross equation. This robust strategy engineers monomer reactivity without the need for chemical modifications. It improves the chemical precision of iCVD polymerization, particularly for an important class of N-containing monomers, which have found broad applications as the polymer− electrolyte interphase in batteries, antifouling coatings in food and water production, and bioactive and functionalizable coatings in sensors.

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Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Curbing Chain Transfer in Initiated Chemical Vapor Deposition (iCVD) via Molecular Vapor Complexation

Chen,

Zhang,

Park

et al. 2024

Chem. Mater.

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“…Rotational symmetry is a ubiquitous order in nature, from rigid molecules, mineral crystals, snowflakes, and corollas to honeycomb arrays in beehives. [1] The self-organization of blockcopolymers, [2,3] colloids, [4,5] and liquid crystals (LCs) [6,7] can spontaneously form aggregations featuring distinct rotational symmetry and thus mimic the above natural systems. Self-assemblies are usually entropy-driven processes accompanied by the emergence of random frustrations and deformations, as well as various topological defects.…”

Section: Introductionmentioning

confidence: 99%

Tailoring on Rotational Symmetry of Liquid Crystal Domain Lattices

Wu,

2023

Advanced Physics Research

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Rotational symmetry is ubiquitous in nature. However, self‐assemblies of soft condensed matter such as liquid crystals (LCs) are entropy‐driven, making the tailoring of rotational symmetry challenging. Here, an approach is proposed to control the rotational symmetry of LC domain lattices based on the anchoring condition predesign and the orientational‐order inheritance during the nematic‐smectic phase transition. By this means, periodic and quasiperiodic LC textures with Ci symmetry (i = 2–6) determined by the preset alignment lattices are realized, and verified by symmetries of diffraction patterns. Topological analysis is carried out to disclose distinct evolutions of orders between disclination line textures and defect wall textures of different rotational symmetries. The influences of anchoring conditions, phase transitions, and mechanical stress on the self‐assembly of LCs, as well as the underlying mechanisms and dynamics, are investigated. This work realizes controllable rotational symmetry for large‐area self‐organized LCs and brings new insights to soft condensed matter.

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“…Inspired by the abundant patterned surfaces in nature, such as imprinting, [4][5][6] and photolithography, [7][8] tailored to various practical applications. [9][10][11] Despite the potential offered by these top-down patterning technologies, their broader utilization is hindered by various challenges, including intricate fabrication procedures, elevated expenses, constraints regarding specific geometries, and the absence of dynamic regulation capabilities. In contrast to these conventional top-down methods, surface patterns in nature often emerge spontaneously and through self-organization, offering advantages such as simplicity in the preparation process, low cost, and noncontact characteristics of these bottom-up approach.…”

Section: Introductionmentioning

confidence: 99%

Deformation‐Induced Photoprogrammable Pattern of Polyurethane Elastomers Based on Poisson Effect

Yan,

Deng,

Chen

et al. 2023

Advanced Materials

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Elastomers with high aspect ratio surface patterns are a promising class of materials for designing soft machines in the future. Here, a facile method for fabricating surface patterns on polyurethane elastomer by subtly utilizing the Poisson effect and gradient photocrosslinking is demonstrated. By applying uniaxial tensile strains, the aspect ratio of the surface patterns can be optionally manipulated. At prestretched state, the pattern on the polyurethane elastomer can be readily constructed through compressive stress, resulting from the gradient photocrosslinking via selective photodimerization of an anthracene‐functionalized polyurethane elastomer (referred to as ANPU). The macromolecular aggregation structures during stretching deformation significantly contribute to the fabrication of high aspect ratio surface patterns. The insightful finite element analysis well demonstrates that the magnitude and distribution of internal stress in the ANPU elastomer can be regulated by selectively gradient crosslinking, leading to polymer chains migrate from the exposed region to the unexposed region, thereby generating a diverse array of surface patterns. Additionally, the periodic surface patterns exhibit tunable structural color according to the different stretching states and are fully reversible over multiple cycles, opening up avenues for diverse applications such as smart displays, stretchable strain sensors, and anticounterfeiting devices.

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Recent progress in non-photolithographic patterning of polymer thin films

Cited by 12 publications

References 407 publications

Curbing Chain Transfer in Initiated Chemical Vapor Deposition (iCVD) via Molecular Vapor Complexation

Curbing Chain Transfer in Initiated Chemical Vapor Deposition (iCVD) via Molecular Vapor Complexation

Tailoring on Rotational Symmetry of Liquid Crystal Domain Lattices

Deformation‐Induced Photoprogrammable Pattern of Polyurethane Elastomers Based on Poisson Effect

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