Tin Dichalcogenides Research Articles

Rashba spin-splitting in Janus SnXY/WXY (X, Y = S, Se, Te; X ≠ Y) heterostructures.

Janus transition metal dichalcogenide monolayers have shown a lack of mirror symmetry perpendicular to the 2D plane. The breaking of out-of-plane symmetry, along with the spin-orbit coupling, induces Rashba spin-splitting in these materials. In this work, Rashba spin splitting in Janus tin dichalcogenide monolayers are studied. In addition, the heterostructures of Janus SnXY and WXY (X, Y = S, Se, Te; X 6 = Y) monolayers are discussed. A Rashba spin-splitting energy of about 43 meV, more significant than the room temperature energy, is observed in the Janus SnSSe/WSSe heterostructure. The consequences of vertical strain on the semiconducting heterostructure are examined. Compressive vertical strain enhances the Rashba splitting, and tensile strain reduces the spin-splitting. For the compressive strain of 10.4%, Janus SnSSe/WSSe heterostructure remains semiconductor with only Rashba bands surrounding near the Fermi level. Enhanced Rashba parameter of about 0.96 eVÅ and splitting energy of about 72 meV are observed. These findings confirm that Janus SnSSe/WSSe heterostructure is a productive Rashba material for spintronic device applications.

The pressure response of SnSxSe2-x tin dichalcogenide alloys studied by Raman spectroscopy

High-pressure Raman spectroscopic experiments were conducted in a diamond anvil cell to investigate the pressure response of the phonon modes of SnSxSe2-x (x = 0.6, 0.8, 1) tin dichalcogenide alloys up to 8 GPa. Owing to the two-mode behavior of the Eg and A1g modes in these ternary alloys, up to four Raman bands are observed at ambient conditions and the frequency evolution of three of them {Eg(SnSe2-like), A1g(SnSe2-like) and A1g(SnS2-like)} is followed with pressure. With increasing pressure, all the Raman bands shift quasi-linearly and reversibly to higher frequencies, reflecting the bond stiffening due to the volume reduction and the absence of any phase transition. Despite the stronger intralayer covalent bonding compared to the much weaker interlayer van der Waals interactions along the c-axis, the in-plane Eg(SnSe2-like) mode has larger pressure coefficient than those of the two stronger in intensity A1g modes along the c-axis. The pressure coefficient of the A1g(SnS2-like) mode gradually increases from 3.60 to 3.93 cm−1GPa−1 with increasing sulfur content (x). On the other hand, the pressure coefficient of the A1g(SnSe2-like) mode decreases from 3.08 to 2.72 cm−1GPa−1 with increasing x. The extracted Grüneisen parameters of all the A1g Raman peaks indicate the stronger Sn–S interaction along the c-axis compared to that of Sn–Se.

Recent advances of substitutionally doped tin dichalcogenides

Substitutionally doped tin dichalcogenides have potential for electric, photoelectric and thermoelectric applications.

Atmospheric pressure chemical vapor deposition growth of vertically aligned SnS2 and SnSe2 nanosheets.

Laminated metal dichalcogenides are candidates for different potential applications ranging from catalysis to nanoelectronics. However, efforts are still needed to optimize synthesis methods aiming to control the number of layers, morphology, and crystallinity, parameters that govern the properties of the synthesized materials. Another important parameter is the thickness and the length of the samples with the possibility of large-scale growth of target homogeneous materials. Here, we report a chemical vapor deposition method at atmospheric pressure to produce vertically aligned tin dichalcogenide based-materials. Tin disulfide (SnS2) and tin diselenide (SnSe2) vertically aligned nanosheets have been synthesized and characterized by different methods showing their crystallinity and purity. Homogenous crystalline 2H-phase SnS2 nanosheets with high purity were synthesized with vertical orientation on substrates; sulfur vacancies were observed at the edges of the sheets. Similarly, in the crystalline 2H phase SnSe2 nanosheets selenium vacancies were observed at the edges. Moreover, these nanosheets are larger than the SnS2 nanosheets, show lower nanosheet homogeneity on substrates and contamination with selenium atoms from the synthesis was observed. The synthesized nanomaterials are interesting in various applications where the edge accessibility and/or directionality of the nanosheets play a major role as for example in gas sensing or field emission.

