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All sourcesNASA NTRSDOE OSTI
NASA NTRS1980

Moderate temperature sodium cells. I - Transition metal disulfide cathodes

TiS2, VS2, and Nb(1.1)S2 transition metal disulfides were evaluated as cathode materials for a moderate temperature rechargeable Na cell operating at 130 C. The 1st discharge of TiS2 results in a capacity of 0.85 eq/mole; approximately half of the Na in the 1st phase spanning the Na range from zero to 0.30 and almost all the Na in the 2nd phase spanning the 0.37 to 0.80 range are rechargeable. VS2 intercalates up to one mole of Na/mole of VS2 in the 1st discharge; the resulting Na(x)VS2 ternary consists of 3 phases in the 3 ranges of Na from zero to 1. Niobium disulfide undergoes a phase change in the 1st discharge; the average rechargeable capacity in extended cycling of this cathode is 0.50 eq/mole.

Abraham, K. M.↗
DOE OSTI2021

Conduction via surface states in antiferromagnetic Mott-insulating Ni S 2 single crystals

Pyrite structure transition-metal disulfides exhibit diverse ground states vs d-band filling, spanning diamagnetic semiconducting, ferromagnetic metallic, antiferromagnetic Mott insulating, and superconducting in FeS 2 , CoS 2 , NiS 2 , and CuS 2 . NiS is particularly interesting and poorly understood as its Mott insulating behavior is accompanied by complex antiferromagnetic ordering below ~38 K and perplexing weak ferromagnetism below ~30 K. Temperature-, pressure-, and composition-dependent insulator-metal transitions also occur, particularly in bandwidth-controlled NiS 2–x Se x , hole-doped Ni 1–x Co x S 2 , etc. Here, we use high-quality chemical-vapor-transport-grown NiS 2 single crystals characterized by x-ray diffraction, energy-dispersive x-ray spectroscopy, magnetometry, and extensive transport and magnetotransport measurements, to generate new insight into this system. In particular, resistivity, magnetoresistance, and Hall effect analyses vs temperature, thickness, and surface preparation, provide unequivocal evidence of surface conduction, where the more conductive surface shunts essentially all current at low temperatures. The surface transport changes from two dimensional and insulating to three dimensional and metallic as the surface preparation is varied (also displaying intriguing sensitivity to magnetic ordering), significantly clarifying literature ambiguities with respect to the electronic ground state. These results have immediate implications. First, the temperature-, pressure-, and composition-dependent insulator-metal transitions deduced in the extensive prior work on NiS 2-x Se x , Ni 1–x Co x S 2 , etc., must clearly be reexamined in light of rife metallic surface conduction, not previously taken into account. Second, NiS 2 now joins FeS 2 and CoS 2 as systems in which bulk and surface electronic behaviors are strikingly different, suggesting that metallic surface states could be a universal feature of pyrite structure transition-metal disulfides.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Excitonic Dynamics in Janus MoSSe and WSSe Monolayers

We report here details of steady-state and time-resolved spectroscopy of excitonic dynamics for Janus transition metal dichalcogenide monolayers, including MoSSe and WSSe, which were synthesized by low-energy implantation of Se into transition metal disulfides. Absorbance and photoluminescence spectroscopic measurements determined the room-temperature exciton resonances for MoSSe and WSSe monolayers. Transient absorption measurements revealed that the excitons in Janus structures form faster than those in pristine transition metal dichalcogenides by about 30% due to their enhanced electron–phonon interaction by the built-in dipole moment. Here, by combining steady-state photoluminescence quantum yield and time-resolved transient absorption measurements, we find that the exciton radiative recombination lifetime in Janus structures is significantly longer than in their pristine samples, supporting the predicted spatial separation of the electron and hole wave functions due to the built-in dipole moment. These results provide fundamental insight in the optical properties of Janus transition metal dichalcogenides.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Nickel particle–enabled width-controlled growth of bilayer molybdenum disulfide nanoribbons

Transition metal dichalcogenides exhibit a variety of electronic behaviors depending on the number of layers and width. Therefore, developing facile methods for their controllable synthesis is of central importance. We found that nickel nanoparticles promote both heterogeneous nucleation of the first layer of molybdenum disulfide and simultaneously catalyzes homoepitaxial tip growth of a second layer via a vapor-liquid-solid (VLS) mechanism, resulting in bilayer nanoribbons with width controlled by the nanoparticle diameter. Simulations further confirm the VLS growth mechanism toward nanoribbons and its orders of magnitude higher growth speed compared to the conventional noncatalytic growth of flakes. Width-dependent Coulomb blockade oscillation observed in the transfer characteristics of the nanoribbons at temperatures up to 60 K evidences the value of this proposed synthesis strategy for future nanoelectronics.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Anodic Dissolution Rates Accelerate with Decreasing MoS 2 Nanoflake Thickness

