Lattice Parameters Research Articles

A DFT study to explore structural, elastic, mechanical, electronic and optical properties of inverse perovskite SbPMg3 for solar cell applications

This study presents the structural, mechanical and optoelectronic properties of inverse perovskite SbPMg3 for optoelectronic applications. The structural optimization is carried out by employing Generalized Gradient Approximation of Wu–Cohen, Perdew–Burke–Ernzerhof and PBE revised for solids. The optimized lattice constant and bulk modulus of SbPMg3 is 4.85 Å and 54.20 GPa with WC-GGA scheme. The positive phonon frequencies are indicating that SbPMg3 is dynamically stable. The mechanical properties were calculated by obtaining elastic constants C11, C12 and C44. The structural stability is evaluated according to Born–Huang stability criteria. The band gap, static dielectric constant and static refractive index is 1.70 eV, 8.23 and 2.87 calculated with WC-mBJ exchange and correlation functional. The band structures show that inverse perovskite SbPMg3 possesses direct band gap nature. The absorption peaks in visible and ultraviolet energy region anticipates that SbPMg3 is promising novel material for optoelectronic applications.

Effects of K, Rb, and Br doping on Cs3Bi2I9 perovskites: A design of experiments approach

This work presents the effect of doping with different species on the structural sites of lead-free halide perovskites, aiming to evaluate the potential of the produced materials as photoabsorbing layers in 3rd generation solar cells. Lead-free perovskite films of Cs3Sb2I9, CsCu2I3, Cs3Bi2I9, and CsPbI3 were synthesized via the spin-coating method and characterized using X-ray diffraction, scanning electron microscopy with chemical microanalysis (SEM-EDS), and Uv-Vis spectroscopy. Computational models based on Density Functional Theory (DFT) were used to simulate the structures and properties of some of the perovskites synthesized in this study, in order to validate the experimentally obtained data. The Cs3Bi2I6Br3 perovskite was subjected to modification through A-site doping with K and Rb and X-site doping with Br, with a comprehensive study on the effects of processing variables, anti-solvent quantity, and crystallization temperature using a 23 experimental design. The outcomes highlighted the critical role of the anti-solvent quantity in structure formation and electronic properties. Toluene, as an anti-solvent, produced unique morphologies not commonly reported. Computational studies were performed using Density Functional Theory (DFT) to complement the experimental findings. The optimization process revealed that Cs3Bi2I9 structures mainly constituted [CsI12] and [BrI6] clusters, with Cs–I and Bi–I average bond lengths consistent with experimental results. X-site Br doping induced slight distortion, while A-site Rb/K doping showed minimal lattice parameter changes. Notably, K-induced morphological alterations suggested potential electronic transformations. From an electronic structure perspective, Cs3Bi2I9 had a band gap of 2.07 eV, slightly increased to 2.10 eV with Br doping. Rb maintained Br-doped structure, while K significantly reduced the band gap to 1.96 eV. These computational results align well with our experimental data, showcasing the accuracy of our calculations in predicting material properties. The results confirmed that the perovskites selected through experimental design and validated by computational simulation are promising semiconductor materials for photovoltaic applications, as well as being a lead-free photoabsorbing material option.

(Invited) Development of Single Crystal Nbn Superconductor on Wide Bandgap GaN By Sputtering and Thermal Annealing

