Antisite Defects in Layered Multiferroic CuCr0.9In0.1P2S6

He, Qian; Belianinov, Alex; Dziaugys, Andrius; Maksymovych, Petro; Vysochanskii, Yulian; Kalinin, Sergei V.; Borisevich, Albina Y.

doi:10.1039/C5NR04779J

Title: Antisite Defects in Layered Multiferroic CuCr_0.9In_0.1P₂S₆

Abstract

The CuCr_1-xIn_xP₂S₆ system represents a large family of metal chalcogenophosphates that are unique and promising candidates for 2D materials with functionalities such as ferroelectricity. We carried out detailed microstructural and chemical characterization of these compounds using aberration-corrected STEM, in order to understand the origin of these different ordering phenomena. Quantitative STEM-HAADF imaging and analysis identified the stacking order of an 8-layer thin flake, which leads to the identification of anti-site In³⁺(Cu⁺) doping. We believe that these findings will pave the way towards understanding the ferroic coupling phenomena in van der Waals lamellar compounds, as well as the potential applications in 2-D electronics.

Authors:

He, Qian ^[1]; Belianinov, Alex ^[1]; Dziaugys, Andrius ^[2]; Maksymovych, Petro ^[1]; Vysochanskii, Yulian ^[3]; Kalinin, Sergei V. ^[1]; Borisevich, Albina Y. ^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Vilnius Univ. (Lithuania)
Uzhgorod Univ. (Ukraine)

Publication Date:: Tue Oct 06 00:00:00 EDT 2015

Research Org.:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1240543

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Nanoscale

Additional Journal Information:: Journal Volume: 7; Journal Issue: 44; Journal ID: ISSN 2040-3364

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE

Citation Formats


                    He, Qian, Belianinov, Alex, Dziaugys, Andrius, Maksymovych, Petro, Vysochanskii, Yulian, Kalinin, Sergei V., and Borisevich, Albina Y. Antisite Defects in Layered Multiferroic CuCr0.9In0.1P2S6.  United States: N. p., 2015. 
Web.  doi:10.1039/C5NR04779J.

Copy to clipboard


                    He, Qian, Belianinov, Alex, Dziaugys, Andrius, Maksymovych, Petro, Vysochanskii, Yulian, Kalinin, Sergei V., & Borisevich, Albina Y. Antisite Defects in Layered Multiferroic CuCr0.9In0.1P2S6.  United States.  https://doi.org/10.1039/C5NR04779J

Copy to clipboard


                    He, Qian, Belianinov, Alex, Dziaugys, Andrius, Maksymovych, Petro, Vysochanskii, Yulian, Kalinin, Sergei V., and Borisevich, Albina Y. Tue .  
"Antisite Defects in Layered Multiferroic CuCr0.9In0.1P2S6".  United States.  https://doi.org/10.1039/C5NR04779J.  https://www.osti.gov/servlets/purl/1240543.

Copy to clipboard


                    
@article{osti_1240543,

  title        = {Antisite Defects in Layered Multiferroic CuCr0.9In0.1P2S6},

  author       = {He, Qian and Belianinov, Alex and Dziaugys, Andrius and Maksymovych, Petro and Vysochanskii, Yulian and Kalinin, Sergei V. and Borisevich, Albina Y.},

  abstractNote = {The CuCr1-xInxP2S6 system represents a large family of metal chalcogenophosphates that are unique and promising candidates for 2D materials with functionalities such as ferroelectricity. We carried out detailed microstructural and chemical characterization of these compounds using aberration-corrected STEM, in order to understand the origin of these different ordering phenomena. Quantitative STEM-HAADF imaging and analysis identified the stacking order of an 8-layer thin flake, which leads to the identification of anti-site In3+(Cu+) doping. We believe that these findings will pave the way towards understanding the ferroic coupling phenomena in van der Waals lamellar compounds, as well as the potential applications in 2-D electronics.},

  doi          = {10.1039/C5NR04779J},

  journal      = {Nanoscale},

  number       = 44,

  volume       = 7,

  place        = {United States},

  year         = {Tue Oct 06 00:00:00 EDT 2015},

  month        = {Tue Oct 06 00:00:00 EDT 2015}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1039/C5NR04779J

