Antimony Iodide Research Articles

Pressure‐Regulated Photovoltaic Response in Antimony Triiodide With Asymmetric Metal Contact

AbstractThe effective modification of photovoltaic activities in photoelectric devices is significant for enhancing energy conversion efficiency. Here, the pressure‐tunable photovoltaic properties in the SbI3 device with Au/Pt asymmetric electrodes are demonstrated. At initial pressure, the SbI3 device exhibits an anticipated self‐driven photoresponse characteristic at zero external bias, and a significant enhancement in photocurrent response is observed with increasing bias to −0.2 V, nearly two orders of magnitude higher than the initial value. With increasing pressure, the SbI3 device exhibits tunable photocurrent response, reaching a maximum value at ≈1.2 GPa, while the photovoltage response decreases monotonously during compression, which is closely associated with the dynamic evolution of the work function and bandgap of SbI3 upon successive compression. These findings signify that SbI3 is a promising candidate for future photoelectric devices, which opens a new window of opportunity for further exploration, regulation, and understanding of high‐performance photovoltaic devices under extreme conditions.

Photoelectric properties surge driven by molecular-ionic crystal transition in layered antimony triiodide under high pressure

Photoelectric properties surge driven by molecular-ionic crystal transition in layered antimony triiodide under high pressure

Preparation and characterization of SbSeI thin films

Metal chalcohalides are promising candidates for next-generation technologies that include energy conversion, information storage, and quantum computing. Among them, antimony selenoiodide (SbSeI) has received rising interest for different optoelectronic devices, including photovoltaics, due to its bandgap energy, strong optical absorption, stability, and earth abundant, low-cost, and low toxicity constituents. In this work, SbSeI thin films were prepared through a two-step process. At first, antimony selenide (Sb2Se3) thin films were deposited at 300 °C (Sb2Se3-300) and at room temperature (Sb2Se3-RT) onto molybdenum covered soda-lime glass substrates by a magnetron sputtering method. The formation of SbSeI thin films was performed by isothermally annealing the as-deposited Sb2Se3 thin films in sealed quartz ampoules in the atmosphere of antimony iodide (SbI3) with the presence of 100 Torr of argon pressure. The influence of the annealing temperature and time during the iodization of different types of substrates on the morphology and composition of SbSeI thin films was investigated. The well-oriented and dense single-phase SbSeI thin films with stoichiometric composition and single-crystal micro-columnar structures were achieved by annealing Sb2Se3-RT in SbI3 atmosphere at 250 °C for 5 min under 100 Torr of Ar pressure. The room temperature photoluminescence (RT-PL) of SbSeI exhibited a broad asymmetric PL band with a maximum at 1.67 eV. The low-temperature (T = 8 K) PL study of SbSeI showed a broad and asymmetric PL band at 1.4 eV, being quite distant from the bandgap. This PL band at 1.4 eV with obtained small thermal quenching activation energy of 12.7 meV is proposed to originate from the deep donor-deep acceptor pair (DD-DA) recombination.

Cesium antimony iodide perovskite thin films by rapid iodization of Sb2S3-CsCl precursor under ambient conditions

In the present work, we report the synthesis of lead free cesium antimony iodide (Cs3Sb2I9) perovskite thin films by rapid iodization of Sb2S3-CsCl precursors under ambient conditions. In this method, first, Sb2S3 thin films were deposited using a chemical bath containing SbCl3 and Na2S2O3, following drop casting and spin coating of CsCl with varying molarities. These Sb2S3-CsCl precursor layers were iodized and the resulting films were investigated for their structure and morphology. X-ray diffraction and scanning electron microscopy studies revealed the formation of phase pure hexagonal structured Cs3Sb2I9 (P63/mmc) thin films with uniform surface coverage, exhibiting distinct morphologies for drop casting and spin coating cases. Moreover, Cs3Sb2I9 films obtained by varying iodization times (30 s – 10 min) were analyzed. The optical studies showed a direct band gap in the range of ∼ 1.8–1.96 eV for both drop casting and spin coating films. The Cs3Sb2I9 films were photoconductive and exhibited photodetection properties at zero bias voltage, functioning as self-powered photodetecors. Furthermore, we investigated stability of the self-powered photodetectors. Our work offers a facile synthesis process for producing photoconductive Cs3Sb2I9 thin films with inherent self-biased photodetection properties.

