Progress in the preparation and physical properties of two-dimensional Cr-based chalcogenide materials and heterojunctions

doi:10.1007/s11467-023-1342-y

Front. Phys.

2024, Vol. 19

Issue (2) : 23401 https://doi.org/10.1007/s11467-023-1342-y

TOPICAL REVIEW

Progress in the preparation and physical properties of two-dimensional Cr-based chalcogenide materials and heterojunctions

Xiulian Fan¹, Ruifeng Xin¹, Li Li^2,³, Bo Zhang⁴, Cheng Li¹, Xilong Zhou¹, Huanzhi Chen¹, Hongyan Zhang⁴, Fangping OuYang^1,^4,⁵, Yu Zhou^1,⁵(

)

¹. School of Physics and Electronics, Hunan Key Laboratory of Nanophotonics and Devices, Central South University, Changsha 410083, China
². Jincheng Research Institute of Opto-mechatronics Industry, Jincheng 048000, China
³. Shanxi Key Laboratory of Advanced Semiconductor Optoelectronic Devices and Integrated Systems, Jincheng 048000, China
⁴. School of Physical Science and Technology, Xinjiang University, Urumqi 830046, China
⁵. State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, China

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Abstract

Two-dimensional transition metal dichalcogenides (TMDs) exhibit promising application prospects in the domains of electronic devices, optoelectronic devices and spintronic devices due to their distinctive energy band structures and spin−orbit coupling properties. Cr-based chalcogenides with narrow or even zero bandgap, covering from semiconductors to metallic materials, have considerable potential for wide-band photodetection and two-dimensional magnetism. Currently, the preparation of 2D CrX_n (X = S, Se, Te) nanosheets primarily relies on chemical vapor deposition (CVD) and molecule beam epitaxy (MBE), which enable the production of high-quality large-area materials. This review article focuses on recent progress of 2D Cr-based chalcogenides, including unique crystal structure of the CrX_n system, phase-controlled synthesis, and heterojunction construction. Furthermore, a detailed introduction of room-temperature ferromagnetism and electrical/optoelectronic properties of 2D CrX_n is presented. Ultimately, this paper summarizes the challenges associated with utilizing 2D Cr-based chalcogenides in preparation strategies, optoelectronics devices, and spintronic devices while providing further insights.

Keywords physical properties two-dimensional materials Cr-based chalcogenide controlled synthesis heterojunction eletronic and optoelectronic devices

Corresponding Author(s): Yu Zhou

Just Accepted Date: 28 August 2023 Issue Date: 07 October 2023

Cite this article:

Xiulian Fan,Ruifeng Xin,Li Li, et al. Progress in the preparation and physical properties of two-dimensional Cr-based chalcogenide materials and heterojunctions[J]. Front. Phys. , 2024, 19(2): 23401.

URL:

https://academic.hep.com.cn/fop/EN/10.1007/s11467-023-1342-y
https://academic.hep.com.cn/fop/EN/Y2024/V19/I2/23401

Fig.1 A comprehensive review on the structure, synthesis, and emerging physical properties of two-dimensional Cr-based chalcogenides.

Fig.2 Structure and magnetic properties of 2D magnetic materials. (a) Crystal structure and MOKE measurement of CrI₃ single layer [31]. (b) Optical morphology and temperature-dependent Kerr rotation of bilayer Cr₂Ge₂Te₆ [32]. (c) Atomic structure and layer-dependent variation of ferromagnetic phase diagram of monolayer Fe₃GeTe₂ [33]. (d) The electronic band structures of Cr₂S₃, Cr₂Se₃ and Cr₂Te₃ [57].

Fig.3 Typical CrX_n crystal structure for different atomic ratios. (a) Calculation of the theoretically predicted atomic structures of different space groups of CrTe: Cmca, P6₃/mmc, R

3 ¯

m and Fm

3 ¯

m [59]. (b) Top and side views of the atomic structure of CrS₂ in the 2H, 1T and 1T' phase [62]. (c) Atomic structures of air-stable α-Cr₂S₃, β-Cr₂S₃ and theoretically predicted metastable phase γ-Cr₂S₃ [63]. (d) Crystal structure of Cr_1+xTe₂ formed by different Cr atom intercalation filling rates [51].