The field of quantum computing is rapidly evolving, and Niobium Nitride (NbN) superconductors have emerged as a pivotal component in the field of quantum computing due to their unique properties. NbN possesses relatively higher superconducting transition temperature (Tc = 15-17 K) as compared to traditional superconductors, making it a promising material for various applications, including superconductor quantum computers, single photon detectors, and hot electron bolometers [1]. The investigation of NbN's superconductivity has been a subject of extensive research over the past few decades. Given that the properties of NbN are intricately linked to its crystal structure, lattice constant, and nitrogen content, precise control of the structural and electrical characteristics of NbN films is essential for the realization of NbN based quantum devices. The (111) planes of δ-NbN exhibit relatively small lattice mismatches with group-III nitride semiconductors (~0.2% for AlN and ~2.7% for GaN) [2], suggesting the potential for integrating crystalline NbN superconductors with nitride semiconductors on a single wafer. Notably, N-polar AlGaN/GaN high electron mobility transistors have been successfully fabricated on NbN films, operating under Tc with a negative differential resistance [3], indicating that the integration of nitride semiconductors and superconductors can be harnessed to create Josephson junctions. To achieve high-quality all-nitride NbN/group-III nitride/NbN Josephson junctions, a comprehensive understanding of the NbN/GaN heterointerfaces is crucial. Despite limited reports on the epitaxial growth of NbN films on nitride semiconductors, little is known about the structural and transport properties of such NbN films. Previously, MBE growth of NbN films have been demonstrated on GaN substrate, showing superconducting critical temperatures exceeding 10 K [4]. In this presentation, our efforts on the development of single crystal NbN thin films on wide bandgap GaN substrate using cost efficient sputtering technique followed by a subsequent high-temperature annealing will be presented. Commercially available single-crystalline GaN (0001)/sapphire templates as well as differently oriented (c and a-planes) sapphire substrates are used as the substrates for the sputtered deposition of NbN films at 20 °C. After the deposition, a high temperature annealing was performed separately at 950 °C for 30 mins under Ar as well as N2 atmosphere. While the as-deposited NbN film on GaN did not exhibit a discernible peak in the high-resolution XRD measurement, a high-intensity, single crystal (111)-oriented NbN film emerged prominently after annealing in both N2 and Ar environments. This suggests a notable enhancement in the crystalline quality of the superconducting material attributable to the thermal annealing process. Although the crystallinity of the NbN layer improves post-annealing, there is an associated increase in grain size and surface roughness. Preliminary findings indicate a reduction in the critical temperature of the NbN film from 12.82 K to 8.69 K after high-temperature annealing, potentially linked to the incorporation of impurities and crystallographic defects during this process. Further investigations using atomic resolution transmission electron microscopy, secondary ion mass spectrometry and X-ray photoelectron spectroscopy will be performed to investigate the influence of annealing duration, temperature, and conditions on the critical temperature, impurity incorporation and defect formation in NbN films deposited with different thickness.In continuation of our recent exploration into depositing crystalline superconducting NbN films on III-nitride semiconductors, this presentation will also focus on our recent advancement of ultrawide bandgap semiconductor materials such as the growth of high-quality quality β-Ga2O3 films and its ternary (AlxGa1-x)2O3 alloys, using metalorganic (MOCVD) and low-pressure (LPCVD) chemical vapor deposition growth techniques. Ga2O3 and (AlxGa1-x)2O3 have emerged as a promising semiconductor material platform for applications in high-power electronics and ultraviolet optoelectronics due to their excellent chemical and thermal stability, as well as high breakdown field strengths. The structural and electrical characteristics of Si-doped β-Ga2O3 and (AlxGa1-x)2O3 thin films will be presented. Additionally, we will present recent findings on achieving phase-pure β-(AlxGa1-x)2O3 films with a record-high Al composition (< 99%) [5]. Our research efforts into understanding the orientation-dependent Al incorporation in β-(AlxGa1-x)2O3 thin films and the determination of band offsets at β-(AlxGa1-x)2O3/β-Ga2O3 heterostructures will be presented. Furthermore, the presentation will touch upon the heteroepitaxial development of other phases of Ga2O3 and (AlxGa1-x)2O3, including α, γ, and κ. Acknowledgment: Dr. Bhuiyan acknowledges the support and guidance of his PhD advisor- Dr. Hongping Zhao at The Ohio State University for the MOCVD growth and characterization of β-Ga2O3 and (AlxGa1-x)2O3 films conducted in Zhao's group. Reference: Yamashita et al., Phys. Rev. Appl. 8, 054028 (2017).Kobayashi et al., Appl. Phys. Express 13, 061006 (2020).Yan et al., Nature 555, 183 (2018).G. Wright et al., APL Mater. 10, 051103 (2022).Bhuiyan et. al, Phys. Status Solidi RRL 17, 2300224 (2023). Figure 1

Energy Changing Paths for Li-Ion Batteries Under Nonequilibrium Process

It has been discovered that the electrodes of Li-ion batteries have abnormal phase transition phenomena during nonequilibrium process. As a two-phase-coexistence material, LiFePO4 (LFP) shows single phase during both high-rate lithiation and delithiation. Furthermore, a far from equilibrium state results in LFP particles with meta-stable amorphous structures and layered oxides exhibiting two-phase-coexistence during high rate delithiation. It is well known that a stable single-phase structure is an important characteristic for the electrodes with better high-rate performance, since the energy barriers of nucleation and growth for new phases are eliminated. Understanding the mechanisms of the abnormal phase transition during nonequilibrium process is therefore essential for designing the electrodes with fast (dis)charging. In this work, we model the free energy of electrodes with a series of order parameters based on nonequilibrium thermodynamics and continuum mechanics. Developed governing equations for the kinetics of the order parameters reveal the mechanism of the abnormal phase transitions for LFP and layered oxides under high rate (de)lithiation. The generation of dislocations is cross-coupled with the chemical reaction of Li-ion on the surface of electrode particles. Such coupling is the origin of materials choosing various energy changing paths under different (dis)charging conditions and resulting in various lattice parameters and structures. The dislocation density is the key parameter for the path selection since it alters dislocation-induced energy. In the simulations for LFP and layered oxides, the changes of order parameters agree with the abnormal phase transition observed in existing experimental studies. Our study indicates a potential strategy of introducing dislocations with surface engineering for optimizing the (dis)charging path of electrode materials to obtain stable single-phase characteristics and promote the kinetic capability.

