Structure Of Sb2S3 Research Articles

Investigation the optical and structural properties of Mn-doped Sb2S3 nanocrystals embedded in host glass

The search for earth-abundant and non-toxic elements is essential for the manufacture of sustainable optical devices. In this context, dilute magnetic semiconductor (DMS) xMn-doped Sb2S3 nanocrystals (NCs) embedded in host glass were synthesized by the fusion method. Differential Thermal Analysis shows evidence of Sb2S3 phase crystallization peak and changes in glass transition and crystallization temperatures of the host glass with the presence of xMn-doped Sb2S3 NCs. Transmission electron microscopy images show the formation of xMn-doped Sb2S3 NCs with increasing size (2.1–3.8 nm) as a function of concentration (x = 0.00 to 0.40), respectively. X-ray diffraction measurements reinforced the evidence for the orthorhombic structure of xMn-doped Sb2S3 NCs embedded in glass. Energy dispersive X-ray spectroscopy analyses confirm the S, Sb and Mn precursor elements of DMS NCs. Atomic and magnetic force microscopy measurements show the magnetic contrast patterns resulting from the incorporation of Mn atoms into the Sb2S3 structure. The electronic paramagnetic resonance spectrum confirms the presence of Mn2+ ions (3d5) located in the crystal field of the Sb2S3 semiconductor due to six hyperfine transitions. The redshift of the Raman vibrational mode (1Ag) with increasing xMn concentration gives strong evidence for the presence of Mn2+ ions in sulfur vacancies (VS) in the Sb2S3 unit cell. Optical absorption and photoluminescence (PL) spectroscopy measurements for xMn-doped Sb2S3 NCs show the subtle tunable redshift of the band gap and excitonic recombination in the green-red region, with increasing x concentration. PL confirms that dopant Mn2+ ions fill VS2 that are dominant in Sb2S3. Therefore, the position of the energy states after the increasing concentration of Mn2+ dopant ions gives rise to insight into luminescence for future research scenarios and applications involving sustainable DMS NCs.

Influence of Sulfurization Time on Sb2S3 Synthesis Using a New Graphite Box Design.

In recent years, antimony sulfide (Sb2S3) has been investigated as a photovoltaic absorber material due to its suitable absorber coefficient, direct band gap, extinction coefficient, earth-abundant, and environmentally friendly constituents. Therefore, this work proposes Sb2S3 film preparation by an effective two-step process using a new graphite box design and sulfur distribution, which has a high repeatability level and can be scalable. First, an Sb thin film was deposited using the RF-Sputtering technique, and after that, the samples were annealed with elemental sulfur into a graphite box, varying the sulfurization time from 20 to 50 min. The structural, optical, morphological, and chemical characteristics of the resulting thin films were analyzed. Results reveal the method's effectivity and the best properties were obtained for the sample sulfurized during 40 min. This Sb2S3 thin film presents an orthorhombic crystalline structure, elongated grains, a band gap of 1.69 eV, a crystallite size of 15.25 Å, and a nearly stoichiometric composition. In addition, the formation of a p-n junction was achieved by depositing silver back contact on the Glass/FTO/CdS/Sb2S3 structure. Therefore, the graphite box design has been demonstrated to be functional to obtain Sb2S3 by a two-step process.

Tri-chalcogenides (Sb2S3/Bi2S3) solar cells with double electron transport layers: design and simulation

To make technology accessible to everyone, it is essential to focus on affordability and durability of the devices. Antimony trisulfide (Sb2S3) and bismuth (III) sulfide (Bi2S3) are low-cost and stable materials that are commonly used in photovoltaic devices due to their non-toxic nature and abundance. These materials are particularly promising for photovoltaic applications as they are effective light-absorbing materials. In this study, we utilized the Solar cell Capacitance Simulator- One-Dimensional (SCAPS-1D) software to investigate the parameters of a double electron transport layer (ETL) solar cell based on Sb2S3/ Bi2S3. The parameters examined included thickness of the absorber layer, overall defect density, density of acceptors, radiative recombination coefficient, series and shunt resistance, and work function of the back contact. The solar cell structure studied was FTO/SnO2/CdS/ Sb2S3 and Bi2S3/Spiro-OMeTAD/Au. By incorporating a SnO2 electron transport layer (ETL) into the double ETL structure of Sb2S3 and Bi2S3 solar cells, we observed a significant enhancement in the power conversion efficiency (PCE). Specifically, the PCE increased to 19.71% for the Sb2S3 solar cell and 24.05% for the Bi2S3 solar cell. In contrast, without SnO2, the single ETL-based CdS solar cell achieved a maximum PCE of 18.27 and 23.05% for Sb2S3 and Bi2S3, respectively.

