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Title: Tunable electroresistance and electro-optic effects of transparent molecular ferroelectrics

Abstract

Recent progress in molecular ferroelectrics (MOFEs) has been overshadowed by the lack of high-quality thin films for device integration. We report a water-based air-processable technique to prepare large-area MOFE thin films, controlled by supersaturation growth at the liquid-air interface under a temperature gradient and external water partial pressure. We used this technique to fabricate ImClO4 thin films and found a large, tunable room temperature electroresistance: a 20-fold resistance variation upon polarization switching. The as-grown films are transparent and consist of a bamboo-like structure of ($$2,\overline{1},0$$) and ($$1,0,\overline{2}$$) structural variants of R3m symmetry with a reversible polarization of 6.7 μC/cm2. The resulting ferroelectric domain structure leads to a reversible electromechanical response of d33 = 38.8 pm/V. Polarization switching results in a change of the refractive index, n, of single domains, $$\frac{Δn}{n}$$ = 0.3. The remarkable combination of these characteristics renders MOFEs a prime candidate material for new nanoelectronic devices. The information that we present in this work will open a new area of MOFE thin-film technologies.

Authors:
 [1];  [2];  [2]; ORCiD logo [3];  [3];  [4]; ORCiD logo [2];  [1]
  1. Temple University, Philadelphia, PA (United States). Department of Mechanical Engineering and Temple Materials Institute
  2. Southeast University, Nanjing (China)
  3. Temple University, Philadelphia, PA (United States). Department of Chemistry
  4. Univ. of Maryland, College Park, MD (United States). Department of Materials Science and Engineering
Publication Date:
Research Org.:
Temple Univ., Philadelphia, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1429329
Grant/Contract Number:  
SC0017928; SC0010307
Resource Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 3; Journal Issue: 8; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Zhang, Zhuolei, Li, Peng-Fei, Tang, Yuan-Yuan, Wilson, Andrew J., Willets, Katherine, Wuttig, Manfred, Xiong, Ren-Gen, and Ren, Shenqiang. Tunable electroresistance and electro-optic effects of transparent molecular ferroelectrics. United States: N. p., 2017. Web. doi:10.1126/sciadv.1701008.
Zhang, Zhuolei, Li, Peng-Fei, Tang, Yuan-Yuan, Wilson, Andrew J., Willets, Katherine, Wuttig, Manfred, Xiong, Ren-Gen, & Ren, Shenqiang. Tunable electroresistance and electro-optic effects of transparent molecular ferroelectrics. United States. doi:10.1126/sciadv.1701008.
Zhang, Zhuolei, Li, Peng-Fei, Tang, Yuan-Yuan, Wilson, Andrew J., Willets, Katherine, Wuttig, Manfred, Xiong, Ren-Gen, and Ren, Shenqiang. Wed . "Tunable electroresistance and electro-optic effects of transparent molecular ferroelectrics". United States. doi:10.1126/sciadv.1701008. https://www.osti.gov/servlets/purl/1429329.
@article{osti_1429329,
title = {Tunable electroresistance and electro-optic effects of transparent molecular ferroelectrics},
author = {Zhang, Zhuolei and Li, Peng-Fei and Tang, Yuan-Yuan and Wilson, Andrew J. and Willets, Katherine and Wuttig, Manfred and Xiong, Ren-Gen and Ren, Shenqiang},
abstractNote = {Recent progress in molecular ferroelectrics (MOFEs) has been overshadowed by the lack of high-quality thin films for device integration. We report a water-based air-processable technique to prepare large-area MOFE thin films, controlled by supersaturation growth at the liquid-air interface under a temperature gradient and external water partial pressure. We used this technique to fabricate ImClO4 thin films and found a large, tunable room temperature electroresistance: a 20-fold resistance variation upon polarization switching. The as-grown films are transparent and consist of a bamboo-like structure of ($2,\overline{1},0$) and ($1,0,\overline{2}$) structural variants of R3m symmetry with a reversible polarization of 6.7 μC/cm2. The resulting ferroelectric domain structure leads to a reversible electromechanical response of d33 = 38.8 pm/V. Polarization switching results in a change of the refractive index, n, of single domains, $\frac{Δn}{n}$ = 0.3. The remarkable combination of these characteristics renders MOFEs a prime candidate material for new nanoelectronic devices. The information that we present in this work will open a new area of MOFE thin-film technologies.},
doi = {10.1126/sciadv.1701008},
journal = {Science Advances},
number = 8,
volume = 3,
place = {United States},
year = {2017},
month = {8}
}

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Cited by: 6 works
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Works referenced in this record:

Ferroelectric Metal−Organic Framework with a High Dielectric Constant
journal, May 2006

