Results in Physics 54 (2023) 107047

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Results in Physics
journal homepage: www.elsevier.com/locate/rinp

Tuning the metal–semiconductor contact nature in MXene-based van der

Waals heterostructures
Yu-Han Wu a, Jia-Cheng Luo a, Jing Zhang a, Zi-Cheng He a, Yu Lan b, *, Gui-Fang Huang c,
Wangyu Hu d, Wei-Qing Huang c, *
a
Department of Physics and Electronic Information Science, Nanyue College, Hengyang Normal University, Hengyang 421008, China
b
College of Physics and Electronic Engineering, Hengyang Normal University, Hengyang 421002, China
c
Department of Applied Physics, School of Physics and Electronics, Hunan University, Changsha 410082, China
d
School of Materials Science and Engineering, Hunan University, Changsha 410082, China

A R T I C L E I N F O A B S T R A C T

Keywords: Two-dimensional (2D) transition metal carbides, nitrides, or carbonitrides (MXenes) have emerged as promising
Schottky barrier ultrathin materials for nanoelectronics and optoelectronics. However, the contact barrier at metal­
Metal–semiconductor contact –semiconductor (MS) junctions still significantly limits the device’s performance. Here, we propose a novel
van der Waals heterostructure
strategy—functionalizing accompanied with external electric fields—to tune the MS contact nature in MXene-
Electric field
First-principles calculations
based van der Waals (vdW) heterostructures, taking 2D Ti2C as an example, by means of first-principles calcu­
lations. Different Ti2CO2/Ti2CX2 (X = OH or S) vdW heterostructures are designed via functionalizing Ti2C
metals to contact with 2D Ti2CO2. We reveal that OH functionalized vdW MS heterostructure (Ti2CO2/Ti2C
(OH)2) can be tuned to the Ohmic contact owing to the strong interlayer interaction inducing a large number of
interlayer transferred electrons; while for the sulfurized vdW MS heterostructure (Ti2CO2/Ti2CS2), its Schottky
barrier height and contact type can be effectively tuned by external electric field due to the rather weak inter­
layer interaction. Our work paves a new way for the construction of 2D MXene-based vdW MS heterostructures
and demonstrates the great potential of 2D MXenes in future nanoelectronics and optoelectronics.

Introduction
Two-dimensional (2D) materials [1–7] have been intensively studied
due to their emerging novel properties and promising applications, and
van der Waals (vdW) heterostructures constructed by different 2D ma­
terials have been increasingly developed to eliminate the weakness of
individual 2D components or acquire advanced functionalities [8–15].
Among 2D vdW heterostructures, metal–semiconductor (MS) hetero­
structures play a key role in nanoelectronics and optoelectronics as MS
contact is indispensible in actual applications. To date, many 2D MS
heterostructures have been investigated theoretically and experimen­
tally, such as graphene/MoS2 [10,16,17], graphene/MoTe2 [18,19],
graphene/phosphorene [20], Ti3C2/porous g-C3N4 [21], MoSe2/Ti3C2
[22], and so on. It is crucial to understand the contact nature (Schottky
contact or Ohmic contact, p-type or n-type) and Schottky barrier height
(SBH) [23] in MS heterostructures since these factors may significantly
impact the performance of corresponding devices.
MXenes [24] as a new family of 2D materials have been regarded as
the potential candidate materials in the application of various fields due
to their versatile functionalities [24–45]. The general formula for
MXenes is Mn+1XnTx [24–26,31,43], where M represents an early tran­
sition metal, X stands for carbon and/or nitrogen, and Tx are the surface
terminations [24,25]. Like other 2D materials, MXenes are widely
employed to constructed vdW heterostructures with high performance
to enhance their possibilities in actual applications. For example, Co-
doped MoS2 is coupled with Mo2CTx to produce the Co-MoS2/Mo2CTx
nanohybrids [46], which show superior hydrogen evolution reaction in
alkaline media; the 2D phosphorene/Ti3C2Tx heterostructure [47] was
prepared as the electrodes for sodium-ion batteries and exhibits high
reversible capacity and excellent cycling stability. Tang et al. designed
16 different heterostructures composed by MXenes and transition-metal
dichalcogenides [48] by density functional theory (DFT) and found that
they have great potential in the application of sodium-ion batteries or
Na–O2 batteries. Although most MXenes belong to metals, some func­
tionalized MXenes tend to be semiconductors [25,49,50]. This means
that MXenes could act as both the metal and semiconductor materials

