Sb2S3 Crystals Research Articles

Electronic and optical properties of Sb2Se3 and Sb2S3: theoretical investigations

Abstract In recent developments in solar energy research, Sb2Se3 and Sb2S3 emerge as environment friendly photovoltaic absorber materials, distinguished by their narrow bandgap and high absorption coefficient. Theoretical investigations to determine the electronic structure, effective density of states, dielectric function, and absorption coefficient of Sb2Se3 and Sb2S3 crystals have been performed using first-principle methods. The results reveal band gap values of about 0.822 and 1.757 eV (PBE method), 1.114 and 1.778 eV (HSE06 method) for Sb2Se3 and Sb2S3, respectively. The valence band and conduction band edges are primarily formed by Se 4p, S 3p, and Sb 5p hybridized orbitals. The effective density of states (DOS) exhibit magnitudes on the order of 1019 cm−3. Notably, anisotropic characteristics are observed in the real and imaginary parts of the dielectric function. Furthermore, the absorption coefficient surpasses 105 cm−1 at 1 and 1.2 eV for both Sb2Se3 and Sb2S3. The result indicates that these highly efficient absorber materials are suitable in collecting solar energy.

Coagulation morphology and performance analysis of antimony sulfide crystals during vacuum evaporation

The controllable preparation of materials with unique structures and morphologies has become an important field in the development of nanomaterials. In this study, Sb2S3 was used as the evaporation source to controllably prepare Sb2S3 crystals with various morphologies under a vacuum. At 873 K and 30 min, antimony sulfide in the form of cauliflower-like was effectively made. At the same temperature and for 60 min, tubular antimony sulfide was formed. The initial forming conditions of fascicle-like antimony sulfide were at 873 K and 100 min and did not change with the increase in temperature. During the evaporation process, some antimony sulfide will condense into lumps, showing irregular feather-like and round particles. The products prepared by this method were analyzed and tested. The results showed that the grade of antimony sulfide prepared by this method was further improved, and the content of Sb and S increases by 1.64% and 1.21% on average. This method offers a simple production process, a more regular product shape, and does not require the use of any additives.

Solution-processed Sb2Se3 nanorod array and its photovoltaic performance

A heterogeneous nucleation strategy is developed to prepare solution-processed Sb2Se3 single-crystalline nanorod array. With tiny Sb2S3 crystals as heterogeneous nuclei, [001]-oriented Sb2Se3 nanorod array is vertically grown on polycrystalline TiO2 nanoparticle film, offering a new materials system of Sb2Se3/TiO2-based nanoarray heterojunction. With a polymeric hole transporting layer, the Sb2Se3 nanorod array solar cell is successfully obtained on transparent substrate.

Polarization and Surface Effects on the Seed Orientation of Laser-Induced Sb2S3 Crystals on Sb-S-I Glass

Polarization and Surface Effects on the Seed Orientation of Laser-Induced Sb₂S₃ Crystals on Sb-S-I Glass

Structural and kinetic aspects of electron-beam crystallization of amorphous films of antimony sulfide

Electron-beam crystallization of amorphous films of Sb2S3 of both stoichiometric composition and with the excess of Sb was studied by the methods of transmission electron microscopy “in situ” with video registration of structural changes. It was revealed, that Sb2S3 films of stoichiometric composition crystallize polymorphous in a single stage. Films with the excess of Sb crystallize in two stages. There is predominant crystallization of Sb during the first stage of the process, and subsequent crystallization of matrix of Sb2S3 during the second stage. The kinetic curves, demonstrating the dependence on time of the density and size of micro-crystals of Sb, as well as of the dependence on time of the size of Sb2S3 crystals and of fraction of the crystalline phase were obtained with the help of frame-by-frame analysis of the video. Primary crystallization of Sb2S3 occurs in accordance with the layer polymorphous crystallization mode with the relative length δ0 ≈ 4992. The dependence on time of the fraction crystallized has a quadratic character. Secondary crystallization of Sb2S3 occurs also in accordance with the layer polymorphous crystallization mode with the relative length δ0 ≈ 9725. The dependence on time of the fraction crystallized can be described by power function with the exponent 0.68.