Improved hydrogen production using lead-free and air stable perovskite-like Cs3Sb2I9

In previous years, lead (Pb) free all-inorganic perovskite like materials have been widely used for photovoltaic applications. Herein, we have fabricated cesium antimony iodide (Cs3Sb2I9) perovskite like-material by simple and effective approach. Further, phase and purity of Cs3Sb2I9 perovskite like material was confirmed by XRD. The structural surface of Cs3Sb2I9 perovskite like material was checked by SEM. The elemental composition of Cs3Sb2I9 perovskite like material was determined by XPS. Further, we have investigated the photo-catalytic properties of Cs3Sb2I9 perovskite like material for hydrogen production application. Cs3Sb2I9 showed hydrogen generation of 95.54 μmol g−1. Platinum was used as bi-catalyst and obtained results for Cs3Sb2I9/Pt (2 mg) showed excellent hydrogen generation of 804.54 μmol g−1 with decent stability up to 50 h.

Anisotropic excitonic absorption in SbI3 films: Theory and experiment

Structurally characterized antimony triiodide films grown by vacuum thermal evaporation exhibit anisotropic exciton formation at room temperature for different (hkl) oriented growth. Band structure of monoclinic SbI3 was calculated using Density functional Theory with appropriate functional along with the absorption spectra of different (hkl) planes for comparing with the experimental results. The indirect band gap of 2.8 eV determined by measured absorption spectra matches closely with the calculated 2.66 eV. All (hkl) oriented films show one exciton at 3.56 eV which can be interpreted as direct type along D symmetry from the band structure. Similarly, the two excitons at 2.95 eV and 3.30 eV appearing for (130) oriented films can also be direct either at D or B symmetry. All three excitonic transitions are found to be from Iodine p states to Antimony p states.

Inorganic antimony-based rudorffite photo-responsive electrochemical capacitor utilizing non-aqueous polyvinylpyrrolidone polymer gel electrolyte for hybrid energy harvesting and storage applications

Herein, we report the fabrication and characterization of a copper-halide perovskite-based (CHP) photo-responsive electrochemical capacitor (EC). A chemically stable and optically viable lead-free inorganic copper antimony iodide (Cu3SbI6) rudorffite is used as the active bi-functional symmetric electrodes. Non-aqueous HAAP gel electrolyte is sandwiched between the Cu3SbI6 electrodes to obtain the CHP photo-responsive EC. The HAAP gel electrolyte is characterized by FTIR, linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). SEM is used to study the Cu3SbI6 electrodes. The CHP photo-responsive EC electrochemical energy storage performance is investigated by cyclic voltammetry (CV) and EIS, under dark and illuminated conditions. A capacitance augmentation of 462 % is achieved for the CHP photo-responsive EC, under illuminated condition, Maximum energy density and power density of 9.98 μWh/cm2, and 3.18 mW/cm2, respectively, are attained under illumination. The CHP photo-responsive EC exhibits excellent cyclic charge–discharge stability by retaining 93 % of its initial capacitance, after 10,000 cycles.

Pressure-driven structural and electronic transitions in a quasimolecular layered compound of antimony triiodide

High-pressure structural and electronic transitions of SbI3 under different hydrostatic environments were investigated using synchrotron X-ray diffraction, Raman spectroscopy, electrical conductivity and first-principles theoretical calculations.

Boosting efficiency above 28% using effective charge transport layer with Sr3SbI3 based novel inorganic perovskite.

