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Wafer-Scale Production of Patterned Transition Metal Ditelluride Layers For Two-Dimensional Metal-Semiconductor Contacts at The Schottky-Mott Limit
Wafer-Scale Production of Patterned Transition Metal Ditelluride Layers For Two-Dimensional Metal-Semiconductor Contacts at The Schottky-Mott Limit
https://doi.org/10.1038/s41928-020-0396-x
A key challenge in the development of two-dimensional (2D) devices is the fabrication of metal–semiconductor junctions with
minimal contact resistance and depinned energy levels. An ideal solution for practical applications is to make contacts between
2D van der Waals semiconductors and 2D van der Waals metals. Here we report the wafer-scale production of patterned layers
of metallic transition metal ditellurides on different substrates. Our tungsten ditelluride and molybdenum ditelluride layers,
which are grown using a tellurization process applied to a precursor transition metal layer, have an electronic performance
comparable to that of mechanically exfoliated flakes and can be combined with the 2D semiconductor molybdenum disulfide.
The resulting metal–semiconductor junctions are free from significant disorder effects and Fermi-level pinning, and are used to
create monolayer molybdenum disulfide field-effect transistors. The Schottky barrier heights of the devices also largely follow
the trend of the Schottky–Mott limit.
E
lectrical contacts are crucial to the operation and perfor- uniform materials, which results in a poor electrical performance
mance of semiconductor devices, as every device has a of the resulting MSJs. However, recent studies have demonstrated
metal–semiconductor junction (MSJ)1–4. MSJs are character- impressive advances towards fabricating high-quality top contacts
ized by an energy level known as the Schottky barrier (SB), which on 2D semiconductors10,12,13, which are the most practical contact
has a Schottky barrier height (SBH) that can be theoretically pre- structures manufactured using standard lithographic techniques.
dicted by the Schottky–Mott rule based on the relative alignment of For example, vdW contacts formed by transferring graphene12 and
energy levels1. Improved electronic devices could be developed by metallic transition metal chalcogenides13 onto few-layered 2D semi-
qualitatively tuning the SBHs of the MSJs3,5. However, in reality, the conductors demonstrate good contact properties. However, for the
Schottky–Mott rule generally provides incorrect predictions for the approach to be practical and scalable, limitations in terms of fabri-
SBH due to the Fermi level at the MSJ being pinned. This is due to the cating position-controlled 2D metal contacts on a large scale need
types of chemical interactions that occur at the contact of the metal to be addressed.
and semiconductor, such as an atomic discontinuity at the metal– Heterostructures that consist of 2D vdW metals are typically
semiconductor interface, microscopic defects or clusters of metal– prepared via mechanical exfoliation or chemical vapour deposi-
semiconductor phases and other effects that form surface states that tion (CVD) of small flakes with random shapes5,14–16. Although
are pinned closely in energy to the Fermi level6. The recent devel- the CVD growth of graphene on metal surfaces (such as Cu or
opment of two-dimensional (2D) nanoscale devices has created Cu/Ni alloy) is well-developed for large areas and enables good
interfaces between 2D van der Waals (vdW) semiconductors and electrical properties, the transfer process (which includes the use of
3D (or bulk) metals, which inevitably result in an atomically sharp wet chemistry and/or polymers and the introduction of mechani-
discontinuity, chemical disorder and Fermi-level pinning (FLP) at cal damage or excessive stress) is a limiting step for contact per-
the interface7–9. This produces large contact resistances. Intrinsically, formance. Furthermore, the metallization of graphene, which is
the nature of 2D semiconductors (with atomic-scale thicknesses and required for electrical characterization, typically results in variation
pristine vdW surfaces) makes it difficult to reduce the contact resis- of the carrier injection efficiency depending on the deposited metal.
tance and fabricate ideal MSJs with conventional 3D metals9,10. For example, Ti/graphene-contacted MoS2 field-effect transistors
One approach to address this challenge is to form ‘seamless’ edge (FETs) exhibited a contact resistance of around 2,000 kΩ μm com-
contacts between a 2D vdW metal and a 2D vdW semiconductor pared to the Ag/graphene contact resistance of around 115 kΩ μm
using phase engineering or lateral epitaxial growth7,11. However, the (ref. 12), which highlights the importance of material selection for
approach is still at an early stage and often does not prepare spatially the contact pad and metallization process.
