Bulk Crystalline Research Articles

High-performance single crystal Ni-rich cathode with regulated lattice and interface constructed by separated lithiation and crystallization calcination

Incorporating high valence dopants, such as W6+ and Mo6+ has been verified to be effective for tuning the microstructure and grain boundary of polycrystal Ni-rich cathode. However, the hindered consolidation of primary particles induced by dopants during lithiation calcination limits the utilization of those dopants to crystalize single-crystal Ni-rich cathodes with stabilized lattice and surface. Herein, high performance single crystal LiNi0.84Co0.11Mn0.05O2 cathode with Al3+ and W6+ regulated lattice and boundary phase was construed based on commercial process with two-step calcination process containing separated lithiation and crystallization. The introduction of appropriate amount of Al3+ in the first lithiation calcination of 6 h endows the bulk of crystalline with enhanced lattice stability, while the incorporation of W6+ with stoichiometrical LiOH in the secondary crystallization calcination of 6 h renders uniformly distributed surface layer without hampering the growth of single-crystal. With the Al3+ doped bulk lattice, W6+ doped subsurface region and hetero-epitaxially grown Li2WO4, the cathode infused by two-step calcination exhibits high discharge capacity, rate performance, and cycling stability. Specifically, the modified LiNi0.84Co0.11Mn0.05O2 exhibits exceptional capacity retention, maintaining 88.98% of its initial capacity after 200 cycles at a rate of 1 C within a voltage window of 2.7–4.3 V at a temperature of 25 °C in half-cell. This performance is markedly superior to the capacity retention of 72.96% observed for pristine cathode. Even when subjected to a stringent test after 200 cycles at the same rate, the modified cathode sustains an impressive capacity retention of 82.41% at an elevated cut-off voltage of 4.5 V and a temperature of 30 °C.

Electrolyte-Induced Fe-Doping of LaNiO3 Model Surfaces for Water Electrolysis

Renewable energy needs to be store in different energy forms for the energy transition away from fossil fuels. One of most promising forms is chemicals such as H2 and C-based fuels obtained via electrochemical reactions. The common hinderance in such reactions is the sluggish oxygen evolution reaction (OER), which causes low energy efficiency in conversion devices. Developing highly active, earth-abundant OER electrocatalysts in alkaline media is necessary to boost the performance of such devices. Fe ion content in electrolyte is known to influence the OER-activity of metal oxide electrocatalysts. For example, the Fe incorporation in NiOOH is a well-established and important effect for OER.[1] Here, we present the effect of absorbed Fe on the OER activity of the epitaxial Ni-surface terminated LaNiO3 thin films. The correlation between surface species and OER activity of electrocatalysts was investigated using surface-sensitive low-energy ion scattering and X-ray photoemission spectroscopies. We observe more than an order-of-magnitude boost in OER activity during initial cycling, from 0.15 mAcm-2 to 3.40 mAcm-2 at 1.60 V vs. reversible hydrogen electrode. The activity increase was mainly caused by the incorporation of up to 5 % Fe at the top surface of LaNiO3 film (less than ~1 nm) even though only a very trace amount of Fe ion, 30 ppb, is present in the 0.1 M electrolyte of high purity KOH 99.99 %. Our results demonstrate that the disordered active surface phase, which develops even on single crystalline surfaces, is a complex interplay between the as-prepared (surface) crystalline structure, composition of the solid electrocatalyst and the liquid electrolyte, and has strong impact on the final OER activity, implying that we need to think differently about the crystalline electrocatalysts: crystalline bulk and dynamically changing surface layer.[1] L. Trotochaud, S.L. Young, J.K. Ranney, S.W. Boettcher, Nickel–Iron Oxyhydroxide Oxygen-Evolution Electrocatalysts: The Role of Intentional and Incidental Iron Incorporation, J. Am. Chem. Soc. 136 (2014) 6744–6753.

