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Two-dimensional transition metal dichalcogenides van der Waals heterojunctions with

broken-gap for tunnel field-effect transistors applications

Yixin Liu, Fei Wang, Liang Yang, Yuhuai Liu

PII: S1386-9477(24)00085-7
DOI: https://doi.org/10.1016/j.physe.2024.115981
Reference: PHYSE 115981

To appear in: Physica E: Low-dimensional Systems and Nanostructures

Received Date: 24 February 2024

Revised Date: 11 April 2024
Accepted Date: 27 April 2024

Please cite this article as: Y. Liu, F. Wang, L. Yang, Y. Liu, Two-dimensional transition metal
dichalcogenides van der Waals heterojunctions with broken-gap for tunnel field-effect transistors
applications, Physica E: Low-dimensional Systems and Nanostructures (2024), doi: https://
doi.org/10.1016/j.physe.2024.115981.

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© 2024 Published by Elsevier B.V.

Two-dimensional transition metal dichalcogenides van der Waals
heterojunctions with broken-gap for tunnel field-effect transistors
applications
Yixin Liu1,, Fei Wang1,*, Liang Yang2, Yuhuai Liu3, *

1
International Laboratory for Quantum Functional Materials of Henan, School of Physics and
Microelectronics, Zhengzhou University, Zhengzhou 450001, China
2
School of Materials Science and Engineering, Hainan University, Haikou 570228, China
3
National Center for International Joint Research of Electronic Materials and Systems, Henan
Province International Joint Laboratory of Electronic Materials and Systems, School of
Electrical and Information Engineering, Zhengzhou University, Zhengzhou 450001, China

Abstract

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The scaling down of transistors is nearing the limits dictated by Moore’s Law, primarily

due to the quantum tunneling effect. This challenge has spurred considerable interest in

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exploring novel materials characterized by broken-gap band alignment. Among these materials,

two-dimensional (2D) materials-based van der Waals heterojunctions (vdWHs) have emerged
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as promising candidates, owing to their nanoscale dimensions, which render them suitable for
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transistor construction. Type-III vdWHs, in particular, have been investigated for their ability

to facilitate rapid quantum Band-To-Band Tunneling (BTBT), thereby enabling low-power

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charge transport. In our study, we conducted a detailed analysis of four vdWHs comprised of
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HfSe2 and WXY (where X and Y represent Se or Te). Our findings indicate that 2D WSeTe (or
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WTe2)/HfSe2 vdWHs exhibit a broken-gap band alignment (type-Ⅲ) under the influence of an

external electric field, thus showcasing potential for integration into future tunnel field-effect

transistors (TFETs). Additionally, our investigation revealed that the band gap of two other

vdWHs, WTeSe (or WSe2)/HfSe2, varies linearly with the external electric field, fluctuating

between 0.4 eV and 1.0 eV. This characteristic makes them well-suited for application as

infrared detectors. By unveiling the distinct properties of these vdWH configurations, our

research not only anticipates the emergence of a notable type-III band alignment vdWH but

also underscores the potential of 2D vdWHs in optical sensor applications.

Keywords
Transition metal dichalcogenides, Van der Waals heterojunctions, Broken-gap

*
Correspondence author: [email protected], [email protected]
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1. Introduction
For over 60 years, silicon-based integrated circuits have been evolving in line with Moore's
Law[1] , with a focus on smaller transistor size, higher integration density, and greater energy
efficiency. However, the miniaturization of silicon-based devices is nearing its limits due to
quantum and interface effects[2]. Traditional silicon transistors are based on three-
dimensional(3D) bulk semiconductors, which pose challenges for electron flow through
nanoscale channels[3]. To further reduce transistor size and enable relatively unrestricted
charge flow, 2D materials have emerged as a promising option[4,5]. These materials allow for
the creation of atomic-level ultra-thin crystalline chips[6]. Recently, Miao et al. has designed a
vdWH tunneling transistor based on 2D atomic crystals with silicon semiconductors[7]. It is
reported that by capacitive coupling the gate-to-source electrostatic field , they were able to

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control the energy band structure of the semiconductor heterojunction, effectively regulating

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the electron's BTBT efficiency[8,9]. Other significant breakthrough[10], such as, Jang et al.

