Wen-Hao
Chang
a,
Chun-I
Lu
a,
Tilo H.
Yang
a,
Shu-Ting
Yang
a,
Kristan Bryan
Simbulan
ab,
Chih-Pin
Lin
c,
Shang-Hsien
Hsieh
d,
Jyun-Hong
Chen
e,
Kai-Shin
Li
e,
Chia-Hao
Chen
df,
Tuo-Hung
Hou
c,
Ting-Hua
Lu
a and
Yann-Wen
Lan
*a
aDepartment of Physics, National Taiwan Normal University, Taipei 116, Taiwan. E-mail: ywlan@ntnu.edu.tw
bDepartment of Mathematics and Physics, University of Santo Tomas, Manila 1008, Philippines
cDepartment of Electronics Engineering & Institute of Electronics, National Yang Ming Chiao Tung University, Hsinchu 300, Taiwan
dNational Synchrotron Radiation Research Center, Hsinchu 300, Taiwan
eTaiwan Semiconductor Research Institute, National Applied Research Laboratories, Hsinchu 300, Taiwan
fDepartment of Electrophysics, National Yang Ming Chiao Tung University, Hsinchu 300, Taiwan
First published on 18th October 2022
The negative differential resistance (NDR) effect has been widely investigated for the development of various electronic devices. Apart from traditional semiconductor-based devices, two-dimensional (2D) transition metal dichalcogenide (TMD)-based field-effect transistors (FETs) have also recently exhibited NDR behavior in several of their heterostructures. However, to observe NDR in the form of monolayer MoS2, theoretical prediction has revealed that the material should be more profoundly affected by sulfur (S) vacancy defects. In this work, monolayer MoS2 FETs with a specific amount of S-vacancy defects are fabricated using three approaches, namely chemical treatment (KOH solution), physical treatment (electron beam bombardment), and as-grown MoS2. Based on systematic studies on the correlation of the S-vacancies with both the device's electron transport characteristics and spectroscopic analysis, the NDR has been clearly observed in the defect-engineered monolayer MoS2 FETs with an S-vacancy (VS) amount of ∼5 ± 0.5%. Consequently, stable NDR behavior can be observed at room temperature, and its peak-to-valley ratio can also be effectively modulated via the gate electric field and light intensity. Through these results, it is envisioned that more electronic applications based on defect-engineered layered TMDs will emerge in the near future.
New conceptsIn this research, defect-engineered monolayer MoS2 field-effect transistors are fabricated using physical and chemical treatments. Based on the results of electrical characteristics and spectroscopic analysis to determine the amount of sulfur vacancy defects, the negative differential resistance (NDR) can be reliably obtained in the monolayer MoS2 FETs with a sulfur vacancy amount of ∼5 ± 0.5%. Furthermore, this NDR behavior is stable at room temperature, and its peak-to-valley ratio can be effectively modulated via the gate electric field and light intensity. |
In this work, initially, two post-treatment approaches are used, namely soaking in alkaline solution (KOH) and electron beam bombardment, to determine the amount of defects in monolayer MoS2 that would cause NDR behavior. To evaluate the correlation of the percentage of S-vacancy defects with the electrical characteristics and spectroscopic analysis, we perform electrical measurements, and carry out Raman, photoluminescence (PL), and X-ray photoemission spectroscopy (XPS) analysis on monolayer MoS2 that contains defects. Based on the results of the abovementioned approaches, the NDR is observed in the defect-engineered MoS2 with an S-vacancy VS amount of ∼4.5–5% at room temperature. The amount of S-vacancies is determined from the atomic S/Mo ratio in the experimental XPS data.24 Accordingly, using the direct growth method with a specific amount of S-vacancies, the as-grown monolayer MoS2 FETs clearly show stable NDR behavior that can be actively modulated via the gate electric field and light intensity. Density-functional theory (DFT) simulations were also conducted to confirm the occurrence of the NDR phenomenon at the said amount of S-vacancies in monolayer MoS2. Therein, the band structure will have additional defect states formed in the bandgap, which will assist the electron tunneling. With the NDR effect successfully observed in FETs formed using defect-containing monolayer MoS2, given a specific amount of S-vacancy defects, we believe that defect engineering on 2D materials could attract more attention in exploring diverse applications for quantum technologies in the future.