1
School of Materials Science and Engineering and Center for Future Semiconductor Technology (FUST), Ulsan National Institute of Science and Technology
(UNIST), Ulsan, Korea. 2Center for Multidimensional Carbon Materials, Institute for Basic Science (IBS), Ulsan, Korea. 3Department of Physics, Sogang
University, Seoul, Korea. 4Beijing Academy of Quantum Information Sciences, Beijing, P. R. China. 5International Center for Quantum Materials, School of
Physics, Peking University, Beijing, P. R. China. ✉e-mail: sykwon@unist.ac.kr
a b
Patterned
(W,Mo)/substrate (W,Mo)Te2
(W,Mo)/substrate Ar
c d e
A42 A18 A1
5
A1
2
SiO2/Si
(002)
9
A1
Intensity (a.u.)
Intensity (a.u.)
(006)
(004)
(008)
100 150 200 250 10 20 30 40 50 60
2 cm
Raman shift (cm–1) 2θ (°)
f g h i
This study 1h
64 4.26 nm 4.4 104
Exfoliated31 12 h
W-Te
Te-W MBE grown32
Intensity (a.u.)
Intensity (a.u.)
168 h
Rs (Ω sq–1)
W-Te 24
Ra (nm)
Te-W 2.1
H (nm)
3
10
11
Te-O W-O 1.0
6
4 0.7
102 WF = 4.40 eV
45 40 35 30 1 2 3 8 20 0 10 20 30 40 4.1 4.2 4.3 4.4 4.5
Binding energy (eV) H of pre-W (nm) H (nm) hν – Eb – EF (eV)
Fig. 1 | Position-controllable growth of WTe2 atomic layers directly on a SiO2/Si substrate. a,b, Experimental scheme to prepare patterned WTe2 films
on a substrate. a, Schematic of Te-gas confined reactor, consists of NixTey on a transition metal precursor film in the furnace. b, Drawings showing the
procedure for the synthesis of a WTe2 thin film in a position-controllable way, which includes a photolithography process before tellurization. c, Optical
image of as-grown large-scale WTe2 patterns on a 4-inch-scale SiO2/Si substrate (left) and representative OM images of the thin film captured at marked
points on the left image (right), which represents a uniform contrast of WTe2 (light green) to the substrate. Scale bar, 100 μm. d, Raman spectra of WTe2
thin film captured randomly at the 4-inch-scale patterns having the characteristic five vibrational modes of the material. e, XRD pattern of the as-grown
thin film showing peaks for the (002l) planes of WTe2. f, XPS profile (W 4f/Te 4d scan) of a WTe2 film without any traces of impurities or oxides. g, H and
Ra of an as-grown WTe2 thin film modulated by the thickness of a W precursor film (H of pre-W), characterized by AFM. Inset: AFM image of the thinnest
WTe2 film we obtained, 4.26-nm thick. Scale bar, 2 μm. h, Sheet resistance (Rs) as a function of film thickness (H) measured by a four-probe method. Rs
values of mechanically exfoliated31 and MBE-grown32 high-quality WTe2 flakes are also displayed for comparison. i, Ultraviolet photoelectron spectra of
WTe2 thin films dependent on air exposure times t using a He I source (ultraviolet emission at hν = 21.2 eV) near the onset of the secondary emission cutoff
edge. The spectra are displayed in the form of hν – Eb – EF to designate WFs of the film as the x intercept of the fitted linear line, where Eb is the binding
energy and EF is the Fermi energy (see Supplementary Fig. 6 for more details) a.u., arbitrary units.
In terms of potential vdW metals, transition metal ditellurides, In this article, we report the wafer-scale production of patterned
such as tungsten ditelluride (WTe2) and molybdenum ditellu- metallic WTe2 and MoTe2 layers on various substrates. The grown
ride (MoTe2), in a distorted 1T structure (1T′ phase) demonstrate materials have a high electrical performance and spatial homogene-
many attractive features as potential n-type contacts for 2D semi- ity. We also show that monolayer MoS2 FETs can be created that
conductors, which include a pristine vdW surface17, high conduc- contain 2D (W,Mo)Te2/MoS2 vdW MSJs with near-ideal interfaces.
