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Title: High Tc layered ferrielectric crystals by coherent spinodal decomposition

Abstract

Research in the rapidly-developing field of 2D-electronic materials has thus far been focused on metallic and semiconducting materials. However, complementary dielectric materials such as non-linear dielectrics are needed to enable realistic device architectures. Candidate materials require tunable dielectric properties and pathways for heterostructure assembly. Here we report on a family of cation-deficient transition metal thiophosphates whose unique chemistry makes them a viable prospect for these applications. In these materials, naturally occurring ferrielectric heterostructures composed of centrosymmetric In4/3P2S6 and ferrielectrically-active CuInP2S6 are realized by controllable chemical phase separation in van-der-Waals bonded single crystals. CuInP2S6 by itself is a layered ferrielectric with Tc just over room-temperature which rapidly decreases with homogenous doping. Surprisingly, in our composite materials, the ferrielectric Tc of the polar CuInP2S6 phase increases. This effect is enabled by unique spinodal decomposition that retains the overall van-der-Waals layered morphology of the crystal, but chemically separates CuInP2S6 and In4/3P2S6 within each layer. The average spatial periodicity of the distinct chemical phases can be finely controlled by altering the composition and/or synthesis conditions. One intriguing prospect for such layered spinodal alloys is large volume synthesis of 2D in-plane heterostructures with periodically alternating polar and non-polar phases.

Authors:
 [1];  [1];  [1];  [1];  [1];  [2];  [2];  [1];  [1];  [1];  [3]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Georgia Inst. of Technology, Atlanta, GA (United States)
  3. ORNL
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). High Temperature Materials Lab. (HTML); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Joint Institute for Computational Sciences (JICS)
Sponsoring Org.:
USDOE
OSTI Identifier:
1286887
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 9; Journal Issue: 12; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Susner, Michael A., Belianinov, Alex, Borisevich, Albina Y., He, Qian, Chyasnavichyus, Marius, Demir, Hakan, Sholl, David, Ganesh, Panchapakesan, Abernathy, Douglas L., McGuire, Michael A., and Maksymovych, Petro. High Tc layered ferrielectric crystals by coherent spinodal decomposition. United States: N. p., 2015. Web. doi:10.1021/acsnano.5b05682.
Susner, Michael A., Belianinov, Alex, Borisevich, Albina Y., He, Qian, Chyasnavichyus, Marius, Demir, Hakan, Sholl, David, Ganesh, Panchapakesan, Abernathy, Douglas L., McGuire, Michael A., & Maksymovych, Petro. High Tc layered ferrielectric crystals by coherent spinodal decomposition. United States. https://doi.org/10.1021/acsnano.5b05682
Susner, Michael A., Belianinov, Alex, Borisevich, Albina Y., He, Qian, Chyasnavichyus, Marius, Demir, Hakan, Sholl, David, Ganesh, Panchapakesan, Abernathy, Douglas L., McGuire, Michael A., and Maksymovych, Petro. 2015. "High Tc layered ferrielectric crystals by coherent spinodal decomposition". United States. https://doi.org/10.1021/acsnano.5b05682. https://www.osti.gov/servlets/purl/1286887.
@article{osti_1286887,
title = {High Tc layered ferrielectric crystals by coherent spinodal decomposition},
author = {Susner, Michael A. and Belianinov, Alex and Borisevich, Albina Y. and He, Qian and Chyasnavichyus, Marius and Demir, Hakan and Sholl, David and Ganesh, Panchapakesan and Abernathy, Douglas L. and McGuire, Michael A. and Maksymovych, Petro},
abstractNote = {Research in the rapidly-developing field of 2D-electronic materials has thus far been focused on metallic and semiconducting materials. However, complementary dielectric materials such as non-linear dielectrics are needed to enable realistic device architectures. Candidate materials require tunable dielectric properties and pathways for heterostructure assembly. Here we report on a family of cation-deficient transition metal thiophosphates whose unique chemistry makes them a viable prospect for these applications. In these materials, naturally occurring ferrielectric heterostructures composed of centrosymmetric In4/3P2S6 and ferrielectrically-active CuInP2S6 are realized by controllable chemical phase separation in van-der-Waals bonded single crystals. CuInP2S6 by itself is a layered ferrielectric with Tc just over room-temperature which rapidly decreases with homogenous doping. Surprisingly, in our composite materials, the ferrielectric Tc of the polar CuInP2S6 phase increases. This effect is enabled by unique spinodal decomposition that retains the overall van-der-Waals layered morphology of the crystal, but chemically separates CuInP2S6 and In4/3P2S6 within each layer. The average spatial periodicity of the distinct chemical phases can be finely controlled by altering the composition and/or synthesis conditions. One intriguing prospect for such layered spinodal alloys is large volume synthesis of 2D in-plane heterostructures with periodically alternating polar and non-polar phases.},
doi = {10.1021/acsnano.5b05682},
url = {https://www.osti.gov/biblio/1286887}, journal = {ACS Nano},
issn = {1936-0851},
number = 12,
volume = 9,
place = {United States},
year = {Fri Nov 13 00:00:00 EST 2015},
month = {Fri Nov 13 00:00:00 EST 2015}
}

