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Title: Printing 2D Conjugated Polymer Monolayers and Their Distinct Electronic Properties

Abstract

Abstract Recently, 2D monolayer films of conjugated polymers have gained increasing attention owing to the preeminence of 2D inorganic films that exhibit unique optoelectronic and mechanical properties compared to their bulk analogs. Despite numerous efforts, crystallization of semiconducting polymers into highly ordered 2D monolayer films still remains challenging. Herein, a dynamic‐template‐assisted meniscus‐guided coating is utilized to fabricate continuous, highly ordered 2D monolayer films of conjugated polymers over a centimeter scale with enhanced backbone π–π stacking. In contrast, monolayer films printed on solid substrates confer upon the 1D fiber networks strong alkyl side‐chain stacking at the expense of backbone packing. From single‐layers to multilayers, the polymer π‐stacks change from edge‐on to bimodal orientation as the film thickness reaches ≈20 nm. Spectroscopic and cyclic voltammetry analysis reveals an abrupt increase in J‐aggregation and absorption coefficient and a decrease in bandgap and highest occupied molecular orbital level until critical thickness, possibly arising from the straightened polymer backbone. This is corroborated by an abrupt increase in hole mobility with film thickness, reaching a maximum of 0.7 cm 2 V −1 s −1 near the critical thickness. Finally, fabrication of chemical sensors incorporating polymer films of various thicknesses is demonstrated, and an ultrahigh sensitivity ofmore » the ≈7 nm thick ultrathin film (bilayers) to 1 ppb ammonia is shown.« less

Authors:
 [1];  [1];  [2];  [1];  [2]; ORCiD logo [1]
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  1. Department of Chemical and Biomolecular Engineering University of Illinois at Urbana‐Champaign 600 South Mathews Avenue Urbana IL 61801 USA
  2. Department of Chemistry University of Illinois at Urbana‐Champaign 505 S Mathews Avenue Urbana IL 61801 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1598082
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Name: Advanced Functional Materials Journal Volume: 30 Journal Issue: 12; Journal ID: ISSN 1616-301X
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Kafle, Prapti, Zhang, Fengjiao, Schorr, Noah B., Huang, Kai‐Yu, Rodríguez‐López, Joaquín, and Diao, Ying. Printing 2D Conjugated Polymer Monolayers and Their Distinct Electronic Properties. Germany: N. p., 2020. Web. doi:10.1002/adfm.201909787.
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Kafle, Prapti, Zhang, Fengjiao, Schorr, Noah B., Huang, Kai‐Yu, Rodríguez‐López, Joaquín, & Diao, Ying. Printing 2D Conjugated Polymer Monolayers and Their Distinct Electronic Properties. Germany. https://doi.org/10.1002/adfm.201909787
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Kafle, Prapti, Zhang, Fengjiao, Schorr, Noah B., Huang, Kai‐Yu, Rodríguez‐López, Joaquín, and Diao, Ying. Thu . "Printing 2D Conjugated Polymer Monolayers and Their Distinct Electronic Properties". Germany. https://doi.org/10.1002/adfm.201909787.
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@article{osti_1598082,
title = {Printing 2D Conjugated Polymer Monolayers and Their Distinct Electronic Properties},
author = {Kafle, Prapti and Zhang, Fengjiao and Schorr, Noah B. and Huang, Kai‐Yu and Rodríguez‐López, Joaquín and Diao, Ying},
abstractNote = {Abstract Recently, 2D monolayer films of conjugated polymers have gained increasing attention owing to the preeminence of 2D inorganic films that exhibit unique optoelectronic and mechanical properties compared to their bulk analogs. Despite numerous efforts, crystallization of semiconducting polymers into highly ordered 2D monolayer films still remains challenging. Herein, a dynamic‐template‐assisted meniscus‐guided coating is utilized to fabricate continuous, highly ordered 2D monolayer films of conjugated polymers over a centimeter scale with enhanced backbone π–π stacking. In contrast, monolayer films printed on solid substrates confer upon the 1D fiber networks strong alkyl side‐chain stacking at the expense of backbone packing. From single‐layers to multilayers, the polymer π‐stacks change from edge‐on to bimodal orientation as the film thickness reaches ≈20 nm. Spectroscopic and cyclic voltammetry analysis reveals an abrupt increase in J‐aggregation and absorption coefficient and a decrease in bandgap and highest occupied molecular orbital level until critical thickness, possibly arising from the straightened polymer backbone. This is corroborated by an abrupt increase in hole mobility with film thickness, reaching a maximum of 0.7 cm 2 V −1 s −1 near the critical thickness. Finally, fabrication of chemical sensors incorporating polymer films of various thicknesses is demonstrated, and an ultrahigh sensitivity of the ≈7 nm thick ultrathin film (bilayers) to 1 ppb ammonia is shown.},
doi = {10.1002/adfm.201909787},
journal = {Advanced Functional Materials},
number = 12,
volume = 30,
place = {Germany},
year = {Thu Feb 06 00:00:00 EST 2020},
month = {Thu Feb 06 00:00:00 EST 2020}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1002/adfm.201909787
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Works referenced in this record:

Integrated circuits based on conjugated polymer monolayer
journal, January 2018

Sensors for Breath Testing: From Nanomaterials to Comprehensive Disease Detection
journal, August 2013

  • Konvalina, Gady; Haick, Hossam
  • Accounts of Chemical Research, Vol. 47, Issue 1
  • DOI: 10.1021/ar400070m

Semiconductive Single Molecular Bilayers Realized Using Geometrical Frustration
journal, April 2018

  • Arai, Shunto; Inoue, Satoru; Hamai, Takamasa
  • Advanced Materials, Vol. 30, Issue 23
  • DOI: 10.1002/adma.201707256

Dynamic-template-directed multiscale assembly for large-area coating of highly-aligned conjugated polymer thin films
journal, July 2017

  • Mohammadi, Erfan; Zhao, Chuankai; Meng, Yifei
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms16070

Microstructure-Dependent Charge Carrier Transport of Poly(3-hexylthiophene) Ultrathin Films with Different Thicknesses
journal, April 2017

Influence of Alkyl Chain Branching Positions on the Hole Mobilities of Polymer Thin-Film Transistors
journal, September 2012

2D materials: to graphene and beyond
journal, January 2011

  • Mas-Ballesté, Rubén; Gómez-Navarro, Cristina; Gómez-Herrero, Julio
  • Nanoscale, Vol. 3, Issue 1
  • DOI: 10.1039/C0NR00323A

Tuning conformation, assembly, and charge transport properties of conjugated polymers by printing flow
journal, August 2019

  • Park, Kyung Sun; Kwok, Justin J.; Dilmurat, Rishat
  • Science Advances, Vol. 5, Issue 8
  • DOI: 10.1126/sciadv.aaw7757

Macroscopic and high-throughput printing of aligned nanostructured polymer semiconductors for MHz large-area electronics
journal, September 2015

  • Bucella, Sadir G.; Luzio, Alessandro; Gann, Eliot
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9394

Effect of the Phase States of Self-Assembled Monolayers on Pentacene Growth and Thin-Film Transistor Characteristics
journal, August 2008

  • Lee, Hwa Sung; Kim, Do Hwan; Cho, Jeong Ho
  • Journal of the American Chemical Society, Vol. 130, Issue 32
  • DOI: 10.1021/ja800142t

Understanding Film-To-Stripe Transition of Conjugated Polymers Driven by Meniscus Instability
journal, October 2018

  • Qu, Ge; Kwok, Justin J.; Mohammadi, Erfan
  • ACS Applied Materials & Interfaces, Vol. 10, Issue 47
  • DOI: 10.1021/acsami.8b13790

Solution-printed organic semiconductor blends exhibiting transport properties on par with single crystals
journal, November 2015

  • Niazi, Muhammad R.; Li, Ruipeng; Qiang Li, Er
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9598

2D materials and van der Waals heterostructures
journal, July 2016

The dedicated high-resolution grazing-incidence X-ray scattering beamline 8-ID-E at the Advanced Photon Source
journal, June 2012

  • Jiang, Zhang; Li, Xuefa; Strzalka, Joseph
  • Journal of Synchrotron Radiation, Vol. 19, Issue 4
  • DOI: 10.1107/S0909049512022017

Tailoring Structure and Field-Effect Characteristics of Ultrathin Conjugated Polymer Films via Phase Separation
journal, February 2018

  • Ge, Feng; Wei, Shiyu; Liu, Zhen
  • ACS Applied Materials & Interfaces, Vol. 10, Issue 11
  • DOI: 10.1021/acsami.7b19171

Dimensionality of charge transport in organic field-effect transistors
journal, June 2012

2D Organic Materials for Optoelectronic Applications
journal, October 2017

  • Yang, Fangxu; Cheng, Shanshan; Zhang, Xiaotao
  • Advanced Materials, Vol. 30, Issue 2
  • DOI: 10.1002/adma.201702415

Mechanism of Crystallization and Implications for Charge Transport in Poly(3-ethylhexylthiophene) Thin Films
journal, April 2014