Stability in Photoluminescence and Photovoltaic Properties of Formamidinium Lead Iodide Quantum Dots

Formamidinium lead iodide (FAPI) thin films in the perovskite crystalline phase have piqued interest for single-junction solar cells due to their optimal bandgap, long photocarrier lifetime, and intrinsic structural stability. However, trap states on the surface and within the lattice impede the performance and stability of FAPI bulk crystalline film cells. Strategies such as film crystallization, deposition optimization, precursor engineering, and interface property tailoring aim to overcome these limitations. One approach involves forming FAPI quantum dots (QDs). By reducing the size, we achieve better quality and stable alpha-phase FAPI on a nanometer scale. In this contribution, we report synthesizing of alpha-phase FAPI QDs with a mean size distribution of 20 nm. These QDs exhibit a narrow photoluminescence emission peak at 1.61 eV and higher absolute quantum yields ranging from 70% to 86%. Compared to bulk FAPI with a 1.54 eV gap, a blue shift is observed due to the quantum confinement effect.However, achieving degradation-free perovskite solar cells under prolonged light soaking remains a challenge. Furthermore, we investigate the stability of FAPI bulk and QDS films in a humid chamber and after exposure to AM1.5G light in a humid setting (RH ~ 30%, T ~ 28°C). Our approach allows us to form homogeneously dispersed films of quantum dots with thicknesses of several hundred nanometers. These films are studied for photoluminescence and photovoltaic properties. Prototype solar cells incorporating synthesized FAPI QDs showed a power conversion efficiency of around 8%. These findings indicate considerably more stability in photoluminescence and photovoltaic properties of FAPI QDs for enhanced light-soaking stability compared to bulk FAPI films.

A lamellar-morphology-based computational modeling for predicting the thermal conductivity of semicrystalline polymers

Molecular-scale design of crystal structures is an emerging approach for significantly improving the intrinsic properties of polymers. In this study, we performed computational modeling to quantitatively predict the thermal conductivity of polymers based on their crystal morphology. Polyethylene lamellae with alternating crystalline and amorphous phases were prepared using isothermal crystallization within a coarse-grained molecular dynamics framework. The crystalline bulk, transient, and amorphous regions were clearly distinguished based on the distribution of the Steinhardt-bond order parameter. The thermal conductivity of the local regions was estimated discretely by applying a steady heat flow, facilitating a bottom-up prediction of the thermal response depending on the morphology of the lamellae. In particular, the integration with homogenization theory can evaluate the effective thermal conductivity of the system in terms of crystallinity, temperature, lamella thickness and orientation. The modeling successfully provided quantitative predictions for two representative hierarchical structures: spherulites and oriented crystals. Therefore, this study serves as a theoretical guide for molecular-level rational design of semicrystalline materials with high thermal conductivity.

Coalescence of Porous Coordination Cages into Crystalline and Amorphous Bulk Solids.

Discrete porous coordination cages are attractive as a solution processable material whose porosity is not predicated on a network structure. Here, we leverage the peripheral functionalization of these cage structures to obtain 12 novel, solution processable, porous coordination cages that afford crystalline and amorphous single-phase millimeter-scale monolithic bulk structures (six of each) upon solidification. These structures are based upon prototypal metal-organic polyhedra [Cu24(5-x-isophthalate)24] (where x = NH2, OH), wherein meta-substitution of linker ligands with acyl chloride or isocyanate moieties afforded amide and urethane functional groups, respectively. These porous cage structures were obtainable via direct synthesis between a metal salt and a ligand as well as postsynthetic modification of the cage and formed monoliths following centrifugation and drying of the product. We rationalize their self-assembly as colloidal packing of nanoscale cuboctahedral cages through weak interactions between their hydrophobic alkyl/aromatic surfaces. In general, amorphous solids were obtained via rapid precipitation from the mother liquor upon methanol addition, while crystalline solids could be obtained only following further chloroform and pyridine additions. The structure of the materials is confirmed via gas sorption and spectroscopic methods, while powder X-ray diffraction and transmission electron microscopy are used to determine the nature of these bulk solids.

Enhanced Catalytic Activity of Crystalline Phosphorus Nanosheets Fabricated via Solvothermal Phase Transformation.

