Electrochromic enhancement of poly(3,4‐ethylenedioxythiophene) films functionalized with hydroxymethyl and ethylene oxide

2‐((2,3‐Dihydrothieno[3,4‐b]dioxin‐2‐yl)methoxy)methyl oxirane (EDOT‐MO) was successfully synthesized by the reaction of epichlorohydrin with hydroxymethylated‐3,4‐ethylenedioxylthiophene (EDOT‐MeOH), which was synthesized via a simple four‐step sequence. Poly(hydroxymethylated‐3,4‐ethylenedioxylthiophene) (PEDOT‐MeOH) and poly(2‐((2,3‐dihydrothieno[3,4‐b]dioxin‐2‐yl)methoxy)methyl oxirane) (PEDOT‐MO) were electrosynthesized through electropolymerization of EDOT‐MeOH and EDOT‐MO, respectively. Structural, electrochemical, optical, and thermal properties of as‐formed polymers were investigated by FTIR, cyclic voltammetry, UV–vis, and thermogravimetry. Spectroelectrochemistry studies demonstrated that PEDOT‐MeOH and PEDOT‐MO could be reversibly oxidized and reduced accompany with obvious color changes. Further kinetic studies demonstrated that the introduction of hydroxymethyl or ethylene oxide group significantly improved electrochromic properties of 3,4‐ethylenedioxythiophene (PEDOT) and resulted in high contrast ratios (57.3% at 585 nm) and coloration efficiencies (338.5 cm² C^?1), low switching voltages, and fast response time. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1989–1999     

A Free‐standing electrochromic material of poly(5,7‐bis(2‐(3,4‐ethylenedioxy)thienyl)‐indole) and its application in electrochromic device

Free‐standing poly(5,7‐bis(2‐(3,4‐ethylenedioxy)thienyl)‐indole) (PETI) was electrochemically obtained from 5,7‐bis(2‐(3,4‐ethylenedioxy)thienyl)‐indole (ETI) prepared by Stille coupling reaction of 5,7‐dibromoindole and 3,4‐ethylenedioxythiophene. For comparison, poly(5,7‐bis(2‐thiophene)‐indole) was also electrosynthesized from 5,7‐bis(2‐thiophene)‐indole (BTI) which was prepared from the 5,7‐dibromoindole and thiophene. Characterizations of ETI and BTI were performed by cyclic voltammetry, scanning electron microscopy, ¹H NMR, and ¹³C NMR spectroscopy. Spectroelectrochemical studies showed PETI had better electrochromic properties and showed two different colors (brown and blue‐violet) under various potentials with better maximum contrast (ΔT%) and coloration efficiency (CE). An electrochromic device (ECD) based on PETI and poly(3,4‐ethylenedioxythiophene) (PEDOT) was also constructed and characterized. This ECD had fast response time, high CE, better optical memory, and long‐term stability. These results indicated that PETI had potential applications for ECD. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2356–2364     

Thermoelectric properties of PEDOT films prepared by electrochemical polymerization

Thermoelectric (TE) properties of flexible and free‐standing poly(3,4‐ethylenedioxythiophene) (PEDOT) films synthesized via galvanostatic polymerization of 3,4‐ethylenedioxythiophene in propylene carbonate containing sulfated poly(β‐hydroxyethers) (S‐PHE) as polymer electrolyte were elaborately studied. Both electrical conductivities (σ ) and Seebeck coefficients (S ) of the PEDOT:S‐PHE films were increased by decreasing the temperature (T ) or by increasing the current density (J ) during electrosynthesis. Possible reasons for the lack of a trade‐off relation commonly observed between σ and S are discussed on the basis of SEM and oxidation‐level measurements. Preparation of the PEDOT:S‐PHE films was optimized with respect to T and J . In addition, the oxidation level of the PEDOT:S‐PHE films was controlled by potential and the change of their TE performances was discussed in conjunction with the change of chemical species involved. The power factor (PF = σS ²) of the PEDOT:S‐PHE films reached 7.9 μW m^?1 K^?2, leading to a dimensionless TE figure‐of‐merit (ZT ) of 0.013. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 524–531     

