TaS2 Research Articles

Atomic layer deposition of transition metal chalcogenide TaSx using Ta[N(CH3)2]3[NC(CH3)3] precursor and H2S plasma

As a transition metal chalcogenide, tantalum sulfide (TaSx) is of interest for semiconductor device applications, for example, as a diffusion barrier in Cu interconnects. For deposition of ultrathin nanolayers in such demanding 3D structures, a synthesis method with optimal control is required, and therefore, an atomic layer deposition (ALD) process for TaSx was developed. ALD using (tert)-butylimidotris(dimethylamido)tantalum (Ta[N(CH3)2]3[NC(CH3)3]) as the precursor and an H2S-based plasma as the coreactant results in linear growth of TaSx films as a function of the number of cycles for all temperatures in the range 150–400 °C with growth per cycle values between 1.17±0.03 Å and 0.87±0.08 Å. Saturation of the precursor and plasma dose times, established at 300 °C, was reached after 20 and 10 s, respectively. Variation of the table temperature or the plasma composition offers the possibility to tune the film properties. At 300 °C, amorphous TaS3 films were grown, while addition of H2 to the plasma led to polycrystalline TaS2 films. The difference in sulfur content in the films correlates to a change in resistivity, where the least resistive film had the lowest S content.

Interlayer Delocalized Electrons Activate Basal Plane for Ultrahigh-Current-Density Hydrogen Evolution.

The basal plane of transition metal dichalcogenides (TMDCs) is inert for the hydrogen evolution reaction (HER) due to its low-efficiency charge transfer kinetics. We propose a strategy of filling the van der Waals (vdW) layer with delocalized electrons to enable vertical penetration of electrons from the collector to the adsorption intermediate vertically. Guided by density functional theory, we achieve this concept by incorporating Cu atoms into the interlayers of tantalum disulfide (TaS2). The delocalized electrons of d-orbitals of the interlayered Cu can constitute the charge transfer pathways in the vertical direction, thus overcoming the hopping migration through vdW gaps. The vertical conductivity of TaS2 increased by 2 orders of magnitude. The TaS2 basal plane HER activity was extracted with an on-chip microcell. Modified by the delocalized electrons, the current density increased by 20 times, reaching an ultrahigh value of 800 mA cm-2 at -0.4 V without iR compensation.

2D Tantalum Disulfide Reduction Strategy Customized Ta2O5/rGO Heterointerface Aerogel Toward Boosting Electromagnetic Wave Absorption and Flame Retardancy.

The exceptional and substantial electron affinity, as well as the excellent chemical and thermal stability of transition metal oxides (TMOs), infuse infinite vitality into multifunctional applications, especially in the field of electromagnetic wave (EMW) absorption. Nonetheless, the suboptimal structural mechanical properties and absence of structural regulation continue to hinder the advancement of TMOs-based aerogels. Herein, a novel 2D tantalum disulfide (2H-TaS2) reduction strategy is demonstrated to synthesize Ta2O5/reduced graphene oxide (rGO) heterointerface aerogels with unique characters. As the prerequisite, the defects, interfaces, and configurations of aerogels are regulated by varying the concentration of 2H-TaS2 to ensure the Ta2O5/rGO heterointerface aerogels with appealing EMW absorption properties such as a minimum reflection loss (RLmin) of -61.93dB and an effective absorption bandwidth (EAB) of 8.54GHz (7.80-16.34GHz). This strategy provides valuable insights for designing advanced EMW absorbers. Meanwhile, the aerogel exhibits favorable thermal insulation performance with a value of 36mW m-1 K-1, outstanding fire resistance capability, and exceptional mechanical energy dissipation performance, making it promising for applications in the aerospace industry and consumer electronics devices.

Engineering Charge Density Waves by Stackingtronics in Tantalum Disulfide.