Tuning Van Der Waals Heterostructure of WS2/SrTiO3 Via in Situ Transmission Electron Microscopy

Monolayer two-dimensional (2D) materials have been widely researched and discussed in recent years, while multi-layers have received comparatively less attention. Nowadays, combining different materials to create heterostructures has become mainstream. In semiconductor industry, heterostructure can form devices such as lasers, light-emitting diodes, fast transistors and so on. Heterostructures can create well electronic properties by combining two different materials together. Therefore, heterostructures become a great tool to manipulate the electronic structures. In traditional heterostructures, the interfaces between two different materials are formed by covalent bonds, hence it requires similar lattice constants and structures. On the other hand, novel van der Waal heterostructures (vdW-heterostructure), formed by 2D materials, do not require the same strict similarity as traditional ones. VdW-heterostructures, which create 3D structures through van der Waals forces, provide a new perspective. In this study, we created a vdW-heterostructures by stacking tungsten disulfide (WS2) with single-crystal strontium titanate, SrTiO3 (STO), shown in Figure 1a,b. The crystalline atomic-layer WS2 and STO were synthesized by chemical vapor deposition (CVD) and pulsed laser deposition (PLD), respectively. They are analyzed by high-resolution transmission electron microscope (HRTEM) shown in Figure 1c-h. Once the vdW-heterostructures are formed, we conducted in situ heating by TEM. Through the advanced in situ technique, we observed the change of the twisted stacking angle by heating the vdW-heterostructure. Ultimately, the lattices will shift and rotate, minimizing the free energy, so that the vdW-heterostructure will be aligned and formed epitaxially. In addition, we utilized atomic resolution scanning transmission electron microscope (STEM) to identify the stacking images and the moiré pattern of the vdW-heterostructure. During the rotation, we can observed different moiré patterns by various twisted stacking angles. These different moiré patterns can produce different electrical properties, which can be applied to advanced semiconductor devices. Keywords: high-resolution TEM/STEM, in situ heating, 2D materials, van der Waal heterostructures, moiré pattern Figure 1. The vdW-heterostructure of STO/WS2. a) The diagram showing that the formation process of WS2/STO vdW-heterostructures which have different twisted stacking angles. b) The low-magnification SEM image showing that the single crystal STO thin film is transferred onto the TEM heating chips. The circles in the middle are the observation windows for transmission electrons. c-e) HRTEM images. f-g) Diffraction patterns of HRTEM. c,f) Single crystal STO thin film with d-spacing (1−10) = 0.284 nm. d,g) Monolayer single crystal WS2 with d-spacing (−110) = 0.274 nm. e,h) WS2(red)/STO(yellow) vdW-heterostructure with stacking angle 3.6°. Figure 1

Electrodeposition of Non-Noble High-Entropy Alloys for Effective Hydrogen Evolution Electrocatalysts

As society works towards reducing its carbon footprint, various sectors such as energy, steelmaking and fertilizer production have begun to look increasingly towards decarbonization. Hydrogen production through electrolysis, when linked to renewables (solar, wind), provides a promising low-emission alternative as an energy carrier and chemical feedstock. With the decreasing cost of said renewables, greater focus is now on the capital cost of the electrolyser, and particularly the membrane/electrode structures. Conventional Proton Exchange Membrane (PEM) electrolysers rely on the use of electrocatalysts made with expensive noble metals such as platinum, ruthenium, and palladium [1]. Anion Exchange Membrane (AEM) electrolysers present an effective means of alkaline water splitting with low carbon emissions and can effectively utilize non-noble metal electrocatalysts for the Hydrogen Evolution Reaction (HER). A novel class of materials, High-Entropy Alloys (HEAs), made of non-noble metals or with reduced noble metal content have shown great promise as active electrocatalytic materials [2]. HEAs are typically defined as metal alloys made of five or more constituent elements each comprising at least 5% of the total material [3]. Having such a large number of principal alloying elements can lead to enhanced phase stability due to an increased configurational entropy, have unique chemical clustering, and can help prevent degradation of the material in harsh environments [2]. Additionally, the large lattice parameter mismatch between constituent elements can result in a high degree of strain which can help shift electronic states in a way that is favourable to hydrogen electrocatalysis [4]. These properties along with the so called “cocktail effect,” whereby combining multiple elements can result in unexpected synergistic interactions, makes HEAs uniquely suited to electrocatalytic applications [5].In this work, we investigate the electrocatalytic performance of electrodeposited FeNiCoMoW HEAs. The goal is to combine three hyper-d transition metals with two hypo-d transition metals to alter the electronic structure and improve electrocatalytic performance. Using chronoamperometric measurements, the Tafel slopes for FeNiCoMoW HEAs electrodeposited at pH 5, 6 and 7 were determined, with the pH 5 HEA demonstrating the smallest average Tafel slope of approximately 83 mV/dec. Compared to some electrodeposited binary alloys reported on in the literature, this marks an improvement and may be the result of unexpected interactions within the compositionally complex alloy. In the FeNiCoMoW HEA, the magnitude of the Tafel slope increased in tandem with the electrochemically active surface area (ECSA) as determined by Cyclic Voltammetry (CV) which suggests that the composition may be more important for improving performance. As the pH of the electrodeposition solution increased, the amount of cobalt in the as-deposited HEA decreased while the amounts of molybdenum and tungsten remained constant. The composition of nickel and iron appeared to vary inversely, reaching a maximum and minimum respectively at pH 6. From these results it seems that maximizing cobalt content and minimizing nickel content could potentially help to improve HER performance in the FeNiCoMoW system.