Electrochemical gating of 2D transition metal dichalcogenide (TMD) electrodes is an emerging frontier in the field of semiconductor electrochemistry. In this approach, an applied bias modifies the charge carrier concentration of the 2D TMD, causing band edge shifts and drastic changes in charge transfer rates. However, leveraging this effect for (photo)electrocatalysis is practically limited by the stability of the TMD material under gating conditions. Gerischer showed anodic dissolution of bulk TMD electrodes can occur in the dark and hypothesized that the reaction proceeds via an electron tunneling mechanism from surface states to the TMD conduction band [H. Gerischer, D. Ross, and M. Lubke, Z. Physickalische Chem., 139, 1 (1984)]. Here we investigate this possibility in single MoS 2 nanoflakes using in situ optical microscopy and explore whether Gerischer’s electron tunneling mechanism can explain anodic dissolution rates of thin 2D semiconductors. Here, spatially resolved measurements show anodic dissolution initiates at perimeter edge sites and accelerates exponentially with decreasing layer thickness, consistent with Gerischer’s tunneling mechanism. Interestingly, single layer MoS 2 is impervious to anodic dissolution at applied potentials >200 mV more positive than those required to drive dissolution in bulk and multilayer-thick nanoflakes.

2D semiconductor↗
DOE OSTI2024

Metal DiSulfide thin films synthesized by pulsed ion beam ablation: Self-assembled structures with improved mechanical properties in humid conditions

Thin films composed of transition metal dichalcogenides such as molybdenum disulfide (MoS 2 ) or tungsten disulfide (WS 2 ) are well known for their solid lubricating behavior in dry environments such as space, but deteriorate rapidly in environments where oxygen is present. There have been many attempts over recent decades to improve MoS 2 lubricating performance in humid environments by addition of metals such as titanium to the film. The additions have come in the form of co-sputtering with the MoS 2 , or formation of nano multilayer coatings. We have previously reported on the synthesis of MoS 2 films by high-power ion beam ablation [Prasad et al, Matls. Lett. 65 (2010) 4–6]. The resulting films are observed to contain spheres of pure Mo of 10–100 nm size evenly dispersed throughout the ~1 μm-thick film, a form of self-assembly not before seen in films produced by sputtering or by pulsed laser deposition (PLD). The remaining Mosingle bondS matrix was observed to crystalize in situ under frictional contact into MoS 2 with the basal planes orienting themselves in the direction of sliding underneath the wear surface. The present study concerns metal additions in the form of alternating layers with MoS 2 deposited in between from an ablation target. The addition of Ti resulted in the extension of good tribological performance to humid air conditions, but the path to good performance appears to be relatively narrow. The same distributed Mo spheres were present in the new film, and similar self-assembled morphologies when V was substituted for the Ti, and when multilayers were formed of WS 2 with Zr additions. Furthermore, it appears that addition of Ti resulted in improvements in mechanical film strength that contributed to the wear ability in humid conditions.

Intense ion beams↗
DOE OSTI2026

Characterization of Electronic Stress-Induced Changes in Multilayer MoS 2

Transition metal dichalcogenides like molybdenum disulfide (MoS 2 ) are compelling for next-generation electronic devices. In this work, we investigate the impact of electronic stress on MoS 2 to illustrate that observational and phenomenological information on multiple devices can be useful to describe changes in the device, and caution against the rationalization of paltry results as representative or correlative to device behavior. Here, we stress MoS 2 by applying a sustained 20 V DC bias to study the material’s response. Post-stress electronic characterization revealed nonuniform shifts in current–voltage (I–V) behavior alongside microscale changes. Complementary mechanical, spectroscopic, and scanning microwave impedance measurements showed that stress-induced features locally modulate stiffness, surface potential, Raman intensity, and charge carrier density. We correlated I–V behavior with morphological features (wrinkles, tears, folds, height) and device-level geometry (MoS 2 overlap with electrodes, channel area, contact length) on 50 test structures across five chips to move beyond anecdotal conclusions. We found no universal correlations before DC stress. However, device-level geometry was correlated with I–V behavior after DC stress, suggesting that electrode contacts play a more dominant role than morphology in determining performance. Delamination and thinning induced by DC stress led to localized reductions in charge carrier density within the affected regions. Further, delamination and thinning appear to map to I–V device performance in a few samples, but the correlation is lost when a larger sample size is considered. This suggests significant sample-to-sample variability in surface electronic states of the test structures. We also discuss how environmental factors introduced during fabrication may contribute to the observed heterogeneous device response. Progress will require high-resolution, multimodal analysis across many samples constructed under controlled, clean conditions. By building data sets that capture variability, we can better identify the true drivers of performance.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Basal Plane Doping to Activate Colloidal MoS 2 Nanosheets for Catalytic Hydrodeoxygenation of para- Cresol