In the realm of condensed matter physics and materials science, charge density waves (CDWs) have emerged as a captivating way to modulate correlated electronic phases and electron oscillations in quantum materials. However, collectively and efficiently tuning CDW order is a formidable challenge. Herein, we introduced a novel way to modulate the CDW order in 1T-TaS2 via stacking engineering. By introducing shear strain during the electrochemical exfoliation, the thermodynamically stable AA-stacked TaS2 consecutively transform into metastable ABC stacking, resulting in unique 3a × 1a CDW order. By decoupling atom coordinates, we atomically deciphered the 3D subtle structural variations in trilayer samples. As suggested by density functional theory (DFT) calculations, the origin of CDWs is presumably due to collective excitations and charge modulation. Therefore, our works shed light on a new avenue to collectively modulate the CDW order via stackingtronics and unveiled novel mechanisms for triggering CDW formation via charge modulation.

Two-dimensional van der Waals stack heterostructures for flexible thermoelectrics

The incorporation of disparate materials into heterostructures has arisen as a formidable technique for modulating interfaces and electronic configurations. The introduction of two-dimensional (2D) materials has unveiled unparalleled prospects for generating innovative heterostructures in the guise of van der Waals stacks. Tantalum sulfide (TaS2), a prominent 2D material, has been extensively studied across various domains, faces constraints in thermoelectric conversion attributed to its diminished absolute Seebeck coefficient below 10 μV K−1. By constructing a two-dimensional van der Waals stack heterostructure, TaS2/organics/TiS2, a significantly enhanced absolute Seebeck coefficient of 38.3 μV K−1 was obtained, mostly attributed to the induced interfacial effect. The power factor reached 87.6 μW m−1 K−2, marking a sevenfold increase compared to the original. The thermoelectric generator demonstrated a maximum power of 86.4 nW at a temperature difference of 40 K. Employing such heterostructure films in tactile and respiration sensors demonstrated encouraging prospects for aiding the visually impaired with language assistance and facilitating real-time monitoring of respiratory rates for health monitoring purposes. This study highlights the expansive potential of two-dimensional van der Waals stack heterostructure technology for use in flexible thermoelectric generators, wearable sensors, and beyond.

Phase and Composition Engineering of Self-Intercalated 2D Metallic Tantalum Sulfide for Second-Harmonic Generation.

Self-intercalation in two-dimensional (2D) materials is significant, as it offers a versatile approach to modify material properties, enabling the creation of interesting functional materials, which is essential in advancing applications across various fields. Here, we define ic-2D materials as covalently bonded compounds that result from the self-intercalation of a metal into layered 2D compounds. However, precisely growing ic-2D materials with controllable phases and self-intercalation concentrations to fully exploit the applications in the ic-2D family remains a great challenge. Herein, we demonstrated the controlled synthesis of self-intercalated H-phase and T-phase Ta1+xS2 via a temperature-driven chemical vapor deposition (CVD) approach with a viable intercalation concentration spanning from 10% to 58%. Atomic-resolution scanning transmission electron microscopy-annular dark field imaging demonstrated that the self-intercalated Ta atoms occupy the octahedral vacancies located at the van der Waals gap. The nonperiodic Ta atoms break the centrosymmetry structure and Fermi surface properties of intrinsic TaS2. Therefore, ic-2D T-phase Ta1+xS2 consistently exhibit a spontaneous nonlinear optical (NLO) effect regardless of the sample thickness and self-intercalation concentrations. Our results propose an approach to activate the NLO response of centrosymmetric 2D materials, achieving the modulation of a wide range of optoelectronic properties via nonperiodic self-intercalation in the ic-2D family.

Unidirectional growth of epitaxial tantalum disulfide triangle crystals grown on sapphire by chemical vapour deposition with a separate-flow system

Tantalum disulfide has been attracting considerable attention due to its rich phase diagram that includes polytypes and charge density waves, thus having potential for electrical device applications.

Atomically Unraveling Highly Crystalline Self-Intercalated Tantalum Sulfide with Correlated Stacking Registry-Dependent Magnetism.