* Corresponding authors.
E-mail addresses: ylan@bnu.edu.cn (Y. Lan), wqhuang@hnu.edu.cn (W.-Q. Huang).

https://doi.org/10.1016/j.rinp.2023.107047
Received 6 July 2023; Received in revised form 20 September 2023; Accepted 30 September 2023
Available online 2 October 2023
2211-3797/© 2023 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
Y.-H. Wu et al.
within 2D MS heterostructures, thereby significantly enhancing their
potential applications.
Recently we developed a MXene-based heterostructure Ti2CO2/
Ti2CF2 [51], which exhibits robust Schottky barriers under different
magnitudes of electric field. However, in order to meet the specific
application requirements, tuning the SBH is very important for MS
heterostructures because the SBH and contact type have great impact on
the performance of devices. In present study, we have used different
functionalized MXenes with metal characteristic to contact with semi­
conducting Ti2CO2 to form MS heterostructures in order to derive
tunable contact nature. First-principles calculations has been carried out
to study the electronic properties of these heterostructures. Two heter­
ostructures, Ti2CO2/Ti2C(OH)2 and Ti2CO2/Ti2CS2, are chosen as ex­
amples to address the tunable contact nature in MXene-based MS
heterostructures. The results demonstrate that using Ti2C(OH)2 to con­
tact with Ti2CO2 along the vertical direction can modulate the con­
structed MS heterostructure to the Ohmic contact, while employing
Ti2CS2 to stack onto Ti2CO2 can effectively tune the Schottky barriers
between the Ti2CS2 and Ti2CO2 layers via applying vertical electric field.
Computational methods
Theoretical investigation was carried out by the Vienna Ab-initio
Simulation Package (VASP) [52–54] based on DFT, while post-data
processing was handled under the help of VASPKIT package [55]. Ion-
electron interaction was modeled by the projector augmented wave
(PAW) [56] approach, and electron exchange correlation was treated by
the Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation
(GGA) [57]. The plane-wave cutoff energy was set as large as 600 eV,
and an 8 × 8 × 1 (12 × 12 × 1) k-points grid of the Brillouin Zone with a
Γ-centered mesh was sampled in geometric optimizations (self-consis­
tent computations). The energy convergence accuracy was always set to
10− 6 eV, however, it was adjusted to 10− 5 eV to expedite the calcula­
tions in situations involving an external electric field. The geometric
optimization was carried out until the residual forces were lower than
0.01 eV/Å. The zero damping Grimme DFT-D3 scheme [53,58] was used
to correctly evaluate the weak vdW interaction between layers in the
constructed heterostructures. To avoid the possibilities of under­
estimated band gaps, the Heyd–Scuseria–Ernzerhof (HSE06) [59] hybrid
functional was adopted in the calculations except for geometric
Fig. 1. The geometric structures of (a) Ti2CO2, (b) Ti2CS2 and (c) Ti2C(OH)2, and the side view of geometric structures of the (d) Ti2CO2/Ti2CS2 and (e) Ti2CO2/Ti2C
(OH)2 heterostructures. The parallelogram with dashed line in each figure denotes the 2D unit cell.
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Results in Physics 54 (2023) 107047
optimization. The Z-direction lattice constant was fixed at 25 Å to avoid
interactions between periodic images of the system.
Results and discussion
We firstly obtained the optimized geometric structures of Ti2CO2,
Ti2CS2 and Ti2C(OH)2 by relaxation calculations and the results are
plotted in Fig. 1. As seen from Fig. 1, the geometric structures of the
three crystals are all hexagonal lattices, and for each crystal the carbon
layer is sandwiched by two titanium layers with functionalized groups
(O, S or OH) on two surfaces. The optimized lattice constants of Ti2CO2
and Ti2C(OH)2 are 3.03 Å and 3.06 Å, respectively, which are highly
consistent with other theoretical work [50,51,60–64]. The optimized