Growth of single crystal Sb2S3 semiconductor pillars by sol-gel method

The binary compound semiconductor Sb2S3 was fabricated on solid substrate by spin coating based on a sol-gel method. In this study, it was observed that crystallinity appeared differently depending on the type of substrate material used to fabricate the Sb2S3 structure, and this mechanism was investigated. As the substrate, bare FTO glass and FTO glass coated with Mo, Ni, and Au were used. In the case of Sb2S3 grown on bare FTO glass and FTO glass coated with Mo, crystals are formed in-plane, whereas in the case of Sb2S3 grown on FTO glass substrate coated with FCC-structured metals such as Au and Ni, crystals are formed out-of-plane. It was observed that the single crystal growth of rectangular pillar-shaped Sb2S3 was closely related to the formation of regularly ordered compounds at the interface between the Sb2S3 pillar and the FCC metal substrate.

Amorphous non-doped and Se-, Cu-, and Zn-doped Sb2S3 nanoparticles prepared by a hot-injection method: bandgap tuning and possible observation of the quantum size effect

Amorphous, non-doped, and copper- and selenium-doped Sb2S3 nanoparticles were synthesized by a hot-injection method. Zinc-doped Sb2S3 nanoparticles were prepared for the first time using the same approach. Electron microscopy revealed that spherical nanoparticles of 1–4 nanometers aggregated into larger spherical clusters. Introducing dopants into the Sb2S3 structure neither influenced the samples’ spherical morphology nor their sizes. The presence of the dopants (Cu, Se, or Zn) was confirmed by energy dispersive X-ray (EDX) and, in the case of Zn, also by inductively coupled plasma-mass spectrometry (ICP-MS). The X-ray powder diffraction (XRPD) patterns of the non-doped and doped samples imply an amorphous structure. Crystalline Zn-doped Sb2S3 revealed defined peaks from only the Sb2S3 phase, indicating successful doping. Diffuse reflectance spectroscopy (DRS) revealed high optical bandgap energies (2.03–2.12 eV) compared to the values (1.6–1.7 eV) for large non-doped and doped particles obtained at 240 °C, which might be attributed to a quantum size effect. X-ray photoelectron spectroscopy (XPS) revealed a phase without any impurities for the undoped and characteristic peaks for copper, selenium, and zinc Auger for the doped samples. XPS valence band confirm for the Zn-doped particles a shift towards lower binding energy compared to the non-doped samples, indicating successful doping. Photoluminescence (PL) measurements show that embedding Zn into the Sb2S3 host lattice suppresses the wide luminescence band related to intrinsic vacancy defects. Narrow peaks at 1.7–2.4 eV were found to be associated with singlet excitons. The energy dependence of the light emission on the synthesized nanoparticles’ size suggests quantum confinement.

Bifunctional structure modulation of Sb-based sulfide for boosting fast and high-capacity sodium storage

A novel bimetallic sulfide CrSbS3 with both high sodium storage capacity and good rate performance is synthesized by introducing Cr atoms into the Sb2S3 structure.

