Doping Of MoS2 Research Articles

Layered material GeSe and vertical GeSe/MoS2 p-n heterojunctions

Group-IV monochalcogenides are emerging as a new class of layered materials beyond graphene, transition metal dichalcogenides (TMDCs), and black phosphorus (BP). In this paper, we report experimental and theoretical investigations of the band structure and transport properties of GeSe and its heterostructures. We find that GeSe exhibits a markedly anisotropic electronic transport, with maximum conductance along the armchair direction. Density functional theory calculations reveal that the effective mass is 2.7 times larger along the zigzag direction than the armchair direction; this mass anisotropy explains the observed anisotropic conductance. The crystallographic orientation of GeSe is confirmed by angleresolved polarized Raman measurements, which are further supported by calculated Raman tensors for the orthorhombic structure. Novel GeSe/MoS2 p-n heterojunctions are fabricated, combining the natural p-type doping in GeSe and n-type doping in MoS2. The temperature dependence of the measured junction current reveals that GeSe and MoS2 have a type-II band alignment with a conduction band offset of ~0.234 eV. The anisotropic conductance of GeSe may enable the development of new electronic and optoelectronic devices, such as high-efficiency thermoelectric devices and plasmonic devices with resonance frequency continuously tunable through light polarization direction. The unique GeSe/MoS2 p-n junctions with type-II alignment may become essential building blocks of vertical tunneling field-effect transistors for low-power applications. The novel p-type layered material GeSe can also be combined with n-type TMDCs to form heterogeneous complementary metal oxide semiconductor (CMOS) circuits.

Charge transport study of P3HT blended MoS2

Hybrid organic–inorganic hetero-structures, especially inorganic two-dimensional (2D) materials and organic semiconductors are attracting great attention for optoelectronic applications. The quantum confinement effects of 2D materials and their low-cost processing and high performance in devices enable a high degree of tunable optoelectronic properties for these heterostructure. Herein, we attempted to doped poly(3-hexylthiophene) (P3HT) with 2D nanosheets of Molybdenum sulfide (MoS2) to improve its mobility. We synthesized 2D MoS2 nanosheets using ultrasonication method for exfoliation of MoS2. The successful synthesis of 2D MoS2 monolayers is evidenced through substantial characterization viz Atomic Force Microscopy and UV-visible Spectroscopy. The thickness of these nanosheets varies between 8 and 10 nm. The doping of MoS2 significantly improved the mobility of the P3HT as evident from the enhanced drain current of organic field effect transistors (OFET) as compared to the undoped P3HT.

Adsorbate doping of MoS2 and WSe2: the influence of Na and Co

We have investigated the influence of metal adsorbates (sodium and cobalt) on the occupied and unoccupied electronic structure of MoS2(0 0 0 1) and WSe2(0 0 0 1), through a combination of both photoemission and inverse photoemission. The electronic structure is rigidly shifted in both the WSe2 and MoS2 systems, with either Na or Co adsorption, generally as predicted by accompanying density functional theory based calculations. Na adsorption is found to behave as an electron donor (n-type) in MoS2, while Co adsorption acts as an electron acceptor (p-type) in WSe2. The n-type transition metal dichalcogenide (MoS2) is easily doped more n-type with Na deposition while the p-type transition metal dichalcogenide (WSe2) is easily doped more p-type with Co deposition. The binding energy shifts have some correlation with the work function differences between the metallic adlayer and the transition metal dichalcogenide substrate.

