Polymorphic Phases of Metal Chlorides in the Confined 2D Space of Bilayer Graphene

Yung Chang Lin; Amane Motoyama; Silvan Kretschmer; Sadegh Ghaderzadeh; Mahdi Ghorbani-Asl; Yuji Araki; Arkady V. Krasheninnikov; Hiroki Ago; Kazu Suenaga

doi:10.1002/adma.202105898

Polymorphic Phases of Metal Chlorides in the Confined 2D Space of Bilayer Graphene

Yung Chang Lin^*
, Amane Motoyama
, Silvan Kretschmer
, Sadegh Ghaderzadeh
, Mahdi Ghorbani-Asl
, Yuji Araki
, Arkady V. Krasheninnikov
, Hiroki Ago
, Kazu Suenaga

^*Corresponding author for this work

Department of Applied Physics

National Institute of Advanced Industrial Science and Technology
Kyushu University
Helmholtz-Zentrum Dresden-Rossendorf
Osaka University

Research output: Contribution to journal › Article › Scientific › peer-review

24 Citations (Scopus)

Abstract

Unprecedented 2D metal chloride structures are grown between sheets of bilayer graphene through intercalation of metal and chlorine atoms. Numerous spatially confined 2D phases of AlCl₃ and CuCl₂ distinct from their typical bulk forms are found, and the transformations between these new phases under the electron beam are directly observed by in situ scanning transmission electron microscopy (STEM). The density functional theory calculations confirm the metastability of the atomic structures derived from the STEM experiments and provide insights into the electronic properties of the phases, which range from insulators to semimetals. Additionally, the co-intercalation of different metal chlorides is found to create completely new hybrid systems; in-plane quasi-1D AlCl₃/CuCl₂ heterostructures are obtained. The existence of polymorphic phases hints at the unique possibilities for fabricating new types of 2D materials with diverse electronic properties confined between graphene sheets.

Original language	English
Article number	2105898
Number of pages	8
Journal	Advanced Materials
Volume	33
Issue number	52
Early online date	18 Oct 2021
DOIs	https://doi.org/10.1002/adma.202105898
Publication status	Published - 29 Dec 2021
MoE publication type	A1 Journal article-refereed

Funding

Y.‐C.L. and K.S. acknowledge JSPS‐KAKENHI (JP16H06333 and 18K14119), the JST‐CREST program (JPMJCR20B1, JMJCR20B5, and JPMJCR1993), the JSPS A3 Foresight Program, and the Kazato Research Encouragement Prize. H.A. acknowledges JSPS‐KAKENHI (18H03864 and 19K22113) and the JST‐CREST program (JPMJCR20B1). A.V.K. thanks the German Research Foundation (DFG; project KR 4866/2‐1) for support. The authors thank HRLS Stuttgart, Germany, TU Dresden (Taurus cluster), and CSC Finland for generously providing computing time. The authors acknowledge Dr. Pablo Solís‐Fernández and Prof. Rika Matsumoto for providing high‐quality BLG and facilitating valuable discussions.

Keywords

EELS
graphene intercalation
metal chloride
phase transitions

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10.1002/adma.202105898

https://www.hzdr.de/publications/Publ-33831

Cite this

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title = "Polymorphic Phases of Metal Chlorides in the Confined 2D Space of Bilayer Graphene",

abstract = "Unprecedented 2D metal chloride structures are grown between sheets of bilayer graphene through intercalation of metal and chlorine atoms. Numerous spatially confined 2D phases of AlCl3 and CuCl2 distinct from their typical bulk forms are found, and the transformations between these new phases under the electron beam are directly observed by in situ scanning transmission electron microscopy (STEM). The density functional theory calculations confirm the metastability of the atomic structures derived from the STEM experiments and provide insights into the electronic properties of the phases, which range from insulators to semimetals. Additionally, the co-intercalation of different metal chlorides is found to create completely new hybrid systems; in-plane quasi-1D AlCl3/CuCl2 heterostructures are obtained. The existence of polymorphic phases hints at the unique possibilities for fabricating new types of 2D materials with diverse electronic properties confined between graphene sheets.",

keywords = "EELS, graphene intercalation, metal chloride, phase transitions",

author = "Lin, \{Yung Chang\} and Amane Motoyama and Silvan Kretschmer and Sadegh Ghaderzadeh and Mahdi Ghorbani-Asl and Yuji Araki and Krasheninnikov, \{Arkady V.\} and Hiroki Ago and Kazu Suenaga",