Strontium antimony iodide (Sr3SbI3) is one of the emerging absorbers materials owing to its intriguing structural, electronic, and optical properties for efficient and cost-effective solar cell applications. A comprehensive investigation on the structural, optical, and electronic characterization of Sr3SbI3 and its subsequent applications in heterostructure solar cells have been studied theoretically. Initially, the optoelectronic parameters of the novel Sr3SbI3 absorber, and the possible electron transport layer (ETL) of tin sulfide (SnS2), zinc sulfide (ZnS), and indium sulfide (In2S3) including various interface layers were obtained by DFT study. Afterward, the photovoltaic (PV) performance of Sr3SbI3 absorber-based cell structures with SnS2, ZnS, and In2S3 as ETLs were systematically investigated at varying layer thickness, defect density bulk, doping density, interface density of active materials including working temperature, and thereby, optimized PV parameters were achieved using SCAPS-1D simulator. Additionally, the quantum efficiency (QE), current density-voltage (J-V), and generation and recombination rates of photocarriers were determined. The maximum power conversion efficiency (PCE) of 28.05% with JSC of 34.67 mA cm-2, FF of 87.31%, VOC of 0.93 V for SnS2 ETL was obtained with Al/FTO/SnS2/Sr3SbI3/Ni structure, while the PCE of 24.33%, and 18.40% in ZnS and In2S3 ETLs heterostructures, respectively. The findings of this study contribute to in-depth understanding of the physical, electronic, and optical properties of Sr3SbI3 absorber perovskite and SnS2, ZnS, and In2S3 ETLs. Additionally, it provides valuable insights into the potential of Sr3SbI3 in heterostructure perovskite solar cells (PSCs), paving the pathway for further experimental design of an efficient and stable PSC devices.

Синтез и строение комплексов сурьмы [n-C5H11PPh3]2[Sb2I8(acetone)2] и [Ph4P]3[Sb2I9]∙EtO(CH2)2OH

The interaction of antimony iodide with n-pentyltriphenylphosphonium iodide (1:1 mol.) in acetone and tetraphenylphosphonium iodide (3:2 mol.) in ethylene glycol monoethyl ether (ethyl cellosolve) has been used to synthesize ionic complexes [n-C5H11PPh3]2[Sb2I8(acetone)2] and [Ph4P]3[Sb2I9]∙EtO(CH2)2OH. According to the X-ray analysis data obtained on an automatic diffractometer D8 Quest Bruker (MoKa-radiation, λ = 0.71073 Å, graphite monochromator) at 293 K, of crystals 1 [C26H32OPI4Sb, M 1020.84, the triclinic syngony, the symmetry group Р-1; cell parameters: a = 10.573(4) Å, b = 13.303(5) Å, c = 13.569(5) Å, α = 117.749(16) degrees, β = 95.534(17) degrees, γ = 100.715(14) degrees; V = 1622.4(10) Å3; the crystal size is 0.32 × 0.22 × 0.13 mm; intervals of reflection indexes are -16 ≤ h ≤ 16, -20 ≤ k ≤ 20, -21 ≤ l ≤ 21; total reflections 98254; independent reflections 13003; Rint 0.0285; GOOF 1.037; R1 = 0.0438, wR2 = 0.0745; residual electron density 1.25/-2.06 e/Å3] and 2 [C76H70I9O2P3Sb2, M 2493.83, the triclinic syngony, the symmetry group Р–1; cell parameters: a = 10.881(7) Å, b = 16.549(7) Å, c = 25.287(12) Å, α = 109.03(2) degrees, β = 94.67(2) degrees, γ = 98.52(3) degrees; V = 4216(4) Å3; the crystal size is 0.37×0.11×0.07 mm; intervals of reflection indexes are -14 ≤ h ≤ 14, -22 ≤ k ≤ 22, -33 ≤ l ≤ 33; total reflections 146846; independent reflections 21003; Rint 0.0708; GOOF 1.014; R1 = 0.0763, wR2 = 0.0967; residual electron density 1.23/-1.06 e/Å3], the phosphorus atoms in cations have a slightly distorted tetrahedral coordination with the CPC bond angles 107.48(11)-111.52(11) and 106.5(3)-113.3(3) degrees and similar P–C bond lengths 1.795(3)–1.802(2) Å and 1.787(5)–1.809(6) Å in 1 and 2, respectively. In the centrosymmetric [Sb2I8(acetone)2]2– anion, the antimony atoms have a distorted octahedral coordination (trans-angles 171.476(9)–176.33(3) degrees, the acetone molecule occupies an axial position being coordinated by the oxygen atom (Sb∙∙∙O 2.820(10) Å). The Sb–Ib. bonds (3.0997(12) Å) are longer than Sb–Iterm: 2.7780(8)–2.9553(10) Å. In the [Sb2I9]3– anion trans-ISbI angles vary in the range 169.612(17)–173.426(19) degrees, Sb–Iterm. bonds 2.8613(13)–2.9609(12) Å are shorter than Sb–Ib: 3.0986(12)–3.2760(13) Å. Solvate ethyl cellosolve mole-cules form dimers via hydrogen bonds O(1)∙∙∙H(2A) 2.11 Å. Complete tables of coordinates of atoms, bond lengths and valence angles for structures 1 and 2 are deposited at the Cambridge Structural Data Bank (no. 1984511 (1), 2157456 (2); deposit@ccdc.cam.ac.uk; http: //www.ccdc.cam.ac.uk).