Fig.4 Crystal structure of the non-stoichiometric ratio Cr_1+xTe₂. (a) Top and side views of the crystal structures of CrTe [79]. (b) Schematic diagram of Cr intercalated CrTe₂ structure and side view of Cr_1.53Te₂ [37]. (c) Crystal structure of Cr_1.2Te₂ composed of Cr intercalated CrTe₂ van der Waals gap [80]. (d) Side view of the intercalated atomic structure of Cr_4.14Te₈ [81].

Fig.5 The main preparation methods of Cr-based sulfur nanomaterials. (a) OM and AFM images of a few atomic layers of Cr_1.2Te₂ and CrTe₂ prepared by liquid-phase exfoliation method [73, 80]. (b) SEM image of Cr₂S₃ nanorods prepared by solution method [89]. (c) SEM image of hydrothermally synthesized h-Cr₂Se₃ nanosheets [90]. (d) Schematic diagram and STM topography image of CrTe₂ films synthesized on graphene by MBE (top) [91]; atomic-resolution STM images of 1T-CrSe₂ and 1T'-CrSe₂ and STM image of Cr₂Se₃ grown by MBE (bottom) [92]. (e) Schematic diagram of interface connection of dangling bond (top), van der Waals gap (middle) and quasi van der Waals gap (bottom) [93]. (f) Schematic diagram of improved CVD synthesis of 2D Cr₅Te₈ crystals and OM images of the grown Cr₅Te₈ nanosheets at different temperatures (left) [94]; schematic illustration of 2D Cr₂S₃ crystals by confined-space CVD, accompanied by OM and AFM images of Cr₂S₃ nanoflakes (right) [65].

CrX_n (X=S/Se/Te)	Structure	Space group	Synthesis	Refs.

S	CrS₂	P6₃/mmc, P3 $m ¯$ 1	CVD	[62]
	Cr₂S₃	R $3 ¯$ , P $3 ¯$ 1c	CVD	[106]
	Cr₃S₄	P $3 ¯$ m1	−	[107]
	Cr₅S₆	P $3 ¯$ 1c	−	[108]
Se	CrSe	P6₃/mmc	CVD, MBE, CBD	[61, 97, 101]
	CrSe₂	P $3 ¯$ m1, R $3 ¯$ m	Solvothermal, CVD, MBE	[92, 95, 109]
	Cr₂Se₃	R $3 ¯$ , P $3 ¯$ m1	CVD, Hydrothermal	[69, 90]
	Cr₃Se₄	P $3 ¯$ m1	−	[110]
Te	CrTe	Cmca, P6₃/mmc, R $3 ¯$ m, Fm $3 ¯$ m	MBE, CVD	[111, 112]
	CrTe₂	P $3 ¯$ m1, P3m1	CVT, CVD, MBE	[87, 113, 114]
	Cr₂Te₃	P $3 ¯$ 1c	MBE, CVD	[74, 100]
	Cr₃Te₄	C2/m	MBE, CVD	[75, 115]
	Cr₅Te₈	P $3 ¯$ m1	CVD, CVT	[25, 55]
	CrTe₃	P2/m	MBE	[116]

Tab.1 Structures and synthesis of 2D Cr-based chalcogenides compounds.

Fig.6 Schematic illustration and characterization of the synthesis of 2D Cr-based chalcogenides in different phases based on chemical vapor deposition. (a) ADF-STEM and SAED images of Cr₂S₃ at 25, 400, and 600 °C, respectively (left); schematic representation of the atomic movement process of Cr in Cr₂S₃ during the phase transition (right) [117]. (b) PECVD synthetic process for N-doping in Cr₂S₃ nanosheets, and the OM images of P-Cr₂S₃ and N-Cr₂S₃ synthesized on SiO₂/Si substrates [118]. (c) Schematic illustration of CVD synthesis of Cr₂Se₃ (top left) and XRD spectra of two-dimensional Cr₂Se₃ nanosheets (top right); OM images of the synthesized Cr₂Se₃ nanosheets at different temperatures (bottom) [70]. (d) SEM image of Cr₃Te₄ nanoflakes and corresponding EDS mapping images with Cr and Te (left); the cross-sectional ADF-STEM image of Cr₃Te₄ nanoflakes and corresponding atomic structures (right) [119]. (e) A CVD synthesis route of 1T-CrTe₂ and atomic-resolution STEM-HADDF images of top-view and cross-section [113].