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 6 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

Graphene Oxide as an Optical Biosensing Platform
journal, May 2012

Morales-Narváez, Eden; Merkoçi, Arben
Advanced Materials, Vol. 24, Issue 25
DOI: 10.1002/adma.201200373

Nanosheets of Oxides and Hydroxides: Ultimate 2D Charge-Bearing Functional Crystallites
journal, October 2010

Ma, Renzhi; Sasaki, Takayoshi
Advanced Materials, Vol. 22, Issue 45
DOI: 10.1002/adma.201001722

An Overview of the Applications of Graphene-Based Materials in Supercapacitors
journal, April 2012

Huang, Yi; Liang, Jiajie; Chen, Yongsheng
Small, Vol. 8, Issue 12
DOI: 10.1002/smll.201102635

Two-Dimensional Dielectric Nanosheets: Novel Nanoelectronics From Nanocrystal Building Blocks
journal, October 2011

Osada, Minoru; Sasaki, Takayoshi
Advanced Materials, Vol. 24, Issue 2, p. 210-228
DOI: 10.1002/adma.201103241

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

The two-dimensional phase of boron nitride: Few-atomic-layer sheets and suspended membranes
journal, March 2008

Pacilé, D.; Meyer, J. C.; Girit, Ç. Ö.
Applied Physics Letters, Vol. 92, Issue 13
DOI: 10.1063/1.2903702

The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets
journal, April 2013

Chhowalla, Manish; Shin, Hyeon Suk; Eda, Goki
Nature Chemistry, Vol. 5, Issue 4, p. 263-275
DOI: 10.1038/nchem.1589

High-Mobility Few-Layer Graphene Field Effect Transistors Fabricated on Epitaxial Ferroelectric Gate Oxides
journal, April 2009

Hong, X.; Posadas, A.; Zou, K.
Physical Review Letters, Vol. 102, Issue 13
DOI: 10.1103/PhysRevLett.102.136808

Wafer-scale graphene/ferroelectric hybrid devices for low-voltage electronics
journal, January 2011

Zheng, Yi; Ni, Guang-Xin; Bae, Sukang
EPL (Europhysics Letters), Vol. 93, Issue 1
DOI: 10.1209/0295-5075/93/17002

Ferroelectric polymer-gated graphene memory with high speed conductivity modulation
journal, April 2013

Hwang, Hyeon Jun; Yang, Jin Ho; Lee, Young Gon
Nanotechnology, Vol. 24, Issue 17
DOI: 10.1088/0957-4484/24/17/175202

Terahertz plasmonics in ferroelectric-gated graphene
journal, May 2013

Jin, Dafei; Kumar, Anshuman; Hung Fung, Kin
Applied Physics Letters, Vol. 102, Issue 20
DOI: 10.1063/1.4807762

Ferroelectric-field-effect-enhanced electroresistance in metal/ferroelectric/semiconductor tunnel junctions
journal, May 2013

Wen, Zheng; Li, Chen; Wu, Di
Nature Materials, Vol. 12, Issue 7
DOI: 10.1038/nmat3649

Ionic conductivity in ferroic CuInP ₂ S ₆ and CuCrP ₂ S ₆
journal, May 1997

Maisonneuve, V.; Reau, J. M.; Dong, Ming
Ferroelectrics, Vol. 196, Issue 1
DOI: 10.1080/00150199708224175

Ferrielectric ordering in lamellar ${CuInP}_{2} S_{6}$
journal, November 1997

Maisonneuve, V.; Cajipe, V. B.; Simon, A.
Physical Review B, Vol. 56, Issue 17
DOI: 10.1103/PhysRevB.56.10860

On CuCrP2S6: Copper Disorder, Stacking Distortions, and Magnetic Ordering
journal, April 1995

Maisonneuve, V.; Payen, C.; Cajipe, V. B.
Journal of Solid State Chemistry, Vol. 116, Issue 1
DOI: 10.1006/jssc.1995.1204

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

Maisonneuve, V.; Evain, M.; Payen, C.
Journal of Alloys and Compounds, Vol. 218, Issue 2
DOI: 10.1016/0925-8388(94)01416-7