  • Duong, Duc T.; Ho, Victor; Shang, Zhengrong
  • Advanced Functional Materials, Vol. 24, Issue 28
  • DOI: 10.1002/adfm.201304247

Calculating the trap density of states in organic field-effect transistors from experiment: A comparison of different methods
journal, January 2010

Charge transport in monolayer poly(3-hexylthiophene) thin-film transistors
journal, April 2014

Monolayer Transistor Using a Highly Ordered Conjugated Polymer as the Channel
journal, December 2006

  • Scott, J. Campbell; Samuel, J. D. Jeyaprakash; Hou, Jennifer H.
  • Nano Letters, Vol. 6, Issue 12
  • DOI: 10.1021/nl0622449

Human exhaled air analytics: biomarkers of diseases
journal, January 2007

  • Buszewski, Bogusław; Kęsy, Martyna; Ligor, Tomasz
  • Biomedical Chromatography, Vol. 21, Issue 6
  • DOI: 10.1002/bmc.835

High‐Performance Organic Thin‐Film Transistors through Solution‐Sheared Deposition of Small‐Molecule Organic Semiconductors
journal, July 2008

  • Becerril, Héctor A.; Roberts, Mark E.; Liu, Zihong
  • Advanced Materials, Vol. 20, Issue 13, p. 2588-2594
  • DOI: 10.1002/adma.200703120

Exploring the origin of high optical absorption in conjugated polymers
journal, May 2016

  • Vezie, Michelle S.; Few, Sheridan; Meager, Iain
  • Nature Materials, Vol. 15, Issue 7
  • DOI: 10.1038/nmat4645

Electrical Contact Properties between the Accumulation Layer and Metal Electrodes in Ultrathin Poly(3-hexylthiophene)(P3HT) Field Effect Transistors
journal, May 2011

  • Park, Byoungnam; Aiyar, Avishek; Hong, Jung-il
  • ACS Applied Materials & Interfaces, Vol. 3, Issue 5
  • DOI: 10.1021/am200143g

Molecular field‐effect transistors using conducting polymer Langmuir–Blodgett films
journal, March 1990

  • Paloheimo, J.; Kuivalainen, P.; Stubb, H.
  • Applied Physics Letters, Vol. 56, Issue 12
  • DOI: 10.1063/1.103182

Poly(3-hexylthiophene) monolayer nanowhiskers
journal, January 2013

  • Guo, Yan; Jiang, Lang; Ma, Xiaojing
  • Polymer Chemistry, Vol. 4, Issue 16
  • DOI: 10.1039/c3py00728f

Morphology control strategies for solution-processed organic semiconductor thin films
journal, January 2014

  • Diao, Ying; Shaw, Leo; Bao, Zhenan
  • Energy Environ. Sci., Vol. 7, Issue 7
  • DOI: 10.1039/C4EE00688G

Recent Advances in Ultrathin Two-Dimensional Nanomaterials
journal, March 2017

Ultrathin Regioregular Poly(3-hexyl thiophene) Field-Effect Transistors
journal, December 2002

  • Sandberg, Henrik G. O.; Frey, Gitti L.; Shkunov, Maxim N.
  • Langmuir, Vol. 18, Issue 26
  • DOI: 10.1021/la0261444

Enabling high-mobility, ambipolar charge-transport in a DPP-benzotriazole copolymer by side-chain engineering
journal, January 2015

  • Gruber, Mathias; Jung, Seok-Heon; Schott, Sam
  • Chemical Science, Vol. 6, Issue 12
  • DOI: 10.1039/C5SC01326G

H- and J-Aggregate Behavior in Polymeric Semiconductors
journal, April 2014

Field-Effect Carrier Transport in Poly(3-alkylthiophene) Nanofiber Networks and Isolated Nanofibers
journal, October 2010

  • Samitsu, Sadaki; Shimomura, Takeshi; Heike, Seiji
  • Macromolecules, Vol. 43, Issue 19, p. 7891-7894
  • DOI: 10.1021/ma101655s

Switching between H- and J-type electronic coupling in single conjugated polymer aggregates
journal, November 2017

High-Performance Ambipolar Diketopyrrolopyrrole-Thieno[3,2- b ]thiophene Copolymer Field-Effect Transistors with Balanced Hole and Electron Mobilities
journal, October 2011

  • Chen, Zhuoying; Lee, Mi Jung; Shahid Ashraf, Raja
  • Advanced Materials, Vol. 24, Issue 5
  • DOI: 10.1002/adma.201102786