28Fig. 1e demonstrates the Raman shift as a function of the KOH soaking time, and shows that the E2g peak (in-plane mode) redshifts and the A1g peak (out-of-plane mode) blueshifts. A comparison of the overall spectra, including the silicon peak for all conditions, is given to address concerns about the influence of the measurement setup. It turns out that the Si Raman peak measured in our system remains at the same position, as demonstrated in Fig. S1b of the ESI.† The redshifting of the E2g peak and the blueshifting of the A1g peak can also be attributed to defect-induced strain.27,29,30 These phenomena are different from the electron doping effect, which may result in an almost unaffected E2g peak and a redshifted A1g peak.31 Similar defects that affect the Raman shifts have also been discussed in monolayer MoS2 treated using ion23,24 or electron26 irradiation.
To evaluate the percentage of S-vacancies in the KOH-treated MoS2 at various soaking times, we exhibit the evolution of the XPS spectrum in the Mo 3d (left panel) and S 2p (right panel) regions, recorded from pristine MoS2 (bottom panel) to the 90 minute-treated (top panel) samples as demonstrated in Fig. 2a. The additional peaks of Mo 3d3/2 and Mo 3d5/2 that appear at slightly lower binding energy values for the 90 minute treatment (top panel) correspond to the defect-containing MoS2 with S-vacancies.32–34 For the semiquantitative analysis of the S/Mo ratio, the XPS spectra are fitted with Lorentzian functions to acquire the area underneath the curves and the S/Mo ratio is normalized to 2, assuming that the S-vacancy in pristine MoS2 is negligible. By following the equation proposed by Bertolazzi et al.,24 the S-vacancy (VS) amount can be expressed as VS = 1 − r/2, where r is the S/Mo ratio. Fig. 2b exhibits a decrease in the normalized S/Mo ratio (left y-axis) and an increase in VS (right y-axis) with increasing soaking time. With these observed relationships, it can be said that, in Fig. 2c, the peak positions of both Mo 3d5/2 and S 2p3/2 shift to lower binding energies with an increasing amount of S-vacancies, resulting in metallic-like behavior.22 Accordingly, to further verify whether the aforementioned defect-induced phenomena also exist in the other two defect-engineered techniques, we also performed XPS experiments on the electron-beam-bombarded MoS2. After testing several electron beam bombardment conditions (as displayed in Fig. S2, ESI†), we irradiated monolayer MoS2 at varying dosages under a fixed electron acceleration voltage (Vacc = 15 kV) and current (I = 0.49 nA) as presented in Fig. S3 of the ESI.† The XPS results of the electron-beam-bombarded MoS2 are consistent with the results observed in the chemically-treated MoS2, wherein a decreasing normalized S/Mo ratio is accompanied by a lowering binding energy as the e-beam dosage is increased (more details can be seen in Fig. S4, ESI†).
Based on the aforementioned results that include PL, Raman and XPS, defect-engineered MoS2 FETs with an appropriate amount of S-vacancies can be controlled and adopted to observe NDR behavior using either chemical or physical treatments. Fig. 3a–c present the Id–Vg characteristics of three MoS2 FET devices, which are chemically treated with KOH in 0, 15 and 30 minute durations, respectively, corresponding to S-vacancies from 0 to 4.5%. The optical microscope (OM) images of the measured devices are shown in the insets. The Id–Vg curves progressively become less gate dependent when the duration of the treatment is lengthened, indicating a transition from semiconducting to metallic-like properties. This result can be attributed to the defect states induced by the S-vacancies, which may shift the Fermi level toward the conduction band edge, resulting in metallic-like behavior.35,36 Accordingly, Fig. 3d–f display the corresponding Id–Vg characteristics, respectively, where the NDR effect can be seen clearly in Fig. 3f. It turns out that with a specific amount of S-vacancies (∼4.5%), similar results can also be observed in another 30 minute KOH-treated device presented in Fig. S5 (ESI†). The inset shown in Fig. 3f displays the shifting of the NDR peak positions, which is represented by the correlating bias voltage versus the applied gate voltage. It shows the linear dependence of the NDR peak positions to the gate voltage in the range of −60 V to + 40 V. The gate voltage could possibly shift the Fermi level and align it with the defect/quantum states, causing more tunneling electrons, while the increasing bias voltage may generate more diffusing holes. Consequently, the competition between electrons and holes could result in a shifting of the NDR peak position with increasing Vg.14,17,37 To prove that the S-vacancies in defect-containing MoS2 could result in defect states that can further affect the device's electron transport, we also performed electrical measurements on devices bombarded with different electron beam dosages and observed the resulting NDR behavior at a dosage of ∼5 × 105 μC cm−2, which corresponds to VS ≈ 5% (determined from Fig. S4b, ESI†), as demonstrated in Fig. S6 (ESI†). However, the electrical signal becomes noisy due to the severe damage caused by the physical electron beam bombardment.