Variations of Contact Resistance in Dual-Gated Monolayer Molybdenum Disulfide Transistors Depending on Gate Bias Selection

Monolayer molybdenum disulfide (MoS2) is considered an alternative two-dimensional material for high performance ultra-thin field-effect transistors. MoS2 is a triple atomic layer with a direct 1.8 eV bandgap. Bulk MoS2 has an additional indirect bandgap of 1.2 eV, which leads to high current on/off ratio around 108. Flakes of MoS2 can be obtained by mechanical exfoliation or grown by chemical vapor deposition. Intrinsic cut-off frequency of multilayer MoS2 transistor has reached 42 GHz. Chemical doping of MoS2 is challenging and results in reduction of contact resistance. This paper focuses on modeling of dual-gated monolayer MoS2 transistors with effective mobility of carriers varying from 0.6 cm2/V s to 750 cm2/V s. In agreement with experimental data, the model demonstrates that in back-gate bias devices, the contact resistance decreases almost exponentially with increasing gate bias, whereas in top-gate bias devices, the contact resistance stays invariant when varying gate bias.

A New Insight in the Physical and Photoelectrochemical Properties of Molybdenum Disulfide Alpha-Hematite Nanocomposite Films

The alpha (α)-hematite (Fe2O3) as photoanode has been used for photoelectrochemical applications due to low bandgap, low cost, high chemical stability, nontoxicity, and abundance in nature. The doping with various transition metals, formation of nanostructured and nanocomposite of α-Fe2O3 have been attempted to enrich the carrier mobility, surface kinetics and carrier diffusion properties. The manuscript is an attempt to improve the photoelectrochemical properties of α-Fe2O3 by formation of nanocomposite with dichalcogenide (molybdenum disulfide (MoS2) nanomaterials. The nanocomposite of MoS2-α-Fe2O3 have been synthesized by varying the amount of MoS2 in sol-gel synthesis process. The nanocomposite MoS2-α-Fe2O3 materials were characterized using UV-visible, FTIR, SEM, X-ray diffraction, Raman and particle analyzer. The photoelectrochemical properties were investigated using cyclic voltammetry and chronoamperometry studies. The optical and structural properties of MoS2-α-Fe2O3 nanocomposite have been found to be dependent on MoS2 doping. The band gap has shifted whereas; the structure is more prominent as flower-like morphology, which is a result of doping of MoS2. The photocurrent is more pronounced with and without light exposition to MoS2-α-Fe2O3 based electrode in photoelectrochemical cell. We have understood the photoelectrochemical water splitting using nanocomposite α-Fe2O3-MoS2 through schematic representation based on experimental results. The enhanced photoelectrochemical properties of nanocomposite α-Fe2O3-MoS2 films have been observed as compared to pristine α-Fe2O3 and transition metal doped α-Fe2O3 nanostructured films.

Highly efficient and stable MoS2 FETs with reversible n-doping using a dehydrated poly(vinyl-alcohol) coating.

Despite rapid progress in 2D molybdenum disulfide (MoS2) research in recent years, MoS2 field-effect transistors (FETs) still suffer from a high metal-to-MoS2 contact resistance and low intrinsic mobility, which are major hindrances to their future application. We report an efficient technique to dope thin-film MoS2 FETs using a poly(vinyl-alcohol) (PVA) polymeric coating. This results in a reduction of the contact resistance by up to 30% as well as a reduction in the channel resistance to 20 kΩ sq-1. Using a dehydration process, we were able to effectively control the surface interactions between MoS2 and the more electropositive hydroxyl groups (-OH) of PVA, which provided a controllable and yet reversible increase in the charge carrier density to a value of 8.0 × 1012 cm-2. The non-covalent, thus non-destructive, PVA doping of MoS2 increases the carrier concentration without degrading the mobility, which shows a monotonic increase while enhancing the doping effect. The PVA doping technique is then exploited to create heavily doped access regions to the intrinsic MoS2 channel, which yields 200% increase of the ON-state source-drain current. This establishes PVA doping as an effective approach to enhance the transport properties of MoS2 FETs for a variety of applications.