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Works referenced in this record:

Scalable Synthesis of Uniform Few-Layer Hexagonal Boron Nitride Dielectric Films
journal, December 2012


Electron transport of WS2 transistors in a hexagonal boron nitride dielectric environment
journal, May 2014


Boron nitride substrates for high-quality graphene electronics
journal, August 2010


Metal-Insulator Transition in Graphene on Boron Nitride
journal, August 2014


Tunable metal–insulator transition in double-layer graphene heterostructures
journal, October 2011


Ferroelectric tunnel junctions with graphene electrodes
journal, November 2014


Nonlinear TE-polarized surface polaritons on graphene
journal, January 2014


Van der Waals heterostructures
journal, July 2013


Copper sublattice ordering in layered CuMP2Se6 (M=In, Cr)
journal, February 1999


Quaternary selenodiphosphates(IV): MIMIII[P2Se6], (MI =Cu, Ag; MIII = Cr, Al, Ga, In)
journal, July 1992


Magnetic and polar phases and dynamical clustering in multiferroic layered solid solutions CuCr 1 x In x P 2 S 6
journal, September 2011


Asymmetric phase diagram of mixed CuInP 2 ( S x Se 1 x ) 6 crystals
journal, August 2008


Phase diagram of mixed Cu(In x Cr 1 x )P 2 S 6 crystals
journal, April 2012


CuInP 2 S 6 Room Temperature Layered Ferroelectric
journal, May 2015


Ferrielectric ordering in lamellar CuInP 2 S 6
journal, November 1997


Electrostrictive and electrostatic responses in contact mode voltage modulated scanning probe microscopies
journal, June 2014


Defect-Mediated Polarization Switching in Ferroelectrics and Related Materials: From Mesoscopic Mechanisms to Atomistic Control
journal, January 2010


Domain Wall Conduction and Polarization-Mediated Transport in Ferroelectrics
journal, April 2013


Dielectric Properties of CuInP[sub 2](Se[sub x]S[sub 1 – ][sub x])[sub 6] Solid Solutions
journal, January 2005


Dielectric properties of CuInP_{2}S_{6} crystals under high pressure
journal, March 2007


Broadband dielectric investigations of indium rich CuInP 2 S 6 layered crystals
journal, February 2011


Room-temperature crystal structure of the layered phase CuIInIIIP2S6
journal, March 1995


The structural chemistry of indium phosphorus chalcogenides
journal, April 1978


Crystal growth and characterization of
journal, June 1976


Resonance enhancement in piezoresponse force microscopy: Mapping electromechanical activity, contact stiffness, and Q factor
journal, July 2006


Materials Design of Spinodal Nanodecomposition in CuIn 1- x Ga x Se 2 for High-Efficiency Solar Energy Conversion
journal, September 2010


A grid-based Bader analysis algorithm without lattice bias
journal, January 2009


Improved grid-based algorithm for Bader charge allocation
journal, January 2007


Computer Simulation of Liquids
journal, March 1989


X-ray diffraction study of molybdenum disulfide to 38.8GPa
journal, September 2006


Pressure and Temperature Dependence of the Ferroelectric–Paraelectric Phase Transition in PbTiO3
journal, September 2002


Growth of high-quality (Al,Ga)N and (Ga,In)N heterostructures on SiC(0001) by both plasma-assisted and reactive molecular beam epitaxy
journal, January 2000

  • Ploog, K. H.; Brandt, O.; Muralidharan, R.
  • Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 18, Issue 4
  • https://doi.org/10.1116/1.1305288

Electric Field Effect in Atomically Thin Carbon Films
journal, October 2004


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006


Works referencing / citing this record:

Tunable quadruple-well ferroelectric van der Waals crystals
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Metal Thio- and Selenophosphates as Multifunctional van der Waals Layered Materials
journal, August 2017


Recent Progress in Two‐Dimensional Ferroelectric Materials
journal, November 2019


New Frontiers on van der Waals Layered Metal Phosphorous Trichalcogenides
journal, July 2018


Thickness dependence of domain size in 2D ferroelectric CuInP 2 S 6 nanoflakes
journal, November 2019


Deep neural networks for understanding noisy data applied to physical property extraction in scanning probe microscopy
journal, February 2019


Size-effect in layered ferrielectric CuInP2S6
journal, October 2016


Origin of giant negative piezoelectricity in a layered van der Waals ferroelectric
journal, April 2019


Origin of giant negative piezoelectricity in a layered van der Waals ferroelectric
journal, April 2019