A TEM Study of Structural Degradation in LiFePO4 Batteries after Hybrid Vehicle Use

Establishing a robust, efficient circular economy for batteries hinges on understanding how they decay over time under various conditions. This understanding is crucial to maximize material use before recycling or disposal. A key aspect of this endeavor is the study of lithium iron phosphate (LiFePO4), a pivotal battery technology whose structural integrity over time remains a subject of inquiry.1 Known aging mechanisms in LiFePO4 (LFP) batteries include electrode degradation, SEI growth, and electrolyte decomposition.1 These processes extend to the cathode, where degradation can manifest as Fe dissolution, Li inventory loss, Fe/Li anti-site defects, and LFP amorphization.1–3 However, these mechanisms are typically studied in lab-aged cells under controlled conditions, leaving a gap in our understanding of their behavior in real-life, commercialized applications.Our research aims to bridge this gap by characterizing the degradation mechanisms of LFP cathode material in various states of health (SOH) after use in a hybrid vehicle. We sourced our cathode samples from 26650 cells extracted from a BAE ESS-A123 hybrid bus battery pack. After selecting cells with drastically different SOHs based on previous analyses,4 we employed transmission electron microscopy (TEM) for detailed characterization.In this talk, we will share insights gained from high-resolution TEM characterization, alongside chemical analysis using energy-filtered TEM and electron energy loss spectroscopy (EELS). Our focus will be on changes in the olivine structure, including lattice parameter alterations, Li and Fe migration, and Fe oxidation. By combining cell-level SOH analyses with TEM characterization, we will highlight how electrochemical test results correlate with material degradation mechanisms, enhancing our understanding of battery health, longevity, and diagnostics. Wang, L. et al. Insights for understanding multiscale degradation of LiFePO4 cathodes. eScience 2, 125–137 (2022). Li, X. et al. First Atomic-Scale Insight into Degradation in Lithium Iron Phosphate Cathodes by Transmission Electron Microscopy. J. Phys. Chem. Lett. 11, 4608–4617 (2020). Xu, P. et al. Efficient Direct Recycling of Lithium-Ion Battery Cathodes by Targeted Healing. Joule 4, 2609–2626 (2020). Ramirez-Meyers, K., Rawn, B. & Whitacre, J. F. A statistical assessment of the state-of-health of LiFePO4 cells harvested from a hybrid-electric vehicle battery pack. J. Energy Storage 59, 106472 (2023).

Solid Solution Behavior of High Performance BiOBrxI1-X Photoanodes Probed Using Solid-State NMR, XRD and Optical Spectroscopy

