Tantalum(IV) sulfide

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Tantalum(IV) sulfide
Molybdenite-3D-balls.png
Crystal structure showing two stacked S-Ta-S sheets
Names
Other names
tantalum disulfide
Identifiers
3D model (JSmol)
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PubChem CID
  • InChI=1S/2S.Ta
  • S=[Ta]=S
Properties
TaS2
Molar mass 245.078 g/mol [1]
Appearancegolden or black crystals, depending on polytype [1]
Density 6.86 g/cm3 [1]
Melting point >3000 °C [1]
Insoluble [1]
Related compounds
Other anions
Tantalum telluride
Tantalum diselenide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Tantalum(IV) sulfide is an inorganic compound with the formula Ta S2. It is a layered compound with three-coordinate sulfide centres and trigonal prismatic or octahedral metal centres. [2] It is structurally similar to molybdenum disulfide MoS2, and numerous other transition metal dichalcogenides. Tantalum disulfide has three polymorphs 1T-TaS2, 2H-TaS2, and 3R-TaS2, representing trigonal, hexagonal, and rhombohedral respectively.

Contents

The properties of the 1T-TaS2 polytype have been described. [3] [4] [5]

CDW, the periodic distortion induced by the electron-phonon interaction, [6] is manifested by formation of a superlattice constituted by clusters of 13 atoms, which is called the Star of David (SOD), where the surrounding 12 Ta atoms move slightly towards the centre of the star. [7] there are three 1T-TaS2 charge density wave phases: commensurate charge density wave (CCDW), nearly commensurate charge density wave (NCCDW), and incommensurate charge density wave (ICCDW). In the CCDW phase, the entire material is covered with the superlattice, but in the ICCDW phase, the atoms do not move. NCCDW is the phase between the two as the SOD clusters are confined within the nearly hexagonal-shaped areas. The phase transition of 1T-TaS2 could be achieved via temperature difference, as it is one of the most investigated methods to achieve phase transition of the material. In common with many other transition metal dichalcogenide (TMD) compounds, which are metallic at high temperatures, it exhibits a series of charge-density-wave (CDW) phase transitions from 550 K to 50 K. It is unusual amongst them in showing a low-temperature insulating state below 200 K, which is believed to arise from electron correlations, similar to many oxides. The insulating state is commonly attributed to a Mott state. [8] When cooling down to 550K, 1T-TaS2 transitions from metallic to ICCDW, then the material achieves NCCDW when cooling below 350K, and finally entering CCDW below 180K. However, if the temperature change is achieved by raising the temperature, another phase could appear between the CCDW phase and the NCCDW phase. The Triclinic Charge Density Wave (TCDW) is again the hybrid state between CCDW and ICCDW, the difference is that instead of forming an enclosed hexagon area, the material forms strips with different atom shifts. When 1T-TaS2 is heated at a lower temperature, the first transition is from CCDW to TCDW at 220K; Then, continue heating the material above 280K the phase of the material transits to NCCDW. [9] [10] It is also superconducting under pressure or upon doping, with a familiar dome-like phase diagram as a function of dopant, or substituted isovalent element concentration.

Metastability. 1T-TaS2 is unique, not only amongst TMDs but also amongst 'quantum materials' in general, in showing a metastable metallic state at low temperatures. [11] Switching from the insulating to the metallic state can be achieved either optically or by the application of electrical pulses. The metallic state is persistentbelow ~20K, but its lifetime can be tuned by changing the temperature. The metastable state lifetime can also be tuned by strain. The electrically-induced switching between states is of current interest, because it can be used for ultrafast energy-efficient memory devices. [12]

Because of the frustrated triangular arrangement of localized electrons, the material is suspected of supporting some form of quantum spin liquid state. It has been the subject of numerous studies as a host for intercalation of electron donors. [13]

Preparation

TaS2 is prepared by reaction of powdered tantalum and sulfur at ~900 °C. [15] It is purified and crystallized by chemical vapor transport using iodine as the transporting agent: [16]

TaS2 + 2 I2⇌ TaI4 + 2 S

It can be easily cleaved and has a characteristic golden sheen. Upon extended exposure to air, the formation of an oxide layer causes darkening of the surface. Thin films can be prepared by chemical vapour deposition and molecular beam epitaxy.

Properties

Three major crystalline phases are known for TaS2: trigonal 1T with one S-Ta-S sheet per unit cell, hexagonal 2H with two S-Ta-S sheets, and rhombohedral 3R with three S-Ta-S sheets per cell; 4H and 6R phases are also observed, but less frequently. These polymorphs mostly differ by the relative arrangement of the S-Ta-S sheet rather than the sheet structure. [17]

2H-TaS2 is a superconductor with the bulk transition temperature TC = 0.5 K, which increases to 2.2 K in flakes with a thickness of a few atomic layers. [15] The bulk TC value increases up to ~8 K at 10 GPa and then saturates with increasing pressure. [18] In contrast, 1T-TaS2 starts superconducting only at ~2 GPa; as a function of pressure its TC quickly rises up to 5 K at ~4 GPa and then saturates. [8]

At ambient pressure and low temperatures 1T-TaS2 is a Mott insulator. [8] Upon heating it changes to a Triclinic charge density wave (TCDW) state at TTCDW ~ 220 K, [19] [20] [21] to a nearly commensurate charge density wave (NCCDW) state at TNCCDW ~ 280 K, [2] to an incommensurate CDW (ICCDW) state at TICCDW ~ 350 K, [2] and to a metallic state at TM ~ 600 K. [14]