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

Belianinov, A.; He, Q.; Dziaugys, A.
Nano Letters, Vol. 15, Issue 6
DOI: 10.1021/acs.nanolett.5b00491

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

Kleemann, W.; Shvartsman, V. V.; Borisov, P.
Physical Review B, Vol. 84, Issue 9
DOI: 10.1103/PhysRevB.84.094411

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

Dziaugys, A.; Shvartsman, V. V.; Macutkevic, J.
Physical Review B, Vol. 85, Issue 13
DOI: 10.1103/PhysRevB.85.134105

Disordered Multiferroics
journal, June 2012

Kleemann, Wolfgang
Solid State Phenomena, Vol. 189
DOI: 10.4028/www.scientific.net/SSP.189.41

Three-Dimensional Location of a Single Dopant with Atomic Precision by Aberration-Corrected Scanning Transmission Electron Microscopy
journal, March 2014

Ishikawa, Ryo; Lupini, Andrew R.; Findlay, Scott D.
Nano Letters, Vol. 14, Issue 4
DOI: 10.1021/nl500564b

Atomic-scale imaging of individual dopant atoms and clusters in highly n-type bulk Si
journal, April 2002

Voyles, P. M.; Muller, D. A.; Grazul, J. L.
Nature, Vol. 416, Issue 6883
DOI: 10.1038/416826a

Advanced Computing in Electron Microscopy
book, January 2010

Kirkland, Earl J.
DOI: 10.1007/978-1-4419-6533-2

Strong Photoluminescence Enhancement of MoS ₂ through Defect Engineering and Oxygen Bonding
journal, May 2014

Nan, Haiyan; Wang, Zilu; Wang, Wenhui
ACS Nano, Vol. 8, Issue 6
DOI: 10.1021/nn500532f

Electrical Conduction Mechanisms of M _x PS ₃ , M _1−x M' _x PS ₃ and their Intercalation Compounds
journal, April 2000

Ichimura, Kenji; Nakano, Hiroyuki; Takashima, Masanao
Molecular Crystals and Liquid Crystals Science and Technology. Section A. Molecular Crystals and Liquid Crystals, Vol. 341, Issue 2
DOI: 10.1080/10587250008026126

Works referencing / citing this record:

Exfoliated CrPS ₄ with Promising Photoconductivity
journal, December 2019

Budniak, Adam K.; Killilea, Niall A.; Zelewski, Szymon J.
Small, Vol. 16, Issue 1
DOI: 10.1002/smll.201905924

Similar Records in DOE PAGES and OSTI.GOV collections:

Structural phase transitions of robust insulating Bi{sub 1-x}La{sub x}Fe{sub 1-y}Ti{sub y}O{sub 3} multiferroics

Journal Article Zhang, Linlin ; Yu, Jian ; Itoh, Mitsuru - Journal of Applied Physics

In contrast to leaky BiFeO{sub 3}, of which two structural phase transitions of cycloidal modulated antiferromagnetic-paramagnetic and ferroelectric-paraelectric are observed below 850 °C, chemical co-substitution to form Bi{sub 1−x}La{sub x}Fe{sub 1−y}Ti{sub y}O{sub 3} ternary solid solution makes these multiferroic ceramics become robust insulating low dielectric loss and exhibit rich structural phase transitions. Differential thermal analysis and temperature-dependent X-ray diffraction measurements probe four first-order structural phase transitions, e.g., T{sub H} = 305 °C, T{sub N} = 365 °C, T{sub C} = 810 °C, and T{sub S} = 830 °C observed in the Bi{sub 0.98}La{sub 0.02}Fe{sub 0.99}Ti{sub 0.01}O{sub 3} system, which are reasonably attributed to Brazovskii-type cycloidal modulated antiferromagnetic-helimagnetic (at T{sub H}) and helimagnetic-paramagnetic (atmore »« less
https://doi.org/10.1063/1.4869743
Spin correlated dielectric memory and rejuvenation in multiferroic CuCrS{sub 2}

Journal Article Karmakar, A. ; Dey, K. ; Majumdar, S. ; ... - Applied Physics Letters

