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Title: Addition of the Lewis Acid Zn(C6F5)2 Enables Organic Transistors with a Maximum Hole Mobility in Excess of 20 cm2 V–1 s–1

Abstract

Incorporating the molecular organic Lewis acid tris(pentafluorophenyl)borane [B(C6F5)3] into organic semiconductors has shown remarkable promise in recent years for controlling the operating characteristics and performance of various opto/electronic devices, including, light-emitting diodes, solar cells, and organic thin-film transistors (OTFTs). Despite the demonstrated potential, however, to date most of the work has been limited to B(C6F5)3 with the latter serving as the prototypical air-stable molecular Lewis acid system. Herein, the use of bis(pentafluorophenyl)zinc [Zn(C6F5)2] is reported as an alternative Lewis acid additive in high-hole-mobility OTFTs based on small-molecule:polymer blends comprising 2,7-dioctyl[1]benzothieno [3,2-b][1]benzothiophene and indacenodithiophene–benzothiadiazole. Systematic analysis of the materials and device characteristics supports the hypothesis that Zn(C6F5)2 acts simultaneously as a p-dopant and a microstructure modifier. It is proposed that it is the combination of these synergistic effects that leads to OTFTs with a maximum hole mobility value of 21.5 cm2 V–1 s–1. In conclusion, the work not only highlights Zn(C6F5)2 as a promising new additive for next-generation optoelectronic devices, but also opens up new avenues in the search for high-mobility organic semiconductors.

Authors:
 [1]; ORCiD logo [2];  [3];  [1]; ORCiD logo [1];  [1]; ORCiD logo [4]; ORCiD logo [4];  [1];  [1]; ORCiD logo [4]; ORCiD logo [1]
  1. King Abdullah Univ. of Science and Technology, Thuwal (Saudi Arabia)
  2. National Technical Univ. of Athens, Athens (Greece)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
  4. Imperial College London, London (United Kingdom)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1542777
Alternate Identifier(s):
OSTI ID: 1511885
Report Number(s):
BNL-211853-2019-JAAM
Journal ID: ISSN 0935-9648
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Volume: 31; Journal Issue: 27; Journal ID: ISSN 0935-9648
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; carrier mobility; Lewis acid; molecular doping; organic semiconductors; organic thin‐film transistors

Citation Formats

Paterson, Alexandra F., Tsetseris, Leonidas, Li, Ruipeng, Basu, Aniruddha, Faber, Hendrik, Emwas, Abdul ‐Hamid, Panidi, Julianna, Fei, Zhuping, Niazi, Muhammad R., Anjum, Dalaver H., Heeney, Martin, and Anthopoulos, Thomas D. Addition of the Lewis Acid Zn(C6F5)2 Enables Organic Transistors with a Maximum Hole Mobility in Excess of 20 cm2 V–1 s–1. United States: N. p., 2019. Web. doi:10.1002/adma.201900871.
Paterson, Alexandra F., Tsetseris, Leonidas, Li, Ruipeng, Basu, Aniruddha, Faber, Hendrik, Emwas, Abdul ‐Hamid, Panidi, Julianna, Fei, Zhuping, Niazi, Muhammad R., Anjum, Dalaver H., Heeney, Martin, & Anthopoulos, Thomas D. Addition of the Lewis Acid Zn(C6F5)2 Enables Organic Transistors with a Maximum Hole Mobility in Excess of 20 cm2 V–1 s–1. United States. https://doi.org/10.1002/adma.201900871
Paterson, Alexandra F., Tsetseris, Leonidas, Li, Ruipeng, Basu, Aniruddha, Faber, Hendrik, Emwas, Abdul ‐Hamid, Panidi, Julianna, Fei, Zhuping, Niazi, Muhammad R., Anjum, Dalaver H., Heeney, Martin, and Anthopoulos, Thomas D. Fri . "Addition of the Lewis Acid Zn(C6F5)2 Enables Organic Transistors with a Maximum Hole Mobility in Excess of 20 cm2 V–1 s–1". United States. https://doi.org/10.1002/adma.201900871. https://www.osti.gov/servlets/purl/1542777.
@article{osti_1542777,
title = {Addition of the Lewis Acid Zn(C6F5)2 Enables Organic Transistors with a Maximum Hole Mobility in Excess of 20 cm2 V–1 s–1},
author = {Paterson, Alexandra F. and Tsetseris, Leonidas and Li, Ruipeng and Basu, Aniruddha and Faber, Hendrik and Emwas, Abdul ‐Hamid and Panidi, Julianna and Fei, Zhuping and Niazi, Muhammad R. and Anjum, Dalaver H. and Heeney, Martin and Anthopoulos, Thomas D.},
abstractNote = {Incorporating the molecular organic Lewis acid tris(pentafluorophenyl)borane [B(C6F5)3] into organic semiconductors has shown remarkable promise in recent years for controlling the operating characteristics and performance of various opto/electronic devices, including, light-emitting diodes, solar cells, and organic thin-film transistors (OTFTs). Despite the demonstrated potential, however, to date most of the work has been limited to B(C6F5)3 with the latter serving as the prototypical air-stable molecular Lewis acid system. Herein, the use of bis(pentafluorophenyl)zinc [Zn(C6F5)2] is reported as an alternative Lewis acid additive in high-hole-mobility OTFTs based on small-molecule:polymer blends comprising 2,7-dioctyl[1]benzothieno [3,2-b][1]benzothiophene and indacenodithiophene–benzothiadiazole. Systematic analysis of the materials and device characteristics supports the hypothesis that Zn(C6F5)2 acts simultaneously as a p-dopant and a microstructure modifier. It is proposed that it is the combination of these synergistic effects that leads to OTFTs with a maximum hole mobility value of 21.5 cm2 V–1 s–1. In conclusion, the work not only highlights Zn(C6F5)2 as a promising new additive for next-generation optoelectronic devices, but also opens up new avenues in the search for high-mobility organic semiconductors.},
doi = {10.1002/adma.201900871},
journal = {Advanced Materials},
number = 27,
volume = 31,
place = {United States},
year = {Fri May 10 00:00:00 EDT 2019},
month = {Fri May 10 00:00:00 EDT 2019}
}