The newly reported crystalline phosphorus nanosheets (cryst-P NSs) exhibit promising features for industrial applications, including outstanding air-water stability and facile large-scale production. However, their complex crystallization impedes a priori tailoring. Herein, the temporal evolution of cryst-P NSs was investigated with the optimized synthesis parameters. The occurrence of self-assembly and solid-state rearrangement unveiled the existence of an intermediate phase as the bulk crystalline precursor and the predominance of nonclassical crystallization pathway(s). With the upgraded synthesis protocol simultaneously strengthening the merits of cryst-P NSs, their catalytic performances were evaluated in various electro- and/or photocatalytic reactions spanning hydrogen and oxygen evolution, full water splitting, CO2 reduction, and organic pollutant decomposition. Superior catalytic activities and orders of magnitude longer lifetimes were consistently discerned compared with the widely employed black phosphorus nanosheets with similar size and thickness. The exciting discoveries in both fundamental crystallization and catalytic applications drastically thrust the comprehension of elemental phosphorus, shedding light on the encouraging capabilities of solvothermal synthesis strategies in the design and systematic tailoring of phosphorus materials.

Toward 1D Transport in 3D Materials: SOC-Induced Charge-Transport Anisotropy in Sm3ZrBi5.

1D charge transport offers great insight into strongly correlated physics, such as Luttinger liquids, electronic instabilities, and superconductivity. Although 1D charge transport is observed in nanomaterials and quantum wires, examples in bulk crystalline solids remain elusive. In this work, it is demonstrated that spin-orbit coupling (SOC) can act as a mechanism to induce quasi-1D charge transport in the Ln3MPn5 (Ln = lanthanide; M = transition metal; Pn = Pnictide) family. From three example compounds, La3ZrSb5, La3ZrBi5, and Sm3ZrBi5, density functional theory calculations with SOC included show a quasi-1D Fermi surface in the bismuthide compounds, but an anisotropic 3D Fermi surface in the antimonide structure. By performing anisotropic charge transport measurements on La3ZrSb5, La3ZrBi5, and Sm3ZrBi5, it is demonstrated that SOC starkly affects their anisotropic resistivity ratios (ARR) at low temperatures, with an ARR of ≈4 in the antimonide compared to ≈9.5 and ≈22 (≈32 after magnetic ordering) in La3ZrBi5 and Sm3ZrBi5, respectively. This report demonstrates the utility of spin-orbit coupling to induce quasi-low-dimensional Fermi surfaces in anisotropic crystal structures, and provides a template for examining othersystems.

Calorimetry of amorphous calcium carbonate is correlated with its lithification and durability as synthetic stone—implications for CO2 storage and utilization

The properties of amorphous calcium carbonate (ACC) and its transformations to crystalline polymorphs are frequently studied in aqueous systems and in small quantities. In this study, synthetic calcium carbonate stones are created from bulk ACC and crystalline polymorphs, which were precipitated from gaseous CO2, at a gradient of end pH. Some of the ACCs hardened into stones which are durable against an abrasion and impact test, while some of the ACCs create fragile, friable stones. When ACCs which transform to durable stones and those which transform into fragile stones were subject to calorimetry, significant differences were observed. These stones, synthesized from gaseous CO2, can be used as a storage reservoir for utilized CO2 in construction and other infrastructure applications.

Secondary-electron imaging of bulk crystalline specimens in an aberration corrected STEM

Atomic-scale electron microscopy traditionally probes thin specimens, with thickness below 100 nm, and its feasibility for bulk samples has not been documented. In this study, we explore the practicality of scanning transmission electron microscope (STEM) imaging with secondary electrons (SE), using a silicon-wedge specimen having a maximum thickness of 18 μm. We find that the atomic structure is present in the entire thickness range of the SE images although the background intensity increases moderately with thickness. The consistent intensity of secondary electron (SE) images at atomic positions and the modest increase in background intensity observed in silicon suggest a limited contribution from SEs generated by backscattered electrons, a conclusion supported by our multislice calculations. We conclude that achieving atomic resolution in SE imaging for bulk specimens is indeed attainable using aberration-corrected STEM and an aberration-corrected scanning electron microscope (SEM) may have the capacity for atomic-level resolution, holding great promise for future strides in materials research.

Quality-by-Design Approach to Process Intensification of Bioinspired Silica Synthesis.