tivity and current-carrying capacity18, and a low work function To synthesize the materials, we used a Te source of eutectic alloy
(WF) (<4.4 eV) (ref. 3). In addition, the higher atomic mass of directly on top of a transition metal precursor to constantly supply
Te compared with that of other chalcogen atoms leads to a toler- Te, and thus avoid Te deficiency during the process. Consequently,
ance to high-energy bombardment: an electron energy of around the obtained wafer-scale (W,Mo)Te2 thin films exhibit a high stoi-
270 keV is required to create a chalcogen vacancy for MoTe2, chiometric nature with a uniform thickness down to around
whereas around 90 keV is needed to create a vacancy for MoS2 by 4.26 nm and electrical performance comparable to that of mechani-
ballistic electron impacts19. This means that transition metal ditel- cally exfoliated single crystals. FETs were prepared through the
luride can maintain its own electronic structure without defect- simple transfer of a semiconducting channel material (MoS2) on the
induced states during additional metallization (for example, Ag position-controlled grown WTe2 or MoTe2 contact. The monolayer
deposition on MoTe2 (ref. 20)). However, the wafer-scale produc- MoS2 FETs operated by the WTe2 electrode demonstrate n-type
tion of high-quality stoichiometric transition metal ditellurides behaviour with a higher on-current, higher electron mobility and
remains challenging, mainly due to the low environmental stability lower SBH compared to those of FETs contacted to conventional
and chemical activity of Te and to difficulties in Te incorporation 3D metals (such as Ti or Au). The WTe2 and MoTe2 contacts have
during growth21,22. a relatively low WF, which causes a low SBH without a noticeable
Ids (mA)
MR (%)
4
R (kΩ)
0 1.6
2
1.2 L = 1 mm
–0.2
0
0.8 2RC = 904 Ω
–0.4 –2
–0.2 0 0.2 0 50 100 150 –9 –6 –3 0 3 6 9
Vds (V) L (µm) B (T)
Fig. 2 | Electro- and magnetotransporting behaviours of WTe2 films. a,b, Electrical characterization of a ~6.2-nm-thick TLM device. a, Ids–Vds curves
of device of various L. Inset: OM image of the corresponding device. Scale bar, 250 μm. b, L-dependent resistance (R) of the WTe2 TLM device. Rc was
extracted by linear fitting and noted in the plot. c, MR versus applied magnetic field (B) of the Hall bar device with a 4.26-nm-thick WTe2 channel.
Inset: OM image of measured device. Scale bar, 250 μm.
deviation from the ideal Schottky–Mott model. We also fabricated c-plane-oriented texture specified by the (002l) peaks (Fig. 1e and
electrical devices that consisted of position-controlled, ultrathin Supplementary Fig. 3) as well as by the absence of any peaks related
WTe2 channels with different shapes, which could be used to manu- to an incomplete reaction (Supplementary Fig. 3b). Using a com-
facture atomically thin circuitry. bination of transmission electron microscopy (TEM) techniques,
which include selective area diffraction pattern and annular dark-
Fabrication of patterned (W,Mo)Te2 thin films field TEM, we found that the grain sizes in the WTe2 layers were
A schematic of the process used for the production of patterned several tens of nanometres, comparable to those of predeposited W
transition metal ditellurides is shown in Fig. 1a,b. We demonstrate grains, and the synthesized atomic layers were polycrystalline, with
the capabilities of the method using SiO2/Si, graphene and quartz five ring shapes for the WTe2 planes of {010}, {110}, {120}, {030}
substrates (Supplementary Fig. 1). First, a transition metal layer was and {200} (Supplementary Fig. 4). The precise chemical composi-
deposited on the substrates using a d.c. magnetron sputter and then tion and high quality of our WTe2 films (that is, with no significant
patterned by photolithography and reactive ion etching. This pat- oxygen-related impurities29) were further verified by X-ray photo-
terned transition metal/substrate was placed directly over a NixTey/ electron spectroscopy (XPS) (Fig. 1f and Supplementary Fig. 5a–c)
SiO2/Si wafer (Supplementary Fig. 2) for source contact geometry, and TEM energy-dispersive X-ray spectroscopy (Supplementary
and this assembly was heated to temperatures (T) as high as ~500 °C Fig. 4c–f).
for short times t with a flow of inert Ar gas. The NixTey eutectic alloy We examined the surface roughness (Ra) and thickness (H) of the
was chosen because it has a high solubility for Te and the Te vapour as-synthesized WTe2 film as a function of the predeposited W film
could be constantly supplied from NixTey at a T higher than its eutec- thickness before the tellurization process (H of predeposited W),
tic point (~449 °C; Supplementary Fig. 2b), both of which facilitate characterized by atomic force microscopy (AFM) (Fig. 1g).