Construction of hollow core–shell Sb2S3/S@S-doped C composite based on complexation reaction for high performance anode of sodium-ion batteries

Although the high-capacity Sb2S3-based anode materials for sodium-ion batteries can combine the advantages of multi-step conversion of Sb2S3 to Sb and alloying reaction between Sb and Na for improving the performance, the slow reaction kinetics, low electronic conductivity, and poor reversibility of the sodium storage process have limited their practical application. To effectively improve the electrochemical performance, a three-dimensional Sb2S3/S@S-doped carbon composite with a hollow core–shell structure based on the combination of template method and coupling reaction is successfully synthesized. By combining the finite element simulation, dynamic analysis, and density functional theory calculation, the respective roles of S-composite and hollow core–shell structure in boosting performance are revealed. The internal S and external S-doped carbon can interact with Sb2S3 to improve its reactivity with Na+, and effectively release the stress of Sb2S3 in the sodiation process. The S-doped carbon can accelerate Na+ diffusion and further stabilize the structure of Sb2S3. Benefited from the special structure, the as-prepared anode displays high reversible capacity, superior cycle performance and high rate capability. The assembled full battery also exhibits an excellent energy density under high power, and can still maintain a high reversible capacity of 310 mAh/g at 1 A/g over 500 cycles.

Exploration of the structural, optoelectronic and vibrational behavior of Sb2S3 through the first principles approach for phenomenal applications in solar cells

In order to study any material the first principles approach has been considered an appropriate forum and deemed the best remedy to ensure the validity of the achievements/results obtained either theoretically or experimentally. We are, therefore, motivated to use this approach to explore the structural, optoelectronic and vibrational properties of Sb2S3 while utilizing the plane-wave pseudopotential technique and conjugate gradient method employed through the CASTEP simulation code. The crystal structure of Sb2S3 is optimized in orthorhombic phase having space group Pnma with lattice parameters a = 11.31 Å, b = 3.84 Å and c = 11.23 Å. It is noticed that magnitude of these lattice parameters approximately replicate the formerly reported theoretical as well as experimental results. The energy band gap is found to be 1.012 eV, which is utter evidence that the studied compound belongs to semiconductor category of the materials. The optical parameters unveil that Sb2S3 is capable to absorb wide range of radiations from the ultraviolet (UV) portion of the spectrum. The dynamical analysis through density functional perturbation theory (DFPT) shows that there is no soft mode which further ensures dynamical stability of Sb2S3. The optical analysis of the studied compound are enough to declare it a potential material for applications in solar cells.

Sb2S3microbars prepared via the solvothermal method: Precursor sulfur source's effect on structural and optical properties for solar cell applications

In this study, antimony sulfide Sb2S3microbarswere successfully fabricated via the solvothermal method using different sulfur sources at 180oC for 14 h. The effects of different sulfur sources including natrium thiosulfate, thiourea, sulfur, and l-cystine on the structural, compositional, and optical properties of the Sb2S3 microbars were inspected using XRD, TEM, XPS, FE-SEM, EDX, UV–vis spectra and Raman scattering. The XRD and Raman spectral studies indicated theSb2S3 microbars’ high purity, crystalline nature, single phase, and orthorhombic structure of in the preferred (1 3 0) orientation. The TEM images showed the formation of well-defined Sb2S3microbars and confirmed the crystallinity. The EDX investigation indicated that the Sb/S atomic ratio was close to2:3, revealing the nearly stoichiometric nature of the Sb2S3 structure. The XPS analysis demonstrated the elemental composition and chemical states. The microbars had absorption coefficients over 104 cm−1and energy gaps between 1.53 and 1.81 eV depending on the precursor sulfur used. The Sb2S3 thin film-based microbars were smooth, compact, and free from holes and cracks with grain sizes of more than 1.5 μm. The highest power conversion efficiency of 3.63% was achieved in the Mo/Sb2S3/CdS/ITO/Ag solar cell structure, with open-circuit voltage Voc = 465 mV, short-circuit current density Jsc = 12.83 mA/cm2, and a fill factor FF = 60.9%when thiourea was used as the sulfur source.

XPS study of iodine and tin doped Sb2S3 nanostructures affected by non-uniform charging

X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) measurements are used for investigating incorporation of iodine and tin into the stibnite (Sb2S3) lattice, as well as for determining surface composition and structure, respectively. The XRD analysis revealed the visible presence of a single phase, that of pure orthorhombic Sb2S3 structure. XPS survey spectra confirmed the presence of expected elements (Sb, S, Sn and I) at the surface of corresponding samples. Since the bonding identification was hindered by non-uniform charging of samples during acquiring the photoelectron spectra, a novel approach for the analysis of high resolution spectra was proposed and successfully implemented. XPS results showed that surface composition of the non-doped sample coincides with that of the bulk, while doping strongly affects surface of the samples. Sn-doped sample appears to be prone to surface oxidation. The presence of Sb2S3, Sb2O3, SnS2 and Sn(0) phases at the surface was revealed. Strong segregation of antimony was observed in the I-doped Sb2S3 sample. Iodine is also present at the surface in the form of the SbI3 phase, while the detected sulphur signal most probably corresponds to S atoms from unaltered deeper layers.