Low band‐gap diketopyrrolopyrrole‐containing polymers for near infrared electrochromic and photovoltaic applications

Donor–acceptor type polymers bearing diketopyrrolopyrrole and 3,4‐ethylenedioxythiophene units are reported. The polymers are green and exhibit very low band‐gaps (1.19 eV) with strong and broad absorption (maxima of about 830 nm) in the near infrared (NIR) region in their neutral film states. The polymers display color changes between dark green and light blue with exceptional optical contrasts in the NIR regions of up to 78 and 63% as thin films and single‐layer electrochromic devices, respectively. Fast switching, good stabilities as well as high coloration efficiencies (743–901 cm² C^?1) were also observed. The polymers could also be potentially used as photovoltaic material, with a power conversion efficiency of up to 1.68%. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1287–1295     

Effects of additives and post‐treatment on the thermoelectric performance of vapor‐phase polymerized PEDOT films

Vapor‐phase polymerization (VPP) is an important method for the fabrication of high‐quality conducting polymers, especially poly(3,4‐ethylenedioxythiophene) (PEDOT). In this work, the effects of additives and post‐treatment solvents on the thermoelectric (TE) performance of VPP‐PEDOT films were systematically investigated. The use of 1‐butyl‐3‐menthylinidazolium tetrafluoroborate ([BMIm][BF₄], an ionic liquid) was shown to significantly enhance the electrical conductivity of VPP‐PEDOT films compared with other additives. The VPP‐PEDOT film post‐treated with mixed ethylene glycol (EG)/[BMIm][BF₄] solvent displayed the high power factor of 45.3 μW m^?1 K^?2 which is 122% higher than that prepared without any additive or post‐treatment solvent, along with enhanced electrical conductivity and Seebeck coefficient. This work highlighted the superior effect of the [BMIm][BF₄] additive and the EG/[BMIm][BF₄] solvent post‐treatment on the TE performance of the VPP‐PEDOT film. These results should help with developing the VPP method to fabricate high‐performance PEDOT films. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 1738–1744     

Improvement in carrier mobility of poly(3,4‐ethylenedioxythiophene) nanowires synthesized in porous alumina templates

Polymeric nanowires of poly(3,4‐ethylenedioxythiophene) (PEDOT) are electrochemically synthesized using porous anodic alumina oxide (AAO) membranes as templates. Four‐point resistivity measurements on more than 100 PEDOT nanowires with different diameters (50–250 nm) reveal a statistically significant size‐dependent phenomenon in which the nanowires with a smaller diameter exhibit higher conductivity. Structural characterization with Raman spectroscopy and doping level estimation with energy‐dispersive X‐ray spectrometry and X‐ray photoelectron spectroscopy indicate that the observed conductivity enhancement can be attributed to improved carrier mobility in PEDOT nanowires having an elongated conjugation structure because of the effect of the AAO template. From the estimated doping levels (～5%) and conductivity data (～100 S/cm), it is found that the carrier mobility reach 2.0 cm²/V s for the nanowire with the smallest diameter, as compared with 4.0 × 10^?4 cm²/V s for a bulk PEDOT film. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Fabrication of poly(vinyl alcohol)‐graphene quantum dots coated with poly(3,4‐ethylenedioxythiophene) for supercapacitor

Conducting nanofiber composed of poly(vinyl alcohol) (PVA), graphene quantum dots (GQDs) and poly(3,4‐ethylenedioxythiophene) (PEDOT) was prepared for symmetrical supercapacitor through electrospinning and electropolymerization techniques. The formation of PVA nanofibers with the addition of GQDs was excellently prepared with the average diameter of 55.66 ± 27 nm. Field emission scanning electron microscopy images revealed that cauliflower‐like structure of PEDOT was successfully coated on PVA‐GQD electrospun nanofibers. PVA‐GQD/PEDOT nanocomposite exhibited the highest specific capacitance of 291.86 F/g compared with PVA/PEDOT (220.73 F/g) and PEDOT (161.48 F/g). PVA‐GQD/PEDOT also demonstrated a high specific energy and specific power of 16.95 and 984.48 W/kg, respectively, at 2.0 A/g current density. PVA‐GQD/PEDOT exhibited the lowest resistance of charge transfer (R_ct) and equivalent series resistance compared with PEDOT and PVA/PEDOT, indicating that the fast ion diffusion between the electrode and electrolyte interface. PVA‐GQD/PEDOT nanocomposite also showed an excellent stability with retention of 98% after 1000 cycles. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 50–58     