Fabricating antimony sulfide Sb2S3 microbars using solvothermal synthesis: effect of the solvents used on the optical, structural, and morphological properties

Antimony trisulfide (Sb2S3) is a promising candidate for cell absorbers due to its appropriate band gap, abundant constituents, non-toxicity, simple composition, and long-term stability. In this study, highly oriented Sb2S3 microbars were prepared utilizing an easy, low-cost solvothermal approach. The effects of the solvents used on the morphological and the crystal structure and optical properties of the Sb2S3 films were inspected using X-ray powder direction (XRD), UV/Vis spectroscopy, and field emission scanning electron microscopy (FESEM). The XRD analysis demonstrated that the Sb2S3 crystals had an orthorhombic phase. The Sb2S3 nanorods/bars mostly grew along the (010) direction. Energy-dispersive X-ray analysis (EDX) peaks had an atomic ratio of 2:3 for Sb:S. UV/Vis absorption spectroscopy showed that the optical energy gap of the Sb2S3 microbars was 1.5 with ethylene glycol as the solvent. Aberration-corrected high-resolution transmission electron microscopy (HRTEM) micrographs demonstrated that the Sb2S3 was dendrite-like consisting of microbars with a standard a length of 8–15 µm and width of 250–400 nm.

Preparation and characterization of antimony sulphide nanostructure

Designing and Controlling of the size and morphology of the nanostructured materials is important for photovoltaic and photocatalytic applications. Herein, we report a new efficient approach to prepare different nanostructures of antimony sulphide. The conventional hydrothermal routes can be modified to control the size and morphology of the materials we have been prepared pedicellate flower-like nanostructure of antimony sulphide by quenched hydrothermal method (modified hydrothermal method). The prepared nanostructured materials were analysed using XRD, SEM. The powder X-ray diffraction pattern shows the Sb2S3 crystals belong to the orthorhombic phase with calculated lattice parameters a = 1.190 nm, b = 1.132 nm, and c = 0.390 nm. The morphological changes have been recorded using scanning electron microscope.

Fabrication of single crystal architecture in Sb-S-I glass: Transition from dot to line

We have investigated the occurrence of the sometimes observed grain boundaries, as initial seed is extended to form line in laser-fabricated single-crystal architecture in glass (SCAG). In particular, for Sb2S3 SCAG in Sb-S-I glass as a model system, grain boundaries are formed during the transition from laser-written initial seed dot to crystal line. Such grain boundaries during the growth of Sb2S3 crystals occur in 16SbI3–84Sb2S3 glass, whereas they are absent in Sb2S3 glass. We correlate this difference in tendency to form multiple grains with the relative glass forming ability i.e. the dynamics of nucleation and crystal growth as determined by differential scanning calorimetry (DSC). On the basis of this understanding, methods to minimize the appearance of grain boundaries in the transition region are suggested.

Unveiling the Unique Phase Transformation Behavior and Sodiation Kinetics of 1D van der Waals Sb2S3 Anodes for Sodium Ion Batteries

Carbon‐coated van der Waals stacked Sb2S3 nanorods (SSNR/C) are synthesized by facile hydrothermal growth as anodes for sodium ion batteries (SIBs). The sodiation kinetics and phase evolution behavior of the SSNR/C anode during the first and subsequent cycles are unraveled by coupling in situ transmission electron microscopy analysis with first‐principles calculations. During the first sodiation process, Na+ ions intercalate into the Sb2S3 crystals with an ultrafast speed of 146 nm s−1. The resulting amorphous NaxSb2S3 intermediate phases undergo sequential conversion and alloying reactions to form crystalline Na2S, Na3Sb, and minor metallic Sb. Upon desodiation, Na+ ions extract from the nanocrystalline phases to leave behind the fully desodiated Sb2S3 in an amorphous state. Such unique phase evolution behavior gives rise to superb electrochemical performance and leads to an unexpectedly small volume expansion of ≈54%. The first‐principles calculations reveal distinctive phase evolution arising from the synergy between the extremely low Na+ ion diffusion barrier of 190 meV and the sharply increased electronic conductivity upon the formation of amorphous NaxSb2S3 intermediate phases. These findings highlight an anomalous Na+ ion storage mechanism and shed new light on the development of high performance SIB anodes based on van der Waals crystals.

Rotating lattice single crystal architecture on the surface of glass.