  • Ye, Qiong; Song, Yu-Mei; Wang, Guo-Xi
  • Journal of the American Chemical Society, Vol. 128, Issue 20
  • DOI: 10.1021/ja060856p

Molecular ferroelectrics: where electronics meet biology
journal, January 2013

  • Li, Jiangyu; Liu, Yuanming; Zhang, Yanhang
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 48
  • DOI: 10.1039/c3cp52501e

Dielectric and Thermal Study of Tri-Glycine Sulfate and Tri-Glycine Fluoberyllate
journal, September 1957


Multi-Stimuli-Responsive Charge-Transfer Hydrogel for Room-Temperature Organic Ferroelectric Thin-Film Devices
journal, June 2016

  • Pandeeswar, Makam; Senanayak, Satyaprasad P.; Narayan, K. S.
  • Journal of the American Chemical Society, Vol. 138, Issue 26
  • DOI: 10.1021/jacs.6b03811

Molecule-Based Ferroelectric Thin Films: Mononuclear Lanthanide Enantiomers Displaying Room-Temperature Ferroelectric and Dielectric Properties
journal, September 2007

  • Li, Xi-Li; Chen, Kai; Liu, Yu
  • Angewandte Chemie International Edition, Vol. 46, Issue 36
  • DOI: 10.1002/anie.200701802

Ferroelectric, dielectric and piezoelectric properties of ferroelectric thin films and ceramics
journal, September 1998


Organic non-volatile memories from ferroelectric phase-separated blends
journal, June 2008

  • Asadi, Kamal; de Leeuw, Dago M.; de Boer, Bert
  • Nature Materials, Vol. 7, Issue 7
  • DOI: 10.1038/nmat2207

Piezoelectric and ferroelectric materials and structures for energy harvesting applications
journal, January 2014

  • Bowen, C. R.; Kim, H. A.; Weaver, P. M.
  • Energy Environ. Sci., Vol. 7, Issue 1
  • DOI: 10.1039/C3EE42454E

High-Temperature Ferroelectricity and Photoluminescence in a Hybrid Organic–Inorganic Compound: (3-Pyrrolinium)MnCl 3
journal, September 2015

  • Ye, Heng-Yun; Zhou, QiongHua; Niu, XiangHong
  • Journal of the American Chemical Society, Vol. 137, Issue 40
  • DOI: 10.1021/jacs.5b08290

Room-temperature ferroelectricity in supramolecular networks of charge-transfer complexes
journal, August 2012

  • Tayi, Alok S.; Shveyd, Alexander K.; Sue, Andrew C. -H.
  • Nature, Vol. 488, Issue 7412
  • DOI: 10.1038/nature11395

Size sorting of floating spheres based on Marangoni forces in evaporating droplets
journal, June 2013


Self-powered nanowire devices
journal, March 2010

  • Xu, Sheng; Qin, Yong; Xu, Chen
  • Nature Nanotechnology, Vol. 5, Issue 5, p. 366-373
  • DOI: 10.1038/nnano.2010.46

Preparation and Characterization of High Temperature Perovskite Ferroelectrics in the Solid-Solution (1- x )BiScO 3x PbTiO 3
journal, April 2002

  • Eitel, Richard E.; Randall, Clive A.; Shrout, Thomas R.
  • Japanese Journal of Applied Physics, Vol. 41, Issue Part 1, No. 4A
  • DOI: 10.1143/JJAP.41.2099

Ferroelectric Memories
journal, December 1989


What Determines the Lamellar Orientation on Substrates?
journal, May 2011

  • Yang, Ju-Ping; Liao, Qi; Zhou, Jian-Jun
  • Macromolecules, Vol. 44, Issue 9
  • DOI: 10.1021/ma102973w

Polarization dependence of optical pump-induced change of graphene extinction coefficient
journal, January 2015

  • Yao, Jun; Zhao, Xin; Yan, Xiao-Qing
  • Optical Materials Express, Vol. 5, Issue 7
  • DOI: 10.1364/OME.5.001550

In situ video observation of 180° domain kinetics in congruent LiNbO3 crystals
journal, October 1999

  • Gopalan, Venkatraman; Jia, Q. X.; Mitchell, T. E.
  • Applied Physics Letters, Vol. 75, Issue 16
  • DOI: 10.1063/1.125055

Unit-cell refinement from powder diffraction scans
journal, December 1981


In situ video observation of 180° domain switching in LiTaO3 by electro-optic imaging microscopy
journal, February 1999

  • Gopalan, Venkatraman; Mitchell, Terence E.
  • Journal of Applied Physics, Vol. 85, Issue 4
  • DOI: 10.1063/1.369542