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Works referenced in this record:

Doping of organic semiconductors
journal, December 2012


Highly Efficient Organic Devices Based on Electrically Doped Transport Layers
journal, April 2007

  • Walzer, K.; Maennig, B.; Pfeiffer, M.
  • Chemical Reviews, Vol. 107, Issue 4
  • DOI: 10.1021/cr050156n

Doping: A Key Enabler for Organic Transistors
journal, August 2018


Doped Organic Transistors
journal, October 2016


Molecular Electrical Doping of Organic Semiconductors: Fundamental Mechanisms and Emerging Dopant Design Rules
journal, February 2016


Controlling Molecular Doping in Organic Semiconductors
journal, September 2017


Lewis Acid Doping Induced Synergistic Effects on Electronic and Morphological Structure for Donor and Acceptor in Polymer Solar Cells
journal, March 2018


Color Tuning in Polymer Light-Emitting Diodes with Lewis Acids
journal, June 2012

  • Zalar, Peter; Henson, Zachary B.; Welch, Gregory C.
  • Angewandte Chemie International Edition, Vol. 51, Issue 30
  • DOI: 10.1002/anie.201202570

Increased Mobility Induced by Addition of a Lewis Acid to a Lewis Basic Conjugated Polymer
journal, October 2013

  • Zalar, Peter; Kuik, Martijn; Henson, Zachary B.
  • Advanced Materials, Vol. 26, Issue 5
  • DOI: 10.1002/adma.201303357

Highly Sensitive NH 3 Detection Based on Organic Field-Effect Transistors with Tris(pentafluorophenyl)borane as Receptor
journal, September 2012

  • Huang, Weiguo; Besar, Kalpana; LeCover, Rachel
  • Journal of the American Chemical Society, Vol. 134, Issue 36
  • DOI: 10.1021/ja305287p

Nature of Tris(pentafluorophenyl)borane as a Functional Additive and Its Contribution to High Rate Performance in Lithium-Ion Secondary Battery
journal, January 2010

  • Lee, Yong Min; Lee, Young-Gi; Kang, Yong-Mook
  • Electrochemical and Solid-State Letters, Vol. 13, Issue 5
  • DOI: 10.1149/1.3329703

p-Type Doping of Poly(3-hexylthiophene) with the Strong Lewis Acid Tris(pentafluorophenyl)borane
journal, September 2016