Molecular doping of MoS2 transistors by self-assembled oleylamine networks

Thin MoS2 films continue to be of key interest for numerous applications; however, effective doping and high metal to MoS2 contact resistance are challenges for future applications. We report on the self-assembly of oleylamine on top of MoS2 thin-films and the effective doping of MoS2 thin-film field effect transistors by oleylamine. Atomic force microscopy revealed that oleylamine organizes in lamellae domains on MoS2 thin films with similar characteristics of those previously observed on highly ordered pyrolytic graphite. A carrier concentration increase from 7.1 × 1011 cm−2 up to 1.9 × 1013 cm−2 at 0 V gate voltage is achieved together with a reduction of the contact resistance by a factor of 5 when using gold as metal contact. Furthermore, this non-covalent doping proves to be removable and reproducible among different flakes and does not degrade the electron mobility. Thus, this work opens the path for future works on controlling the doping of MoS2 by proper selection of the self-assembled species.

Improving the Photoelectric Characteristics of MoS2 Thin Films by Doping Rare Earth Element Erbium.

We investigated the surface morphologies, crystal structures, and optical characteristics of rare earth element erbium (Er)-doped MoS2 (Er: MoS2) thin films fabricated on Si substrates via chemical vapor deposition (CVD). The surface mopography, crystalline structure, light absorption property, and the photoelectronic characteristics of the Er: MoS2 films were studied. The results indicate that doping makes the crystallinity of MoS2 films better than that of the undoped film. Meanwhile, the electron mobility and conductivity of the Er-doped MoS2 films increase about one order of magnitude, and the current-voltage (I-V) and the photoelectric response characteristics of the Er:MoS2/Si heterojunction increase significantly. Moreover, Er-doped MoS2 films exhibit strong light absorption and photoluminescence in the visible light range at room temperature; the intensity is enhanced by about twice that of the undoped film. The results indicate that the doping of MoS2 with Er can significantly improve the photoelectric characteristics and can be used to fabricate highly efficient luminescence and optoelectronic devices.

Introduction of Interfacial Charges to Black Phosphorus for a Family of Planar Devices.

The capabilities to tune the conduction properties of materials by doping or electric fields are essential for the design of electronic devices. However, in two-dimensional materials substitutional doping has been achieved in only a few systems, such as Nb substitutional doping in MoS2. Surface charge transfer is still one of the popular ways to control whether the conduction is dominated by holes or electrons. Here, we demonstrate that a capping layer of cross-linked poly(methyl methacrylate) modifies the potential in a black phosphorus (BP) layer so that conduction in the absence of an external electric field is dominated by electrons, rather than holes. Using this technique to form adjoining regions dominated by hole and electron conduction, a family of novel planar devices, such as BP-gated diodes, BP bidirectional rectifier, and BP logic inverters, can be fabricated. The devices are potentially useful for electronic applications, including rectification and switching.

Plasmonic ambient light sensing with MoS2-graphene heterostructures

We present experimental results on plasmonic photodetection of ambient light using MoS2-graphene heterostructures illuminated with three very-low-power light emitting diodes (LEDs) radiating in blue, green, and red, respectively. The working principle of this photodetector validates the recent predictions of hot-carrier plasmonic doping of MoS2. The obtained responsivity for each spectral domain is in agreement with photopic standards of the luminosity function. The response time of the detector is less than the eye blinking time.

Covalent Nitrogen Doping and Compressive Strain in MoS2 by Remote N2 Plasma Exposure.

Controllable doping of two-dimensional materials is highly desired for ideal device performance in both hetero- and p-n homojunctions. Herein, we propose an effective strategy for doping of MoS2 with nitrogen through a remote N2 plasma surface treatment. By monitoring the surface chemistry of MoS2 upon N2 plasma exposure using in situ X-ray photoelectron spectroscopy, we identified the presence of covalently bonded nitrogen in MoS2, where substitution of the chalcogen sulfur by nitrogen is determined as the doping mechanism. Furthermore, the electrical characterization demonstrates that p-type doping of MoS2 is achieved by nitrogen doping, which is in agreement with theoretical predictions. Notably, we found that the presence of nitrogen can induce compressive strain in the MoS2 structure, which represents the first evidence of strain induced by substitutional doping in a transition metal dichalcogenide material. Finally, our first principle calculations support the experimental demonstration of such strain, and a correlation between nitrogen doping concentration and compressive strain in MoS2 is elucidated.

