Non-stoichiometric Composition Research Articles

Development of pyrargyrite Ag3SbS3 absorber films through sulfurization of Ag–Sb stacks for thin-film photovoltaics

Pyrargyrite Ag3SbS3, which consists of naturally abundant and non-toxic elements, has attracted attention as a promising solar cell material. A two-stage fabrication method has been developed to synthesize Ag3SbS3 thin films through a solid-state reaction between Sb and Ag metallic layers by sulfurizing at 250–350 oC. The Ag3SbS3 film prepared at a sulfurization temperature of 250 °C contained Ag2S and Sb2S3 secondary phases with non-stoichiometric composition, distinct grain growth, a bandgap energy of 1.4 eV, and an electrical resistivity of 5.74 × 10−4 Ω cm. Through sulfurization of the stacks at 300 °C, the Ag2S and Sb2S3 secondary phases disappeared, and dominant Ag3SbS3 films were obtained with a minor AgSbS2 secondary phase. A compact and uniform near-stoichiometric Ag3SbS3 composition with large grains was obtained with an increased bandgap energy of 1.64 eV and electrical resistivity of 6.19 × 104 Ω cm. A further increase in the sulfurization temperature to 350 °C resulted in an increase in the crystallite and grain sizes of Ag3SbS3 with a decreased bandgap energy of 1.62 eV and electrical resistivity of 2.90 × 104 Ω cm. AgSbS2 remained as a minor secondary phase in this film. Thin-film solar cells prepared with the Ag3SbS3 absorber synthesized at a sulfurization temperature of 300 °C exhibited an open-circuit voltage of 473.85 mV, short-circuit current density of 1.47 mA/cm2, fill factor of 41.6 %, and an efficiency of 0.3 %. These results demonstrate that Ag3SbS3 is a potential candidate for thin-film solar cells.

Electrochemical properties of B-site non-stoichiometric layered perovskite SmBa0.5Sr0.5CoxO5+d (x=1.9–2.1) cathodes for IT-SOFC

In this study, layered perovskites were synthesized using a non-stoichiometric synthesis strategy that allowed the variation of the amount of Co substitution in the basic composition of SmBa0.5Sr0.5Co2O5+d (SBSCO), used as a cathode material for Intermediate Temperature-operating Solid Oxide Fuel Cells (IT-SOFCs).SmBa0.5Sr0.5CoxO5+d (x = 1.9–2.1, SBSCO-1.9–2.1), B-site non-stoichiometric layered perovskites, were analyzed to characterize the electrical and electrochemical properties with respect to the Co substitution. Among them, SmBa0.5Sr0.5Co2.05O5+d (SBSCO-2.05) exhibited the best electrical and electrochemical properties with an ASR of 0.082 Ωcm2 and an electrical conductivity of 268.42 S/cm at 700 °C (measured in air within a series of measurements of increasing measuring temperature). Therefore, B-site non-stoichiometric perovskite compositions with increased Co substitution on their B sites represent a key strategy for achieving high performance cathodes compared to cathodes with stoichiometric compositions.

Signatures of nearly compensated magnetism and spin glass behavior in highly frustrated β-Mn-type Mn50Fe25+xAl25-x Heusler alloys.

The present study examines the effect of Fe/Al concentration on the structural and magnetic properties of Mn-rich Mn50Fe25+xAl25-x (x = 5, 10, 15) Heusler alloys through x-ray diffraction, temperature- and field-dependent DC magnetization, thermoremanent magnetization, magnetic memory effect, AC susceptibility measurements, and DFT calculations. The samples crystallize in a cubic β-Mn structure. The trend shows a reduction in lattice parameters (unit cell volume) with the increasing Fe proportion. These alloys exhibit strong antiferromagnetic interactions with large frustration parameters, indicating the presence of competing magnetic interactions. The DC magnetization data reveal spin glass-like features with a peak at spin glass freezing temperature (Tf). The observation of bifurcation in temperature-dependent zero-field-cooled and field-cooled magnetization curves, exponential dependence of the temperature variation of remanence and coercivity, magnetic relaxation, and magnetic memory effect below Tf support the spin-glass character of these alloys. The frequency dependence of Tf is also examined in the context of dynamic scaling laws, such as the Vogel-Fulcher law and critical slowing down model, which further supports the presence of spin glass behavior. In the theoretical DFT calculations, the electronic structure is found to be metallic and similar for both spin projections. Moreover, the antiferromagnetic arrangement of the magnetic moments, in line with the experimental observations, is stabilized by exchange interactions, resulting in an almost compensated total magnetic moment of 0.02-0.38µB/f.u. This is probably caused by the frustrated structure and non-stoichiometric compositions of Mn50Fe25+xAl25-x.