We report a rare consequence of memory effect in dielectric response (ϵ) and magnetic field induced rejuvenation in a relaxor-type multiferroic chalcogenide, CuCrS{sub 2}. Despite reasonably high conductivity, we are able to detect significant spontaneous polarization using an improvised technique verifying ferroelectric (FE) order. Concomitant appearance of both FE and antiferromagnetic orders authenticates multiferroicity. A smeared out FE transition and strong frequency dependence of the broadened peak in ϵ obeying Dynamical scaling law signify relaxor properties. We discuss the role of geometrical frustration in the antiferromagnetically coupled layered triangular lattice and metal ligand hybridization for these unusual properties.
https://doi.org/10.1063/1.4863937
Multiferroicity in atomic van der Waals heterostructures

Journal Article Gong, Cheng ; Kim, Eun Mi ; Wang, Yuan ; ... - Nature Communications

Materials that are simultaneously ferromagnetic and ferroelectric - multiferroics - promise the control of disparate ferroic orders, leading to technological advances in microwave magnetoelectric applications and next generation of spintronics. Single-phase multiferroics are challenged by the opposite d-orbital occupations imposed by the two ferroics, and heterogeneous nanocomposite multiferroics demand ingredients' structural compatibility with the resultant multiferroicity exclusively at inter-materials boundaries. Here we propose the two-dimensional heterostructure multiferroics by stacking up atomic layers of ferromagnetic Cr₂Ge₂Te₆ and ferroelectric In₂Se₃, thereby leading to all-atomic multiferroicity. Through first-principles density functional theory calculations, we find as In₂Se₃ reverses its polarization, the magnetism of Cr₂Ge₂Te₆more »« less
Cited by 135
https://doi.org/10.1038/s41467-019-10693-0

Full Text Available
From spin induced ferroelectricity to spin and dipolar glass in a triangular lattice: The CuCr{sub 1−x}V{sub x}O{sub 2} (0≤x≤0.5) delafossite

Journal Article Kumar, S. ; Singh, K. ; Miclau, M. ; ... - Journal of Solid State Chemistry

The change from antiferromagnetism induced ferroelectricity to spin glass ferroelectric relaxor has been studied along the CuCr{sub 1−x}V{sub x}O{sub 2} (0≤x≤0.5) solid solution of polycrystalline samples. As x increases from CuCrO{sub 2} (x=0) to CuCr{sub 0.82}V{sub 0.18}O{sub 2}, it is found that the Néel temperature decreases from ∼24 K down to ∼13 K. This progressive weakening of the antiferromagnetism of CuCrO{sub 2} induces a rapid decrease of the spin induced ferroelectricity with polarization values going from ∼44 μC/m{sup 2} down to ∼1.5 μC/m{sup 2} for x=0.04 and x=0.08, respectively. Beyond x=0.18 (0.20≤x≤0.50), ac-magnetic susceptibility and magnetization measurements evidence a spinmore »« less
https://doi.org/10.1016/J.JSSC.2013.04.003
Self-Assembled Room Temperature Multiferroic BiFeO₃-LiFe₅O₈ Nanocomposites

Journal Article Sharma, Yogesh ; Agarwal, Radhe ; Collins, Liam ; ... - Advanced Functional Materials

Multiferroic materials have driven significant research interest due to their promising technological potential. Developing new room-temperature multiferroics and understanding their fundamental properties are important to reveal unanticipated physical phenomena and potential applications. Here, a new room temperature multiferroic nanocomposite comprised of an ordered ferrimagnetic spinel α-LiFe₅O₈ (LFO) and a ferroelectric perovskite BiFeO₃ (BFO) is presented. It is observed that lithium (Li)-doping in BFO favors the formation of LFO spinel as a secondary phase during the synthesis of Li_xBi_1-xFeO₃ ceramics. Multimodal functional and chemical imaging methods are used to map the relationship between doping-induced phase separation and local ferroic properties inmore »« less
Cited by 11
https://doi.org/10.1002/adfm.201906849

Full Text Available

Similar Records

Title: Antisite Defects in Layered Multiferroic CuCr0.9In0.1P2S6

Abstract

Citation Formats

Graphene Oxide as an Optical Biosensing Platform journal, May 2012

Nanosheets of Oxides and Hydroxides: Ultimate 2D Charge-Bearing Functional Crystallites journal, October 2010