Theoretical and Experimental Study of Methyl Ammonium Antimony Iodide-Based Lead-Free Perovskite Solar Cells

Methyl ammonium antimony iodide (MA3Sb2I9) perovskite-like materials have gained enormous attention from the scientific community because of their excellent aerobic stability, good optical properties, and less-toxic nature. Herein, we report on the simulation of FTO/TiO2/MA3Sb2I9/spiro-OMeTAD via solar cell capacitance (SCAPS) software. The thickness of the absorber layer, hole-transport layer, or electron-transport layer may significantly impact the photovoltaic performance of the perovskite solar cells (PSCs). In this connection, the thickness of the absorber layer, hole-transport layer, or electron-transport layer was varied during the simulation process and the optimized PSCs demonstrated a good efficiency of 14.90% including an excellent open circuit voltage (Voc) of 1.41 V. Furthermore, we also fabricated MA3Sb2I9-based PSCs and their photovoltaic performance was evaluated. The fabricated PSCs showed a reasonably good efficiency of 1.27% and Voc of 0.51 V.

Establishing Family Relations in Group 15 Halogenido Metalates with the Largest Molecular Antimony Iodide Anion.

Studying structurally related families of compounds is a valuable tool in understanding and predicting material properties and has been extensively used for metal halide perovskites. Due to the variable anion structures in group 15 halogenido metalates, similar family relations are still largely missing. Herein, we present compounds featuring the [Sb2n I6n+4 ]4- family of anions, including the first n=5 member in [Hpyz]4 [Sb10 I34 ] (Hpyz=pyrazinium), which contains the largest halogenido pentelate anion reported to date. The optical properties of compounds featuring n=1-5 anions show a clear trend as well as an outlier, a low band gap of 1.72 eV for [Hpyz]4 [Sb10 I34 ], that can be well understood using quantum chemical investigations. Also using SbI3 and [H2 NMe2 ]3 [SbI6 ], a compound featuring a single octahedral [SbI6 ]3- unit, as limiting cases, we show that structure-property relationships can be established in group 15 halogenido metalates in a similar way as in metal halide perovskites, thus providing a framework for understanding new and known compounds in this emerging class of materials.

Perovskite Dimensional Evolution Through Cations Engineering to Tailor the Detection Limit in Hard X-ray Response.

Halide perovskites with various compositions are potential candidates in low-dosage X-ray detection due to their large sensitivity and tunable optoelectronic properties. Here, cations engineering induced dimensional evolution of halide perovskites between 0D, 2D, and 3D is reported. Centimeter-sized 2D lead-free perovskite single-crystal of 4-fluorophenethylammonium antimony iodide (FPEA3 SbI6 ) is synthesized. In contrast to the 0D phenethylammonium antimony iodide (PEA3 Sb2 I9 ), face-shared [Sb2 I9 ]3- of the bi-octahedral structure of PEA3 Sb2 I9 is split into corner-shared [SbI6 ]3- by intermolecular interactions and steric hindrance of FPEA+ ions in 2D FPEA3 SbI6 . Two Sb3+ ions share three octahedral [SbI6 ]3- , leaving one-third of Sb3+ vacancies in the framework of FPEA3 SbI6 . Furthermore, Sn2+ ions can be filled into the vacancies to form continuous 2D frameworks to tune the anisotropic conductivity and device sensitivity to hard X-rays. The dimensional evolution of perovskite single-crystals from 3D to 2D or 0D to 2D maximizes the signal/noise ratio to facilize the adjustability of detection limit in hard X-ray detection, which is determined by both device sensitivity and device noise current. A record low detection limit coefficient of 0.65 is achieved in the 2D FPEA3 SbSn0.5 I7 single-crystal sample, which results from selective charges collection over mobile ions/noise current in the 2D perovskite structure.