the direct growth of high-quality stoichiometric WTe2 atomic lay- The synthesized WTe2 films had uniform thicknesses down to
ers. This source contact mode allows the effective confinement of H ≈ 4.26 ± 0.41 nm (five to six layers) while sustaining remark-
vapours to maintain a Te-rich environment, which cannot easily be ably smooth surfaces with roughnesses (Ra = 0.64 ± 0.09 nm) as
achieved using other growth modes (for example, metal–organic small as the interlayer spacing of the layered WTe2 (~0.75 nm)
CVD23, tellurization using an isothermal close space24 and postan- (refs. 17,30). The sheet resistances Rs of ~4,092 ± 468 Ω sq–1 and
nealing of predeposited precursors of transition metal ditellurides25) ~147.7 ± 25.8 Ω sq–1 were extracted from the four-point probe
owing to the low environmental stability and activity of Te, and the measurements of the WTe2 layers (~1 × 1 cm2) with thicknesses of
difficulties in Te incorporation during growth26,27. These limita- ~4.26 nm and ~39.8 nm, respectively (Fig. 1h). We note that these
tions mean the above-mentioned approaches23–25 require a very long Rs values are comparable to those of mechanically exfoliated sin-
growth time (>24 hours), H2 gas as a reducing agent in addition to gle-crystalline31 and molecular-beam epitaxy (MBE)-grown32 WTe2
the carrier gas and a carefully designed furnace or crucible system; layers, which further confirms the high quality of the crystals. The
moreover, the loss of the Te resource is high. In addition, even the increased Rs of the thinner WTe2 layer compared to that of the bulk
resultant structure has extra Te on the film. Therefore, it is necessary can be attributed to surface-carrier scattering31. Ultraviolet pho-
to design simple and efficient methods to grow high-quality transi- toelectron spectroscopy characterization showed that WTe2 has a
tion metal ditellurides on a large scale with electrical performances valance level with a low WF of ~4.40 eV (Fig. 1i and Supplementary
comparable to those of mechanically exfoliated flakes. For example, Fig. 5d), similar to the theoretical value3 and to that of an exfoliated
when Te powder was used instead of the Te-rich confined space, sample33. This assures its use as an n-type electrode for electrical
WTe2 could not be obtained (Supplementary Fig. 2c,d), which is applications. Interestingly, we found that the WF of the air-exposed
contradictory behaviour with respect to the suggested strategy. WTe2 layers is relatively insensitive to material degradation, prob-
Figure 1c presents the patterned WTe2 films grown directly on ably because of FLP at the semiconducting WOx/metallic WTe2
a 4 inch (101.6 mm) SiO2/Si wafer in this study. It also shows their interface (Supplementary Fig. 6).
wafer-scale homogeneity and intrinsic optical properties. An opti-
cal microscopy (OM) image displays a homogeneous contrast for Electrical and magnetic properties of WTe2
the entire patterned WTe2-grown region with various aspect ratios. Given the growth mechanism, we can achieve any shape of the film,
All the measured Raman spectra have the same peak positions as which can be utilized to design electric circuitries composed of
in the exfoliated few-layer WTe2 samples28, regardless of the loca- transition metal ditellurides. Patterns for the transfer line method
tions of the measurements (Fig. 1d). An X-ray diffraction (XRD) (TLM) (Fig. 2a,b) and Hall bar devices (Fig. 2c) were defined
characterization shows a successfully synthesized WTe2 film with a and characterized. Figure 2a,b shows the drain source current
(Ids) versus voltage (Vds) characteristics of a ~6.2-nm-thick TLM evaporation for electrode comparison and for their use as contact
device with a width (W) of 10 μm under vacuum as a function of pads on WTe2 (Supplementary Fig. 9a,b). Note that the deposition
the channel length (L). Regardless of L, linear Ids – Vds dependences of Ti did not affect the WTe2 crystal’s atomic and electronic struc-
were obtained (which indicates a well-defined ohmic contact) and tures, and thereby avoided the formation of defect-induced states
the TLM-extracted resistivity ρ was calculated as ~0.559 mΩ cm. It (Supplementary Fig. 10). We observed the highly isotropic charge
is worth noting that the linear relation between R and L (that is, transport at the WTe2/MoS2 interface, which was attributed to the
R = ρL/WH) indicates that the growth method employed is repro- polycrystalline nature of our WTe2 patterns (Supplementary Fig. 4)
ducible for the long channel at least up to 150 μm. The calculated because it is independent of the relative in-plane orientation between
ρ, contact resistance Rc = 452 Ω (at the interface of Ti and WTe2), the two lattices. The Raman spectra of the WTe2/MoS2 interface
and even data obtained for wider films were similar to those of exhibit all the expected peak positions for WTe2 and MoS2 (Fig. 3c
the mechanically exfoliated flakes28,34 (Supplementary Fig. 7a,b). and Supplementary Fig. 9). The electron energy-loss spectroscopy
Furthermore, the gate voltage (Vg) dependence was tiny, as in a (EELS) mapping images (Supplementary Fig. 11) show the hetero-
previous report35 (Supplementary Fig. 7c), which indicates the high structures without oxidation-related features at WTe2, although the
quality of our WTe2 films. The Rc of Ti/WTe2 (~0.5–1 kΩ μm) has a fabrication process was conducted under ambient conditions. Both
low value compared to those reported for 3D metal/2D metal sys- the passivated regions in WTe2 (Ti contact pad and MoS2 layer) and
tems34 (even smaller than those of the general Rc for 3D metal/gra- the self-limited oxidation process43 further give rise to the air-stable
phene (~2–102 kΩ μm) (refs. 36–39); Supplementary Table 1), which performance of the MSJ device (Supplementary Fig. 12).