  • Pingel, Patrick; Arvind, Malavika; Kölln, Lisa
  • Advanced Electronic Materials, Vol. 2, Issue 10
  • DOI: 10.1002/aelm.201600204

Enhanced Efficiency and Long-Term Stability of Perovskite Solar Cells by Synergistic Effect of Nonhygroscopic Doping in Conjugated Polymer-Based Hole-Transporting Layer
journal, December 2017

  • Koh, Chang Woo; Heo, Jin Hyuck; Uddin, Mohammad Afsar
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 50
  • DOI: 10.1021/acsami.7b12973

Improved Performance and Reproducibility of Perovskite Solar Cells by Well-Soluble Tris(pentafluorophenyl)borane as a p-Type Dopant
journal, May 2017

  • Ye, Tengling; Wang, Junhai; Chen, Wenbo
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 21
  • DOI: 10.1021/acsami.7b02969

Recent Progress in High-Mobility Organic Transistors: A Reality Check
journal, July 2018

  • Paterson, Alexandra F.; Singh, Saumya; Fallon, Kealan J.
  • Advanced Materials, Vol. 30, Issue 36
  • DOI: 10.1002/adma.201801079

Essential Effects on the Mobility Extraction Reliability for Organic Transistors
journal, August 2018


Assessment of the Factors Influencing Charge-Carrier Mobility Measurements in Organic Field-Effect Transistors
journal, August 2018

  • Li, Haoyuan; Tessler, Nir; Brédas, Jean-Luc
  • Advanced Functional Materials, Vol. 28, Issue 39
  • DOI: 10.1002/adfm.201803096

Critical assessment of charge mobility extraction in FETs
journal, December 2017

  • Choi, Hyun Ho; Cho, Kilwon; Frisbie, C. Daniel
  • Nature Materials, Vol. 17, Issue 1
  • DOI: 10.1038/nmat5035

The Synthesis, Molecular Structures, and Supramolecular Architecture of Amine Adducts of Bis(pentafluorophenyl)zinc
journal, July 2006

  • Mountford, Andrew J.; Lancaster, Simon J.; Coles, Simon J.
  • Organometallics, Vol. 25, Issue 16
  • DOI: 10.1021/om060319d

Small Molecule/Polymer Blend Organic Transistors with Hole Mobility Exceeding 13 cm 2 V −1 s −1
journal, July 2016

  • Paterson, Alexandra F.; Treat, Neil D.; Zhang, Weimin
  • Advanced Materials, Vol. 28, Issue 35
  • DOI: 10.1002/adma.201601075

The Impact of Molecular p-Doping on Charge Transport in High-Mobility Small-Molecule/Polymer Blend Organic Transistors
journal, December 2017

  • Paterson, Alexandra F.; Lin, Yen-Hung; Mottram, Alexander D.
  • Advanced Electronic Materials, Vol. 4, Issue 10
  • DOI: 10.1002/aelm.201700464

Impact of the Gate Dielectric on Contact Resistance in High‐Mobility Organic Transistors
journal, March 2019

  • Paterson, Alexandra F.; Mottram, Alexander D.; Faber, Hendrik
  • Advanced Electronic Materials, Vol. 5, Issue 5
  • DOI: 10.1002/aelm.201800723

Enhanced n-Doping Efficiency of a Naphthalenediimide-Based Copolymer through Polar Side Chains for Organic Thermoelectrics
journal, January 2018


Anion-induced N-doping of naphthalenediimide polymer semiconductor in organic thin-film transistors
journal, April 2018


Spectroscopic Studies of the Intermediates in the Conversion of 1,4,11,12-Tetrahydro-9,10-anthraquinone to 9,10-Anthraquinone by Reaction with Oxygen under Basic Conditions
journal, December 2004

  • Mattar, Saba M.; Emwas, Abdul H.; Calhoun, Larry A.
  • The Journal of Physical Chemistry A, Vol. 108, Issue 52
  • DOI: 10.1021/jp040280v

Accurate computations of the methyl isotropic hyperfine coupling constants in 2-methyl-1,4-benzosemiquinone radical intermediate
journal, September 2002


Generation and spectroscopic characterization of the 2,3,5,6-tetramethoxy-1,4-benzosemiquinone reactive intermediate
journal, January 2002


Utilizing NMR and EPR spectroscopy to probe the role of copper in prion diseases: Role of copper in prion diseases
journal, February 2013

