Through the positive role of alkali halides in realizing large area growth of transition metal-di-chalcogenide layers has been validated, the film-growth kinematics has not yet been fully established. This work presents a systematic analysis of the MoS$_2$ morphology for films grown under various pre-treatment conditions of the substrate with sodium chloride (NaCl). At an optimum NaCl concentration, the domain size of the monolayer increased by almost two orders of magnitude compared to alkali-free growth of MoS$_2$. The results show an inverse relationship between fractal dimension and areal coverage of the substrate with monolayers and multi-layers, respectively. Using the Fact-Sage software, the role of NaCl in determining the partial pressures of Mo- and S-based compounds in gaseous phase at the growth temperature is elucidated. The presence of alkali salts is shown to affect the domain size and film morphology by affecting the Mo and S partial pressures. Compared to alkali-free synthesis under the same growth conditions, MoS$_2$ film growth assisted by NaCl results in $\approx$ 81$\%$ of the substrate covered by monolayers. Under ideal growth conditions, at an optimum NaCl concentration, nucleation was suppressed, and domains enlarged, resulting in large area growth of MoS$_2$ monolayers. The monolayers were found to be free of unintentional doping with alkali metal and halogen atoms and exhibit high crystallinity and excellent opto-electronic quality.
Direct growth of flat micrometer-sized bilayer graphene islands in between molybdenum disulfide sheets is achieved by chemical vapor deposition of ethylene at about 800 °C. The temperature assisted decomposition of ethylene takes place mainly at molybdenum disulfide step edges. The carbon atoms intercalate at this high temperature, and during the deposition process, through defects of the molybdenum disulfide surface such as steps and wrinkles. Post growth atomic force microscopy images reveal that circular flat graphene islands have grown at a high yield. They consist of two graphene layers s…
Two-dimensional (2D) molybdenum disulfide (MoS2) holds great promise in electronic and optoelectronic applications owing to its unique structure and intriguing properties. The intrinsic defects such as sulfur vacancies (SVs) of MoS2 nanosheets are found to be detrimental to the device efficiency. To mitigate this problem, functionalization of 2D MoS2 using thiols has emerged as one of the key strategies for engineering defects. Herein, we demonstrate an approach to controllably engineer the SVs of chemically exfoliated MoS2 nanosheets using a series of substituted thiophenols in solution. The …
Single layered molybdenum disulfide with a direct bandgap is a promising two-dimensional material that goes beyond graphene for next generation nanoelectronics. Here, we report the controlled vapor phase synthesis of molybdenum disulfide atomic layers and elucidate a fundamental mechanism for the nucleation, growth, and grain boundary formation in its crystalline monolayers. Furthermore, a nucleation-controlled strategy is established to systematically promote the formation of large-area single- and few-layered films. The atomic structure and morphology of the grains and their boundaries in th…
A simple band model such as the effective mass approximation (EMA) can be used to quickly obtain the lower-energy region for the band structure of monolayer molybdenum disulfide. But the EMA band model cannot give the correct description for the band structure in the higher-energy region. To address this major issue, we propose an analytical band calculation (ABC) model to study monolayer molybdenum disulfide. Important parameters of the ABC model are obtained by fitting the three-direction band structure of monolayer molybdenum disulfide obtained from the first-principles (FP) method. The pro…
Molybdenum disulfide is a novel two-dimensional semiconductor with potential applications in electronic and optoelectronic devices. However, the nature of charge transport in back-gated devices still remains elusive as they show much lower mobility than theoretical calculations and native n-type doping. Here we report transport study in few-layer molybdenum disulfide, together with transmission electron microscopy and density functional theory. We provide direct evidence that sulfur vacancies exist in molybdenum disulfide, introducing localized donor states inside the bandgap. Under low carrie…