enabled an enhanced carrier injection through the interface, and the Figure 3d,e shows the output and transfer curves of the fabri-
material structure was used for the MSJ. Notably, the two-terminal cated MoS2 FETs with asymmetric contacts, where the carriers are
WTe2 device sustained a considerably high current density (J = F/ρ, injected from the WTe2 (red) and Ti (black) electrodes. All the
where F is the applied electric field) of ~11.61 MA cm–2 at a low F electrical measurements depicted in Fig. 3d–f were performed at
(0.4 kV cm–1; Supplementary Fig. 7d), even larger than the current- room temperature. The reverse-biased contact (source) consumes
carrying capacities of the conventional interconnect metals (that is, most of the voltage drop and dominates the transistor behaviour
Cu and Al) (ref. 18), which demonstrates its potential for use as a for n-type MoS2 MSJ FETs, which enables a systematic electrical
local electrode or interconnect. characterization, depending on the asymmetric interface. The on-
We further investigated the magnetoresistance (MR) of the state current (Ion) of the WTe2 (source)-contacted MoS2 device was
WTe2 device (H ≈ 4.26 nm) to study the disorder effect (Fig. 2c ~216 nA μm–1, more than five times higher than that of the Ti–MoS2
and Supplementary Fig. 8). The four-probe device exhibited a MR FET (~38 nA μm–1), the same behaviour as in the output character-
(= (Rxx(B) – Rxx(0))/Rxx(0)) behaviour. The MR value reached ~5.3% istics (Fig. 3d and Supplementary Fig. 13a–d). In addition, the two-
at B = 8 T (Supplementary Fig. 8a), higher than those of the previ- terminal field-effect mobility (μFET) can be calculated as9:
ously reported synthesized polycrystalline WTe2 thin films29,30,40.
Generally, the disorder could substantially suppress the MR when dIds L
μFET ¼ ð1Þ
the layer is thinner as it breaks the balance of electron and hole dVg WCi Vds
pockets30; accordingly, the observed larger MR indicates that the
quality of the crystal is superior, with a smaller disorder effect. where Vg is the applied back gate voltage and Ci is the capacitance
The sharp curves superimposed on the quadratic classical back- of the SiO2 dielectric layer (~11.5 nF cm−2). The deduced μFET for the
ground in MR near-zero fields reflect the weak localization due WTe2-contacted MoS2 FET was ~2.20 cm2 V−1 s−1, also almost twice
to quantum interference, which indicates the presence of strong as high as that of the device with the Ti contacts. We also fabri-
spin–orbit coupling as the layer contains a heavy element, W. The cated and characterized FETs with asymmetry contacts that com-
device exhibited a signal of disorder (or band structure alteration), prised Ti and metallic 1T′ MoTe2 (which was obtained via the same
indicated by the decreased MR under a high bias41, compared to growth scheme as used for WTe2, depicted in Supplementary Fig.
the MR behaviour of the bulk WTe2. The effect of the disorder on 14). However, the performance improvement by the MoTe2 was tiny
the thin film is also observed in the R–T curve (Supplementary compared to that for WTe2 (Supplementary Fig. 13e–h). For a larger
Fig. 8c), where R increases when T decreases (positive tempera- number (>10) of FET devices with symmetry contacts, we extracted
ture coefficient of resistivity ∝ (dρ/dT) > 0), which is referred the Ion and μFET and proved the validity of the electrical perfor-
to as an Anderson localization. These phenomena were attrib- mance enhancement through the introduction of the WTe2 con-
uted to the disorders frequently observed in atomically thin sys- tact, as summarized in Fig. 3f (see more details in Supplementary
tems, particularly in materials with strong spin–orbit coupling42. Fig. 15 and Supplementary Table 2). The superior performance of
Nevertheless, the metallic behaviour still existed for the ~4.26-nm- the WTe2-contacted FET devices (with their μFET values as high as
thick WTe2, indicated by the positive slope of the reduced activation ~7.33 cm2 V−1 s−1 and average μFET value close to ~1.73 cm2 V−1 s−1)
energy (W = –d(ln R)/d(ln T)) versus T curve at low temperatures compared to those of the other FETs with different contacts could
(Supplementary Fig. 8d). probably be attributed to the smaller contact barrier at the 2D vdW
interface between WTe2 and MoS2.