Simulation and fabrication of all-inorganic antimony halide perovskite-like material based Pb-free perovskite solar cells

Recently, numerical simulation of lead (Pb)-free perovskite solar cells (LFPSCs) has attracted scientific community and received great attention. All-inorganic cesium antimony iodide (Cs3Sb2I9) which is perovskite-like material has been widely explored as light absorbing layer in the development of LFPSCs. In present work, we have reported the numerical simulation of LFPSCs with device architecture of FTO/TiO2/Cs3Sb2I9/spiro-OMeTAD/Au. The thickness of electron-transport layer (ETL), light absorber layer, and hole-transport layer (HTL) were optimized to achieve the highest efficiency. The optimized LFPSCs exhibited excellent efficiency of 12.54% using SCAPS-1D. Further, Cs3Sb2I9 films were obtained and their physiochemical and optical properties were examined by X-ray diffraction (XRD), scanning-electron spectroscopy (SEM), and ultraviolet–visible (UV–vis) absorption spectroscopy. Furthermore, LFPSCs device (FTO/TiO2/Cs3Sb2I9/spiro-OMeTAD/Au) was fabricated under controlled humidity (∼30–40%). The fabricated LFPSCs showed good efficiency of 1.07%.

XPS studies on silver ion conducting solid electrolyte SbI3-Ag2MoO4

The silver ion conducting solid electrolyte containing antimony triiodide and silver molybdate synthesized by rapid melt quenching method in different stoichiometric compositions exhibits a high ionic conductivity value of 4.1 × 10−3 S cm−1 in a particular stoichiometric composition (SbI3)0.3-(Ag2MoO4)0.7. Generally, High ionic conductivity values in silver ion conductors may be due to the formation of silver iodide, AgI. The reason for high conductivity values was analyzed in terms of structural changes in this synthesized compound. In the present study, the expected presence of Ag+ and I- ions with their due binding energy and orbital state in XPS spectra were analyzed. In this XPS investigation, the presence of Ag metal in 3d3/2 and 3d5/2 states with a binding energy value of 373.8 and 367.8 eV respectively were ascertained. Similarly, I2 is in a 3d orbital state with 3d3/2 and 3d5/2 states with a binding energy value of 631.3 and 619.8 eV respectively. Respective photoemission values of Ag and I2 were found to be 6.0 and 11.5 eV. These values are in very good agreement with reference values quoted in the literature.

Sn(IV) Inserted Lead‐Free Perovskite Materials (MA3(Bi1−xSnx)2I9) as Light Absorbers: Bandgap Engineering and Enhanced Photovoltaic Performance

Recently, methyl ammonium bismuth iodide (MA3Bi2I9) and methyl ammonium antimony iodide (MA3Sb2I9) perovskite structures have received enormous attention because of their good aerobic stability. In particular, MA3Bi2I9 perovskite‐like material is widely explored as a visible light absorber in the construction of lead‐free perovskite solar cells (LFPSCs) because of its nontoxic nature and optoelectronic properties. However, the wide bandgap (2.2 eV) of the MA3Bi2I9 perovskite‐like material is the major drawback, which may be responsible for poor light absorption and lower performance of the developed LFPSC devices. Thus, it is believed that the optical features of the MA3Bi2I9 perovskite may be tuned using bandgap engineering approach.