The valorization of biomass into biofuels is a critical process for producing renewable fuels. Hydrodeoxygenation (HDO), particularly over doped molybdenum disulfide (MoS 2 ), a transition metal dichalcogenide (TMD) material, is a common representative catalytic reaction system for converting biomass-derived materials into useful hydrocarbons. However, the location and role of dopants, such as Co, in HDO is not fully understood. The effects of dopant location and oxidation state are often precluded by inhomogeneity in the ensemble properties of nanosheet size and dopant dispersion, as well as difficulty in observing the behavior of atomic site behavior directly. Using a colloidal approach to synthesize cobalt-doped MoS 2 nanosheets with controlled dopant concentration, combined with X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations, we determine that basal plane doped Co (25% Co:Mo mole ratio) shows peak catalytic activity in HDO of para-cresol, a model biomass-derived compound, and that basal Co sites are demonstrably more active than edge sites. By observing these doping effects in MoS 2 catalysts for HDO, we can further optimize not only the production of carbon-neutral fuels but also direct the tailoring of doped TMD catalysts toward their intended applications.

36 MATERIALS SCIENCE↗
DOE OSTI2021

MoS 2 for beyond lithium-ion batteries

As a typical transition-metal chalcogenide material, molybdenum disulfide (MoS 2 ) has received tremendous attention because of its unique layered structure and versatile chemical, electronic, and optical properties. With the focus of this Perspective on the energy storage area, one of the most important contributions of MoS 2 is that it sparked the birth of the rechargeable lithium battery in the early 1980s, which later formed the foundation of commercial lithium batteries. After four decades, admitting that MoS 2 is still playing a significant role in the lithium-ion battery field and considerable effort was made to decipher the mechanism through ex situ and in situ studies and by means of MoS 2 nanostructure engineering that advances the lithium battery performance, it is also used in beyond lithium-ion batteries, such as sodium, magnesium, calcium, and aluminum energy storage systems. Such alternative battery systems are desirable because of the safety concerns of lithium and the depletion of lithium reserves and corresponding increase in cost. In this Perspective, recent development on the fabrication of novel MoS 2 nanostructures was discussed, followed by the scrutinization of their application in beyond lithium-ion batteries and the in situ/operando methods involved in these studies. Finally, a brief summary and outlook that may help with the future advancement of the beyond lithium-ion batteries are presented.

25 ENERGY STORAGE↗
DOE OSTI2023

Hysteresis-free high mobility graphene encapsulated in tungsten disulfide

High mobility is a crucial requirement for a large variety of electronic device applications. The state of the art for high-quality graphene devices is based on heterostructures made with graphene encapsulated in >40 nm-thick flakes of hexagonal boron nitride (hBN). Unfortunately, scaling up multilayer hBN while precisely controlling the number of layers remains an outstanding challenge, resulting in a rough material unable to enhance the mobility of graphene. This leads to the pursuit of alternative, scalable materials, which can be used as substrates and encapsulants for graphene. Tungsten disulfide (WS2) is a transition metal dichalcogenide, which was grown in large (∼mm-size) multi-layers by chemical vapor deposition. However, the resistance vs gate voltage characteristics when gating graphene through WS2 exhibit largely hysteretic shifts of the charge neutrality point on the order of Δn∼ 3 × 1011 cm−2, hindering the use of WS2 as a reliable encapsulant. The hysteresis originates due to the charge traps from sulfur vacancies present in WS2. In this work, we report the use of WS2 as a substrate and overcome the hysteresis issues by chemically treating WS2 with a super-acid, which passivates these vacancies and strips the surface from contaminants. The hysteresis is significantly reduced by about two orders of magnitude, down to values as low as Δn∼ 2 × 109 cm−2, while the room-temperature mobility of WS2-encapsulated graphene is as high as ∼62 × 103 cm2 V−1 s−1 at a carrier density of n ∼ 1 ×1012 cm−2. Our results promote WS2 as a valid alternative to hBN as an encapsulant for high-performance graphene devices.

