SbBr3 Research Articles

Blue-Light-Excitable Red-Emitting Organic Antimony Halides as a Reversible Humidity Sensor.

Zero-dimensional organic antimony halides have attracted significant attention recently due to their structural variety, tunable optical properties, and high luminescence efficiency. Here, a new series of antimony bromide hybrid structures with seesaw [SbBr4] and pyramidal [SbBr5] geometries are reported with low band gaps and blue-light excited red emissions. Their luminescence is attributed to self-trapped excitons with a broadband emission of a large Stokes shift. Their photoluminescence signal is sensitive to water molecules, with a reversible positive correlation in a relative humidity range of 30-90%, enabling them as potential materials for real-time, self-consistent humidity sensors.

Solvent-Induced Bright Emission in Lead-Free Organic-Inorganic Antimony Bromides with Reversible Transformation.

Lead-free low-dimensional organic-inorganic metal halides have gained increasing attention in a wide range of applications due to their low toxicity, outstanding optical performance, and structural tunability. In this work, a general method of incorporating organic molecule into sodium antimony bromides is introduced. The 1D Na3SbBr6(C2H6OS)6 and Na3SbBr6(C4H8OS)6 single crystals exhibit bright yellow and orange emission with PL peaks at 610 and 664nm, and high photoluminescence quantum yields (PLQYs) of 85% and 60%, respectively. These two compounds can be reversibly converted into each other by the removal and addition of the organic components. Their exceptional luminescent performance enables them to be used as solid-state phosphors for the fabrication of yellow and orange down-conversion LEDs. A white LED with a high color rendering index (CRI) of 95 is also fabricated by using Na3SbBr6(C2H6OS)6 as the yellow phosphor. The universality of this method is demonstrated by synthesizing other members of this family with diverse A-groups, including methylammonium (MA) and formamidinium (FA). This work provides an effective strategy for the development of diverse lead-free and high-performance organic-inorganic hybrid materials and indicates these organic-inorganic hybrid compounds are promising luminescent materials for lighting or displays.

Discovery of eight-coordinated layered phase of SbBr3 under high pressure

Layered trihalides have attracted significant interest due to their potential applications in optical and spintronic devices. Herein, we report a combined experimental and theoretical investigation of antimony tribromide (SbBr3) under high pressure (up to 30 GPa) using synchrotron x-ray diffraction, Raman spectroscopy, alternating current (AC) impedance measurements, and first-principles calculations. The results indicate that SbBr3 transforms from a molecular phase (space group Pbnm) to an eight-coordinated layered phase (space group P21/a) at 7.6 GPa. A partial density of states analysis reveals that the eight-coordinated layered geometry of SbBr3 is rooted in the electron transfer from the Sb p orbital to the Br p orbital. Furthermore, based on AC impedance measurements, the resistance decreases with increasing pressure due to the gradual narrowing of the bandgap of SbBr3 in the Pbnm phase. The positive resistance–pressure relationship in the P21/a phase is attributed to the low carrier mobility caused by lattice distortion. Our current findings not only provide information on the phase diagram and electronic transport of SbBr3 but also expand the realm of layered functional materials in molecular trihalides.

Improved photoluminescence stability and defect passivation in SbBr3 post-treated CsPbBr3 quantum dots under ambient conditions.