Ultrahigh strain and piezoelectric behavior in relaxor based ferroelectric single crystals
journal, August 1997

  • Park, Seung-Eek; Shrout, Thomas R.
  • Journal of Applied Physics, Vol. 82, Issue 4
  • DOI: 10.1063/1.365983

Diisopropylammonium Bromide Is a High-Temperature Molecular Ferroelectric Crystal
journal, January 2013


Printable Ferroelectric PVDF/PMMA Blend Films with Ultralow Roughness for Low Voltage Non-Volatile Polymer Memory
journal, September 2009

  • Kang, Seok Ju; Park, Youn Jung; Bae, Insung
  • Advanced Functional Materials, Vol. 19, Issue 17
  • DOI: 10.1002/adfm.200900589

Organic ferroelectrics
journal, May 2008

  • Horiuchi, Sachio; Tokura, Yoshinori
  • Nature Materials, Vol. 7, Issue 5, p. 357-366
  • DOI: 10.1038/nmat2137

Maze solving using temperature-induced Marangoni flow
journal, January 2015

  • Lovass, Petra; Branicki, Michal; Tóth, Rita
  • RSC Advances, Vol. 5, Issue 60
  • DOI: 10.1039/C5RA08207B

Flexible organic ferroelectric films with a large piezoelectric response
journal, June 2015

  • Gao, Wenxiu; Chang, Lei; Ma, He
  • NPG Asia Materials, Vol. 7, Issue 6
  • DOI: 10.1038/am.2015.54

In-situ visualization, monitoring and analysis of electric field domain reversal process in ferroelectric crystals by digital holography
journal, January 2004

  • Grilli, Simonetta; Ferraro, Pietro; Paturzo, Melania
  • Optics Express, Vol. 12, Issue 9
  • DOI: 10.1364/OPEX.12.001832

Ferroelectric ordering in imidazolium perchlorate
journal, April 2006

  • Pająk, Z.; Czarnecki, P.; Szafrańska, B.
  • The Journal of Chemical Physics, Vol. 124, Issue 14
  • DOI: 10.1063/1.2185098

Organic Nonvolatile Memory Devices Based on Ferroelectricity
journal, August 2009

  • Naber, Ronald C. G.; Asadi, Kamal; Blom, Paul W. M.
  • Advanced Materials, Vol. 22, Issue 9
  • DOI: 10.1002/adma.200900759

Molecular Ferroelectric with Most Equivalent Polarization Directions Induced by the Plastic Phase Transition
journal, September 2016

  • Ye, Heng-Yun; Ge, Jia-Zhen; Tang, Yuan-Yuan
  • Journal of the American Chemical Society, Vol. 138, Issue 40
  • DOI: 10.1021/jacs.6b08817

Piezo-Electric and Allied Phenomena in Rochelle Salt
journal, April 1921


A general mechanism of polycrystalline growth
journal, August 2004

  • Gránásy, László; Pusztai, Tamás; Börzsönyi, Tamás
  • Nature Materials, Vol. 3, Issue 9
  • DOI: 10.1038/nmat1190

Epitaxial BiFeO3 Multiferroic Thin Film Heterostructures
journal, March 2003


A review of power harvesting using piezoelectric materials (2003–2006)
journal, May 2007


Linear electro‐optic effects in polymer‐dispersed ferroelectric liquid crystals
journal, June 1992

  • Kitzerow, Heinz‐S.; Molsen, Henning; Heppke, Gerd
  • Applied Physics Letters, Vol. 60, Issue 25
  • DOI: 10.1063/1.106762

Above-room-temperature ferroelectricity in a single-component molecular crystal
journal, February 2010

  • Horiuchi, Sachio; Tokunaga, Yusuke; Giovannetti, Gianluca
  • Nature, Vol. 463, Issue 7282, p. 789-792
  • DOI: 10.1038/nature08731

Molecular Ferroelectric Pyridin-4-ylmethanaminium Perchlorate Undergoes Paraelectric–Ferroelectric and Ferroelectric–Ferroelectric Phase Transitions
journal, February 2016

  • Cui, Zepeng; Gao, Kaige; Liu, Chuang
  • The Journal of Physical Chemistry C, Vol. 120, Issue 5
  • DOI: 10.1021/acs.jpcc.5b12348

Nonlinear Optics of Organic Molecules and Polymers
journal, September 1997


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    journal, May 2019

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    • DOI: 10.1002/anie.201904305

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    journal, May 2019

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    • DOI: 10.1002/anie.201904305

    Piezoactive amino acid derivatives containing fragments of planar-chiral ortho -carboranes
    journal, January 2018

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    • DOI: 10.1039/c8tc02266f

    Metal-free three-dimensional perovskite ferroelectrics
    journal, July 2018