Bulk 1T Research Articles

Topology Hierarchy of Transition Metal Dichalcogenides Built from Quantum Spin Hall Layers.

The evolution of the physical properties of two-dimensional material from monolayer limit to the bulk reveals unique consequences from dimension confinement and provides a distinct tuning knob for applications. Monolayer 1T'-phase transition metal dichalcogenides (1T'-TMDs) with ubiquitous quantum spin Hall (QSH) states are ideal two-dimensional building blocks of various three-dimensional topological phases. However, the stacking geometry was previously limited to the bulk 1T'-WTe2 type. Here, we introduce the novel 2M-TMDs consisting of translationally stacked 1T'-monolayers as promising material platforms with tunable inverted bandgaps and interlayer coupling. By performing advanced polarization-dependent angle-resolved photoemission spectroscopy as well as first-principles calculations on the electronic structure of 2M-TMDs, we revealed a topology hierarchy: 2M-WSe2 , MoS2, and MoSe2 are weak topological insulators (WTIs), whereas 2M-WS2 is a strong topological insulator (STI). Further demonstration of topological phase transitions by tunning interlayer distance indicates that band inversion amplitude and interlayer coupling jointly determine different topological states in 2M-TMDs. We propose that 2M-TMDs are parent compounds of various exotic phases including topological superconductors and promise great application potentials in quantum electronics due to their flexibility in patterning with two-dimensional materials. This article is protected by copyright. All rights reserved.

Structural Phase Transition and Interlayer Coupling in Few-Layer 1T' and Td MoTe2.

We performed polarized Raman spectroscopy on mechanically exfoliated few-layer MoTe2 samples and observed both 1T' and Td phases at room temperature. Few-layer 1T' and Td MoTe2 exhibited a significant difference especially in interlayer vibration modes, from which the interlayer coupling strengths were extracted using the linear chain model: strong in-plane anisotropy was observed in both phases. Furthermore, temperature-dependent Raman measurements revealed a peculiar phase transition behavior in few-layer 1T' MoTe2. In contrast to bulk 1T' MoTe2 crystals, where the phase transition to the Td phase occurs at ∼250 K, the temperature-driven phase transition to the Td phase is increasingly suppressed as the thickness is reduced, and the transition and the critical temperature varied dramatically from sample to sample even for the same thickness. Raman spectra of intermediate phases that correspond to neither 1T' nor Td phase with different interlayer vibration modes were observed, which suggests that several metastable phases exist with similar total energies.

Selective phase growth and precise-layer control in MoTe2

Minor structural changes in transition metal dichalcogenides can have dramatic effects on their electronic properties. This makes the quest for key parameters that enable a selective choice between the competing metallic and semiconducting phases in the 2D MoTe2 system compelling. Herein, we report the optimal conditions at which the choice of the initial seed layer dictates the type of crystal structure of atomically-thin MoTe2 films grown by chemical vapour deposition (CVD). When Mo metal is used as a seed layer, semiconducting 2H-MoTe2 is the only product. Conversely, MoO3 leads to the preferential growth of metallic 1T′-MoTe2. The control over phase growth allows for simultaneous deposition of both 2H-MoTe2 and 1T′-MoTe2 phases on a single substrate during one CVD reaction. Furthermore, Rhodamine 6G dye can be detected using few-layered 1T′-MoTe2 films down to 5 nM concentration, demonstrating surface enhanced Raman spectroscopy (SERS) with sensitivity several orders of magnitude higher than for bulk 1T′-MoTe2.

Thickness dependent electronic properties of Pt dichalcogenides

Platinum-based transition metal dichalcogenides have been gaining renewed interest because of the development of a new method to synthesize thin film structures. Here, using first-principles calculation, we explore the electronic properties of PtX2 (X = S, Se, and Te) with respect to film thickness. For bulk and layered structures (1 to 10 layers), octahedral 1T is the most stable. Surprisingly, we also find that the 3R structure has comparable stability relative to the 1T, implying possible synthesis of 3R. For a bulk 1T structure, PtS2 is semiconducting with an indirect band gap of 0.25 eV, while PtSe2 and PtTe2 are both semi-metallic. Still, all their corresponding monolayers exhibit an indirect semiconducting phase with band gaps of 1.68, 1.18, and 0.40 eV for PtS2, PtSe2, and PtTe2, respectively. For the band properties, we observe that all these materials manifest decreasing/closing of indirect band gap with increasing thickness, a consequence of quantum confinement and interlayer interaction. Moreover, we discover that controlling the thickness and applying strain can manipulate van Hove singularity resulting to high density of states at the maximum valence band. Our results exhibit the sensitivity and tunability of electronic properties of PtX2, paving a new path for future potential applications.

Structural Determination and Nonlinear Optical Properties of New 1T‴-Type MoS2 Compound.

Noncentrosymmetric MoS2 semiconductors (1H, 3R) possess not only novel electronic structures of spin-orbit coupling (SOC) and valley polarization but also remarkable nonlinear optical effects. A more interesting noncentrosymmetric structure, the so-called 1T‴-MoS2 layers, was predicted to be built up from [MoS6] octahedral motifs by theoreticians, but the bulk 1T‴ MoS2 or its single crystal structure has not been reported yet. Here, we have successfully harvested 1T‴ MoS2 single crystals by a topochemical method. The new layered structure is determined from single-crystal X-ray diffraction. The crystal crystallizes in space group P31m with a cell of a = b = 5.580(2) Å and c = 5.957(2) Å, which is a √3 a × √3 a superstructure of 1T MoS2 with corner-sharing Mo3 triangular trimers observed by the STEM. 1T‴ MoS2 is verified to be semiconducting and possesses a band gap of 0.65 eV, different from metallic nature of 1T or 1T' MoS2. More surprisingly, the 1T‴ MoS2 does show strong optical second-harmonic generation signals. This work provides the first layered noncentrosymmetric semiconductor of edge-sharing MoS6 octahedra for the research of nonlinear optics.