Characterizing nanomaterials is challenging due to their macromolecular nature, requiring suites of physicochemical analysis to fully resolve their structure. As such, their synthesis and scale-up are notoriously complex, especially when compared to small molecules or bulk crystalline materials, which can be provided a unique fingerprint from nuclear magnetic resonance (NMR) or X-ray diffraction (XRD) alone. In this study, we address this challenge by adopting a three-step quality-by-design (QbD) approach to the scale-up of bioinspired silica nanomaterials, demonstrating its utility toward synthesis scale-up and intensification for this class of materials in general. First, we identified material-specific surface area, pore-size distribution, and reaction yield as critical quality attributes (CQAs) that could be precisely measured and controlled by changing reaction conditions. We then identified the critical process parameters (CPPs) controlling bioinspired synthesis properties, exploring different process routes, incorporating commercial reagents, and optimizing reagent ratios, comparing silica properties against original CQA values to identify acceptable limits to each CPP. Finally, we intensified the synthesis by increasing reagent concentration while simultaneously incorporating the optimized CPPs, thereby modifying the bioinspired silica synthesis to make it compatible with existing manufacturing methods. We increased the specific yield from ca. 1.1 to 38 g/L and reduced the additive intensity from ca. 1 to 0.04 g/g product, greatly reducing both synthesis cost and waste production. These results identify a need for mapping the effects of critical process parameters on material formation pathways and CQAs to enable accelerated scale-up and transition from the lab to the market.

Ultrahigh-quality-factor micro- and nanomechanical resonators using dissipation dilution.

Mechanical resonators are widely used in sensors, transducers and optomechanical systems, where mechanical dissipation sets the ultimate limit to performance. Over the past 15 years, the quality factors in strained mechanical resonators have increased by four orders of magnitude, surpassing the previous state of the art achieved in bulk crystalline resonators at room temperature and liquid helium temperatures. In this Review, we describe how these advances were made by leveraging 'dissipation dilution'-where dissipation is reduced through a combination of static tensile strain and geometric nonlinearity in dynamic strain. We then review the state of the art in strained nanomechanical resonators and discuss the potential for even higher quality factors in crystalline materials. Finally, we detail current and future applications of dissipation-diluted mechanical resonators.

Sol-gel Chemistry Approaches for the Manufacturing of Innovative Functional Composites for the Aerospace Sector

Sol-Gel is a “bottom-up” synthesis method that enables the production of films, nano/microparticles, fibers, gels, and bulk materials, both glassy and crystalline. Sol-Gel chemistry can be a vital tool for solving problems in several industrial applications where nanotechnology is necessary to overcome constraints. Here, various examples involving silicate-based materials are discussed. Silicatic materials with a variety of morphologies and applications, e.g., monodisperse SiO2 particles ranging in size from a few nanometers to a micron, can be synthesized through hydrolysis and polycondensation reactions of silicon alkoxide precursors. Using an environmentally friendly electrospinning process, silica nanoparticles can be incorporated into polyvinylpyrrolidone (PVP) fibers to create novel, fire-resistant sound absorbers. Additionally, by employing hybrid techniques based on Sol-Gel, the flame retardance of nanocomposites made of silica and epoxy resin as well as epoxy-based composites including hemp, even cured with cycloaliphatic hardeners, can be enhanced. The development of novel materials beneficial for aviation applications, such as hydrophobic (potentially self-anti-icing) coatings, is a further proof of the effectiveness of Sol-Gel chemistry.

Crystal net catalog of model flat band materials

Flat band systems are currently under intense investigation in quantum materials, optical lattices, and metamaterials. These efforts are motivated by potential realization of strongly correlated phenomena enabled by frustration-induced flat band dispersions; identification of candidate platforms plays an important role in these efforts. Here, we develop a high-throughput materials search for bulk crystalline flat bands by automated construction of uniform-hopping near-neighbor tight-binding models. We show that this approach captures many of the essential features relevant to identifying flat band lattice motifs in candidate materials in a computationally inexpensive manner, and is of use to identify systems for further detailed investigation as well as theoretical and metamaterials studies of model systems. We apply this algorithm to 139,367 materials in the Materials Project database and identify 63,076 materials that host at least one flat band elemental sublattice. We further categorize these candidate systems into at least 31,635 unique flat band crystal nets and identify candidates of interest from both lattice and band structure perspectives. This work expands the number of known flat band lattices that exist in physically realizable crystal structures and classifies the majority of these systems by the underlying lattice, providing additional insights for familiar (e.g., kagome, pyrochlore, Lieb, and dice) as well as previously unknown motifs.