In order to minimize the noisy signal caused by the damage caused by the electron beam bombardment, using as-grown monolayer MoS2 with specific amounts of S-vacancies is an appropriate method to achieve stable NDR behavior. We thus synthesized such MoS2 flakes with a particular range of S/Mo ratios using the CVD method under low S supply conditions.38 Accordingly, the as-grown monolayer MoS2 samples with different amounts of S-vacancies, from ∼1% to ∼6%, along with their corresponding XPS results are shown in Fig. S7 (ESI†). Based on the aforementioned results of NDR behavior under the specified S-vacancy conditions, we intentionally fabricated such a MoS2 device with VS ≈ 5%, which was precisely determined through its XPS data shown in Fig. S8 (ESI†). In this device, the observation of NDR can be seen in the Id–Vg curves at different gate voltages without light illumination, as shown in Fig. 4a, while a clearer NDR performance is perceived at a fixed gate voltage Vg = +10 V with different light illumination power values as presented in Fig. 4b. A larger peak to valley ratio is observed since more majority carriers can be induced in the n-type monolayer MoS2 at either Vg = +10 V or at higher light illumination powers. More details of the device's electrical characteristics at different light power values and gate voltages can be seen in Fig. S9 (ESI†). Additionally, another as-grown MoS2 FET with VS ≈ 4.5%, identically confirmed by XPS data, also exhibits NDR behavior, as presented in Fig. S10 (ESI†). Consequently, by growing to achieve a certain range of S-vacancies (∼5 ± 0.5%), the NDR behavior can be reproduced in another MoS2 device, as displayed in Fig. S11 (ESI†). Since the competition between the field-dependent carrier density and the drift velocity determines whether or not the NDR can be observed, we speculate that the defect states at the interface between MoS2 and the electrodes affect the contact resistance, which could further dominate the tunneling mechanism.14,39 However, the hugely different current level appearing in the two types of device, namely the KOH-treated MoS2 and the as-grown MoS2, which correspond to μA and pA current levels, respectively, is probably due to either the channel resistance or contact issues. It is obvious that the devices with a shorter channel length of ∼2 μm have a higher current level, as shown in Fig. 3a–c, than that with a longer channel length of ∼65 μm, as presented in Fig. 4a. Furthermore, according to ref. 40 and our recent experimental results, using semimetallic bismuth (Bi) instead of titanium (Ti) as the buffer layer of the electrodes can achieve almost ohmic contact behavior. Therefore, we believe that the devices designed and fabricated with the shorter channel length and Bi-MoS2 contacts can help to reach a higher current level for approaching the requirement of real applications.
In order to figure out the possible mechanism, the density of states (DOS) of monolayer MoS2 with S-vacancies is evaluated and a density-functional theory (DFT) simulation is performed using the Vienna ab initio simulation package (VASP).41,42Fig. 4c and d present the simulated DOS of monolayer MoS2 for the pristine sample and that with VS ≈ 4.2%, respectively, in which an additional defect-induced DOS can clearly be seen in the band gap as illustrated in Fig. 4d. A similar defect-induced DOS is obtained for VS from ∼4 to 6%, and it could be responsible for the observation of the NDR behavior. More details about the simulated DOS of MoS2 from pristine condition up to that with VS ≈ 12.6% are presented in Fig. S12 (ESI†), wherein the energy bands move toward to the Fermi level and the number of defect states increases in the bandgap with increasing S-vacancies.30 Consequently, the increasing number of defect states helps more electrons to tunnel through the barrier causing the defect-containing MoS2 FETs to exhibit metallic-like properties. To clearly understand the potential mechanism for NDR behavior, the band diagrams are proposed as demonstrated in Fig. 4e–g. Fig. 4e is the band diagram at thermal equilibrium conditions for MoS2 with an appropriate number of S-vacancies contacted with the metal of Ti, in which an additional defect-induced state is located in the band gap. When a small bias voltage (Vd) is applied to the device with a suitable gate voltage (Vg), the defect-induced state will be aligned to the Fermi level of Ti. Subsequently, the current (Id) will increase due to both the thermionic emission and resonance tunneling mechanisms as presented in Fig. 4f. However, if the bias voltage (Vd) is increased slightly further, the defect-induced state is not aligned with the Fermi level of Ti, and only thermionic emission contributes to the electron transport as demonstrated in Fig. 4g, leading to the decreased current forming an NDR peak as shown in Fig. 4a and b. Therefore, with an appropriate amount of S-vacancies, the NDR behavior can be theoretically predicted and experimentally observed.
Footnote |
| † Electronic supplementary information (ESI) available. See DOI: https://doi.org/10.1039/d2nh00396a |
| This journal is © The Royal Society of Chemistry 2022 |