lattice constant of Ti2CS2 is 3.19 Å, which is also in good agreement with
previous results [65,66]. Then the electronic properties of the three free-
standing monolayers, Ti2CO2, Ti2C(OH)2 and Ti2CS2 are investigated,
and the band structures are shown in Fig. 2, where the Fermi Level (FL)
of each crystal is set to zero. The Ti2CO2 monolayer is found to be a
semiconductor with a band gap of 0.93 eV, and the valence band
maximum (VBM) and conduction band minimum (CBM) are located at
the Γ and M points, respectively, in agreement with previous results
[50,51]. The Ti2C(OH)2 and Ti2CS2 monolayers are both metals, making
them appropriate in device applications.
The difference between the lattice constants of Ti2CO2 and Ti2CS2 is
0.16 Å, leading to a 5.3 % mismatch which is greater than 5 %. Then in
order to eliminate the effect of lattice mismatch, Ti2CX2 (X = S or OH) is
compressed to match the optimized lattice constant of Ti2CO2 since the
metal characteristic is not sensitive to strain. For convenience, here we
just consider a rather energetically stable stacking pattern to construct
Ti2CO2/Ti2CX2 vdW heterostructures, i. e., the X functionalized groups
of Ti2CX2 at the interface side sitting atop the titanium atoms of Ti2CO2
near the interface side. In this stacking pattern, the Ti2CO2 layer and the
Ti2CX2 layer overlap with each other along the vertical direction, and
the side view of lattice structures of the Ti2CO2/Ti2C(OH)2 and Ti2CO2/
Ti2CS2 heterostructures are plotted in Fig. 1(d) and (e), respectively. All
the atoms are fully optimized with the shape and size of the unit cell
being fixed. For Ti2CO2/Ti2CS2, the equilibrium distance between the
Ti2CO2 layer and Ti2CS2 layer is 2.86 Å, which is close to the typical
interlayer distance of vdW heterostructures [12,67,68]. For Ti2CO2/
Ti2C(OH)2, the equilibrium distance between the Ti2CO2 layer and Ti2C
Y.-H. Wu et al.
Fig. 2. Band structures of (a) Ti2CO2, (b) Ti2C(OH)2, and (c) Ti2CS2. The Fermi level is set to zero.
(OH)2 layer is 1.65 Å, which seems much smaller than the typical dis­
tance for vdW interactions. However, the minimal distance between the
hydrogen atom in the Ti2C(OH)2 layer and the oxygen atom in the
Ti2CO2 layer is 2.41 Å, which is significantly larger than the sum of the
covalent radii of hydrogen atom and oxygen atom (0.37 Å and 0.73 Å) as
well as the length of the O-H bonds in the Ti2C(OH)2 layer (0.98 Å),
confirming that there are no covalent bonds between the two layers.
Moreover, the minimal distance of 2.41 Å is even greater than the typical
length of hydrogen bonds (≤2.0 Å), indicating the absence of hydrogen
bonds at the interface. These results suggest that the interlayer inter­
action should belong to the vdW type. The energetic stability of a 2D
vdW heterostructure can be evaluated by the formation energy
∑ reduced from 3.19 Å to 3.03 Å. However, the metal characteristic is well
Ef = E h − Ei (1)
i
where Eh and Ei are the total energies of the heterostructure and each 2D
component, respectively. The formation energies of Ti2CO2/Ti2C(OH)2
and Ti2CO2/Ti2CS2 are − 2.31 eV and − 1.63 eV, respectively, which
suggests that the two heterostructures are truly rather energetically
stable. In particular, the formation energy of Ti2CO2/Ti2C(OH)2 is much
lower than that of Ti2CO2/Ti2CS2, which is consistent with the results of
equilibrium interlayer distances of the two heterostructures, indicating
that the interlayer interaction in Ti2CO2/Ti2C(OH)2 is much stronger
than that in Ti2CO2/Ti2CS2.
The low formation energy of the Ti2CO2/Ti2C(OH)2 heterostructure
indicates the interlayer interaction is rather strong and may greatly
affect the band structures of the Ti2CO2 and Ti2C(OH)2 layers. To see the
interlayer interaction effect on the band structures more clearly, we
have investigated the band structure of the Ti2CO2/Ti2C(OH)2 hetero­
structure, and the result is shown in Fig. 3(a). It can be seen from Fig. 3