Room temperature polymerization of poly(3,4‐ethylenedioxythiophene) as transparent counter electrodes for dye‐sensitized solar cells

Poly(3,4‐ethylenedioxythiophene) (PEDOT) counter electrode is prepared with in situ polymerization of 3,4‐ethylenedioxythiophene on a fluorine‐doped tin oxide over‐layer glass at room temperature. The cyclic voltammetry, electrochemical impedance spectroscopy, and Tafel polarization are measured to evaluate the catalytic activity of PEDOT counter electrode for I₃^?/I^? redox couple. Comparing the data with that of traditional thermal decomposed Pt counter electrode, it is found that PEDOT has higher catalytic activity than that of Pt counterpart. Power conversion efficiency of the dye‐sensitized solar cell (DSC) with PEDOT counter electrode can attain to 7.713%, a little higher than that of the cell with Pt counter electrode (7.300%). Taking the advantage of high transparency of PEDOT counter electrode, an Ag mirror is put on the back side of PEDOT counter electrode of the DSC to reflect light back for power conversion. Power conversion efficiency of the DSC with this special structure can be further enhanced to 8.359%, which mainly stems from the improved short‐circuit current density by the increased irradiated light intensity. Copyright © 2014 John Wiley & Sons, Ltd.     

Tuning of PEDOT:PSS Properties Through Covalent Surface Modification

Conductive polymer (poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonate) (PEDOT:PSS) is an attractive platform for the design of flexible electronic, optoelectronic, and (bio)sensor devices. Practical application of PEDOT:PSS often requires an incorporation of specific molecules or moieties for tailoring of its physical–chemical properties. In this article, a method for covalent modification of PEDOT:PSS using arenediazonium tosylates was proposed. The procedure includes two steps: chemisorption of diazo‐cations on the PEDOT:PSS surface followed by thermal decomposition of the diazonium salt and the covalent bond formation. Structural and surface properties of the samples were evaluated by XPS, SEM‐EDX, AFM, goniometry, and a range of electric and optical measurements. The developed modification procedure enables tuning of the PEDOT:PSS surface properties such as conductivity and optical absorption. The possibility to introduce various organic functional groups (from hydrophilic to hydrophobic) and to create new groups for further functionalization makes the developed procedure multipurpose. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 378–387     

Synthesis,characterization, and electroluminescence of novel copolyfluorenes and their applications in white light emission

New copolyfluorenes (PC8OF0–PC8OF50) comprised of 9,9‐dioctylfluorene and jacketed units 2,5‐bis[(5‐octyloxy‐phenyl)‐1,3,4‐ oxadiazole]‐1‐(3,5‐dibromophenyl)‐benzene (35C8) were synthesized by palladium‐catalyzed Suzuki coupling reaction. They were characterized by molecular weight determination, ¹H NMR, elemental analysis, DSC, TGA, absorption and emission spectroscopy, and cyclic voltammetry (CV). These copolymers were readily soluble in common organic solvents and exhibited high glass transition temperature and thermal stability.The copolymer films showed absorption peaks from 381 nm to 351 nm, and PL peaks from 432 nm to 421 nm with a blue shift originated from 35C8 units. Both the HOMO energy levels and LUMO levels changed little as the content of 35C8 units increased (?5.59 eV to ?5.48 eV and ?2.60 eV to ?2.49 eV). Electroluminescent devices: ITO/PEDOT:PSS[poly(ethylenedioxythiophene):polystyrenesulfonate]/polymer/Ca (25 nm)/Ag(80 nm) (a), ITO/PEDOT:PSS/polymer/TPBI [1,3,5‐ tris(N‐phenylbenzimidazol‐2‐yl)benzene](15 nm)/Mg:Ag(10:1, wt)/Ag (b), and ITO/ PEDOT:PSS/PVK[Poly(N‐vinylcarbazole)]/polymer/TPBI(15 nm)/Ca(25 nm)/Ag(80 nm) (c) were fabricated to investigate the influence of jacketed contents and device architectures on emission characteristics. The maximum brightness and current efficiency of the PC8OF25 device (5097.8 cd/m² and 0.484 cd/A) surpassed those of the PC8OF0 device (3122.8 cd/m² and 0.416 cd/A). The EL emissions of PC8OF0 – PC8OF50 were pure blue and low‐energy excimer emission bands were successfully suppressed, indicating that these copolymers could be good candidates for blue light‐emitting materials. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4555–4565, 2009     