Enhanced monolayer MoS2/InP heterostructure solar cells by graphene quantum dots

We demonstrate significantly improved photovoltaic response of monolayer molybdenum disulfide (MoS2)/indium phosphide (InP) van der Waals heterostructure induced by graphene quantum dots (GQDs). Raman and photoluminescence measurements indicate that effective charge transfer takes place between GQDs and MoS2, which results in n-type doping of MoS2. The doping effect increases the barrier height at the MoS2/InP heterojunction, thus the averaged power conversion efficiency of MoS2/InP solar cells is improved from 2.1% to 4.1%. The light induced doping by GQD provides a feasible way for developing more efficient MoS2 based heterostructure solar cells.

Preparing molybdenum disulphide by vapour deposition

Two-dimensional graphene-like molybdenum disulphide with many unique properties, a relatively new and exciting transition metal dichalcogenide, has been extensively researched. This review discusses preparing molybdenum disulphide by vapour deposition, which has many advantages, including good spreadability, film uniformity and strong bonding forces with the substrate. We also review the compositing, decorating and doping of MoS2 by vapour deposition, and briefly discuss the applications of MoS2 produced by vapour deposition.

(Invited) An Overview of Doping Studies in MoS2

The advent of 2D materials in recent years has brought the potential for new device applications at ever decreasing transistor design nodes. Transition metal dichalcogenides have received much of that attention, with much of the focus on MoS2 thanks to its desirable bandgap. Studies have shown the advantages of MoS2 devices in key performance metrics such as a high ION/IOFF ratio and a subthreshold swing that approaches or potentially exceeds the fundamental 60 mV/dec limit. However, the contact resistance remains prohibitively high, and questions remain regarding the ability to dope these materials. Numerous routes for doping MoS2 have been reported, including surface charge transfer via molecular adsorption, cation substitution during growth, chalcogenide substitution via immersion in solution, and plasma-assisted doping. The effectiveness of these doping methods is displayed by reductions in contact resistance, increases in drive current, and in some instances a change from n-type to p-type behavior. This talk will review these recent reports on MoS2 doping. Recent experiments have begun to explore the possibility of doping MoS2 by ion-implantation, which is a legacy doping technique that is often avoided with 2D materials due to their ultra-thin nature. These experiments utilize ultra low implant energies of 200 eV which places the species of interest (Cl+ and Ar+) completely within the 3-5 layers of MoS2 being investigated. Cl is potentially a donor in MoS2 whereas Ar was used to determine the effect of the implant damage on the electrical properties. These studies focused on room temperature implants at doses between 1 x 1013/cm2 and 1 x 1015/cm2. Preliminary structural studies utilizing angle-resolved XPS indicate a Cl peak is around 1 nm deep into the MoS2, in rough agreement with Monte Carlo TRIM calculations. STM studies have revealed a number of defects present after implantation, including sub-surface defects that may be sulfur vacancies as well as surface sulfur vacancies. The density of these defects track with the dose. Relative to the pristine surface, STS studies have shown little change in tunneling current associated with the sub-surface defects, but enhanced tunneling current associated with the sulfur vacancies. It was observed that as the dose increases the oxidation of the surface as measured by XPS after exposure to the air increases. Additionally, we are performing transmission line measurements to observe the electrical effect of the implantation. Using lithography, transmission line masks were patterned onto individual exfoliated flakes. Photoresist was used as a mask to protect the channel and the implantation preceded contact metal (Ni/Au) deposition. Thus, only the contact area was implanted. Prior to implantation, primarily non-linear IDS-VDS curves are observed for few-layer (<=10 layers) MoS2 flakes with no applied back-gate voltage. After implantation at lower doses, linear IDS-VDS curves are observed implying more ohmic contacts. This is prior to annealing implying the electrical nature of the implant damage is contributing to better contacts. However the effect is greater for Cl+ implants than Ar+ implants implying that the effect is not strictly a damage-related phenomenon. At higher doses the contacts went back to being non-ohmic and this may be associated with the aforementioned oxidation after higher dose implantation. The dose dependence of the role of implant doping on contact resistivity will be discussed as well as the results from post implant annealing to facilitate dopant activation.