In self-intercalated two-dimensional (ic-2D) materials, understanding the local chemical environment and the topology of the filling site remains elusive, and the subsequent correlation with the macroscopically manifested physical properties has rarely been investigated. Herein, highly crystalline gram-scale ic-2D Ta1.33S2 crystals were successfully grown by the high-pressure high-temperature method. Employing combined atomic-resolution scanning transmission electron microscopy annular dark field imaging and density functional theory calculations, we systematically unveiled the atomic structures of an atlas of stacking registries in a well-defined √3(a) × √3(a) Ta1.33S2 superlattice. Ferromagnetic order was observed in the AC' stacking registry, and it evolves into an antiferromagnetic state in AA/AB/AB' stacking registries; the AA' stacking registry shows ferrimagnetic ordering. Therefore, we present a novel approach for fabricating large-scale highly crystalline ic-2D crystals and shed light on a powerful means of modulating the magnetic order of ic-2D systems via stacking engineering, i.e., stackingtronics.

Sub-50 nm perovskite-type tantalum-based oxynitride single crystals with enhanced photoactivity for water splitting

A long-standing trade-off exists between improving crystallinity and minimizing particle size in the synthesis of perovskite-type transition-metal oxynitride photocatalysts via the thermal nitridation of commonly used metal oxide and carbonate precursors. Here, we overcome this limitation to fabricate ATaO2N (A = Sr, Ca, Ba) single nanocrystals with particle sizes of several tens of nanometers, excellent crystallinity and tunable long-wavelength response via thermal nitridation of mixtures of tantalum disulfide, metal hydroxides (A(OH)2), and molten-salt fluxes (e.g., SrCl2) as precursors. The SrTaO2N nanocrystals modified with a tailored Ir–Pt alloy@Cr2O3 cocatalyst evolved H2 around two orders of magnitude more efficiently than the previously reported SrTaO2N photocatalysts, with a record solar-to-hydrogen energy conversion efficiency of 0.15% for SrTaO2N in Z-scheme water splitting. Our findings enable the synthesis of perovskite-type transition-metal oxynitride nanocrystals by thermal nitridation and pave the way for manufacturing advanced long-wavelength-responsive particulate photocatalysts for efficient solar energy conversion.

A Tantalum Disulfide (TaS2) Mediated Long-Range Surface Plasmon Resonance Refractive Index Sensor with Improved Performance

A Tantalum Disulfide (TaS2) Mediated Long-Range Surface Plasmon Resonance Refractive Index Sensor with Improved Performance

Photoelectric properties and magnetic changes of defective tantalum disulfide adsorbed (non -) metal atoms

Transition disulfide metallides (TMDC), a unique class of two-dimensional materials, are essential to achieving the transition between semiconductors and metals. In this study, for the first time, a sulfur defect (VS) with a vacancy defect concentration of 3.84 % was introduced based on the material model, and (non-) metal atoms(H, B, N, C, O, F, Fe, Ag, Au, Pt) were adsorbed on the surface of the single-layer TaS2. The photoelectric and magnetic properties of TaS2 under the composite action were investigated. The findings indicate that TaS2 has superior adsorption capability in the defect state than standard semiconductors and that the structure distortion is more significant. After adsorbing some of the atoms, the metal TaS2 transforms into a semiconductor. Magnetic atoms can effectively increase the magnetic moment of TaS2 and strengthen the ferromagnetic coupling between atoms. After adsorption, the optical properties of TaS2 are significantly improved, and it can be effectively applied to infrared and visible light regions.

Tantalum Disulfide (TaS2)–Based Symmetrical Long-Range Surface Plasmon Resonance Biosensor with Ultrahigh Imaging Sensitivity and Figure of Merit

Tantalum Disulfide (TaS2)–Based Symmetrical Long-Range Surface Plasmon Resonance Biosensor with Ultrahigh Imaging Sensitivity and Figure of Merit

Light-induced hexatic state in a layered quantum material

The tunability of materials properties by light promises a wealth of future applications in energy conversion and information technology. Strongly correlated materials such as transition metal dichalcogenides offer optical control of electronic phases, charge ordering and interlayer correlations by photodoping. Here, we find the emergence of a transient hexatic state during the laser-induced transformation between two charge-density wave phases in a thin-film transition metal dichalcogenide, 1T-type tantalum disulfide (1T-TaS2). Introducing tilt-series ultrafast nanobeam electron diffraction, we reconstruct charge-density wave rocking curves at high momentum resolution. An intermittent suppression of three-dimensional structural correlations promotes a loss of in-plane translational order caused by a high density of unbound topological defects, characteristic of a hexatic intermediate. Our results demonstrate the merit of tomographic ultrafast structural probing in tracing coupled order parameters, heralding universal nanoscale access to laser-induced dimensionality control in functional heterostructures and devices.