In Situ Growth of [hk1]‐Oriented Sb2S3 for Solution‐Processed Planar Heterojunction Solar Cell with 6.4% Efficiency

AbstractBinary compound antimony sulfide (Sb2S3) with its nontoxic and earth‐abundant constituents, is a promising light‐harvesting material for stable and high efficiency thin film photovoltaics. The intrinsic quasi‐1D (Q1D) crystal structure of Sb2S3 is known to transfer photogenerated carriers rapidly along the [hk1] orientation. However, producing Sb2S3 devices with precise control of [hk1] orientation is challenging and unfavorable crystal orientations of Sb2S3 result in severe interface and bulk recombination losses. Herein, in situ vertical growth of Sb2S3 on top of ultrathin TiO2/CdS as the electron transport layer (ETL) by a solution method is demonstrated. The planar heterojunction solar cell using [hk1]‐oriented Sb2S3 achieves a power conversion efficiency of 6.4%, performing at almost 20% higher than devices based on a [hk0]‐oriented absorber. This work opens up new prospects for pursuing high‐performance Sb2S3 thin film solar cells by tailoring the crystal orientation.

First-principles study of electronic and optical properties of antimony sulphide thin film

First-principles quantum mechanical computational methods are significant tools to understand the details of crystal structures which might be difficult through experimentation. In this paper, we have presented the electronic and optical properties of the thin film structure of Sb2S3 in (001) orientation. Density functional theory based approaches are employed to determine the band structure, density of states (DOS), dielectric function and other optical parameters. Here, the investigations have been performed by full-potential linearized augmented plane-wave method (FP-LAPW) within the WIEN2k computational code. The band structure computations are done at the level of LDA-PW, PBE-GGA, PBE-GGA with SOC and PBE-GGA with mBJ potential, whereas for optical properties only PBE-GGA with mBJ potential was applied. Our calculations revealed that similar to optical properties, Sb2S3 (001) oriented thin film had shown a reduction in the band gap energy than its counterpart bulk structure. This reduction, in the electronic and optical parameters, might be better understood in the course of quantum confinement effect for improving its performance for optoelectronics applications.

Electrochemical performance of Sb2S3/CNT free-standing flexible anode for Li-ion batteries

Sb2S3/CNT composite has been synthesized through ethylene glycol-mediated solvothermal process, and binderless, free-standing, flexible anode is prepared from the composite through vacuum filtration technique. The 1-D rod-like structure of Sb2S3 prevents self-agglomeration and exhibits well-guided charge–discharge kinetics and high surface area enhancing their electrochemical performance in Li-ion batteries. The introduction of CNTs to the Sb2S3 facilitates the preparation of free-standing flexible anodes as well as buffers the volume changes that occur during repeated cycling, thereby improving the cycling stability. The Sb2S3/CNT free-standing anode exhibits a high initial discharge capacity of 930 mAhg−1 at a current rate of 200 mAg−1. The anode also exhibits excellent lifetime stability and rate capability by cycling at different current rates up to 1200 mAg−1. Sb2S3/CNT anode gives a stable capacity of 443 mAhg−1 after 100 cycles at a current density of 200 mAg−1, while Sb2S3 rods deliver only 293 mAhg−1 after 100 cycles at the same current rate. This free-standing flexible Sb2S3/CNT anode is highly promising in comparison with conventional graphite powder anode.