Physics↗
DOE OSTI2020

Disentangling Oxygen and Water Vapor Effects on Optoelectronic Properties of Monolayer Tungsten Disulfide

By understanding how the environmental composition impacts the optoelectronic properties of transition metal dichalcogenide monolayers, we demonstrate that simple photoluminescence (PL) measurements of tungsten disulfide (WS 2 ) monolayers can differentiate relative humidity environments. In this paper, we examine the PL and photoconductivity of chemical vapor deposition grown WS 2 monolayers under three carefully controlled environments: inert gas (N 2 ), dry air (O 2 in N 2 ), and humid nitrogen (H 2 O vapor in N 2 ). The WS 2 PL is measured as a function of 532 nm laser power and exposure time and can be decomposed into the exciton, trion, and lower energy state(s) contributions. Under continuous illumination in either O 2 or H 2 O vapor environment, we find dramatic (and reversible) increases in PL intensity relative to the PL in an inert environment. The PL bathochromically shifts in an O 2 environment and is dominated by increased trion emission and diminished exciton emission. In contrast, the WS 2 PL increase in a H 2 O environment results from an overall increase in emission from all spectral components where the exciton contribution dominates. The drastic increases in PL are anticorrelated with corresponding decreases in photoconductivity, as measured by time-resolved microwave conductivity. The results suggest that both O 2 and H 2 O react photochemically with the WS 2 monolayer surface, modifying the optoelectronic properties, but do so via distinct pathways. Thus, we use these optoelectronic differences to differentiate the amount of humidity in the air, which we show with 0%, 40%, and 80% relative humidity environments. This deeper understanding of how ambient conditions impact WS 2 monolayers enables novel humidity sensors as well as a better understanding of the correlation between TMDC surface chemistry, light emission, and photoconductivity. Moreover, these WS 2 measurements highlight the importance of considering the impact of the local environment on reported results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Electronic structure and charge-density wave transition in monolayer $\mathrm{VS}_2$

Vanadium disulfide (VS 2 ) attracts elevated interests for its charge-density wave (CDW) phase transition, ferromagnetism, and catalytic reactivity, but the electronic structure of monolayer has not been well understood yet. Here we report synthesis of epitaxial 1T VS 2 monolayer on bilayer graphene grown by molecular-beam epitaxy (MBE). Angle-resolved photoemission spectroscopy (ARPES) measurements reveal that Fermi surface with six elliptical pockets centered at the M points shows gap opening at low temperature. Temperature-dependence of the gap size suggests existence of CDW phase transition above room temperature. Here, our observations provide important evidence to understand the strongly correlated electron physics and the related surface catalytic properties in two-dimensional transition-metal dichalcogenides (TMDCs).

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Clean 2D superconductivity in a bulk van der Waals superlattice

Alternative route to a 2D superconductor Single layers of transition metal dichalcogenides exhibit exotic properties, including superconductivity. The usual route to obtaining such samples is to exfoliate a three-dimensional (3D) crystal. Devarakonda et al. instead grew a superlattice comprising alternating layers of the transition metal dichalcogenide hexagonal NbS 2 and the material Ba 3 NbS 5 (see the Perspective by Schoop). The inert Ba 3 NbS 5 layers serve to dissociate the superconducting NbS 2 layers from one another, resulting in 2D superconductivity with high carrier mobility. The combination of high mobility and reduced dimensionality may give rise to exotic quantum phases. Science , this issue p. 231 see also p. 170

Science & Technology - Other Topics↗
DOE OSTI2020

Intentional carbon doping reveals CH as an abundant charged impurity in nominally undoped synthetic WS 2 and WSe 2

Understanding the physical properties and controlling the generation of intrinsic and extrinsic defects is central to the technological adoption of 2D materials in devices. Here we identify a charged carbon-hydrogen complex at a chalcogen site (CH X ) as a common, charged impurity in synthetically grown transition metal dichalcogenides (TMDs). This conclusion is drawn by comparing high resolution scanning probe microscopy measurements of nominally undoped and intentionally carbon doped TMD samples. While CH impurity densities in undoped CVD-grown WS 2 and MOCVD-grown WSe 2 can range anywhere from parts per million to parts per thousand, CH densities in the percentage levels were selectively generated by a post-synthetic methane plasma treatment. Our study indicates that methane plasma treatment is a selective and clean method for the controlled introduction of a charged carbon-hydrogen complex at a surface chalcogen site, adefect that is commonly present in synthetic TMDs.

36 MATERIALS SCIENCE↗