Piezoelectricity offers precise and robust conversion between electricity and mechanical force. Here we report the first experimental evidence of piezoelectricity in a single layer of molybdenum disulfide (MoS2) crystal as a result of inversion symmetry breaking of the atomic structure, with measured piezoelectric coefficient e11 = 2.9e-10 C/m. Through the angular dependence of electro-mechanical coupling, we uniquely determined the two-dimensional (2D) crystal orientation. We observed that only MoS2 membranes with odd number of layers exhibited piezoelectricity, in sharp contrast to the conve…
Atomically-thin molybdenum disulfide is emerging as a new nanomaterial with potential applications in the fields of electronic and photonics. Charge carrier dynamics plays an essential role in determining its electronic and optical properties. We report spatially and temporally resolved pump-probe studies of charge carriers in atomically-thin molybdenum disulfide samples fabricated by mechanical exfoliation. Carriers are injected by interband absorption of a 390-nm pump pulse and detected by measuring differential reflection of a time-delayed and spatially-scanned probe pulse that is tuned to …
Control over thickness, size, and area of chemical vapor deposition (CVD) grown molybdenum disulfide (MoS2) flakes is crucial for device application. Herein, we report a quantitative comparison of CVD synthesis of MoS2 on SiO2/Si substrate using three different precursors viz., molybdenum trioxide (MoO3), ammonium heptamolybdate (AHM), and tellurium (Te). A three-step chemical reaction mechanism of evolution of MoS2 from MoO3 micro-crystals is proposed for MoO3 precursor. Furthermore, a strategy based on growth temperature and ratio of amount of precursors is developed to systematically contro…
A simple band model using higher order non-parabolic effect was adopted for single layer molybdenum tungsten alloy disulfide (i.e., $\mathrm{Mo}_{1-x}\mathrm{W}_x\mathrm{S}_2$). The first-principles method considering $2\times2$ supercell was used to study band structure of single layer alloy $\mathrm{Mo}_{1-x}\mathrm{W}_x\mathrm{S}_2$ and a simple band (i.e., effective mass approximation model, EMA) model with higher order non-parabolic effect was used to fit the first-principle band structures in order to calculate corresponding the hole mobility. In addition, we investigate the alloy scatte…
Molybdenum disulfide is considered as one of the most promising two-dimensional semiconductors for electronic and optoelectronic device applications. So far, the charge transport in monolayer molybdenum disulfide is dominated by extrinsic factors such as charged impurities, structural defects and traps, leading to much lower mobility than the intrinsic limit. Here, we develop a facile low-temperature thiol chemistry to repair the sulfur vacancies and improve the interface, resulting in significant reduction of the charged impurities and traps. High mobility greater than 80cm2 V-1 s-1 is achiev…
The growth of large crystallite continuous monolayer materials like molybdenum disulfide (MoS$_2$) with desired morphology via chemical vapor deposition (CVD) remains a challenge. In CVD, the complex interplay of various factors like growth temperature, precursors, and nature of the substrate decides the crystallinity, crystallite size, and coverage area of the grown MoS$_2$ monolayer. In the present work, we report about the role of weight fraction of molybdenum trioxide (MoO$_3$), Sulfur, and carrier gas flow rate towards nucleation and monolayer growth. The concentration of MoO$_3$ weight f…
One important use of layered semiconductors such as molybdenum disulfide (MoS2) could be in making novel heterojunction devices leading to functionalities unachievable using conventional semiconductors. Here we demonstrate an ultrafast metal-semiconductor-metal heterojunction photodetector, made of MoS2 and amorphous silicon (a-Si), with rise and fall times of about 0.3 ms. This is more than an order of magnitude improvement over response times of conventional a-Si (~5 ms) and best reported MoS2 devices (~50 ms). The van-der-waals heterojunction presented here yields a high photoresponsivity o…
The strong light emission and absorption exhibited by single atomic layer transitional metal dichalcogenides in the visible to near-infrared wavelength range makes them attractive for optoelectronic applications. In this work, using two-pulse photovoltage correlation technique, we show that monolayer molybdenum disulfide photodetector can have intrinsic response times as short as 3 ps implying photodetection bandwidths as wide as 300 GHz. The fast photodetector response is a result of the short electron-hole and exciton lifetimes in this material. Recombination of photoexcited carriers in most…