Bismuth and antimony chalcogenides: Peculiarities of electron density distribution, unusual magnetic properties and superconductivity

Abstract Electron band structure calculations and analysis of critical points parameters in the electron density distribution in Bi2Te3, Bi2Se3, Bi2S3, α-Bi2O3, Sb2Te3, Sb2Se3 and Sb2S3 at ambient and high pressures were performed to determine interrelations between the crystal structure, unusual physical (including magnetic and superconducting) properties and peculiarities in the electron density distribution. The programming code WIEN2k was used for band structure calculations. The previously found correlation between the superconducting transition temperature Tc and the electron density Laplacian value in the bond critical point with the highest electron density was confirmed by the calculations made for crystal structures under high pressure. The revealed parameters of bond critical points indicate the significant role of charge density fluctuations in the compounds studied. The 121, 123Sb NQR spin echo envelopes assigned to the ν1 transition (Δm = 1/2–3/2) were measured for the two crystallographic positions of Sb atoms in the Sb2S3 structure. Unexpectedly deep oscillations of NQR spin echo envelopes were observed in very small (1–3 Oe) external magnetic fields, evidencing for the existence of local magnetic fields in Sb2S3 similar to those earlier observed in bismuth oxide compounds.

Tin‐Assisted Sb2S3 Nanoparticles Uniformly Grafted on Graphene Effectively Improves Sodium‐Ion Storage Performance

AbstractHerein, composites of tin‐assisted antimony sulfide decorated on reduced graphene oxide (Sn@Sb2S3‐rGO) were prepared by using a simple hydrothermal method. As an anode material of sodium‐ion batteries, the Sn@Sb2S3‐rGO composites exhibited good electrochemical performance with an initial discharge (sodiation) specific capacity of 1002.0 mAh g−1, and they maintained a specific capacity of approximately 600 mAh g−1 at a current density of 200 mA g−1 after 60 cycles. The good performances could be explained by the composite with graphene and a bimetallic synergistic effect, both of which have an impact on the structure of Sb2S3 and subsequent electrochemical performance. This approach to the bimetallic synergistic effect for graphene composites could be a promising new idea to design other high‐performance energy storage materials.

Synthesis, characterization and photovoltaic properties of Mn-doped Sb2S3thin film

AbstractSynthesis and characterization of Mn-doped Sb2S3thin films (TFs) prepared by chemical bath deposition (CBD) at room temperature have been documented and their structural, optical, morphological, magnetic and photovoltaic properties have been examined for the first time. Their structural properties reveal that the Mn-doped Sb2S3TF has an orthorhombic phase structure of Sb2S3, and that the grain size of the Mn-doped Sb2S3TF (72.9 nm) becomes larger than that of undoped Sb2S3TF (69.3 nm). It has been observed that Mn content causes the Sb2S3TF band gap to decrease. This situation clearly correlates with band tailing due to the impurities that are involved. The morphological properties have revealed that the shape of the Mn-doped Sb2S3TF is more uniform than the shape of its undoped counterpart. The study on its magnetic properties has demonstrated that the Mn-doped Sb2S3TF exhibits paramagnetic behavior. Its paramagnetic Curie-Weiss temperature was found to be -4.1 K. This result suggests that there is an anti-ferromagnetic interaction between Mn moments in the Mn-doped Sb2S3TF. Incident photon to electron conversion efficiency (IPCE) and J-V measurements were also carried out for the Mn-doped Sb2S3TF for the first time. The results have indicated that the Mn-doped Sb2S3TF can be utilized as a sensitizer to improve the performance of solar cells. Another important observation on the photovoltaic properties of Mn-doped Sb2S3TF is that the spectral response range is wider than that of undoped Sb2S3TF. Our study suggests that the introduction of dopant could serve as an effective means of improving the device performance of solar cells.