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successfully developed electronic and logic devices based on 2D semiconductors using a novel
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ultra-thin electrode material and Chien et al. fabricated memtransistor-like operation of devices
made by vdWHs[11]. This innovative material offers the ability to freely control the electrical
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performance of the devices. Additionally, recent successful synthesis of wafer-scale 2D
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transition metal dichalcogenides (TMDCs) [12–14] has paved the way for integrated device
array applications. Overall, these advancements in 2D materials and heterojunction design
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present exciting prospects for pushing the boundaries of integrated circuit technology and
overcoming the limitations faced by conventional silicon-based devices.
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The band alignment type is a crucial aspect of 2D vdWHs[15,16], categorized into type-I,
type-II, and type-III [17,18]. Among these, type-III vdWHs exhibit desirable properties such as
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quantum spin Hall phase,[19] low-voltage operation, higher peak tunneling currents, and a
steeper subthreshold[20–22], making them ideal building blocks for TFETs [23]. A promising
material for vdWHs is the 2D TMDCs with a Janus structure[24,25] , which has attracted
significant interest. In 2D Janus vdWHs, the physical and chemical properties of the
monolayers on both sides of the heterojunction can be preserved due to the weak interlayer
coupling caused by van der Waals interactions between layers[26]. The polarization induced by
the broken symmetry within and between the layers makes the properties of 2D Janus vdWHs,
such as bandgap and band-edge position, sensitive to external electric fields and strains[27,28].
As a result, the behavior of 2D Janus vdWHs can be more flexibly modulated than conventional
heterojunctions under external perturbations[29,30]. With their versatility, Janus TMDC-based
vdWHs have the potential to uncover various intriguing physical phenomena[31]. They offer
exciting opportunities for further research and exploration in the field.
In our study, we focus our research on the WSeTe/HfSe2 vdWH. Our aim is to

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comprehensively investigate the electronic properties of the WSeTe/HfSe2 vdWH under
external electric fields and unveil the underlying physical mechanism for type-III band
alignment. Additionally, we have conducted an analysis of three other WXY (X,
Y=Se,Te)/HfSe2 vdWHs, including their fundamental structural parameters and electronic
properties under external electric fields. Our findings not only shed light on the intricate
electronic behavior of the WSeTe/HfSe2 vdWH but also suggest potential avenues for designing
high-performance TFETs based on versatile vdWHs capable of multifunctional optoelectronic
applications.
2. Computational methods
The first-principles calculations were performed using the plane-wave pseudopotential as
implemented in the Vienna Ab initio Simulation Package (VASP) code[32,33]. The electron-

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core interactions were described with the frozen-core projector-augmented wave

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pseudopotentials[34] as parameterization by the Perdew–Burke–Ernzerhof for the exchange

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correlation function[35]. The cut-off energy 500 eV was used for electronic properties
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calculation of monolayer material and structure relaxation. The cut-off energy 400 eV was used
for calculations of vdWHs. The convergence criteria of force on each atom converge to 0.01
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eV/Å and the total energy is 1.0 × 10−5 eV when optimizing the geometric structure. The DFT-
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D2 method of Grimme[36] is considered to including the vdW interaction. To avoid the effect
of periodic images, in all the calculations, the z-direction of supercell was set to 25 Å. The
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dipole correction is incorporated in all calculations in the Janus WXY and heterojunctions. The
Heyd-Scuseria-Ernzerhof(HSE06) [37] method of calculations are used for all of the electronic
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properties. The optical calculations are performed using the HSE06 and independent particle
approximation calculations. The VASPKIT toolkit code[38] has been used pre and post-data
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processes in our calculations.

3. Results and discussion
Initially, we assess the structural parameters of monolayer unit cells for WSeTe and HfSe2
before constructing the heterojunction. The optimized lattice constants for 2D WSeTe and
HfSe2 are determined to be 3.40 Å and 3.68 Å, respectively, aligning well with prior
research[39,40]. The band gap of 2D WSeTe is 1.37 eV by using the PBE method and 1.81 eV
by using the HSE06 method, with the experimental value falling between these two values [41].
Similarly, the band gap of 2D HfSe2 is calculated to be 0.65 eV with the PBE method, 1.33 eV
with the HSE06 method, and the experimental value reported at 1.13 eV [42]. Given the closer
alignment of the HSE06 method with the experimental data, we opt for this method to compute
electronic properties in subsequent analyses. Notably, the HSE06 method yields values slightly
higher than the experimental data [43]. In terms of electronic structure, the valence band
maximum (VBM) and conduction band minimum (CBM) of 2D WSeTe, identified as a direct-