(a) that the main band features of Ti2CO2 and Ti2C(OH)2 are preserved,
and the contributions by the Ti2CO2 and Ti2C(OH)2 components are
almost separated from each other, implying that the Ti2CO2 layer and
Ti2C(OH)2 layer should be bound by vdW interaction though two layers
are quite close to each other along the Z-direction. However, the inter­
layer interaction seems somewhat stronger than other typical vdW
heterostructures, resulting in some changes to the bands of both the
Ti2CO2 and Ti2C(OH)2 components. The conduction band of the Ti2CO2
Fig. 3. Projected band structures of (a) Ti2CO2/Ti2C(OH)2 and (b) Ti2CO2/
Ti2CS2. The Fermi level is set to zero.
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Results in Physics 54 (2023) 107047
layer shifts significantly towards the FL, with the FL finally being located
above the conduction band minimum (CBM) of the Ti2CO2 layer,
causing the Ti2CO2 layer to become a conductor, thus transforming the
MS contact into an Ohmic contact. The band gap of the Ti2CO2 layer is
also reduced by the strong interlayer interaction, decreasing from the
value of 0.93 eV in the pristine Ti2CO2 monolayer to the current value of
0.78 eV.
The characteristics of band structure of the Ti2CO2/Ti2CS2 hetero­
structure are somewhat different from that of the Ti2CO2/Ti2C(OH)2
heterostructure, as can be seen from Fig. 3(b). The contribution by the
Ti2CS2 layer undergoes some changes compared with that of pristine
Ti2CS2 due to a 5 % compressive strain with the lattice constant being
preserved. One amazing feature is that the band structure of Ti2CO2/
Ti2CS2 can be deemed as the simple combination of band structures of
the Ti2CO2 layer and Ti2CS2 layer, indicating that the interaction be­
tween the two layers is rather weak. In particular, the band structure of
the Ti2CO2 layer is preserved quite well, with the band gap of 0.95 eV
which remains almost unchanged after forming the heterostructure.
These results further support the dominance of vdW interaction between
the Ti2CO2 layer and Ti2CS2 layer. However, in comparison to the
pristine Ti2CO2 monolayer where the FL is slightly higher than the
valence band maximum (VBM), the FL now resides near the middle of
band gap of the Ti2CO2 layer.
When a metal contacts with a semiconductor, a band bending would
occur, which can be evaluated by [69,70]
ΔEF = Wh − Ws (2)
where Wh and Ws are the work functions of the MS heterostructure and
the corresponding semiconductor monolayer, respectively. The work
function is defined as the energy difference between the vacuum level
and FL. For the Ti2CO2/Ti2C(OH)2 heterostructure, a significant charge
transfer between the two layers (will be discussed in detail later) creates
a strong built-in electric field, resulting in the tilt of the vacuum level,
making it inappropriate to evaluate the work function in this scenario.
The calculated work function of the Ti2CO2/Ti2CS2 heterostructure is
6.00 eV, while the work function of Ti2CO2 is 6.30 eV, as shown in Fig. 4
(a). Then ΔEF = − 0.30 eV < 0, which means that electrons will transfer
from Ti2CO2/Ti2CS2 to the noncontacted Ti2CO2 region. According to
the above results, we designed a MS junction transistor as shown in
Fig. 4(b), where the metal Ti2CS2 acts as both source and drain while the
semiconductor Ti2CO2 acts as the channel material.
Charge carriers will encounter an energy barrier (Schottky barrier)
when they transport across a MS junction. The SBHs for electrons and
holes can be determined by [23,71–73]
ΦBn = EC − EFh , ΦBp = EFh − EV (3)
respectively, where EFh is the FL of the MS heterostructure, and EC and
EV are the CBM and VBM of the semiconductor layer in the hetero­
structure, respectively. If the FL locates in the band gap region of the
semiconductor layer, the MS contact belongs to a Schottky contact. The
Schottky contact is n-type for ΦBn < ΦBp , otherwise, the Schottky
Y.-H. Wu et al. Results in Physics 54 (2023) 107047