Facile and Reliable Thickness Identification of Atomically Thin Dichalcogenide Semiconductors Using Hyperspectral Microscopy.

Although large-scale synthesis of layered two-dimensional (2D) transition metal dichalcogenides (TMDCs) has been made possible, mechanical exfoliation of layered van der Waals crystal is still indispensable as every new material research starts with exfoliated flakes. However, it is often a tedious task to find the flakes with desired thickness and sizes. We propose a method to determine the thickness of few-layer flakes and facilitate the fast searching of flakes with a specific thickness. By using hyperspectral wild field microscopy to acquire differential reflectance and transmittance spectra, we demonstrate unambiguous recognition of typical TMDCs and their thicknesses based on their excitonic resonance features in a single step. Distinct from Raman spectroscopy or atomic force microscopy, our method is non-destructive to the sample. By knowing the contrast between different layers, we developed an algorithm to automatically search for flakes of desired thickness in situ. We extended this method to measure tin dichalcogenides, such as SnS2 and SnSe2, which are indirect bandgap semiconductors regardless of the thickness. We observed distinct spectroscopic behaviors as compared with typical TMDCs. Layer-dependent excitonic features were manifested. Our method is ideal for automatic non-destructive optical inspection in mass production in the semiconductor industry.

Strain tunable structural, mechanical and electronic properties of monolayer tin dioxides and dichalcogenides SnX2 (X[dbnd]O, S, Se, Te)

Based on first-principles calculations, we investigate the structural, mechanical and electronic properties of monolayer tin dioxides and dichalcogenides SnX2 (XO, S, Se, Te) under uniaxial and biaxial strains. Our results show that monolayer 1T-SnX2 is energetically more stable than 2H-SnX2, while the stiffness of 2H-SnX2 is much higher. The unstrained SnX2 is thermodynamically and dynamically more stable than the strained ones. We also show that when external strain is applied, the band gaps of both 2H- and 1T-SnO2 decrease linearly with increasing strain, which is contributed by the strain induced orbital redistribution of the decomposition of the p orbital of X atom and s, p orbitals of Sn atom. Notably, the slope of the band gap variation of the biaxial strained 1T-SnO2 reaches up to -0.16 eV/1%. In our calculations, strain can result in a semiconductor–metal transition of 2H-SnX2, while it only affects the band gap of 1T-SnX2.

Strain-induced electronic properties of van der Waals heterostructures based on tin dichalcogenides

As a newly emerged form of two-dimensional material, tin dichalcogenides have attracted considerable interest, and building van der Waals (vdW) heterostructures based on them could open up new applications. Here, six vdW heterostructures based on SnS2 and SnSe2 are investigated via first-principle calculations. Except for graphene/SnS2(SnSe2), which behaves as a metal, the other heterostructures including HfS2/SnS2(SnSe2) and ZrS2/SnS2(SnSe2) all behave as a semiconductor. Furthermore, particular attention is paid to the tunable electronic properties of the semiconductor heterolayers under differing in-plane biaxial strain. It is found that both tensile and compressive strain can effectively modulate the band structures and carrier effective mass. The strain changes the band gaps of the semiconductor heterostructures considerably, ultimately causing either a semiconductor-to-metal transition or a variation in the band edge. Analyzing the projected density of states and charge density difference shows that these changes are due mainly to the shifts in energy states and interlayer charge transfer of the vdW heterostructures. The present study suggests that vdW heterostructures based on tin dichalcogenides are viable candidates for nanoscale electronic and optoelectronic applications.

Stabilities, and electronic and piezoelectric properties of two-dimensional tin dichalcogenide derived Janus monolayers

First-principles calculations were performed to investigate the stabilities, and electronic and piezoelectric properties of Janus SnXY monolayers (X = O, S, Se, Te; Y = O, S, Se, Te; X ≠ Y).