Monolayer MoS2 FETs with (W,Mo)Te2 contacts To validate the better contact of the MoS2/WTe2 MSJ, we extracted
Considering the low WF (~4.40 eV in Fig. 1i) and vdW clean sur- the Rc using the TLM devices (Supplementary Fig. 16). The Rc of
face of metallic 1T′-structured WTe2, it could be an efficient n-type WTe2/MoS2 was substantially small (~57 kΩ μm, which included Rc
contact for 2D semiconductors. The quality (that is, contact resis- of the Ti/WTe2 interface) at Vg = 80 V, almost an order of magni-
tance and SBH) of the metal contacts is critical for the proper func- tude lower than that of Ti/MoS2 (Supplementary Fig. 16a,b), which
tioning of the entire device. However, no extensive studies on this enabled the higher performance of the MSJ. In Supplementary Fig.
hypothesis have been carried out, probably owing to the challenge 16c,d and Supplementary Table 3, we summarize and compare the
of material preparation. As our growth mode enables us to obtain Rc values for different contacts with MoS2 gathered from values
position-controlled ~4.26-nm-thick WTe2 patterns with a small reported in the literature12,14,44–53. The Rc of our WTe2/MoS2 is one of
roughness (Ra = 0.64 nm) at a large scale, we were able to fabricate a the lowest among the MSJ FETs composed of monolayer MoS2 with
monolayer MoS2 FET with a WTe2/MoS2 MSJ simply by transferring 2D12,14,44,45 and 3D vertical contacts12,45,50,51 (Supplementary Table 3
a CVD-grown monolayer MoS2 on the WTe2 patterns (Fig. 3a,b). and Supplementary Fig. 16c). For a fair comparison of 2D metal
The Ti (or Au) layers were also defined by typical electron-beam contacts for the monolayer MoS2 FET, we also plotted Rc values as
Intensity (a.u.)
9
A1
8
A1
Ti A1g
A14
Ti MoS2 E2g
WTe2 MoS2
10 µm
100 150 200 350 400 450
Raman shift (cm–1)
Ids (A µm–1)
0.3 Vg = 30 V
–9
Vg = 40 V 10 150
Vg = 50 V 10–1
0.2 10–10
100
0.1 10–11 10–2
50
–12
10
0 0 10–3
10–13
0 0.3 0.6 0.9 –100 –50 0 50 100 Au Ti WTe2
Vds (V) Vg (V)
Fig. 3 | Atomically thin FETs composed of the MoS2 channel and WTe2 contact. a–e, Characterization of a monolayer MoS2 FET with asymmetric
contacts of Ti and WTe2. a, Schematic of the MoS2 FET device in contact with position-controlled grown 4.26-nm-thick WTe2 and Ti. b, OM image of
the fabricated device. c, Raman spectrum of the WTe2/MoS2 heterostructure marked as a red circle in b, which shows strong signals of each material.
d, Room-temperature Ids–Vds output curves of MoS2 FET characterized by different carrier injections from WTe2 (red) and Ti (black) electrodes. e, Room-
temperature Ids–Vg characteristics of the corresponding device in linear (open shapes, right axis) and logarithm (solid lines, left axis) scales at Vds = 1.0 V.
f, Comparison of the room-temperature μFET of monolayer MoS2 devices with those of symmetric metal contacts, such as WTe2 (red circles), Ti (black
squares) and Au (blue triangles).
a function of carrier density (n2D) (Supplementary Fig. 16d). Given mostly with thermionic emission at a Vg lower than that of the flat-
the relation between n2D and Rc, our WTe2 technique provides a band voltage (VFB), with field emission starting to contribute with
low Rc in an order comparable to that of the graphene contact, the increased Vg (>VFB). For a largely induced Vg, the MoS2 band sub-
most widely used 2D metal contact. The superior carrier injection stantially bends downwards and the SB width is reduced, which
through the Ti/WTe2/MoS2 system may be attributed to the higher allows the injection of electrons into the channel by field emission.