Unlocking the potential of Cu3SbSe3: Ultralow thermal conductivity and enhanced thermoelectric performance

Cu3SbSe3, with its ultralow thermal conductivity and Earth-abundant elements, has emerged as a promising thermoelectric material. However, synthesizing its pure phase and achieving effective doping have proven to be challenging. In this study, we present our findings on the investigation of thermoelectric properties of stoichiometric and off-stoichiometric Cu3SbSe3 compositions along with various doping strategies. Our results demonstrate that samples with non-stoichiometric compositions and Bi doping further reduces the lattice thermal conductivity of 0.16 W/mK. The consistently moderate Seebeck coefficient leads to a zT value of 0.25 at 650 K across all cation-deficient samples. Furthermore, we observed that 5% Bi doping further enhances the zT value to 0.35, representing a 52% improvement over pristine Cu3SbSe3. We believe that the compositional insensitivity of zT and the enhanced performance achieved through Bi doping offer new opportunities for exploring materials with ultra-low thermal conductivity in the field of thermoelectrics.

A review on ultra‐small undoped MoS2 as advanced catalysts for renewable fuel production

AbstractMolybdenum disulfide (MoS2) has garnered significant attention in the field of catalysis due to the high density of active sites in its unique two‐dimensional (2D) structure, which could be developed into numerous high‐performance catalysts. The synthesis of ultra‐small MoS2 particles (<10 nm) is highly desired in various experimental studies. The ultra‐small structure could often lead to a distinct S–Mo coordination state and nonstoichiometric composition in MoSx, minimizing in‐plane active sites of the 2D structure and making it probable to regulate the atomic and electronic structure of its intrinsic active sites on a large extent, especially in MoSx clusters. This article summarizes the recent progress of catalysis over ultra‐small undoped MoS2 particles for renewable fuel production. Through a systematic review of their synthesis, structural, and spectral characteristics, as well as the relationship between their catalytic performance and inherent defects, we aim to provide insights into catalysis over this matrix that may potentially enable advancement in the development of high‐performance MoS2‐based catalysts for sustainable energy generation in the future.

SurfFlow: High-throughput surface energy calculations for arbitrary crystals

We introduce SurfFlow, an open-source high-throughput workflow package designed for automated first-principles calculations of surface energies in arbitrary crystals. Our package offers a comprehensive solution capable of handling multi-element crystals, nonstoichiometric compositions, and asymmetric slabs, for all potential terminations. To streamline the computational process, SurfFlow employs an efficient pre-screening method that discards surfaces with suspected high surface energy before conducting resource-intensive density functional theory computations. The results generated are seamlessly compiled into an optimade-compliant database, ensuring easy access and compatibility. Additionally, a user-friendly web interface facilitates workflow submission and management, provides result visualization, and enables the examination of Wulff shapes. SurfFlow represents a valuable tool for researchers looking to explore surface energies and their implications in a diverse range of systems.