Structure Re‐determination and Superconductivity Observation of Bulk 1T MoS2

Abstract2H MoS2 has been intensively studied because of its layer‐dependent electronic structures and novel physical properties. Though the metastable 1T MoS2 with a [MoS6] octahedron was observed over the microscopic area, the true crystal structure of 1T phase has not been strictly determined. Moreover, the true physical properties have not been demonstrated from experiments owing to the challenge for the preparation of pure 1T MoS2 crystals. 1T MoS2 single crystals were successfully synthesized and the crystal structure of 1T MoS2 re‐determined from single‐crystal X‐ray diffraction. 1T MoS2 crystallizes in the space group P m1 with a cell of a=b=3.190(3) Å and c=5.945(6) Å. The individual MoS2 layer consists of MoS6 octahedra sharing edges with each other. More surprisingly, the bulk 1T MoS2 crystals undergo a superconducting transition of Tc=4 K, which is the first observation of superconductivity in pure 1T MoS2 phase.

Structure Re-determination and Superconductivity Observation of Bulk 1T MoS2.

2H MoS2 has been intensively studied because of its layer-dependent electronic structures and novel physical properties. Though the metastable 1T MoS2 with a [MoS6 ] octahedron was observed over the microscopic area, the true crystal structure of 1T phase has not been strictly determined. Moreover, the true physical properties have not been demonstrated from experiments owing to the challenge for the preparation of pure 1T MoS2 crystals. 1T MoS2 single crystals were successfully synthesized and the crystal structure of 1T MoS2 re-determined from single-crystal X-ray diffraction. 1T MoS2 crystallizes in the space group P3‾ m1 with a cell of a=b=3.190(3) Å and c=5.945(6) Å. The individual MoS2 layer consists of MoS6 octahedra sharing edges with each other. More surprisingly, the bulk 1T MoS2 crystals undergo a superconducting transition of Tc =4 K, which is the first observation of superconductivity in pure 1T MoS2 phase.

Characterization of Few-Layer 1T' MoTe2 by Polarization-Resolved Second Harmonic Generation and Raman Scattering.

We study the crystal symmetry of few-layer 1T' MoTe2 using the polarization dependence of the second harmonic generation (SHG) and Raman scattering. Bulk 1T' MoTe2 is known to be inversion symmetric; however, we find that the inversion symmetry is broken for finite crystals with even numbers of layers, resulting in strong SHG comparable to other transition-metal dichalcogenides. Group theory analysis of the polarization dependence of the Raman signals allows for the definitive assignment of all the Raman modes in 1T' MoTe2 and clears up a discrepancy in the literature. The Raman results were also compared with density functional theory simulations and are in excellent agreement with the layer-dependent variations of the Raman modes. The experimental measurements also determine the relationship between the crystal axes and the polarization dependence of the SHG and Raman scattering, which now allows the anisotropy of polarized SHG or Raman signal to independently determine the crystal orientation.

Bandgap opening in few-layered monoclinic MoTe2

Layered transition metal dichalcogenides (TMDs) have attracted renewed interest owing to their potential use as two-dimensional components in next-generation devices1,2. Although group 6 TMDs, such as MX2 with M = (Mo, W) and X = (S, Se, Te), can exist in several polymorphs3, most studies have been conducted with the semiconducting hexagonal (2H) phase as other polymorphs often exhibit inhomogeneous formation1,4,5,6. Here, we report a reversible structural phase transition between the hexagonal and stable monoclinic (distorted octahedral or 1T′) phases in bulk single-crystalline MoTe2. Furthermore, an electronic phase transition from semimetallic to semiconducting is shown as 1T′-MoTe2 crystals go from bulk to few-layered. Bulk 1T′-MoTe2 crystals exhibit a maximum carrier mobility of 4,000 cm2 V−1 s−1 and a giant magnetoresistance of 16,000% in a magnetic field of 14 T at 1.8 K. In the few-layered form, 1T′-MoTe2 exhibits a bandgap opening of up to 60 meV, which our density functional theory calculations identify as arising from strong interband spin–orbit coupling. We further clarify that the Peierls distortion is a key mechanism to stabilize the monoclinic structure. This class of semiconducting MoTe2 unlocks the possibility of topological quantum devices based on non-trivial Z2-band-topology quantum spin Hall insulators in monoclinic TMDs (ref. 7).

Metal-Insulator Transition in 1T-TaS2: A Real-Space Dynamical Mean-Field Study

Much dispute remains as concerns the origin of the metal-insulator transition in layered compounds 1T -TaS2. Considering the disordered stacking of the atomic layers along the c-axis, we map the low-temperature phase of the transition metal dichalcogenide into a one-dimensional correlated system with the presence of disordered hopping integrals. To illustrate how the electronic correlations compete with the off-diagonal disorder, we employ the real-space dynamical mean-field theory to treat interactions and disorder on equal footing. We find that the Mott gap survives the strong off-diagonal disorder, which rules out the possibility of a metallic phase introduced by the disordered hoping integrals. Moreover, the lattice-size scaling of the generalized inverse participation ratio demonstrates that all electronic states are Anderson localized when the effect of disorder is being considered, and thus the optical conductivity shows insulating behavior for the bulk 1T -TaS2 compounds.