An Overview of the Applications of Graphene-Based Materials in Supercapacitors journal, April 2012

Two-Dimensional Dielectric Nanosheets: Novel Nanoelectronics From Nanocrystal Building Blocks journal, October 2011

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

The two-dimensional phase of boron nitride: Few-atomic-layer sheets and suspended membranes journal, March 2008

The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets journal, April 2013

High-Mobility Few-Layer Graphene Field Effect Transistors Fabricated on Epitaxial Ferroelectric Gate Oxides journal, April 2009

Wafer-scale graphene/ferroelectric hybrid devices for low-voltage electronics journal, January 2011

Ferroelectric polymer-gated graphene memory with high speed conductivity modulation journal, April 2013

Terahertz plasmonics in ferroelectric-gated graphene journal, May 2013

Ferroelectric-field-effect-enhanced electroresistance in metal/ferroelectric/semiconductor tunnel junctions journal, May 2013

Ionic conductivity in ferroic CuInP 2 S 6 and CuCrP 2 S 6 journal, May 1997

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

On CuCrP2S6: Copper Disorder, Stacking Distortions, and Magnetic Ordering journal, April 1995

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

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

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

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

Disordered Multiferroics journal, June 2012

Three-Dimensional Location of a Single Dopant with Atomic Precision by Aberration-Corrected Scanning Transmission Electron Microscopy journal, March 2014

Atomic-scale imaging of individual dopant atoms and clusters in highly n-type bulk Si journal, April 2002

Advanced Computing in Electron Microscopy book, January 2010

Strong Photoluminescence Enhancement of MoS 2 through Defect Engineering and Oxygen Bonding journal, May 2014

Electrical Conduction Mechanisms of M x PS 3 , M 1−x M' x PS 3 and their Intercalation Compounds journal, April 2000

Exfoliated CrPS 4 with Promising Photoconductivity journal, December 2019

Title: Antisite Defects in Layered Multiferroic CuCr_0.9In_0.1P₂S₆

Graphene Oxide as an Optical Biosensing Platform
journal, May 2012

Nanosheets of Oxides and Hydroxides: Ultimate 2D Charge-Bearing Functional Crystallites
journal, October 2010

An Overview of the Applications of Graphene-Based Materials in Supercapacitors
journal, April 2012

Two-Dimensional Dielectric Nanosheets: Novel Nanoelectronics From Nanocrystal Building Blocks
journal, October 2011

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

The two-dimensional phase of boron nitride: Few-atomic-layer sheets and suspended membranes
journal, March 2008

The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets
journal, April 2013

High-Mobility Few-Layer Graphene Field Effect Transistors Fabricated on Epitaxial Ferroelectric Gate Oxides
journal, April 2009

Wafer-scale graphene/ferroelectric hybrid devices for low-voltage electronics
journal, January 2011

Ferroelectric polymer-gated graphene memory with high speed conductivity modulation
journal, April 2013

Terahertz plasmonics in ferroelectric-gated graphene
journal, May 2013

Ferroelectric-field-effect-enhanced electroresistance in metal/ferroelectric/semiconductor tunnel junctions
journal, May 2013

Ionic conductivity in ferroic CuInP ₂ S ₆ and CuCrP ₂ S ₆
journal, May 1997

Ferrielectric ordering in lamellar ${CuInP}_{2} S_{6}$
journal, November 1997

On CuCrP2S6: Copper Disorder, Stacking Distortions, and Magnetic Ordering
journal, April 1995

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

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

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

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

Disordered Multiferroics
journal, June 2012

Three-Dimensional Location of a Single Dopant with Atomic Precision by Aberration-Corrected Scanning Transmission Electron Microscopy
journal, March 2014

Atomic-scale imaging of individual dopant atoms and clusters in highly n-type bulk Si
journal, April 2002

Advanced Computing in Electron Microscopy
book, January 2010

Strong Photoluminescence Enhancement of MoS ₂ through Defect Engineering and Oxygen Bonding
journal, May 2014

Electrical Conduction Mechanisms of M _x PS ₃ , M _1−x M' _x PS ₃ and their Intercalation Compounds
journal, April 2000

Exfoliated CrPS ₄ with Promising Photoconductivity
journal, December 2019