Enzymatic‐catalyzed polymerization of water‐soluble electrically conductive polymer PEDOT:PSS

Water‐soluble electrically conductive polymer poly(3,4‐ethylenedioxythiophene) (PEDOT) was synthesized by the enzymatic‐catalyzed method using 3,4‐ethylenedioxythiophene (EDOT) as monomer, poly(styrenesulfonate) (PSS) as water‐soluble polyelectrolyte, horseradish peroxidase enzyme as catalyst, and hydrogen peroxide (H₂O₂) as oxidant. Fourier transform infrared spectra and UV–vis absorption spectra confirm the successful enzymatic‐catalyzed polymerization of PEDOT. Dynamic light scattering data confirm the formation of a stable PEDOT:PSS aqueous dispersion. The thermo gravimetric data show that the obtained PEDOT is stable over a fairly high range of temperatures. The atomic force microscopy height images show that the PEDOT:PSS aqueous dispersion can form excellent homogeneous and smooth films on various substrates by conventional solution processing techniques, which renders this PEDOT:PSS aqueous dispersion a very promising candidate for various application in electronic devices. This enzymatic polymerization is a new approach for the synthesis of optical and electrical active PEDOT polymer, which benefits simple setting, high yields, and environmental friendly route. Copyright © 2014 John Wiley & Sons, Ltd.     

Highly enhanced thermoelectric performance of WS2 nanosheets upon embedding PEDOT:PSS

Two‐dimensional (2D) WS₂ nanosheets (NSs) as a promising thermoelectric (TE) material have gained great concern recently. The low electrical conductivity significantly limits its further development. Herein, we reported an effective method to enhance the TE performance of WS₂ NSs by combining poly(3,4‐ethylenedioxythiophene):poly(4‐styrenesulfonate) (PEDOT:PSS). The restacked WS₂ NSs thin film with 1T phase structure obtained by a common chemical lithium intercalation show a high Seebeck coefficient of 98 μV K^?1 and a poor electrical conductivity of 12.5 S cm^?1. The introduction of PEDOT:PSS with different contents obviously improve the electrical conductivity of WS₂ NSs thin films. Although a declining Seebeck coefficient was observed, an optimized TE power factor of 45.2 μW m^?1 k^?1 was achieved for WS₂/PEDOT:PSS composite thin film. Moreover, the as‐prepared WS₂/PEDOT:PSS thin film can be easily peeled off and transferred to other substrate leading to a more promising application. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 997–1004     

Enhancing electrochromic properties of conducting polymers via copolymerization: Copolymer of 1‐(4‐fluorophenyl)‐2,5‐di(thiophen‐2‐yl)‐1H‐pyrrole with 3,4‐ethylene dioxythiophene

A copolymer of 1‐(4‐fluorophenyl)‐2,5‐di(thiophen‐2‐yl)‐1H‐pyrrole (FPTP) with 3,4‐ethylene dioxythiophene (EDOT) was electrochemically synthesized and characterized. While poly(FPTP) (P(FPTP)) has only two colors in its oxidized and neutral states (blue and yellow), its copolymer with EDOT has five different colors (purple, red, light gray, green, and blue). Electrochromic devices based on P(FPTP‐co‐EDOT) and poly(3,4‐ethylenedioxythiophene) (PEDOT) were constructed and characterized. The oxidized state of the device shows blue color whereas it shows purple for the reduced state. At several potentials the device has good transparency with green and gray colors. Maximum contrast (Δ%T) and switching time of the device were measured as 23% and 1.1 s at 555 nm. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4496–4503, 2007     