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gap semiconductor [44], are both situated at the K point. In contrast, 2D HfSe2 demonstrates
semiconducting characteristics with an indirect band gap type [45]. The VBM of 2D HfSe2 lies
at the Γ point and the CBM lies at the M point. Additionally, for both structures, the CBM is
mostly provided by the metal d orbital, similar to the majority of other semiconducting 2D

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TMDCs, and the VBM is predominated by chalcogen p and metal d orbitals[46].
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Fig. 1. (a) Crystal structure of WSeTe/HfSe2 from the top views. The black rhombus marks the unit
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cell of vdWH. (b)The band structure of monolayer WSeTe and HfSe2, where the red and blue are
given by the PBE and HSE06 method, respectively. The VBM is set to 0 eV.
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The WSeTe/HfSe2 vdWH, as shown in Fig. 1 (a), comprises a √19 × √19Janus WSeTe
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single-layer supercell combined with a 4×4 HfSe2 single-layer supercell. Remarkably, the
lattice mismatch between these constituents amounts to a mere 0.39%. This minuscule disparity
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suggests the feasibility of experimental fabrication for such a vdWH. To evaluate the stability
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of these configurations, the binding energies[47], expressed as Eb = Etotal − EWSeTe − EHfSe2 are
calculated. Here, Etotal represents the total energies of WSeTe/HfSe2 or WTeSe/HfSe2 vdWH,
while EWSeTe and EHfSe2 denote the individual energies of 2D WSeTe and 2D HfSe2, respectively.
Extending this analysis, we establish and delineate the binding energies for additional vdWHs
such as WTe2/HfSe2 and WSe2/HfSe2 in a similar fashion. Table 1 outlines the calculated
binding energies alongside the interlayer distances. Notably, all calculated binding energies, as
depicted in Table 1, manifest as negative values, a testament to the inherent stability in these
heterojunctions[48].

Table 1. The stable binding energy, interlayer distance, lattice mismatch, accumulated charges on
the HfSe2 (the charge 352 is for the pristine of HfSe2), band gap, and band alignment type of four
WXY/HfSe2 vdWHs.

WSeTe/HfSe2 WTe2/HfSe2 WSe2/HfSe2 WTeSe/HfSe2

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 −2
-40.50 -48.69 -45.27 -28.50
Binding energy (meV Å )

Interlayer distance(Å) 3.520 3.494 3.362 3.342

Lattice mismatch 0.39% 2.54% 0.89% 0.39%

Charge on HfSe 352.44 352.59 352.09 352.13

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Band gap (eV) 0.09 0.11 0.66 0.82

Band alignment type Ⅱ Ⅱ Ⅱ Ⅱ

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Fig. 2. Band structures of WSeTe/ HfSe2 vdWH under electric fields, with the green and pink lines
marking the contributions from the HfSe2 and WSeTe layers, respectively. The VBM is set to 0 eV.
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We delve into the fundamental mechanism governing the the WSeTe/HfSe2 vdWH. The
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work function[49], serving as an inherent benchmark for band alignment, is calculated by

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using the equation: Φ = Evac − Ef. In this formula, Evac represents the energy level of a stationary
electron near the surface in a vacuum, while Ef signifies the Fermi level energy. Prior to their
contact, the Fermi level of 2D WSeTe (-5.44 eV) is higher than that of HfSe2 (- 5.78 eV). After
the formation of the heterojunction, electrons would spontaneously float from WSeTe to
HfSe2 due to the distinction in their work functions. Consequently, the Fermi level of 2D HfSe2
and WSeTe shift upward and downward, eventually stabilizing at the same level. The resultant
work function of the vdWH is -5.66 eV, as anticipated, slightly lower than that of 2D HfSe2 yet
higher than that of 2D WSeTe. Simultaneously, as charges accumulate within HfSe2 in the
WSeTe/HfSe2 vdWH and deplete within WSeTe, a built-in electric field[50] emerges, directed
from WSeTe to HfSe2, as depicted in Fig. 3 (a). Moreover, as illustrated in Fig. 2, the band
alignment of the WSeTe/ HfSe2 vdWH, in the absence of an external electric field, assumes a
type-II configuration.