out-of-plane interaction of WTe2 (ref. 34) (Supplementary Note 1), These processes are qualitatively explained by band diagrams in
as indicated by the smaller Rc of our Ti/WTe2 (>1.03 kΩ μm) than Supplementary Fig. 18. To elucidate this mechanism, we electrically
the general Rc for 3D metal/graphene36–39 (2–102 kΩ μm), as sum- characterized the MoS2 MSJ FET at low temperatures. The repre-
marized in Supplementary Table 1. Together with the relative merit sentative transfer curves of the device are shown in Fig. 4a. We first
of WTe2 from the perspective of the material processing compared see that the monolayer MoS2 follows the phonon-limited μFET at
with that of graphene (for example, the growth compatibility with a ~T–γ (γ ≈ 0.46 for our WTe2/MoS2 MSJ, as shown in Supplementary
low thermal budget effect (Supplementary Fig. 17) and the robust- Fig. 19)54, and it is notably affected by the dense distribution of
ness against interface issues (Supplementary Fig. 10)), the low Rc trap states at the SiO2 interface (Supplementary Fig. 19c). Next, we
promises its future applications as the contact and interconnects obtained the SBH (ΦB) at the WTe2/MoS2 interface from the slope
for 2D transition metal chalcogenide-based electronics. Recently, of a linear fit to ln(Ids/T2) as a function of 1/kBT (Fig. 4b), using the
Wang et al. demonstrated ultraclean vdW contacts on monolayer following thermionic emission model11:
MoS2 using 3D metal53. The Rc value of the 3D In/Au electrodes was
~3.0 kΩ μm, which is among the lowest observed for 3D metal elec- qΦB qVds
Ids ¼ AA* T 2 exp � exp �1 ð2Þ
trodes deposited onto 2D monolayer MoS2, indicative of defect-free kB T kB T
interfaces. However, this assumes that the further device integra-
tion stage does not involve any high-temperature process steps that where A is the junction area and A* is the effective Richardson–
damage the 3D In/Au layers, which may not be the case given the Boltzmann constant. The obtained ΦB as a function of Vg is shown
soft nature of In (with a low melting point of ~156 °C). We expect in Fig. 4c. For Vg < VFB, ΦB are the exact values of the effective SBH
that there is a crucial advantage and opportunity for WTe2, which because the dominant transport mechanism was the thermionic
exhibits a high current-carrying capacity and a superior electrical process in the subthreshold regime. However, when Vg > VFB, the
robustness against Joule heating (note that the melting point of thermionic assistant tunnelling current starts to contribute. As the
WTe2 is ~1,020 °C (ref. 26))18. thermionic-assistant tunnelling through the bent band (SB width) is
also temperature dependent, the ΦB values extracted from Vg > VFB
Controllable SBs between MoS2 and (W,Mo)Te2 can be interpreted as ‘thermionic emission’ barrier values, which
We studied the carrier transport mechanism in the WTe2/MoS2 MSJ are not the actual SBHs at those Vg values55 (more details on the
FET. According to the general SB FET theory7, there are two mecha- behaviour of ΦB are described in Supplementary Note 2). Therefore,
nisms by which charges can be injected across the MSJ: thermionic the SBH of the WTe2/MoS2 interface was extracted at the VFB as
emission over the SB and field emission (namely, tunnelling) across ~98.9 ± 11.1 meV (averaged value for >15 devices; Supplementary
the SB. In general, for 2D semiconductors, such as MoS2, we deal Fig. 20e). This is very close to the theoretical value (~100 meV)
ФB (meV)
T = 258 K
Ids (nA)
ln(Ids /T 2)
6,000 –27 150 150
4,000 100
100 100
2,000 –30
Vg = 0 V 50 50
0 VFB 0
–33 0 0
–80 –40 0 40 80 40 50 60 70 80 90 0 5 10 15
Ti
WTe2
MoTe2
Vg (V) 1/KBT Vg (V)
d 600 e 600
S=1
NbS2
500 500
Ti
400 Au Pd 400
SBH (meV)
SBH (meV)
Ti S=1
300 S = 0.067 300
Ag MoTe2
200 Ti MoTe2 200 MXene
Ti Cr Graphene
100 100 Mo2C
WTe2 WTe2 TaS2
0 0
4.0 4.5 5.0 5.5 6.0 4.0 4.5 5.0 5.5 6.0
WF (eV) WF (eV)
Fig. 4 | Low SB nature of (W,Mo)Te2 contacts for atomically thin FETs. a–c, Temperature-dependent electrical characterization of the WTe2-contacted
monolayer MoS2 FET to observe barrier properties at a MoS2/WTe2 interface. a, Temperature-dependent WTe2-contacted two-terminal Ids of the device as
a function of Vg at Vds = 1 V. b, Corresponding linear fit of the Arrhenius plot of ln(Ids/T2) versus 1/kBT for the device shown in a. c, (Left) Barrier height (ΦB)
at the MoS2/WTe2, MoS2/MoTe2 (green line) and MoS2/Ti (blue line) interfaces with Vg dependence. SBH at the VFB was extracted for each interface. Solid
lines are fits to show thermionic regime before reaching flat band condition (Vg < VFB). (Right) Calculated SBHs at the WTe2/MoS2, MoTe2/MoS2, and
Ti/MoS2 interfaces using the Schottky–Mott model to compare with experimentally obtained values on the left. d,e, Comparisons of the extracted SBH at
VFB between monolayer MoS2 and the electrodes of conventional metals (that is, Ti (refs. 2,9,12, square, circle and triangle, respectively), Cr (ref. 9), Ag
(ref. 12), Au (ref. 9) and Pd (ref. 9) (d) and vertically transferred vdW layered metals (for example, graphene12, TaS2 (ref. 13), MXene5, NbS2 (ref. 16) and Mo2C
(ref. 11) (e) with respect to the metals’ WF. The deduced SBHs of 98.9 ± 11.1, 209.8 ± 26.0 and 131.8 ± 29.6 meV for the WTe2-, MoTe2- and Ti-contacted
FETs, respectively, are also shown. The WTe2 contact had a relatively low WF, which caused a low SBH without a noticeable deviation from the ideal
Schottky–Mott model (that is, strength of FML, S = d(SBH)/d(WF) = 1, indicated as a red dashed line), whereas conventional and even some vdW metals
show differences. Note that S (= 0.067) of the bulk metal contacts was calculated by fitting to the SBH versus WF plot, shown as a grey dashed line in d.