Photosensitive antimony triiodide thin films by rapid iodization of chemically deposited antimony sulfide

In this work, we report the synthesis of antimony triiodide (SbI3) thin films via a simple and facile process of iodizing chemically deposited antimony sulfide (Sb2S3) thin films. Density functional theory (DFT) calculations were employed to determine the electronic band structure of SbI3. The crystal structure, morphology, composition, and optoelectronic properties of SbI3 films formed at different conditions were investigated. The structural and morphological analyses revealed hexagonal SbI3 thin films with compact and granular surface morphology. EDS analysis showed a nearly stoichiometric composition of the SbI3 phase. The experimentally estimated direct bandgaps were in the range of 2.3−2.1 eV in correlation with the DFT calculations. Further, stable photodetector devices were fabricated using the SbI3 films. The devices displayed good reproducibility and a significant response to the visible light. This novel strategy for the synthesis opens a new opportunity for this metal iodide based optoelectronic and photovoltaic devices.

Formation of stable 2D methylammonium antimony iodide phase for lead-free perovskite-like solar cells**Dedicated to Dr Klaus Römer on the occasion of his 80th birthday.

The presence of lead in novel hybrid perovskite-based solar cells remains a significant issue regarding commercial applications. Therefore, antimony-based perovskite-like A3M2X9 structures are promising new candidates for low toxicity photovoltaic applications. So far, MA3Sb2I9 was reported to only crystallize in the ‘zero-dimensional’ (0D) dimer structure with wide indirect bandgap properties. However, the formation of the 2D layered polymorph is more suitable for solar cell applications due to its expected direct and narrow bandgap. Here, we demonstrate the first synthesis of phase pure 2D layered MA3Sb2I9, based on antimony acetate dissolved in alcoholic solvents. Using in situ XRD methods, we confirm the stability of the layered phase towards high temperature, but the exposure to 75% relative humidity for several hours leads to a rearrangement of the phase with partial formation of the 0D structure. We investigated the electronic band structure and confirmed experimentally the presence of a semi-direct bandgap at around 2.1 eV. Our work shows that careful control of nucleation via processing conditions can provide access to promising perovskite-like phases for photovoltaic applications.

Degradation Studies of Cs3Sb2I9: A Lead-Free Perovskite

Lead-free halide perovskites have attracted interest in the photovoltaic industry out of concern for the toxic nature of the lead. Antimony-based perovskite, cesium antimony iodide (Cs3Sb2I9), is o...

Synthesis, characterization and biological evaluation of novel antimony(III) iodide complexes with tetramethylthiourea and N-ethylthiourea

Novel trivalent antimony(III) complexes with tetramethylthiourea (TMTU) and N-ethylthiourea (NETU) were synthesized by the reaction of antimony(III) iodide (SbI3). Antimony(III) iodide complexes of formulae {[SbI2(µ2-I)(TMTU)2]2} (1) and {[(NETU)SbI2(µ2-I)2(µ2-S-NETU)SbI2(NETU)]} (2) were characterized by spectroscopic techniques (FT-IR, FT-Raman, 1H and 13C NMR), TG-DTA analysis and X-ray diffraction (XRD) analysis. Single-crystal X-ray diffraction studies showed that the complexes existed as doubly bridged (1) and triply bridged (2) dimers. Crystal structure of the ligand N-ethylthiourea was also determined with single crystal X-ray diffraction analysis.Complexes 1 and 2 were evaluated for their in vitro cytotoxic activity against human adenocarcinoma cells HeLa (cervix). The toxicity of 1 and 2 was evaluated on normal human fetal lung fibroblast cells (MRC-5). Both complexes showed selectivity against the cancerous, than normal cells. The influence of 1 and 2, on the catalytic peroxidation of the linoleic acid by the enzyme lipoxygenase (LOX) was determined experimentally and theoretically. The complexes 1 and 2 exhibited higher activity than free ligands against LOX. The in vitro antibacterial activities of free ligands and their antimony(III) iodide complexes 1 and 2 were tested against two Gram-negative (Escherichia coli ATCC 25922, Pseudomonas aeruginosa ATCC 27853) and two Gram-positive (Staphylococcus aureus ATCC 25923, Enterococcus faecalis ATCC 29212) bacteria. The complexes 1 and 2 were much more effective in terms of antimicrobial activity compared to the free ligands.