Critical Role of Surface Energy in Guiding Crystallization of Solution-Coated Conjugated Polymer Thin Films
journal, October 2017

Efficient two layer leds on a polymer blend basis
journal, June 1995

From Convective Assembly to Landau−Levich Deposition of Multilayered Phospholipid Films of Controlled Thickness
journal, March 2009

  • Le Berre, Maël; Chen, Yong; Baigl, Damien
  • Langmuir, Vol. 25, Issue 5
  • DOI: 10.1021/la803646e

Drying of a Solution in a Meniscus: A Model Coupling the Liquid and the Gas Phases
journal, September 2010

Solution-Processed Nanoporous Organic Semiconductor Thin Films: Toward Health and Environmental Monitoring of Volatile Markers
journal, May 2017

  • Zhang, Fengjiao; Qu, Ge; Mohammadi, Erfan
  • Advanced Functional Materials, Vol. 27, Issue 23
  • DOI: 10.1002/adfm.201701117

Controlling Rigidity and Planarity in Conjugated Polymers: Poly(3,4-ethylenedithioselenophene)
journal, July 2009

  • Wijsboom, Yair H.; Patra, Asit; Zade, Sanjio S.
  • Angewandte Chemie International Edition, Vol. 48, Issue 30
  • DOI: 10.1002/anie.200901231

The meniscus-guided deposition of semiconducting polymers
journal, February 2018

Tuning charge transport in solution-sheared organic semiconductors using lattice strain
journal, December 2011

  • Giri, Gaurav; Verploegen, Eric; Mannsfeld, Stefan C. B.
  • Nature, Vol. 480, Issue 7378, p. 504-508
  • DOI: 10.1038/nature10683

A few-layer molecular film on polymer substrates to enhance the performance of organic devices
journal, December 2017

Mercury : visualization and analysis of crystal structures
journal, May 2006

  • Macrae, Clare F.; Edgington, Paul R.; McCabe, Patrick
  • Journal of Applied Crystallography, Vol. 39, Issue 3
  • DOI: 10.1107/S002188980600731X

From Monolayer to Multilayer N-Channel Polymeric Field-Effect Transistors with Precise Conformational Order
journal, January 2012

  • Fabiano, Simone; Musumeci, Chiara; Chen, Zhihua
  • Advanced Materials, Vol. 24, Issue 7
  • DOI: 10.1002/adma.201103800

Molecular Packing of High-Mobility Diketo Pyrrolo-Pyrrole Polymer Semiconductors with Branched Alkyl Side Chains
journal, September 2011

  • Zhang, Xinran; Richter, Lee J.; DeLongchamp, Dean M.
  • Journal of the American Chemical Society, Vol. 133, Issue 38
  • DOI: 10.1021/ja204515s

Theory of optical transitions in conjugated polymers. II. Real systems
journal, October 2014

  • Marcus, Max; Tozer, Oliver Robert; Barford, William
  • The Journal of Chemical Physics, Vol. 141, Issue 16
  • DOI: 10.1063/1.4897985

Microstructure Evolution and Device Performance in Solution-Processed Polymeric Field-Effect Transistors: The Key Role of the First Monolayer
journal, February 2012

  • Wang, Suhao; Kiersnowski, Adam; Pisula, Wojciech
  • Journal of the American Chemical Society, Vol. 134, Issue 9
  • DOI: 10.1021/ja211630w

Langmuir−Blodgett Films of Regioregular Poly(3-hexylthiophene) as Field-Effect Transistors
journal, February 2000

  • Xu, Guofeng; Bao, Zhenan; Groves, John T.
  • Langmuir, Vol. 16, Issue 4
  • DOI: 10.1021/la9904455

Quantitative Image Analysis of Fractal‐Like Thin Films of Organic Semiconductors
journal, August 2019

  • Zhu, Weikun; Mohammadi, Erfan; Diao, Ying
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 57, Issue 23
  • DOI: 10.1002/polb.24875

Ultrathin Film Organic Transistors: Precise Control of Semiconductor Thickness via Spin-Coating
journal, November 2012

  • Zhang, Fengjiao; Di, Chong-an; Berdunov, Nikolai
  • Advanced Materials, Vol. 25, Issue 10
  • DOI: 10.1002/adma.201204075

Mitigating Meniscus Instabilities in Solution-Sheared Polymer Films for Organic Field-Effect Transistors
journal, July 2019

  • Teixeira da Rocha, Cecilia; Qu, Ge; Yang, Xuegeng
  • ACS Applied Materials & Interfaces, Vol. 11, Issue 33
  • DOI: 10.1021/acsami.9b07832
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