Inorganic cesium lead halide perovskites have evoked wide popularity because of their excellent optoelectronic properties, high photoluminescence (PL) quantum yield (PLQY), and narrowband emission. Here, cesium lead bromide (CsPbBr3 ) quantum dots (QDs) were synthesized via the ligand-assisted re-precipitation method. Post-synthesis treatment of CsPbBr3 QDs using antimony tribromide improved the PL stability and optoelectronic properties of the QDs. In addition, the PLQY of the post-treated sample was enhanced to 91% via post-treatment, and the luminescence observed was maintained for 8 days. The post-synthesis treatment ensured defect passivation and improved the stability of CsPbBr3 perovskite QDs. High-resolution transmission electron microscopy revealed the presence of more ordered, uniform-sized CsPbBr3 QDs after post-synthesis treatment, and the uniformity of the sample improved as the day passed. The formation of a mixed crystal phase was observed from X-ray diffraction in both as-synthesized, as well as post-treated QDs samples with the possibility of a polycrystalline nature in the post-treated CsPbBr3 QDs as per the selected area electron diffraction pattern. The X-ray photoelectron spectroscopy spectra confirmed the presence of antimony and the possibility of defect passivation in the post-treated samples. These QDs can act as potential candidates in various optoelectronic applications such as photodetectors and light-emitting diodes due to their high PLQY and longer lifetime.

Volume contractible Antimony bromide electrode as negative electrode for long-lasting Li-ion batteries

Antimony is one of the promising anode materials for lithium-ion batteries due to its high volumetric and gravimetric capacity (theoretical specific capacity 660 mAh g-1) and stable voltage window (0.87-0.91V vs Li/Li+). However, a high-volume expansion ( ∼130%) of Sb on lithiation degrades the electrochemical performance and restricts its application. In this work, a novel strategy is explored to use antimony halide (SbBr3) instead of Sb as the starting anode material. In the first step, Li will react with SbBr3 to form LiBr and pure Sb, leading to a 78% contraction in volume, and then this pure Sb further lithiates to form Li3Sb expanding the volume (of the lithiated Sb by 130%). LiBr, which is a byproduct of the first reaction, dissolves into the solvent, leaving a porous Sb. In a nutshell, the two-step lithiation process results in a net volume-contacted porous antimony, ideal as an electrode to counter volumetric stress in subsequent charge-discharge cycles. The electrochemical performance of this electrode is much superior when compared with the pure antimony electrode, taking advantage of initial volume reduction and porous scaffold. It achieves a high specific discharge capacity of 345 mAh g-1 at a rate of 100mAg-1 even after the end of the 100th cycle and losing only 20% of its capacity. This shows that this volume contractible technique can be successfully employed for metals and metallic alloys having drastically higher Li-storing capacities than graphite.

Antimony Bromide Organic-Inorganic Hybrid Compound with a Long-Chain Diamine Showing Switchable Phase Transition and Second-Harmonic Generation Properties.

Organic-inorganic hybrid metal halides have attracted significant attention in recent years due to their excellent optoelectronic properties and potential applications in solar cells. Herein, the organic-inorganic hybrid molecule [N,N-dimethyl-1,3-propanediamine]SbBr5 (1) was synthesized by reacting a long-chain organic diamine N,N-dimethyl-1,3-propanediamine with SbBr3 as a metal halide precursor in HBr aqueous solution. Compound 1 possesses a one-dimensional chainlike structure with the second-harmonic generation switch and two continuous phase transitions above room temperature. The band gap of compound 1 is about 2.62 eV, exhibiting a semiconductive property, which may have important implications for the development of new optoelectronic devices.

Perovskite quantum‐dots glasses with excellent stability and optical properties for laser projection

AbstractDue to the instability of perovskite quantum‐dots (PQDs), their applications in optoelectronic devices, in reality, are limited. In this paper, Cs(Pb,Sb)Br3 PQDs@glasses were successfully prepared by traditional melting quenching and heat treatment methods. The optical characterization shows that Cs(Pb0.7Sb0.3)Br3 PQDs@glasses has an emission peak of 518 nm and a full width at half maximum of 20 nm, and the photoluminescence quantum yield (PLQY) is 58%. The electronic structure of Cs(Pb0.875Sb0.125)Br3 has been studied by first principles. The stable range of chemical potential of each element in CsPbBr3 is calculated by first principles. It is proved that CsPbBr3 is an excellent PQDs luminescent material. The thermal analysis and temperature‐dependent photoluminescence spectra prove the stability of the PQDs@glass within 200°. The thermal distribution of the sample under laser irradiation is measured by a finite element method. In addition, Cs(Pb,Sb)Br3 PQDs@glasses are combined with AlN‐(Ca,Eu)AlSiN3 ceramic phosphors to prepare phosphor wheels, which shows that these materials have potential application prospects in the field of display.