  • Emwas, Abdul-Hamid M.; Al-Talla, Zeyad A.; Guo, Xianrong
  • Magnetic Resonance in Chemistry, Vol. 51, Issue 5
  • DOI: 10.1002/mrc.3936

Doping effect of solution-processed thin-film transistors based on polyfluorene
journal, January 2007

  • Lim, Eunhee; Jung, Byung-Jun; Chikamatsu, Masayuki
  • Journal of Materials Chemistry, Vol. 17, Issue 14
  • DOI: 10.1039/b615720c

Control of threshold voltage in pentacene thin-film transistors using carrier doping at the charge-transfer interface with organic acceptors
journal, October 2005

  • Abe, Y.; Hasegawa, T.; Takahashi, Y.
  • Applied Physics Letters, Vol. 87, Issue 15
  • DOI: 10.1063/1.2099540

On the Extraction of Charge Carrier Mobility in High-Mobility Organic Transistors
journal, November 2015

  • Uemura, Takafumi; Rolin, Cedric; Ke, Tung-Huei
  • Advanced Materials, Vol. 28, Issue 1
  • DOI: 10.1002/adma.201503133

Avoid the kinks when measuring mobility
journal, June 2016


Mobility overestimation due to gated contacts in organic field-effect transistors
journal, March 2016

  • Bittle, Emily G.; Basham, James I.; Jackson, Thomas N.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms10908

Device Physics of Contact Issues for the Overestimation and Underestimation of Carrier Mobility in Field-Effect Transistors
journal, September 2017


High-Performance Polymer-Small Molecule Blend Organic Transistors
journal, March 2009

  • Hamilton, Richard; Smith, Jeremy; Ogier, Simon
  • Advanced Materials, Vol. 21, Issue 10-11, p. 1166-1171
  • DOI: 10.1002/adma.200801725

Solution-Processed Small Molecule-Polymer Blend Organic Thin-Film Transistors with Hole Mobility Greater than 5 cm2/Vs
journal, April 2012

  • Smith, Jeremy; Zhang, Weimin; Sougrat, Rachid
  • Advanced Materials, Vol. 24, Issue 18
  • DOI: 10.1002/adma.201200088

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

Inkjet printing of single-crystal films
journal, July 2011

  • Minemawari, Hiromi; Yamada, Toshikazu; Matsui, Hiroyuki
  • Nature, Vol. 475, Issue 7356, p. 364-367
  • DOI: 10.1038/nature10313

Molecular Ordering of High-Performance Soluble Molecular Semiconductors and Re-evaluation of Their Field-Effect Transistor Characteristics
journal, July 2008

  • Izawa, Takafumi; Miyazaki, Eigo; Takimiya, Kazuo
  • Advanced Materials, Vol. 20, Issue 18
  • DOI: 10.1002/adma.200800799

Elastomeric Transistor Stamps: Reversible Probing of Charge Transport in Organic Crystals
journal, March 2004

  • Sundar, Vikram C.; Zaumseil, Jana; Podzorov, Vitaly
  • Science, Vol. 303, Issue 5664, p. 1644-1646
  • DOI: 10.1126/science.1094196

Controllable growth of C 8 -BTBT single crystalline microribbon arrays by a limited solvent vapor-assisted crystallization (LSVC) method
journal, January 2018

  • Jiang, Longfeng; Liu, Jie; Lu, Xiuqiang
  • Journal of Materials Chemistry C, Vol. 6, Issue 10
  • DOI: 10.1039/C8TC00447A

Role of Polymorphism and Thin-Film Morphology in Organic Semiconductors Processed by Solution Shearing
journal, February 2018


Electric Field Tuning Molecular Packing and Electrical Properties of Solution-Shearing Coated Organic Semiconducting Thin Films
journal, January 2017

  • Molina-Lopez, Francisco; Yan, Hongping; Gu, Xiaodan
  • Advanced Functional Materials, Vol. 27, Issue 8
  • DOI: 10.1002/adfm.201605503

Molecular origin of high field-effect mobility in an indacenodithiophene–benzothiadiazole copolymer
journal, July 2013

  • Zhang, Xinran; Bronstein, Hugo; Kronemeijer, Auke J.
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3238

Doping of Organic Semiconductors: Impact of Dopant Strength and Electronic Coupling
journal, June 2013