Correlation between charge density wave phase transition and hydrogen adsorption in 1T-TaS2 thin film devices

Thin films of tantalum disulfide in the 1T-polytype structural phase (1T-TaS2), a type of metallic two-dimensional (2D) transition metal dichalcogenides (TMDs), are reactive to H2. Interestingly, in the incommensurate charge-density wave (ICCDW) phase with a metallic state, the electrical resistance of the 1T-TaS2 thin film decreases when H2 is adsorbed on it and returns to its initial value upon desorption. In contrast, the electrical resistance of the film in the nearly commensurate CDW (NCCDW) phase, which has a subtle band overlap or a small bandgap, does not change upon H2 adsorption/desorption. This difference in H2 reactivity is a result of differences in the electronic structure of the two 1T-TaS2 phases, namely, the ICCDW and NCCDW phases. Compared to other semiconductor 2D-TMDs such as MoS2 and WS2, the metallic TaS2 has been theoretically proven to capture gas molecules more easily because Ta has a stronger positive charge than Mo or W. Our experimental results provide evidence of this. Notably, this study is the first example of H2 sensing using 1T-TaS2 thin films and demonstrates the possibility of controlling the reactivity of the sensors to the gas by changing the electronic structure via CDW phase transitions.

Thickness-tunable magnetic and electronic transport properties of the quasi-two-dimensional van der Waals ferromagnet Co0.27TaS2 with disordered intercalation

The intercalation of magnetic elements in nonmagnetic van der Waals (vdW) materials is an effective way to design different (quasi) 2D magnets and produce exotic properties. More specifically, how exactly the intercalator is distributed within the synthetic crystal can also affect the physical properties substantially. In contrast to conventional $3d$ transition-metal intercalates of niobium and tantalum dichalcogenides, which commonly have $2\ifmmode\times\else\texttimes\fi{}2$ or $\sqrt{3}\ifmmode\times\else\texttimes\fi{}\sqrt{3}$ type ordered intercalation, we report a disordered intercalation of Co atoms between the vdW gaps of $2H$-tantalum disulfide ($2H\text{-Ta}{\mathrm{S}}_{2}$). The obtained quasi-vdW ferromagnet ${\mathrm{Co}}_{0.27}\mathrm{Ta}{\mathrm{S}}_{2}$ shows both perpendicular magnetic anisotropy and thickness-tunable magnetic properties. More interestingly, the temperature dependence of electrical resistivity shows a semiconductorlike behavior, in contrast to the metallic feature of other analogs in this material family. This unexpected phenomenon can be understood through a variable-range hopping mechanism, which is due to highly disordered intercalation. Moreover, ${\mathrm{Co}}_{0.27}\mathrm{Ta}{\mathrm{S}}_{2}$ shows a side-jump scattering dominated anomalous Hall effect, which can also be related to the disordered distribution of Co intercalators.

Nucleation Stage for the Oriented Growth of Tantalum Sulfide Monolayers on Au(111)

Nucleation Stage for the Oriented Growth of Tantalum Sulfide Monolayers on Au(111)

Superstructures, Commensurations, and Rotation of Single-Layer TaS2 on Au(111) Induced by Cs Intercalation/Deintercalation