Efficient Red Light Emitting Diodes Based on a Zero-Dimensional Organic Antimony Halide Hybrid.

Zero-dimensional (0D) organic metal halide hybrids (OMHHs) have recently emerged as a new class of light emitting materials with exceptional color tunability. While near-unity photoluminescence quantum efficiencies (PLQEs) are routinely obtained for a large number of 0D OMHHs, it remains challenging to apply them as emitter for electrically driven light emitting diodes (LEDs), largely due to the low conductivity of wide bandgap organic cations. Here, the development of a new OMHH, triphenyl(9-phenyl-9H-carbazol-3-yl) phosphonium antimony bromide (TPPcarzSbBr4 ), as emitter for efficient LEDs, which consists of semiconducting organic cations (TPPcarz+ ) and light emitting antimony bromide anions (Sb2 Br8 2- ), is reported. By replacing one of the phenyl groups in a well-known tetraphenylphosphonium cation (TPP+ ) with an electroactive phenylcarbazole group, a semiconducting TPPcarz+ cation is developed for the preparation of red emitting 0D TPPcarzSbBr4 single crystals with a high PLQE of 93.8%. With solution processed TPPcarzSbBr4 thin films (PLQE of 86.1%) as light emitting layer, red LEDs are fabricated to exhibit an external quantum efficiency (EQE) of 5.12%, a peak luminance of 5957cd m-2 , and a current efficiency of 14.2cd A-1 , which are the best values reported to date for electroluminescence devices based on 0D OMHHs.

Synthetic-Method-Dependent Antimony Bromides and Their Photoluminescent Properties.

Recently, excellent optical properties of low-dimensional organic-inorganic metal halides, stemming from their tunable structure and optoelectronic properties, have been demonstrated. The synthetic method is critical because it is highly related to the structure and properties of the halide. Herein, we obtain two different antimony bromides, (Bmpip)2SbBr5 and (Bmpip)3Sb2Br9, which both possess the P21/c space group having different crystal structures, and this confirms the important influence of synthesis on the single-crystal structure. (Bmpip)2SbBr5 contains Bmpip+ and [SbBr5]2- pyramids, and (Bmpip)3Sb2Br9 consists of Bmpip+ and Sb-based dimers [Sb2Br9]3-. Under 400 nm excitation, (Bmpip)2SbBr5 exhibits a 640 nm orange emission with a quantum yield of ∼11.5% owing to Sb 5s2 electron luminescence. A diode was fabricated by (Bmpip)2SbBr5 and commercial phosphors and showed a high color render index of 92. Our work reveals the effect of the preparation method on the crystal structure. A luminescent material was finally identified.

Efficiency enhancement of triple absorber layer perovskite solar cells with the best materials for electron and hole transport layers: numerical study

In this paper, a novel perovskite solar cell (PSC) with a triple absorber layer is numerically simulated using Solar Cell Capacitance One-Dimensional software. The initial simulation of the structure (FTO/TiO2/CsSnI3/CsSnGeI3/Cs3Sb2Br9/spiro-OMeTAD/Au) reveals that by combining cesium tin triiodide (CsSnI3), cesium tin-germanium triiodide (CsSnGeI3) and cesium antimony bromide (Cs3Sb2Br9) as triple absorber layer, we obtain a higher efficiency (31.81%) than the single (CsSnI3), and double (CsSnI3/CsSnGeI3) layer structures, whose efficiencies are 12.87% and 29.41%, respectively. Then, to optimize the proposed structure, different parameters like; thicknesses of the triple absorber layer, different materials of electron transport layer (ETL) and hole transport layer (HTL), thicknesses of ETL and HTL, as well as the operating temperature have been investigated. The optimized structure (0.4/0.1/0.1 µm of CsSnI3/CsSnGeI3/Cs3Sb2Br9 as triple absorber layer; 0.1 µm of tungsten trioxide WO3 as ETL and 0.35 µm of copper(I) oxide Cu2O as HTL, as well as an optimum temperature of 300 K) shows a remarkable photovoltaic parameters i.e. J SC = 32.640 774 mA cm−2, V OC= 1.2442 V, FF = 89.17% and η = 36.21% (which corresponds to an improvement of 4.4% compared to the initial proposed structure (31.81%)). This study’s simulation results open a better route toward fabricating highly efficient PSCs.