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Fig. 3. (a) Schematic diagram of the built-in electric field of WSeTe/HfSe2 vdWH. The applied
positive electric field is in the same direction as the built-in electric field. (b) Plane-averaged charge
density difference of WSeTe/HfSe2 vdWH. Insets of (b) are the corresponding 3D isosurfaces of
the electron density difference, where the yellow and blue isosurfaces represent electron

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accumulation and depletion, respectively. (c) Schematic diagram of a purposed device based on
WSeTe/HfSe2 vdWH.

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The formation of vdWH induces the establishment of an inherent electric field between
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the layers of vdWH and prompts the rearrangement of interface charges. Table 1 provides
insights into the charge distribution within the layers of HfSe2 in WSeTe/HfSe2 and WTe2/HfSe2,
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accumulating 0.44 and 0.59 electrons, respectively. Additionally, HfSe2 in WSe2/HfSe2 and
WTeSe/HfSe2 accumulates 0.09 and 0.13 electrons. Comparing these values with pristine HfSe2,
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the change in electron density is relatively modest post-vdWH formation. To elucidate this
formation mechanism further, we investigate the redistribution of charge density in
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WSeTe/HfSe2 vdWH. The plane-averaged charge density difference for the vdWH is
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calculated using Δρ(z) = Δρ(WSeTe/HfSe2)−Δρ(WSeTe)−Δρ(HfSe2). Here, Δρ(WSeTe/HfSe2),

Δρ(WSeTe), and Δρ(HfSe2) represent the plane-averaged charge density of WSeTe/HfSe2
vdWH, isolated WSeTe layer, and isolated HfSe2 layer, respectively. The calculated plane-
averaged charge density difference and the 3D isosurface of the charge density difference are
depicted in the insert of Fig. 3 (b). Notably, the WSeTe layer exhibits a charge depletion, while
the HfSe2 layer indicates charge accumulation, signifying an electron transfer between WSeTe
and HfSe2. These transferred charges, induced by the built-in electric field in the heterojunction,
coupled with the built-in electric field of intra-layer in Janus TMDCs [51], as illustrated in Fig.
3 (a), influence the electronic properties of the heterojunction and can be further modulated by
external fields.
Subsequently, we delve into the band structure of the four vdWHs. The band gap type of
the four vdWHs are all indirect and the band alignment type are all type-II. The band gap of
WSeTe/HfSe2 is 0.09 eV which can be seen in Table 1. As previously noted, the band gap value
obtained using HSE06 slightly exceeds the experimental measurement. Moreover, the minute

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nature of the 0.09 eV band gap leads us to infer that the experimental value is likely very close
to 0 eV. Under these circumstances, the VBM surpasses the CBM, suggesting that the
heterojunction likely possesses a broken-gap type-III band alignment. It is noteworthy that
electrons exhibit a high susceptibility to tunnel directly from the VBM of the WSeTe layer to
the CBM of the HfSe2 layer—a phenomenon known as BTBT transport. This characteristic
proves robust against thermal distribution and holds significant promise for TFETs.
To comprehensively investigate the broken-gap band alignment of WSeTe/HfSe2 vdWH ,
we applied external electric field to modulate the band structure. The electric field was applied
perpendicular to the stacking layers, with the positive direction pointing from the WSeTe layer
to the HfSe2 layer, and the negative direction pointing in the reverse (see Fig. 3 (a)). Fig. 2
illustrate the band edge positions and band structures of the WSeTe/HfSe2 vdWH under varying

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electric fields. As the positive electric field increases, the band gap of the WSeTe/HfSe2 vdWH

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monotonously decreases. When the positive electric field reaches 0.2 eV, the band gap of
WSeTe/HfSe2 vdWH closes, and the band alignment transitions from type-II to type-III,

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holding promise for applications in TFETs. Conversely, when applying the negative electric
field, the band gap of the WSeTe/HfSe2 vdWH monotonously increase, maintaining a type-II
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band alignment. These distinct electronic responses to electric fields are crucial for designing
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innovative digital devices. Building on these findings, we propose a versatile prototype based
on the WSeTe/HfSe2 vdWH, depicted in Fig. 3 (c). The device comprises a source, a drain, a
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channel, and two gates for introducing the external electric field. By applying a positive gate
voltage, this device transitions from a type-II to a type-III band alignment, making it suitable
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for TFETs. Conversely, applying a negative gate voltage maintains the type-II band alignment,
rendering the device applicable for optical sensor devices.
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Fig. 4. The variation of the four vdW heterojunctions band gap under the external electric field.