Fig. 4. (a) Band alignments of the Ti2CO2 monolayer and Ti2CO2/Ti2CS2 heterostructure. EVAC , EFs , and EFh represent the vacuum level, the Fermi level of Ti2CO2
monolayer, and the Fermi level of Ti2CO2/Ti2CS2, respectively. (b) Schematic diagram of a Ti2CO2/Ti2CS2 based transistor. The arrows show the direction of
electron transfer.

contact becomes p-type. When the FL lies in the conduction band or

valence band of the semiconductor layer, leading to ΦBn < 0 or
ΦBp < 0, the MS contact turns into the Ohmic contact. For the Ti2CO2/
Ti2C(OH)2 heterostructure ΦBn = t0.29 eV due to strong interlayer
interaction, so the Ti2CO2 layer is changed to a metal, inducing an
Ohmic contact. For the Ti2CO2/Ti2CS2 heterostructure, ΦBn = 0.42 eV
and ΦBp = 0.53 eV, leading to the n-type Schottky contact. For the
Schottky-Mott model without interaction between the metal and semi­
conductor, the SBHs can be evaluated as
ΦBn = Wm − χ e , ΦBp = Wm − χ I (4)

where Wm , χ e and χ I are the work function of the metal, the electron
affinity and ionization potential of the semiconductor, respectively. The
calculated ΦBn and ΦBp of the Ti2CO2/Ti2CS2 heterostructure according
to Eq. (4) are 0.41 eV and 0.52 eV, respectively, which are almost the
same as the results obtained from band structures, further indicating
that the interaction between the Ti2CO2 layer and Ti2CS2 layer is rather
weak vdW interaction.
In order to meet the requirements of actual applications, regulating
the electronic band structure and SBH is desirable. To this end, it is an
effective method to apply a perpendicular electric field or gate voltage to
the MS junction transistor. We have carried out a series of calculations of
the electronic band structure of the Ti2CO2/Ti2CS2 heterostructure
under different intensities of external electric field which is perpendic­
ular to the Ti2CO2 or Ti2CS2 layer. Fig. 5 shows evolution of the band Fig. 5. Evolution of projected band structure of Ti2CO2/Ti2CS2 with respect to
structure of the Ti2CO2/Ti2CS2 heterostructure with respect to electric electric field. (a), (b), (c) and (d) are the results of − 0.2 V/Å, − 0.1 V/Å, 0.1 V/Å
field, where the direction for the positive electric field points from the and 0.2 V/Å, respectively. The heights of cyan and grey rectangles represent the
Ti2CS2 layer to the Ti2CO2 layer. When negative electric field is applied values of ΦBn and ΦBp , respectively. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of
to the heterostructure, the valence band of the Ti2CO2 layer shifts away
this article.)
the FL while the conduction band shifts towards the FL, leading to the
decrease of ΦBn . On applying positive electric field, the valence band and
conduction band behave oppositely, resulting in the decrease of ΦBp . To gain further insight into the contact nature and the mechanism of
These results suggest that applying vertical electric field can effectively tuning the Schottky barriers, we have analyzed the charge density dif­
ference (CDD) which can be calculated by
tune the band structure and SBH of the Ti2CO2/Ti2CS2 heterostructure.
∑
To see more clearly the electric field dependent behavior of the SBH, ΦBn Δ ρ = ρh − ρi (5)
and ΦBp as functions of electric field are plotted in Fig. 6. Without an i
electric field, the CBM of the Ti2CO2 layer is closer to the FL than the
VBM, leading to a n-type Schottky barrier. When an electric filed is where ρh and ρi are the charge densities of the heterostructure and each
applied to the heteorostructure, ΦBn and ΦBp both vary gradually with layer, respectively. The CDDs of the Ti2CO2/Ti2C(OH)2 and Ti2CO2/
changing the magnitude of electric field. For negative values of electric Ti2CS2 heterostructures are shown in Fig. 7, where the cyan and yellow
field, the Schottky barrier always remains n-type, with ΦBn decreasing colors denote depletion and accumulation of electrons, respectively. To
and ΦBp increasing linearly as the electric field becomes more negative. see more clearly the properties of electron transfer, the plane average of
ΦBn approaches zero when the electric field is lower than − 0.3 V/Å. On CDD 〈Δρ〉 along the Z-direction is also depicted as a blue curve in each
the positive side of electric field, ΦBn and ΦBp maintain their linear figure. Fig. 7(a) reveals a significant charge redistribution occurring
variation with respect to electric field. When the positive electric field around interface of the Ti2CO2/Ti2C(OH)2 heterostructure, with a
exceeds 0.04 V/Å, ΦBp becomes smaller than ΦBn , resulting in a switch considerable number of electrons moving from the Ti2C(OH)2 layer to
from an n-type to a p-type Schottky contact. ΦBp gets close to zero when the Ti2CO2 layer. Bader charge analysis indicates that approximately
0.198 e of electrons are transferred per unit cell. Consequently, these
the electric field is greater 0.3 V/Å. Obviously, the SBH and Schottky
additional electrons originating from the Ti2C(OH)2 layer cause the
contact types of the Ti2CO2/Ti2CS2 heterostructure can be effectively
conduction band of the Ti2CO2 layer to shift towards the FL. The FL
modulated by electric field which is perpendicular to the
finally stay in the region of conduction band, leading to the metallic
heterostructure.
characteristic of Ti2CO2. These results also suggest that choosing