Pd-Bi-Based Catalysts for Selective Oxidation of Glucose into Gluconic Acid: The Role of Local Environment of Nanoparticles in Dependence of Their Composition

Palladium–bismuth nanomaterials are used in various chemical applications such detectors, electrodes, and catalysts. Pd-Bi catalysts are attracting widespread interest because these catalysts enable the production of valuable products quickly and efficiently, and are environmentally friendly. However, the composition of the catalyst can have a significant impact on its catalytic performance. In this work, we identified a correlation between the composition of the catalyst and its efficiency in converting glucose into sodium gluconate. It was found that the conversion decreases with increasing bismuth content. The most active catalyst was the 0.35Bi:Pd sample with a lower bismuth content (glucose conversion of 57%). TEM, SEM, EXAFS, and XANES methods were used to describe, in detail, the surface properties of the xBi:Pd/Al2O3 catalyst samples. The increase in particle size with increasing bismuth content, observed in the TEM micrographs, was associated with the low melting point of bismuth (271 °C). The SEM method showed that palladium and bismuth particles were uniformly distributed over the surface of the support in close proximity to each other, which allowed us to conclude that an alloy of non-stoichiometric composition was formed. The EXAFS and XANES methods established that bismuth was located on the surface of the nanoparticle predominantly in an oxidized state.

Large Electromechanical Response in a Polycrystalline Alkali-Deficient (K,Na)NbO3 Thin Film on Silicon.

The demand for large electromechanical performance in lead-free polycrystalline piezoelectric thin films is driven by the need for compact, high-performance microelectromechanical systems (MEMS) based devices operating at low voltages. Here we significantly enhance the electromechanical response in a polycrystalline lead-free oxide thin film by utilizing lattice-defect-induced structural inhomogeneities. Unlike prior observations in mismatched epitaxial films with limited low-frequency enhancements, we achieve large electromechanical strain in a polycrystalline (K,Na)NbO3 film integrated on silicon. This is achieved by inducing self-assembled Nb-rich planar faults with a nonstoichiometric composition. The film exhibits an effective piezoelectric coefficient of 565 pm V-1 at 1 kHz, surpassing those of lead-based counterparts. Notably, lattice defect growth is substrate-independent, and the large electromechanical response is extended to even higher frequencies in a polycrystalline film. Improved properties arise from unique lattice defect morphology and frequency-dependent relaxation behavior, offering a new route to remarkable electromechanical response in polycrystalline thin films.

Unraveling the Effect of Compositional Ratios on the Kesterite Thin-Film Solar Cells Using Machine Learning Techniques

In the Kesterite family, the Cu2ZnSn(S,Se)4 (CZTSSe) thin-film solar cells (TFSCs) have demonstrated the highest device efficiency with non-stoichiometric cation composition ratios. These composition ratios have a strong influence on the structural, optical, and electrical properties of the CZTSSe absorber layer. So, in this work, a machine learning (ML) approach is employed to evaluate effect composition ratio on the device parameters of CZTSSe TFSCs. In particular, the bi-metallic ratios like Cu/Sn, Zn/Sn, Cu/Zn, and overall Cu/(Zn+Sn) cation composition ratio are investigated. To achieve this, different machine learning algorithms, such as decision trees (DTs) and classification and regression trees (CARTs), are used. In addition, the output performance parameters of CZTSSe TFSCs are predicted by both continuous and categorical approaches. Artificial neural networks (ANN) and XGBoost (XGB) algorithms are employed for the continuous approach. On the other hand, support vector machine and k-nearest neighbor’s algorithms are also used for the categorical approach. Through the analysis, it is observed that the DT and CART algorithms provided a critical composition range well suited for the fabrication of highly efficient CZTSSe TFSCs, while the XGB and ANN showed better prediction accuracy among the tested algorithms. The present work offers valuable guidance towards the integration of the ML approach with experimental studies in the field of TFSCs.