Enhanced Photoluminescence Quantum Yield, Lifetime, and Photodetector Responsivity of CsPbBr3 Quantum Dots via Antimony Tribromide Post-Treatment

Enhanced Photoluminescence Quantum Yield, Lifetime, and Photodetector Responsivity of CsPbBr₃ Quantum Dots via Antimony Tribromide Post-Treatment

Arylantimony Derivatives of Three-Coordinated Carbon

New ionic antimony complexes with a three-coordinated carbon atom in their cations, namely, [(Ph4SbO)3C]+[OSO2C6H3(NO2)2-2,4]– ⋅ 3PhH (32%) and [(p-Tol4SbO)3C]+Br– (traces), have been isolated when the products of reactions between pentaphenylantimony and 2,4-dinitrobenzenesulfonic acid and between penta(p-tolyl)antimony and hydrobromic acid were crystallized from a benzene–octane mixture in air along with the target products, such as tetraphenylantimony 2,4-dinitrobenzenesulfonate and tetra(p-tolyl)antimony bromide. The cations have nearly planar СO3Sb3 cores. The ОСО and COSb angles are close to 120°, whereas the C–O bonds vary within 1.277(4)–1.290(3) A, and the Sb–O distances (2.266(2)–2.299(2) A) exceed the sum of the covalent radii of antimony and oxygen atoms. It has been experimentally established that these complexes are formed as a result of interactions between the target products of the above-mentioned reactions with bis(tetraarylantimony) carbonates, which are also formed under the conditions of these reactions from pentaarylantimony and atmospheric carbon dioxide.

Synthesis, Characterization, Thermal Analysis, Nucleation Kinetics and DFT Studies of Bis(thiourea) Antimony Tribromide as Potential NLO Material: Comparison of Experimental and Computational Studies

Semi organic non linear optical single crystals of bis (thiourea) antimony tribromide (BTAB) have been grown and harvested using slow solvent evaporation technique. The single crystal X-ray diffraction analysis indicated the orthorhombic and non centrosymmetric nature of the title compound. The powder XRD and High resolution XRD patterns pronounced the crystalline nature of the BTAB sample. The laser damage threshold (LDT) value of BTAB has been determined as 3.98 GW/cm2 from LDT analysis. The values of thermodynamic parameters like energy of activation, frequency factor, enthalpy change, entropy change and Gibbs free energy change have been calculated from Coats–Redfern model of thermal analysis. Computational studies have been carried out using the Density functional theory (DFT) and the values of hyper polarizability, dipole moment and polarizability of BTAB have been deduced. In order to comprehend the nature of charge distributions and donor–acceptor interactions prevailing in BTAB crystal, Natural bond analysis (NBO) has been carried out. The frontier orbital HOMO–LUMO approach has been employed to arrive at the values of the global chemical molecular reactivity descriptors.