4
Y.-H. Wu et al.
Fig. 6. Evolution of the Schottky barriers of the Ti2CO2/Ti2CS2 heterostructure
with respect to electric field.
Fig. 7. Charge density differences of (a) Ti2CO2/Ti2C(OH)2 and (b) Ti2CO2/
Ti2CS2 with isosurface values of 0.001 e/Å3 and 0.00006 e/Å3, resepctively.
The yellow and cyan colors represent electron accumulation and depletion,
respectively. The blue curves are the corresponding plane-average plots along
the Z-direction. (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)
appropriate functionalized Ti2C metals to contact with Ti2CO2 can tune
the Schottky contact to the Ohmic one. Electron redistribution also oc­
curs in the interface region of Ti2CO2/Ti2CS2 during the contact for­
mation. From the CDD image there may be a bit of confusion with some
extra electrons accumulating around the sulfur atoms beyond the
interface, however, electrons in general transfer from the Ti2CS2 layer to
the Ti2CO2 layer, with an amount of 0.008 e transferring charge for a
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Results in Physics 54 (2023) 107047
unit cell according to Bader charge analysis. The number of electrons
which transfer to the Ti2CO2 layer due to the interface interaction is
much fewer than the case in the Ti2CO2/Ti2C(OH)2 heterostructure,
leading to that the FL remains in the band gap of the Ti2CO2 layer after
forming the Ti2CO2/Ti2CS2 heterostructure.
The mechanism of electric field effect on the Schottky barriers of the
Ti2CO2/Ti2CS2 heterostructure can be understood through the interlayer
charge transfer, as plotted in Fig. 8. As mentioned earlier, when the
Ti2CO2 and Ti2CS2 layers are stacked, the Ti2CO2 layer acquires elec­
trons from the Ti2CS2 layer, resulting in an n-type Schottky contact.
When the negative electric field (pointing from the Ti2CO2 layer to the
Ti2CS2 layer) is applied, more electrons transfer from the Ti2CS2 layer to
the Ti2CO2 layer compared to the case without an electric field. The
stronger the magnitude of the electric field is, the more electrons
transfer, resulting in the increasing of interlayer charge transfer, as
clearly shown in Fig. 8. Hence the conduction band of the Ti2CO2 layer
shift toward the FL with increasing the number of electrons, leading to
the decrease of ΦBn , as shown in Fig. 7. On the contrary, the positive
electric field reduces the interlayer charge transfer. Then the valence
band of the Ti2CO2 layer shifts toward to the FL, resulting in the decrease
of ΦBp , as shown in Fig. 7. Consequently, the changes in Schottky bar­
riers with respect to an external electric field are primarily caused by the
modulation of charge transfer between layers induced by the electric
field. In the electric field range of − 0.3 V/Å to 0.3 V/Å, the number of
interlayer transferred electrons varies linearly with electric field with a
low changing rate. This electric field range corresponds to the linear
variation range for ΦBn and ΦBp . When the negative electric field is lower
than − 0.3 V/Å or positive electric field is greater than 0.3 V/Å, the
varying rate of interlayer transfer charge increases abruptly. This elec­
tric field range corresponds to the range that ΦBn or ΦBp approaches
zero, indicating that the heterostructure is probably tuned to the Ohmic
contact thus leading to the sudden increasing of transferred electrons.
Conclusion