Effects of intrinsic and extrinsic multi-phased lattice structure and chemical heterogeneity on the control of ferrimagnetic properties in Co rich spinel ferrite

The present work reports the structural and magnetic properties in spinel ferrite composition around Co2.25Fe0.75O4 as the function of self-composite structure (ratio of two spinel phase components), coexisting impurity phase of hematite, and non-stoichiometric chemical composition. The neutron diffraction patterns have been used to determine lattice structure and magnetic moment. The neutron depolarization experiments have indicated spin reorientation at lower temperature for the single phased sample. The magnetization measurements confirmed the blocking of magnetic domains, possible magnetic spin compensation and magnetic exchange bias effect. The sample coexisting with small hematite phase has shown the maximum coercivity (∼14.682 kOe), remanent magnetization (∼1.4657 μB) and saturation magnetization (∼2.027 μB) with small exchange bias shift (- 71 Oe) at 5 K. The single phased sample exhibited the lowest magnetic moment (∼0.3775 μB) with maximum exchange bias shift (- 543 Oe) and the highest cooling-field induced enhancement of coercivity (3691 Oe). The experiments confirmed a large scope of tuning the ferrimagnetic parameters by controlling the phase fraction and interfacial phases in Co rich spinel ferrite.

Carbonate-hosted manganese deposits and ocean anoxia

Late Devonian (ca. 360 Ma), Early Carboniferous (ca. 330 Ma), and Early Triassic (ca. 250 Ma) manganese deposits in the South China Block support an emerging view that some Mn carbonates form through direct synsedimentary (authigenic) precipitation. These Mn carbonates accumulated on distal shelves and are interbedded with lime mudstone and heterozoan carbonates that accumulated in coastal upwelling environments. Lithofacies, Ce anomalies combined with vanadium, uranium, and molybdenum enrichments indicate that the Mn carbonates were primarily precipitated under anoxic conditions. We provide a robust dataset to clarify the precipitation pathway of these Mn carbonates and explore the implications of using them as proxies of regional shallow water and deep-ocean anoxia. In the studied deposits, Mn calcite encases dolomite rhombs (<10 μm) or aggregates, indicating heterogenous nucleation, which is supported by similar lattice parameters of both minerals with a small lattice mismatch (<2.1%). The presence of micro-sized euhedral rhombs and subhedral aggregates of rhombs, the non-stoichiometric compositions, and characteristic organic matter Raman spectroscopy peaks near the D and G bands in the dolomite nuclei suggest an organogenic origin. Authigenic organogenic dolomite precipitation is interpreted to have preconditioned the sediment with nucleation sites for the subsequent precipitation of Mn carbonates in the shallow seafloor. This is consistent with δ13C values (−2.61‰) of Mn carbonate bulk samples that are slightly lower than coeval seawater (0.31‰, from host rocks), suggesting incorporation of 12C during microbial respiration of sedimentary organic matter during the precipitation of organogenic dolomite and hydrothermal sourced inorganic carbon. The absence of Mn in shallow facies suggests terrestrial input of Mn was minimal. Geochemical and sedimentologic evidence suggests that coastal upwelling delivered manganous anoxic deep waters to the shelves. Eu/Eu⁎ ratios (<1.5) and decoupling of Fe and Mn imply long-range transport of hydrothermal Mn, during which hydrothermal fingerprints were muted through mixing with ambient seawater. The transport of hydrothermal Mn to shelves indicates that the regional deep oceans at the time must have been anoxic, as Mn2+ would be easily oxidized and become insoluble under oxygen-rich conditions, preventing its long-distance transport. This precipitation pathway and depositional model implies that Mn carbonates are a largely unrecognized proxy for tracking ancient oceanic redox fluctuations, particularly during times of well-oxygenated global oceans. Hence, these Mn deposits record at least transient regional deep-ocean oxygen depletion in the generally well-oxygenated Late Paleozoic and Early Triassic oceans. The recognition that this periodic anoxia was broadly coeval with the anoxia-related Hangenberg, Serpukhovian, and Permian-Triassic biotic crises suggests a potential relationship between Mn carbonate accumulation and extinction events.