We use in situ synchrotron grazing incidence X-ray diffraction and X-ray reflectivity to investigate with high resolution the structure of a two-dimensional single layer of tantalum sulfide grown on a Au(111) surface and its evolution during intercalation by Cs atoms and deintercalation, which decouples and recouples the two materials, respectively. The grown single layer consists of a mixture of TaS2 and its S-depleted version, TaS, both aligned with gold, and forming moirés where 7 (respectively 13) lattice constants of the 2D layer almost perfectly match 8 (respectively 15) substrate lattice constants. Intercalation fully decouples the system by lifting the single layer by ∼370 pm and induces an increase of its lattice parameter by 1-2 picometers. The system gradually evolves, during cycles of intercalation/deintercalation assisted by an H2S atmosphere, toward a final coupled state consisting of the fully stoichiometric TaS2 dichalcogenide whose moiré is found very close to the 7/8 commensurability. The reactive H2S atmosphere appears necessary to achieve full deintercalation, presumably by preventing S depletion and the concomitant strong bonding with the intercalant. The structural quality of the layer improves during the cyclic treatment. In parallel, because they are decoupled from the substrate by the intercalation of cesium, some of the TaS2 flakes rotate by 30°. These produce two additional superlattices with characteristic diffraction patterns of different origins. The first is aligned with gold's high symmetry crystallographic directions and is a commensurate moiré ((6 × 6)-Au(111) coinciding with (3√3 × 3√3)R30°-TaS2). The second is incommensurate and corresponds to a near coincidence of (6 × 6) unit cells of 30°-rotated TaS2 with (4√3 × 4√3)Au(111) surface ones. This structure, which is less coupled to gold, might be related to the ∼(3× 3) charge density wave previously reported even at room temperature in TaS2 grown on noninteracting substrates. A (3 × 3) superstructure of 30°-rotated TaS2 islands is indeed revealed by complementary scanning tunneling microscopy.

Molecular interactions induced collapse of charge density wave quantum states in 2H tantalum disulfide nanosheets

Molecular interactions induced collapse of charge density wave quantum states in 2H tantalum disulfide nanosheets

Self-Assembled TaOX/2H-TaS2 as a van der Waals Platform of a Multilevel Memristor Circuit Integrated with a β-Ga2O3 Transistor.

Two-dimensional (2D)-layered material tantalum disulfide (2H-TaS2) is known to be a van der Waals conductor at room temperature. Here, 2D-layered TaS2 has been partially oxidized by utraviolet-ozone (UV-O3) annealing to form a 12-nm-thin TaOX on conducting TaS2, so that the TaOX/2H-TaS2 structure might be self-assembled. Utilizing the TaOX/2H-TaS2 structure as a platform, each device of a β-Ga2O3 channel MOSFET and a TaOX memristor has been successfully fabricated. An insulator structure of Pt/TaOX/2H-TaS2 shows good a dielectric constant (k ∼ 21) and strength (∼3 MV/cm) of achieved TaOX, which is enough to support a β-Ga2O3 transistor channel. Based on the quality of TaOX and low trap density of the TaOX/β-Ga2O3 interface, which is achieved via another UV-O3 annealing, excellent device properties such as little hysteresis (<∼0.04 V), band-like transport, and a steep subthreshold swing of ∼85 mV/dec are achieved. With a Cu electrode on top of the TaOX/2H-TaS2 structure, the TaOX acts as a memristor operating around ∼2 V for nonvolatile bipolar and unipolar mode memories. The functionalities of the TaOX/2H-TaS2 platform become more distinguished finally when the Cu/TaOX/2H-TaS2 memristor and β-Ga2O3 MOSFET are integrated to form a resistive memory switching circuit. The circuit nicely demonstrates the multilevel memory functions.

Phase engineering in tantalum sulfide monolayers on Au(111)

We prepare monolayers of tantalum sulfide on Au(111) by evaporation of Ta in a reactive background of H2S. Under sulfur-rich conditions, monolayers of 2H-TaS2 develop, whereas under sulfur-poor conditions TaS forms, a structure that can be derived from 2H-TaS2 by removal of the bottom S layer. We analyze the alignment of the layers with respect to the substrate and the relation with the domains in the Au(111) herringbone reconstruction using scanning tunneling microscopy. With the help of density functional theory calculations we can determine the registry of the two phases with the substrate. We develop a growth process that allows preparation of uniquely oriented 2H-TaS2 on Au(111). 2H-TaS2 and TaS have a remarkably similar in-plane lattice structure and we observe the formation of lateral 2H-TaS2-TaS heterostructures with atomically well-defined and defect-free boundaries. We observe mirror twin boundaries within 2H-TaS2 along the S- and Ta-edge.