Locally Gated SnS2/hBN Thin Film Transistors with a Broadband Photoresponse

Next-generation flexible and transparent electronics demand newer materials with superior characteristics. Tin dichalcogenides, Sn(S,Se)2, are layered crystal materials that show promise for implementation in flexible electronics and optoelectronics. They have band gap energies that are dependent on their atomic layer number and selenium content. A variety of studies has focused in particular on tin disulfide (SnS2) channel transistors with conventional silicon substrates. However, the effort of interchanging the gate dielectric by utilizing high-quality hexagonal boron nitride (hBN) still remains. In this work, the hBN coupled SnS2 thin film transistors are demonstrated with bottom-gated device configuration. The electrical transport characteristics of the SnS2 channel transistor present a high current on/off ratio, reaching as high as 105 and a ten-fold enhancement in subthreshold swing compared to a high-κ dielectric covered device. We also demonstrate the spectral photoresponsivity from ultraviolet to infrared in a multi-layered SnS2 phototransistor. The device architecture is suitable to promote diverse studied on flexible and transparent thin film transistors for further applications.

Trends on band alignments: Validity of Anderson's rule inSnS2- andSnSe2-based van der Waals heterostructures

Van der Waals (vdW) heterostructures are promising candidates for building blocks in novel electronic and optoelectronic devices with tailored properties, since their electronic action is dominated by the band alignments upon their contact. In this work, we analyze 10 vdW heterobilayers based on tin dichalcogenides by first-principles calculations. Structural studies show that all systems are stable, and that commensurability leads to smaller interlayer distances. Using hybrid functional calculations, we derive electronic properties and band alignments for all the heterosystems and isolated two-dimensional (2D) crystals. Natural band offsets are derived from calculated electron affinities and ionization energies of 11 freestanding 2D crystals. They are compared with band alignments in true heterojunctions, using a quantum mechanical criterion, and available experimental data. For the ${\mathrm{hBN}/\mathrm{SnSe}}_{2}$ system, we show that hBN suffers an increase in band gap, while leaving almost unchanged the electronic properties of ${\mathrm{SnSe}}_{2}$. Similarly, ${\mathrm{MX}}_{2}$ (M = Mo, W; X = S, Se) over ${\mathrm{SnX}}_{2}$ preserve the natural discontinuities from each side of the heterobilayer. Significant charge transfer occurs in junctions with graphene, which becomes p-doped and forms an Ohmic contact with ${\mathrm{SnX}}_{2}$. Zirconium and hafnium dichalcogenides display stronger interlayer interactions, leading to larger shifts in band alignments with tin dichalcogenides. Significant orbital overlap is found, which creates zero conduction band offset systems. The validity of the Anderson electron affinity rule is discussed. Failures of this model are traced back to interlayer interaction, band hybridization, and quantum dipoles. The systematic work sheds light on interfacial engineering for future vdW electronic and optoelectronic devices.

Tin(iv) chalcogenoether complexes as single source precursors for the chemical vapour deposition of SnE2 and SnE (E = S, Se) thin films.

The molecular Sn(iv) complexes, [SnCl4{nBuS(CH2)3SnBu}] (2), [SnCl4(nBu2S)2] (3) and [SnCl4(nBu2Se)2] (4) have been prepared in good yield from reaction of SnCl4 with the appropriate chalcogenoether ligand in anhydrous hexane and, together with the known [SnCl4{nBuSe(CH2)3SenBu}] (1), employed as single source precursors for the low pressure chemical vapour deposition of the corresponding tin dichalcogenide thin films. At elevated temperatures the bidentate ligand precursors, (1) and (2), also form the tin monochalcogenides, SnSe and SnS, respectively. In contrast, (3) gave a mixture of phases, SnS2, Sn2S3 and SnS and (4) gave SnSe2 only. The morphologies, elemental compositions and crystal structures of the resulting films have been determined by scanning electron microscopy, energy dispersive X-ray spectroscopy, grazing incidence X-ray diffraction and Raman spectroscopy. Van der Pauw measurements on the SnS2, SnS and SnSe2 films confirm their resistivities to be 2.9(9), 266(3) and 4.4(3) Ω cm, respectively.