NMR spectroscopy study of the structure of hypromellose phthalate, a component of enteric coatings of medicinal products

Scientific relevance. Hypromellose phthalate is a component of enteric coatings used to modify active substance release from oral medicinal products in the small intestine. The release rate directly depends on the non-stoichiometric composition of the polymer, first of all, on the proportion of phthalate groups in the macromolecule. It is therefore necessary to develop reliable analytical procedures for determining the structure of hypromellose phthalate to evaluate the dissolution rate of medicinal products containing the polymer.Aim. The study aimed to develop an analytical procedure for quantifying the proportion of phthalate groups in hypromellose phthalate samples using NMR spectroscopy and to determine the relationship between the polymer dissolution rate in aqueous buffer solutions and its structural features (degree of molar substitution and molecular mass).Materials and methods. The study examined hypromellose phthalate samples isolated from enteric coatings of proton-pump inhibitors and used the reference standard for hypromellose phthalate. The non-stoichiometric composition of the polymer was determined by 13C NMR spectroscopy.Results. The authors established the conditions required to separate hypromellose phthalate from the other coating components and identified the characteristic 13C NMR signals that may be used to differentiate between the structural fragments of hypromellose phthalate. The study demonstrated the relationship between the dissolution rate and the structure of the polymer. Commercial grades of hypromellose phthalate were shown to differ in composition and, as a result, in their dissolution kinetics (in particular, the threshold pH for the onset of dissolution (5.0–5.5), as well as the dissolution rates at the same pH).Conclusions. The authors developed NMR-based procedures to determine the proportion of phthalate groups on the basis of their mass fraction in a weighted hypromellose phthalate sample and the degree of molar substitution of the polymer. The results support the applicability of these analytical procedures to the characterisation of sample composition in polymer dissolution rate studies. In principle, it is possible to derive a multiple linear regression equation that describes the dissolution rate of hypromellose phthalate as a function of the molecular mass and the molar substitution with phthalate groups. Further investigation of a larger number of polymer samples with different compositions is needed to improve the regression model and demonstrate its statistical significance. In addition to the proportion of phthalate groups, the pharmacopoeial analysis of hypromellose phthalate should also control the molecular mass of the polymer.

Response of nonstoichiometric pyrochlore composition Nd1.8Zr2.2O7.1 to electronic excitations

AbstractIn response of swift heavy ion (100 MeV I9+) irradiation, the irradiation‐induced disordering in nonstoichiometric pyrochlore composition (Nd1.8Zr2.2O7.1) was compared to that of stoichiometric composition Nd2Zr2O7. Both compositions were prepared through auto gel‐combustion followed by sintering under the identical conditions. Systematic analysis of the compositions before and after irradiation was performed with X‐ray diffraction (XRD), Raman spectroscopy, and plane‐view high‐resolution transmission electron microscopy (HRTEM) techniques. Irradiation caused pyrochlore to amorphous phase transformation was observed in both compositions except the slower rate of amorphization in Nd1.8Zr2.2O7.1. The amorphization was achieved as a consequence of isolated disordered track overlapping at higher ion fluence with the estimated track diameter 2.73 ± 0.05 and 3.46 ± 0.30 nm for Nd1.8Zr2.2O7.1 and Nd2Zr2O7, respectively, employing the framework of single‐ion impact model to XRD results. HRTEM micrographs also revealed the less prevalence of irradiation‐induced amorphization in Nd1.8Zr2.2O7.1 with the observed irradiation‐induced modified track region composed of defect‐rich pyrochlore structure, anion‐deficient fluorite structure, and amorphous domains; with the diameter of 3.0 ± 1.0 nm and 5.0 ± 1.0 nm in Nd1.8Zr2.2O7.1 and Nd2Zr2O7, respectively. The preexisting anion‐deficient fluorite structure in Nd1.8Zr2.2O7.1 helps in its epitaxial growth as recovered structure from melted ion track during irradiation‐induced rapid cooling.