Recent progress in large-area synthesis of monolayer molybdenum disulfide, a new two-dimensional direct-bandgap semiconductor, is paving the way for applications in atomically thin electronics. Little is known, however, about the microstructure of this material. Here we have refined chemical vapor deposition synthesis to grow highly crystalline islands of monolayer molybdenum disulfide up to 120 um in size with optical and electrical properties comparable or superior to exfoliated samples. Using transmission electron microscopy, we correlate lattice orientation, edge morphology, and crystallin…
The microscopic process of oxidative etching of two-dimensional molybdenum disulfide (2D MoS2) at an atomic scale is investigated using a correlative TEM-etching study. MoS2 flakes on graphene TEM grids are precisely tracked and characterized by TEM before and after the oxidative etching. This allows us to determine the structural change with an atomic resolution on the edges of the domains, of well-oriented triangular pits and along the grain boundaries. We observe that the etching mostly starts from the open edges, grain boundaries and pre-existing atomic defects. A zigzag Mo edge is assigne…
Porous single layer molybdenum disulfide (MoS$_2$) is a promising material for applications such as DNA sequencing and water desalination. In this work, we introduce irradiation with highly charged ions (HCIs) as a new technique to fabricate well-defined pores in MoS$_2$. Surprisingly, we find a linear increase of the pore creation efficiency over a broad range of potential energies. Comparison to atomistic simulations reveals the critical role of energy deposition from the ion to the material through electronic excitation in the defect creation process, and suggests an enrichment in molybdenu…
Doping is an effective way to modify the electronic property of two-dimensional (2D) materials and endow them with new functionalities. However, wide-range control of the substitutional doping concentration with large scale uniformity remains challenging in 2D materials. Here we report in-situ chemical vapor deposition growth of vanadium (V) doped monolayer molybdenum disulfide (MoS2) with widely tunable doping concentrations ranging from 0.3 to 13.1 at%. The key to regulate the doping concentration lies in the use of appropriate V precursors with different doping abilities, which also generat…
Molybdenum disulfide has recently emerged as a promising two-dimensional semiconducting material for nano-electronic, opto-electronic and spintronic applications. However, demonstrating spin-transport through a semiconducting MoS2 channel is challenging. Here we demonstrate the electrical spin injection and detection in a multilayer MoS2 semiconducting channel. A magnetoresistance (MR) around 1% has been observed at low temperature through a 450nm long, 6 monolayer thick channel with a Co/MgO spin injector and detector. From a systematic study of the bias voltage, temperature and back-gate vol…
We explore the collective electronic excitations of bilayer molybdenum disulfide (MoS$_2$) using the density functional theory together with the random phase approximation. The many-body dielectric function and electron energy-loss spectra are calculated using an {\it ab initio} based model involving material-realistic physical properties. The electron energy-loss function of bilayer MoS$_2$ system is found to be sensitive to either electron or hole doping and it is owing to the fact that the Kohn-Sham band dispersions are not symmetric for energies above and below the zero Fermi level. Three …
Edge structures are highly relevant to the electronic, magnetic and catalytic properties of two-dimensional (2D) transition metal dichalcogenides (TMDs) and their one dimensional (1D) counterpart, i.e., nanoribbons, which should be precisely tailored for the desirable applications. In this work, we report the formation of novel Mo6S6 nanowire (NW) terminated edges in a monolayer molybdenum disulfide (MoS2) via an e-beam irradiation process combined with high temperature heating in a scanning transmission electron microscope (STEM). Atomic structures of NW terminated edges and the dynamic forma…
Ultrathin two-dimensional semiconductors obtained from layered transition-metal dichalcogenides such as molybdenum disulfide (MoS2) are promising for ultimately scaled transistors beyond Si. Although the shortening of the semiconductor channel is widely studied, the narrowing of the channel, which should also be important for scaling down the transistor, has been examined to a lesser degree thus far. In this study, the impact of narrowing on mechanically exfoliated MoS2 flakes was investigated according to the channel-width-dependent Schottky barrier heights at Cr/Au contacts. Narrower channel…
