Recent advances in the synthesis of conducting polymers from the vapour phase

Brooke, Robert; Cottis, Philip; Talemi, Pejman; Fabretto, Manrico; Murphy, Peter; Evans, Drew

doi:10.1016/j.pmatsci.2017.01.004

Cited by 116 publications

(92 citation statements)

References 147 publications

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“…The strong interest to PEDOT is motivated by a number of reasons: a doped and post‐treated PEDOT exhibits a high electrical conductivity exceeding 3000 S cm −1 with excellent optical properties being transparent in the visible range but changing color upon doping . PEDOT is one of the most air‐ and thermally stable conducting polymers with well‐developed and relative simple synthesis methods allowing device manufacturing and printing on a large scale . Also, PEDOT supports both electronic and ionic transport, which makes it the material of choice for biolectronics applications as well as for energy devices such as supercapacitors and fuel cells …”

Section: Introduction and Formulation Of The Problemmentioning

confidence: 99%

Understanding the Impact of Film Disorder and Local Surface Potential in Ultraviolet Photoelectron Spectroscopy of PEDOT

Muñoz

Crispin

Fahlman

et al. 2017

Macromol. Rapid Commun.

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The spectra of conducting polymers obtained using ultraviolet photoelectron spectroscopy (UPS) exhibit a typical broadening of the tail σ ≈ 1 eV, which by an order of magnitude exceeds a commonly accepted value of the broadening of the tail of the density of states σ ≈ 0.1 eV obtained using transport measurements. In this work, an origin of this anomalous broadening of the tail of the UPS spectra in a doped conducting polymer, PEDOT (poly(3,4-ethylenedioxythiophene)), is discussed. Based on the semiempirical approach and using a realistic morphological model, the density of valence states in PEDOT doped with molecular counterions is computed. It is shown that due to a disordered character of the material with randomly distributed counterions, the localized charge carriers in PEDOT crystallites experience spatially varying electrostatic potential. This leads to spatially varying local vacuum levels and binding energies. Taking this variation into account the UPS spectrum is obtained with the broadening of the tail comparable to the experimentally observed one. The results imply that the observed broadening of the tail of the UPS spectra in PEDOT provides information about a disordered spatially varying potential in the material rather than the broadening of the DOS itself.

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Section: Introduction and Formulation Of The Problemmentioning

confidence: 99%

Understanding the Impact of Film Disorder and Local Surface Potential in Ultraviolet Photoelectron Spectroscopy of PEDOT

Muñoz

Crispin

Fahlman

et al. 2017

Macromol. Rapid Commun.

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“…The oxidant strength is related to the standard electrode potential of the cation. CuCl 2 with the standard electrode potential of 0.33 V is a weaker oxidant in comparison with the FeCl 3 with the standard electrode potential of 0.77 V …”

Section: Ocvd Synthesis Chemistrymentioning

confidence: 94%

“…The Fe(Tos) 3 exhibits a lower vapor pressure than FeCl 3 , making Fe(Tos) 3 more difficult to use for oCVD or oMLD. Additionally, Fe(Tos) 3 has a weaker oxidation strength, and a slower polymerization rate compared to the FeCl 3 . The summary of common monomers and oxidants in the oCVD method is listed in Table 1 .…”

Section: Ocvd Synthesis Chemistrymentioning

confidence: 99%

“…In the case of PECVD, the plasma excitation results in some degree of monomer fragmentation and the resulting films have limited electrical conductivity. The VPP approach, which has recently been reviewed, requires two steps: application of an oxidant as a solid or solution, followed by exposure to monomer vapors. As the VPP oxidant is consumed, the ratio of oxidant to monomer at the surface varies over the deposition period.…”

Section: Introductionmentioning

confidence: 99%

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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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“…The efficient and low‐cost synthetic methods for manufacturing PEDOT have been developed continuously to broaden the list of potential applications . Among various methods, vapor phase polymerization (VPP) has many advantages in the design and fabrication of ordered crystal structures of PEDOT films as compared to chemical oxidation and electrochemical polymerization in solution .…”

Section: Introductionmentioning

confidence: 99%

Efficient enhancement of the thermoelectric performance of vapor phase polymerized poly(3,4‐ethylenedioxythiophene) films with poly(ethyleneimine)

Jia

Liu

et al. 2019

J Polym Sci B Polym Phys

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Tuning the molecular rearrangement and oxidation level has been proven to be effective strategies for optimizing the thermoelectric (TE) performance of PEDOT. It is difficult to achieve these effects simultaneously via a one‐step process, however. In this work, we combined vapor phase polymerization (VPP) and H2SO4 post‐treatment to obtain a highly conductive PEDOT film. A novel strategy using polyethylenemine (PEI) as an effective reducing agent was employed to enhance the thermopower of the PEDOT film. Grazing‐Incidence Wide‐Angle X‐ray Scattering analysis and the changes in the oxidation level allow us to elucidate the role of PEI and its transport mechanism. It is demonstrated that the thermopower of well‐ordered crystallites in the PEDOT film significantly increases more than five times (from 11 to 59 μV K−1) by the PEI‐DMF solution immersion process, while the electrical conductivity is maintained at 100 S cm−1. The promising method connecting VPP, H2SO4, and PEI shows great potential for effectively tuning the thermopower of organic TE materials. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019, 57, 257–265

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Recent advances in the synthesis of conducting polymers from the vapour phase

Cited by 116 publications

References 147 publications

Understanding the Impact of Film Disorder and Local Surface Potential in Ultraviolet Photoelectron Spectroscopy of PEDOT

Understanding the Impact of Film Disorder and Local Surface Potential in Ultraviolet Photoelectron Spectroscopy of PEDOT

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

Efficient enhancement of the thermoelectric performance of vapor phase polymerized poly(3,4‐ethylenedioxythiophene) films with poly(ethyleneimine)

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