In summary, we propose a new strategy—functionalizing accompa­
nied with external fields—to tune the MS contact nature in MXene-based
van der Waals (vdW) heterostructures. We used different functionalized
Ti2C to contact with Ti2CO2 to search MXene-based MS heterostructures
with tunable contact nature, and then tried to apply electric field to the
corresponding heterostructures to modulate the Schottky barrier. We
mainly take two heterostructures, Ti2CO2/Ti2C(OH)2 and Ti2CO2/
Fig. 8. Interlayer charge transfer of the Ti2CO2/Ti2CS2 heterostructure with
respect to electric field. The positive value represents electrons transferring
from the Ti2CS2 layer to the Ti2CO2 layer.
Y.-H. Wu et al.
Ti2CS2, as the examples to address the issue. The calculated results
demonstrate that the main band features of the Ti2CO2 layer and Ti2C
(OH)2 layer are preserved in the Ti2CO2/Ti2C(OH)2 heterostructure,
however, due to strong interlayer interaction a large number of electrons
transfer from the Ti2C(OH)2 layer to the Ti2CO2 layer, which leads to
that the conduction band of the Ti2CO2 layer shift towards the FL. After
forming the Ti2CO2/Ti2C(OH)2 heterostructure, the FL is finally located
above the CBM thus resulting in the metallic characteristic of the Ti2CO2
layer and the Ohmic contact of the heterostructure. Nevertheless, the
interlayer interaction in the Ti2CO2/Ti2CS2 heterostructure is much
weaker than that in the Ti2CO2/Ti2C(OH)2 heterostructure, with much
fewer electrons transferring from the metal layer to the semiconductor
layer. Then the FL still maintains in the band gap region and locates
slightly above the middle band gap of the Ti2CO2 layer, leading to the n-
type Schottky contact. In particular, our results suggest that electric field
perpendicular to the Ti2CO2/Ti2CS2 heterostructure can effectively tune
the number of interlayer transferred electrons, thus resulting in the
tunability of the band structure and SBH of the heterostructure. The
results also suggest that using different functionalized Ti2C metals like
Ti2C(OH)2 to form Ti2CO2/Ti2CX2 heterostructures can modulated the
electronic band structure, SBH and contact nature of the MS junctions.
Our work can not only offer insights into the properties of 2D MXene-
based vdW MS heterostructures but also demonstrates the great poten­
tial of 2D MXenes in future nanoelectronics and optoelectronics.
CRediT authorship contribution statement
Yu-Han Wu: Data curation, Formal analysis, Investigation, Visuali­
zation, Writing – original draft. Jia-Cheng Luo: Investigation, Valida­
tion, Visualization. Jing Zhang: Investigation, Validation,
Visualization. Zi-Cheng He: Investigation, Validation, Visualization. Yu
Lan: Conceptualization, Methodology, Resources, Project administra­
tion, Writing – review & editing. Gui-Fang Huang: Conceptualization,
Methodology. Wangyu Hu: Resources, Supervision. Wei-Qing Huang:
Conceptualization, Methodology, Supervision, Writing – review &
editing.
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.
Data availability
Data will be made available on request.
Acknowledgements
The authors would like to thank Dr. Ke Yang for helpful discussions.
This work was supported by the National Innovation and Entrepre­
neurship Program for College Students (Grant No. 202112659006).
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