Bismuth oxyhalides (BIOX) are a family of solution-synthesizable 2D layered semiconductors constituted of earth-abundant elements namely bismuth, oxygen and the halogens. BIOX based thin films and heterojunctions are the subject of immense scientific interest due to their impressive performance in photocatalytic and photoelectrochemical devices. Solid solutions of Br/I bismuth oxyhalides exhibit continuously tunable absorption and emission spectra similar to that observed in mixed halide MAPbClxBryI3-x-y perovskites and mixed anion III-V GaAsxP1-x semiconductors. The excited state decay showed two components for all the mixed halide BiOX semiconductors with a dominant short-lived component in the nanosecond range and a weaker longer-lived component of ~100 ns. The average photoluminescence (PL) lifetime varied from 5.4 ns in bare BiOI to 1.49 ns in bare BiOBr with intermediate compositions exhibiting monotonically increasing average PL lifetimes with increasing iodine content. Using a combination of characterization techniques such as solid-state nuclear magnetic resonance (ssNMR), x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS) and optical spectroscopy, we demonstrate the formation of atomic level solid solutions in Br/I bismuth oxyhalides. Through refinement of the lattice parameters using powder XRD and complementary atomic-level 209Bi SSNMR spectroscopy, we found that Vegard's law was obeyed by the BIOBrxI1-x solid solutions. By varying the Br:I ratio, it is also possible to tune the electronic band gap as well as the energy levels corresponding to the conduction band minimum (ECB, min) and the valence band maximum (EVB, max), thus allowing control over the thermodynamic driving force available to drive chemical reactions using photogenerated or electrically injected charge carriers. Suppression of the longitudinal optical phonon in solid solutions of Br/I bismuth oxyhalides is suggestive of lower phonon scattering of charge carriers and improved electronic transport. A synergistic enhancement of more than 1 order of magnitude in the photoelectrochemical water-splitting performance was obtained for the optimized solid solution (BiOBr0.67I0.33) under AM 1.5G 1 sun illumination. Our results pave the way for a one pot synthesis protocol to form BiOX thin films, powders and colloidal suspensions with deterministic control over the stoichiometry.

Lithium Superoxide in Li-O2 Batteries: Performance and Mechanisms

Lithium superoxide (LiO2) is generally regarded as an intermediate formed during the Li-O2 battery discharge and transformed into lithium peroxide (Li2O2). Indeed, its chemical/electrochemical stability is low, making it recognized as a temporary discharge product in Li-O2 battery chemistry. However, in 2016, utilizing an iridium (Ir)-based electrocatalyst, Curtiss and Amine et al. found that LiO2 can be epitaxially grown on the surface of Ir catalyst and can be stable under cycling conditions.1 In the study, a templating mechanism was suggested, where a good lattice matching of LiIr3 surfaces (formed on the Ir catalyst) with that of LiO2 facilitates LiO2 formation as a singular discharge product. Following studies showed some superior electrochemical properties of LiO2 in comparison to Li2O2, including lower charge overpotentials. Meanwhile, some other transition metal compounds have recently exhibited LiO2 formation, where the formation mechanism suggested may not be a templating method. In this case, there could be strong adsorption of LiO2 in specific structures, resulting in suppressed Li2O2 generation. Herein, we will present experimental and computational results on some new catalysts for LiO2 formation and discuss possible underlying mechanisms.AcnowledgementThis work was primarily supported by the US Department of Energy under contract DE-AC02-06CH11357 from the Vehicle Technologies Office, Department of Energy, Office of Energy Efficiency and Renewable Energy.Reference1 Curtiss. L. and Amine. K. et al. A lithium–oxygen battery based on lithium superoxide. Nature 2016, 529, 377-382

Flux Synthesis of Alkaline-Earth Lanthanide Borates as Potential Nuclear Waste Forms.

Neodymium is typically considered the best surrogate for trivalent americium and can be used to identify Am3+ containing materials that are likely to form. We have explored the alkaline-earth lanthanide borate phase space using alkaline-earth halide/carbonate fluxes. This resulted in the synthesis of new compounds AE5Ln(BO3)4X (AE = Ca, Sr; Ln = Pr, Nd, Eu, Tb; X = Cl, Br) and AE3Ln2(BO3)4 (AE = Sr, Ba; Ln = Pr, Nd) as well as the synthesis of two compounds of Ba8Ln2(BO3)6(B2O5) (Ln = Eu, Tb) crystallizing in a new structure type. Ba8Ln2(BO3)6(B2O5) crystallizes in the space group P21/n with lattice parameters a = 8.6002(3) Å, b = 7.9245(3) Å, c = 17.6697(7) Å, and β = 91.3560(10)° for the Eu analogue, and the structure contains isolated LnO8 polyhedra connected into a framework by BO3 and B2O5 units. The fluorescence emission spectra of AE5Ln(BO3)4X (AE = Ca, Sr; Ln = Eu, Tb; X = Cl, Br) and Ba8Ln2(BO3)6(B2O5) (Ln = Eu, Tb) are reported.