calculated by the Schottky–Mott rule, indicative of close-to-perfect 3D metal electrodes. Notably, as the vdW contact has no strong
interfaces (SBH = WF – χs for an n-type semiconductor, where χs orbital overlaps at the interface, the impact of the vdW gap can
is the electron affinity of the n-type semiconductor (for example, lower the charge injection by producing an additional square tun-
χs of the monolayer MoS2 is 4.3 eV (ref. 9). In addition, the SBH of nelling barrier57 (Supplementary Note 2). Nevertheless, the effective
WTe2/MoS2 is slightly lower than that of the Ti-contacted MoS2 FET thermionic barrier (ΦB) for the WTe2/MoS2 MSJ was still smaller
(~131.8 ± 29.6 meV, shown in blue in Fig. 4c), which is surprising as than that for Ti/MoS2 in the tunnelling-dominant transport regime
Ti has a WF of 4.3 eV, lower than that of WTe2. (Vg > VFB). Furthermore, their slopes were comparable (Fig. 4c),
Typically, a bulk metal contact on a vdW semiconductor can which implies that the decrease in tunnelling probability through
create metal-induced gap states or disorders at the interface8, the vdW gap is minor compared with the field emission through the
which induce a deviation from the ideal WF alignment. For our SB at Ti/MoS2. A smaller charge tunnelling (thicker SB) of Ti/MoS2
Ti-contacted MoS2 FET, the same effect possibly occurs and pins is also suggested by the strong dependence of conductivity on low
the Fermi level in the gap, which leads to an SBH much larger than temperatures of MoS2 at a high Vg (Supplementary Fig. 22).
the value calculated (~0 meV) using the Schottky–Mott theory. Figure 4d summarizes the relation between the SBH (at the VFB)
Interestingly, we obtained a relatively lower SBH for Ti/MoS2 com- of the MSJs and the WF of conventional 3D metals in contact with
pared to those of previous studies2,9,12 (Supplementary Figs. 13 and the monolayer MoS2, and includes the as-prepared Ti and (W,Mo)
14). We propose that the Ti is gently deposited on the monolayer Te2 in this study. Compared to other conventional 3D metals, WTe2
MoS2 owing to ultrahigh vacuum electron-beam evaporation (with promises substantial advantages as an n-type electrode with respect
a deposition rate of <0.1 Å s–1), which results in a better interface56; to the SBH (Fig. 4d). Note that this value (~98.9 meV) is, so far, the
however, the creations of non-stoichiometric MoxSy and TixSy alloys lowest SBH observed for metal electrodes formed onto monolayer
could not be avoided (Supplementary Fig. 21), which possibly MoS2, given that SBH is expected to depend strongly on the num-
formed interface states and pinned the Fermi level. Compared to ber of MoS2 layers (generally, in the range of 1–3 layers) because
WTe2, metallic 1T′-MoTe2 has a WF of ~4.50 eV (Supplementary the bandgap increases as the thickness decreases9 (that is, increasing
Fig. 11h–j), which gave rise to the larger SBH between the metal and SBHs with decreasing MoS2 thickness12). It can also be seen from
MoS2 (~209.8 ± 26.0 meV, shown in green in Fig. 4c), as expected Fig. 4d that the SBH depends weakly on the WFs of conventional 3D
by the computed value using the ideal law (~200 meV). This result metals (S = 0.067, dashed grey line), but that the SBHs for WTe2 and
indicates that employing (W,Mo)Te2 vertical contacts provides the MoTe2 are in the Schottky–Mott limit (S = 1, dashed red line), where
advantage of controlling the SBH in a predictable way, which is a S = |d(SBH)/d(WF)| indicates the strength of the FLP and S = 1
challenge to fulfil by means of the typical deposition process for corresponds to the ideal case (or Schottky–Mott limit) and S ≈ 0