Multicomponent Mixed Ionic and Electronic Conducting (MIEC) Air Electrodes and Their Heterointerface for Effective Application in Reversible Solid Oxide Cell (R-SOC): Efficacy of Stoichiometric and Off-Stoichiometric Compositions

Reversible solid oxide cell (R-SOC) has triggered research interest from the past few years for its reversible applicability for power-to-fuel (P2F) in electrolyser cell (SOEC) to generate hydrogen by splitting of high temperature steam and fuel-to-power (F2P) in fuel cell (SOFC) mode of operation to produce power by oxidation of fuel with >80% conversion efficiency [1]. Primarily, R-SOC consists of a dense electrolyte conventionally yttria stabilized zirconia (YSZ), bridged between two porous electrodes, e.g., strontium doped lanthanum manganite (LSM) as air electrode and Nickel (Ni)-YSZ cermet as fuel electrode. Significant research has been devoted to carry out the long-term stability (≥ 2000 h) degradation in endurance test primarily due to major challenges like highly humid environment in the fuel electrode, microstructural flaws and polarization losses under high operational temperature. In this context, mixed ionic and electronically conducting (MIEC) oxide-based La-Sr-Co-Fe-O (LSCF) and Ba-Sr-Co-Fe-O (BSCF) air electrodes has drawn significant attention for the effective oxygen reduction (ORR) and oxygen evolution (OER) reaction in the context of SOFC and SOEC operational mode [2,3].An attempt has been made in this present research work to establish the effect of off-stoichiometry in A-site lattice over the stoichiometric pristine compositions of La/Ba-Sr-Co-Fe-O (LSCF/BSCF)-based multicomponent MIEC-oxides and their associated heterostructure with optimised off-stoichiometric compositions that governs the electrochemical redox phenomena in conjunction with the functionally engineered Gd-doped ceria-based interlayer and buffer layer. Vacancy driven oxygen reduction (ORR) and oxide ion oxidation (OER) kinetics as a function of aliovalent charge compensation mechanism associated with the defect chemistry has also been investigated for these A-site non-stoichiometric compositions in the range of 1-0.92 for La/Ba(1-x)SrxCo1-yFeyO3-δ [x=0.4 and y=0.2]. A comparative study between the performance of the off-stoichiometric heterostructure synthesised using the optimised pristine compositions with that of the stoichiometric heterointerface has also been evaluated for their efficiency as catalyst for OER/ORR in reversible SOC mode of operation. The increasing trend of oxygen non-stoichiometry (δ) upon the transition from A-site stoichiometry to non-stoichiometric compositions reflected the formation of higher aliovalent cation of ‘Co’ to maintain the charge neutrality and thereby accelerates the associated oxygen redox kinetics. An optimum δ-value of 0.33 and 0.37 are found for LSCF and BSCF-compositions respectively having A-site non-stoichiometry of 0.94. Current density of 0.45 A.cm-2 at an applied voltage of 1.5 V @800℃ is obtained for stoichiometric composition of LSCF wherein 0.5 A.cm-2 is found for the off-stoichiometric batch corresponding to the hydrogen flux of 0.21Nl.h-1.cm-2. Such augmentation in performance may be related to the formation of higher lattice defect which eases the path for oxide ion oxidation. Formation of the interpenetrating heterointerface network at the air electrodes and electrode/electrolyte interfaces in the morphologically engineered cells having gradation in porosity has further been confirmed from Transmission Electron Microscopy (TEM) studies involving the high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and the STEM-EDS elemental spectrum mapping images of the cross-section of the sintered cells and clinically corelated with SOC performances. Orientation of the crystal lattice planes in the two types of grains across the heterojunction has also been determined from the High-Resolution Transmission Electron Microscopy (HRTEM) images. Further study to envisage the presumed hypothesis, based on the rate determining steps involving the defect lattice formation and probable mechanism for selective ORR/OER application, will also be described through hole and/or oxygen vacancy formalism using XPS and density functional theory (DFT) for such hetero-interpenetrating air electrodes.

Direct Detection of Paired Aluminum Heteroatoms in Chabazite Zeolite Catalysts and Their Significance for Methanol Dehydration Reactivity.