Mn2+ vs Co2+ substitution into β-TCP: Structural details and bone cells response

This work investigated the range of substitution of two biologically relevant ions, namely Mn2+ and Co2+, into the structure of β-tricalcium phosphate, as well as their influence on bone cells response. To this aim, β-TCP was synthesized by solid state reaction in the presence of increasing amount of the substituent ions. The results of the X-ray diffraction analysis reveal that just limited amounts of these ions can enter into the β-TCP structure: 15 at% and 20 at% for cobalt and manganese, respectively. Substitution provokes aggregation of the micrometric particles and reduction of the lattice constants. In particular, the dimension of the c-parameter exhibits a discontinuity at about 10 at% for both cations, although with different trend. Moreover, Rietveld refinement demonstrates a clear preference of both manganese and cobalt for the octahedral site (V). The influence of these ions on cell response was tested on osteoblast, osteoclast and endothelial cells. The results indicate that the presence of manganese promotes a good osteoblast viability, significantly enhances the expression of osteoblast key genes and the angiogenic process of endothelial cells, while inhibiting osteoclast resorption. At variance, osteoblast viability appears reduced in the presence of Co samples, on which osteoblast genes reach higher expression than on β-TCP just in a few cases. On the other hand, the results clearly show that cobalt significantly stimulates the angiogenic process and inhibits osteoclast resorption.

Lanthanide-based F-MOFs: Structure, hydrolytic stability, spectral and magnetic properties

A series of five novel lanthanide-based fluorinated metal-organic frameworks (Ln-F-MOFs) have been synthesized under solvothermal conditions by the reaction of 3,3′-bis(trifluoromethyl)-[1,1′-biphenyl]-4,4′-dicarboxylic acid (H2L) and lanthanide Ln(III) ions (Ln(III)La, Ce, Pr, Nd and Eu). Powder X-ray diffraction (PXRD) analysis revealed that all prepared complexes are isostructural. A single-crystal X-ray crystallographic study of one representative of the isostructural group, namely {[La2(L)3(DMF)2(H2O)2]}n showed, that compound crystallizes in a triclinic system with space group P-1. The lattice parameter values are a = 8.563(2) Å, b = 13.199(3) Å, c = 16.008(4) Å, α = 104.588(7) °, β = 92.904(7) ° and γ = 92.717(7) °, with two formula units in the unit cell. The overall structure is formed by 2D polymeric layers, which are arranged into a semi-3D supramolecular structure through hydrogen bonds and other intramolecular interactions. The study of the hydrophobic properties of the complexes showed that the complexes exhibit surface hydrophobicity with a “rose petal effect” and a contact angle of approximately 107°. However, the structures are not hydrolytically stable in the long term and the structure starts to delaminate after two days in water. This is a manifestation of the fact that the complexes do not form a 3D polymer network, it is made up of 2D layers connected only by weak non-bonding interactions. The photoluminescence properties of the Ln(III) complexes are determined by the characteristic 5d-4f or 4f-4f electron transitions for the individual lanthanide ions. The magnetic properties of Nd(III), Pr(III) and Eu(III) variants were studied. The magnetic properties of {[Pr2(L)3(DMF)2(H2O)2]}n are characterized by the presence of a low-lying quasi-doublet with 15.6 cm−1 energy splitting, whereas Eu(III) variant is nonmagnetic at low temperatures, but the magnetic 7F1 state is accessible by thermal excitation. For Nd(III) complex, the X-band EPR measurements were performed. Since 1D channels with dimensions of 4.90 × 7.23 Å2 are present within the structure, the adsorption of N2, CO2 and H2 gases was also studied.

Engineering the Crystalline Architecture for Enhanced Properties in Fast-Rate Processing of Poly(ether ether ketone) (PEEK) Nanocomposites.

Rapid cooling in fast-rate manufacturing processes such as additive manufacturing and stamp forming limits the development of crystallinity in semicrystalline polymer nanocomposites and, therefore, potential improvements in the mechanical performance. While the nucleation, chain mobility, and crystallization time from rapid cooling are known competing mechanisms in crystallization, herein we elucidate that the crystalline morphology and architecture also play a key role in tuning the mechanical performance. We explore how modifying the spherulite morphology via a cellulose nanocrystal (CNC) and graphene nanoplatelet (GNP) hybrid system in their pristine form can improve or preserve the mechanical properties of poly(ether ether ketone) (PEEK) nanocomposites under two extreme cooling rates (fast -460 °C/min and slow -0.7 °C/min). A scalable manufacturing methodology using water as the medium to disperse the powder system was developed, employing a CNC as a dispersing agent and stabilizer for PEEK and GNP. Despite the expected limited mechanical reinforcement due to thermal degradation, CNCs significantly impacted PEEK's crystalline architecture and mechanical performance, suggesting that surface interactions via lattice matching with PEEK's (200) crystallographic plane play a critical role in engineering the microstructure. In fast cooling, the CNC and CNC:GNP systems reduced the crystallinity, respectively, yet led to minimizing the reduction in the tensile strength and maintaining the tensile modulus at the Neat level in slow cooling. With slow cooling, crystallinity remained relatively unchanged; however, the addition of CNC:GNP improved the strength and modulus by ∼10% and ∼16%, respectively. These findings demonstrate that a hybrid nanomaterial system can tailor PEEK's crystalline microstructure, thus presenting a promising approach for enhancing the mechanical properties of PEEK nanocomposites in fast-rate processes.