Since the stacking order sensitively affects various physical properties of layered materials, accurate determination of the stacking order is important for studying the basic properties of these materials as well as for device applications. Because 2H-molybdenum disulfide (MoS2) is most common in nature, most studies so far have focused on 2H-MoS2. However, we found that the 2H, 3R, and mixed stacking sequences exist in few-layer MoS2 exfoliated from natural molybdenite crystals. The crystal structures are confirmed by HR-TEM measurements. The Raman signatures of different polytypes are inves…
Layered molecular materials and especially MoS2 are already accepted as promising candidates for nanoelectronics. In contrast to the bulk material, the observed electron mobility in single-layer MoS2 is unexpectedly low. Here we reveal the occurrence of intrinsic defects in MoS2 layers, known as inversion domains, where the layer changes its direction through a line defect. The line defects are observed experimentally by atomic resolution TEM. The structures were modeled and the stability and electronic properties of the defects were calculated using quantum-mechanical calculations based on th…
Two-dimensional Molybdenum Disulfide (MoS2) has shown promising prospects for the next generation electronics and optoelectronics devices. The monolayer MoS2 can be patterned into quasi-one-dimensional anisotropic MoS2 nanoribbons (MNRs), in which theoretical calculations have predicted novel properties. However, little work has been carried out in the experimental exploration of MNRs with a width of less than 20 nm where the geometrical confinement can lead to interesting phenomenon. Here, we prepared MNRs with width between 5 nm to 15 nm by direct helium ion beam milling. High optical anisot…
The electrical conductivity and Raman spectroscopy measurements have been performed on MoS$_2$ at high pressures up to 90 GPa and variable temperatures down to 5 K. We find that the temperature dependence of the resistance in a metallic 2H$_a$ phase has an anomaly (a hump) which shifts with pressure to higher temperature. Concomitantly, a new Raman phonon mode appears in the metallic state suggesting that the electrical resistance anomaly may be related to a structural transformation. We suggest that this anomalous behavior is due to a charge density wave state, the presence of which is indica…
Layered two-dimensional (2D) semiconducting transition metal dichalcogenides (TMD) have been widely isolated, synthesized, and characterized recently. Numerous 2D materials are identified as the potential candidates as channel materials for future thin film technology due to their high mobility and the exhibiting bandgaps. While many TMD filed-effect transistors (FETs) have been widely demonstrated along with a significant progress to clearly understand the device physics, large contact resistance at metal/semiconductor interface still remain a challenge. From 2D device research point of view,…
The two-dimensional (2D) semiconductor molybdenum disulfide (MoS2) has attracted widespread attention for its extraordinary electrical, optical, spin and valley related properties. Here, we report on spin polarized tunneling through chemical vapor deposited (CVD) multilayer MoS2 (~7 nm) at room temperature in a vertically fabricated spin-valve device. A tunnel magnetoresistance (TMR) of 0.5 - 2 % has been observed, corresponding to spin polarization of 5 - 10 % in the measured temperature range of 300 - 75 K. First principles calculations for ideal junctions results in a tunnel magnetoresistan…
We study the optical properties of MoS$_2$ nanotubes (NTs) with walls comprising dozens of monolayers. We reveal strong peaks in micro-photoluminescence ($μ$-PL) spectra when detecting the light polarized along the NT axis. We develop a model describing the optical properties of the nanotubes acting as optical resonators which support the quantization of whispering gallery modes inside the NT wall. The experimental observation of the resonances in $μ$-PL allows one to use them as a contactless method of the estimation of the wall width. Our findings open a way to use such NTs as polarization-s…
We present the discovery of a charge density wave (CDW) ground state in heavily electron-doped molybdenum disulfide (MoS$_2$). This is the first observation of a CDW in any $d^2$ (column 6) transition metal dichalcogenide (TMD). The band structure of MoS$_2$ is distinct from the $d^0$ and $d^1$ TMDs in which CDWs have been previously observed, facilitating new insight into CDW formation. We demonstrate a metal-insulator transition at 85 K, a 25 meV gap at the Fermi level, and two distinct CDW modulations, $(2\sqrt{3}\times2\sqrt{3})$R$30^\circ$ and $2\times2$, attributable to Fermi surface nes…