Improvement of antimony sulfide photo absorber performance by interface modification in Sb2S3–ZnO hybrid nanostructures

Metal-oxide chalcogenide nanostructures as part of hybrid systems are very important for photovoltaic and optoelectronic applications. It is however known that the various interfaces within the hybrid structures play a crucial role in limiting the efficiency of these devices. Here we report on the improvement of Sb2S3 structure through modification of interface between Zn-oxide nanostructures and chalcogenides. ZnO nanorods were grown on fluorine doped tin oxide (FTO) substrate by chemical bath deposition (CBD) method. X-ray diffraction (XRD) and SEM analysis confirmed the single phase wurtzite structure and c-axis orientation of the ZnO nanorod arrays. Antimony tri-sulfide (Sb2S3) was deposited on ZnO nanords by CBD and subsequently annealed at 300°C in argon environment for 30min. XRD and the XPS analysis of ZnO–Sb2S3 system showed the dominant presence of Sb2O3 rather than Sb2S3. Since oxidation of Sb2S3 is understood to proceed mainly from the ZnO–Sb2S3 interface, a ZnS interlayer was introduced between ZnO nanorods and Sb2S3 by chemical route. The subsequent structural and optical properties of the ZnO–ZnS–Sb2S3 system are analyzed in detail. The introduction of sulfide interlayer prevents the oxidation of Sb2S3 which is evident from reduced oxide phase in Sb2S3. Significant improvement in the structural and optical properties of Sb2S3 are reported as compared to the parent ZnO–Sb2S3 system. This gain in the optical properties of hybrid ZnO–ZnS–Sb2S3 nanostructures is explained as being related to successful prevention of Sb2O3 formation at the Sb–ZnO interface and stabilization of the desired Sb2S3.

Enhanced Sb2S3 crystallisation by electric field induced silver doping

This work reveals that doping Ag into Sb2S3 substantially decreases its crystallisation temperature. We show that applying an electric field to Sb2S3 through Ag electrodes provides control of the crystallisation temperature and crystallisation rate. The crystal nuclei incubation time decreases substantially when the applied electric field is set to 200kV/m. The applied electric field appears to force the Ag cations through the amorphous chalcogenide film resulting in Ag doped Sb2S3 filaments that extend from the cathode to the anode. This was confirmed by X-ray fluorescence composition mapping. Density functional theory molecular dynamics modelling of Ag doped Sb2S3 reveals that the diffusion constant of Ag is twice that of Sb or S over a wide temperature range, which implies that the Ag atoms are mobile in the amorphous Sb2S3 structure. The applied electric field provides a mechanism to enhance the crystallisation kinetics of Ag-doped Sb2S3.

Hybrid solar cells using solution-processed TiO2/Sb2S3 bilayer as electron transport layer

Efficient inverted hybrid solar cells using poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) bulk heterojunction as active layers and TiO2/Sb2S3 bilayers as electron transport layers (ETL) have been prepared in ambient air. The microstructural, photoelectronic, and electrochemical characteristics on these cells have been investigated. Photoluminescence measurement indicates that the exciton dissociation in TiO2/Sb2S3 is more effective than that in ITO/Sb2S3 structure. The Nyquist plots obtained from electrochemical impedance spectroscopy implies that charge recombination has been suppressed in TiO2/Sb2S3 with respect to Sb2S3 structure. In addition, the TiO2/Sb2S3 bilayer structure exhibits significantly enhanced external quantum efficiency in the visible region. The cell structure consisting of ITO/TiO2/Sb2S3/P3HT:PCBM/PEDOT:PSS/Ag with the TiO2/Sb2S3 bilayer synthesized under the optimized conditions gains an average efficiency of 3.52%, which is enhanced for ∼28.5% and ∼209% referring to the cells only with the TiO2 layer and Sb2S3 layer as the ETL, respectively.

Assessment of Hybrid Organic-Inorganic Antimony Sulfides for Earth-Abundant Photovoltaic Applications.

Hybrid organic-inorganic solar absorbers are currently the subject of intense interest; however, the highest-performing materials contain Pb. Here we assess the potential of three Sb-based semiconductors: (i) Sb2S3, (ii) Cs2Sb8S13, and (iii) (CH3NH3)2Sb8S13. While the crystal structure of Sb2S3 is composed of 1D chains, 2D layers are formed in the ternary cesium and hybrid methylammonium antimony sulfide compounds. In each case, a stereochemically active Sb 5s(2) lone pair is found, resulting in a distorted coordination environment for the Sb cations. The bandgap of the binary sulfide is found to increase, while the ionization potential also changes, upon transition to the more complex compounds. Based on the predicted electronic structure, device configurations are suggested to be suitable for photovoltaic applications.