Controllable colloidal synthesis of anisotropic tin dichalcogenide nanocrystals for thin film thermoelectrics.

Tin chalcogenides have shown promise in applications including energy storage, optoelectronics, photovoltaics, and thermoelectrics. Here, we present a colloidal synthesis strategy to produce tin dichalcogenide nanocrystals (NCs) with controllable stoichiometry, vacancies, shape, and crystal structure. Compared with previously reported methods, we use less expensive precursors, such as tin(iv) chloride and sulfur or selenium powder, to produce tin(iv) chalcogenide NCs. SnS2 and SnSe2 NCs with novel NC morphologies including SnS2 nanoflowers/nanoflakes, SnSe2 nanosheets with circular and hexagonal shapes, as well as mixtures of nanospheres and nanoflakes were prepared by varying the solvents and anion precursors. We were also able to reduce tin(iv) to tin(ii) to produce tin(ii) chalcogenide NCs. The corresponding thin films were prepared by spin-coating, followed by post-treatment to study their thermoelectric properties. Room temperature Seebeck coefficients of -150 μV K-1 and -126 μV K-1 were measured for SnS2 and SnSe2 films, demonstrating their promise as thin film thermoelectric materials.

New signature discovered characterizes structural defects in tin dichalcogenides

A cathodoluminescence spectroscopy technique provides a way for researchers to assess how tin disulfide crystals degrade over time, paving the way for broader use of tin dichalcogenides.

Luminescence of defects in the structural transformation of layered tin dichalcogenides

Layered tin sulfide semiconductors are both of fundamental interest and attractive for energy conversion applications. Sn sulfides crystallize in several stable bulk phases with different Sn:S ratios (SnS2, Sn2S3, and SnS), which can transform into phases with a lower sulfur concentration by introduction of sulfur vacancies (VS). How this complex behavior affects the optoelectronic properties remains largely unknown but is of key importance for understanding light-matter interactions in this family of layered materials. Here, we use the capability to induce VS and drive a transformation between few-layer SnS2 and SnS by electron beam irradiation, combined with in-situ cathodoluminescence spectroscopy and ab-initio calculations to probe the role of defects in the luminescence of these materials. In addition to the characteristic band-edge emission of the endpoint structures, our results show emerging luminescence features accompanying the SnS2 to SnS transformation. Comparison with calculations indicates that the most prominent emission in SnS2 with sulfur vacancies is not due to luminescence from a defect level but involves recombination of excitons bound to neutral VS in SnS2. These findings provide insight into the intrinsic and defect-related optoelectronic properties of Sn chalcogenide semiconductors.

Compelling experimental evidence of a Dirac cone in the electronic structure of a 2D Silicon layer

The remarkable properties of graphene stem from its two-dimensional (2D) structure, with a linear dispersion of the electronic states at the corners of the Brillouin zone (BZ) forming a Dirac cone. Since then, other 2D materials have been suggested based on boron, silicon, germanium, phosphorus, tin, and metal di-chalcogenides. Here, we present an experimental investigation of a single silicon layer on Au(111) using low energy electron diffraction (LEED), high resolution angle-resolved photoemission spectroscopy (HR-ARPES), and scanning tunneling microscopy (STM). The HR-ARPES data show compelling evidence that the silicon based 2D overlayer is responsible for the observed linear dispersed feature in the valence band, with a Fermi velocity of comparable to that of graphene. The STM images show extended and homogeneous domains, offering a viable route to the fabrication of silicene-based opto-electronic devices.

Anisotropic phonon transport and lattice thermal conductivities in tin dichalcogenides SnS2 and SnSe2

In recent years, layered semiconductor tin dichalcogenides, SnX2 (X = S and Se), have received great attention owing to their wide applications in numerous fields.

Strain tunable magnetism in SnX2 (X = S, Se) monolayers by hole doping.