The design and development of inexpensive highly efficient electrocatalysts for hydrogen production, underpins several emerging clean-energy technologies. In this work, for the first time, molybdenum disulfide (MoS2) nanodots have been synthesized by ionic liquid assisted grinding exfoliation of bulk platelets and isolated by sequential centrifugation. The nanodots have a thickness of up to 7 layers (4 nm) and an average lateral size smaller than 20 nm. Detailed structural characterization established that the nanodots retained the crystalline quality and low oxidation states of the bulk mater…
Intercalation of alkali atoms within the lamellar transition metal dichalcogenides is a possible route toward a new generation of batteries. It is also a way to induce structural phase transitions authorizing the realization of optical and electrical switches in this class of materials. The process of intercalation has been mostly studied in three-dimensional dichalcogenide films. Here, we address the case of a single-layer of molybdenum disulfide (MoS$_2$), deposited on a gold substrate, and intercalated with cesium (Cs) in ultra-clean conditions (ultrahigh vacuum). We show that intercalation…
Molybdenum disulfide (MoS2) is a particularly interesting member of the family of two-dimensional (2D) materials due to its semiconducting and tunable electronic properties. Currently, the most reliable method for obtaining high-quality industrial scale amounts of 2D materials is chemical vapor deposition (CVD), which results in polycrystalline samples. As grain boundaries (GBs) are intrinsic defect lines within CVD-grown 2D materials, their atomic structure is of paramount importance. Here, through atomic-scale analysis of micrometer-long GBs, we show that covalently bound boundaries in 2D Mo…
Large scale implementation of electrochemical water splitting for hydrogen evolution requires cheap and efficient catalysts to replace expensive platinum. Molybdenum disulfide is one of the most promising alternative catalysts but its intrinsic activity is still inferior to platinum. There is therefore a need to explore new active site origins in molybdenum disulfide with ultrafast reaction kinetics and to understand their mechanisms. Here, we report a universal cold hydrogen plasma reduction method for synthesizing different single atoms sitting on two-dimensional monolayers. In case of molyb…
Monolayer Molybdenum Disulfide (MoS2) with a direct band gap of 1.8 eV is a promising two-dimensional material with a potential to surpass graphene in next generation nanoelectronic applications. In this letter, we synthesize monolayer MoS2 on Si/SiO2 substrate via chemical vapor deposition (CVD) method and comprehensively study the device performance based on dual-gated MoS2 field-effect transistors. Over 100 devices are studied to obtain a statistical description of device performance in CVD MoS2. We examine and scale down the channel length of the transistors to 100 nm and achieve record hi…
Structural defects in the molybdenum disulfide (MoS2) monolayer are widely known for strongly altering its properties. Therefore, a deep understanding of these structural defects and how they affect MoS2 electronic properties is of fundamental importance. Here, we report on the incorporation of atomic hydrogen in mono-layered MoS2 to tune its structural defects. We demonstrate that the electronic properties of single layer MoS2 can be tuned from the intrinsic electron (n) to hole (p) doping via controlled exposure to atomic hydrogen at room temperature. Moreover, this hydrogenation process rep…
Monolayer transition metal dichalcogenides (TMDCs) are two-dimensional (2D) materials with many potential applications. Chemical vapour deposition (CVD) is a promising method to synthesize these materials. However, CVD-grown materials generally have poorer quality than mechanically exfoliated ones and contain more defects due to the difficulties in controlling precursors' distribution and concentration during growth where solid precursors are used. Here, we propose to use thiol as a liquid precursor for CVD growth of high quality and uniform 2D MoS2. Atomic-resolved structure characterizations…