Growth of poly(3,4‐ethylenedioxythiophene) films prepared by base‐inhibited vapor phase polymerization

Transparent [90% transmittance at 550 nm at a sheet resistance (R_s) of 279 Ω sq^?1] poly(3,4‐ethylenedioxythiophene) (PEDOT) films with electrical conductivities up to 1354 S cm^?1 are prepared using base‐inhibited vapor phase polymerization at atmospheric pressure. The influence of reaction conditions, such as temperature and growth time, on the film formation is investigated. A simple and convenient two‐electrode method is used for the in situ measurement of resistance, enabling to investigate the growth mechanism of polymer films and the influence of different parameters (relative humidity and the amount of oxidant) on the film growth. Low humidity exerts a detrimental effect on film growth and conductivity. In situ R_s measurements suggest that a large structural change occurs upon washing the PEDOT‐oxidant film. © 2014 Wiley Periodicals, Inc. J Polym Sci Part B: Polym. Phys. 2014 , 52, 561–571     

Properties of In situ polymerized poly(3,4‐ethylenedioxythiophene)/alumina composites for energy storage applications

Composites formed by poly(3,4‐ethylenedioxythiophene) and alumina (PEDOT/Al₂O₃) have been prepared by in situ anodic polymerization. For this purpose, the stability of 1:1 and 4:1 monomer:alumina aqueous solutions has been examined as a function of the pH (2.3, 4.0, 7.0, 8.8, or 10.8). Results indicate that the monomer behaves as a dispersant that remains stable at the studied basic pHs despite they are close to the isoelectric point of alumina. Although the thermal stability of the composites is considerably affected by the pH of the reaction medium, its influence on the surface morphology is very small. Independently, of the synthetic conditions, the electrochemical properties were better for PEDOT/Al₂O₃ than for pure PEDOT, reflecting that alumina particles promote the charge mobility. The highest specific capacitance (SC; 141 F/g), which was 55% higher than that obtained for pure PEDOT, was achieved for the composite prepared at pH = 8.8 using a 4:1 monomer:alumina ratio. These conditions favor the participation of OH^– groups as secondary doping agents without degrading the polymer matrix and enhance the specific surface of the films, facilitating the ionic mobility. On the other hand, application of a multi‐step polymerization strategy has shown that interfaces originated by consecutive steps enhance the SC. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1131–1141     

Effect of (3‐glycidyloxypropyl)trimethoxysilane (GOPS) on the electrical properties of PEDOT:PSS films

Poly(3,4‐ethylenedioxythiophene) doped with poly(styrenesulfonate) (PEDOT:PSS) has been reported as a successful functional material in a broad variety of applications. One of the most important advantages of PEDOT:PSS is its water‐solubility, which enables simple and environmental friendly manufacturing processes. Unfortunately, this also implies that pristine PEDOT:PSS films are unsuitable for applications in aqueous environments. To reach stability in polar solvents, (3‐glycidyloxypropyl)trimethoxysilane (GOPS) is typically used to cross‐link PEDOT:PSS. Although this strategy is widely used, its mechanism and effect on PEDOT:PSS performance have not been articulated yet. Here, we present a broad study that provides a better understanding of the effect of GOPS on the electrical and electronic properties of PEDOT:PSS. We show that the GOPS reacts with the sulfonic acid group of the excess PSS, causing a change in the PEDOT:PSS film morphology, while the oxidation level of PEDOT remains unaffected. This is at the origin of the observed conductivity changes. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 814–820     

One‐step Synthesis and Enhanced Thermoelectric Properties of Polymer–Quantum Dot Composite Films