First-principles study of non-linear thermal expansion in cadmium titanate by molecular dynamics incorporating nuclear quantum effects

First-principles molecular dynamics (FPMD) simulations were applied for analyzing structural evolutions around the paraelectric-ferroelectric phase transition temperature in the perovskite-type cadmium titanate, CdTiO3. Since the phase transition is reported to occur at the low temperature around 80 K, the quantum thermal bath (QTB) method was utilized in this study, which incorporates the nuclear quantum effects (NQEs). The structural evolutions in the QTB-FPMD simulations are in reasonable agreement with the experimental results, by contrast in the conventional FPMD simulations using the classical thermal bath (CTB-FPMD). Especially, the non-linear thermal expansion of lattice constants around the phase transition temperature was well reproduced in the QTB-FPMD with the NQEs. Thus, the NQEs are of importance in phase transitions at low temperatures, particularly below the room temperature, and the QTB is useful in that it incorporates the NQEs in MD simulations with low computational costs comparable to the conventional CTB.

Water Effect on the Electronic Properties and Lithium-Ion Conduction in a Defect-Engineered LiFePO4 Electrode

Defect-engineering accelerates the conduction of lithium ions in the cathode materials of lithium-ion batteries. However, the effects of defect-engineering on ion conduction and its mechanisms in humid environments remain unclear in the academic discourse. Here, we report on the effect of vacancy defects on the electronic properties of and Li-ion diffusion in a LiFePO4 material in humid environments. The research findings indicate that vacancy defects reduce the lattice constant and unit cell volume of LiFePO4. Additionally, the water molecules occupy the Li-ion vacancies, leading to an increase in the lattice constant of LiFePO4. The computational results of the electronic properties show that the introduction of water molecules induces a transition in LiFePO4 from a semiconductor to a metallic behavior, with a transfer of 0.38 e of charge from the water molecules to LiFePO4. Additionally, the migration barrier for Li ions in the H2O + LiFePO4 system is found to be 0.50 eV, representing an 11.1% increase compared to the pristine LiFePO4 migration barrier. Our findings suggest that water molecules impede the migration of Li ions and provide important insights into the effect of defect-engineering on electronic properties and ion conduction under humid conditions.

Systematic improvement of x -dependent unpolarized nucleon generalized parton distributions in lattice-QCD calculation

We present a first study of the effects of renormalization-group resummation (RGR) and leading-renormalon resummation (LRR) on the systematic errors of the unpolarized isovector nucleon generalized parton distribution in the framework of large-momentum effective theory. This work is done using lattice gauge ensembles generated by the MILC Collaboration, consisting of 2+1+1 flavors of highly improved staggered quarks with a physical pion mass at lattice spacing a≈0.09 fm and a box width L≈5.76 fm. We present results for the nucleon H and E generalized parton distributions (GPDs) with average boost momentum Pz≈2 GeV at momentum transfers Q2=[0,0.97] GeV2 at skewness ξ=0 as well as Q2∈0.23 GeV2 at ξ=0.1, renormalized in the modified minimal subtraction (MS¯) scheme at scale μ=2.0 GeV, with two- and one-loop matching, respectively. We demonstrate that the simultaneous application of RGR and LRR significantly reduces the systematic errors in renormalized matrix elements and distributions for both the zero and nonzero skewness GPDs, and that it is necessary to include both RGR and LRR at higher orders in the matching and renormalization processes. Published by the American Physical Society 2024

Synthesis and characterization of novel double perovskite K2AgBiBr6

Over the past few years, Lead-free halide double perovskites have attracted a tremendous attention such that it is demonstrated by the power conversion efficiency's sharp increase of over 25 %. It has also stimulated a widespread application of halide metal perovskites in other fields, such as light-emitting diodes, field-effect transistors, detectors, and lasers. Double perovskites have been put forth as an alternative to hybrid lead halide perovskites in the last decade because of their efficiency in doing away with the existing toxicity and instability. It is probably the first attempt, to date, that lead-free halide double perovskite K2AgBiBr6 has been made with a cheap, easy-to-use solution-state reaction method. To determine their structure, single crystal X-ray diffraction and PXRD analysis have been employed. The synthesized K2AgBiBr6 adopts the cubic structure with Fm‾3m symmetry and lattice parameters of a = 6.606 (9) Å at room temperature, according to the diffraction result. Energy dispersive X-ray spectroscopy (EDX), elemental mapping, and scanning electron microscopy (SEM) have all been employed to analyze the morphology and elemental composition. Elements including K, Bi, Ag, and Br have been confirmed to be present in the synthesized sample by the EDX technique. For K2AgBiBr6, the 2.859 eV (indirect) and 3.076 eV (direct) bandgaps have been estimated by employing the UV–Vis absorption spectra. Furthermore, the K2AgBiBr6 double perovskite nanocrystal's thermogravimetric analysis/differential thermal and differential scanning analysis (TG/DTA and DSC) curves at 20–800 °C have been measured. An analysis has been conducted on the mechanism of thermal decomposition of synthesized double perovskite. This work demonstrates great promise for future band gap engineering-based photovoltaic and other optoelectronic applications, and it offers a novel path to obtaining premium K2AgBiBr6 double perovskite.