  • Méndez, Henry; Heimel, Georg; Opitz, Andreas
  • Angewandte Chemie International Edition, Vol. 52, Issue 30
  • DOI: 10.1002/anie.201302396

Dioxygen Reactivity with a Ferrocene-Lewis Acid Pairing: Reduction to a Boron Peroxide in the Presence of Tris(pentafluorophenyl)borane
journal, September 2014

  • Henthorn, Justin T.; Agapie, Theodor
  • Angewandte Chemie International Edition, Vol. 53, Issue 47
  • DOI: 10.1002/anie.201408462

NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010

  • Valiev, M.; Bylaska, E. J.; Govind, N.
  • Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
  • DOI: 10.1016/j.cpc.2010.04.018

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Doping: A Key Enabler for Organic Transistors
journal, July 2019


Color Tuning in Polymer Light-Emitting Diodes with Lewis Acids
journal, June 2012

  • Zalar, Peter; Henson, Zachary B.; Welch, Gregory C.
  • Angewandte Chemie, Vol. 124, Issue 30
  • DOI: 10.1002/ange.201202570

Doping of Organic Semiconductors: Impact of Dopant Strength and Electronic Coupling
journal, June 2013

  • Méndez, Henry; Heimel, Georg; Opitz, Andreas
  • Angewandte Chemie, Vol. 125, Issue 30
  • DOI: 10.1002/ange.201302396

Dioxygen Reactivity with a Ferrocene-Lewis Acid Pairing: Reduction to a Boron Peroxide in the Presence of Tris(pentafluorophenyl)borane
journal, September 2014


Highly Efficient Organic Devices Based on Electrically Doped Transport Layers
journal, July 2007


Works referencing / citing this record:

Contact Resistance in Organic Field‐Effect Transistors: Conquering the Barrier
journal, September 2019

  • Waldrip, Matthew; Jurchescu, Oana D.; Gundlach, David J.
  • Advanced Functional Materials, Vol. 30, Issue 20
  • DOI: 10.1002/adfm.201904576

Printable Semiconductors for Backplane TFTs of Flexible OLED Displays
journal, August 2019

  • Zhu, Huihui; Shin, Eun‐Sol; Liu, Ao
  • Advanced Functional Materials, Vol. 30, Issue 20
  • DOI: 10.1002/adfm.201904588

High‐Speed Organic Single‐Crystal Transistor Responding to Very High Frequency Band
journal, February 2020

  • Yamamura, Akifumi; Sakon, Takaaki; Takahira, Kayo
  • Advanced Functional Materials, Vol. 30, Issue 11
  • DOI: 10.1002/adfm.201909501

Doping High‐Mobility Donor–Acceptor Copolymer Semiconductors with an Organic Salt for High‐Performance Thermoelectric Materials
journal, January 2020

  • Guo, Jing; Li, Guodong; Reith, Heiko
  • Advanced Electronic Materials, Vol. 6, Issue 3
  • DOI: 10.1002/aelm.201900945

Bar‐Coated Organic Thin‐Film Transistors with Reliable Electron Mobility Approaching 10 cm 2 V −1 s −1
journal, December 2019

  • Bai, Junhua; Jiang, Yu; Wang, Zhongli
  • Advanced Electronic Materials, Vol. 6, Issue 1
  • DOI: 10.1002/aelm.201901002

Polymer Light‐Emitting Transistors With Charge‐Carrier Mobilities Exceeding 1 cm 2 V −1 s −1
journal, November 2019

  • Chaudhry, Mujeeb Ullah; Panidi, Julianna; Nam, Sungho
  • Advanced Electronic Materials, Vol. 6, Issue 1
  • DOI: 10.1002/aelm.201901132

P3HT with Zn(C 6 F 5 ) 2 as p‐Type Dopant for the Enhanced Performance of Planar Perovskite Solar Cells
journal, October 2019


Reducing contact resistance in bottom contact organic field effect transistors for integrated electronics
journal, January 2019

  • Han, Lei; Huang, Yukun; Tang, Wei
  • Journal of Physics D: Applied Physics, Vol. 53, Issue 1
  • DOI: 10.1088/1361-6463/ab42a9

P3HT with Zn(C 6 F 5 ) 2 as p‐Type Dopant for the Enhanced Performance of Planar Perovskite Solar Cells
journal, October 2019