Conventional syntheses of polymer–inorganic composite thermoelectric materials suffer major problems such as inhomogeneity, large particle size, and oxidation that result in ineffective loading. Now a one‐step synthesis can be used to fabricate high‐quality small‐sized anions codoped poly(3,4‐ethylenedioxythiophene):dodecylbenzenesulfonate/Cl‐tellurium (PEDOT:DBSA/Cl‐Te) composite films using a series of novel Te^IV‐based oxidants. The synchronized production of PEDOT and Te results in thick and homogeneous films containing evenly distributed and well‐protected Te quantum dots. Owing to the heavily doped crystalline polymer matrix as well as the <5 nm unoxidized Te quantum dot loading, at low Te concentrations as 2.1–5.8 wt %, the films exhibits high power factors of about 100 μW m^?1 K^?2, which is 50 % higher compared to a pure PEDOT:DBSA film.     

Improved Electrochromic Performance of Poly(3,4‐ethylenedioxythiophene) by Incorporating a Three‐Dimensionally Ordered Macroporous Structure

In this paper, three‐dimensionally ordered macroporous (3DOM) poly(3,4‐ethylenedioxythiophene) (PEDOT) films were electropolymerized from an ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([Bmim]PF₆). The electrochromic performances of the 3DOM PEDOT films were studied. The 3DOM films exhibited high transmittance modulation (41.2 % at λ=580 nm), high ionic fast switching speeds (0.7 and 0.7 s for coloration and bleaching, respectively), and enhanced cycling stability relative to that exhibited by the dense PEDOT film. The relationship between the declining behavior of the transmittance modulation and the nanostructure of the film was investigated. A three‐period decay process was proposed to understand the declining behavior. The 3D interconnected macroporous nanostructure is beneficial for fast ion and electron transportation, high ion accessibility, and maintenance of structure integrity, which result in enhanced cycling stability and fast switching speeds.     

A Solution‐processible,n‐dopable polypyrrole derivative

In this study, soluble, n‐dopable, florescent, electrochromic polypyrrole derivative was synthesized through both chemical and electrochemical polymerization of 2‐[6‐(1H‐pyrrol‐1‐yl)hexyl]‐1H‐benzo[de]isoquinoline‐1,3(2H)‐dione (PyNI). The polymer synthesized through chemical polymerization had PL emission maxima at 471 and 543 nm and exhibited two redox couples at E_1/2,p = ?1.48 V and E_1/2,p = 1.12 V due to n‐type and p‐type doping, respectively. Electrochromic properties of electrochemically synthesized poly(PyNI) (PPyNI) were investigated via spectroelectrochemistry, kinetic studies, coloration efficiency, and colorimetry measurements. The optical band gap of PPyNI was calculated as 2.99 and 2.37 eV. Spectroelectrochemistry analysis of PPyNI reflected electronic transitions at 330–418 nm and 704 nm due to π–π* transition and charge carrier band formation, respectively. The polymer exhibited a switching time of 1.63 s and an optical contrast of 33.37%. Furthermore, dual‐type, complementary‐colored polymer electrochromic device in ITO/PPyNI/PEDOT/ITO configuration was assembled and characterized. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Charge transport and structure in semimetallic polymers

Owing to changes in their chemistry and structure, polymers can be fabricated to demonstrate vastly different electrical conductivities over many orders of magnitude. At the high end of conductivity is the class of conducting polymers, which are ideal candidates for many applications in low‐cost electronics. Here, we report the influence of the nature of the doping anion at high doping levels within the semi‐metallic conducting polymer poly(3,4‐ethylenedioxythiophene) (PEDOT) on its electronic transport properties. Hall effect measurements on a variety of PEDOT samples show that the choice of doping anion can lead to an order of magnitude enhancement in the charge carrier mobility > 3 cm²/Vs at conductivities approaching 3000 S/cm under ambient conditions. Grazing Incidence Wide Angle X‐ray Scattering, Density Functional Theory calculations, and Molecular Dynamics simulations indicate that the chosen doping anion modifies the way PEDOT chains stack together. This link between structure and specific anion doping at high doping levels has ramifications for the fabrication of conducting polymer‐based devices. © 2017 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 97–104