Tuning the photo-response in monolayer MoS2 by plasmonic nano-antenna.

Monolayer molybdenum disulfide (MoS2) has recently attracted intense interests due to its remarkable optical properties of valley-selected optical response, strong nonlinear wave mixing and photocurrent/photovoltaic generation and many corresponding potential applications. However, the nature of atomic-thin thickness of monolayer MoS2 leads to inefficient light-matter interactions and thereby hinders its optoelectronic applications. Here we report on the enhanced and controllable photo-response in MoS2 by utilizing surface plasmonic resonance based on metallic nano-antenna with characteristic lateral size of 40 × 80 nm. Our nano-antenna is designed to have one plasmonic resonance in the visible range and can enhance the MoS2 photoluminescence intensity up to 10 folds. The intensity enhancement can be effectively tuned simply by the manipulation of incident light polarization. In addition, we can also control the oscillator strength ratio between exciton and trion states by controlling polarization dependent hot carrier doping in MoS2. Our results demonstrate the possibility in controlling the photo-response in broad two-dimensional materials by well-designed nano-antenna and facilitate its coming optoelectronic applications.

Few-Layer MoS2 p-Type Devices Enabled by Selective Doping Using Low Energy Phosphorus Implantation

P-type doping of MoS2 has proved to be a significant bottleneck in the realization of fundamental devices such as p-n junction diodes and p-type transistors due to its intrinsic n-type behavior. We report a CMOS compatible, controllable and area selective phosphorus plasma immersion ion implantation (PIII) process for p-type doping of MoS2. Physical characterization using SIMS, AFM, XRD and Raman techniques was used to identify process conditions with reduced lattice defects as well as low surface damage and etching, 4X lower than previous plasma based doping reports for MoS2. A wide range of nondegenerate to degenerate p-type doping is demonstrated in MoS2 field effect transistors exhibiting dominant hole transport. Nearly ideal and air stable, lateral homogeneous p-n junction diodes with a gate-tunable rectification ratio as high as 2 × 10(4) are demonstrated using area selective doping. Comparison of XPS data from unimplanted and implanted MoS2 layers shows a shift of 0.67 eV toward lower binding energies for Mo and S peaks indicating p-type doping. First-principles calculations using density functional theory techniques confirm p-type doping due to charge transfer originating from substitutional as well as physisorbed phosphorus in top few layers of MoS2. Pre-existing sulfur vacancies are shown to enhance the doping level significantly.

Tuning the threshold voltage from depletion to enhancement mode in a multilayer MoS2 transistor via oxygen adsorption and desorption.

Selective chemical doping in two-dimensional (2D) molybdenum disulfide (MoS2) is attractive for tailoring electrical properties according to device requirements. However, the ultra-thin 2D nature of MoS2 makes it difficult to realize effective doping by conventional ion implantation. Here, a simple method based on low-temperature (150 °C) annealing in air is developed for effective chemical doping in MoS2. We have demonstrated that the threshold voltage (V(th)) of multilayer MoS2 FET can be effectively tuned from depletion mode (V(th) = -1.8 V) to enhancement mode (V(th) = 1.1 V) by annealing in air at 150 °C. An energy band model based on electron trapping/detrapping due to oxygen adsorption on the MoS2 surface is proposed to explain the underlying mechanism. The model is consistent with an oxygen adsorption-desorption process evidenced by vacuum annealing that recovers the V(th) to its original value. These results can provide a simple approach for V(th) engineering and make a significant step toward 2D nanoelectronic device applications.

