Tunable Low Bandgap Polyisothianaphthene via Oxidative Chemical Vapor Deposition

Borrelli, David C.; Gleason, Karen K.

doi:10.1021/ma400890a

Cited by 17 publications

(10 citation statements)

References 81 publications

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Section: Step Growth Polymerization: Ocvdmentioning

confidence: 99%

“…Thus, by controlling those parameters as well as the monomer flow rate, the resulting PT film properties, such as conductivity and absorption maximum, were tuned. Work on oCVD polyisothianaphthene (PITN) has shown the importance of the stage temperature during deposition 44. PITN is of interest for its various appealing properties, including its low bandgap of 1 eV in the neutral state.…”

Section: Step Growth Polymerization: Ocvdmentioning

confidence: 99%

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25th Anniversary Article: CVD Polymers: A New Paradigm for Surface Modifi cation and Device Fabrication

et al. 2013

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Well-adhered, conformal, thin (<100 nm) coatings can easily be obtained by chemical vapor deposition (CVD) for a variety of technological applications. Room temperature modification with functional polymers can be achieved on virtually any substrate: organic, inorganic, rigid, flexible, planar, three-dimensional, dense, or porous. In CVD polymerization, the monomer(s) are delivered to the surface through the vapor phase and then undergo simultaneous polymerization and thin film formation. By eliminating the need to dissolve macromolecules, CVD enables insoluble polymers to be coated and prevents solvent damage to the substrate. CVD film growth proceeds from the substrate up, allowing for interfacial engineering, real-time monitoring, and thickness control. Initiated-CVD shows successful results in terms of rationally designed micro- and nanoengineered materials to control molecular interactions at material surfaces. The success of oxidative-CVD is mainly demonstrated for the deposition of organic conducting and semiconducting polymers.

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Section: Step Growth Polymerization: Ocvdmentioning

confidence: 99%

Section: Step Growth Polymerization: Ocvdmentioning

confidence: 99%

25th Anniversary Article: CVD Polymers: A New Paradigm for Surface Modifi cation and Device Fabrication

et al. 2013

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“…The oCVD copolymerization of EDOT with the solid monomers anthracene or biphenyl produced systematic bandgap tuning . The low‐bandgap semiconductor 1,3‐dihydroisothianaphthene (DHITN) has been demonstrated with a modified oCVD process. In addition, successful oCVD film from dopamine (DA) monomer has recently been reported …”

Section: Ocvd Synthesis Chemistrymentioning

confidence: 99%

Device Fabrication Based on Oxidative Chemical Vapor Deposition (oCVD) Synthesis of Conducting Polymers and Related Conjugated Organic Materials

Gharahcheshmeh

Gleason

2018

Adv Materials Inter

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lightweight, wearable, and stretchable properties of CPs relative to traditional materials highlight the areas where CPs may find their niche in modern devices. [2] The fabrication of uniform CPs in large scale with high throughput roll-to-roll process is of great importance in industrial sectors. To achieve this purpose, chemical vapor deposition (CVD) along with other vapor deposition methods are the promising approaches to expedite the commercialization process of CPs in large-scale applications.For polymers which dissolve, films can be formed by solution-based methods such as dip-coating and spin-coating. However, CPs, particularly those formed from unfunctionalized monomers, are often insoluble or require solvents which are unsafe and costly to use. The lack of solubility is typically associated with a rigid backbone structure that promotes crystallite formation. As a result, dissolution requires overcoming the associated enthalpy of crystallization.The need for solubilizing polymers is eliminated by employing CVD as the thin film formation technique. A variety of different CVD processes have been developed for vapor phase reactants to undergo similar polymerization mechanisms as those reported for solution synthesis. [3] These include CVD polymer methods for chain growth by free radical or cationic initiation, or by condensation polymerization. For most conjugated macromolecules, the desired variant of the CVD method needs to mimic the step-growth polymerization mechanism in order to obtain optimized properties, such as electrical conductivity. This motivated the invention of oxidative CVD (oCVD) in which the vacuum chamber design, strategy for reactant vapor introduction, and process conditions are optimized for step-growth polymerization. Vapor deposition methods which are not mechanistically motivated, such as thermal evaporation, pulsed laser deposition, and plasma-enhanced CVD, can result in conjugated polymer films having properties that are insufficient for integration into many types of devices. Thus, one major significance of achieving conjugated polymers having highly desirable characteristics by oCVD is the ability to fabricate state-of-the-art optoelectronic and energy storage devices.The oCVD process is a single-step method to convert vapor phase monomers, along with vapors of oxidant, into thin CP films. [3,4] At the surface of the substrate, step-growth Conducting polymers (CPs) combine electronic conductivity, optical transparency, and mechanical flexibility compatible with lightweight substrates. Due to these features CPs exhibit promising performance for a wide range of applications including electronic, optoelectronic, electrochemical, optochemical, and energy storage and harvesting devices. Fabrication of high-quality CPs thin film in a large scale is of high demand in multiple industrial sectors. Chemical vapor deposition (CVD) is a promising approach for scale-up and commercialization of CPs in large-scale thin film applications by a roll-to-roll process. The CVD technique is a versati...

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“…This change in their redox state is complemented by a change in their absorption characteristics, making them great candidate as electrochromic materials. [94][95][96] PEDOT has become the most useful of the commercially-available electrochromic polymers because of its combination of optical properties, stability, and processability. [94] Ultrathin pinhole-free CVD polymers along with few nanometer thick graphene sheets enable fabrication of devices with enhanced functionality during operation and also flexing conditions.…”

Section: Electrochromic Devicesmentioning

confidence: 99%

CVD Polymers for Devices and Device Fabrication

et al. 2016

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Chemical vapor deposition (CVD) polymerization directly synthesizes organic thin films on a substrate from vapor phase reactants. Dielectric, semiconducting, electrically conducting, and ionically conducting CVD polymers have all been readily integrated into devices. The absence of solvent in the CVD process enables the growth of high-purity layers and avoids the potential of dewetting phenomena, which lead to pinhole defects. By limiting contaminants and defects, ultrathin (<10 nm) CVD polymeric device layers have been fabricated in multiple laboratories. The CVD method is particularly suitable for synthesizing insoluble conductive polymers, layers with high densities of organic functional groups, and robust crosslinked networks. Additionally, CVD polymers are prized for the ability to conformally cover rough surfaces, like those of paper and textile substrates, as well as the complex geometries of micro- and nanostructured devices. By employing low processing temperatures, CVD polymerization avoids damaging substrates and underlying device layers. This report discusses the mechanisms of the major CVD polymerization techniques and the recent progress of their applications in devices and device fabrication, with emphasis on initiated CVD (iCVD) and oxidative CVD (oCVD) polymerization.

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Tunable Low Bandgap Polyisothianaphthene via Oxidative Chemical Vapor Deposition

Cited by 17 publications

References 81 publications

25th Anniversary Article: CVD Polymers: A New Paradigm for Surface Modifi cation and Device Fabrication

25th Anniversary Article: CVD Polymers: A New Paradigm for Surface Modifi cation and Device Fabrication

Device Fabrication Based on Oxidative Chemical Vapor Deposition (oCVD) Synthesis of Conducting Polymers and Related Conjugated Organic Materials

CVD Polymers for Devices and Device Fabrication

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