By first-principles calculations, the magnetism of hole doped tin dichalcogenides SnX2 (X = S, Se) monolayers is systematically studied. It is found that a phase transition from nonmagnetic to ferromagnetic ground state appears once above the critical hole density (~1014 cm−2). The spin magnetic moment can maintain a magnitude of 1.0 μB/hole with excellent stability of ferromagnetic state. Furthermore, we demonstrate that strain is very useful to modulate the DOS near the valence band, resulting in the reduction of the critical hole density to ~1013 cm−2 when the strain reaches 4% (6%) in SnS2 (SnSe2), which can be realized in common field effect transistors. Moreover, the phonon dispersion calculations for the strained SnX2 monolayers indicate that they can keep the dynamical stability under the hole doping. Therefore, the strain tunable magnetic transition in hole doped tin dichalcogenides indicates their potential promising applications in spintronic devices.

Electron-Beam Induced Transformations of Layered Tin Dichalcogenides

By combining high-resolution transmission electron microscopy and associated analytical methods with first-principles calculations, we study the behavior of layered tin dichalcogenides under electron beam irradiation. We demonstrate that the controllable removal of chalcogen atoms due to electron irradiation, at both room and elevated temperatures, gives rise to transformations in the atomic structure of Sn-S and Sn-Se systems so that new phases with different properties can be induced. In particular, rhombohedral layered SnS2 and SnSe2 can be transformed via electron beam induced loss of chalcogen atoms into highly anisotropic orthorhombic layered SnS and SnSe. A striking dependence of the layer orientation of the resulting SnS-parallel to the layers of ultrathin SnS2 starting material, but slanted for transformations of thicker few-layer SnS2-is rationalized by a transformation pathway in which vacancies group into ordered S-vacancy lines, which convert via a Sn2S3 intermediate to SnS. Absence of a stable Sn2Se3 intermediate precludes this pathway for the selenides, hence SnSe2 always transforms into basal plane oriented SnSe. Our results provide microscopic insights into the transformation mechanism and show how irradiation can be used to tune the properties of layered tin chalcogenides for applications in electronics, catalysis, or energy storage.

Tuning band gap and optical properties of SnX2 nanosheets: Hybrid functional studies

Based on hybrid functional calculations, the electronic structures and optical properties are investigated in the monolayer and bilayer tin dichalcogenides SnX2 (X = S and Se) nanosheets. Numerical results show that quantum size effects are obvious on the electronic structures and optical absorption in the SnS2 and SnSe2 nanosheets. The band gap values increase when the nanosheets layer numbers decrease. Moreover, for SnSe2 nanosheet, the optical absorption coefficients are high and its threshold values lie in the visible light activity range. These results are interesting and indicate that SnS2 and SnSe2 nanosheets may serve as the promising candidates for visible optical applications.

Ultra‐Thin Layered Ternary Single Crystals [Sn(SxSe1−x)2] with Bandgap Engineering for High Performance Phototransistors on Versatile Substrates

2D ternary semiconductor single crystals, an emerging class of new materials, have attracted significant interest recently owing to their great potential for academic interest and practical application. In addition to other types of metal dichalcogenides, 2D tin dichalcogenides are also important layered compounds with similar capabilities. Yet, multi‐elemental single crystals enable to assist multiple degrees of freedom for dominant physical properties via ratio alteration. This study reports the growth of single crystals Se‐doped SnS2 or SnSSe alloys, and demonstrates their capability for the fabrication of phototransistors with high performance. Based on exfoliation from bulk high quality single crystals, this study establishes the characteristics of few‐layered SnSSe in structural, optical, and electrical properties. Moreover, few‐layered SnSSe phototransistors are fabricated on both rigid (SiO2/Si) and versatile polyethylene terephthalate substrates and their optoelectronic properties are examined. SnSSe as a phototransistor is demonstrated to exhibit a high photoresponsivity of about 6000 A W−1 with ultra‐high photogain ≈8.8 × 105, fast response time ≈9 ms, and specific detectivity (D*) ≈8.2 × 1012 J. These unique features are much higher than those of recently published phototransistors configured with other few‐layered 2D single crystals, making ultrathin SnSSe a highly qualified candidate for next‐generation optoelectronic applications.