note = "Funding Information: Y.‐C.L. and K.S. acknowledge JSPS‐KAKENHI (JP16H06333 and 18K14119), the JST‐CREST program (JPMJCR20B1, JMJCR20B5, and JPMJCR1993), the JSPS A3 Foresight Program, and the Kazato Research Encouragement Prize. H.A. acknowledges JSPS‐KAKENHI (18H03864 and 19K22113) and the JST‐CREST program (JPMJCR20B1). A.V.K. thanks the German Research Foundation (DFG; project KR 4866/2‐1) for support. The authors thank HRLS Stuttgart, Germany, TU Dresden (Taurus cluster), and CSC Finland for generously providing computing time. The authors acknowledge Dr. Pablo Sol{\'i}s‐Fern{\'a}ndez and Prof. Rika Matsumoto for providing high‐quality BLG and facilitating valuable discussions. Publisher Copyright: {\textcopyright} 2021 Wiley-VCH GmbH",

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AU - Lin, Yung Chang

AU - Motoyama, Amane

AU - Kretschmer, Silvan

AU - Ghaderzadeh, Sadegh

AU - Ghorbani-Asl, Mahdi

AU - Araki, Yuji

AU - Krasheninnikov, Arkady V.

AU - Ago, Hiroki

AU - Suenaga, Kazu

N1 - Funding Information: Y.‐C.L. and K.S. acknowledge JSPS‐KAKENHI (JP16H06333 and 18K14119), the JST‐CREST program (JPMJCR20B1, JMJCR20B5, and JPMJCR1993), the JSPS A3 Foresight Program, and the Kazato Research Encouragement Prize. H.A. acknowledges JSPS‐KAKENHI (18H03864 and 19K22113) and the JST‐CREST program (JPMJCR20B1). A.V.K. thanks the German Research Foundation (DFG; project KR 4866/2‐1) for support. The authors thank HRLS Stuttgart, Germany, TU Dresden (Taurus cluster), and CSC Finland for generously providing computing time. The authors acknowledge Dr. Pablo Solís‐Fernández and Prof. Rika Matsumoto for providing high‐quality BLG and facilitating valuable discussions. Publisher Copyright: © 2021 Wiley-VCH GmbH

PY - 2021/12/29

Y1 - 2021/12/29

N2 - Unprecedented 2D metal chloride structures are grown between sheets of bilayer graphene through intercalation of metal and chlorine atoms. Numerous spatially confined 2D phases of AlCl3 and CuCl2 distinct from their typical bulk forms are found, and the transformations between these new phases under the electron beam are directly observed by in situ scanning transmission electron microscopy (STEM). The density functional theory calculations confirm the metastability of the atomic structures derived from the STEM experiments and provide insights into the electronic properties of the phases, which range from insulators to semimetals. Additionally, the co-intercalation of different metal chlorides is found to create completely new hybrid systems; in-plane quasi-1D AlCl3/CuCl2 heterostructures are obtained. The existence of polymorphic phases hints at the unique possibilities for fabricating new types of 2D materials with diverse electronic properties confined between graphene sheets.

AB - Unprecedented 2D metal chloride structures are grown between sheets of bilayer graphene through intercalation of metal and chlorine atoms. Numerous spatially confined 2D phases of AlCl3 and CuCl2 distinct from their typical bulk forms are found, and the transformations between these new phases under the electron beam are directly observed by in situ scanning transmission electron microscopy (STEM). The density functional theory calculations confirm the metastability of the atomic structures derived from the STEM experiments and provide insights into the electronic properties of the phases, which range from insulators to semimetals. Additionally, the co-intercalation of different metal chlorides is found to create completely new hybrid systems; in-plane quasi-1D AlCl3/CuCl2 heterostructures are obtained. The existence of polymorphic phases hints at the unique possibilities for fabricating new types of 2D materials with diverse electronic properties confined between graphene sheets.

KW - EELS

KW - graphene intercalation

KW - metal chloride

KW - phase transitions

UR - https://www.scopus.com/pages/publications/85117140064

U2 - 10.1002/adma.202105898

DO - 10.1002/adma.202105898

M3 - Article

AN - SCOPUS:85117140064

SN - 0935-9648

VL - 33

JO - Advanced Materials

JF - Advanced Materials

IS - 52

M1 - 2105898

ER -

Polymorphic Phases of Metal Chlorides in the Confined 2D Space of Bilayer Graphene

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