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 The evolution of the band structure under an external electric field can be elucidated by
considering the relationship between the directions of the applied electric field and the intrinsic
built-in electric field. The isolated monolayers WSeTe and WTeSe share identical atomic structures,
thereby exhibiting the same band structures and VBM. However, as a Janus structure, their out-of-
plane symmetry is broken, leading to the formation of a vertical dipole and the establishment of a
built-in intra-layer electric field between the layers. This phenomenon results in varying degrees of
charge transfer and interaction, thereby influencing the electronic properties in vdWH. Specifically,
the differences in inter-layer electric fields induce distinct built-in electric fields in Janus
SeWTe/HfSe2 and TeWSe/HfSe2 vdWHs. Consequently, these variations in built-in electric fields
contribute to different response properties under external electric fields in Janus vdWHs, as
illustrated in Fig. 4. As depicted in Fig. 3 (a), the directions of the built-in electric field and

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positive external electric field are consistent, reinforcing the built-in electric field with an

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increase in the positive electric field strength. Consequently, a greater number of charges
migrate from the WSeTe layer to the HfSe2 layer, leading to the increase of the band offset

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between the WSeTe and HfSe2 layers. On the contrary, the directions of the negative electric
field and the intrinsic built-in electric field are opposite. When applying the negative electric
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field on WSeTe/HfSe2 vdWH, the built-in electric field is weakened, leading to a reduction in
the quantity of charges transferred from the WSeTe to HfSe2 layers. This reduction, in turn,
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diminishes the band offset between the WSeTe and HfSe2 layers.
For our comprehensive exploration, Fig. 4 showcases the band gap behavior of four WXY
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(X, Y=Se, Te)/HfSe2 vdWHs under an external electric field. It is evident that the band gap of
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WTeSe (WSe2)/HfSe2 vdWHs exhibits a linear variation within a range of approximately 0.4
eV to 1.0 eV concerning the strength of the external electric field. This distinct behavior renders
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these two vdWHs viable for application as infrared detectors. In addition, the variation of
WTeSe (WSe2)/HfSe2 vdWHs is very small under certain negative electric field. Interestingly,
the absolute value of the WSe2/HfSe2 vdWHs varies slightly, which is higher than that of
WTeSe/HfSe2 vdWHs. This is because the built-in electric field of intra-layer and the built-in
electric field of inter-layer of WSe2/HfSe2 vdWHs (the structure is similar to what is shown in
Fig. 3(a)) is lower than that of WTeSe/HfSe2 vdWHs. Furthermore, the 2D WSeTe
(WTe2)/HfSe2 vdWHs exhibit a broken-gap band alignment under the influence of an external
electric field, hinting at their potential utilization in TFETs.
4. Conclusions
In summary, our study demonstrates the significant characteristics of 2D WSeTe
(WTe2)/HfSe2 van der Waals heterojunctions (vdWHs) through the application of first-
principles calculations based on density functional theory. Specifically, we unveil that these
vdWHs exhibit a type-III broken-gap band alignment when subjected to an external electric
field. This distinctive property renders them highly suitable for tunnel field-effect transistors
8
(TFETs) and holds immense potential for the future of integrated 2D semiconductor circuits.
Furthermore, our analysis reveals that the other two vdWH configurations, namely WTeSe
(WSe2)/HfSe2, demonstrate a linear fluctuation in their band gaps, ranging from 0.4 eV to 1.0
eV, in response to the application of an external electric field. This behavior positions them as
excellent candidates for infrared detectors. Overall, our findings provide a promising
foundation for TFET design and the advancement of infrared sensor technology, presenting
exciting prospects in both fields.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.

Acknowledgments：

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Supported by National Nature Science Foundation of China (Grant No. 62174148), National
Key Research and Development Program (NKRDP Grant No. 2022YFE0112000, Grant No.
2016YFE0118400), Key Program for International Joint Research of Henan Province (Grant

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No. 231111520300). -p
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(1) The coupling external and internal electric field tune the WSeTe (WTe2)/HfSe2
vdWHs to type-III.

(2) The WTeSe (WSe2)/HfSe2 vdWHs display a linear fluctuation in their band gaps as
the external electric field is applied.

(3) WSeTe (WTe2)/HfSe2 is highly suitable for TFETs and holds great potential for the
future of 2D semiconductor computing.

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Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐ The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

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