In the CDW state the TaS2 lattice deforms to create a periodic Star of David pattern. Application of (e.g. 50fs) optical laser pulses [11] or voltage pulses (~2–3 V) through electrodes [22] or in a scanning tunneling microscope (STM) to the CDW state causes it to drop electrical resistance and creates a "mosaic" or domain state consisting of nanometer-sized domains, where both the domains and their walls exhibit metallic conductivity. This mosaic structure is metastable and gradually disappears upon heating. [16] [23] [22]

Memory devices and other potential applications

Switching of the material to and from the "mosaic", or domain state, by optical or electrical pulses is used for "Charge configuration memory" (CCM) devices. The distinguishing feature of such devices is that they exhibit very efficient and fast non-thermal resistance switching at low temperatures. [12] Room temperature operation of a charge-density-wave oscillator and thermally-driven GHz modulation of the CDW state has been demonstrated. [24] [25]

Related Research Articles

<span class="mw-page-title-main">Tantalum</span> Chemical element, symbol Ta and atomic number 73

Tantalum is a chemical element; it has symbol Ta and atomic number 73. Previously known as tantalium, it is named after Tantalus, a figure in Greek mythology. Tantalum is a very hard, ductile, lustrous, blue-gray transition metal that is highly corrosion-resistant. It is part of the refractory metals group, which are widely used as components of strong high-melting-point alloys. It is a group 5 element, along with vanadium and niobium, and it always occurs in geologic sources together with the chemically similar niobium, mainly in the mineral groups tantalite, columbite and coltan.

<span class="mw-page-title-main">Molybdenum disulfide</span> Chemical compound

Molybdenum disulfide is an inorganic compound composed of molybdenum and sulfur. Its chemical formula is MoS
2.

<span class="mw-page-title-main">Tantalum carbide</span> Chemical compound

Tantalum carbides (TaC) form a family of binary chemical compounds of tantalum and carbon with the empirical formula TaCx, where x usually varies between 0.4 and 1. They are extremely hard, brittle, refractory ceramic materials with metallic electrical conductivity. They appear as brown-gray powders, which are usually processed by sintering.

<span class="mw-page-title-main">Richard Friend</span> British physicist

Sir Richard Henry Friend is a British physicist who was the Cavendish Professor of Physics at the University of Cambridge from 1995 until 2020 and is Tan Chin Tuan Centennial Professor at the National University of Singapore. Friend's research concerns the physics and engineering of carbon-based semiconductors. He also serves as Chairman of the Scientific Advisory Board of the National Research Foundation (NRF) of Singapore.

<span class="mw-page-title-main">Chalcogenide</span>

A chalcogenide is a chemical compound consisting of at least one chalcogen anion and at least one more electropositive element. Although all group 16 elements of the periodic table are defined as chalcogens, the term chalcogenide is more commonly reserved for sulfides, selenides, tellurides, and polonides, rather than oxides. Many metal ores exist as chalcogenides. Photoconductive chalcogenide glasses are used in xerography. Some pigments and catalysts are also based on chalcogenides. The metal dichalcogenide MoS2 is a common solid lubricant.

<span class="mw-page-title-main">Spin density wave</span>

Spin-density wave (SDW) and charge-density wave (CDW) are names for two similar low-energy ordered states of solids. Both these states occur at low temperature in anisotropic, low-dimensional materials or in metals that have high densities of states at the Fermi level . Other low-temperature ground states that occur in such materials are superconductivity, ferromagnetism and antiferromagnetism. The transition to the ordered states is driven by the condensation energy which is approximately where is the magnitude of the energy gap opened by the transition.

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1T may refer to:

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<span class="mw-page-title-main">Titanium disulfide</span> Inorganic chemical compound

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<span class="mw-page-title-main">Niobium triselenide</span> Chemical compound

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<span class="mw-page-title-main">Molybdenum diselenide</span> Chemical compound

Molybdenum diselenide is an inorganic compound of molybdenum and selenium. Its structure is similar to that of MoS
2. Compounds of this category are known as transition metal dichalcogenides, abbreviated TMDCs. These compounds, as the name suggests, are made up of a transition metals and elements of group 16 on the periodic table of the elements. Compared to MoS
2, MoSe
2 exhibits higher electrical conductivity.

<span class="mw-page-title-main">Tungsten diselenide</span> Chemical compound

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<span class="mw-page-title-main">Transition metal dichalcogenide monolayers</span> Thin semiconductors

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<span class="mw-page-title-main">Niobium diselenide</span> Chemical compound

Niobium diselenide or niobium(IV) selenide is a layered transition metal dichalcogenide with formula NbSe2. Niobium diselenide is a lubricant, and a superconductor at temperatures below 7.2 K that exhibit a charge density wave (CDW). NbSe2 crystallizes in several related forms, and can be mechanically exfoliated into monatomic layers, similar to other transition metal dichalcogenide monolayers. Monolayer NbSe2 exhibits very different properties from the bulk material, such as of Ising superconductivity, quantum metallic state, and strong enhancement of the CDW.

<span class="mw-page-title-main">Tantalum diselenide</span> Chemical compound

Tantalum diselenide is a compound made with tantalum and selenium atoms, with chemical formula TaSe2, which belongs to the family of transition metal dichalcogenides. In contrast to molybdenum disulfide (MoS2) or rhenium disulfide (ReS2), tantalum diselenide does not occur spontaneously in nature, but it can be synthesized. Depending on the growth parameters, different types of crystal structures can be stabilized.

References


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