Growth and Characterization of Bis(thiourea) Antimony Tribromide: A Reliable Non-Linear Optical Crystal

Bis(thiourea) antimony tribromide (BTAB) single crystals of semi organic non-linear optical (NLO) crystal category have been effectively grown and harvested by the technique of slow solvent evaporation. The important nucleation kinetic parameter values have been deduced for the title crystal and the agreement between the experimental and theoretical values of interfacial surface energy has been established. The orthorhombic structure and Cmc21 space group have been identified with the aid of single crystal X-ray diffraction studies. To validate the stoichiometry and the purity of the crystals, elemental analysis has been carried out. The UV transmittance spectrum has been employed to deduce the significant optical constant and oscillator parameter values. In the region of absorption edge, Urbach tail energy has been determined to ascertain the crystalline perfection of BTAB. The etching studies inferred the step growth pattern of the crystal. The phase matchable SHG efficiency of BTAB has been tested by Kurtz–Perry technique. The negative photoconductivity and low birefringence values have been revealed by photoconductivity study and birefringence study respectively. Dielectric and ac conductivity studies have helped in calculating the activation energy values of the electrical process. Important solid state parameters such as valence electron plasma energy, Penn gap, Fermi energy and polarisability have been calculated for the BTAB crystal. To assess the mechanical stability of the crystal Vicker’s micro hardness analysis has been performed and important mechanical parameters have been elucidated.

High refractive index immersion liquid for superresolution 3D imaging using sapphire-based aplanatic numerical aperture increasing lens optics.

Optically transparent immersion liquids with refractive index (n∼1.77) to match the sapphire-based aplanatic numerical aperture increasing lens (aNAIL) are necessary for achieving deep 3D imaging with high spatial resolution. We report that antimony tribromide (SbBr3) salt dissolved in liquid diiodomethane (CH2I2) provides a new high refractive index immersion liquid for optics applications. The refractive index is tunable from n=1.74 (pure) to n=1.873 (saturated), by adjusting either salt concentration or temperature; this allows it to match (or even exceed) the refractive index of sapphire. Importantly, the solution gives excellent light transmittance in the ultraviolet to near-infrared range, an improvement over commercially available immersion liquids. This refractive-index-matched immersion liquid formulation has enabled us to develop a sapphire-based aNAIL objective that has both high numerical aperture (NA=1.17) and long working distance (WD=12 mm). This opens up new possibilities for deep 3D imaging with high spatial resolution.

Synthesis, growth and characterization of semi-organic nonlinear optical bis thiourea antimony tri bromide (BTAB) single crystals

A novel nonlinear optical metal-organic, Bis thiourea antimony tri bromide (BTAB) single crystal was grown from aqueous solution by slow cooling technique. The grown crystals have been characterized by different techniques to study the structural, thermal, mechanical, linear and nonlinear optical properties. The powder SHG efficiency was found to be 2.5 times higher than that of the KDP crystal. BTAB is a biaxial and optically positive crystal. The birefringence value of BTAB crystal was found to be 0.112 at the wavelength of 550 nm for a sample thickness of 0.11 mm.The BTAB crystal has refractive indices values of n α =1.539, n β =1.559 and n γ =1.967. BTAB crystallizes in orthorhombic system and the complex formation is established by metal–sulfur bond. BTAB has good optical transmission in the entire visible region, so that it is found to be potential material for nonlinear frequency conversion.

Thermal decomposition study of antimony (III) tribromide and aromatic amine adducts

Solid adducts, SbBr3 � L( L= pyridine, 2-, 3- and 4-methylpyridine; abbreviated as Py, 2MPy, 3MPy and 4MPy) were synthesized and characterized by elemental analysis and IR spectroscopy. According to the results coordination of nitrogen of aromatic ring with antimony atom was supposed. Kinetic studies were accomplished by using thermogravimetric data obtained through non-iso- thermal technique. Determination of activation energy and pre-exponential factor was based on the Coats-Redfern integral Ozawa-Flynn-Wall model-free methods. The kinetics parameters Ea, and log A determined at 5 K min -1 were 150.6 kJ mol -1 , 16.0 and 122.0 kJ mol -1 , 12.4 for SbBr3 � Py and SbBr3 � 4MPy, respectively.