Fig.7 Heterojunction properties of 2D Cr-based sulfides. (a) Energy band distribution of the relative vacuum energy levels of monolayer CrS₂ and InSe and DFT calculation of the electronic energy band structure and density of states of CrS₂/InSe heterojunction [120]. (b) Energy band structure and PDOS of CrS₂/BP heterojunction, where blue and pink lines are CrS₂ and BP, respectively [121]. (c) Projected energy band structures of W atoms in WSe₂/CrSe₂ heterojunctions with no strain, 10% biaxial strain and 10% uniaxial strain [122]. (d) Low-resolution TEM image of the CrSe₂/WSe₂ heterojunction and EDS elemental mapping of Cr, Se, and W, and the SAED pattern of this heterojunction [109]. (e) Cross-sectional HADDF-STEM images of ZrTe₂/CrTe₂ heterojunction and SOT-assisted magnetization switching schematic of ZrTe₂/CrTe₂ heterojunction device [123]. (f) Schematic diagram of the CrTe₂/Bi₂Te₃ bilayer heterojunction structure with a van der Waals gap [124]. (g) The dI/dV conductance mapping at the CrTe₂/CrTe₃ metal-semiconductor lateral heterojunction interface and the STM image of this monolayer lateral heterojunction [125].

Fig.8 Magnetic properties of Cr-based sulfides. (a) Layer-dependent properties of the Curie temperature (T_C) of CrSe₂ and anomalous Hall resistance (R_AHE) variation of seven layers of CrSe₂ at given temperatures [109]. (b) Magnetic moments (μ_B), magnetization (χ) and specific heat (C_V) of monolayers of Cr₃Se₄ and Cr₃Te₄ as a function of temperature, simulated using the Monte Carlo method based on the 2D Heisenberg model [107]. (c) Magnetic temperature curves of CrTe₂ films with different thicknesses in field-cooling mode (left) and vertical magnetization curves of 7 ML CrTe₂ sample at different temperatures (right) [91]. (d) Schematic diagram of electrical transport measurements of Cr₅Te₈ devices under magnetic field and magnetic field-temperature phase diagram of Cr₅Te₈ [25]. (e) Hysteresis curves of Cr₂Te₃ and Cr₂Te₃/Cr₂Se₃ heterojunctions at 10 K and their temperature dependent magnetization intensity after field cooling and zero field cooling [131].

Fig.9 Novel magnetic properties of 2D Cr-based materials. (a) RMCD sweeps of Cr₂Te₃ nanosheets under +0.37% tensile strain (15.4 nm) and −0.37%compressive strain (13.6 nm) at different temperatures [134]. (b) Temperature-dependent characteristics of the out-of-plane phase of magnetization at different frequencies (f = 10, 50, 100 and 500 Hz) [137]. (c) Magnetoresistance (MR) properties of Cr₂Te₃ at parallel (θ = 90°) and perpendicular (θ = 0°) magnetic fields and variation of MR with magnetic field direction at 2 K [100]. (d) Illustration of the measured magnetoresistance of CrTe under an out-of-plane magnetic field and the temperature-dependent characteristics of the resistance at different θ under a 4 T magnetic field [138]. (e) Schematic and optical diagrams of a few-layer CrTe₂ device, and schematic diagrams of anisotropic magnetoresistance measurements [87].

Fig.10 (a) Schematic of SHG measurement of Cr₅Te₈ nanosheets. (b) SHG intensity dependence characteristics with laser power. (c) Angle polarization SHG of Cr₅Te₈ nanosheets [94]. (d) Angle-polarized SHG of monolayer Cr₂S₃ [53]. (e) Schematic diagram and OM image of Cr₂S₃ electrical device. (f) Transfer characteristic curves (I_ds−V_g) of Cr₂S₃ nanosheets with different thicknesses (V_ds = 1 V, thickness of Cr₂S₃ nanosheets are 2.6, 3.6, 4.8, 6 and 7.6 nm, respectively) [106]. (g) Schematic diagram of Cr₂S₃ homojunction transistor [105]. (h) Device schematic of Cr₂S₃ photodetector. (i) Detectivity dependence of Cr₂S₃ photodetector with effective laser power at different laser wavelengths (520, 808 and 1650 nm). (j) Time-resolved photocurrent of Cr₂S₃ photodetector at V_ds = 1 V, a 520 nm laser and 3.28 nW laser power [142]. (k) Conductivity (black) and on/off ratio (red) of Cr₂S₃ transistors with Se doping concentration, respectively. (l) Time-resolved photoresponse of a Se doped Cr₂S₃ transistor at V_ds = 1 V and 3.28 nW laser power [143].

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