The distributions of heteroatoms within zeolite frameworks have important influences on the locations of exchangeable cations, which account for the diverse adsorption and reaction properties of zeolite catalysts. In particular for aluminosilicate zeolites, paired configurations of aluminum atoms separated by one or two tetrahedrally coordinated silicon atoms are important for charge-balancing pairs of H+ cations, which are active for methanol dehydration, or divalent metal cations, such as Cu2+, which selectively catalyze the reduction of NOx, both technologically important reactions. Such paired heteroatom configurations, however, are challenging to detect and probe, due to the typically nonstoichiometric compositions and nonperiodic distributions of aluminum atoms within aluminosilicate zeolite frameworks. Nevertheless, distinct configurations of paired framework aluminum atoms are unambiguously detected and resolved in solid-state 2D 27Al-29Si and 29Si-29Si NMR spectra, which are sensitive to the local environments of covalently bonded 27Al-O-29Si and 29Si-O-29Si moieties, respectively. Specifically, two H+-chabazite zeolites with the same bulk framework aluminum contents are shown to have different types and populations of closely paired aluminum species, which correlate with higher activity for methanol dehydration. The methodologies and insights are expected to be broadly applicable to analyses of heteroatom sites, their distributions, and adsorption and reaction properties in other zeolite framework types.

Rational Design of the Electronic Structure of CdS Nanopowders.

In this study, various techniques, such as energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Raman spectroscopy, and spectrophotometry, were used to analyze the properties of nanometric CdS particles synthesized with varying precursor concentrations. EDX analysis revealed the nonstoichiometric composition manifested by an increase in the Cd/S ratio from 1.02 up to 1.43 with increasing precursor concentration. The growth of lattice parameters and unit cell volume accompanying preferential crystallization of the hexagonal phase along with an increasing Cd/S ratio was confirmed by XRD analysis. This indicated the presence of interstitial cadmium in nonstoichiometric Cd1+xS. The formation of shallow Cdi donor levels below the bottom edge of the conduction band impacts the bang-gap energy; a decrease from 2.56 to 2.21 eV along with increasing nonstoichiometry was observed. This is accompanied by a widening of the range of absorption of light, which creates conditions that can lead to an increase in the efficiency of redox reactions in photochemical processes.

Enhanced zT due to non-stoichiometric induced defects for bismuth telluride thermoelectric materials

Thermoelectric materials have potential applications in energy conversion and waste heat recovery. Thermoelectric materials with non-stoichiometric composition may exhibit improved thermoelectric properties compared to the stoichiometric composition material. Bi2Te3 is one of the best-known thermoelectric materials having optimum performance near room temperature. In the present study, non-stoichiometric bismuth telluride (Bi2±x Te3), x = (0, 0.01, 0.02, 0.03), was synthesized using the co-precipitate method to create imperfections and strains in the crystal structure of the material. The crystal structure of the synthesized bismuth telluride revealed significant changes in the c direction when examined using X-ray diffraction (XRD). Scanning electron microscopy (SEM) revealed the formation of micro-particles. Energy dispersive spectroscopy (EDX) also confirmed the non-stoichiometric elemental composition of Bi and Te rich bismuth telluride. Thermogravimetric analysis (TGA) was performed in a non-inert environment, and an oxidation temperature of 685 ​K was recorded in non-stoichiometric samples. The post-oxidation of stoichiometric and non-stoichiometric Bi Rich and Te Rich bismuth tellurides was also confirmed by XRD and TGA comparison. The thermal conductivity was reduced by the imperfections and defects for all non-stoichiometric compositions, and a zT value of 0.54 at 420 ​K was obtained in the Tellurium Rich bismuth telluride, which is about a 12% improvement compared to the pure sample.

Single‐Crystal Perovskite Light‐Emitting Diodes with External Quantum Efficiency of over 8% Enabled by Nonstoichiometric Composition Tuning