Production of oil with low organobromine content from the pyrolysis of flame retarded HIPS and ABS plastics

Pyrolysis of flame retarded plastics often leads to high concentrations of toxic organobromine compounds in the pyrolysis oil. In this work, we have investigated the pyrolysis of flame retarded high impact polystyrene (HIPS) and acrylonitrile–butadiene–styrene (ABS) over long residence times in a tube reactor with the aim of producing an oil that is free from organobromines. The tube reactor was fitted with a distillation column so that the pyrolysis products could be separated into heavy oil, middle distillate, light oil, and gases. The light pyrolysis products were characterised using GC–MS and GC-FID/ECD, while the total bromine content of the oils was determined by bomb calorimetery. The bromine content of heavy fractions and antimony content of all fractions of pyrolysis (light oil, middle distillates, heavy oil and char) was determined by inductively coupled plasma atomic adsorption spectroscopy (ICP-AAS). Heavy oil fractions were characterised using Fourier Transform-Infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy disperse X-ray analysis (EDAX), and gel permeation chromatography (GPC) techniques. It was found that the light oil produced by the pyrolysis of both flame retarded HIPS and flame retarded ABS mostly consisted of toluene, ethylbenzene, and cumene and had a relatively low bromine content, all of which was inorganic. The middle distillate oils produced by the same plastics had much higher bromine content, but the vast majority of the bromine was inorganic in the form of antimony bromide. The average molecular weights of heavy fractions were affected by the cracking temperature, while the structure of the mentioned fractions did not change considerably with temperature. Light oil fractions had very low amount of contaminants (bromine and antimony), while heavy oils contained them in enormous concentrations.

Effect of decabromodiphenyl ether and antimony trioxide on controlled pyrolysis of high-impact polystyrene mixed with polyolefins

The controlled pyrolysis of polyethylene/polypropylene/polystyrene mixed with brominated high-impact polystyrene containing decabromodiphenyl ether as a brominated flame-retardant with antimony trioxide as a synergist was performed. The effect of decabromodiphenyl ether and antimony trioxide on the formation of its congeners and their effect on distribution of pyrolysis products were investigated. The controlled pyrolysis significantly affected the decomposition behavior and the formation of products. Analysis with gas chromatograph with electron capture detector confirmed that the bromine content was rich in step 1 (oil 1) liquid products leaving less bromine content in the step 2 (oil 2) liquid products. In the presence of antimony containing samples, the major portion of bromine was observed in the form of antimony bromide and no flame-retardant species were found in oil 1. In the presence of synergist, the step 1 and step 2 oils contain both light and heavy compounds. In the absence of synergist, the heavy compounds in step 1 oil and light compounds in step 2 oils were observed. The presence of antimony bromide was confirmed in the step 1 oils but not in step 2 oils.

Removal of organobromine compounds from the pyrolysis oils of flame retarded plastics using zeolite catalysts

Two flame retarded plastics have been pyrolysed in the presence of two zeolite catalysts to remove the organobromine compounds from the derived pyrolysis oil. The flame retarded plastics were, acrylonitrile–butadiene–styrene (ABS) that was flame retarded with tetrabromobisphenol A and high impact polystyrene (HIPS) that was flame retarded with decabromodiphenyl ether. The two catalysts investigated were zeolite ZSM-5 and zeolite Y-Zeolite. Pyrolysis was carried out in a fixed bed reactor at a final pyrolysis temperature of 440 °C. The pyrolysis gases were passed immediately to a fixed bed of the catalyst. It was found that the presence of zeolite catalysts increased the amount of gaseous hydrocarbons produced during pyrolysis but decreased the amount of pyrolysis oil produced. In addition, significant quantities of coke were formed on the surface of the catalysts during pyrolysis. The zeolite catalysts were found to reduce the formation of some valuable pyrolysis products such as styrene and cumene, but other products such as naphthalene were formed instead. The zeolite catalysts, especially Y-Zeolite, were found to be very effective at removing volatile organobromine compounds. However, they were less effective at removing antimony bromide from the volatile pyrolysis products, although some antimony bromide was found on the surfaces of the spent catalysts.