van der Waals layered materials have large crystal anisotropy and crystallize spontaneously into two-dimensional (2D) morphologies. Two-dimensional materials with hexagonal lattices are emerging 2D confined electronic systems at the limit of one or three atom thickness. Often these 2D lattices also form orthorhombic symmetries, but these materials have not been extensively investigated, mainly due to thermodynamic instability during crystal growth. Here, we show controlled polymorphic growth of 2D tin-sulfide crystals of either hexagonal SnS2 or orthorhombic SnS. Addition of H2 during the growth reaction enables selective determination of either n-type SnS2 or p-type SnS 2D crystal of dissimilar energy band gap of 2.77 eV (SnS2) or 1.26 eV (SnS) as a final product. Based on this synthetic 2D polymorphism of p–n crystals, we also demonstrate p–n heterojunctions for rectifiers and photovoltaic cells, and complementary inverters.

Deterministic Two-Dimensional Polymorphism Growth of Hexagonal n-Type SnS2 and Orthorhombic p-Type SnS Crystals

[020]-oriented tin sulfide nanobelts with a length/thickness ratio of 100 have been synthesized by a facile hydrothermal method without any surfactants, and the nanobelts have shown good strain-accommodating properties as well as good electrochemical performance as the anode for Li-ion batteries. The formation of the nanobelts results from a precipitation-dissolution-transformation mechanism, and the [020] oriented growth can be ascribed to the {010} facet family having the lowest atomic density. In particular, SnS shows clear Li-Sn alloying/de-alloying reversible reactions in the potential range 0.1–1.0 V. Based on galvanostatic measurements and electrochemical impedance spectroscopy, SnS nanobelts have shown impressive rate performance. The post-cycled SnS nanobelts were completely transformed into metallic tin, and preserved the one-dimensional structure due to their flexibility which accommodates the large volumetric expansion. 
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Flexible SnS nanobelts: Facile synthesis, formation mechanism and application in Li-ion batteries

SnS is a metal monochalcogenide suitable for use as absorber material in thin film photovoltaic cells. Its structure is an orthorhombic crystal of weakly coupled layers, each layer consisting of strongly bonded Sn-S units. We use first-principles calculations to study model single-layer, double-layer, and bulk structures of SnS in order to elucidate its electronic structure. We find that the optoelectronic properties of the material can vary significantly with respect to the number of layers and the separation between them: the calculated band gap is wider for fewer layers (2.72 eV, 1.57 eV, and 1.07 eV for single-layer, double-layer, and bulk SnS, respectively) and increases with tensile strain along the layer stacking direction (by ∼55 meV/1% strain).

https://scholar.harvard.edu/files/efthimios_kaxiras/files/japplphys_113_233507_2013.pdf

Optoelectronic properties of single-layer, double-layer, and bulk tin sulfide: A theoretical study

A review of tin (II) monosulfide and its potential as a photovoltaic absorber

Sandwich-like SnS/polypyrrole ultrathin nanosheets were synthesized via a pyrrole reduction and in situ polymerization route, in which room-temperature synthesized ZnSn(OH)6 microcubes were used as the tin source. As anode materials for Li-ion batteries, they exhibit an extremely high reversible capacity (about 1000 mA h g–1 at 0.1C), outstanding rate capability (with reversible capabilities of 878, 805, 747, 652, and 576 mA h g–1 at 0.2C, 0.5C, 1C, 2C, and 5C, respectively), stable cycling performance, and high capacity retention (a high capacity of 703 mA h g–1 at 1C after long 500 cycles).

Sandwich-like SnS/Polypyrrole Ultrathin Nanosheets as High-Performance Anode Materials for Li-Ion Batteries.

Tin sulfide (SnS) is a material of interest for use as an absorber in low cost solar cells. Single crystals of SnS were grown by the physical vapor deposition technique. The grown crystals were characterized to evaluate the composition, structure, morphology, electrical and optical properties using appropriate techniques. The composition analysis indicated that the crystals were nearly stoichiometric with Sn-to-S atomic percent ratio of 1.02. Study of their morphology revealed the layered type growth mechanism with low surface roughness. The grown crystals had orthorhombic structure with (0 4 0) orientation. They exhibited an indirect optical band gap of 1.06 eV and direct band gap of 1.21 eV with high absorption coefficient (up to 10(3) cm(-1)) above the fundamental absorption edge. The grown crystals were of p-type with an electrical resistivity of 120 Omega cm and carrier concentration 1.52 x 10(15) cm(-3). Analysis of optical absorption and diffuse reflectance spectra showed the presence of a wide absorption band in the wavelength range 300-1200 nm, which closely matches with a significant part of solar radiation spectrum. The obtained results were discussed to assess the suitability of the SnS crystal for the fabrication of optoelectronic devices. (C) 2011 Elsevier B.V. All rights reserved.

K.A. Chandrasekharan

Papers

Optical and electrical properties of SnS semiconductor crystals grown by physical vapor deposition technique