Defying the requirements of translational periodicity in 3D, rotation of the lattice orientation within an otherwise single crystal provides a new form of solid. Such rotating lattice single (RLS) crystals are found, but only as spherulitic grains too small for systematic characterization or practical application. Here we report a novel approach to fabricate RLS crystal lines and 2D layers of unlimited dimensions via a recently discovered solid-to-solid conversion process using a laser to heat a glass to its crystallization temperature but keeping it below the melting temperature. The proof-of-concept including key characteristics of RLS crystals is demonstrated using the example of Sb2S3 crystals within the Sb-S-I model glass system for which the rotation rate depends on the direction of laser scanning relative to the orientation of initially formed seed. Lattice rotation in this new mode of crystal growth occurs upon crystallization through a well-organized dislocation/disclination structure introduced at the glass/crystal interface. Implications of RLS growth on biomineralization and spherulitic crystal growth are noted.

Synthesis and Catalytic Properties of Sb2S3 Nanowire Bundles as Counter Electrodes for Dye-Sensitized Solar Cells

Through density functional theory (DFT) computations and experimental tests, we investigated the catalytic properties of Sb2S3 crystals with different facets used as counter electrodes (CEs) for dye-sensitized solar cells (DSSCs). The computations show that, compared with the (151) facet, the (211) facet has greater surface activity and better electrical conductivity but markedly lower band-edge levels, resulting in comparable catalytic activities for these two facets. To verify these predictions, we synthesized two Sb2S3 nanowire bundles, predominantly with exposed (151) and (211) facets, and found that DSSCs with these Sb2S3 CEs have similar I–V curves and conversion efficiencies, which confirms the computations and suggests that the surface activity, electrical conductivity, specific surroundings, and band-edge positions should all be considered in the design of semiconductor CEs for DSSCs.

Urchinlike Nanostructure of Single-Crystalline Nanorods of Sb2S3 Formed at Mild Reaction Condition

Urchinlike nanostructure of well-defined Sb(2)S(3) crystals of 3-4 μm in length and 30-150 nm in diameter oriented along [001] direction have been produced at a mild reaction temperature of 90 °C from SbCl(3) and S-methyl 3-phenyldithiocarbazate [C(6)H(5)NHNHC(S)SMe] in ethylene glycol medium. During the reaction, the amorphous Sb(2)S(3) spheres of 1.4 μm in diameter were formed at early reaction stage and then crystalline nanorods were continuously grown at the surface of Sb(2)S(3) spheres while transforming their morphology into urchinlike structure. The urchinlike Sb(2)S(3) was composed of single-crystalline Sb(2)S(3) nanorods, belong to the orthorhombic phase with cell parameters a = 11.307 Å, b = 11.278 Å, c = 3.847 Å and absorbed the light up to 750 nm-wavelength region. The urchinlike Sb(2)S(3) architecture was applied to the photoelectrochemical cell.

Influence of chemical bonds on Bi and Sb XPS shifts in Bi2S3and Sb2S3crystals

The paper presents the results of theoretical calculations of the shifts of Bi and Sb X-ray photoelectron spectra (XPS) due to chemical bond formation in Bi2S3 and Sb2S3 crystals. The energies of core levels of Bi, Sb, and S atoms are calculated by both the Hartree–Fock–Dirac (HFD) and Hartree–Fock methods and compared with the experimental values. The HFD method explains well the experimentally obtained spin–orbit splitting of the XPS. However, both theoretical methods give higher negative core level energies than their experimental values are.

The study of defects in Sb2S3 by method of direct lattice resolution

1.Sb2S3 has the orthorombic lattice with a=11,23;b=11,31; c=3,84 Å. Its crystal structure is constructed of the double ribbons of antimony and sulphur atoms,parallel to [00l].Vacuum deposited films of Sb2S3 re amorphous{they were crystallyzed in spherolite mode by the electronbeam heating.The study of defect structure of the Sb2S3 spherolite crystals by method of direct lattice resolution was the aim of present work.The images of (100),(200),(010),(020),(110) and (110) planes were obtained.2.Several types of the ribbons stacking faults were obserwed in Sb2S3 crystals with (001) parallel to the substrate plane (Fig.1).The stac-kingfault planes and their displacement vectors R are the following: a) (010),(110),R=1/2 [010];b) (100),R=1/2 [210],R=1/4[210].3.There were obtained the images of partial dislocations with b=1/2 [010] and small-andle boundaries,consisted of the dissociated partial dislocation pairs,in Sb2s3 crystals with (100) and (010) planes parallel to the substrate.Small-angle boundaries appeared on initial stage of the spherolite growth,when splitting of spherolite single-crystal nucleus was taking place (Fig.2).