Strain and optical characteristics analyses of three-dimentional self-ordered multilayered SiGe nanodots by photoluminescence and Raman spectroscopy

The strain state, optical properties, and band structure of the self-ordered multilayered silicon-germanium (SiGe) nanodots, which are staggered and dot-on-dot alignment and embedded by Si spacer, were evaluated by Raman spectroscopy and low-temperature photoluminescence (PL). These results suggest that the compressive strain applied to the staggered nanodots is smaller than that of the dot-on-dot nanodots, which contributes to the shrinking of the bandgap of the staggered nanodots. Strong PL intensity was observed from the nanodots compared to the single crystalline bulk SiGe due to the carrier confinement and high crystal quality of the nanodots. The stack-controlled nanodots showed a redshift of the PL peaks compared to the bulk SiGe and the effect of strain induced in SiGe nanodots might not be enough to explain this phenomenon. The cause of the redshift was clarified by considering the hetero band structure of the nanodots and the tensile strained spacer.

Effects of KoBo-Processing and Subsequent Annealing Treatment on Grain Boundary Network and Texture Development in Laser Powder Bed Fusion (LPBF) AlSi10Mg Alloy

It is well known that the properties of polycrystalline metals are related to grain boundaries (GBs), which are fundamental structural elements where crystallographic orientations change abruptly and often exhibit some degree of symmetry. Grain boundaries often exhibit unique structural, chemical, and electronic properties that differ from bulk crystalline domains. Their effects on material properties, including mechanical strength, corrosion resistance, and electrical conductivity, make grain boundaries a focus of intense scientific investigation. In this study, the microstructural transformation of an AlSi10Mg alloy subjected to KoBo extrusion and subsequent annealing is investigated. A notable discovery is the effectiveness of a strain-annealing method for grain boundary engineering (GBE) of the LPBF AlSi10Mg alloy. In particular, this study shows a significant increase in the population of coincidence site lattice boundaries (CSL), which embody the symmetry of the crystal lattice structure. These boundaries, which are characterised by a high degree of symmetry, contribute to their special properties compared to random grain boundaries. The experimental results emphasise the crucial role of strain-induced boundary migration (SIBM) in the development of a brass texture in the microstructure of the alloy after annealing. In addition, the presented results demonstrate the feasibility of applying GBE to materials with high stacking fault energy (SFE), which opens up new possibilities for optimizing their properties.

Halide Heterogeneous Structure Boosting Ionic Diffusion and High-Voltage Stability of Sodium Superionic Conductors.

The development of solid-state sodium-ion batteries (SSSBs) heavily hinges on the development of an superionic Na+ conductor (SSC) that features high conductivity, (electro)chemical stability, and deformability. The construction of heterogeneous structures offers a promising approach to comprehensively enhancing these properties in a way that differs from traditional structural optimization. Here, this work exploits the structural variance between high- and low-coordination halide frameworks to develop a new class of halide heterogeneous structure electrolytes (HSEs). The halide HSEs incorporating a UCl3 -type high-coordination framework and amorphous low-coordination phase achieves the highest Na+ conductivity (2.7 mS cm-1 at room temperature, RT) among halide SSCs so far. By discerning the individual contribution of the crystalline bulk, amorphous region, and interface, this work unravels the synergistic ion conduction within halide HSEs and provides a comprehensive explanation of the amorphization effect. More importantly, the excellent deformability, high-voltage stability, and expandability of HSEs enable effective SSSB integration. Using a cold-pressed cathode electrode composite of uncoated Na0.85 Mn0.5 Ni0.4 Fe0.1 O2 and HSEs, the SSSBs present stable cycle performance with a capacity retention of 91.0% after 100 cycles at 0.2 C.

Controlling Electron Delocalization in Vanadium‐Based Hybrid Bronzes through Molecular Templation

AbstractWe show that the conductivity of hybrid vanadium bronzes—mixed‐valence organic–inorganic vanadium oxides—can be tuned over six orders of magnitude through judicious choice of molecular component. By systematically varying the steric profile, charge density, and propensity to hydrogen bond across a series of eight diammonium‐based molecules, we engender multiple distinct motifs of V−O connectivity within the two‐dimensional vanadium oxide layers of a family of bulk crystalline hybrid materials. A combination of single‐crystal and powder X‐ray diffraction analysis, variable‐temperature electrical transport measurements, and a range of spectroscopic methods, including UV/Visible diffuse reflectance, X‐ray photoelectron, and electron paramagnetic resonance are employed to probe how vanadium oxide layer topology correlates with electron localization. Specifically, alkylammonium molecules yield hybrids featuring more corrugated layers that contain V−O tetrahedra as well as a higher ratio of corner‐sharing to edge‐sharing polyhedra and that exhibit highly localized electronic behavior, while alkyl bipyridinium molecules yield more regular layers with polyhedral edge‐sharing that show substantially delocalized electronic behavior. This work allows for the development of design principles based on structure–property relationships and brings the charge transport capabilities of hybrid vanadium bronzes to more technologically relevant levels.