Interfacial n-Doping Using an Ultrathin TiO2 Layer for Contact Resistance Reduction in MoS2.

We demonstrate a low and constant effective Schottky barrier height (ΦB ∼ 40 meV) irrespective of the metal work function by introducing an ultrathin TiO2 ALD interfacial layer between various metals (Ti, Ni, Au, and Pd) and MoS2. Transmission line method devices with and without the contact TiO2 interfacial layer on the same MoS2 flake demonstrate reduced (24×) contact resistance (RC) in the presence of TiO2. The insertion of TiO2 at the source-drain contact interface results in significant improvement in the on-current and field effect mobility (up to 10×). The reduction in RC and ΦB has been explained through interfacial doping of MoS2 and validated by first-principles calculations, which indicate metallic behavior of the TiO2-MoS2 interface. Consistent with DFT results of interfacial doping, X-ray photoelectron spectroscopy (XPS) data also exhibit a 0.5 eV shift toward higher binding energies for Mo 3d and S 2p peaks in the presence of TiO2, indicating Fermi level movement toward the conduction band (n-type doping). Ultraviolet photoelectron spectroscopy (UPS) further corroborates the interfacial doping model, as MoS2 flakes capped with ultrathin TiO2 exhibit a reduction of 0.3 eV in the effective work function. Finally, a systematic comparison of the impact of selective doping with the TiO2 layer under the source-drain metal relative to that on top of the MoS2 channel shows a larger benefit for transistor performance from the reduction in source-drain contact resistance.

Red-Shift Effect and Sensitive Responsivity of MoS2/ZnO Flexible Photodetectors.

The optoelectronic characteristics of molybdenum disulfide (MoS2)/ZnO flexible photodetectors are investigated. A red-shift effect and improved photocurrent properties of the flexible devices are demonstrated. MoS2 doping improved the photocurrent properties and conductivity. The photocurrent/dark current ratios of pure ZnO and MoS2/ZnO flexible photodetectors were 103 and 104, respectively. The responsivity of MoS2/ZnO increased, and the wavelength was red-shifted.

Doping against the native propensity of MoS2: degenerate hole doping by cation substitution.

Layered transition metal dichalcogenides (TMDs) draw much attention as the key semiconducting material for two-dimensional electrical, optoelectronic, and spintronic devices. For most of these applications, both n- and p-type materials are needed to form junctions and support bipolar carrier conduction. However, typically only one type of doping is stable for a particular TMD. For example, molybdenum disulfide (MoS2) is natively an n-type presumably due to omnipresent electron-donating sulfur vacancies, and stable/controllable p-type doping has not been achieved. The lack of p-type doping hampers the development of charge-splitting p-n junctions of MoS2, as well as limits carrier conduction to spin-degenerate conduction bands instead of the more interesting, spin-polarized valence bands. Traditionally, extrinsic p-type doping in TMDs has been approached with surface adsorption or intercalation of electron-accepting molecules. However, practically stable doping requires substitution of host atoms with dopants where the doping is secured by covalent bonding. In this work, we demonstrate stable p-type conduction in MoS2 by substitutional niobium (Nb) doping, leading to a degenerate hole density of ∼ 3 × 10(19) cm(-3). Structural and X-ray techniques reveal that the Nb atoms are indeed substitutionally incorporated into MoS2 by replacing the Mo cations in the host lattice. van der Waals p-n homojunctions based on vertically stacked MoS2 layers are fabricated, which enable gate-tunable current rectification. A wide range of microelectronic, optoelectronic, and spintronic devices can be envisioned from the demonstrated substitutional bipolar doping of MoS2. From the miscibility of dopants with the host, it is also expected that the synthesis technique demonstrated here can be generally extended to other TMDs for doping against their native unipolar propensity.