Fiber optic probe integrated with colloidal nanoparticles with directional diffraction selectivity for magnetic field vector detection

A fiber optic probe integrated with colloidal nanoparticles with directional diffraction selectivity is proposed for wide-bandwidth magnetic field vector detection. The probe is constructed with the multimode fiber in which the end-surface is integrated with the Fe3O4@C colloidal nanoparticles by a silicone tube. The colloidal nanoparticles form a three-dimensional photonic crystal structure by magnetic field for diffraction selectivity. The lattice constant and diffraction angle are adjusted by the intensity and direction of the magnetic field, respectively. Obtaining the directional diffraction light through the magnetic field-induced photonic band gap shift with the wavelength blue shift and reflectivity change is confirmed by theory and experiment. The results show that the maximum sensitivity reaches up to 19.7 nm/mT in response range from 13 mT to 200 mT. For vector detection, the peak wavelength shift from 740 nm to 485 nm and reflectance shift from 71% to 7% covering the 0–45° region is verified. In addition, the proposed method could decouple intensity and direction of the magnetic field completely. The fiber optic probe integrated with colloidal nanoparticles has wide detection range and high sensitivity with rapid response. It will open up new horizons for inspiring design and application of magnetic field vector detection in robot posture control and motion perception.

The thermal expansion of Ti-substituted CaAl12O19

CaAl12O19, which can incorporate Ti as both Ti3+ and Ti4+ (charge coupled substitution with Mg2+), is one of the first minerals to condense from a gas of solar composition and is used as a ceramic. It is variously known as hibonite, calcium hexaluminate (CaO.6Al2O3), and CA6. The lattice parameters and unit cell volumes of Ti-substituted hibonite (P63/mmc) with the formulae CaAl11.8Ti3+0.2O19 and CaAl9.8Ti3+0.54Mg0.83Ti4+0.83O19 were determined as a function of temperature from ~ 10 to 275 K by neutron powder diffraction. The thermal expansion is highly anisotropic with the expansion in c a factor of ~ 5 greater than that in a. The change in a is approximately equal for the two compounds whereas the change in c is almost 50% larger for CaAl11.8Ti3+0.2O19. CaAl11.8Ti3+0.2O19 also exhibits negative thermal expansion between 10 and 70 K. The change in unit cell volume with temperature of both compositions is well described by a two term Einstein expression. The large change in c is consistent with substitution of Ti onto the M2 and M4 sites of the R-block structural unit.

Structural changes in Ge1−xSnx and Si1−x−yGeySnx thin films on SOI substrates treated by pulse laser annealing

Ge1−xSnx and Si1−x−yGeySnx alloys are promising materials for future opto- and nanoelectronics applications. These alloys enable effective bandgap engineering, broad adjustability of their lattice parameter, exhibit much higher carrier mobility than pure Si, and are compatible with the complementary metal-oxide-semiconductor technology. Unfortunately, the equilibrium solid solubility of Sn in Si1−xGex is less than 1% and the pseudomorphic growth of Si1−x−yGeySnx on Ge or Si can cause in-plane compressive strain in the grown layer, degrading the superior properties of these alloys. Therefore, post-growth strain engineering by ultrafast non-equilibrium thermal treatments like pulse laser annealing (PLA) is needed to improve the layer quality. In this article, Ge0.94Sn0.06 and Si0.14Ge0.8Sn0.06 thin films grown on silicon-on-insulator substrates by molecular beam epitaxy were post-growth thermally treated by PLA. The material is analyzed before and after the thermal treatments by transmission electron microscopy, x-ray diffraction (XRD), Rutherford backscattering spectrometry, secondary ion mass spectrometry, and Hall-effect measurements. It is shown that after annealing, the material is single-crystalline with improved crystallinity than the as-grown layer. This is reflected in a significantly increased XRD reflection intensity, well-ordered atomic pillars, and increased active carrier concentrations up to 4 × 1019 cm−3.