Controlling Electron Delocalization in Vanadium-Based Hybrid Bronzes through Molecular Templation.

We show that the conductivity of hybrid vanadium bronzes-mixed-valence organic-inorganic vanadium oxides-can be tuned over six orders of magnitude through judicious choice of molecular component. By systematically varying the steric profile, charge density, and propensity to hydrogen bond across a series of eight diammonium-based molecules, we engender multiple distinct motifs of V-O connectivity within the two-dimensional vanadium oxide layers of a family of bulk crystalline hybrid materials. A combination of single-crystal and powder X-ray diffraction analysis, variable-temperature electrical transport measurements, and a range of spectroscopic methods, including UV/Visible diffuse reflectance, X-ray photoelectron, and electron paramagnetic resonance are employed to probe how vanadium oxide layer topology correlates with electron localization. Specifically, alkylammonium molecules yield hybrids featuring more corrugated layers that contain V-O tetrahedra as well as a higher ratio of corner-sharing to edge-sharing polyhedra and that exhibit highly localized electronic behavior, while alkyl bipyridinium molecules yield more regular layers with polyhedral edge-sharing that show substantially delocalized electronic behavior. This work allows for the development of design principles based on structure-property relationships and brings the charge transport capabilities of hybrid vanadium bronzes to more technologically relevant levels.

Grain-size effect on Cr3+ and F-centres photoluminescence in nanophase MgAl2O4 ceramics

Photoluminescence (PL) spectroscopy of transparent MgAl2O4 spinel ceramics with grain size between 100 and 300 nm was studied at 7 K temperature in the near-IR-VUV range of spectrum with synchrotron radiation excitation. The PL spectra were composed of optical transitions from spatially different regions of the ceramics, which analysis evidenced grain size effect on the emission line-shapes and intensities. In particular, emission of impurity Cr3+ ions, being structured in the crystalline bulk, became broad-band in the grain boundary regions, which was associated with respectively strong and weak local crystalline fields. It was observed that (i) excitons and F centres transfer energy to Cr3+ and (ii) Cr(2Eg)/Cr(4T2g) and F-centres/Cr3+ PL intensity ratios underwent a linear dependence on the grain size.

Tuning of SiO2/Si interface by a hybrid plasma process combining oxidation and atom-migration

As a common oxide-semiconductor interface, SiO2/Si plays an important role in silicon-based electronics and optoelectronics. In order to effectively obtain an ultra-smooth and thin SiO2/Si interface, a hybrid tuning process based on inductively coupled plasma (ICP) was proposed, which combined oxidation (plasma-OX) and atom-migration manufacturing (plasma-AMM). In plasma-OX process, a thick oxide film was rapidly prepared on Si wafer surface in 2 min, which included a SiO2 layer on the top and a SiOx (x < 2) layer between the top layer and the bulk crystalline silicon (c-Si). In subsequent plasma-AMM process, ICP steadily delivered energy to the Si wafer surface and induced the migration of unsaturated Si from SiOx layer to c-Si, which enhanced the crystallization of silicon wafer. The roughness of SiO2/Si interface was reduced to Sa 0.171 nm at 620 W in 5 min. However, a 2–3 nm thickness SiOx layer still existed, and several defects causing by residual thermal stress can be observed. Further optimizing plasma-AMM process by setting multi-step slow cooling, the SiOx layer can be almost completely decomposed. The interface roughness Sa was reduced to <0.1 nm and the interface thickness was reduced to 1–2 atom layer. Both OX and AMM process were conducted in the same setup, which is convenient for switching. This study proposed and demonstrated the feasibility of a hybrid plasma tuning process, which provided an efficient tuning technology at atomic level for semiconductor interface.