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Title: High electrical conductivity and carrier mobility in oCVD PEDOT thin films by engineered crystallization and acid treatment

Abstract

Air-stable, lightweight, and electrically conductive polymers are highly desired as the electrodes for next-generation electronic devices. However, the low electrical conductivity and low carrier mobility of polymers are the key bottlenecks that limit their adoption. We demonstrate that the key to addressing these limitations is to molecularly engineer the crystallization and morphology of polymers. We use oxidative chemical vapor deposition (oCVD) and hydrobromic acid treatment as an effective tool to achieve such engineering for conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT). We demonstrate PEDOT thin films with a record-high electrical conductivity of 6259 S/cm and a remarkably high carrier mobility of 18.45 cm 2V -1s -1by inducing a crystallite-configuration transition using oCVD. Subsequent theoretical modeling reveals a metallic nature and an effective reduction of the carrier transport energy barrier between crystallized domains in these thin films. To validate this metallic nature, we successfully fabricate PEDOT-Si Schottky diode arrays operating at 13.56 MHz for radio frequency identification (RFID) readers, demonstrating wafer-scale fabrication compatible with conventional complementary metal-oxide semiconductor (CMOS) technology. The oCVD PEDOT thin films with ultrahigh electrical conductivity and high carrier mobility show great promise for novel high-speed organic electronics with low energy consumption and better charge carrier transport.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1];  [1];  [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1];  [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. Baylor Univ., Waco, TX (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Excitonics (CE). Solid-State Solar-Thermal Energy Conversion Center (S3TEC); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1499938
Grant/Contract Number:  
[SC0001088; SC0001299]
Resource Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
[ Journal Volume: 4; Journal Issue: 9]; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 42 ENGINEERING; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wang, Xiaoxue, Zhang, Xu, Sun, Lei, Lee, Dongwook, Lee, Sunghwan, Wang, Minghui, Zhao, Junjie, Shao-Horn, Yang, Dincă, Mircea, Palacios, Tomás, and Gleason, Karen K. High electrical conductivity and carrier mobility in oCVD PEDOT thin films by engineered crystallization and acid treatment. United States: N. p., 2018. Web. doi:10.1126/sciadv.aat5780.
Wang, Xiaoxue, Zhang, Xu, Sun, Lei, Lee, Dongwook, Lee, Sunghwan, Wang, Minghui, Zhao, Junjie, Shao-Horn, Yang, Dincă, Mircea, Palacios, Tomás, & Gleason, Karen K. High electrical conductivity and carrier mobility in oCVD PEDOT thin films by engineered crystallization and acid treatment. United States. doi:10.1126/sciadv.aat5780.
Wang, Xiaoxue, Zhang, Xu, Sun, Lei, Lee, Dongwook, Lee, Sunghwan, Wang, Minghui, Zhao, Junjie, Shao-Horn, Yang, Dincă, Mircea, Palacios, Tomás, and Gleason, Karen K. Fri . "High electrical conductivity and carrier mobility in oCVD PEDOT thin films by engineered crystallization and acid treatment". United States. doi:10.1126/sciadv.aat5780. https://www.osti.gov/servlets/purl/1499938.
@article{osti_1499938,
title = {High electrical conductivity and carrier mobility in oCVD PEDOT thin films by engineered crystallization and acid treatment},
author = {Wang, Xiaoxue and Zhang, Xu and Sun, Lei and Lee, Dongwook and Lee, Sunghwan and Wang, Minghui and Zhao, Junjie and Shao-Horn, Yang and Dincă, Mircea and Palacios, Tomás and Gleason, Karen K.},
abstractNote = {Air-stable, lightweight, and electrically conductive polymers are highly desired as the electrodes for next-generation electronic devices. However, the low electrical conductivity and low carrier mobility of polymers are the key bottlenecks that limit their adoption. We demonstrate that the key to addressing these limitations is to molecularly engineer the crystallization and morphology of polymers. We use oxidative chemical vapor deposition (oCVD) and hydrobromic acid treatment as an effective tool to achieve such engineering for conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT). We demonstrate PEDOT thin films with a record-high electrical conductivity of 6259 S/cm and a remarkably high carrier mobility of 18.45 cm2V-1s-1by inducing a crystallite-configuration transition using oCVD. Subsequent theoretical modeling reveals a metallic nature and an effective reduction of the carrier transport energy barrier between crystallized domains in these thin films. To validate this metallic nature, we successfully fabricate PEDOT-Si Schottky diode arrays operating at 13.56 MHz for radio frequency identification (RFID) readers, demonstrating wafer-scale fabrication compatible with conventional complementary metal-oxide semiconductor (CMOS) technology. The oCVD PEDOT thin films with ultrahigh electrical conductivity and high carrier mobility show great promise for novel high-speed organic electronics with low energy consumption and better charge carrier transport.},
doi = {10.1126/sciadv.aat5780},
journal = {Science Advances},
number = [9],
volume = [4],
place = {United States},
year = {2018},
month = {9}
}

Journal Article:
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Cited by: 16 works
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Figures / Tables:

Fig. 1. Fig. 1.: The crystallization-orientation transition induced by engineered deposition temperature and film thickness. (A) Schematic representation of the face-on stacking in the ultrathin films (left) and the edge-on stacking in the thick films (right). (B) Schematic showing high crystallinity is induced by high deposition temperature in the face-on regime. Themore » chemical structure of PEDOT is shown on the right. (C) Room temperature XRD maps (θ-2θ) of 10-nm PEDOT thin film deposited at 300°C (left) [the inset is the schematic of the face-on stacking (0k0)], 248-nm PEDOT thin film deposited at 190°C (middle) [the inset is the schematic of the edge-on stacking (h00)], and 23-nm PEDOT thin film deposited at 300°C (right). a.u., arbitrary units. (D) Room temperature XRD pattern for face-on samples deposited at different substrate temperatures. Note that the peak intensity is increasing as the deposition temperature increases. The deposition temperature and the film thickness are included in the figure. (E) Bar chart summarizing the room temperature XRD results. The length of each bar is the normalized integrated intensity of the edge-on (red) or face-on (blue) stacking peak. Here, to visualize the intensity of both kinds of peaks together, we normalize the peak intensity by converting the edge-on intensity (at 2θ~ 6.5°) to equivalent face-on intensity (at 2θ~ 26°) using the Lorentz-polarization factor. In the face-on regime, the crystallinity (closely related to the normalized intensity) increases markedly with increasing deposition temperature.« less

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