Although MoS2 field-effect transistors (FETs) with high-k dielectrics are promising for electron device applications, the underlying physical origin of interface degradation remains largely unexplored. Here, we present a systematic analysis of the energy distribution of the interface state density (Dit) and the quantum capacitance (CQ) in a dual-gate monolayer exfoliated MoS2 FET. The CQ analysis enabled us to construct a Dit extraction method as a function of EF. A band tail distribution of Dit with the lowest value of 8*1011 cm-2eV-1 suggests that Dit is not directly related to the sharp pea…
The utilization of alkali salts, such as NaCl and KI, have enabled the successful growth of large single domain and fully coalesced polycrystalline two-dimensional (2D) transition metal dichalcogenide layers. However, the impact of alkali salts on photonic and electronic properties are not fully established. In this work, we report alkali-free epitaxy of MoS2 on sapphire and benchmark the properties against alkali-assisted growth of MoS2. This study demonstrates that although NaCl can dramatically increase the domain size of monolayer MoS2 by 20 times, it can also induce strong optical and ele…
We report on the results of the low-frequency (1/f, where f is frequency) noise measurements in MoS2 field-effect transistors revealing the relative contributions of the MoS2 channel and Ti/Au contacts to the overall noise level. The investigation of the 1/f noise was performed for both as fabricated and aged transistors. It was established that the McWhorter model of the carrier number fluctuations describes well the 1/f noise in MoS2 transistors, in contrast to what is observed in graphene devices. The trap densities extracted from the 1/f noise data for MoS2 transistors, are 1.5 x 10^19 eV-…
Turning non-magnetic two-dimensional molybdenum disulfide into room temperature magnets by the synergistic effect of strain engineering and charge injection
Superconductivity commonly appears under pressure in charge density wave (CDW)-bearing transition metal dichalcogenides (TMDs), but has emerged so far only via either intercalation with electron donors or electrostatic doping in CDW-free TMDs. Theoretical calculations have predicted that the latter should be metallized through bandgap closure under pressure, but superconductivity remained elusive in pristine 2H-MoS2 upon substantial compression, where a pressure of up to 60 GPa only evidenced the metallic state. Here we report the emergence of superconductivity in pristine 2H-MoS2 at 90 GPa. T…
We explore the combined impact of sulfur vacancies and electronic interactions on the optical properties of monolayer MoS$_2$. First, we present a generalized Anderson-Hubbard Hamiltonian that accounts for both randomly distributed sulfur vacancies and the presence of dielectric screening within the material. Second, we parameterize this energy-dependent Hamiltonian from first-principles calculations based on density functional theory and the Green function and screened Coulomb (GW) method. Third, we apply a first-principles-based many-body typical medium method to determine the single-particl…
Innovative applications based on two-dimensional solids require cost-effective fabrication processes resulting in large areas of high quality materials. Chemical vapour deposition is among the most promising methods to fulfill these requirements. However, for 2D materials prepared in this way it is generally assumed that they are of inferior quality in comparison to the exfoliated 2D materials commonly used in basic research. In this work we challenge this assumption and aim to quantify the differences in quality for the prototypical transition metal dichalcogenide MoS$_2$. To this end single …
The ability to synthesize high-quality samples over large areas and at low cost is one of the biggest challenges during the developmental stage of any novel material. While chemical vapor deposition (CVD) methods provide a promising low-cost route for CMOS compatible, large-scale growth of materials, it often falls short of the high-quality demands in nanoelectronics and optoelectronics. We present large-scale CVD synthesis of single- and few- layered MoS2 using direct vapor-phase sulfurization of MoO2, which enables us to obtain extremely high-quality single-crystal monolayer MoS2 samples wit…
Atomically thin two-dimensional (2D) transition metal dichalcogenides (TMDCs) are attractive materials for next generation nanoscale optoelectronic applications. Understanding nanoscale optical behavior of the edges and grain boundaries of synthetically grown TMDCs is vital for optimizing their optoelectronic properties. Elucidating the nanoscale optical properties of 2D materials through far-field optical microscopy requires a diffraction-limited optical beam diameter sub-micron in size. Here we present our experimental work on spatial photoluminescence (PL) scanning of large size ( $\geq 50$…