AbstractPerovskite single crystals (SCs) have been emerging as promising materials for electroluminescence (EL) device applications owing to their superior optoelectronic properties. However, the device performance of single‐crystal perovskite light‐emitting diodes (SC‐PeLEDs) is limited by the lack of effective defect management and energy level modulation. Here, a nonstoichiometric composition tuning (NCT) strategy for the construction of high‐performance SC‐PeLEDs is reported. The NCT strategy, finely tuning the MABr (MA+ = CH3NH3+) excess in the nonstoichiometric MAPbBr3 SCs to enhance the crystal quality, reduce the trap density, and elevate the energy level of the resultant perovskite SC, enables markedly decreased nonradiative recombination and more efficient carrier injection for the devices. In consequence, the optimized SC‐PeLEDs exhibit an ultrahigh peak luminance of 161 900 cd m−2 and a large external quantum efficiency (EQE) of up to 8.1%, representing the most efficient SC‐PeLED reported thus far. This strategy also shows a high universality in enhancing the EL performance of other lead bromide perovskite SC‐PeLEDs, endowing them with luminances and EQEs three times larger than those of the pristine devices. This work opens an avenue for the development of high‐performance EL devices based on perovskite SCs.

Effect of Rare-Earth Oxides on Reaction Sintered Non-Stoichiometric Magnesium Aluminate Spinel

Non-stoichiometric spinel compositions with molar ratio of MgO:Al2O3 = 1:2 and 2:1, were prepared via single-stage reaction sintering technique at 1550°-1600°C using commercial grade oxide reactants. The effect of different rare-earth oxides, viz. CeO2, La2O3 and Y2O3 at 2 wt% level on the properties of different spinel batches was studied. Y2O3 was found to favour densification in both the spinel batches while CeO2 and La2O3 were found to favour densification only in the MgO-rich spinel compositions. Phase analysis revealed that Y2O3 containing Al2O3-rich spinel has a secondary phase with similar crystal structure to spinel (both cubic) and improved densification, while in the MgO-rich condition, Y2O3 remained as secondary phase and assisted in densification. CeO2 and La2O3 in Al2O3-rich samples formed secondary phases with different crystal structures and resulted in reduced densification. While in MgO-rich condition, CeO2 (cubic) did not react with Al2O3 and La2O3 formed a secondary phase with similar crystal structure as that of spinel and therefore assisted in densification. Addition of rare-earth oxides led to improvement in strength of MgO-rich spinels and maximum improvement in strength was observed with the addition of yttria.

Morphology evolution of bimetallic Ni/Zn-MOFs and derived Ni3ZnC0.7/Ni/ZnO used to destabilize MgH2

Herein, 3D porous flower-like Ni/Zn-MOFs are synthesized via a simple solvothermal method. The reaction time shows obvious effects on the morphology evolution of Ni/Zn-MOFs, and the morphology evolution from plate to 3D flower is governed by a “nucleation–dissolution–renucleation” mechanism. Nonstoichiometric bimetallic carbide-containing composites (Ni3ZnC0.7/Ni/ZnO composites) are obtained through the simple calcination of Ni/Zn-MOFs under 4 MPa H2, suggesting that ZnO cannot be reduced and Ni3ZnC0.7 is stable even under 24 h of hydrogen treatment. The MgH2-5 wt% Ni3ZnC0.7/Ni/ZnO-3 composite began to dehydrogenate at 230 °C and 5 wt% H2 can still be released within the initial 1 h at 573 K. The hydrogen absorption capacity of the composite reached 2.57 wt% H2 at 423 K within 600 s. Interestingly, the composite can still absorb 0.78 wt% H2 at 353 K within 60 min. Compared to pure MgH2, the activation energy (Ea) of hydrogen absorption and dehydrogenation of the composite decreased to 44.85 and 93.06 KJ/mol, respectively. Comparing the cases of Ni3ZnC0.7, Ni, and ZnO addition clearly reveals that Ni3ZnC0.7 and Ni are the primary catalysts in these improvements. The Ni3ZnC0.7/Ni/ZnO-3 composite will react with MgH2 during the absorption–desorption cycle, and the in situ generated Mg2Ni/Mg2NiH4 acts as a “hydrogen pump” to reduce the potential barrier for the dissociation and recombination of H2. Trace amounts of MgZn2 can promote the formation of Mg/MgH2 and the resulting minor expansion and contraction during phase changes provides more paths for hydrogen diffusion. This study clearly demonstrates the efficient catalytic activity of nonstoichiometric bimetallic carbides and provides a promising catalyst design for Mg-based hydrogen storage materials.